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Papers by Natalia Voronina

Research paper thumbnail of Engineering Transition Metal Layers for Long Lasting Anionic Redox in Layered Sodium Manganese Oxide

Advanced Functional Materials, Nov 28, 2022

Research paper thumbnail of Single-crystalline particle Ni-based cathode materials for lithium-ion batteries: Strategies, status, and challenges to improve energy density and cyclability

Research paper thumbnail of Engineering Transition Metal Layers for Long Lasting Anionic Redox in Layered Sodium Manganese Oxide

Advanced Functional Materials

Research paper thumbnail of Hysteresis‐Suppressed Reversible Oxygen‐Redox Cathodes for Sodium‐Ion Batteries

Advanced Energy Materials

Research paper thumbnail of KV3O8 with a large interlayer as a viable cathode material for zinc-ion batteries

Journal of Power Sources, 2020

We demonstrate the feasibility of using KV3O8 with an interlayer distance of ~7.7 A as a cathode ... more We demonstrate the feasibility of using KV3O8 with an interlayer distance of ~7.7 A as a cathode material for zinc-ion batteries. Its electrochemical inactivity is circumvented through particle size reduction with an increase in the surface area to 33.2 m2 g−1 from 2.6 m2 g−1. The shortened diffusion path results in significant improvement of the capacity to 249 mAh (g-oxide)−1 (25 mA g−1: 0.1C) despite almost no capacity being delivered by the as-received KV3O8 particles. Structural investigation using ex situ X-ray diffraction and ex situ X-ray absorption near edge structure spectroscopy reveals that KV3O8 undergoes a single-phase reaction assisted by the V5+/4+ redox pair. This monotonous structural change results in capacity retention of approximately 85.1% for 200 cycles. The size effect also affects the rate capability. Namely, the electrode delivers a discharge capacity of 182 mAh g−1 at a rate of 7C (1.75 A g−1), with ~82.8% retention of the initial capacity for 500 cycles i...

Research paper thumbnail of Gifts from Nature: Bio‐Inspired Materials for Rechargeable Secondary Batteries

Advanced Materials

Materials in nature have evolved to the most efficient forms and have adapted to various environm... more Materials in nature have evolved to the most efficient forms and have adapted to various environmental conditions over tens of thousands of years. Because of their versatile functionalities and environmental friendliness, numerous attempts have been made to use bio-inspired materials for industrial applications, establishing the importance of biomimetics. Biomimetics have become pivotal to the search for technological breakthroughs in the area of rechargeable secondary batteries. Here, the characteristics of bio-inspired materials that are useful for secondary batteries as well as their benefits for application as the main components of batteries (e.g., electrodes, separators, and binders) are discussed. The use of bio-inspired materials for the synthesis of nanomaterials with complex structures, low-cost electrode materials prepared from biomass, and biomolecular organic electrodes for lithium-ion batteries are also introduced. In addition, nature-derived separators and binders are discussed, including their effects on enhancing battery performance and safety. Recent developments toward next-generation secondary batteries including sodium-ion batteries, zinc-ion batteries, and flexible batteries are also mentioned to understand the feasibility of using bio-inspired materials in these new battery systems. Finally, current research trends are covered and future directions are proposed to provide important insights into scientific and practical issues in the development of biomimetics technologies for secondary batteries.

Research paper thumbnail of A New Approach to Stable Cationic and Anionic Redox Activity in O3‐Layered Cathode for Sodium‐Ion Batteries

Advanced Energy Materials

Research paper thumbnail of Bio‐Derived Surface Layer Suitable for Long Term Cycling Ni‐Rich Cathode for Lithium‐Ion Batteries

Small

Since Ni-rich cathode material is very sensitive to moisture and easily forms residual lithium co... more Since Ni-rich cathode material is very sensitive to moisture and easily forms residual lithium compounds that degrade cell performance, it is very important to pay attention to the selection of the surface modifying media. Accordingly, hydroxyapatite (Ca5 (PO4 )3 (OH)), a tooth-derived material showing excellent mechanical and thermodynamic stabilities, is selected. To verify the availability of hydroxyapatite as a surface protection material, lithium-doped hydroxyapatite, Ca4.67 Li0.33 (PO4 )3 (OH), is formed with ≈10-nm layer after reacting with residual lithium compounds on Li[Ni0.8 Co0.15 Al0.05 ]O2 , which spontaneously results in dramatic reduction of surface lithium residues to 2879 ppm from 22364 ppm. The Ca4.67 Li0.33 (PO4 )3 (OH)-modified Li[Ni0.8 Co0.15 Al0.05 ]O2 electrode provides ultra-long term cycling stability, enabling 1000 cycles retaining 66.3% of its initial capacity. Also, morphological degradations such as micro-cracking or amorphization of surface are significantly suppressed by the presence of Ca4.67 Li0.33 (PO4 )3 (OH) layer on the Li[Ni0.8 Co0.15 Al0.05 ]O2 , of which the Ca4.67 Li0.33 (PO4 )3 (OH) is transformed to CaF2 via Ca4.67 Li0.33 (PO4 )3 F during the long term cycles reacting with HF in electrolyte. In addition, the authors' density function theory (DFT) results explain the reason of instability of NCA and why CaF2 layers can delay the micro-cracking during electrochemical reaction. Therefore, the stable Ca4.67 Li0.33 (PO4 )3 F and CaF2 layers play a pivotal role to protect the Li[Ni0.8 Co0.15 Al0.05 ]O2 with ultra-long cycling stability.

