{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,27]],"date-time":"2026-09-27T06:57:40Z","timestamp":1790492260989,"version":"4.1.0"},"reference-count":30,"publisher":"Wiley","license":[{"start":{"date-parts":[[2026,9,26]],"date-time":"2026-09-26T00:00:00Z","timestamp":1790380800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,9,26]],"date-time":"2026-09-26T00:00:00Z","timestamp":1790380800000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    Understanding cathode\/electrolyte interfacial reactions is critical for improving the stability of high\u2010voltage Li\u2010ion batteries; however, the molecular mechanisms governing cathode\/electrolyte interphase (CEI) formation remain poorly understood due to the buried and dynamically evolving nature of the interface. Here, we develop an operando attenuated total reflectance far\u2010ultraviolet (ATR\u2010FUV) spectroscopic method to directly probe cathode\/electrolyte interfacial chemistry during electrochemical cycling. With the aid of principal component analysis, we isolate a voltage\u2010dependent interfacial spectral component that emerges at \u223c3.9 V, well below the onset potential of electrochemical electrolyte oxidation. Supported by quantum chemical calculations, this component is assigned to dehydrogenated ethylene carbonate (de\u2010H EC) and vinylene carbonate (VC), revealing a chemically driven proton\u2010abstraction pathway induced by reactive surface oxygen species generated upon Li\n                    <jats:sup>+<\/jats:sup>\n                    deintercalation. This process recurs upon charging, demonstrating a voltage\u2010driven yet chemically initiated interfacial reaction distinct from direct electrochemical oxidation. These findings establish operando ATR\u2010FUV spectroscopy as a powerful tool for resolving transient cathode interfacial chemistry and provide new molecular\u2010level insights into CEI formation relevant to the design of next\u2010generation high\u2010voltage Li\u2010ion batteries.\n                  <\/jats:p>","DOI":"10.1002\/anie.6529709","type":"journal-article","created":{"date-parts":[[2026,9,27]],"date-time":"2026-09-27T06:29:28Z","timestamp":1790490568000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Operando Attenuated Total Reflectance Far\u2010Ultraviolet Spectroscopic Analysis at the Cathode\/Electrolyte Interface"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7547-1902","authenticated-orcid":false,"given":"Chikashi","family":"Ota","sequence":"first","affiliation":[{"name":"Advanced Materials Development Center Panasonic Holdings Corporation  Moriguchi Osaka Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hirotetsu","family":"Suzuki","sequence":"additional","affiliation":[{"name":"Research and Development Center Panasonic Energy Co., Ltd.  Moriguchi Osaka Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Toshihiro","family":"Higuchi","sequence":"additional","affiliation":[{"name":"Advanced Materials Development Center Panasonic Holdings Corporation  Moriguchi Osaka Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6580-3029","authenticated-orcid":false,"given":"Ichiro","family":"Tanabe","sequence":"additional","affiliation":[{"name":"Department of Chemistry, College of Science Rikkyo University  Toshima\u2010ku Tokyo Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,9,26]]},"reference":[{"key":"e_1_2_7_2_1","doi-asserted-by":"crossref","first-page":"11503","DOI":"10.1021\/cr500003w","article-title":"Electrolytes and Interphases in Li\u2010Ion Batteries and Beyond","volume":"114","author":"Xu K.","year":"2014","journal-title":"Chemical Reviews"},{"key":"e_1_2_7_3_1","doi-asserted-by":"crossref","DOI":"10.1002\/admi.202102078","article-title":"Face to Face at the Cathode Electrolyte Interphase: From Interface Features to Interphase Formation and Dynamics","volume":"9","author":"K\u00fchn S. P.","year":"2022","journal-title":"Advanced Materials Interfaces"},{"key":"e_1_2_7_4_1","doi-asserted-by":"crossref","first-page":"1463","DOI":"10.1038\/s41560-024-01639-y","article-title":"Assessing Cathode\u2013Electrolyte Interphases in Batteries","volume":"9","author":"Xiao J.","year":"2024","journal-title":"Nature Energy"},{"key":"e_1_2_7_5_1","doi-asserted-by":"crossref","first-page":"262","DOI":"10.1021\/acsenergylett.3c02534","article-title":"Designing Electrolytes for Stable Operation of High\u2010Voltage LiCoO2 in Lithium\u2010Ion Batteries","volume":"9","author":"Kim S.","year":"2024","journal-title":"ACS Energy