Fluorinated interphase enables reversible aqueous zinc battery chemistries
Metallic zinc is an ideal anode due to its high theoretical capacity (820 mAh g −1 ), low redox potential (−0.762 V versus the standard hydrogen electrode), high abundance and low toxicity. When used in aqueous electrolyte, it also brings intrinsic safety, but suffers from severe irreversibility. Th...
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| Published in | Nature nanotechnology Vol. 16; no. 8; pp. 902 - 910 |
|---|---|
| Main Authors | , , , , , , , , , , , , , , , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
London
Nature Publishing Group UK
01.08.2021
Nature Publishing Group |
| Subjects | |
| Online Access | Get full text |
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| Abstract | Metallic zinc is an ideal anode due to its high theoretical capacity (820 mAh g
−1
), low redox potential (−0.762 V versus the standard hydrogen electrode), high abundance and low toxicity. When used in aqueous electrolyte, it also brings intrinsic safety, but suffers from severe irreversibility. This is best exemplified by low coulombic efficiency, dendrite growth and water consumption. This is thought to be due to severe hydrogen evolution during zinc plating and stripping, hitherto making the in-situ formation of a solid–electrolyte interphase (SEI) impossible. Here, we report an aqueous zinc battery in which a dilute and acidic aqueous electrolyte with an alkylammonium salt additive assists the formation of a robust, Zn
2+
-conducting and waterproof SEI. The presence of this SEI enables excellent performance: dendrite-free zinc plating/stripping at 99.9% coulombic efficiency in a Ti||Zn asymmetric cell for 1,000 cycles; steady charge–discharge in a Zn||Zn symmetric cell for 6,000 cycles (6,000 h); and high energy densities (136 Wh kg
−1
in a Zn||VOPO
4
full battery with 88.7% retention for >6,000 cycles, 325 Wh kg
−1
in a Zn||O
2
full battery for >300 cycles and 218 Wh kg
−1
in a Zn||MnO
2
full battery with 88.5% retention for 1,000 cycles) using limited zinc. The SEI-forming electrolyte also allows the reversible operation of an anode-free pouch cell of Ti||Zn
x
VOPO
4
at 100% depth of discharge for 100 cycles, thus establishing aqueous zinc batteries as viable cell systems for practical applications.
A solid–electrolyte interphase that is permeable to Zn(
ii
) ions but waterproof is formed using an aqueous electrolyte composition. Cycling performances in an anode-free aqueous pouch cell show promise for intrinsically safe energy storage applications. |
|---|---|
| AbstractList | Metallic zinc is an ideal anode due to its high theoretical capacity (820 mAh g-1), low redox potential (-0.762 V versus the standard hydrogen electrode), high abundance and low toxicity. When used in aqueous electrolyte, it also brings intrinsic safety, but suffers from severe irreversibility. This is best exemplified by low coulombic efficiency, dendrite growth and water consumption. This is thought to be due to severe hydrogen evolution during zinc plating and stripping, hitherto making the in-situ formation of a solid-electrolyte interphase (SEI) impossible. Here, we report an aqueous zinc battery in which a dilute and acidic aqueous electrolyte with an alkylammonium salt additive assists the formation of a robust, Zn2+-conducting and waterproof SEI. The presence of this SEI enables excellent performance: dendrite-free zinc plating/stripping at 99.9% coulombic efficiency in a Ti||Zn asymmetric cell for 1,000 cycles; steady charge-discharge in a Zn||Zn symmetric cell for 6,000 cycles (6,000 h); and high energy densities (136 Wh kg-1 in a Zn||VOPO4 full battery with 88.7% retention for >6,000 cycles, 325 Wh kg-1 in a Zn||O2 full battery for >300 cycles and 218 Wh kg-1 in a Zn||MnO2 full battery with 88.5% retention for 1,000 cycles) using limited zinc. The SEI-forming electrolyte also allows the reversible operation of an anode-free pouch cell of Ti||ZnxVOPO4 at 100% depth of discharge for 100 cycles, thus establishing aqueous zinc batteries as viable cell systems for practical applications.Metallic zinc is an ideal anode due to its high theoretical capacity (820 mAh g-1), low redox potential (-0.762 V versus the standard hydrogen electrode), high abundance and low toxicity. When used in aqueous electrolyte, it also brings intrinsic safety, but suffers from severe irreversibility. This is best exemplified by low coulombic efficiency, dendrite growth and water consumption. This is thought