Journal Home > Volume 17 , Issue 5
Nano Research 2024, 17(5): 4163-4170 https://doi.org/10.1007/s12274-023-6353-z
Research Article | Issue | Published: 12 December 2023

All-inorganic nitrate electrolyte for high-performance lithium oxygen battery

Show Author's Information Dongyue Yang1,2,  Jiayi Du1,2,  Kai Chen1,  Haoran Zhang1,2,  Gang Huang1,2,  Tong Liu1,2,  Xinbo Zhang1,2,  Hongjie Zhang1,2( )
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China
Keywords:
Li-O2 batteries, potassium ions, inorganic nitrate electrolyte, solution pathway mechanism
Topics:
Air batteriesLithium batteriesSecondary batteries
Cite this article:
Yang D, Du J, Chen K, et al. All-inorganic nitrate electrolyte for high-performance lithium oxygen battery. Nano Research, 2024, 17(5): 4163-4170. https://doi.org/10.1007/s12274-023-6353-z
Download citation
EndNote(RIS)
BibTeX

294

Views

39

Downloads

Citations

0

Crossref

0

WoS

0

Scopus

0

CSCD

Abstract Full text Electronic supplementary material About this article

Lithium-oxygen (Li-O2) batteries have been regarded as an expectant successor for next-generation energy storage systems owing to their ultra-high theoretical energy density. However, the comprehensive properties of the commonly utilized organic salt electrolyte are still unsatisfactory, not to mention their expensive prices, which seriously hinders the practical production and application of Li-O2 batteries. Herein, we have proposed a low-cost all-inorganic nitrate electrolyte (LiNO3−KNO3−DMSO) for Li-O2 batteries. The inorganic nitrate electrolyte exhibits higher ionic conductivity and a wider electrochemical stability window than the organic salt electrolyte. The existence of K+ can stabilize the O2− intermediate, promoting the discharge process through the solution pathway with an enlarged capacity. Even at an ultra-low concentration of 0.01 M, the K+ can still remain stable to promote the solution discharge process and also possess a new function of inhibiting the dendrite growth by electrostatic shielding, further enhancing the battery stability and contributing to the long cycle lifetime. As a result, in the 0.99 M LiNO3−0.01 M KNO3−DMSO electrolyte, the Li-O2 batteries exhibit prolonged cycling performance (108 cycles) and excellent rate performance (2 A·g−1), significantly superior to the organic salt one.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

All-inorganic nitrate electrolyte for high-performance lithium oxygen battery

Show Author's information Dongyue Yang1,2, Jiayi Du1,2, Kai Chen1, Haoran Zhang1,2, Gang Huang1,2, Tong Liu1,2, Xinbo Zhang1,2, Hongjie Zhang1,2( )
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China

Abstract

Lithium-oxygen (Li-O2) batteries have been regarded as an expectant successor for next-generation energy storage systems owing to their ultra-high theoretical energy density. However, the comprehensive properties of the commonly utilized organic salt electrolyte are still unsatisfactory, not to mention their expensive prices, which seriously hinders the practical production and application of Li-O2 batteries. Herein, we have proposed a low-cost all-inorganic nitrate electrolyte (LiNO3−KNO3−DMSO) for Li-O2 batteries. The inorganic nitrate electrolyte exhibits higher ionic conductivity and a wider electrochemical stability window than the organic salt electrolyte. The existence of K+ can stabilize the O2− intermediate, promoting the discharge process through the solution pathway with an enlarged capacity. Even at an ultra-low concentration of 0.01 M, the K+ can still remain stable to promote the solution discharge process and also possess a new function of inhibiting the dendrite growth by electrostatic shielding, further enhancing the battery stability and contributing to the long cycle lifetime. As a result, in the 0.99 M LiNO3−0.01 M KNO3−DMSO electrolyte, the Li-O2 batteries exhibit prolonged cycling performance (108 cycles) and excellent rate performance (2 A·g−1), significantly superior to the organic salt one.

