Doping-Induced Surface and Grain Boundary Effects in Ni-Rich Layered Cathode Materials.

In this work, the effects of dopant size and oxidation state on the structure and electrochemical performance of LiNi0.8Co0.1Mn0.1O2 (NCM811) are investigated. It is shown that doping with boron (B) which has a small ionic radius and an oxidation state of 3+, leads to the formation of a boron oxide-containing surface coating (probably Li3BO3), mainly on the outer surface of the secondary particles. Due to this effect, boron only slightly affects the size of the primary particle and the initial capacity, but significantly improves the capacity retention. On the other hand, the dopant ruthenium (Ru) with a larger ionic radius and a higher oxidation state of 5+ can be stabilized within the secondary particles and does not experience a segregation to the outer agglomerate surface. However, the Ru dopant preferentially occupies incoherent grain boundary sites, resulting in smaller primary particle size and initial capacity than for the B-doped and pristine NCM811. This work demonstrates that a small percentage of dopant (2 mol%) cannot significantly affect bulk properties, but it can strongly influence the surface and/or grain boundary properties of microstructure and thus the overall performance of cathode materials.

Exploiting High-Voltage Stability of Dual-Ion Aqueous Electrolyte Reinforced by Incorporation of Fiberglass into Zwitterionic Hydrogel Electrolyte.

Rechargeable zinc aqueous batteries are key alternatives for replacing toxic, flammable, and expensive lithium-ion batteries in grid energy storage systems. However, these systems possess critical weaknesses, including the short electrochemical stability window of water and intrinsic fast zinc dendrite growth. Hydrogel electrolytes provide a possible solution, especially cross-linked zwitterionic polymers that possess strong water retention ability and high ionic conductivity. Herein, an in situ prepared fiberglass-incorporated dual-ion zwitterionic hydrogel electrolyte with an ionic conductivity of 24.32 mS cm-1 , electrochemical stability window up to 2.56 V, and high thermal stability is presented. By incorporating this hydrogel electrolyte of zinc and lithium triflate salts, a zinc//LiMn0.6 Fe0.4 PO4 pouch cell delivers a reversible capacity of 130 mAh g-1 in the range of 1.0-2.2 V at 0.1C, and the test at 2C provides an initial capacity of 82.4 mAh g-1 with 71.8% capacity retention after 1000 cycles with a coulombic efficiency of 97%. Additionally, the pouch cell is fire resistant and remains safe after cutting and piercing.

Bio-Derived Surface Layer Suitable for Long Term Cycling Ni-Rich Cathode for Lithium-Ion Batteries.

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.

WO3 Nanowire/Carbon Nanotube Interlayer as a Chemical Adsorption Mediator for High-Performance Lithium-Sulfur Batteries.

We developed a new nanowire for enhancing the performance of lithium-sulfur batteries. In this study, we synthesized WO3 nanowires (WNWs) via a simple hydrothermal method. WNWs and one-dimensional materials are easily mixed with carbon nanotubes (CNTs) to form interlayers. The WNW interacts with lithium polysulfides through a thiosulfate mediator, retaining the lithium polysulfide near the cathode to increase the reaction kinetics. The lithium-sulfur cell achieves a very high initial discharge capacity of 1558 and 656 mAh g-1 at 0.1 and 3 C, respectively. Moreover, a cell with a high sulfur mass loading of 4.2 mg cm-2 still delivers a high capacity of 1136 mAh g-1 at a current density of 0.2 C and it showed a capacity of 939 mAh g-1 even after 100 cycles. The WNW/CNT interlayer maintains structural stability even after electrochemical testing. This excellent performance and structural stability are due to the chemical adsorption and catalytic effects of the thiosulfate mediator on WNW.

KTi2 (PO4 )3 Electrode with a Long Cycling Stability for Potassium-Ion Batteries.

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.

Sodium-ion batteries: present and future.