to be due to severe hydrogen evolution during zinc plating and stripping, hitherto making the in-situ formation of a solid-electrolyte interphase (SEI) impossible. Here, we report an aqueous zinc battery in which a dilute and acidic aqueous electrolyte with an alkylammonium salt additive assists the formation of a robust, Zn2+-conducting and waterproof SEI. The presence of this SEI enables excellent performance: dendrite-free zinc plating/stripping at 99.9% coulombic efficiency in a Ti||Zn asymmetric cell for 1,000 cycles; steady charge-discharge in a Zn||Zn symmetric cell for 6,000 cycles (6,000 h); and high energy densities (136 Wh kg-1 in a Zn||VOPO4 full battery with 88.7% retention for >6,000 cycles, 325 Wh kg-1 in a Zn||O2 full battery for >300 cycles and 218 Wh kg-1 in a Zn||MnO2 full battery with 88.5% retention for 1,000 cycles) using limited zinc. The SEI-forming electrolyte also allows the reversible operation of an anode-free pouch cell of Ti||ZnxVOPO4 at 100% depth of discharge for 100 cycles, thus establishing aqueous zinc batteries as viable cell systems for practical applications. Metallic zinc is an ideal anode due to its high theoretical capacity (820 mAh g ), low redox potential (-0.762 V versus the standard hydrogen electrode), high abundance and low toxicity. When used in aqueous electrolyte, it also brings intrinsic safety, but suffers from severe irreversibility. This is best exemplified by low coulombic efficiency, dendrite growth and water consumption. This is thought to be due to severe hydrogen evolution during zinc plating and stripping, hitherto making the in-situ formation of a solid-electrolyte interphase (SEI) impossible. Here, we report an aqueous zinc battery in which a dilute and acidic aqueous electrolyte with an alkylammonium salt additive assists the formation of a robust, Zn -conducting and waterproof SEI. The presence of this SEI enables excellent performance: dendrite-free zinc plating/stripping at 99.9% coulombic efficiency in a Ti||Zn asymmetric cell for 1,000 cycles; steady charge-discharge in a Zn||Zn symmetric cell for 6,000 cycles (6,000 h); and high energy densities (136 Wh kg in a Zn||VOPO full battery with 88.7% retention for >6,000 cycles, 325 Wh kg in a Zn||O full battery for >300 cycles and 218 Wh kg in a Zn||MnO full battery with 88.5% retention for 1,000 cycles) using limited zinc. The SEI-forming electrolyte also allows the reversible operation of an anode-free pouch cell of Ti||Zn VOPO at 100% depth of discharge for 100 cycles, thus establishing aqueous zinc batteries as viable cell systems for practical applications. Metallic zinc is an ideal anode due to its high theoretical capacity (820 mAh g −1 ), low redox potential (−0.762 V versus the standard hydrogen electrode), high abundance and low toxicity. When used in aqueous electrolyte, it also brings intrinsic safety, but suffers from severe irreversibility. This is best exemplified by low coulombic efficiency, dendrite growth and water consumption. This is thought to be due to severe hydrogen evolution during zinc plating and stripping, hitherto making the in-situ formation of a solid–electrolyte interphase (SEI) impossible. Here, we report an aqueous zinc battery in which a dilute and acidic aqueous electrolyte with an alkylammonium salt additive assists the formation of a robust, Zn 2+ -conducting and waterproof SEI. The presence of this SEI enables excellent performance: dendrite-free zinc plating/stripping at 99.9% coulombic efficiency in a Ti||Zn asymmetric cell for 1,000 cycles; steady charge–discharge in a Zn||Zn symmetric cell for 6,000 cycles (6,000 h); and high energy densities (136 Wh kg −1 in a Zn||VOPO 4 full battery with 88.7% retention for >6,000 cycles, 325 Wh kg −1 in a Zn||O 2 full battery for >300 cycles and 218 Wh kg −1 in a Zn||MnO 2 full battery with 88.5% retention for 1,000 cycles) using limited zinc. The SEI-forming electrolyte also allows the reversible operation of an anode-free pouch cell of Ti||Zn x VOPO 4 at 100% depth of discharge for 100 cycles, thus establishing aqueous zinc batteries as viable cell systems for practical applications. A solid–electrolyte interphase that is permeable to Zn( ii ) ions but waterproof is formed using an aqueous electrolyte composition. Cycling performances in an anode-free aqueous pouch cell show promise for intrinsically safe energy storage applications. Metallic zinc is an ideal anode due to its high theoretical capacity (820 mAh g−1), low redox potential (−0.762 V versus the