The need for high power density cathodes for Li‐ion batteries can be fulfilled by application of ... more The need for high power density cathodes for Li‐ion batteries can be fulfilled by application of a high charging voltage above 4.5 V. As lithium cobalt oxide (LCO) remains a dominant commercial cathode material, tremendous efforts are invested to increase its charging potential toward 4.6 V. Yet, the long‐term performance of high voltage LCO cathodes still remains poor. Here, an integrated approach combining the application of an aluminum fluoride coating and the use of electrolyte solutions comprising 1:1:8 mixtures of difluoroethylene:fluoroethylene carbonate:dimethyl carbonate and 1 m LiPF6 is reported. This results in superior behavior of LCO cathodes charged at 4.6 V with high initial capacity of 223 mAh g−1, excellent long‐term performance, and 78% capacity retention after 500 cycles. Impressive stability is also found at 450 °C with an initial capacity of 220 mAh g−1 and around 84% capacity retention after 100 cycles. Systematic post‐mortem analysis of LCO cathodes and Li ano...
The purpose of this paper is to suggest frontier inter‐disciplinary research directions that can ... more The purpose of this paper is to suggest frontier inter‐disciplinary research directions that can be considered as important horizons of modern electrochemistry in the field of energy storage and conversion. We selected several topics that call for advancements in solid‐state, interfacial, analytical and energy‐related electrochemical science. A dramatic improvement in the performance of energy storage and conversion devices is needed to meet the urgent demands of our society. Significantly more efficient devices are needed to meet two major challenges: electro‐mobility, namely electrochemical propulsion of electric vehicles, and the ability to store and convert large quantities of energy generated from sustainable sources such as sun and wind. We suggest promotion of breakthroughs in several important directions. The examples chosen include: Development of novel in‐situ methodologies for design and testing composite electrodes for advanced energy storage devices; Improving the elect...
Solid electrolytes based on polyethylene oxide (PEO) have been studied for decades, owing to thei... more Solid electrolytes based on polyethylene oxide (PEO) have been studied for decades, owing to their facile and low-cost processing, good electrochemical stability, and excellent complexation with alkali metal salts. Complexes of PEO with appropriate sodium salts are well known for ionic conduction. Here, pristine NaPF6:P(EO)16 and a composite solid electrolyte containing TiO2 nanowires were investigated as candidates for rechargeable solid-state sodium batteries. Comprehensive electrochemical characterizations were carried out, including ionic conductivity, transference number, and structural stability. At elevated temperatures, the specific capacity of an all-solid-state Na3Ti2(PO4)3 (Na/NTP) sodium battery was 110 mAh g−1, higher than room-temperature cells with liquid electrolyte solutions. We attribute this behavior to increased conductivity of the polymer electrolyte, induced by the ceramic nanofiller, combined with enhanced electronic conductivity of the NTP cathode.
Despite the continuous progress in the research and development of Ti3C2Tx (MXene) electrodes for... more Despite the continuous progress in the research and development of Ti3C2Tx (MXene) electrodes for high-power batteries and supercapacitor applications, the role of the anions in the electrochemical energy storage and their ability to intercalate between the MXene sheets upon application of positive voltage have not been clarified. A decade after the discovery of MXenes, the information about the possibility of anion insertion into the restacked MXene electrode is still being questioned. Since the positive potential stability range in diluted aqueous electrolytes is severely limited by anodic oxidation of the Ti, the possibility of anion insertion was evaluated in concentrated aqueous electrolyte solutions and aprotic electrolytes as well. To address this issue, we have conducted in situ gravimetric electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) measurements in highly concentrated LiCl and LiBr electrolytes, which enable a significant extension of the operation range of the MXene electrodes toward positive potentials. Also, halogens are among the smallest anions and should be easier to intercalate between MXene layers, in comparison to multiatomic anions. On the basis of mass change variations in the positive voltage range and complementary density functional theory calculations, it was demonstrated that insertion of anionic species into MXene, within the range of potentials of interest for capacitive energy storage, is not likely to occur. This can be explained by the strong negative charge on Ti3C2Tx sheets terminated by functional groups.
