A mechanistic study of mesoporous TiO2nanoparticle negative electrode materials with varying crystallinity for lithium ion batteries

Deng, Changjian; Lau, Miu Lun; Ma, Chunrong; Skinner, Paige; Liu, Yuzi; Xu, Wenqian; Zhou, Hua; Zhang, Xianghui; Wu, Di; Yin, Yadong; Ren, Yang; Pérez, Jorge; Jaramillo, Diana; Barnes, Pete; Hou, Dewen; Dahl, Michael; Williford, Bethany; Zheng, Chong; Xiong, Hui

doi:10.1039/c9ta12499c

Cited by 36 publications

(27 citation statements)

References 65 publications

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“…These results demonstrate how polydispersity and discontinuous phase transformations within TiO2 nanocrystal ensembles impact charging rates in electrodes at different states of charge. Titania and lithium titanate polymorphs, including spinel Li4Ti5O12, [23][24][25][26][27][28] anatase, [6][7][8][9][10][11][12] TiO2-B bronze [29][30][31][32][33] and amorphous phases, [34][35][36][37] are prototypical Li-ion anodes that charge through lithium insertion and surface reactions in nanostructured electrodes. In particular, anatase TiO2 has charge storage densities competitive with conventional graphite electrodes and a small volume change during Li-ion insertion that allows for high cycle and calendar lifetimes at fast charging rates.…”

Section: Introductionmentioning

confidence: 99%

Dynamics of Lithium Insertion in Electrochromic Titanium Dioxide Nanocrystal Ensembles

et al. 2021

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is a robust model anode for Li-insertion in batteries. The influence of nanocrystal size on the equilibrium potential and kinetics of Li-insertion is investigated with in operando spectroelectrochemistry of thin film electrodes. Distinct visible and infrared responses correlate with Li-insertion and electron accumulation, respectively, and these optical signals are used to deconvolute Li-insertion from other electrochemical responses, such as double-layer capacitance and electrolyte leakage.Electrochemical titration and phase-field simulations reveal that a difference in surface energies between anatase and lithiated phases of TiO 2 systematically tunes Li-insertion potentials with particle size. However, particle size does not affect the kinetics of Li-insertion in ensemble electrodes. Rather, Li-insertion rates depend on applied overpotential, electrolyte concentration, and initial state-of-charge. We conclude that Li diffusivity and phase propagation are not rate-limiting during Li-insertion in TiO 2 nanocrystals. Both of these processes occur rapidly once the transformation between the low-Li anatase and high-Li orthorhombic phases begins in a particle. Instead, discontinuous kinetics of Li accumulation in TiO 2 particles prior to the phase transformations limits (dis)charging rates. We demonstrate a practical means to deconvolute non-equilibrium charging behavior in nanocrystalline electrodes through a combination of colloidal synthesis, phase field simulations and spectroelectrochemistry. File list (2)download file view on ChemRxiv Manuscript_DynamicsofLithiumInsertion.pdf (2.46 MiB) download file view on ChemRxiv SupportingInfo_DynamicsofLithiumInsertion.pdf (3.34 MiB)

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Section: Introductionmentioning

confidence: 99%

Dynamics of Lithium Insertion in Electrochromic Titanium Dioxide Nanocrystal Ensembles

et al. 2021

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“…The results obtained here are strongly reminiscent of what was observed with the reversible Li + insertion in TiO2-based electrodes. 28,[43][44][45][46][47][48][49][50][51][52][53] In anatase, it was established that Li + insertion is accompanied by a reversible phase transition from a lithium-poor tetragonal phase to a lithium-rich orthorhombic Li0.5TiO2 phase. 28,47 This translates into a pair of well-defined faradaic peaks in CV, separated by a significant potential hysteresis under thermodynamic equilibrium (peak-to-peak potential separation Ep > 0), 43,46 as also reported here in Figure 3B.…”

Section: S3mentioning

confidence: 99%

“…In the Frumkin framework, such a phase transformation is thus associated with g < gcrit. 42 On contrario, the insertion of Li + in amorphous TiO2 was characterized by a pair of symmetric but very broad faradaic waves in CV (meaning thus a g value > 0), 44,45,[48][49][50][51][52][53] leading some groups to conclude that in amorphous TiO2, the reversible Li + insertion proceeded through a solid solution reaction over a distribution of insertion potentials (reflecting the highly disordered structure of TiO2). 44,54 To better understand the dynamics of the proton insertioncoupled electron transfer reaction, CVs were recorded at different scan rates ranging from 1 mV•s -1 to 1 V•s -1 ( Figure S3).…”

Section: S3mentioning

confidence: 99%

Evidence of Bulk Proton Insertion in Nanostructured Anatase and Amorphous TiO2 Electrodes

