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缓慢的LiO溶解——解锁高容量锂氧电池的关键。

Sluggish LiO dissolution - a key to unlock high-capacity lithium-oxygen batteries.

作者信息

He Lu, Wang Shuo, Yu Fengjiao, Chen Yuhui

机构信息

State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University Nanjing 211816 China

出版信息

Chem Sci. 2024 Dec 2;16(2):627-636. doi: 10.1039/d4sc05911e. eCollection 2025 Jan 2.

DOI:10.1039/d4sc05911e
PMID:39650218
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11621826/
Abstract

While lithium-oxygen batteries have a high theoretical specific energy, the practical discharge capacity is much lower due to the passivation of the solid discharge product, LiO, on the electrode surface. Herein, we studied and quantified the deposition and dissolution kinetics of LiO using an electrochemical quartz crystal microbalance (EQCM). It is found that the orientation of the electrode greatly influences the formation path and deposition amount of LiO. We identified two distinct dissolution modes: surface dissolution and bulk fragmentation, with the latter 100 times faster than the former. By revealing the underlying factors affecting dissolution, 80% of LiO can dissolve within 3 minutes when a desorption potential of 2.9 V is applied. Consequently, we designed an intermittent-desorption discharge strategy, which increased the discharge capacity by an order of magnitude. This work shows that high practical specific energy of Li-O batteries can be achieved once problems of LiO dissolution are addressed.

摘要

虽然锂氧电池具有较高的理论比能量,但由于固体放电产物LiO在电极表面的钝化,其实际放电容量要低得多。在此,我们使用电化学石英晶体微天平(EQCM)研究并量化了LiO的沉积和溶解动力学。发现电极的取向对LiO的形成路径和沉积量有很大影响。我们确定了两种不同的溶解模式:表面溶解和整体破碎,后者比前者快100倍。通过揭示影响溶解的潜在因素,当施加2.9 V的解吸电位时,80%的LiO可在3分钟内溶解。因此,我们设计了一种间歇解吸放电策略,使放电容量提高了一个数量级。这项工作表明,一旦解决了LiO溶解问题,就可以实现锂氧电池的高实际比能量。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1226/11694948/5694ae04396f/d4sc05911e-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1226/11694948/a44536f47f08/d4sc05911e-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1226/11694948/1c971b93bed9/d4sc05911e-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1226/11694948/6a4fcf9d37f8/d4sc05911e-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1226/11694948/0af7e77d7b17/d4sc05911e-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1226/11694948/5694ae04396f/d4sc05911e-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1226/11694948/a44536f47f08/d4sc05911e-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1226/11694948/1c971b93bed9/d4sc05911e-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1226/11694948/6a4fcf9d37f8/d4sc05911e-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1226/11694948/0af7e77d7b17/d4sc05911e-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1226/11694948/5694ae04396f/d4sc05911e-f5.jpg

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本文引用的文献

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2
Crown Ether Electrolyte Induced LiO Amorphization for Low Polarization and Long Lifespan Li-O Batteries.冠醚电解质诱导Li-O非晶化用于低极化和长寿命锂氧电池
Angew Chem Int Ed Engl. 2024 Jul 1;63(27):e202403521. doi: 10.1002/anie.202403521. Epub 2024 Jun 3.
3
Determinants of the Surface Film during the Discharging Process in Lithium-Oxygen Batteries.
锂氧电池放电过程中表面膜的决定因素
J Phys Chem Lett. 2024 Jan 18;15(2):583-589. doi: 10.1021/acs.jpclett.3c03568. Epub 2024 Jan 10.
4
Aprotic Lithium-Oxygen Batteries Based on Nonsolid Discharge Products.基于非固态放电产物的非质子锂氧电池。
J Am Chem Soc. 2024 Jan 17;146(2):1305-1317. doi: 10.1021/jacs.3c08656. Epub 2024 Jan 3.
5
Towards practical metal-oxygen batteries: general discussion.迈向实用的金属-氧电池:综述
Faraday Discuss. 2024 Jan 29;248(0):392-411. doi: 10.1039/d3fd90062b.
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New Reaction Pathway of Superoxide Disproportionation Induced by a Soluble Catalyst in Li-O Batteries.锂氧电池中可溶催化剂引发的超氧化物歧化反应新途径
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