DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Electrochemically activated spinel manganese oxide for rechargeable aqueous aluminum battery

Abstract

Aluminum is a naturally abundant, trivalent charge carrier with high theoretical specific capacity and volumetric energy density, rendering aluminum-ion batteries a technology of choice for future large-scale energy storage. Nonetheless, the frequent collapse of the host structure of the cathode materials and sluggish kinetics of aluminum ion diffusion have thus far hampered the realization of practical battery devices. Here, we synthesize AlxMnO2•nH2O by an in-situ electrochemical transformation reaction to be used as a cathode material for an aluminum-ion battery with a configuration of Al/Al(OTF)3-H2O/AlxMnO2•nH2O. This cell is not only based on aqueous electrolyte chemistry but also delivers a high specific capacity of 467 mAh g-1 and a record high energy density of 481 Wh kg-1. The high safety of aqueous electrolyte, facile cell assembly and the low cost of materials suggest that this aqueous aluminum-ion battery holds promise for large-scale energy applications.

Authors:
 [1];  [2];  [3];  [2];  [4]; ORCiD logo [4];  [2];  [3];  [2];  [2];  [1];  [3];  [3]; ORCiD logo [4]
  1. Beijing Inst. of Technology, Beijing (China); Collaborative Innovation Center of Electric Vehicles in Beijing, Beijing (China)
  2. Beijing Inst. of Technology, Beijing (China)
  3. Chinese Academy of Sciences (CAS), Beijing (China)
  4. Argonne National Laboratory (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1504227
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Wu, Chuan, Gu, Sichen, Zhang, Qinghua, Bai, Ying, Li, Matthew, Yuan, Yifei, Wang, Huali, Liu, Xinyu, Yuan, Yanxia, Zhu, Na, Wu, Feng, Li, Hong, Gu, Lin, and Lu, Jun. Electrochemically activated spinel manganese oxide for rechargeable aqueous aluminum battery. United States: N. p., 2019. Web. doi:10.1038/s41467-018-07980-7.
Wu, Chuan, Gu, Sichen, Zhang, Qinghua, Bai, Ying, Li, Matthew, Yuan, Yifei, Wang, Huali, Liu, Xinyu, Yuan, Yanxia, Zhu, Na, Wu, Feng, Li, Hong, Gu, Lin, & Lu, Jun. Electrochemically activated spinel manganese oxide for rechargeable aqueous aluminum battery. United States. https://doi.org/10.1038/s41467-018-07980-7
Wu, Chuan, Gu, Sichen, Zhang, Qinghua, Bai, Ying, Li, Matthew, Yuan, Yifei, Wang, Huali, Liu, Xinyu, Yuan, Yanxia, Zhu, Na, Wu, Feng, Li, Hong, Gu, Lin, and Lu, Jun. Tue . "Electrochemically activated spinel manganese oxide for rechargeable aqueous aluminum battery". United States. https://doi.org/10.1038/s41467-018-07980-7. https://www.osti.gov/servlets/purl/1504227.
@article{osti_1504227,
title = {Electrochemically activated spinel manganese oxide for rechargeable aqueous aluminum battery},
author = {Wu, Chuan and Gu, Sichen and Zhang, Qinghua and Bai, Ying and Li, Matthew and Yuan, Yifei and Wang, Huali and Liu, Xinyu and Yuan, Yanxia and Zhu, Na and Wu, Feng and Li, Hong and Gu, Lin and Lu, Jun},
abstractNote = {Aluminum is a naturally abundant, trivalent charge carrier with high theoretical specific capacity and volumetric energy density, rendering aluminum-ion batteries a technology of choice for future large-scale energy storage. Nonetheless, the frequent collapse of the host structure of the cathode materials and sluggish kinetics of aluminum ion diffusion have thus far hampered the realization of practical battery devices. Here, we synthesize AlxMnO2•nH2O by an in-situ electrochemical transformation reaction to be used as a cathode material for an aluminum-ion battery with a configuration of Al/Al(OTF)3-H2O/AlxMnO2•nH2O. This cell is not only based on aqueous electrolyte chemistry but also delivers a high specific capacity of 467 mAh g-1 and a record high energy density of 481 Wh kg-1. The high safety of aqueous electrolyte, facile cell assembly and the low cost of materials suggest that this aqueous aluminum-ion battery holds promise for large-scale energy applications.},
doi = {10.1038/s41467-018-07980-7},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {Tue Jan 08 00:00:00 EST 2019},
month = {Tue Jan 08 00:00:00 EST 2019}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 237 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

