Tomographic reconstruction of oxygen orbitals in lithium-rich battery materials.

The electrification of heavy-duty transport and aviation will require new strategies to increase the energy density of electrode materials1,2. The use of anionic redox represents one possible approach to meeting this ambitious target. However, questions remain regarding the validity of the O2-/O- oxygen redox paradigm, and alternative explanations for the origin of the anionic capacity have been proposed3, because the electronic orbitals associated with redox reactions cannot be measured by standard experiments. Here, using high-energy X-ray Compton measurements together with first-principles modelling, we show how the electronic orbital that lies at the heart of the reversible and stable anionic redox activity can be imaged and visualized, and its character and symmetry determined. We find that differential changes in the Compton profile with lithium-ion concentration are sensitive to the phase of the electronic wave function, and carry signatures of electrostatic and covalent bonding effects4. Our study not only provides a picture of the workings of a lithium-rich battery at the atomic scale, but also suggests pathways to improving existing battery materials and designing new ones.

A near dimensionally invariable high-capacity positive electrode material.

Delivering inherently stable lithium-ion batteries is a key challenge. Electrochemical lithium insertion and extraction often severely alters the electrode crystal chemistry, and this contributes to degradation with electrochemical cycling. Moreover, electrodes do not act in isolation, and this can be difficult to manage, especially in all-solid-state batteries. Therefore, discovering materials that can reversibly insert and extract large quantities of the charge carrier (Li+), that is, high capacity, with inherent stability during electrochemical cycles is necessary. Here lithium-excess vanadium oxides with a disordered rocksalt structure are examined as high-capacity and long-life positive electrode materials. Nanosized Li8/7Ti2/7V4/7O2 in optimized liquid electrolytes deliver a large reversible capacity of over 300 mAh g-1 with two-electron V3+/V5+ cationic redox, reaching 750 Wh kg-1 versus metallic lithium. Critically, highly reversible Li storage and no capacity fading for 400 cycles were observed in all-solid-state batteries with a sulfide-based solid electrolyte. Operando synchrotron X-ray diffraction combined with high-precision dilatometry reveals excellent reversibility and a near dimensionally invariable character during electrochemical cycling, which is associated with reversible vanadium migration on lithiation and delithiation. This work demonstrates an example of an electrode/electrolyte couple that produces high-capacity and long-life batteries enabled by multi-electron transition metal redox with a structure that is near invariant during cycling.

Nanosized and metastable molybdenum oxides as negative electrode materials for durable high-energy aqueous Li-ion batteries.

The development of inherently safe energy devices is a key challenge, and aqueous Li-ion batteries draw large attention for this purpose. Due to the narrow electrochemical stable potential window of aqueous electrolytes, the energy density and the selection of negative electrode materials are significantly limited. For achieving durable and high-energy aqueous Li-ion batteries, the development of negative electrode materials exhibiting a large capacity and low potential without triggering decomposition of water is crucial. Herein, a type of a negative electrode material (i.e., Li x Nb2/7Mo3/7O2) is proposed for high-energy aqueous Li-ion batteries. Li x Nb2/7Mo3/7O2 delivers a large capacity of ∼170 mA ⋅ h ⋅ g-1 with a low operating potential range of 1.9 to 2.8 versus Li/Li+ in 21 m lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) aqueous electrolyte. A full cell consisting of Li1.05Mn1.95O4/Li9/7Nb2/7Mo3/7O2 presents high energy density of 107 W ⋅ h ⋅ kg-1 as the maximum value in 21 m LiTFSA aqueous electrolyte, and 73% in capacity retention is achieved after 2,000 cycles. Furthermore, hard X-ray photoelectron spectroscopy study reveals that a protective surface layer is formed at the surface of the negative electrode, by which the high-energy and durable aqueous batteries are realized with Li x Nb2/7Mo3/7O2 This work combines a high capacity with a safe negative electrode material through delivering the Mo-based oxide with unique nanosized and metastable characters.

Nanoscale domain imaging of Li-rich disordered rocksalt-type cathode materials with X-ray spectroscopic ptychography.

Lithium-rich disordered rocksalt-type cathode materials are promising for high-capacity and high-power lithium-ion batteries. Many of them are synthesized by mechanical milling and may have heterogeneous structures and chemical states at the nanoscale. In this study, we performed X-ray spectroscopic ptychography measurements of Li-rich disordered rocksalt-type oxide particles synthesized by mechanical milling before and after delithiation reaction at the vanadium K absorption edge, and visualized their structures and chemical state with a spatial resolution of ∼100 nm. We classified multiple domains with different chemical states via clustering analysis. A comparison of the domain distribution trends of the particles before and after the delithiation reaction revealed the presence of domains, suggesting that the delithiation reaction was suppressed.