Makivić¹,

Cho²,

Harris³

et al. 2021

Preprint

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Crystalline structures and lattice water molecules are believed to strongly influence the ability of metal oxides to reversibly and rapidly insert protons in aqueous batteries. In the present work, we performed a systematic analysis of the electrochemical charge storage properties of nanostructured TiO2 electrodes composed of either anatase or amorphous TiO2 in a mild buffered aqueous electrolyte. We demonstrate that both materials allow reversible bulk proton insertion up to a maximal reversible gravimetric capacity of ~150 mA·h·g-1. We also show that the TiO2 crystallinity governs the energetics of the charge storage process, with a phase transition for anatase, while having little effect on either the interfacial charge-transfer kinetics or the apparent rate of proton diffusivity within the metal oxide. Finally, with both TiO2 electrodes, reversible proton insertion leads to gravimetric capacities as high as 95 mA·h·g-1 at 75 C. We also reveal two competitive reactions decreasing the Coulombic efficiency at low rates, i.e. hydrogen evolution and a non-faradaic self-discharge reaction. Overall, this work provides a comprehensive overview of the proton-coupled electrochemical reactivity of TiO2 and highlights the key issues to be solved in order to truly benefit from the unique properties of protons as fast charge carriers in metal oxides.

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“…TiO 2 is a nontoxic, chemically stable material that can be easily prepared in so much as it is naturally abundant. It is used in various fields such as solar cells, 41,42 photocatalysis, 43 water splitting, 44 and lithium‐ion battery 45 among others. The successful use of TiO 2 in lithium‐ion batteries spurred intense research for its application as a negative electrode in sodium‐ion batteries 46,47 .…”

Section: Introductionmentioning

confidence: 99%

Impedance studies of biosynthesized Na_0.₈Ni₀_.₃₃Co₀_.₃₃Mn₀_.₃₃O₂applied in an aqueous sodium‐ion battery

et al. 2021

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Summary We studied Na0.8Ni0.33Co0.33Mn0.33O2 nanoparticles synthesized using water‐based extract procured from the dried silk of maize (Zea mays lea) plant. The synthesized Na0.8Ni0.33Co0.33Mn0.33O2 was used as the positive electrode in an aqueous sodium ion battery (SIB). X‐ray diffraction (XRD) studies of the biosynthesized material reveal that it can be indexed to the trigonal structure of Na0.8Ni 0.33Co0.33Mn0.33O2 with an R 3m space group (160), (ICSD 184736) although impurities of Mn2O3 and NiO were detected. Surface morphological studies from a scanning electron microscope (SEM) disclose that the nanoparticles consist of an interspersion of sheath‐like particles with quasi‐spherical nanoparticles of uneven dimensions. The sheath‐like particles seem to agglomerate to form layers that coalesce into flower‐like structures that are spread within the quasi‐spherical nanoparticles. The material yielded a rechargeable discharge capacity of about 86 mA h g−1 in a three‐electrode system consisting of platinum, the Na0.8Ni0.33Co0.33Mn0.33O2 and Ag/AgCl as the counter, working and reference electrodes respectively at a current density of 10 mA g−1. However, a full cell using P25 Degussa TiO2 and the biosynthesized Na0.8Ni0.33Co0.33Mn0.33O2 as the negative and the positive electrode, respectively, and having a mass ratio of 1:1 yielded a discharge capacity of 49 mA h g−1 at a current density of 5 mA g−1. Impedance studies for a symmetrical cell developed showed that the magnitude of the impedance is highest at 0% and 100 state of charge (SOC).

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A mechanistic study of mesoporous TiO₂nanoparticle negative electrode materials with varying crystallinity for lithium ion batteries

Abstract: Nanoscale oxide-based negative electrodes are of great interest for lithium ion batteries due to their high energy/power density, and enhanced safety. The crystallinity effect of mesoporous TiO2 nanoparticle electrode was investigated in this work.

Cited by 36 publications

References 65 publications

Dynamics of Lithium Insertion in Electrochromic Titanium Dioxide Nanocrystal Ensembles

Dynamics of Lithium Insertion in Electrochromic Titanium Dioxide Nanocrystal Ensembles

Evidence of Bulk Proton Insertion in Nanostructured Anatase and Amorphous TiO2 Electrodes

Impedance studies of biosynthesized Na_0.₈Ni₀_.₃₃Co₀_.₃₃Mn₀_.₃₃O₂applied in an aqueous sodium‐ion battery

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A mechanistic study of mesoporous TiO2nanoparticle negative electrode materials with varying crystallinity for lithium ion batteries

Abstract: Nanoscale oxide-based negative electrodes are of great interest for lithium ion batteries due to their high energy/power density, and enhanced safety. The crystallinity effect of mesoporous TiO2 nanoparticle electrode was investigated in this work.

Cited by 36 publications

References 65 publications

Dynamics of Lithium Insertion in Electrochromic Titanium Dioxide Nanocrystal Ensembles

Dynamics of Lithium Insertion in Electrochromic Titanium Dioxide Nanocrystal Ensembles

Evidence of Bulk Proton Insertion in Nanostructured Anatase and Amorphous TiO2 Electrodes

Impedance studies of biosynthesized Na0.8Ni0.33Co0.33Mn0.33O2applied in an aqueous sodium‐ion battery

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A mechanistic study of mesoporous TiO₂nanoparticle negative electrode materials with varying crystallinity for lithium ion batteries

Impedance studies of biosynthesized Na_0.₈Ni₀_.₃₃Co₀_.₃₃Mn₀_.₃₃O₂applied in an aqueous sodium‐ion battery