A Rechargeable Al/S Battery with an Ionic-Liquid Electrolyte
journal, July 2016

  • Gao, Tao; Li, Xiaogang; Wang, Xiwen
  • Angewandte Chemie International Edition, Vol. 55, Issue 34
  • DOI: 10.1002/anie.201603531

A Novel Aluminum-Ion Battery: Al/AlCl 3 -[EMIm]Cl/Ni 3 S 2 @Graphene
journal, April 2016


High-Voltage and Noncorrosive Ionic Liquid Electrolyte Used in Rechargeable Aluminum Battery
journal, October 2016

  • Wang, Huali; Gu, Sichen; Bai, Ying
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 41
  • DOI: 10.1021/acsami.6b10579

Reversible Aluminum-Ion Intercalation in Prussian Blue Analogs and Demonstration of a High-Power Aluminum-Ion Asymmetric Capacitor
journal, November 2014


Copper hexacyanoferrate nanoparticles as cathode material for aqueous Al-ion batteries
journal, January 2015

  • Liu, S.; Pan, G. L.; Li, G. R.
  • Journal of Materials Chemistry A, Vol. 3, Issue 3
  • DOI: 10.1039/C4TA04644G

Issues and challenges facing rechargeable lithium batteries
journal, November 2001

  • Tarascon, J.-M.; Armand, M.
  • Nature, Vol. 414, Issue 6861, p. 359-367
  • DOI: 10.1038/35104644

The Role of Ionic Liquid Electrolyte in an Aluminum–Graphite Electrochemical Cell
journal, February 2017


A novel non-aqueous aluminum sulfur battery
journal, June 2015


An Innovative Freeze-Dried Reduced Graphene Oxide Supported SnS 2 Cathode Active Material for Aluminum-Ion Batteries
journal, March 2017


An ultrafast rechargeable aluminium-ion battery
journal, April 2015

  • Lin, Meng-Chang; Gong, Ming; Lu, Bingan
  • Nature, Vol. 520, Issue 7547
  • DOI: 10.1038/nature14340

Binder-Free V 2 O 5 Cathode for Greener Rechargeable Aluminum Battery
journal, December 2014

  • Wang, Huali; Bai, Ying; Chen, Shi
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 1
  • DOI: 10.1021/am508001h

Reversible Electrochemical Intercalation of Aluminum in Mo 6 S 8
journal, July 2015


Fluorinated Natural Graphite Cathode for Rechargeable Ionic Liquid Based Aluminum–Ion Battery
journal, January 2013

  • Rani, J. Vatsala; Kanakaiah, V.; Dadmal, Tulshiram
  • Journal of The Electrochemical Society, Vol. 160, Issue 10
  • DOI: 10.1149/2.072310jes

Electrochemical Energy Storage with a Reversible Nonaqueous Room-Temperature Aluminum-Sulfur Chemistry
journal, May 2017


Multi-electron reaction materials for high energy density batteries
journal, January 2010

  • Gao, Xue-Ping; Yang, Han-Xi
  • Energy Environ. Sci., Vol. 3, Issue 2
  • DOI: 10.1039/B916098A

An Overview and Future Perspectives of Aluminum Batteries
journal, June 2016

  • Elia, Giuseppe Antonio; Marquardt, Krystan; Hoeppner, Katrin
  • Advanced Materials, Vol. 28, Issue 35
  • DOI: 10.1002/adma.201601357

Aluminum storage behavior of anatase TiO2 nanotube arrays in aqueous solution for aluminum ion batteries
journal, January 2012

  • Liu, S.; Hu, J. J.; Yan, N. F.
  • Energy & Environmental Science, Vol. 5, Issue 12
  • DOI: 10.1039/c2ee22987k

Hexagonal NiS nanobelts as advanced cathode materials for rechargeable Al-ion batteries
journal, January 2016

  • Yu, Zhijing; Kang, Zepeng; Hu, Zongqian
  • Chemical Communications, Vol. 52, Issue 68
  • DOI: 10.1039/C6CC05974K

Anion-effects on electrochemical properties of ionic liquid electrolytes for rechargeable aluminum batteries
journal, January 2015

  • Wang, Huali; Gu, Sichen; Bai, Ying
  • Journal of Materials Chemistry A, Vol. 3, Issue 45
  • DOI: 10.1039/C5TA06187C