Research paper thumbnail of Rational design of Co-free layered cathode material for sodium-ion batteries

Research paper thumbnail of Electronic Structure Engineering of Honeycomb Layered Cathode Material for Sodium‐Ion Batteries

Advanced Energy Materials

Research paper thumbnail of Bismuth telluride anode boosting highly reversible electrochemical activity for potassium storage

Research paper thumbnail of Recent Advances in Electrode Materials with Anion Redox Chemistry for Sodium-Ion Batteries

Energy Material Advances

The development of sodium-ion batteries (SIBs), which are promising alternatives to lithium-ion b... more The development of sodium-ion batteries (SIBs), which are promising alternatives to lithium-ion batteries (LIBs), offers new opportunities to address the depletion of Li and Co resources; however, their implementation is hindered by their relatively low capacities and moderate operation voltages and resulting low energy densities. To overcome these limitations, considerable attention has been focused on anionic redox reactions, which proceed at high voltages with extra capacity. This manuscript covers the origin and recent development of anionic redox electrode materials for SIBs, including state-of-the-art P2- and O3-type layered oxides. We sequentially analyze the anion activity–structure–performance relationship in electrode materials. Finally, we discuss remaining challenges and suggest new strategies for future research in anion-redox cathode materials for SIBs.

Research paper thumbnail of Revealing sodium storage mechanism in lithium titanium phosphate: Combined experimental and theoretical study

Research paper thumbnail of Long Life Anode Material for Potassium Ion Batteries with High-Rate Potassium Storage

Research paper thumbnail of High‐Voltage Oxygen‐Redox‐Based Cathode for Rechargeable Sodium‐Ion Batteries

Advanced Energy Materials

Research paper thumbnail of Recent Progress and Perspective of Advanced High‐Energy Co‐Less Ni‐Rich Cathodes for Li‐Ion Batteries: Yesterday, Today, and Tomorrow

Advanced Energy Materials

Research paper thumbnail of Highly concentrated electrolyte enabling high-voltage application of metallic components for potassium-ion batteries

Research paper thumbnail of High-Voltage Stability in KFSI Nonaqueous Carbonate Solutions for Potassium-Ion Batteries: Current Collectors and Coin-Cell Components

Research paper thumbnail of Co-Free Layered Cathode Materials for High Energy Density Lithium-Ion Batteries

ACS Energy Letters

The sustainable development of plug-in and full electric vehicles and portable electronic devices... more The sustainable development of plug-in and full electric vehicles and portable electronic devices is impossible without solving the problem of limited cobalt resources and their high prices. Curren...

Research paper thumbnail of KTi 2 (PO 4 ) 3 Electrode with a Long Cycling Stability for Potassium‐Ion Batteries

Small

In this work, rhombohedral KTi2 (PO4 )3 is introduced to investigate the related theoretical, str... more In this work, rhombohedral KTi2 (PO4 )3 is introduced to investigate the related theoretical, structural, and electrochemical properties in K cells. The suggested KTi2 (PO4 )3 modified by electro-conducting carbon brings about a flat voltage profile at ≈1.6 V, providing a large capacity of 126 mAh (g-phosphate)-1 , corresponding to 98.5% of the theoretical capacity, with 89% capacity retention for 500 cycles. Structural analyses using electrochemical performance measurements, first-principles calculations, ex situ X-ray absorption spectroscopy, and operando X-ray diffraction provide new insights into the reaction mechanism controlling the (de)intercalation of potassium ions into the host KTi2 (PO4 )3 structure. It is observed that a biphasic redox process by Ti4+/3+ occurs upon discharge, whereas a single-phase reaction followed by a biphasic process occurs upon charge. Along with the structural refinement of the electrochemically reduced K3 Ti2 (PO4 )3 phase, these new findings provide insight into the reaction mechanism in Na superionic conductor (NASICON)-type KTi2 (PO4 )3 . The present approach can also be extended to the investigation of other NASICON-type materials for potassium-ion batteries.