Nanosize Cation-Disordered Rocksalt Oxides: Na2 TiO3 -NaMnO2 Binary System.

To realize the development of rechargeable sodium batteries, new positive electrode materials without less abundant elements are explored. Enrichment of sodium contents in host structures is required to increase the theoretical capacity as electrode materials, and therefore Na-excess compounds are systematically examined in a binary system of Na2 TiO3 -NaMnO2 . After several trials, synthesis of Na-excess compounds with a cation disordered rocksalt structure is successful by adapting a mechanical milling method. Among the tested electrode materials, Na1.14 Mn0.57 Ti0.29 O2 in this binary system delivers a large reversible capacity of ≈200 mA h g-1 , originating from reversible redox reactions of cationic Mn3+ /Mn4+ and anionic O2- /On - redox confirmed by X-ray absorption spectroscopy. Holes in oxygen 2p orbitals, which are formed by electrochemical oxidation, are energetically stabilized by electron donation from Mn ions. Moreover, reversibility of anionic redox is significantly improved compared with a former study on a binary system of Na3 NbO3 -NaMnO2 tested as model electrode materials.

Material Design Concept of Lithium-Excess Electrode Materials with Rocksalt-Related Structures for Rechargeable Non-Aqueous Batteries.

Dependence on lithium-ion batteries for automobile applications is rapidly increasing, and further improvement, especially for positive electrode materials, is indispensable to increase energy density of lithium-ion batteries. In the past several years, many new lithium-excess high-capacity electrode materials with rocksalt-related structures have been reported. These materials deliver high reversible capacity with cationic/anionic redox and percolative lithium migration in the oxide/oxyfluoride framework structures, and recent research progresses on these electrode materials are reviewed. Material design strategies for these lithium-excess electrode materials are also described. Future possibility of high-energy non-aqueous batteries with advanced positive electrode materials is discussed for more details.

High-capacity electrode materials for rechargeable lithium batteries: Li3NbO4-based system with cation-disordered rocksalt structure.

Rechargeable lithium batteries have rapidly risen to prominence as fundamental devices for green and sustainable energy development. Lithium batteries are now used as power sources for electric vehicles. However, materials innovations are still needed to satisfy the growing demand for increasing energy density of lithium batteries. In the past decade, lithium-excess compounds, Li2MeO3 (Me = Mn(4+), Ru(4+), etc.), have been extensively studied as high-capacity positive electrode materials. Although the origin as the high reversible capacity has been a debatable subject for a long time, recently it has been confirmed that charge compensation is partly achieved by solid-state redox of nonmetal anions (i.e., oxide ions), coupled with solid-state redox of transition metals, which is the basic theory used for classic lithium insertion materials, such as LiMeO2 (Me = Co(3+), Ni(3+), etc.). Herein, as a compound with further excess lithium contents, a cation-ordered rocksalt phase with lithium and pentavalent niobium ions, Li3NbO4, is first examined as the host structure of a new series of high-capacity positive electrode materials for rechargeable lithium batteries. Approximately 300 mAh ⋅ g(-1) of high-reversible capacity at 50 °C is experimentally observed, which partly originates from charge compensation by solid-state redox of oxide ions. It is proposed that such a charge compensation process by oxide ions is effectively stabilized by the presence of electrochemically inactive niobium ions. These results will contribute to the development of a new class of high-capacity electrode materials, potentially with further lithium enrichment (and fewer transition metals) in the close-packed framework structure with oxide ions.

All-solid-state ion-selective electrodes with redox-active lithium, sodium, and potassium insertion materials as the inner solid-contact layer.

All-solid-state ion-selective electrodes as potentiometric ion sensors for lithium, sodium, and potassium have been demonstrated by installing a composite layer containing a powder of alkali insertion materials, LixFePO4, Na0.33MnO2, and KxMnO2·nH2O, respectively, as an inner solid-contact layer between the electrode substrate and plasticized poly(vinyl chloride) (PVC)-based ion-sensitive membrane containing the corresponding ionophores for Li+, Na+, and K+ ions. These double-layer ion-selective electrodes, consisting of the composite and PVC layers prepared by a simple drop cast method, exhibit a quick potential response (less than 5 s) to each alkali-metal ion with sufficient Nernstian slopes of calibration curves, ca. 59 mV per decade. The installation of the insertion materials as the inner solid-contact layers is highly efficient for the stabilization of membrane potential, resulting in a prompt response to the alkali ion activity in the analyte, compared to those of the electrodes without the alkali insertion materials. From alternating current impedance measurements for the electrodes, the inner layer of the installed alkali insertion materials drastically reduces the impedance of the membrane/electrode interface, leading to an improvement in their ion-sensing performance.