Building better batteries
journal, February 2008

  • Armand, M.; Tarascon, J.-M.
  • Nature, Vol. 451, Issue 7179, p. 652-657
  • DOI: 10.1038/451652a

Thermodynamic analysis on energy densities of batteries
journal, January 2011

  • Zu, Chen-Xi; Li, Hong
  • Energy & Environmental Science, Vol. 4, Issue 8
  • DOI: 10.1039/c0ee00777c

A rechargeable aluminum-ion battery utilizing a copper hexacyanoferrate cathode in an organic electrolyte
journal, January 2015

  • Reed, L. D.; Ortiz, S. N.; Xiong, M.
  • Chemical Communications, Vol. 51, Issue 76
  • DOI: 10.1039/C5CC06053B

A rechargeable Al-ion battery: Al/molten AlCl 3 –urea/graphite
journal, January 2017

  • Jiao, Handong; Wang, Chen; Tu, Jiguo
  • Chemical Communications, Vol. 53, Issue 15
  • DOI: 10.1039/C6CC09825H

From spinel Mn3O4 to layered nanoarchitectures using electrochemical cycling and the distinctive pseudocapacitive behavior
journal, March 2007

  • Dai, Yang; Wang, Ke; Xie, Jingying
  • Applied Physics Letters, Vol. 90, Issue 10
  • DOI: 10.1063/1.2711286

Rechargeable aqueous zinc-manganese dioxide batteries with high energy and power densities
journal, September 2017


Evaluation of MnO x , Mn 2 O 3 , and Mn 3 O 4 Electrodeposited Films for the Oxygen Evolution Reaction of Water
journal, June 2014

  • Ramírez, Alejandra; Hillebrand, Philipp; Stellmach, Diana
  • The Journal of Physical Chemistry C, Vol. 118, Issue 26
  • DOI: 10.1021/jp500939d

Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011


Layered-to-Spinel Phase Transition in Li[sub x]MnO[sub 2]
journal, January 2001

  • Reed, J.; Ceder, G.; Van Der Ven, A.
  • Electrochemical and Solid-State Letters, Vol. 4, Issue 6
  • DOI: 10.1149/1.1368896

Open-Structured V 2 O 5 · n H 2 O Nanoflakes as Highly Reversible Cathode Material for Monovalent and Multivalent Intercalation Batteries
journal, April 2017

  • Wang, Huali; Bi, Xuanxuan; Bai, Ying
  • Advanced Energy Materials, Vol. 7, Issue 14
  • DOI: 10.1002/aenm.201602720

In Situ X-ray Absorption Spectroscopy Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction
journal, June 2013

  • Gorlin, Yelena; Lassalle-Kaiser, Benedikt; Benck, Jesse D.
  • Journal of the American Chemical Society, Vol. 135, Issue 23
  • DOI: 10.1021/ja3104632

Enhancement effect of Na ions on capacitive behavior of amorphous MnO2
journal, September 2014


Discharge/charge reaction mechanisms of FeS2 cathode material for aluminum rechargeable batteries at 55°C
journal, May 2016


The Li-Ion Rechargeable Battery: A Perspective
journal, January 2013

  • Goodenough, John B.; Park, Kyu-Sung
  • Journal of the American Chemical Society, Vol. 135, Issue 4
  • DOI: 10.1021/ja3091438

High-Performance Aluminum-Ion Battery with CuS@C Microsphere Composite Cathode
journal, December 2016


On the Mechanism of Crystal Water Insertion during Anomalous Spinel-to- Birnessite Phase Transition
journal, July 2016


The High Performance of Crystal Water Containing Manganese Birnessite Cathodes for Magnesium Batteries
journal, May 2015


Direct Observation of an Anomalous Spinel-to-Layered Phase Transition Mediated by Crystal Water Intercalation
journal, October 2015

  • Kim, Sangryun; Nam, Kwan Woo; Lee, Soyeon
  • Angewandte Chemie International Edition, Vol. 54, Issue 50
  • DOI: 10.1002/anie.201505487

The rechargeable aluminum-ion battery
journal, January 2011

  • Jayaprakash, N.; Das, S. K.; Archer, L. A.
  • Chemical Communications, Vol. 47, Issue 47
  • DOI: 10.1039/c1cc15779e

A new aluminium-ion battery with high voltage, high safety and low cost
journal, January 2015