Research paper thumbnail of Engineering Transition Metal Layers for Long Lasting Anionic Redox in Layered Sodium Manganese Oxide

Advanced Functional Materials, Nov 28, 2022

Research paper thumbnail of Single-crystalline particle Ni-based cathode materials for lithium-ion batteries: Strategies, status, and challenges to improve energy density and cyclability

Research paper thumbnail of Engineering Transition Metal Layers for Long Lasting Anionic Redox in Layered Sodium Manganese Oxide

Advanced Functional Materials

Research paper thumbnail of Hysteresis‐Suppressed Reversible Oxygen‐Redox Cathodes for Sodium‐Ion Batteries

Advanced Energy Materials

Research paper thumbnail of KV3O8 with a large interlayer as a viable cathode material for zinc-ion batteries

Journal of Power Sources, 2020

We demonstrate the feasibility of using KV3O8 with an interlayer distance of ~7.7 A as a cathode ... more We demonstrate the feasibility of using KV3O8 with an interlayer distance of ~7.7 A as a cathode material for zinc-ion batteries. Its electrochemical inactivity is circumvented through particle size reduction with an increase in the surface area to 33.2 m2 g−1 from 2.6 m2 g−1. The shortened diffusion path results in significant improvement of the capacity to 249 mAh (g-oxide)−1 (25 mA g−1: 0.1C) despite almost no capacity being delivered by the as-received KV3O8 particles. Structural investigation using ex situ X-ray diffraction and ex situ X-ray absorption near edge structure spectroscopy reveals that KV3O8 undergoes a single-phase reaction assisted by the V5+/4+ redox pair. This monotonous structural change results in capacity retention of approximately 85.1% for 200 cycles. The size effect also affects the rate capability. Namely, the electrode delivers a discharge capacity of 182 mAh g−1 at a rate of 7C (1.75 A g−1), with ~82.8% retention of the initial capacity for 500 cycles i...

Research paper thumbnail of Gifts from Nature: Bio‐Inspired Materials for Rechargeable Secondary Batteries

Advanced Materials

Materials in nature have evolved to the most efficient forms and have adapted to various environm... more Materials in nature have evolved to the most efficient forms and have adapted to various environmental conditions over tens of thousands of years. Because of their versatile functionalities and environmental friendliness, numerous attempts have been made to use bio-inspired materials for industrial applications, establishing the importance of biomimetics. Biomimetics have become pivotal to the search for technological breakthroughs in the area of rechargeable secondary batteries. Here, the characteristics of bio-inspired materials that are useful for secondary batteries as well as their benefits for application as the main components of batteries (e.g., electrodes, separators, and binders) are discussed. The use of bio-inspired materials for the synthesis of nanomaterials with complex structures, low-cost electrode materials prepared from biomass, and biomolecular organic electrodes for lithium-ion batteries are also introduced. In addition, nature-derived separators and binders are discussed, including their effects on enhancing battery performance and safety. Recent developments toward next-generation secondary batteries including sodium-ion batteries, zinc-ion batteries, and flexible batteries are also mentioned to understand the feasibility of using bio-inspired materials in these new battery systems. Finally, current research trends are covered and future directions are proposed to provide important insights into scientific and practical issues in the development of biomimetics technologies for secondary batteries.

Research paper thumbnail of A New Approach to Stable Cationic and Anionic Redox Activity in O3‐Layered Cathode for Sodium‐Ion Batteries

Advanced Energy Materials

Research paper thumbnail of Bio‐Derived Surface Layer Suitable for Long Term Cycling Ni‐Rich Cathode for Lithium‐Ion Batteries

Small

Since Ni-rich cathode material is very sensitive to moisture and easily forms residual lithium co... more Since Ni-rich cathode material is very sensitive to moisture and easily forms residual lithium compounds that degrade cell performance, it is very important to pay attention to the selection of the surface modifying media. Accordingly, hydroxyapatite (Ca5 (PO4 )3 (OH)), a tooth-derived material showing excellent mechanical and thermodynamic stabilities, is selected. To verify the availability of hydroxyapatite as a surface protection material, lithium-doped hydroxyapatite, Ca4.67 Li0.33 (PO4 )3 (OH), is formed with ≈10-nm layer after reacting with residual lithium compounds on Li[Ni0.8 Co0.15 Al0.05 ]O2 , which spontaneously results in dramatic reduction of surface lithium residues to 2879 ppm from 22364 ppm. The Ca4.67 Li0.33 (PO4 )3 (OH)-modified Li[Ni0.8 Co0.15 Al0.05 ]O2 electrode provides ultra-long term cycling stability, enabling 1000 cycles retaining 66.3% of its initial capacity. Also, morphological degradations such as micro-cracking or amorphization of surface are significantly suppressed by the presence of Ca4.67 Li0.33 (PO4 )3 (OH) layer on the Li[Ni0.8 Co0.15 Al0.05 ]O2 , of which the Ca4.67 Li0.33 (PO4 )3 (OH) is transformed to CaF2 via Ca4.67 Li0.33 (PO4 )3 F during the long term cycles reacting with HF in electrolyte. In addition, the authors' density function theory (DFT) results explain the reason of instability of NCA and why CaF2 layers can delay the micro-cracking during electrochemical reaction. Therefore, the stable Ca4.67 Li0.33 (PO4 )3 F and CaF2 layers play a pivotal role to protect the Li[Ni0.8 Co0.15 Al0.05 ]O2 with ultra-long cycling stability.

