Development of KPF6/KFSA Binary-Salt Solutions for Long-Life and High-Voltage K-Ion Batteries
A series of binary-salt electrolytes of KPF6/KN(SO2F)2 (KFSA) in carbonate ester solvents have been developed for high-voltage K-ion batteries by clarifying the effect of salt ratio and different solvents on the physical properties of the electrolyte solutions and electrochemical performance of K-ion batteries. The KPF6/KFSA carbonate ester solutions, such as KPF6/KFSA ethylene carbonate (EC)/diethyl carbonate (DEC), exhibit higher ionic conductivity than single-salt KPF6 one, and higher KFSA content results in higher ionic conductivity. The KPF6-rich binary-salt electrolytes with KPF6/KFSA ratios of ≥3 (mol/mol) provide enough oxidation stability and passivation against Al corrosion at 4.6 V over 100 h, ensuring reversible operation of a 4 V class positive electrode, K2Mn[Fe(CN)6] in half-cell. Graphite negative electrodes exhibit higher Coulombic efficiency and better rate performance in 0.75 mol kg-1 K(PF6)0.9(FSA)0.1/EC/DEC and 1 mol kg-1 K(PF6)0.75(FSA)0.25/EC/DEC electrolytes than those in the KPF6 one. Surface analysis by hard X-ray photoelectron spectroscopy reveals that the decomposition product of N(SO2F)2- anion contributes to stabilizing solid electrolyte interphase on a graphite electrode. From comparing different solvents of EC/DEC, EC/ethyl methyl carbonate, and EC/propylene carbonate (PC), the K2Mn[Fe(CN)6] electrode demonstrates the highest Coulombic efficiency in the EC/PC binary electrolyte, while graphite electrodes exhibit no significant difference. Based on the half-cell tests, we successfully achieve the 3.6 V class full cell of graphite|K(PF6)0.75(FSA)0.25/EC/PC|K2Mn[Fe(CN)6] showing excellent cyclability over 500 cycles, which is far superior to that of the conventional KPF6/EC/DEC electrolyte cell.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2020 |
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| Erschienen: |
2020 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:12 |
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| Enthalten in: |
ACS applied materials & interfaces - 12(2020), 31 vom: 05. Aug., Seite 34873-34881 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Hosaka, Tomooki [VerfasserIn] |
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| Links: |
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| Themen: |
Electrolyte |
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| Anmerkungen: |
Date Revised 18.08.2020 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acsami.0c08002 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM312732503 |
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| 520 | |a A series of binary-salt electrolytes of KPF6/KN(SO2F)2 (KFSA) in carbonate ester solvents have been developed for high-voltage K-ion batteries by clarifying the effect of salt ratio and different solvents on the physical properties of the electrolyte solutions and electrochemical performance of K-ion batteries. The KPF6/KFSA carbonate ester solutions, such as KPF6/KFSA ethylene carbonate (EC)/diethyl carbonate (DEC), exhibit higher ionic conductivity than single-salt KPF6 one, and higher KFSA content results in higher ionic conductivity. The KPF6-rich binary-salt electrolytes with KPF6/KFSA ratios of ≥3 (mol/mol) provide enough oxidation stability and passivation against Al corrosion at 4.6 V over 100 h, ensuring reversible operation of a 4 V class positive electrode, K2Mn[Fe(CN)6] in half-cell. Graphite negative electrodes exhibit higher Coulombic efficiency and better rate performance in 0.75 mol kg-1 K(PF6)0.9(FSA)0.1/EC/DEC and 1 mol kg-1 K(PF6)0.75(FSA)0.25/EC/DEC electrolytes than those in the KPF6 one. Surface analysis by hard X-ray photoelectron spectroscopy reveals that the decomposition product of N(SO2F)2- anion contributes to stabilizing solid electrolyte interphase on a graphite electrode. From comparing different solvents of EC/DEC, EC/ethyl methyl carbonate, and EC/propylene carbonate (PC), the K2Mn[Fe(CN)6] electrode demonstrates the highest Coulombic efficiency in the EC/PC binary electrolyte, while graphite electrodes exhibit no significant difference. Based on the half-cell tests, we successfully achieve the 3.6 V class full cell of graphite|K(PF6)0.75(FSA)0.25/EC/PC|K2Mn[Fe(CN)6] showing excellent cyclability over 500 cycles, which is far superior to that of the conventional KPF6/EC/DEC electrolyte cell | ||
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| 700 | 1 | |a Yasuno, Satoshi |e verfasserin |4 aut | |
| 700 | 1 | |a Komaba, Shinichi |e verfasserin |4 aut | |
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