Deciphering the contributing motifs of reconstructed cobalt (II) sulfides catalysts in Li-CO2 batteries
Abstract Developing highly efficient catalysts is significant for Li-CO2 batteries. However, understanding the exact structure of catalysts during battery operation remains a challenge, which hampers knowledge-driven optimization. Here we use X-ray absorption spectroscopy to probe the reconstruction...
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| Format: | Article |
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Nature Portfolio
2024-03-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-46465-8 |
| _version_ | 1827321336646598656 |
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| author | Yingqi Liu Zhiyuan Zhang Junyang Tan Biao Chen Bingyi Lu Rui Mao Bilu Liu Dashuai Wang Guangmin Zhou Hui-Ming Cheng |
| author_facet | Yingqi Liu Zhiyuan Zhang Junyang Tan Biao Chen Bingyi Lu Rui Mao Bilu Liu Dashuai Wang Guangmin Zhou Hui-Ming Cheng |
| author_sort | Yingqi Liu |
| collection | DOAJ |
| description | Abstract Developing highly efficient catalysts is significant for Li-CO2 batteries. However, understanding the exact structure of catalysts during battery operation remains a challenge, which hampers knowledge-driven optimization. Here we use X-ray absorption spectroscopy to probe the reconstruction of CoSx (x = 8/9, 1.097, and 2) pre-catalysts and identify the local geometric ligand environment of cobalt during cycling in the Li-CO2 batteries. We find that different oxidized states after reconstruction are decisive to battery performance. Specifically, complete oxidation on CoS1.097 and Co9S8 leads to electrochemical performance deterioration, while oxidation on CoS2 terminates with Co-S4-O2 motifs, leading to improved activity. Density functional theory calculations show that partial oxidation contributes to charge redistributions on cobalt and thus facilitates the catalytic ability. Together, the spectroscopic and electrochemical results provide valuable insight into the structural evolution during cycling and the structure-activity relationship in the electrocatalyst study of Li-CO2 batteries. |
| first_indexed | 2024-04-25T01:04:30Z |
| format | Article |
| id | doaj.art-11c0b1b18c724a10b680cf4f1200f568 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-04-25T01:04:30Z |
| publishDate | 2024-03-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-11c0b1b18c724a10b680cf4f1200f5682024-03-10T12:17:17ZengNature PortfolioNature Communications2041-17232024-03-0115111110.1038/s41467-024-46465-8Deciphering the contributing motifs of reconstructed cobalt (II) sulfides catalysts in Li-CO2 batteriesYingqi Liu0Zhiyuan Zhang1Junyang Tan2Biao Chen3Bingyi Lu4Rui Mao5Bilu Liu6Dashuai Wang7Guangmin Zhou8Hui-Ming Cheng9Tsinghua-Berkeley Shenzhen Institute & Tsinghua Shenzhen International Graduate School, Tsinghua UniversityTsinghua-Berkeley Shenzhen Institute & Tsinghua Shenzhen International Graduate School, Tsinghua UniversityTsinghua-Berkeley Shenzhen Institute & Tsinghua Shenzhen International Graduate School, Tsinghua UniversitySchool of Materials Science and Engineering and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin UniversityTsinghua-Berkeley Shenzhen Institute & Tsinghua Shenzhen International Graduate School, Tsinghua UniversityTsinghua-Berkeley Shenzhen Institute & Tsinghua Shenzhen International Graduate School, Tsinghua UniversityTsinghua-Berkeley Shenzhen Institute & Tsinghua Shenzhen International Graduate School, Tsinghua UniversityInstitute of Zhejiang University-Quzhou & Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang UniversityTsinghua-Berkeley Shenzhen Institute & Tsinghua Shenzhen International Graduate School, Tsinghua UniversityShenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of SciencesAbstract Developing highly efficient catalysts is significant for Li-CO2 batteries. However, understanding the exact structure of catalysts during battery operation remains a challenge, which hampers knowledge-driven optimization. Here we use X-ray absorption spectroscopy to probe the reconstruction of CoSx (x = 8/9, 1.097, and 2) pre-catalysts and identify the local geometric ligand environment of cobalt during cycling in the Li-CO2 batteries. We find that different oxidized states after reconstruction are decisive to battery performance. Specifically, complete oxidation on CoS1.097 and Co9S8 leads to electrochemical performance deterioration, while oxidation on CoS2 terminates with Co-S4-O2 motifs, leading to improved activity. Density functional theory calculations show that partial oxidation contributes to charge redistributions on cobalt and thus facilitates the catalytic ability. Together, the spectroscopic and electrochemical results provide valuable insight into the structural evolution during cycling and the structure-activity relationship in the electrocatalyst study of Li-CO2 batteries.https://doi.org/10.1038/s41467-024-46465-8 |
| spellingShingle | Yingqi Liu Zhiyuan Zhang Junyang Tan Biao Chen Bingyi Lu Rui Mao Bilu Liu Dashuai Wang Guangmin Zhou Hui-Ming Cheng Deciphering the contributing motifs of reconstructed cobalt (II) sulfides catalysts in Li-CO2 batteries Nature Communications |
| title | Deciphering the contributing motifs of reconstructed cobalt (II) sulfides catalysts in Li-CO2 batteries |
| title_full | Deciphering the contributing motifs of reconstructed cobalt (II) sulfides catalysts in Li-CO2 batteries |
| title_fullStr | Deciphering the contributing motifs of reconstructed cobalt (II) sulfides catalysts in Li-CO2 batteries |
| title_full_unstemmed | Deciphering the contributing motifs of reconstructed cobalt (II) sulfides catalysts in Li-CO2 batteries |
| title_short | Deciphering the contributing motifs of reconstructed cobalt (II) sulfides catalysts in Li-CO2 batteries |
| title_sort | deciphering the contributing motifs of reconstructed cobalt ii sulfides catalysts in li co2 batteries |
| url | https://doi.org/10.1038/s41467-024-46465-8 |
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