The application of layered oxide compounds as cathode materials for sodium-ion batteries is consi... more The application of layered oxide compounds as cathode materials for sodium-ion batteries is considered a promising direction for the development of high-energy Na-ion batteries. However, despite many efforts, practical implementation of such electrodes is still challenging, mainly due to structural and surface instabilities associated with the high operating voltage of these cathodes. One of the most effective ways to mitigate these undesirable phenomena is the use of atomic layer deposition (ALD) to form a Nano-sized protective layer on the electrode surface. Application of ALD treatment results in increased electrode stability by preventing irreversible interactions between the electrolyte and cathode material. In search of optimal coating formulations, the effect of various ALD coatings viz. sodium-aluminate, lithium-aluminate, and alumina on the electrochemical performance of Na-NCM cathode synthesized by ion-exchange method. While the initial capacity loss attributed to oxygen ...
Nanoporous layers are widely spread in nature and among artificial devices. However, complex char... more Nanoporous layers are widely spread in nature and among artificial devices. However, complex characterization of extensively nanoporous thin films showing porosity-dependent softening lacks consistency and reliability when using different analytical techniques. We introduce herein, a facile and precise method of such complex characterization by multi-harmonic QCM-D (Quartz Crystal Microbalance with Dissipation Monitoring) measurements performed both in the air and liquids (Au-Zn alloy was used as a typical example). The porosity values determined by QCM-D in air and different liquids are entirely consistent with that obtained from parallel RBS (Rutherford Backscattering Spectroscopy) and GISAXS (Grazing-Incidence Small-Angle Scattering) characterizations. This ensures precise quantification of the nanolayer porosity simultaneously with tracking their viscoelastic properties in liquids, significantly increasing sensitivity of the viscoelastic detection (viscoelastic contrast principl...
Development of high power devices with improved energy density is a highly desired target for adv... more Development of high power devices with improved energy density is a highly desired target for advanced energy storage applications.
It is generally accepted that solid-electrolyte interphase formed on the surface of lithium-batte... more It is generally accepted that solid-electrolyte interphase formed on the surface of lithium-battery electrodes play a key role in controlling their cycling performance. Although a large variety of surface-sensitive spectroscopies and microscopies were used for their characterization, the focus was on surface species nature rather than on the mechanical properties of the surface films. Here we report a highly sensitive method of gravimetric and viscoelastic probing of the formation of surface films on composite LiTiO electrode coupled with lithium ions intercalation into this electrode. Electrochemical quartz-crystal microbalance with dissipation monitoring measurements were performed with LiTFSI, LiPF, and LiPF + 2% vinylene carbonate solutions from which structural parameters of the surface films were returned by fitting to a multilayer viscoelastic model. Only a few fast cycles are required to qualify surface films on LiTiO anode improving in the sequence LiPF < LiPF + 2% vinyl...
Using multiharmonic electrochemical quartz crystal microbalance with dissipation (EQCM-D) monitor... more Using multiharmonic electrochemical quartz crystal microbalance with dissipation (EQCM-D) monitoring, a new method of characterization of porous solids in contact with liquids has been developed. The dynamic gravimetric information on the growing, dissolving, or stationary stored solid deposits is supplemented by their precise in-operando porous structure characterization on a mesoscopic scale. We present a very powerful method of quartz-crystal admittance modeling of hydrodynamic solid-liquid interactions in order to extract the porous structure parameters of solids during their formation in real time, using different deposition modes. The unique hydrodynamic spectroscopic characterization of electrolytic and rf-sputtered solid Cu coatings that we use for our "proof of concept" provides a new strategy for probing various electrochemically active thin and thick solid deposits, thereby offering inexpensive, noninvasive, and highly efficient quantitative control over their p...
