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Thermal Decomposition Study on Li₂O₂ for Li₂NiO₂ Synthesis as a Sacrificing Positive Additive of Lithium-Ion Batteries.

ABSTRACT: Herein, thermal decomposition experiments of lithium peroxide (Li₂O₂) were performed to prepare a precursor (Li₂O) for sacrificing cathode material, Li₂NiO₂. The Li₂O₂ was prepared by a hydrometallurgical reaction between LiOH·H₂O and H₂O₂. The overall reaction during annealing was found to involve the following three steps: (1) dehydration of LiOH·H₂O, (2) decomposition of Li₂O₂, and (3) pyrolysis of the remaining anhydrous LiOH. This stepwise reaction was elucidated by thermal gravimetric and quantitative X-ray diffraction analyses. Furthermore, over-lithiated lithium nickel oxide (Li₂NiO₂) using our lithium precursor was synthesized, which exhibited a larger yield of 90.9% and higher irreversible capacity of 261 to 265 mAh g^-1 than the sample prepared by commercially purchased Li₂O (45.6% and 177 to 185 mAh g^-1, respectively) due to optimal powder preparation conditions.

SUBMITTER: Kim J

PROVIDER: S-EPMC6943730 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature

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Thermal Decomposition Study on Li2O2 for Li2NiO2 Synthesis as a Sacrificing Positive Additive of Lithium-Ion Batteries.

Kim Jaekwang J Kang Hyunchul H Hwang Keebum K Yoon Songhun S

Molecules (Basel, Switzerland) 20191217 24

Herein, thermal decomposition experiments of lithium peroxide (Li2O2) were performed to prepare a precursor (Li2O) for sacrificing cathode material, Li2NiO2. The Li2O2 was prepared by a hydrometallurgical reaction between LiOH·H2O and H2O2. The overall reaction during annealing was found to involve the following three steps: (1) dehydration of LiOH·H2O, (2) decomposition of Li ...[more]

PMID: 31861185

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Project description:Fluorinated electrolytes based on fluoroethylene carbonate (FEC) have been considered as promising alternative electrolytes for high-voltage and high-energy capacity lithium-ion batteries (LIBs). However, the compatibility of the fluorinated electrolytes with graphite negative electrodes is unclear. In this paper, we have systematically investigated, for the first time, the stability of fluorinated electrolytes with graphite negative electrodes, and the result shows that unlike the ethylene carbonate (EC)-based electrolyte, the FEC-based electrolyte (EC was totally replaced by FEC) is incapable of forming a protective and effective solid electrolyte interphase (SEI) that protects the electrolyte from runaway reduction on the graphite surface. The reason is that the lowest unoccupied molecular orbital energy levels are also lowered by the introduction of fluorine into the solvent, and the FEC solvent has poorer resistance against reduction, leading to instability on the graphite negative electrode. To tackle this problem, two lithium salts of lithium bis(oxalato)borate and lithium difluoro(oxalato)borate (LiDFOB) have been investigated as negative-electrode film-forming additives. Incorporation of only 0.5 wt % LiDFOB to a FEC-based electrolyte [1.0 M LiPF6 in 3:7 (FEC-ethyl methyl carbonate)] results in excellent cycling performance of the graphite negative electrode. This improved property originates from the generation of a thinner and better quality SEI film with little LiF by the sacrificial reduction of the LiDFOB additive on the graphite negative electrode surface. On the other hand, this additive can stabilize the electrolyte by scavenging HF. Meanwhile, the incorporated LiDFOB additive has positive influence on the interphase layer on the positive electrode surface and significantly decreases the amount of HF formation, finally leading to improved cycling stability and rate capability of LiNi0.5Mn1.5O4 electrodes at a high cutoff voltage of 5 V. The data demonstrate that the LiDFOB additive not only exhibits a superior compatibility with graphite but also improves the electrochemical properties of high-voltage spinel LiNi0.5Mn1.5O4 positive electrodes considerably, confirming its potential as a prospective, multifunctional additive for 5 V fluorinated electrolytes in high-energy capacity lithium-ion batteries (LIBs).

Dataset Information

Thermal Decomposition Study on Li₂O₂ for Li₂NiO₂ Synthesis as a Sacrificing Positive Additive of Lithium-Ion Batteries.

Publications

Thermal Decomposition Study on Li<sub>2</sub>O<sub>2</sub> for Li<sub>2</sub>NiO<sub>2</sub> Synthesis as a Sacrificing Positive Additive of Lithium-Ion Batteries.

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