Energy production and storage technologies have attracted a great deal of attention for day-to-day applications. In recent decades, advances in lithium-ion battery (LIB) technology have improved living conditions around the globe. LIBs are used in most mobile electronic devices as well as in zero-emission electronic vehicles. However, there are increasing concerns regarding load leveling of renewable energy sources and the smart grid as well as the sustainability of lithium sources due to their limited availability and consequent expected price increase. Therefore, whether LIBs alone can satisfy the rising demand for small- and/or mid-to-large-format energy storage applications remains unclear. To mitigate these issues, recent research has focused on alternative energy storage systems. Sodium-ion batteries (SIBs) are considered as the best candidate power sources because sodium is widely available and exhibits similar chemistry to that of LIBs; therefore, SIBs are promising next-generation alternatives. Recently, sodiated layer transition metal oxides, phosphates and organic compounds have been introduced as cathode materials for SIBs. Simultaneously, recent developments have been facilitated by the use of select carbonaceous materials, transition metal oxides (or sulfides), and intermetallic and organic compounds as anodes for SIBs. Apart from electrode materials, suitable electrolytes, additives, and binders are equally important for the development of practical SIBs. Despite developments in electrode materials and other components, there remain several challenges, including cell design and electrode balancing, in the application of sodium ion cells. In this article, we summarize and discuss current research on materials and propose future directions for SIBs. This will provide important insights into scientific and practical issues in the development of SIBs.

Advanced Na[Ni0.25Fe0.5Mn0.25]O2/C-Fe3O4 sodium-ion batteries using EMS electrolyte for energy storage.

While much research effort has been devoted to the development of advanced lithium-ion batteries for renewal energy storage applications, the sodium-ion battery is also of considerable interest because sodium is one of the most abundant elements in the Earth's crust. In this work, we report a sodium-ion battery based on a carbon-coated Fe3O4 anode, Na[Ni0.25Fe0.5Mn0.25]O2 layered cathode, and NaClO4 in fluoroethylene carbonate and ethyl methanesulfonate electrolyte. This unique battery system combines an intercalation cathode and a conversion anode, resulting in high capacity, high rate capability, thermal stability, and much improved cycle life. This performance suggests that our sodium-ion system is potentially promising power sources for promoting the substantial use of low-cost energy storage systems in the near future.

Anatase titania nanorods as an intercalation anode material for rechargeable sodium batteries.

For the first time, we report the electrochemical activity of anatase TiO2 nanorods in a Na cell. The anatase TiO2 nanorods were synthesized by a hydrothermal method, and their surfaces were coated by carbon to improve the electric conductivity through carbonization of pitch at 700 °C for 2 h in Ar flow. The resulting structure does not change before and after the carbon coating, as confirmed by X-ray diffraction (XRD). Transmission electron microscopic images confirm the presence of a carbon coating on the anatase TiO2 nanorods. In cell tests, anodes of bare and carbon-coated anatase TiO2 nanorods exhibit stable cycling performance and attain a capacity of about 172 and 193 mAh g(-1) on the first charge, respectively, in the voltage range of 3-0 V. With the help of the conductive carbon layers, the carbon-coated anatase TiO2 delivers more capacity at high rates, 104 mAh g(-1) at the 10 C-rate (3.3 A g(-1)), 82 mAh g(-1) at the 30 C-rate (10 A g(-1)), and 53 mAh g(-1) at the 100 C-rate (33 A g(-1)). By contrast, the anode of bare anatase TiO2 nanorods delivers only about 38 mAh g(-1) at the 10 C-rate (3.3 A g(-1)). The excellent cyclability and high-rate capability are the result of a Na(+) insertion and extraction reaction into the host structure coupled with Ti(4+/3+) redox reaction, as revealed by X-ray absorption spectroscopy.

Impact of Transition Metal Layer Vacancy on the Structure and Performance of P2 Type Layered Sodium Cathode Material.

This study explores the impact of introducing vacancy in the transition metal layer of rationally designed Na0.6[Ni0.3Ru0.3Mn0.4]O2 (NRM) cathode material. The incorporation of Ru, Ni, and vacancy enhances the structural stability during extensive cycling, increases the operation voltage, and induces a capacity increase while also activating oxygen redox, respectively, in Na0.7[Ni0.2VNi0.1Ru0.3Mn0.4]O2 (V-NRM) compound. Various analytical techniques including transmission electron microscopy, X-ray absorption near edge spectroscopy, operando X-ray diffraction, and operando differential electrochemical mass spectrometry are employed to assess changes in the average oxidation states and structural distortions. The results demonstrate that V-NRM exhibits higher capacity than NRM and maintains a moderate capacity retention of 81% after 100 cycles. Furthermore, the formation of additional lone-pair electrons in the O 2p orbital enables V-NRM to utilize more capacity from the oxygen redox validated by density functional calculation, leading to a widened dominance of the OP4 phase without releasing O2 gas. These findings offer valuable insights for the design of advanced high-capacity cathode materials with improved performance and sustainability in sodium-ion batteries.

