High Pressure Effect on Structural and Electrochemical Properties of Anionic Redox-Based Lithium Transition Metal Oxides

•Structural flexibility and metastability of anionic redox-based materials•Structure reordering strain accumulation under high pressure•Negative bulk compressibility induced by the defect formation Transition metal oxide is one most interesting classes solids, exhibiting many physical properties, including magnetism, piezoelectricity, superconductivity. Lithium transition cornerstone for energy storage through Li intercalation. This work demonstrates that structural defects during electrochemical activation process results in metastable states lithium oxides. The unique provides an opportunity to reveal unusual properties complex materials, such as negative thermal expansion compressibility. Predictive design new materials with extraordinary combinations characteristics can be realized electrochemically controlling intercalation process. richness redox chemistry solid state offers opportunities a possible paradigm shift storage. excess capacity goes beyond conventional theoretical values attributed Li-rich cathodes Li-ion batteries. Their behavior thermodynamically determined evolution. To better understand dependence on factors, we have modifications pristine activated Li1.144Ni0.136Co0.136Mn0.544O2 high-pressure treatment. A cyclical change observed redox-activated material operando pressure sweep, characterized periodic evolution superlattice peak intensity synchrotron X-ray diffraction patterns. During period, decreases, even becoming negative. These insights elucidate which undergo large compressions while delivering good properties. 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Despite above research little known about structure. aim this investigate this, (Li[Li0.144Ni0.136Co0.136Mn0.544]O2, denoted LR-NCM) subjected static treatments two types cells: diamond anvil cells (DACs) 15 GPa (LACs) Belt-type press 4 combination approaches junction molecular (MD) simulations occurrence upon pressure, although incrementally antisite microstrain. all profound impact after Larger (de)intercalation obtained sample, lower average discharge voltage. demonstrate crystal great importance. same batch LR-NCM, applied work,13Qiu loaded into DAC sweep. Figure 1A illustrates working mechanism, transmitting medium allows isotropic sample. Operando (SXRD) data then collected As shown 1B, pure R-3m space group ~15 Obvious broadening SXRD patterns increase strong indication continuous microstrain ~2? 8.4° highlighted enlarged region 1B honeycomb superstructure ordering layers.22Zhang Modified coprecipitation synthesis mesostructure-controlled minimizing degradation.ACS 3369-3376Crossref (13) gradually disappears, becomes partially disordered initial cycle.11Singer One remarkable intensified weakened pattern processing. reaches its maxima 2.73, 5.29, 8.38, 11.78 indicates recovered certain sweep conducted LR-NCM recorded S2. peaks larger angles 2? 8°–9° retained. consistent follow normal inorganic ceramic materials. Rietveld refinements maintained lattice parameters initially presented 1C. c parameter almost linearly decreases ~4% 14.237(8) 13.680(1) Å increases. cycling, unit cell volume expand, increasing.23Liu Chen An Venkatachalam Qian via neutron diffraction.Adv. 1502143Crossref (84) sample reduces more than 5% full reduction suggests reaction produces softer material. Unlike decrease shows period (see shaded area 1C). sharp contrast samples increases S3). Note percentage smaller (2.3%) (2.9%). susceptible deform along axis correlated inter-plane in-plane bonds adjacent ions.21Fell calculated 1D. anomalous parameters. P–V fitted third-order Birch-Murnaghan equation state.24Birch Finite elastic cubic crystals.Phys. Rev. 1947; 71: 809-824Crossref (4175) exhibits moduli 117 111 GPa, respectively. (149 (125 GPa).21Fell stoichiometric presence ions layer. compressibility, reciprocal modulus, based expression 1E. absolute value much positive testing does vary obviously increases, whereas displays takes place. once again manifests response pressure. Similar effect, previously,13Qiu oppose external force sinusoidal waveform implies sensitive recurrent force. that, layer irreversible vacancies, could migration.23Liu alter global structure, disturbing layers. accompanies reinsertion penalty.13Qiu exposed 1.0–4.0 0.5 1.5 h slowly released, powder argon atmosphere further ambient use LAC Belt apparatus preparation sufficient (~0.5 g) multiple characterization tasks signal-to-noise ratio. (1–4 where first selected analysis. ex situ S4. detail refinement C2/m symmetry summarized Table S1. major difference models ideal Li/TM assumption symmetry. atomic occupancy independent C2/m. Compared symmetry, worse R factor assumption. mostly lost, makes appropriate refinement. S5 refined treated pressures h. 2.8582(3) 14.320(4) Å, respectively (Table S2). All display phases, except underwent 4.0 phenomenon observations refinement, composition inductively plasma measurement inferred results. Oxygen identified showed no 2 eV, vacancy nearly impossible pressure.25Lee Persson K.A. Structural LixMnO3 function content first-principles calculations.Adv. 2014; 1400498Crossref (130) fraction cations, migrate fully coordinated octahedral sites nearby forces.26Qian Xu Chi Uncovering roles oxides.in: Physical Chemistry Chemical Physics. Royal Society Chemistry, 2014: 14665-14668Crossref analysis cycle, 0.059(1) 0.173(3) 2A), ~30% trend confirmed other set h, maximum 0.083(1) 2.7 2B). elimination recovers around oxygen, crucial activity.4Seo addition, (antisite NiLi) starts greater S2), hinder diffusion modeled MD solid-state simulation density functional theory (DFT). Isotropic temperature, close conditions, isolate migration. performed supercell model composed two-formula units Li14Ni3Mn7O24. model, there “excess” located Li11/14 concentration chosen simulate discharged (Li11Ni3Mn7O23), absent time S6. stabilized 20 ps. began take place ~22 ps (Video S1), energetically favorable route proceeds 2C, migrated yellow. captured eV Ni2+ 2.6 Mn4+) Li.26Qian Thus, it will longer capture migration, particular https://www.cell.com/cms/asset/45dff0d3-50e2-4e90-ac8a-217c39b03751/mmc2.mp4Loading ... Download .mp4 (0.91 MB) Help files Video Dynamics Simulation Result Pressure Cycled Structure(Green, Li; Purple, Mn; Blue, Ni; Red, Oxygen). https://www.cell.com/cms/asset/2d43858c-8adc-45a0-8fce-c16a5eda1608/mmc3.mp4Loading (0.96 Blu