Keywords: Li-O2 batteries, potassium ions, inorganic nitrate electrolyte, solution pathway mechanism

References(52)

[1]

Jiao, S. H.; Ren, X. D.; Cao, R. G.; Engelhard, M. H.; Liu, Y. Z.; Hu, D. H.; Mei, D. H.; Zheng, J. M.; Zhao, W. G.; Li, Q. Y. et al. Stable cycling of high-voltage lithium metal batteries in ether electrolytes. Nat. Energy 2018, 3, 739–746.
DOI Google Scholar
[2]

Hou, B. W.; He, L.; Feng, X. N.; Zhang, W. F.; Wang, L.; He, X. M. Effect of amine additives on thermal runaway inhibition of SiC||NCM811 batteries. J. Electrochem. 2023, 29, 2211141.
DOI Google Scholar
[3]

Kwak, W. J.; Rosy; Sharon, D.; Xia, C.; Kim, H.; Johnson, L. R.; Bruce, P. G.; Nazar, L. F.; Sun, Y. K.; Frimer, A. A. et al. Lithium-oxygen batteries and related systems: Potential, status, and future. Chem. Rev. 2020, 120, 6626–6683.
DOI Google Scholar
[4]

Cao, R. F.; Cui, Y. F.; Huang, G.; Liu, W. Q.; Liu, J. W.; Zhang, X. B. Designing a photo-assisted Co-C3N4 cathode for high performance Li-O2 batteries. Nano Res. 2023, 16, 8405–8410.
DOI Google Scholar
[5]

Lu, J.; Li, L.; Park, J. B.; Sun, Y. K.; Wu, F.; Amine, K. Aprotic and aqueous Li-O2 batteries. Chem. Rev. 2014, 114, 5611–5640.
DOI Google Scholar
[6]

Chen, K.; Huang, G.; Zhang, X. B. Efforts towards practical and sustainable Li/Na-air batteries. Chin. J. Chem. 2021, 39, 32–42.
DOI Google Scholar
[7]

Zheng, X. Y.; Huang, L. Q.; Ye, X. L.; Zhang, J. X.; Min, F. Y.; Luo, W.; Huang, Y. H. Critical effects of electrolyte recipes for Li and Na metal batteries. Chem 2021, 7, 2312–2346.
DOI Google Scholar
[8]

Mauler, L.; Duffner, F.; Zeier, W. G.; Leker, J. Battery cost forecasting: A review of methods and results with an outlook to 2050. Energy Environ. Sci. 2021, 14, 4712–4739.
DOI Google Scholar
[9]

Guo, R. Q.; Wu, F.; Wang, X. R.; Bai, Y.; Wu, C. Multi-electron reaction-boosted high energy density batteries: Material and system innovation. J. Electrochem. 2022, 28, 2219011.
DOI Google Scholar
[10]

Ding, Z. Y.; Tang, Q. M.; Zhang, Q.; Yao, P. H.; Liu, X. J.; Wu, J. W. A flexible solid polymer electrolyte enabled with lithiated zeolite for high performance lithium battery. Nano Res. 2023, 16, 9443–9452.
DOI Google Scholar
[11]

Xu, J. J.; Zhang, J. X.; Pollard, T. P.; Li, Q. D.; Tan, S.; Hou, S.; Wan, H. L.; Chen, F.; He, H. X.; Hu, E. Y. et al. Electrolyte design for Li-ion batteries under extreme operating conditions. Nature 2023, 614, 694–700.
DOI Google Scholar
[12]

Cai, Y. C.; Hou, Y. P.; Lu, Y.; Zhang, Q.; Yan, Z. H.; Chen, J. Ionic liquid electrolyte with weak solvating molecule regulation for stable Li deposition in high-performance Li-O2 batteries. Angew. Chem., Int. Ed. 2023, 62, e202218014.
DOI Google Scholar
[13]

Liu, B.; Xu, W.; Yan, P. F.; Kim, S. T.; Engelhard, M. H.; Sun, X. L.; Mei, D. H.; Cho, J.; Wang, C. M.; Zhang, J. G. Stabilization of Li metal anode in DMSO-based electrolytes via optimization of salt-solvent coordination for Li-O2 batteries. Adv. Energy Mater. 2017, 7, 1602605.
DOI Google Scholar
[14]