Letters"},{"key":"e_1_2_7_6_1","doi-asserted-by":"crossref","DOI":"10.1016\/j.xcrp.2022.101197","article-title":"Modified Cathode\u2010Electrolyte Interphase Toward High\u2010Performance Batteries","volume":"3","author":"Zhang N.","year":"2022","journal-title":"Cell Reports Physical Science"},{"key":"e_1_2_7_7_1","first-page":"191","article-title":"Breaking the Molecular Symmetricity of Sulfonimide Anions for High\u2010Performance Lithium Metal Batteries Under Extreme Cycling Conditions","volume":"10","author":"Lu Y.","year":"2025","journal-title":"Nature Energy"},{"key":"e_1_2_7_8_1","doi-asserted-by":"crossref","first-page":"5753","DOI":"10.1002\/anie.201209976","article-title":"Preferential Adsorption of Solvents on the Cathode Surface of Lithium Ion Batteries","volume":"52","author":"Yu L.","year":"2013","journal-title":"Angewandte Chemie International Edition"},{"key":"e_1_2_7_9_1","doi-asserted-by":"crossref","DOI":"10.1063\/5.0026283","article-title":"Probing the Electrode\u2013Solution Interfaces in Rechargeable Batteries by Sum\u2010Frequency Generation Spectroscopy","volume":"153","author":"Ge A.","year":"2020","journal-title":"Journal of Chemical Physics"},{"key":"e_1_2_7_10_1","doi-asserted-by":"crossref","first-page":"14476","DOI":"10.1021\/acs.jpcc.7b04132","article-title":"The Chemistry of Electrolyte Reduction on Silicon Electrodes Revealed by in Situ ATR\u2010FTIR Spectroscopy","volume":"121","author":"Shi F.","year":"2017","journal-title":"Journal of Physical Chemistry C"},{"key":"e_1_2_7_11_1","doi-asserted-by":"crossref","first-page":"778","DOI":"10.1002\/batt.202000259","article-title":"In Situ ATR\u2010FTIR Study of the Cathode\u2013Electrolyte Interphase: Electrolyte Solution Structure, Transition Metal Redox, and Surface Layer Evolution","volume":"4","author":"Tr\u00e9moulet de Villers B. J.","year":"2021","journal-title":"Batteries & Supercaps"},{"key":"e_1_2_7_12_1","doi-asserted-by":"crossref","first-page":"8054","DOI":"10.1021\/acs.analchem.8b05819","article-title":"Operando Raman Spectroscopy Measurements of a High\u2010Voltage Cathode Material for Lithium\u2010Ion Batteries","volume":"91","author":"Jehnichen P.","year":"2019","journal-title":"Analytical Chemistry"},{"key":"e_1_2_7_13_1","doi-asserted-by":"crossref","DOI":"10.1016\/j.electacta.2024.144611","article-title":"Operando Raman Observation of Lithium\u2010Ion Battery Graphite Composite Electrodes With Various Densities and Thicknesses","volume":"498","author":"Maruyama S.","year":"2024","journal-title":"Electrochimica Acta"},{"key":"e_1_2_7_14_1","doi-asserted-by":"crossref","first-page":"10917","DOI":"10.1039\/D0CS01602K","article-title":"Advances, Challenges and Perspectives of Quantum Chemical Approaches in Molecular Spectroscopy of the Condensed Phase","volume":"50","author":"Ozaki Y.","year":"2021","journal-title":"Chemical Society Reviews"},{"key":"e_1_2_7_15_1","doi-asserted-by":"crossref","first-page":"1730","DOI":"10.1039\/D3CS00437F","article-title":"ATR\u2010Far\u2010Ultraviolet Spectroscopy: A Challenge to New \u03c3 Chemistry","volume":"53","author":"Ozaki Y.","year":"2024","journal-title":"Chemical Society Reviews"},{"key":"e_1_2_7_16_1","doi-asserted-by":"crossref","first-page":"6375","DOI":"10.1039\/D4CC01775G","article-title":"Electronic Interaction Between Dimethyl Carbonate and Li+ Studied by Attenuated Total Reflectance Far\u2010Ultraviolet Spectroscopy","volume":"60","author":"Sato H.","year":"2024","journal-title":"Chemical Communications"},{"key":"e_1_2_7_17_1","doi-asserted-by":"crossref","first-page":"11232","DOI":"10.1039\/D5SC02406D","article-title":"Electronic States and Contact Ion Pair Formation in Lithium\u2010Ion Electrolytes Investigated by Far\u2010Ultraviolet Spectroscopy and Quantum Chemical Calculations","volume":"16","author":"Sato H.","year":"2025","journal-title":"Chemical Science"},{"key":"e_1_2_7_18_1","doi-asserted-by":"crossref","first-page":"612","DOI":"10.1021\/ac50012a027","article-title":"Determination of the Number of Factors and the Experimental Error in a Data Matrix","volume":"49","author":"Malinowski E. R.","year":"1977","journal-title":"Analytical Chemistry"},{"key":"e_1_2_7_19_1","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.chemolab.2015.10.003","article-title":"A MATLAB Toolbox for Principal Component Analysis and Unsupervised Exploration of Data Structure","volume":"149","author":"Ballabio D.","year":"2015","journal-title":"Chemometrics and Intelligent Laboratory Systems"},{"key":"e_1_2_7_20_1","doi-asserted-by":"crossref","first-page":"8303","DOI":"10.1039\/D5EE02403J","article-title":"An