Gold-Nanolayer-Derived Zincophilicity Suppressing Metallic Zinc Dendrites and Its Efficacy in Improving Electrochemical Stability of Aqueous Zinc-Ion Batteries.

Herein, an Au-coating layer adjusted on the surface of a Zn metal electrode that effectively suppresses the dendrite growth as well as the mechanisms underlying the dendrite suppression as a result of the zincophilic character of Au is introduced. For the Au-coated Zn metal symmetric cell, uniform deposition of Zn-derived compounds was revealed by operando synchrotron tomography. Microscopic studies demonstrate that the Au-coating layer is induced to form a new Zn-Au alloy during the initial Zn deposition, resulting in stabilized long-term stripping/plating of Zn via the 'embracing effect' that intimately accommodates Zn deposition for further cycles. This property supports the successful operation of symmetrical cells up to 50 mA cm-2 . According to Zn electrodeposition simulation, it is verified that the suppression of dendrite growth is responsible for the electro-conducting Au nanolayer that uniformly distributes the electric field and protects the Zn electrode from corrosion, ultimately promoting uniform Zn growth. The compatibility of the Au-coating layer for full cell configuration is verified using NaV3 O8 as a cathode material over 1 000 cycles. This finding provides a new pathway for the enhancement of the electrochemical performance of ZIBs by suppressing the dendritic growth of Zn by means of a zincophilic Au nanolayer.

Nanostructured high-energy cathode materials for advanced lithium batteries.

Nickel-rich layered lithium transition-metal oxides, LiNi(1-x)M(x)O(2) (M = transition metal), have been under intense investigation as high-energy cathode materials for rechargeable lithium batteries because of their high specific capacity and relatively low cost. However, the commercial deployment of nickel-rich oxides has been severely hindered by their intrinsic poor thermal stability at the fully charged state and insufficient cycle life, especially at elevated temperatures. Here, we report a nickel-rich lithium transition-metal oxide with a very high capacity (215 mA h g(-1)), where the nickel concentration decreases linearly whereas the manganese concentration increases linearly from the centre to the outer layer of each particle. Using this nano-functional full-gradient approach, we are able to harness the high energy density of the nickel-rich core and the high thermal stability and long life of the manganese-rich outer layers. Moreover, the micrometre-size secondary particles of this cathode material are composed of aligned needle-like nanosize primary particles, resulting in a high rate capability. The experimental results suggest that this nano-functional full-gradient cathode material is promising for applications that require high energy, long calendar life and excellent abuse tolerance such as electric vehicles.

An advanced sodium-ion rechargeable battery based on a tin-carbon anode and a layered oxide framework cathode.

In this work we report the characteristics and performance of a sodium-ion battery based on a Sn-C anode and a Na(Ni(0.5)Mn(0.5))O(2) cathode. We show that both electrodes behave satisfactorily in terms of capacity delivery and cycle life when tested in sodium semicells. By coupling these electrodes in an electrolyte solution of sodium perchlorate in a mixture of propylene carbonate and 2 %vol of fluoroethylene carbonate, a sodium-ion battery showing promising electrochemical performance is obtained. This sodium ion battery in fact operates at an average voltage of 2.8 V, with a specific capacity of 120 mA h g(-1) and with a life extending to 50 cycles with minor capacity decays.

Preparation of carbon blacks by liquid phase plasma (LPP) process.