Zhang, X. P.; Li, Y. N.; Sun, Y. Y.; Zhang, T. Inverting the triiodide formation reaction by the synergy between strong electrolyte solvation and cathode adsorption for lithium-oxygen batteries. Angew. Chem., Int. Ed. 2019, 58, 18394–18398.
DOI Google Scholar
[15]

Ko, Y.; Park, H.; Lee, K.; Kim, S. J.; Park, H.; Bae, Y.; Kim, J.; Park, S. Y.; Kwon, J. E.; Kang, K. Anchored mediator enabling shuttle-free redox mediation in lithium-oxygen batteries. Angew. Chem., Int. Ed. 2020, 59, 5376–5380.
DOI Google Scholar
[16]

Jung, H. G.; Hassoun, J.; Park, J. B.; Sun, Y. K.; Scrosati, B. An improved high-performance lithium-air battery. Nat. Chem. 2012, 4, 579–585.
DOI Google Scholar
[17]

Ren, X. D.; Zou, L. F.; Cao, X.; Engelhard, M. H.; Liu, W.; Burton, S. D.; Lee, H.; Niu, C. J.; Matthews, B. E.; Zhu, Z. H. et al. Enabling high-voltage lithium-metal batteries under practical conditions. Joule 2019, 3, 1662–1676.
DOI Google Scholar
[18]

Yu, Z. A.; Wang, H. S.; Kong, X.; Huang, W.; Tsao, Y.; Mackanic, D. G.; Wang, K. C.; Wang, X. C.; Huang, W. X.; Choudhury, S. et al. Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries. Nat. Energy 2020, 5, 526–533.
DOI Google Scholar
[19]

McCloskey, B. D.; Valery, A.; Luntz, A. C.; Gowda, S. R.; Wallraff, G. M.; Garcia, J. M.; Mori, T.; Krupp, L. E. Combining accurate O2 and Li2O2 assays to separate discharge and charge stability limitations in nonaqueous Li-O2 batteries. J. Phys. Chem. Lett. 2013, 4, 2989–2993.
DOI Google Scholar
[20]

Veith, G. M.; Nanda, J.; Delmau, L. H.; Dudney, N. J. Influence of lithium salts on the discharge chemistry of Li-air cells. J. Phys. Chem. Lett. 2012, 3, 1242–1247.
DOI Google Scholar
[21]

Freunberger, S. A.; Chen, Y. H.; Peng, Z. Q.; Griffin, J. M.; Hardwick, L. J.; Bardé, F.; Novák, P.; Bruce, P. G. Reactions in the rechargeable lithium-O2 battery with alkyl carbonate electrolytes. J. Am. Chem. Soc. 2011, 133, 8040–8047.
DOI Google Scholar
[22]

Ogasawara, T.; Débart, A.; Holzapfel, M.; Novák, P.; Bruce, P. G. Rechargeable Li2O2 electrode for lithium batteries. J. Am. Chem. Soc. 2006, 128, 1390–1393.
DOI Google Scholar
[23]

Nasybulin, E.; Xu, W.; Engelhard, M. H.; Nie, Z. M.; Burton, S. D.; Cosimbescu, L.; Gross, M. E.; Zhang, J. G. Effects of electrolyte salts on the performance of Li-O2 batteries. J. Phys. Chem. C 2013, 117, 2635–2645.
DOI Google Scholar
[24]

Younesi, R.; Urbonaite, S.; Edström, K.; Hahlin, M. The cathode surface composition of a cycled Li–O2 battery: A photoelectron spectroscopy study. J. Phys. Chem. C 2012, 116, 20673–20680.
DOI Google Scholar
[25]

Chang, Z.; Qiao, Y.; Deng, H.; Yang, H. J.; He, P.; Zhou, H. S. A stable high-voltage lithium-ion battery realized by an in-built water scavenger. Energy Environ. Sci. 2020, 13, 1197–1204.
DOI Google Scholar
[26]

Shao, Y. Y.; Ding, F.; Xiao, J.; Zhang, J.; Xu, W.; Park, S.; Zhang, J. G.; Wang, Y.; Liu, J. Making Li-air batteries rechargeable: Material challenges. Adv. Funct. Mater. 2013, 23, 987–1004.
DOI Google Scholar
[27]