  • Sun, Haobo; Wang, Wei; Yu, Zhijing
  • Chemical Communications, Vol. 51, Issue 59
  • DOI: 10.1039/C5CC00542F

Direct Observation of an Anomalous Spinel-to-Layered Phase Transition Mediated by Crystal Water Intercalation
journal, October 2015


A Rechargeable Al/S Battery with an Ionic-Liquid Electrolyte
journal, July 2016


Reversible Aluminum-Ion Intercalation in Prussian Blue Analogs and Demonstration of a High-Power Aluminum-Ion Asymmetric Capacitor
journal, November 2014


A Novel Aluminum-Ion Battery: Al/AlCl 3 -[EMIm]Cl/Ni 3 S 2 @Graphene
journal, April 2016


Electrochemical Energy Storage with a Reversible Nonaqueous Room-Temperature Aluminum-Sulfur Chemistry
journal, May 2017


Direct Observation of an Anomalous Spinel-to-Layered Phase Transition Mediated by Crystal Water Intercalation
journal, October 2015


Enhancement effect of Na ions on capacitive behavior of amorphous MnO2
journal, September 2014


A novel non-aqueous aluminum sulfur battery
journal, June 2015


Discharge/charge reaction mechanisms of FeS2 cathode material for aluminum rechargeable batteries at 55°C
journal, May 2016


Reversible Electrochemical Intercalation of Aluminum in Mo 6 S 8
journal, July 2015


On the Mechanism of Crystal Water Insertion during Anomalous Spinel-to- Birnessite Phase Transition
journal, July 2016


The High Performance of Crystal Water Containing Manganese Birnessite Cathodes for Magnesium Batteries
journal, May 2015


High-Voltage and Noncorrosive Ionic Liquid Electrolyte Used in Rechargeable Aluminum Battery
journal, October 2016

  • Wang, Huali; Gu, Sichen; Bai, Ying
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 41
  • DOI: 10.1021/acsami.6b10579

High-Performance Aluminum-Ion Battery with CuS@C Microsphere Composite Cathode
journal, December 2016


In Situ X-ray Absorption Spectroscopy Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction
journal, June 2013

  • Gorlin, Yelena; Lassalle-Kaiser, Benedikt; Benck, Jesse D.
  • Journal of the American Chemical Society, Vol. 135, Issue 23
  • DOI: 10.1021/ja3104632

Evaluation of MnO x , Mn 2 O 3 , and Mn 3 O 4 Electrodeposited Films for the Oxygen Evolution Reaction of Water
journal, June 2014

  • Ramírez, Alejandra; Hillebrand, Philipp; Stellmach, Diana
  • The Journal of Physical Chemistry C, Vol. 118, Issue 26
  • DOI: 10.1021/jp500939d

Issues and challenges facing rechargeable lithium batteries
journal, November 2001

  • Tarascon, J.-M.; Armand, M.
  • Nature, Vol. 414, Issue 6861, p. 359-367
  • DOI: 10.1038/35104644

Building better batteries
journal, February 2008

  • Armand, M.; Tarascon, J.-M.
  • Nature, Vol. 451, Issue 7179, p. 652-657
  • DOI: 10.1038/451652a

Rechargeable aqueous zinc-manganese dioxide batteries with high energy and power densities
journal, September 2017


Thermodynamic analysis on energy densities of batteries
journal, January 2011

  • Zu, Chen-Xi; Li, Hong
  • Energy & Environmental Science, Vol. 4, Issue 8
  • DOI: 10.1039/c0ee00777c

The rechargeable aluminum-ion battery
journal, January 2011

  • Jayaprakash, N.; Das, S. K.; Archer, L. A.
  • Chemical Communications, Vol. 47, Issue 47
  • DOI: 10.1039/c1cc15779e

Aluminum storage behavior of anatase TiO2 nanotube arrays in aqueous solution for aluminum ion batteries
journal, January 2012

  • Liu, S.; Hu, J. J.; Yan, N. F.
  • Energy & Environmental Science, Vol. 5, Issue 12
  • DOI: 10.1039/c2ee22987k

Origin of unusual spinel-to-layered phase transformation by crystal water
journal, January 2018

  • Yang, Eunjeong; Kim, Heejin; Kim, Sangryun
  • Chemical Science, Vol. 9, Issue 2
  • DOI: 10.1039/c7sc04114d

From spinel Mn3O4 to layered nanoarchitectures using electrochemical cycling and the distinctive pseudocapacitive behavior
journal, March 2007