In this study, carbon black nanoparticles were synthesized by Liquid Phase Plasma (LPP) technique; plasma generated in the organic solvent of benzene at 4.9 kV with the pulse frequency of 15 kHz and width of 5 micros transformed the carbon atoms in the solvent into carbon blacks by oxidation and reduction reactions. Graphite phase was found to be introduced into the carbon blacks without any additional processes due to the characteristics of LPP process, resulting in a higher G/D ratio of 0.92, compared to 0.83 of commercial Ketjen carbon blacks. For the performance improvement, heat treatment was employed and its parameters such as temperature and duration time were optimized in relation to the crystallinity and specific surface area of the carbon blacks. Carbon blacks heat treated at 450 degrees C in the air for 20 min were measured to have the discharge capacity of 1750 mAh/g and irreversible charging and discharging capacity ratio of 52.6%.

Detailed studies of a high-capacity electrode material for rechargeable batteries, Li2MnO3-LiCo(1/3)Ni(1/3)Mn(1/3)O2.

Lithium-excess manganese layered oxides, which are commonly described by the chemical formula zLi(2)MnO(3)-(1-z)LiMeO(2) (Me = Co, Ni, Mn, etc.), are of great importance as positive electrode materials for rechargeable lithium batteries. In this Article, Li(x)Co(0.13)Ni(0.13)Mn(0.54)O(2-δ) samples are prepared from Li(1.2)Ni(0.13)Co(0.13)Mn(0.54)O(2) (or 0.5Li(2)MnO(3)-0.5LiCo(1/3)Ni(1/3)Mn(1/3)O(2)) by an electrochemical oxidation/reduction process in an electrochemical cell to study a reaction mechanism in detail before and after charging across a voltage plateau at 4.5 V vs Li/Li(+). Changes of the bulk and surface structures are examined by synchrotron X-ray diffraction (SXRD), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectroscopy (SIMS). SXRD data show that simultaneous oxygen and lithium removal at the voltage plateau upon initial charge causes the structural rearrangement, including a cation migration process from metal to lithium layers, which is also supported by XAS. This is consistent with the mechanism proposed in the literature related to the Li-excess manganese layered oxides. Oxygen removal associated with the initial charge on the high voltage plateau causes oxygen molecule generation in the electrochemical cells. The oxygen molecules in the cell are electrochemically reduced in the subsequent discharge below 3.0 V, leading to the extra capacity. Surface analysis confirms the formation of the oxygen containing species, such as lithium carbonate, which accumulates on the electrode surface. The oxygen containing species are electrochemically decomposed upon second charge above 4.0 V. The results suggest that, in addition to the conventional transition metal redox reactions, at least some of the reversible capacity for the Li-excess manganese layered oxides originates from the electrochemical redox reaction of the oxygen molecules at the electrode surface.

Gifts from Nature: Bio-Inspired Materials for Rechargeable Secondary Batteries.

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.

High-energy cathode material for long-life and safe lithium batteries.

Layered lithium nickel-rich oxides, Li[Ni(1-x)M(x)]O(2) (M=metal), have attracted significant interest as the cathode material for rechargeable lithium batteries owing to their high capacity, excellent rate capability and low cost. However, their low thermal-abuse tolerance and poor cycle life, especially at elevated temperature, prohibit their use in practical batteries. Here, we report on a concentration-gradient cathode material for rechargeable lithium batteries based on a layered lithium nickel cobalt manganese oxide. In this material, each particle has a central bulk that is rich in Ni and a Mn-rich outer layer with decreasing Ni concentration and increasing Mn and Co concentrations as the surface is approached. The former provides high capacity, whereas the latter improves the thermal stability. A half cell using our concentration-gradient cathode material achieved a high capacity of 209 mA h g(-1) and retained 96% of this capacity after 50 charge-discharge cycles under an aggressive test profile (55 degrees C between 3.0 and 4.4 V). Our concentration-gradient material also showed superior performance in thermal-abuse tests compared with the bulk composition Li[Ni(0.8)Co(0.1)Mn(0.1)]O(2) used as reference. These results suggest that our cathode material could enable production of batteries that meet the demanding performance and safety requirements of plug-in hybrid electric vehicles.