Zhang, X. Q.; Chen, X.; Hou, L. P.; Li, B. Q.; Cheng, X. B.; Huang, J. Q.; Zhang, Q. Regulating anions in the solvation sheath of lithium ions for stable lithium metal batteries. ACS Energy Lett. 2019, 4, 411–416.
DOI Google Scholar
[28]

Xin, X.; Ito, K.; Dutta, A.; Kubo, Y. Dendrite-free epitaxial growth of lithium metal during charging in Li-O2 batteries. Angew. Chem., Int. Ed. 2018, 57, 13206–13210.
DOI Google Scholar
[29]

Sharon, D.; Hirsberg, D.; Salama, M.; Afri, M.; Frimer, A. A.; Noked, M.; Kwak, W.; Sun, Y. K.; Aurbach, D. Mechanistic role of Li+ dissociation level in aprotic Li-O2 battery. ACS Appl. Mater. Interfaces 2016, 8, 5300–5307.
DOI Google Scholar
[30]

Burke, C. M.; Pande, V.; Khetan, A.; Viswanathan, V.; McCloskey, B. D. Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li-O2 battery capacity. Proc. Natl. Acad. Sci. USA 2015, 112, 9293–9298.
DOI Google Scholar
[31]

Yoo, E.; Zhou, H. S. Enhanced cycle stability of rechargeable Li-O2 batteries by the synergy effect of a LiF protective layer on the Li and DMTFA additive. ACS Appl. Mater. Interfaces 2017, 9, 21307–21313.
DOI Google Scholar
[32]

Xu, J. J.; Liu, Q. C.; Yu, Y.; Wang, J.; Yan, J. M.; Zhang, X. B. In situ construction of stable tissue-directed/reinforced bifunctional separator/protection film on lithium anode for lithium-oxygen batteries. Adv. Mater. 2017, 29, 1606552.
DOI Google Scholar
[33]

Chen, K.; Huang, G.; Ma, J. L.; Wang, J.; Yang, D. Y.; Yang, X. Y.; Yu, Y.; Zhang, X. B. The stabilization effect of CO2 in lithium-oxygen/CO2 batteries. Angew. Chem., Int. Ed. 2020, 59, 16661–16667.
DOI Google Scholar
[34]
Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H. et al. Gaussian 09, Revision A.02; Gaussian, Inc.: Wallingford CT, 2016.
[35]

Becke, A. D. Density-functional exchange-energy approximation with correct asymptotic behavior. Phys. Rev. A 1988, 38, 3098–3100.
DOI Google Scholar
[36]

Lee, C.; Yang, W. T.; Parr, R. G. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B 1988, 37, 785–789.
DOI Google Scholar
[37]

Becke, A. D. A new mixing of Hartree-Fock and local density-functional theories. J. Chem. Phys. 1993, 98, 1372–1377.
DOI Google Scholar
[38]

Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. J. Phys. Chem. B 2009, 113, 6378–6396.
DOI Google Scholar
[39]

Meng, J. W.; Lei, M.; Lai, C. Z.; Wu, Q. P.; Liu, Y. Y.; Li, C. L. Lithium ion repulsion-enrichment synergism induced by core–shell ionic complexes to enable high-loading lithium metal batteries. Angew. Chem., Int. Ed. 2021, 60, 23256–23266.
DOI Google Scholar
[40]

Qin, L.; Schkeryantz, L.; Zheng, J. F.; Xiao, N.; Wu, Y. Y. Superoxide-based K-O2 batteries: Highly reversible oxygen redox solves challenges in air electrodes. J. Am. Chem. Soc. 2020, 142, 11629–11640.
DOI Google Scholar
[41]

Younesi, R.; Hahlin, M.; Björefors, F.; Johansson, P.; Edström, K. Li-O2 battery degradation by lithium peroxide (Li2O2): A model study. Chem. Mater. 2013, 25, 77–84.
DOI Google Scholar
[42]

Lu, Y. C.; Crumlin, E. J.; Veith, G. M.; Harding, J. R.; Mutoro, E.; Baggetto, L.; Dudney, N. J.; Liu, Z.; Shao-Horn, Y. In situ ambientpressure X-ray photoelectron spectroscopy studies of lithium-oxygenredox reactions. Sci. Rep. 2012, 2, 715.
DOI Google Scholar
[43]

