{"title":"固态电池TiO2/LiPON和LNMC/LiPON固体电极/电解质界面的椭圆偏振光谱研究","authors":"Simran Atwal, Vidha Bhasin, Chandrani Nayak, Abharana Nagendra, Vijay Karki, Pratap Kumar Sahoo, Kaustava Bhattacharyya, Dibyendu Bhattacharyya and Arup Biswas*, ","doi":"10.1021/acsaem.5c0102310.1021/acsaem.5c01023","DOIUrl":null,"url":null,"abstract":"<p >In all-solid-state thin-film batteries, the interface properties between solid electrolytes and solid electrodes are the major factors limiting their performances; however, knowledge of the interface properties is limited in most of the cases. Using the magnetron sputtering technique, thin films of Li<sub>3+<i>x</i></sub>PO<sub>4–<i>x</i></sub>N<sub><i>x</i></sub> (LiPON) solid-state electrolyte along with LiPON/TiO<sub>2</sub> (anode) and LiPON/LiNi<sub>0.33</sub>Mn<sub>0.33</sub>Co<sub>0.33</sub>O<sub>2</sub> (LNMC) (cathode) thin-film bilayers have been prepared under different sputtering conditions and characterized by spectroscopic ellipsometry to study the properties of electrolyte/anode and electrolyte/cathode interfaces of Li-ion solid-state batteries. Spectroscopic ellipsometry, X-ray photoelectron spectroscopy, and secondary ion mass spectrometry studies of single-layer LiPON showed that radiofrequency (RF) power and nitrogen pressure used during deposition control the nitrogen and lithium contents of the film. Films deposited at a higher RF power showed a lower refractive index, which signifies a lower nitrogen content and a more Li<sub>3</sub>PO<sub>4</sub>-like film; impedance measurements also confirmed this result. The interface width found from the ellipsometric study of the LiPON/TiO<sub>2</sub> and LiPON/LNMC bilayer films showed that the nitrogen content of the LiPON layer has a very strong effect on the interface as well as on the lithiation of the TiO<sub>2</sub> layer during LiPON sputtering; higher nitrogen content in the LiPON layer increases both. This finding has also been supported by cross-sectional FESEM results. Hybrid half-cells of the TiO<sub>2</sub> anode and LNMC cathodes have been prepared using a higher nitrogen content LiPON electrolyte. The stable electrochemical performance of the cells manifests that higher interface width favors the formation of a stable solid electrolyte interface layer at the anode–electrolyte interface.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"8 11","pages":"7730–7743 7730–7743"},"PeriodicalIF":5.5000,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Spectroscopic Ellipsometry Study of TiO2/LiPON and LNMC/LiPON Solid Electrode/Electrolyte Interfaces of Solid-State Batteries\",\"authors\":\"Simran Atwal, Vidha Bhasin, Chandrani Nayak, Abharana Nagendra, Vijay Karki, Pratap Kumar Sahoo, Kaustava Bhattacharyya, Dibyendu Bhattacharyya and Arup Biswas*, \",\"doi\":\"10.1021/acsaem.5c0102310.1021/acsaem.5c01023\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >In all-solid-state thin-film batteries, the interface properties between solid electrolytes and solid electrodes are the major factors limiting their performances; however, knowledge of the interface properties is limited in most of the cases. Using the magnetron sputtering technique, thin films of Li<sub>3+<i>x</i></sub>PO<sub>4–<i>x</i></sub>N<sub><i>x</i></sub> (LiPON) solid-state electrolyte along with LiPON/TiO<sub>2</sub> (anode) and LiPON/LiNi<sub>0.33</sub>Mn<sub>0.33</sub>Co<sub>0.33</sub>O<sub>2</sub> (LNMC) (cathode) thin-film bilayers have been prepared under different sputtering conditions and characterized by spectroscopic ellipsometry to study the properties of electrolyte/anode and electrolyte/cathode interfaces of Li-ion solid-state batteries. Spectroscopic ellipsometry, X-ray photoelectron spectroscopy, and secondary ion mass spectrometry studies of single-layer LiPON showed that radiofrequency (RF) power and nitrogen pressure used during deposition control the nitrogen and lithium contents of the film. Films deposited at a higher RF power showed a lower refractive index, which signifies a lower nitrogen content and a more Li<sub>3</sub>PO<sub>4</sub>-like film; impedance measurements also confirmed this result. The interface width found from the ellipsometric study of the LiPON/TiO<sub>2</sub> and LiPON/LNMC bilayer films showed that the nitrogen content of the LiPON layer has a very strong effect on the interface as well as on the lithiation of the TiO<sub>2</sub> layer during LiPON sputtering; higher nitrogen content in the LiPON layer increases both. This finding has also been supported by cross-sectional FESEM results. Hybrid half-cells of the TiO<sub>2</sub> anode and LNMC cathodes have been prepared using a higher nitrogen content LiPON electrolyte. The stable electrochemical performance of the cells manifests that higher interface width favors the formation of a stable solid electrolyte interface layer at the anode–electrolyte interface.</p>\",\"PeriodicalId\":4,\"journal\":{\"name\":\"ACS Applied Energy Materials\",\"volume\":\"8 11\",\"pages\":\"7730–7743 7730–7743\"},\"PeriodicalIF\":5.5000,\"publicationDate\":\"2025-05-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Applied Energy Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acsaem.5c01023\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Applied Energy Materials","FirstCategoryId":"88","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsaem.5c01023","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Spectroscopic Ellipsometry Study of TiO2/LiPON and LNMC/LiPON Solid Electrode/Electrolyte Interfaces of Solid-State Batteries
In all-solid-state thin-film batteries, the interface properties between solid electrolytes and solid electrodes are the major factors limiting their performances; however, knowledge of the interface properties is limited in most of the cases. Using the magnetron sputtering technique, thin films of Li3+xPO4–xNx (LiPON) solid-state electrolyte along with LiPON/TiO2 (anode) and LiPON/LiNi0.33Mn0.33Co0.33O2 (LNMC) (cathode) thin-film bilayers have been prepared under different sputtering conditions and characterized by spectroscopic ellipsometry to study the properties of electrolyte/anode and electrolyte/cathode interfaces of Li-ion solid-state batteries. Spectroscopic ellipsometry, X-ray photoelectron spectroscopy, and secondary ion mass spectrometry studies of single-layer LiPON showed that radiofrequency (RF) power and nitrogen pressure used during deposition control the nitrogen and lithium contents of the film. Films deposited at a higher RF power showed a lower refractive index, which signifies a lower nitrogen content and a more Li3PO4-like film; impedance measurements also confirmed this result. The interface width found from the ellipsometric study of the LiPON/TiO2 and LiPON/LNMC bilayer films showed that the nitrogen content of the LiPON layer has a very strong effect on the interface as well as on the lithiation of the TiO2 layer during LiPON sputtering; higher nitrogen content in the LiPON layer increases both. This finding has also been supported by cross-sectional FESEM results. Hybrid half-cells of the TiO2 anode and LNMC cathodes have been prepared using a higher nitrogen content LiPON electrolyte. The stable electrochemical performance of the cells manifests that higher interface width favors the formation of a stable solid electrolyte interface layer at the anode–electrolyte interface.
期刊介绍:
ACS Applied Energy Materials is an interdisciplinary journal publishing original research covering all aspects of materials, engineering, chemistry, physics and biology relevant to energy conversion and storage. The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrate knowledge in the areas of materials, engineering, physics, bioscience, and chemistry into important energy applications.