standard hydrogen electrode), high abundance and low toxicity. When used in aqueous electrolyte, it also brings intrinsic safety, but suffers from severe irreversibility. This is best exemplified by low coulombic efficiency, dendrite growth and water consumption. This is thought to be due to severe hydrogen evolution during zinc plating and stripping, hitherto making the in-situ formation of a solid–electrolyte interphase (SEI) impossible. Here, we report an aqueous zinc battery in which a dilute and acidic aqueous electrolyte with an alkylammonium salt additive assists the formation of a robust, Zn2+-conducting and waterproof SEI. The presence of this SEI enables excellent performance: dendrite-free zinc plating/stripping at 99.9% coulombic efficiency in a Ti||Zn asymmetric cell for 1,000 cycles; steady charge–discharge in a Zn||Zn symmetric cell for 6,000 cycles (6,000 h); and high energy densities (136 Wh kg−1 in a Zn||VOPO4 full battery with 88.7% retention for >6,000 cycles, 325 Wh kg−1 in a Zn||O2 full battery for >300 cycles and 218 Wh kg−1 in a Zn||MnO2 full battery with 88.5% retention for 1,000 cycles) using limited zinc. The SEI-forming electrolyte also allows the reversible operation of an anode-free pouch cell of Ti||ZnxVOPO4 at 100% depth of discharge for 100 cycles, thus establishing aqueous zinc batteries as viable cell systems for practical applications.A solid–electrolyte interphase that is permeable to Zn(ii) ions but waterproof is formed using an aqueous electrolyte composition. Cycling performances in an anode-free aqueous pouch cell show promise for intrinsically safe energy storage applications. Metallic zinc is an ideal anode due to its high theoretical capacity (820 mAh g-1), low redox potential (-0.762 V versus the standard hydrogen electrode), high abundance and low toxicity. When used in aqueous electrolyte, it also brings intrinsic safety, but suffers from severe irreversibility. This is best exemplified by low coulombic efficiency, dendrite growth and water consumption. This is thought to be due to severe hydrogen evolution during zinc plating and stripping, hitherto making the in-situ formation of a solid-electrolyte interphase (SEI) impossible. Here, we report an aqueous zinc battery in which a dilute and acidic aqueous electrolyte with an alkylammonium salt additive assists the formation of a robust, Zn2+-conducting and waterproof SEI. The presence of this SEI enables excellent performance: dendrite-free zinc plating/stripping at 99.9% coulombic efficiency in a Ti||Zn asymmetric cell for 1,000 cycles; steady charge-discharge in a Zn||Zn symmetric cell for 6,000 cycles (6,000 h); and high energy densities (136 Wh kg-1 in a Zn||VOPO4 full battery with 88.7% retention for >6,000 cycles, 325 Wh kg-1 in a Zn||O2 full battery for >300 cycles and 218 Wh kg-1 in a Zn||MnO2 full battery with 88.5% retention for 1,000 cycles) using limited zinc. The SEI-forming electrolyte also allows the reversible operation of an anode-free pouch cell of Ti||ZnxVOPO4 at 100% depth of discharge for 100 cycles, thus establishing aqueous zinc batteries as viable cell systems for practical applications. |
| Author | Ding, Michael Wang, Chunsheng Gaskell, Karen Li, Dan Deng, Tao Li, Qin Ma, Lin Fourkas, John T. Zhang, Bao Borodin, Oleg Vatamanu, Jenel Hou, Singyuk Cao, Longsheng Yang, Chongyin Pollard, Travis Yang, Xiao-Qing Chen, Long Xu, Kang Hu, Enyuan Hourwitz, Matt J. |
| Author_xml | – sequence: 1 givenname: Longsheng orcidid: 0000-0002-2917-6523 surname: Cao fullname: Cao, Longsheng organization: Department of Chemical and Biomolecular Engineering, University of Maryland – sequence: 2 givenname: Dan surname: Li fullname: Li, Dan organization: Department of Chemical and Biomolecular Engineering, University of Maryland – sequence: 3 givenname: Travis orcidid: 0000-0001-6240-5423 surname: Pollard fullname: Pollard, Travis organization: Battery Science Branch, Energy Science Division, Sensor and Electron Devices Directorate, US Army Research Laboratory – sequence: 4 givenname: Tao surname: Deng fullname: Deng, Tao organization: Department of Chemical and Biomolecular Engineering, University of Maryland – sequence: 5 givenname: Bao surname: Zhang fullname: Zhang, Bao organization: Department of Chemical and Biomolecular Engineering, University of Maryland – sequence: 6 givenname: Chongyin orcidid: 0000-0002-7127-3087 surname: Yang fullname: Yang, Chongyin organization: Department of Chemical and Biomolecular Engineering, University of Maryland – sequence: 7 givenname: Long surname: Chen fullname: Chen, Long organization: Department of Chemical and Biomolecular Engineering, University of Maryland – sequence: 8 givenname: Jenel surname: Vatamanu fullname: Vatamanu, Jenel organization: Battery Science Branch, Energy Science Division, Sensor and Electron Devices Directorate, US Army Research Laboratory – sequence: 9 givenname: Enyuan orcidid: 0000-0002-1881-4534 surname: Hu fullname: Hu, Enyuan organization: Chemistry Division, Brookhaven National Laboratory – sequence: 10 givenname: Matt J. surname: Hourwitz fullname: Hourwitz, Matt J. organization: Department of Chemistry and Biochemistry, University of Maryland – sequence: 11 givenname: Lin surname: Ma fullname: Ma, Lin organization: Department of Chemical and Biomolecular Engineering, University of Maryland, Battery Science Branch, Energy Science Division, Sensor and Electron Devices Directorate, US Army Research Laboratory – sequence: 12 givenname: Michael surname: Ding fullname: Ding, Michael organization: Battery Science Branch, Energy Science Division, Sensor and Electron Devices Directorate, US Army Research Laboratory – sequence: 13 givenname: Qin surname: Li fullname: Li, Qin organization: Department of Chemical and Biomolecular Engineering, University of Maryland – sequence: 14 givenname: Singyuk surname: Hou fullname: Hou, Singyuk organization: Department of Chemical and Biomolecular Engineering, University of Maryland – sequence: 15 givenname: Karen surname: Gaskell fullname: Gaskell, Karen organization: Department of Chemical and Biomolecular Engineering, University of Maryland – sequence: 16 givenname: John T. surname: Fourkas fullname: Fourkas, John T. organization: Department of Chemistry and Biochemistry, University of Maryland, Institute for Physical Science and Technology, University of Maryland – sequence: 17 givenname: Xiao-Qing orcidid: 0000-0002-3625-3478 surname: Yang fullname: Yang, Xiao-Qing organization: Chemistry Division, Brookhaven National Laboratory – sequence: 18 givenname: Kang orcidid: 0000-0002-6946-8635 surname: Xu fullname: Xu, Kang email: conrad.k.xu.civ@mail.mil organization: Battery Science Branch, Energy Science Division, Sensor and Electron Devices Directorate, US Army Research Laboratory – sequence: 19 givenname: Oleg orcidid: 0000-0002-9428-5291 surname: Borodin fullname: Borodin, Oleg email: oleg.a.borodin.civ@mail.mil organization: Battery Science Branch, Energy Science Division, Sensor and Electron Devices Directorate, US Army Research Laboratory – sequence: 20 givenname: Chunsheng orcidid: 0000-0002-8626-6381 surname: Wang fullname: Wang, Chunsheng email: cswang@umd.edu organization: Department of Chemical and Biomolecular Engineering, University of Maryland, Department of Chemistry and Biochemistry, University of Maryland |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/33972758$$D View this record in MEDLINE/PubMed https://www.osti.gov/servlets/purl/1787833$$D View this record in Osti.gov |
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| Snippet | Metallic zinc is an ideal anode due to its high theoretical capacity (820 mAh g
−1
), low redox potential (−0.762 V versus the standard hydrogen electrode),... Metallic zinc is an ideal anode due to its high theoretical capacity (820 mAh g ), low redox potential (-0.762 V versus the standard hydrogen electrode), high... Metallic zinc is an ideal anode due to its high theoretical capacity (820 mAh g−1), low redox potential (−0.762 V versus the standard hydrogen electrode), high... Metallic zinc is an ideal anode due to its high theoretical capacity (820 mAh g-1), low redox potential (-0.762 V versus the standard hydrogen electrode), high... Metallic zinc is an ideal anode due to its high theoretical capacity (820 mAh g-1), low redox potential (-0.762 V versus the standard hydrogen electrode), high... |
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| SubjectTerms | 140/131 140/133 140/146 639/4077/4079 639/4077/4079/891 639/638/161/891 Anodes Aqueous electrolytes Batteries Battery cycles Chemistry and Materials Science Dendrites Dendritic structure Discharge Electrolytes ENERGY STORAGE Hydrogen evolution Interphase Intrinsically safe Manganese dioxide Materials Science Nanotechnology Nanotechnology and Microengineering Redox potential Retention Titanium Toxicity Water consumption Zinc Zinc plating |
| Title | Fluorinated interphase enables reversible aqueous zinc battery chemistries |
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