  • Dai, Yang; Wang, Ke; Xie, Jingying
  • Applied Physics Letters, Vol. 90, Issue 10
  • DOI: 10.1063/1.2711286

Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011


Layered-to-Spinel Phase Transition in Li[sub x]MnO[sub 2]
journal, January 2001

  • Reed, J.; Ceder, G.; Van Der Ven, A.
  • Electrochemical and Solid-State Letters, Vol. 4, Issue 6
  • DOI: 10.1149/1.1368896

Fluorinated Natural Graphite Cathode for Rechargeable Ionic Liquid Based Aluminum–Ion Battery
journal, January 2013

  • Rani, J. Vatsala; Kanakaiah, V.; Dadmal, Tulshiram
  • Journal of The Electrochemical Society, Vol. 160, Issue 10
  • DOI: 10.1149/2.072310jes

Works referencing / citing this record:

Self‐Limiting Galvanic Growth of MnO 2 Monolayers on a Liquid Metal—Applied to Photocatalysis
journal, July 2019

  • Ghasemian, Mohammad B.; Mayyas, Mohannad; Idrus‐Saidi, Shuhada A.
  • Advanced Functional Materials, Vol. 29, Issue 36
  • DOI: 10.1002/adfm.201901649

A High‐Energy Aqueous Aluminum‐Manganese Battery
journal, September 2019

  • He, Shiman; Wang, Jie; Zhang, Xu
  • Advanced Functional Materials, Vol. 29, Issue 45
  • DOI: 10.1002/adfm.201905228

The Compensation Effect Mechanism of Fe–Ni Mixed Prussian Blue Analogues in Aqueous Rechargeable Aluminum‐Ion Batteries
journal, January 2020


Facile Synthesis of Copper Sulfide Nanosheet@Graphene Oxide for the Anode of Potassium‐Ion Batteries
journal, September 2019


Advanced Functional Fiber and Smart Textile
journal, July 2019


A rechargeable aqueous aluminum–sulfur battery through acid activation in water-in-salt electrolyte
journal, January 2020

  • Hu, Zhiqiu; Guo, Yue; Jin, Hongchang
  • Chemical Communications, Vol. 56, Issue 13
  • DOI: 10.1039/c9cc08415k

Voltage issue of aqueous rechargeable metal-ion batteries
journal, January 2020

  • Liu, Zhuoxin; Huang, Yan; Huang, Yang
  • Chemical Society Reviews, Vol. 49, Issue 1
  • DOI: 10.1039/c9cs00131j

Synthesis of ternary metal oxides as positive electrodes for Mg–Li hybrid ion batteries
journal, January 2020

  • Asif, Muhammad; Rashad, Muhammad; Ali, Zeeshan
  • Nanoscale, Vol. 12, Issue 2
  • DOI: 10.1039/c9nr08758c

On the unsuspected role of multivalent metal ions on the charge storage of a metal oxide electrode in mild aqueous electrolytes
journal, January 2019

  • Kim, Yee-Seul; Harris, Kenneth D.; Limoges, Benoît
  • Chemical Science, Vol. 10, Issue 38
  • DOI: 10.1039/c9sc02397f

Use of a water-in-salt electrolyte to avoid organic material dissolution and enhance the kinetics of aqueous potassium ion batteries
journal, January 2020

  • Chen, Hong; Zhang, Zhongyu; Wei, Zhixuan
  • Sustainable Energy & Fuels, Vol. 4, Issue 1
  • DOI: 10.1039/c9se00545e

A low-cost and dendrite-free rechargeable aluminium-ion battery with superior performance
journal, January 2019

  • Pan, Wending; Wang, Yifei; Zhang, Yingguang
  • Journal of Materials Chemistry A, Vol. 7, Issue 29
  • DOI: 10.1039/c9ta05207k

A one-dimensional channel self-standing MOF cathode for ultrahigh-energy-density flexible Ni–Zn batteries
journal, January 2019

  • Man, Ping; He, Bing; Zhang, Qichong
  • Journal of Materials Chemistry A, Vol. 7, Issue 48
  • DOI: 10.1039/c9ta11759h

Beyond Lithium-Based Batteries
journal, January 2020

  • Biemolt, Jasper; Jungbacker, Peter; van Teijlingen, Tess
  • Materials, Vol. 13, Issue 2
  • DOI: 10.3390/ma13020425