{"doi":"10.48550/arxiv.2403.02520","title":"Layered-to-Spinel Phase Transformation in Li$_{0.5}$NiO$_2$ from First Principles","abstract":"The phase transition layered Li$_{0.5}$NiO$_2$ to spinel Li(NiO$_2$)$_2$ is a potential degradation pathway in LiNiO$_2$-based lithium-ion battery cathodes. We investigated the mechanism of this phase transformation from first principles. Consistent with experimental observations reported in the literature, our results indicate a high energy barrier for the transformation due to high defect-formation energies, a complex charge-transfer mechanism, and electronic frustration. Our results suggest that partially inverse spinel phases are unlikely to form for Li$_{0.5}$NiO$_2$, a qualitative difference from the chemically similar Li$_{0.5}$MnO$_2$, in which the transformation occurs at room temperature. We show that Ni and Li atoms migrate concertedly towards their respective spinel sites for the layered-to-spinel transformation to occur. We investigated the charge ordering in layered phases along the LiNiO$_2$-NiO$_2$ composition line, finding a pronounced impact of the symmetry and space group on the layered-to-spinel transition in Li$_{0.5}$NiO$_2$. Finally, we evaluated the relative stability of different spinel space groups, finding that previously reported experimental observations are consistent with a temperature-averaged structure rather than the 0 Kelvin ground-state structure of Li(NiO$_2$)$_2$ spinel.","journal":"arXiv (Cornell University)","year":2024,"id":494991,"datarank":0.0,"base_score":0.0,"endowment":0.0,"self_citation_contribution":0.0,"citation_network_contribution":0.0,"self_endowment_contribution":0.0,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":0,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9502,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2024-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":1341499,"name":"Alan C. West","orcid":"0000-0002-9934-0034","position":1,"is_corresponding":false},{"id":314057,"name":"Alexander Urban","orcid":"0000-0002-9021-279X","position":2,"is_corresponding":false},{"id":1193163,"name":"Cem Komurcuoglu","orcid":null,"position":0,"is_corresponding":true}],"reference_count":0,"raw_metadata":null,"created_at":"2026-07-19T02:09:15.528853Z","pmid":null,"pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}