Electrochemical lithiation performance and characterization of silicon-graphite composites with lithium, sodium, potassium, and ammonium polyacrylate binders.

Poly(acrylic acid) (PAH), which is a water soluble polycarboxylic acid, is neutralized by adding different amounts of LiOH, NaOH, KOH, and ammonia (NH4OH) aqueous solutions to fix neutralization degrees. The differently neutralized polyacid, alkali and ammonium polyacrylates are examined as polymeric binders for the preparation of Si-graphite composite electrodes as negative electrodes for Li-ion batteries. The electrode performance of the Si-graphite composite depends on the alkali chemicals and neutralization degree. It is found that 80% NaOH-neutralized polyacrylate binder (a pH value of the resultant aqueous solution is ca. 6.7) is the most efficient binder to enhance the electrochemical lithiation and de-lithiation performance of the Si-graphite composite electrode compared to that of conventional PVdF and the other binders used in this study. The optimum polyacrylate binder highly improves the dispersion of active material in the composite electrode. The binder also provides the strong adhesion, suitable porosity, and hardness for the composite electrode with 10% (m/m) binder content, resulting in better electrochemical reversibility. From these results, the factors of alkali-neutralized polyacrylate binders affecting the electrode performance of Si-graphite composite electrodes are discussed.

Fabrication of carbon-felt-based multi-enzyme immobilized anodes to oxidize sucrose for biofuel cells.

A carbon-felt-based multi-enzyme immobilized bioanode for biofuel cells has been successfully developed. The combination of four enzymes, namely, invertase, mutarotase, glucose oxidase, and fructose dehydrogenase, makes it possible to use sucrose--a disaccharide--as fuel for the bioanode. The new electrode exhibits a high oxidation current density of about 12 mA cm(-2) (0.25 V vs. Ag/AgCl) in a McIlvaine buffer solution containing sucrose at pH 6.0 in the half-cell configuration. A sucrose/O(2) biofuel cell composed of the bioanode and an opposite biocathode, including bilirubin oxidase as the enzymatic electrocatalyst, was fabricated, and the new device demonstrated a maximum power density of 2.90 mW cm(-2) with an open-circuit voltage of 0.69 V in the McIlvaine buffer solution. The biofuel cell fabricated using our multi-enzyme anode operates in commercially available beverages that contain only sugar, even without glucose.

Negative electrodes for Na-ion batteries.

Research interest in Na-ion batteries has increased rapidly because of the environmental friendliness of sodium compared to lithium. Throughout this Perspective paper, we report and review recent scientific advances in the field of negative electrode materials used for Na-ion batteries. This paper sheds light on negative electrode materials for Na-ion batteries: carbonaceous materials, oxides/phosphates (as sodium insertion materials), sodium alloy/compounds and so on. These electrode materials have different reaction mechanisms for electrochemical sodiation/desodiation processes. Moreover, not only sodiation-active materials but also binders, current collectors, electrolytes and electrode/electrolyte interphase and its stabilization are essential for long cycle life Na-ion batteries. This paper also addresses the prospect of Na-ion batteries as low-cost and long-life batteries with relatively high-energy density as their potential competitive edge over the commercialized Li-ion batteries.

Recent research progress on iron- and manganese-based positive electrode materials for rechargeable sodium batteries.

Large-scale high-energy batteries with electrode materials made from the Earth-abundant elements are needed to achieve sustainable energy development. On the basis of material abundance, rechargeable sodium batteries with iron- and manganese-based positive electrode materials are the ideal candidates for large-scale batteries. In this review, iron- and manganese-based electrode materials, oxides, phosphates, fluorides, etc, as positive electrodes for rechargeable sodium batteries are reviewed. Iron and manganese compounds with sodium ions provide high structural flexibility. Two layered polymorphs, O3- and P2-type layered structures, show different electrode performance in Na cells related to the different phase transition and sodium migration processes on sodium extraction/insertion. Similar to layered oxides, iron/manganese phosphates and pyrophosphates also provide the different framework structures, which are used as sodium insertion host materials. Electrode performance and reaction mechanisms of the iron- and manganese-based electrode materials in Na cells are described and the similarities and differences with lithium counterparts are also discussed. Together with these results, the possibility of the high-energy battery system with electrode materials made from only Earth-abundant elements is reviewed.

Virtues of Cold Isostatic Pressing for Preparation of All-Solid-State-Batteries with Poly(Ethylene Oxide).