The need for high power density cathodes for Li‐ion batteries can be fulfilled by application of ... more The need for high power density cathodes for Li‐ion batteries can be fulfilled by application of a high charging voltage above 4.5 V. As lithium cobalt oxide (LCO) remains a dominant commercial cathode material, tremendous efforts are invested to increase its charging potential toward 4.6 V. Yet, the long‐term performance of high voltage LCO cathodes still remains poor. Here, an integrated approach combining the application of an aluminum fluoride coating and the use of electrolyte solutions comprising 1:1:8 mixtures of difluoroethylene:fluoroethylene carbonate:dimethyl carbonate and 1 m LiPF6 is reported. This results in superior behavior of LCO cathodes charged at 4.6 V with high initial capacity of 223 mAh g−1, excellent long‐term performance, and 78% capacity retention after 500 cycles. Impressive stability is also found at 450 °C with an initial capacity of 220 mAh g−1 and around 84% capacity retention after 100 cycles. Systematic post‐mortem analysis of LCO cathodes and Li ano...
The purpose of this paper is to suggest frontier inter‐disciplinary research directions that can ... more The purpose of this paper is to suggest frontier inter‐disciplinary research directions that can be considered as important horizons of modern electrochemistry in the field of energy storage and conversion. We selected several topics that call for advancements in solid‐state, interfacial, analytical and energy‐related electrochemical science. A dramatic improvement in the performance of energy storage and conversion devices is needed to meet the urgent demands of our society. Significantly more efficient devices are needed to meet two major challenges: electro‐mobility, namely electrochemical propulsion of electric vehicles, and the ability to store and convert large quantities of energy generated from sustainable sources such as sun and wind. We suggest promotion of breakthroughs in several important directions. The examples chosen include: Development of novel in‐situ methodologies for design and testing composite electrodes for advanced energy storage devices; Improving the elect...
Solid electrolytes based on polyethylene oxide (PEO) have been studied for decades, owing to thei... more Solid electrolytes based on polyethylene oxide (PEO) have been studied for decades, owing to their facile and low-cost processing, good electrochemical stability, and excellent complexation with alkali metal salts. Complexes of PEO with appropriate sodium salts are well known for ionic conduction. Here, pristine NaPF6:P(EO)16 and a composite solid electrolyte containing TiO2 nanowires were investigated as candidates for rechargeable solid-state sodium batteries. Comprehensive electrochemical characterizations were carried out, including ionic conductivity, transference number, and structural stability. At elevated temperatures, the specific capacity of an all-solid-state Na3Ti2(PO4)3 (Na/NTP) sodium battery was 110 mAh g−1, higher than room-temperature cells with liquid electrolyte solutions. We attribute this behavior to increased conductivity of the polymer electrolyte, induced by the ceramic nanofiller, combined with enhanced electronic conductivity of the NTP cathode.
Despite the continuous progress in the research and development of Ti3C2Tx (MXene) electrodes for... more Despite the continuous progress in the research and development of Ti3C2Tx (MXene) electrodes for high-power batteries and supercapacitor applications, the role of the anions in the electrochemical energy storage and their ability to intercalate between the MXene sheets upon application of positive voltage have not been clarified. A decade after the discovery of MXenes, the information about the possibility of anion insertion into the restacked MXene electrode is still being questioned. Since the positive potential stability range in diluted aqueous electrolytes is severely limited by anodic oxidation of the Ti, the possibility of anion insertion was evaluated in concentrated aqueous electrolyte solutions and aprotic electrolytes as well. To address this issue, we have conducted in situ gravimetric electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) measurements in highly concentrated LiCl and LiBr electrolytes, which enable a significant extension of the operation range of the MXene electrodes toward positive potentials. Also, halogens are among the smallest anions and should be easier to intercalate between MXene layers, in comparison to multiatomic anions. On the basis of mass change variations in the positive voltage range and complementary density functional theory calculations, it was demonstrated that insertion of anionic species into MXene, within the range of potentials of interest for capacitive energy storage, is not likely to occur. This can be explained by the strong negative charge on Ti3C2Tx sheets terminated by functional groups.