Unwanted Guest in the Electrochemical Oxidation of High\u2010Voltage Li\u2010Ion Battery Electrolytes: The Life of Highly Reactive Protons","volume":"18","author":"Ilic S.","year":"2025","journal-title":"Energy & Environmental Science"},{"key":"e_1_2_7_21_1","doi-asserted-by":"crossref","first-page":"3416","DOI":"10.1039\/D1EE04053G","article-title":"Two Electrolyte Decomposition Pathways at Nickel\u2010Rich Cathode Surfaces in Lithium\u2010Ion Batteries","volume":"15","author":"Rinkel B. L. D.","year":"2022","journal-title":"Energy & Environmental Science"},{"key":"e_1_2_7_22_1","doi-asserted-by":"crossref","first-page":"3881","DOI":"10.1021\/acs.jpclett.7b01655","article-title":"Chemical Reactivity Descriptor for the Oxide\u2010Electrolyte Interface in Li\u2010Ion Batteries","volume":"8","author":"Giordano L.","year":"2017","journal-title":"Journal of Physical Chemistry Letters"},{"key":"e_1_2_7_23_1","doi-asserted-by":"crossref","first-page":"E3059","DOI":"10.1149\/2.009408jes","article-title":"Crystal Surface and State of Charge Dependencies of Electrolyte Decomposition on LiMn2O4 Cathode","volume":"161","author":"Kumar N.","year":"2014","journal-title":"Journal of the Electrochemical Society"},{"key":"e_1_2_7_24_1","doi-asserted-by":"crossref","DOI":"10.1088\/0957-4484\/26\/35\/354003","article-title":"Towards High Throughput Screening of Electrochemical Stability of Battery Electrolytes","volume":"26","author":"Borodin O.","year":"2015","journal-title":"Nanotechnology"},{"key":"e_1_2_7_25_1","doi-asserted-by":"crossref","first-page":"291","DOI":"10.1038\/s41560-020-0567-z","article-title":"A Cyclic Phosphate\u2010Based Battery Electrolyte for High Voltage and Safe Operation","volume":"5","author":"Zheng Q.","year":"2020","journal-title":"Nature Energy"},{"key":"e_1_2_7_26_1","doi-asserted-by":"crossref","DOI":"10.1149\/1945-7111\/ab8f57","article-title":"Assessing the Oxidation Behavior of EC:DMC Based Electrolyte on Non\u2010Catalytically Active Surface","volume":"167","author":"Azcarate I.","year":"2020","journal-title":"Journal of the Electrochemical Society"},{"key":"e_1_2_7_27_1","doi-asserted-by":"crossref","DOI":"10.1016\/j.mser.2026.101177","article-title":"High\u2010Voltage and Wide\u2010Temperature Lithium Metal Batteries With High\u2010Safety Enabled by Non\u2010Flammable Electrolytes","volume":"169","author":"Liang H.","year":"2026","journal-title":"Materials Science and Engineering: R: Reports"},{"key":"e_1_2_7_28_1","doi-asserted-by":"crossref","first-page":"2444","DOI":"10.1021\/acsenergylett.5c03592","article-title":"Electrolyte and Electrode Interfacial Model: Five Years\u2032 Research Progress and Perspectives","volume":"11","author":"Ma Z.","year":"2026","journal-title":"ACS Energy Letters"},{"key":"e_1_2_7_29_1","doi-asserted-by":"crossref","first-page":"5345","DOI":"10.1021\/acsenergylett.5c02695","article-title":"Moderate Dissociating Solvation Structure\u2010Mediated Electrolytes for High\u2010Voltage Lithium\u2010Ion Batteries","volume":"10","author":"Li Y.","year":"2025","journal-title":"ACS Energy Letters"},{"key":"e_1_2_7_30_1","doi-asserted-by":"crossref","DOI":"10.1002\/anie.202504490","article-title":"Ether\u2010Oxygen Groups Modified Carboxylic Ester Enabling High\u2010Voltage Lithium Metal Batteries","volume":"64","author":"Li S.","year":"2025","journal-title":"Angewandte Chemie International Edition"},{"key":"e_1_2_7_31_1","doi-asserted-by":"crossref","DOI":"10.1002\/eem2.12494","article-title":"Solvation Effects on the Dielectric Constant of 1 M LiPF6 in Ethylene Carbonate: Ethyl Methyl Carbonate (3:7)","volume":"7","author":"Self J.","year":"2024","journal-title":"Energy & Environmental Materials"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.6529709","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.6529709","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.6529709","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,27]],"date-time":"2026-09-27T06:29:32Z","timestamp":1790490572000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.6529709"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,26]]},"references-count":30,"alternative-id":["10.1002\/anie.6529709"],"URL":"https:\/\/doi.org\/10.1002\/anie.6529709","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,26]]},"assertion":[{"value":"2026-02-24","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-09-05","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-09-26","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e6529709"}}