物理化学学报 >> 2022, Vol. 38 >> Issue (8): 2009071.doi: 10.3866/PKU.WHXB202009071
锂-空气电池的实用化之路：规避二氧化碳负面效应
王天杰1, 王耀伟1,2, 陈宇辉1,*(
), 刘建鹏2, 史会兵2, 郭丽敏3,*(), 赵志伟4, 刘春太5, 彭章泉4,6,*()
- 1 南京工业大学能源科学与工程学院，材料化学工程国家重点实验室，江苏 南京 211816
2 山东京博石化有限公司，山东 博兴 256500
3 大连交通大学环境与化工学院，辽宁 大连 116028
4 中国科学院大连化学物理研究所，谱学电化学与锂离子电池实验室，辽宁 大连 116023
5 郑州大学材料科学与工程学院，材料成型及模具技术教育部重点实验室，河南 郑州 450002
6 五邑大学应用物理与材料学院，广东 江门 529020
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收稿日期:2020-09-21录用日期:2020-10-16发布日期:2020-10-22 -
通讯作者:陈宇辉,郭丽敏,彭章泉 E-mail:cheny@njtech.edu.cn;lmguo@ciac.ac.cn;zqpeng@dicp.ac.cn -
作者简介:Yuhui Chen obtained his Bachelor degree in Fudan University in 2009, and received his Ph.D. degree from University of St Andrews (United Kingdom) in 2014. Later, he worked with Prof. Peter Bruce at the University of Oxford (United Kingdom) on the topic of metal-air batteries. Since 2017, he is the professor at Nanjing Tech University. His research interests include CO2 electrochemical catalysis and novel batteries such as metal-air batteries
Limin Guo obtained her MSc and Ph.D. degrees from Changchun Institute of Applied Chemistry (CIAC) in 2004 and 2016, respectively. In 2018 she worked as an assistant professor in Jilin Engineering Normal University and promoted to full professor in 2020. Currently she is a professor in the College of Environment & Chemical Engineering of Dalian Jiaotong University. Her research interests include non-aqueous lithium-ion and lithium-air batteries investigated by the in situ electrochemistry techniques
Zhangquan Peng obtained his Bachelor degree in Wuhan University in 1997, and received his MSc and Ph.D. degrees from Changchun Institute of Applied Chemistry (CIAC) in 2000 and 2003, respectively. He continued by working as a postdoctoral researcher at University of Dusseldorf (Germany), University of Aarhus (Denmark) and University of St Andrews (United Kingdom) from 2004 to 2012. From 2012 to 2020, he worked as a principle investigator on the topic of interfacial electrochemistry of various energy storage devices in CIAC. Currently, he is the supervisor of the Laboratory of Advanced Spectro-electrochemistry and Li-ion Batteries, Dalian Institute of Chemical Physics (DICP). His research interests include in situ electrochemistry coupled with theoretical calculation focusing on Li-ion and Li-O2 batteries第一联系人：†These authors contributed equally to this work.
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基金资助:国家重点研发计划(2016YFB0100100);国家重点研发计划(2018YFB0104400);国家自然科学基金(21972055);国家自然科学基金(21825202);国家自然科学基金(21575135);国家自然科学基金(21733012);国家自然科学基金(51773092);国家自然科学基金(21975124);国家自然科学基金(21972133);英国皇家学会牛顿基金(NAF/R2/180603)
Toward Practical Lithium-Air Batteries by Avoiding Negative Effects of CO2
Tianjie Wang1, Yaowei Wang1,2, Yuhui Chen1,*(), Jianpeng Liu2, Huibing Shi2, Limin Guo3,*(), Zhiwei Zhao4, Chuntai Liu5, Zhangquan Peng4,6,*()
- 1 State Key Laboratory of Materials-Oriented Chemical Engineering, School of Energy Science and Engineering, Nanjing Tech University, Nanjing 211816, Jiangsu Province, China
2 Shandong Chambroad Petrochemicals Co., Ltd., Boxing 256500, Shandong Province, China
3 College of Environment & Chemical Engineering, Dalian Jiaotong University, Dalian 116028, Liaoning Province, China
4 Laboratory of Spectro-electrochemistry and Li-ion Batteries, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China
5 College of Materials Science and Engineering, the Key Laboratory of Advanced Materials Processing & Mold of Ministry of Education, Zhengzhou University, Zhengzhou 450002, Henan Province, China
6 School of Applied Physics and Materials, Wuyi University, Jiangmen 529020, Guangdong Province, China
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Received:2020-09-21Accepted:2020-10-16Published:2020-10-22 -
Contact:Yuhui Chen,Limin Guo,Zhangquan Peng E-mail:cheny@njtech.edu.cn;lmguo@ciac.ac.cn;zqpeng@dicp.ac.cn -
About author:Email: zqpeng@dicp.ac.cn (Z.P.)
Email: lmguo@ciac.ac.cn (L.G.)
Email: cheny@njtech.edu.cn (Y.C.)