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

Cu, Al, and 316L stainless steel are the main components of the current collectors and coin-type cells used in the characterization of potassium-ion battery (KIB) materials and are expected to be electrochemically inactive. Herein, their electrochemical stabilities in a nonaqueous potassium-bis(fluorosulfonyl)imide (KFSI)-based electrolyte are investigated. In dynamic- and transient-mode polarization, passivation of each metal is observed to occur below 3.9, 3.8, and 4.05 V versus K+/K for Cu, Al, and 316L stainless steel, respectively, which are considered the threshold potentials. The composition of the passive layers of each metal is determined using time-of-flight secondary-ion mass spectrometry. The passive layers of Cu and Al consist of Cu-O (CuO or Cu2O) and Al-O (Al2O3), respectively, and 316L stainless steel is passivated with an outermost Cr-F (CrF3) layer and an inner Cr-O (Cr2O3) layer. Above the threshold potentials, however, severe corrosion of each metal occurs accompanied by the dissolution of metal ions, which could affect the reliability of experimental results for KIBs using KFSI-based electrolytes.

Nature-Derived Cellulose-Based Composite Separator for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are emerging power sources for the replacement of lithium-ion batteries. Recent studies have focused on the development of electrodes and electrolytes, with thick glass fiber separators (~380 µm) generally adopted. In this work, we introduce a new thin (~50 µm) cellulose-polyacrylonitrile-alumina composite as a separator for SIBs. The separator exhibits excellent thermal stability with no shrinkage up to 300°C and electrolyte uptake with a contact angle of 0°. The sodium ion transference number, t Na + , of the separator is measured to be 0.78, which is higher than that of bare cellulose ( t Na + : 0.31). These outstanding physical properties of the separator enable the long-term operation of NaCrO2 cathode/hard carbon anode full cells in a conventional carbonate electrolyte, with capacity retention of 82% for 500 cycles. Time-of-flight secondary-ion mass spectroscopy analysis reveals the additional role of the Al2O3 coating, which is transformed into AlF3 upon long-term cycling owing to HF scavenging. Our findings will open the door to the use of cellulose-based functional separators for high-performance SIBs.

Layered K0.28MnO2·0.15H2O as a Cathode Material for Potassium-Ion Intercalation.

Here, we present K0.28MnO2·0.15H2O, which has a two-dimensional open framework, as an intercalation host for potassium ions. K0.28MnO2·0.15H2O has a layered structure consisting of edge-sharing MnO6 octahedra with a large basal spacing of ∼7.3 Å, which facilitates K+-ion mobility. Water molecules in the interlayers between the MnO2 layers play an important role as a pillar to support the structure during repetitive de/potassiation cycles, as confirmed by an operando X-ray diffraction study. As a result, the large K+ ions readily migrate into the crystal structure, resulting in satisfactory electrochemical performance in K-cells. With the aid of the structural pillar, the K0.28MnO2·0.15H2O cathode delivers a high reversible capacity of 150 mA h g-1 over 100 cycles at a rate of 0.1 C (15 mA g-1), with acceptable power capability up to 5 C-rates.

P2-Na2/3MnO2 by Co Incorporation: As a Cathode Material of High Capacity and Long Cycle Life for Sodium-Ion Batteries.

The P2-Na2/3MnO2 compound is one of the attractive cathodes for sodium-ion batteries due to its high initial capacity and abundance of Na and Mn elements in nature. The existence of Mn3+ Jahn-Teller ion, however, impedes electrode performance for long term. Here, we challenge to minimize the effect of the Jahn-Teller distortion caused by Mn3+ in the structure, via substitution of Mn3+ by Co3+ in P2-Na2/3[Mn1-xCox]O2 (x = 0-0.3). The P2-Na2/3[Mn0.8Co0.2]O2 compound substantializes the electrochemical performance with a capacity of about 175 mAh g-1 (26 mA g-1) and retained over 90% of its initial capacity for 300 cycles at 0.1 C (26 mA g-1) and 10 C (2.6 A g-1). The operando X-ray diffraction study indicates that a single-phase reaction is associated with the insertion of sodium ions into the structure, accompanied by a small volume change of approximately 3%. Furthermore, ex situ X-ray diffraction and high-resolution transmission electron microscopy results show that the crystal structure remained after 300 continuous cycles. It is believed that such good electrode performances attribute to the structural stabilization assisted by the presence of Co3+ in the crystal structure. Our finding provides a way to take advantage of low-cost Mn-rich cathode materials for sodium-ion batteries.