Thermal Phase Behavior and Electrochemical/Physicochemical Properties of Carbonate and Ester Electrolytes with LiBF<sub>4</sub>, LiDFOB and LiBOB

Allen, Joshua L.; Seo, Daniel M.; McOwen, Dennis W.; Han, Sang‐Don; Knight, Bradford A.; Boyle, Paul D.; Henderson, Wesley A.

doi:10.1149/05026.0381ecst

Cited by 3 publications

(5 citation statements)

References 21 publications

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“…The band at 1763 cm −1 corresponds to the C═O stretching of GBL in 0.5 m LiDFOB-GBL electrolyte, and the typical bands located at 740 and 1280 cm −1 represent the P─O─C and P═O stretching of TMP in 0.5 m LiDFOB-TMP electrolyte. [33,34] As the TMP content increases, the C═O stretching of GBL in 0.5 m LiDFOB-GBL/TMP hybrid electrolytes gradually shifts to higher wavenumbers in Figure 3d, which is in accordance with the FTIR spectra.…”

Section: Resultssupporting

confidence: 77%

Endowing the Operability of Supercapacitors at High Temperatures by Regulating the Solvation Structure in Dilute Hybrid Electrolyte with Trimethyl Phosphate Cosolvent

Wu,

Wang,

Zhang

et al. 2023

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The redox stabilities of different oxygen donor solvents (C═O, P═O and S═O) and lithium salt anions for supercapacitors (SCs) electrolytes have been compared by calculating the frontier molecular orbital energy. Among six lithium difluoro(oxalate)borate (LiDFOB)‐based mono‐solvent electrolytes, the dilute LiDFOB‐1,4‐butyrolactone (GBL) electrolyte exhibits the highest operating voltage but suffers from electrolyte breakdown at elevated temperatures. Trimethyl phosphate (TMP) exhibits the highest redox stability and a strongly negative electrostatic potential (ESP), making it suitable for promoting the dissolution of LiDFOB as expected. Therefore, TMP is selected as a co‐solvent into LiDFOB‐GBL electrolyte to regulate Li+ solvation structure and improve the operability of electrolytes at high temperatures. The electrochemical stable potential window (ESPW) of 0.5 m LiDFOB‐G/T(5/5) hybrid electrolyte can reach 5.230 V. The activated carbon (AC)‐based symmetric SC using 0.5 m LiDFOB‐G/T(5/5) hybrid electrolyte achieves a high energy density of 54.2 Wh kg−1 at 1.35 kW kg−1 and the capacitance retention reaches 89.2% after 10 000 cycles. The operating voltage of SC can be maintained above 2 V when the temperature rises to 60 °C.

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Section: Resultssupporting

confidence: 77%

Endowing the Operability of Supercapacitors at High Temperatures by Regulating the Solvation Structure in Dilute Hybrid Electrolyte with Trimethyl Phosphate Cosolvent

Wu,

Wang,

Zhang

et al. 2023

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“…LiBOB, LiDFOB, and LiNO 3 , have been previously reported as anionic additives that have the relatively strong ionic association strength, and preferential electrochemical reduction may be related to the presence of CIP or AGG solution structures. [44][45][46]…”

Section: Discussionmentioning

confidence: 99%

Lithium Salt Effects on Silicon Electrode Performance and Solid Electrolyte Interphase (SEI) Structure, Role of Solution Structure on SEI Formation

Yoon

Chapman

Seo

et al. 2017

J. Electrochem. Soc.

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Silicon electrodes were cycled with electrolytes containing different salts to investigate the effect of salt on the electrochemical performance and SEI structure. Comparable capacity retention were observed for the 1.2 M LiPF 6 , LiTFSI and LiClO 4 electrolytes in ethylene carbonate (EC):dimethyl carbonate (DEC), 1:1, but severe fading was observed for the 1.2 M LiBF 4 electrolyte. The differential capacity plots and EIS analysis reveals that failure of the 1.2 M LiBF 4 electrolyte is attributed to large surface resistance and increasing polarization upon cycling. However, when LiBF 4 was added as an electrolyte additive (10% LiBF 4 and 90% LiPF 6 ), the capacity retention and Coulombic efficiency were improved. The SEI was analyzed by FTIR and XPS for each electrolyte. Both spectroscopic methods suggest that the main components of the SEI are lithium ethylene dicarbonate (LEDC) and Li 2 CO 3 in the 1.2 M LiPF 6 , LiTFSI and LiClO 4 electrolytes, while an inorganic-rich SEI, composed of LiF and borates, was generated for both the Silicon negative electrodes for lithium ion batteries have attracted academic and industrial interest, since they provide ∼10 times more specific capacity (3579 mA g −1 ) than graphite (372 mA g −1 ). However, the large volumetric changes during lithiation and delithiation limits commercial application.1 The volume changes result in mechanical stress to individual Si particles and the binder which maintains physical contact between electrode components, thus degenerating the electrode laminate upon repeated lithiation/delithiation. 2,3In particular, it has been demonstrated that the electric contact loss becomes severe during delithiation when the Si particles are contracted. Thus, incomplete delithiation due to contact resistance has been reported as one of dominant failure mechanisms. [4][5][6][7] In addition to the volume contraction, the solid electrolyte interphase (SEI) has been reported to be another factor that impedes the reversibility of lithiation. 5,7 When the SEI on silicon is modified by fluoroethylene carbonate (FEC), the capacity retention, reversibility of lithiation, and suppression of electrolyte decomposition are observed. 5,7,8 Since the improvement of the SEI is critical for improving the electrochemical performance of Si electrodes, great efforts have been devoted to modify the SEI by using electrolyte additives, surface coatings, or concentrated electrolytes. [9][10][11][12][13][14][15][16] Recently, it has been reported that the SEI can be significantly modified by changing the electrolyte concentration. [16][17][18] For instance, propylene carbonate (PC)-based electrolytes do not generate a stable passivation layer on graphite at low salt concentration. However, upon dissolving high concentrations of either LiPF 6 or LiTFSI into PC a LiF rich passivation layer is generated on graphite affording electrochemical reversibility of the graphite. 16,18 The change in salt concentration has been reported to result in a change solution structure of the electrolyte. 16,...