The application of layered oxide compounds as cathode materials for sodium-ion batteries is consi... more The application of layered oxide compounds as cathode materials for sodium-ion batteries is considered a promising direction for the development of high-energy Na-ion batteries. However, despite many efforts, practical implementation of such electrodes is still challenging, mainly due to structural and surface instabilities associated with the high operating voltage of these cathodes. One of the most effective ways to mitigate these undesirable phenomena is the use of atomic layer deposition (ALD) to form a Nano-sized protective layer on the electrode surface. Application of ALD treatment results in increased electrode stability by preventing irreversible interactions between the electrolyte and cathode material. In search of optimal coating formulations, the effect of various ALD coatings viz. sodium-aluminate, lithium-aluminate, and alumina on the electrochemical performance of Na-NCM cathode synthesized by ion-exchange method. While the initial capacity loss attributed to oxygen ...
Nanoporous layers are widely spread in nature and among artificial devices. However, complex char... more Nanoporous layers are widely spread in nature and among artificial devices. However, complex characterization of extensively nanoporous thin films showing porosity-dependent softening lacks consistency and reliability when using different analytical techniques. We introduce herein, a facile and precise method of such complex characterization by multi-harmonic QCM-D (Quartz Crystal Microbalance with Dissipation Monitoring) measurements performed both in the air and liquids (Au-Zn alloy was used as a typical example). The porosity values determined by QCM-D in air and different liquids are entirely consistent with that obtained from parallel RBS (Rutherford Backscattering Spectroscopy) and GISAXS (Grazing-Incidence Small-Angle Scattering) characterizations. This ensures precise quantification of the nanolayer porosity simultaneously with tracking their viscoelastic properties in liquids, significantly increasing sensitivity of the viscoelastic detection (viscoelastic contrast principl...
Development of high power devices with improved energy density is a highly desired target for adv... more Development of high power devices with improved energy density is a highly desired target for advanced energy storage applications.
It is generally accepted that solid-electrolyte interphase formed on the surface of lithium-batte... more It is generally accepted that solid-electrolyte interphase formed on the surface of lithium-battery electrodes play a key role in controlling their cycling performance. Although a large variety of surface-sensitive spectroscopies and microscopies were used for their characterization, the focus was on surface species nature rather than on the mechanical properties of the surface films. Here we report a highly sensitive method of gravimetric and viscoelastic probing of the formation of surface films on composite LiTiO electrode coupled with lithium ions intercalation into this electrode. Electrochemical quartz-crystal microbalance with dissipation monitoring measurements were performed with LiTFSI, LiPF, and LiPF + 2% vinylene carbonate solutions from which structural parameters of the surface films were returned by fitting to a multilayer viscoelastic model. Only a few fast cycles are required to qualify surface films on LiTiO anode improving in the sequence LiPF < LiPF + 2% vinyl...
Using multiharmonic electrochemical quartz crystal microbalance with dissipation (EQCM-D) monitor... more Using multiharmonic electrochemical quartz crystal microbalance with dissipation (EQCM-D) monitoring, a new method of characterization of porous solids in contact with liquids has been developed. The dynamic gravimetric information on the growing, dissolving, or stationary stored solid deposits is supplemented by their precise in-operando porous structure characterization on a mesoscopic scale. We present a very powerful method of quartz-crystal admittance modeling of hydrodynamic solid-liquid interactions in order to extract the porous structure parameters of solids during their formation in real time, using different deposition modes. The unique hydrodynamic spectroscopic characterization of electrolytic and rf-sputtered solid Cu coatings that we use for our "proof of concept" provides a new strategy for probing various electrochemically active thin and thick solid deposits, thereby offering inexpensive, noninvasive, and highly efficient quantitative control over their p...
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