Research paper thumbnail of Rational design of Co-free layered cathode material for sodium-ion batteries

Research paper thumbnail of Electronic Structure Engineering of Honeycomb Layered Cathode Material for Sodium‐Ion Batteries

Advanced Energy Materials

Research paper thumbnail of Bismuth telluride anode boosting highly reversible electrochemical activity for potassium storage

Research paper thumbnail of Recent Advances in Electrode Materials with Anion Redox Chemistry for Sodium-Ion Batteries

Energy Material Advances

The development of sodium-ion batteries (SIBs), which are promising alternatives to lithium-ion b... more The development of sodium-ion batteries (SIBs), which are promising alternatives to lithium-ion batteries (LIBs), offers new opportunities to address the depletion of Li and Co resources; however, their implementation is hindered by their relatively low capacities and moderate operation voltages and resulting low energy densities. To overcome these limitations, considerable attention has been focused on anionic redox reactions, which proceed at high voltages with extra capacity. This manuscript covers the origin and recent development of anionic redox electrode materials for SIBs, including state-of-the-art P2- and O3-type layered oxides. We sequentially analyze the anion activity–structure–performance relationship in electrode materials. Finally, we discuss remaining challenges and suggest new strategies for future research in anion-redox cathode materials for SIBs.

Research paper thumbnail of Revealing sodium storage mechanism in lithium titanium phosphate: Combined experimental and theoretical study

Research paper thumbnail of Long Life Anode Material for Potassium Ion Batteries with High-Rate Potassium Storage

Research paper thumbnail of High‐Voltage Oxygen‐Redox‐Based Cathode for Rechargeable Sodium‐Ion Batteries

Advanced Energy Materials

Research paper thumbnail of Recent Progress and Perspective of Advanced High‐Energy Co‐Less Ni‐Rich Cathodes for Li‐Ion Batteries: Yesterday, Today, and Tomorrow

Advanced Energy Materials

Research paper thumbnail of Highly concentrated electrolyte enabling high-voltage application of metallic components for potassium-ion batteries

Research paper thumbnail of High-Voltage Stability in KFSI Nonaqueous Carbonate Solutions for Potassium-Ion Batteries: Current Collectors and Coin-Cell Components

Research paper thumbnail of Co-Free Layered Cathode Materials for High Energy Density Lithium-Ion Batteries

ACS Energy Letters

The sustainable development of plug-in and full electric vehicles and portable electronic devices... more The sustainable development of plug-in and full electric vehicles and portable electronic devices is impossible without solving the problem of limited cobalt resources and their high prices. Curren...

Research paper thumbnail of KTi 2 (PO 4 ) 3 Electrode with a Long Cycling Stability for Potassium‐Ion Batteries

Small

In this work, rhombohedral KTi2 (PO4 )3 is introduced to investigate the related theoretical, str... more In this work, rhombohedral KTi2 (PO4 )3 is introduced to investigate the related theoretical, structural, and electrochemical properties in K cells. The suggested KTi2 (PO4 )3 modified by electro-conducting carbon brings about a flat voltage profile at ≈1.6 V, providing a large capacity of 126 mAh (g-phosphate)-1 , corresponding to 98.5% of the theoretical capacity, with 89% capacity retention for 500 cycles. Structural analyses using electrochemical performance measurements, first-principles calculations, ex situ X-ray absorption spectroscopy, and operando X-ray diffraction provide new insights into the reaction mechanism controlling the (de)intercalation of potassium ions into the host KTi2 (PO4 )3 structure. It is observed that a biphasic redox process by Ti4+/3+ occurs upon discharge, whereas a single-phase reaction followed by a biphasic process occurs upon charge. Along with the structural refinement of the electrochemically reduced K3 Ti2 (PO4 )3 phase, these new findings provide insight into the reaction mechanism in Na superionic conductor (NASICON)-type KTi2 (PO4 )3 . The present approach can also be extended to the investigation of other NASICON-type materials for potassium-ion batteries.