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“…According to the radial distribution functions (RDFs), the Li–F peak of PF 6 – and Li–O peak of EC, DMC, and TMEB are in the electrolyte (Figure e). The Li–O peak of TMEB appears at 1.78 Å, indicating the participation of TMEB in the Li + solvation sheath, which is in good agreement with the references …”

Section: Resultsmentioning

confidence: 92%

“…The Li−O peak of TMEB appears at 1.78 Å, indicating the participation of TMEB in the Li + solvation sheath, which is in good agreement with the references. 20 The NCM523||Li cells with the baseline electrolyte and TMEB containing electrolytes experience 5 cycles at 0.2 C from 3.0 to 4.5 V as the activation process. After the initial 5 cycles at 0.2 C, the NCM523||Li cells with the baseline electrolyte and 0.5, 1, and 2 wt % TMEB containing electrolytes are cycled for 200 cycles at 1.0 C. Figure 3b shows the first charge/discharge curves of the cells at 0.2 C. The initial capacity of the cell with the baseline electrolyte is lower than the ones with the TMEB containing electrolytes.…”

Section: Resultsmentioning

confidence: 99%

“…Therefore, continuous consumption of the electrolyte proceeds, and the reversible capacity gradually fades. Manipulation of solvent components has been reported to tune the solvation structure and inhibit solvent decomposition. , However, few studies have been reported about using the film-forming additive to tune the solvation structure and CEI layer construction simultaneously.…”

Section: Introductionmentioning

confidence: 99%

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Dual Role of Bis(borate) Additive in Electrode/Electrolyte Interface Layer Construction for High-Voltage NCM 523 Cathode

Xiao

Shi

Zheng

et al. 2023

ACS Appl. Energy Mater.

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Increasing the working voltage of a layered oxide cathode is an efficient way to lift the energy density of lithium-ion batteries. However, uncontrollable side reactions and excessive electrolyte decomposition take place at high voltage. Bulk cathode structure degradation and formation of a high working voltage induce excessive growth of the solid-electrolyte interface (SEI) layer and overconsumption of the electrolyte. Construction of a high-voltage stable SEI layer is crucial to enhance the electrochemical performance. In this work, trimethylene borate (TMEB) as a borate ester additive is used to improve the cycled stability of NCM523 cells at 4.5 V charging-cutoff voltage. On one hand, TMEB can be preferentially decomposed during cycling and participate in the film formation process on the surfaces of both anode and cathode. On the other hand, TMEB can tune the solvation sheath by expelling the carbonate solvent molecules out of the solvation sheath to suppress decomposition of the electrolyte. The cells cycled with the 0.5 wt % TMEB-containing electrolyte exhibit improved cycling stability after 200 cycles with the capacity retention of 90.9% indicating TMEB to be an effective additive to improve the lithium-ion batteries at higher charging-cutoff voltage.

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Thermal Phase Behavior and Electrochemical/Physicochemical Properties of Carbonate and Ester Electrolytes with LiBF₄, LiDFOB and LiBOB

Cited by 3 publications

References 21 publications

Endowing the Operability of Supercapacitors at High Temperatures by Regulating the Solvation Structure in Dilute Hybrid Electrolyte with Trimethyl Phosphate Cosolvent

Endowing the Operability of Supercapacitors at High Temperatures by Regulating the Solvation Structure in Dilute Hybrid Electrolyte with Trimethyl Phosphate Cosolvent

Lithium Salt Effects on Silicon Electrode Performance and Solid Electrolyte Interphase (SEI) Structure, Role of Solution Structure on SEI Formation

Dual Role of Bis(borate) Additive in Electrode/Electrolyte Interface Layer Construction for High-Voltage NCM 523 Cathode

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Thermal Phase Behavior and Electrochemical/Physicochemical Properties of Carbonate and Ester Electrolytes with LiBF4, LiDFOB and LiBOB

Cited by 3 publications

References 21 publications

Endowing the Operability of Supercapacitors at High Temperatures by Regulating the Solvation Structure in Dilute Hybrid Electrolyte with Trimethyl Phosphate Cosolvent

Endowing the Operability of Supercapacitors at High Temperatures by Regulating the Solvation Structure in Dilute Hybrid Electrolyte with Trimethyl Phosphate Cosolvent

Lithium Salt Effects on Silicon Electrode Performance and Solid Electrolyte Interphase (SEI) Structure, Role of Solution Structure on SEI Formation

Dual Role of Bis(borate) Additive in Electrode/Electrolyte Interface Layer Construction for High-Voltage NCM 523 Cathode

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Thermal Phase Behavior and Electrochemical/Physicochemical Properties of Carbonate and Ester Electrolytes with LiBF₄, LiDFOB and LiBOB