Lithium-ion secondary batteries using polymer electrolytes based on lithium-salt complexes of polyethers have attracted much attention because of their potential for practical applications, such as electric-, hybrid-, or fuel-cell vehicles. [1] Although enhancement of the charge-transfer reaction rate is important to fabricate high-power-density batteries, only a few investigations have been focused on the charge-transfer reaction at the electrode/polymer electrolyte interfaces.[2]Herein we describe a significant enhancement of the charge-transfer reaction rate by addition of Lewis acid to polymer electrolytes. This is, to our knowledge, the first report about the achievement of a high rate by the addition of additives to electrolytes.Recently, we reported that poly(ethylene glycol) (PEG)-borate ester increases the ionic conductivity and transport number of lithium ions or magnesium ions of polymer electrolytes.[3] Since the borate ester groups, which act as Lewis acids, prefer to interact with anions, the increase in the conductivity and transport number is induced by enhancing the dissociation of the salts in polymer electrolytes.[3] These results indicate that the activity of lithium ions in the polymer electrolytes increases on addition of the PEG-borate ester. Therefore, the charge-transfer reaction rate should be enhanced by the addition of the Lewis acid, because the rate is proportional to the activity of lithium ions.[4]Herein, we investigate the influence of the PEG-borate ester on the electrokinetics of the Li + /Li couple in poly-(ethylene glycol) dimethyl ether (PEGDME) based electrolytes. PEGDME solutions of LiCF 3 SO 3 are used as a model of polymer electrolytes, and is similar to the amorphous conducting phase in high-molecular-weight poly(ethylene oxide). To evaluate the charge-transfer reaction rate at the electrode/electrolyte interfaces, the exchange current densities were studied by chronoamperometry with a microelectrode technique. Microelectrodes have several properties that facilitate the electrochemical analyses, such as minimization of the ohmic (IR) drop and charge current, and enhancement of the transport of electroactive ions to the electrode surface by spherical diffusion. [2,5] Chronoamperometry was performed to obtain the exchange current densities. The measured coulombic efficiency of lithium deposition and dissolution was over 90 % in all cases, which means that no significant secondary reaction occurred at the interfaces. The exchange current densities obtained in the electrolytic solutions with various amounts of the PEG-borate ester are summarized in Figure 1. Significant increases in the exchange current densities of the electrolytes were found when the PEG-borate ester was added. Furthermore, the values of the exchange current densities show a maximum at each temperature with a PEG-borate ester content of 25 wt % to the standard solvent, PEGDME, which corresponds to a molar ratio of PEG-borate ester:the anion of almost 1:1. The maximum value at 333 K was 2.88 mA cm À2 whi...
The exchange current densities of the Li + /Li couple reaction in polyether based electrolytes, 0.5 M LiCF 3 -SO 3 /poly(ethylene glycol) dimethyl ether whose molecular weight is 500 (PEGDME500), were investigated for the studies about charge-transfer reaction rate at the electrode/electrolyte interfaces. It was found that the exchange current densities in the PEGDME500 based electrolytes decreased with increasing amounts of PEGDME1000 (molecular weight: 1000). Raman spectroscopic studies indicated that the activity of lithium ions, which is a factor for the exchange current densities, was found to be the almost constant even with the addition of PEGDME1000 in to the electrolytes. The Gibbs activation energies for the interfacial reaction were also the almost constant. Meanwhile, inversely proportional relationships between the exchange current densities and viscosities of the electrolytes were observed. Our studies elucidated that viscosity of the electrolytes was the only important factor for the charge-transfer reaction rate at polyether based electrolyte/electrode interfaces.
Lithium-ion secondary batteries using polymer electrolytes based on lithium-salt complexes of polyethers have attracted much attention because of their potential for practical applications, such as electric-, hybrid-, or fuel-cell vehicles. [1] Although enhancement of the charge-transfer reaction rate is important to fabricate high-power-density batteries, only a few investigations have been focused on the charge-transfer reaction at the electrode/polymer electrolyte interfaces.[2]Herein we describe a significant enhancement of the charge-transfer reaction rate by addition of Lewis acid to polymer electrolytes. This is, to our knowledge, the first report about the achievement of a high rate by the addition of additives to electrolytes.Recently, we reported that poly(ethylene glycol) (PEG)-borate ester increases the ionic conductivity and transport number of lithium ions or magnesium ions of polymer electrolytes.[3] Since the borate ester groups, which act as Lewis acids, prefer to interact with anions, the increase in the conductivity and transport number is induced by enhancing the dissociation of the salts in polymer electrolytes.[3] These results indicate that the activity of lithium ions in the polymer electrolytes increases on addition of the PEG-borate ester. Therefore, the charge-transfer reaction rate should be enhanced by the addition of the Lewis acid, because the rate is proportional to the activity of lithium ions.[4]Herein, we investigate the influence of the PEG-borate ester on the electrokinetics of the Li + /Li couple in poly-(ethylene glycol) dimethyl ether (PEGDME) based electrolytes. PEGDME solutions of LiCF 3 SO 3 are used as a model of polymer electrolytes, and is similar to the amorphous conducting phase in high-molecular-weight poly(ethylene oxide). To evaluate the charge-transfer reaction rate at the electrode/electrolyte interfaces, the exchange current densities were studied by chronoamperometry with a microelectrode technique. Microelectrodes have several properties that facilitate the electrochemical analyses, such as minimization of the ohmic (IR) drop and charge current, and enhancement of the transport of electroactive ions to the electrode surface by spherical diffusion. [2,5] Chronoamperometry was performed to obtain the exchange current densities. The measured coulombic efficiency of lithium deposition and dissolution was over 90 % in all cases, which means that no significant secondary reaction occurred at the interfaces. The exchange current densities obtained in the electrolytic solutions with various amounts of the PEG-borate ester are summarized in Figure 1. Significant increases in the exchange current densities of the electrolytes were found when the PEG-borate ester was added. Furthermore, the values of the exchange current densities show a maximum at each temperature with a PEG-borate ester content of 25 wt % to the standard solvent, PEGDME, which corresponds to a molar ratio of PEG-borate ester:the anion of almost 1:1. The maximum value at 333 K was 2.88 mA cm À2 whi...
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