Tułodziecki, M.; Leverick, G. M.; Amanchukwu, C. V.; Katayama, Y.; Kwabi, D. G.; Bardé, F.; Hammond, P. T.; Shao-Horn, Y. The role of iodide in the formation of lithium hydroxide in lithium-oxygen batteries. Energy Environ. Sci. 2017, 10, 1828–1842.
DOI Google Scholar
[44]

Matsuda, S.; Kubo, Y.; Uosaki, K.; Nakanishi, S. Potassium ions promote solution-route Li2O2 formation in the positive electrode reaction of Li-O2 batteries. J. Phys. Chem. Lett. 2017, 8, 1142–1146.
DOI Google Scholar
[45]

Zhao, S.; Wang, C. C.; Du, D. F.; Li, L.; Chou, S. L.; Li, F. J.; Chen, J. Bifunctional effects of cation additive on Na-O2 batteries. Angew. Chem., Int. Ed. 2021, 60, 3205–3211.
DOI Google Scholar
[46]

Ding, F.; Xu, W.; Graff, G. L.; Zhang, J.; Sushko, M. L.; Chen, X. L.; Shao, Y. Y.; Engelhard, M. H.; Nie, Z. M.; Xiao, J. et al. Dendrite-free lithium deposition via self-healing electrostatic shield mechanism. J. Am. Chem. Soc. 2013, 135, 4450–4456.
DOI Google Scholar
[47]

Yang, Q. F.; Hu, J. L.; Meng, J. W.; Li, C. L. C-F-rich oil drop as a non-expendable fluid interface modifier with low surface energy to stabilize a Li metal anode. Energy Environ. Sci. 2021, 14, 3621–3631.
DOI Google Scholar
[48]

Cong, G. T.; Wang, W. W.; Lai, N. C.; Liang, Z. J.; Lu, Y. C. A high-rate and long-life organic-oxygen battery. Nat. Mater. 2019, 18, 390–396.
DOI Google Scholar
[49]

Zhang, X. P.; Sun, Y. Y.; Sun, Z.; Yang, C. S.; Zhang, T. Anode interfacial layer formation via reductive ethyl detaching of organic iodide in lithium-oxygen batteries. Nat. Commun. 2019, 10, 3543.
DOI Google Scholar
[50]

Wu, X. H.; Niu, B.; Zhang, H. T.; Li, Z. G.; Luo, H. Y.; Tang, Y. L.; Yu, X. Y.; Huang, L.; He, X. R.; Wang, X. et al. Enhancing the reaction kinetics and reversibility of Li-O2 batteries by multifunctional polymer additive. Adv. Energy Mater. 2023, 13, 2203089.
DOI Google Scholar
[51]

Cai, Y. C.; Zhang, Q.; Lu, Y.; Hao, Z. M.; Ni, Y. X.; Chen, J. An ionic liquid electrolyte with enhanced Li+ transport ability enables stable Li deposition for high-performance Li-O2 batteries. Angew. Chem., Int. Ed. 2021, 60, 25973–25980.
DOI Google Scholar
[52]

Tong, B.; Huang, J.; Zhou, Z. B.; Peng, Z. Q. The salt matters: Enhanced reversibility of Li-O2 batteries with a Li[(CF3SO2)( n-C4F9SO2)N]-based electrolyte. Adv. Mater. 2018, 30, 1704841.
DOI Google Scholar
File
12274_2023_6353_MOESM1_ESM.pdf (2.9 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 22 October 2023
Revised: 18 November 2023
Accepted: 20 November 2023
Published: 12 December 2023
Issue date: May 2024

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This work was financially supported by the National Key R&D Program of China (No. 2020YFE0204500), the National Natural Science Foundation of China (Nos. 52171194 and 52271140), the CAS Project for Young Scientists in Basic Research (No. YSBR-058), the Youth Innovation Promotion Association CAS (No. 2020230), and the National Natural Science Foundation of China Outstanding Youth Science Foundation of China (Overseas).

Return