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Title: High‐Temperature Treatment of Li‐Rich Cathode Materials with Ammonia: Improved Capacity and Mean Voltage Stability during Cycling

Abstract

Li‐rich electrode materials of the family x Li 2 MnO 3 ·(1− x )LiNi a Co b Mn c O 2 ( a + b + c = 1) suffer a voltage fade upon cycling that limits their utilization in commercial batteries despite their extremely high discharge capacity, ≈250 mA h g −1 . Li‐rich, 0.35Li 2 MnO 3 ·0.65LiNi 0.35 Mn 0.45 Co 0.20 O 2 , is exposed to NH 3 at 400 °C, producing materials with improved characteristics: enhanced electrode capacity and a limited average voltage fade during 100 cycles in half cells versus Li. Three main changes caused by NH 3 treatment are established. First, a general bulk reduction of Co and Mn is observed via X‐ray photoelectron spectroscopy and X‐ray absorption near edge structure. Next, a structural rearrangement lowers the coordination number of CoO and MnO bonds, as well as formation of a surface spinel‐like structure. Additionally, Li + removal from the bulk causes the formation of surface LiOH, Li 2 CO 3 , and Li 2 O. These structural and surface changes can enhance the voltage and capacity stability of the Li‐rich material electrodes after moderate NH 3 treatment times of 1–2 h.

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [1];  [1];  [3];  [1];  [1];  [4];  [5];  [5];  [1];  [2];  [1]
+ Show Author Affiliations
  1. Department of Chemistry Faculty of Exact Sciences Bar‐Ilan University Ramat‐Gan 5290002 Israel
  2. Department of Materials Science and Chemical Engineering Stony Brook University Stony Brook NY 11794 USA
  3. Wolfson Applied Materials Research Center Tel‐Aviv University Tel‐Aviv 69978 Israel
  4. Department of Materials Engineering Ben Gurion University of the Negev Beer‐Sheva 8410501 Israel
  5. BASF SE 67063 Ludwigshafen am Rhein Rheinland‐Pfalz Germany
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1393303
Grant/Contract Number:  
DE‐AC02‐06CH11357
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Name: Advanced Energy Materials Journal Volume: 7 Journal Issue: 18; Journal ID: ISSN 1614-6832
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Erickson, Evan M., Sclar, Hadar, Schipper, Florian, Liu, Jing, Tian, Ruiyuan, Ghanty, Chandan, Burstein, Larisa, Leifer, Nicole, Grinblat, Judith, Talianker, Michael, Shin, Ji‐Yong, Lampert, Jordan K., Markovsky, Boris, Frenkel, Anatoly I., and Aurbach, Doron. High‐Temperature Treatment of Li‐Rich Cathode Materials with Ammonia: Improved Capacity and Mean Voltage Stability during Cycling. Germany: N. p., 2017. Web. doi:10.1002/aenm.201700708.
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Erickson, Evan M., Sclar, Hadar, Schipper, Florian, Liu, Jing, Tian, Ruiyuan, Ghanty, Chandan, Burstein, Larisa, Leifer, Nicole, Grinblat, Judith, Talianker, Michael, Shin, Ji‐Yong, Lampert, Jordan K., Markovsky, Boris, Frenkel, Anatoly I., & Aurbach, Doron. High‐Temperature Treatment of Li‐Rich Cathode Materials with Ammonia: Improved Capacity and Mean Voltage Stability during Cycling. Germany. https://doi.org/10.1002/aenm.201700708
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Erickson, Evan M., Sclar, Hadar, Schipper, Florian, Liu, Jing, Tian, Ruiyuan, Ghanty, Chandan, Burstein, Larisa, Leifer, Nicole, Grinblat, Judith, Talianker, Michael, Shin, Ji‐Yong, Lampert, Jordan K., Markovsky, Boris, Frenkel, Anatoly I., and Aurbach, Doron. Mon . "High‐Temperature Treatment of Li‐Rich Cathode Materials with Ammonia: Improved Capacity and Mean Voltage Stability during Cycling". Germany. https://doi.org/10.1002/aenm.201700708.
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@article{osti_1393303,
title = {High‐Temperature Treatment of Li‐Rich Cathode Materials with Ammonia: Improved Capacity and Mean Voltage Stability during Cycling},
author = {Erickson, Evan M. and Sclar, Hadar and Schipper, Florian and Liu, Jing and Tian, Ruiyuan and Ghanty, Chandan and Burstein, Larisa and Leifer, Nicole and Grinblat, Judith and Talianker, Michael and Shin, Ji‐Yong and Lampert, Jordan K. and Markovsky, Boris and Frenkel, Anatoly I. and Aurbach, Doron},
abstractNote = {Li‐rich electrode materials of the family x Li 2 MnO 3 ·(1− x )LiNi a Co b Mn c O 2 ( a + b + c = 1) suffer a voltage fade upon cycling that limits their utilization in commercial batteries despite their extremely high discharge capacity, ≈250 mA h g −1 . Li‐rich, 0.35Li 2 MnO 3 ·0.65LiNi 0.35 Mn 0.45 Co 0.20 O 2 , is exposed to NH 3 at 400 °C, producing materials with improved characteristics: enhanced electrode capacity and a limited average voltage fade during 100 cycles in half cells versus Li. Three main changes caused by NH 3 treatment are established. First, a general bulk reduction of Co and Mn is observed via X‐ray photoelectron spectroscopy and X‐ray absorption near edge structure. Next, a structural rearrangement lowers the coordination number of CoO and MnO bonds, as well as formation of a surface spinel‐like structure. Additionally, Li + removal from the bulk causes the formation of surface LiOH, Li 2 CO 3 , and Li 2 O. These structural and surface changes can enhance the voltage and capacity stability of the Li‐rich material electrodes after moderate NH 3 treatment times of 1–2 h.},
doi = {10.1002/aenm.201700708},
journal = {Advanced Energy Materials},
number = 18,
volume = 7,
place = {Germany},
year = {Mon May 22 00:00:00 EDT 2017},
month = {Mon May 22 00:00:00 EDT 2017}
}
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https://doi.org/10.1002/aenm.201700708
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