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Supported by:the National Key R&D Program of China(2016YFB0100100);the National Key R&D Program of China(2018YFB0104400);the National Natural Science Foundation of China(21972055);the National Natural Science Foundation of China(21825202);the National Natural Science Foundation of China(21575135);the National Natural Science Foundation of China(21733012);the National Natural Science Foundation of China(51773092);the National Natural Science Foundation of China(21975124);the National Natural Science Foundation of China(21972133);the Newton Advanced Fellowships of Royal Society of England(NAF/R2/180603)
摘要：
与其他的锂电池体系相比，锂-空气电池具有最高的理论比能量，被认为有潜力成为终极能量转换和储存装置。目前的锂-空气电池常常使用气体钢瓶提供纯氧气，而非空气中的氧气，这种电池设计极大降低了锂-空气电池的能量密度和实用性。然而，当空气作为锂-空气电池的氧气供给源时，二氧化碳作为杂质会引起严重的副反应，从而降低锂-空气电池的性能。要解决二氧化碳引起的副反应，理解其反应机制至关重要。本文综述了锂-空气电池中有关二氧化碳诱发的化学/电化学反应的研究进展; 总结了可缓解二氧化碳负面效应的有效策略。此外，对二氧化碳选透膜材料和分离技术用于锂-空气电池进行了展望。
引用本文
王天杰, 王耀伟, 陈宇辉, 刘建鹏, 史会兵, 郭丽敏, 赵志伟, 刘春太, 彭章泉. 锂-空气电池的实用化之路：规避二氧化碳负面效应[J]. 物理化学学报, 2022, 38(8), 2009071. doi: 10.3866/PKU.WHXB202009071
Tianjie Wang, Yaowei Wang, Yuhui Chen, Jianpeng Liu, Huibing Shi, Limin Guo, Zhiwei Zhao, Chuntai Liu, Zhangquan Peng. Toward Practical Lithium-Air Batteries by Avoiding Negative Effects of CO2[J]. Acta Phys. -Chim. Sin. 2022, 38(8), 2009071. doi: 10.3866/PKU.WHXB202009071
Fig 1
Schematic illustration of the formation mechanism of Li2CO3. (a) Electrochemical pathway, (b) chemical pathway, (c) pathway determined by dielectric constant, (d) pathway determined by DN value, (e) in situ spectroscopy determines the reaction mechanism. Adapted from Ref. 43 for (a), Ref. 44 for (b), Ref. 46 for (c), Ref. 47 for (d) and Ref. 48 for (e)."
Fig 2
Schematic illustration of the decomposition mechanism of Li2CO3."
Fig 3
In situ SERS characterization of the electrodes with and without the Ru catalyst during discharge and recharge under CO2 atmosphere using LiCF3SO3-TEGDME (mole ratio of 1 : 4) as the electrolyte. (a) electrode without the Ru catalyst, (b) electrode with the Ru catalyst; DEMS results of gas evolution rates for CO2 and O2 during cell charging: at (c) 500 mA∙g−1 and (d) 2000 mA∙g−1 current density after discharged to point-B. Adapted from Ref. 50 for (a–b) and Ref. 51 for (c–d)."
Fig 4
SEM characterizations of CNTs cathodes at the end of discharge using (a) TEGDME electrolyte and (b) GPE electrolyte. Adapted from Ref. 54."
Fig 5
(a) In situ Raman spectra collected at the end of each discharge (red) and charge (blue) states among typical cycles during cycling with a fixed capacity of 200 mAh∙g−1 (at a current density of 400 mA∙g−1), (b) initial cycle at current densities from 200 to 600 mA∙g−1, (c) full discharge–charge profiles over 20 cycles within potential window of 2.6 to 3.65 V at 400 mA∙g−1. Adapted from Ref. 55."
Fig 6
(a) Proposed mechanism of the charging process with LiBr as the redox mediator in Li-CO2 batteries; (b) Raman spectra of Li2CO3, LiCoO2, and Li2CO3/LiCoO2 composites charged to various potentials; (c) charge voltage profiles of B4C and Ir/B4C-Li2CO3 electrodes in Ar, the inset shows the charge profiles of the bare B4C and the Ir/B4C electrodes without preloaded Li2CO3; SEM images of CNT@RuO2 cathodes with preloaded Li2CO3 at different states (d) before and (e) after charge; in situ FTIR characterization of Ru/NiO@Ni/CNT electrodes during the (f) discharge and (g) recharge process. Adapted from Ref. 56 for (a), Ref. 59 for (b), Ref. 60 for (c), Ref. 61 for (d–e) and Ref. 62 for (f–g)."
Fig 7
Schematic illustration of the MMM based on CAU-1-NH2@PDA (PDA: polydopamine) and PMMA polymer for repelling H2O and CO2 molecules in breathing air. Adapted from Ref. 68."
Fig 8
(a) CO2 uptake during adsorption at 20 ℃ and an air relative humidity of 20%, 40%, 60%, and 80%; (b) specific adsorbed/desorbed amounts of CO2 and H2O in multicycle experiment at 20 ℃ and an air relative humidity of 40%; (c) schematic illustration of PEI distribution in HP20 resin; (d) the amount of CO2 on HP20/PEI-50 at 25 ℃ adsorbed from artificial air containing 400 ppm CO2 in five adsorption cycles; (e) breakthrough curves for CO2 as a function of temperature at various feed flow rates of I) 40, II) 60, and III) 90 cm3∙min−1; (f) pseudo-equilibrium and breakthrough CO2 capacity under dry and humid adsorption conditions at 35 ℃. C0 for CO2 concentration in the feed; breakthrough capacities determined from the breakthrough curves and defined at 5% of C0; pseudo-equilibrium capacities determined from the breakthrough curves and defined at 95% of C0. Adapted from Ref. 72 for (a–b), Ref. 73 for (c–d) and Ref. 74 for (e–f)."
Fig 9
(a) CO2 (left y-axis; black column) adsorption capacity and CO2/N2 adsorption selectivity (right y-axis; red column) at 50 Pa and 25 ℃ on the 5A and MLD-coated 5A zeolite calcined at different conditions and (b) CO2 adsorption kinetic uptake curve on the 5A zeolite (black symbol) and 5A-MLD-250-2h (red symbol). Adapted from Ref. 81."
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