All-solid-state-batteries (ASSBs) necessitate the preparation of a solid electrolyte and an electrode couple with individually dense and compact structures with superior interfacial contact to minimize overall cell resistance. A conventional preparation method of solid polymer electrolyte (SPE) with polyethylene-oxide (PEO) generally consists in employing uni-axial hot press (HP) to densify SPE. However, while uni-axial press with moderate pressure effectively densifies PEO with Li salts, excessive pressure also unavoidably results in perpendicular elongation and deformation for polymer matrix. In this research, to overcome this limitation for the uni-axial press technique, a cold isostatic press (CIP) is applied to the fabrication of ASSB with PEO and LiFePO4 . CIP effectively and uniformly applies pressure as high as 500 MPa without deformation. Characterizations confirm that CIP treated SPE has enhanced mechanical puncture strength, increasing from 499.3±22.6 to 539.3±22.6 g, and ionic conductivity, increasing from 1.04×10-4 to 1.91×10-4  S cm-1 at 50 °C. ASSB treated by CIP demonstrates remarkably enhanced rate capability and cyclability compared with the cell processed by HP, which is further evidenced by improvement of the apparent Li ion diffusion constant based on Sand equation analysis. The improvement enabled by CIP treatment originates from the superior interface uniformity between electrodes and SPE and from the densification of the LiFePO4 and SPE composite electrode.

Efficient Surface Passivation of Ti-Based Layered Materials by a Nonfluorine Branched Copolymer for Durable and High-Power Sodium-Ion Batteries.

There is a crucial need for low-cost energy storage technology based on abundant sodium ions to realize sustainable development with renewable energy resources. Poly(vinylidene fluoride) (PVDF) is applied as a binder in sodium-ion batteries (SIBs). Nevertheless, PVDF is also known to suffer from a larger irreversible capacity, especially when PVDF is used as the binder of negative electrode materials. In this research, a poly(acrylonitrile)-grafted poly(vinyl alcohol) copolymer (PVA-g-PAN) is tested as a binder with Ti-based layered oxides as potential negative electrode materials for SIBs. The chemical stability tests of PVDF and PVA-g-PAN contacted with metallic sodium have been conducted, which reveals that PVDF experiences a defluorination process, while PVA-g-PAN demonstrates excellent chemical stability. Composite electrodes with PVA-g-PAN demonstrate superior electrochemical performances when compared with the PVDF binder, allowing improvement for initial CE, higher rate capability, and long cyclability over 1500 cycles. Detailed characterization of electrodes via soft X-ray photoelectron spectroscopy and field emission scanning electron microscopy demonstrates that the PVA-g-PAN branched structure allows a more uniform distribution of acetylene black with higher coatability, unlocking enhanced rate performances and efficient passivation of Ti-based oxides without the excessive electrolyte decomposition. These findings open a new way to design practical and durable sodium-ion batteries with a high-power density.

P2-type Na(x)[Fe(1/2)Mn(1/2)]O2 made from earth-abundant elements for rechargeable Na batteries.

Rechargeable lithium batteries have risen to prominence as key devices for green and sustainable energy development. Electric vehicles, which are not equipped with an internal combustion engine, have been launched in the market. Manganese- and iron-based positive-electrode materials, such as LiMn(2)O(4) and LiFePO(4), are used in large-scale batteries for electric vehicles. Manganese and iron are abundant elements in the Earth's crust, but lithium is not. In contrast to lithium, sodium is an attractive charge carrier on the basis of elemental abundance. Recently, some layered materials, where sodium can be electrochemically and reversibly extracted/inserted, have been reported. However, their reversible capacity is typically limited to 100 mAh g(-1). Herein, we report a new electrode material, P2-Na(2/3)[Fe(1/2)Mn(1/2)]O(2), that delivers 190 mAh g(-1) of reversible capacity in the sodium cells with the electrochemically active Fe(3+)/Fe(4+) redox. These results will contribute to the development of rechargeable batteries from the earth-abundant elements operable at room temperature.

A comparative study of LiCoO2 polymorphs: structural and electrochemical characterization of O2-, O3-, and O4-type phases.

O4-type LiCoO2 as a third polymorph of LiCoO2 is prepared by an ion-exchange method in aqueous media from OP4-[Li, Na]CoO2, which has an intergrowth structure of O3-LiCoO2 and P2-Na0.7CoO2. O4-type LiCoO2 is characterized by synchrotron X-ray diffraction, neutron diffraction, and X-ray absorption spectroscopy. Structural characterization reveals that O4-type LiCoO2 has an intergrowth structure of O3- and O2-LiCoO2 with stacking faulted domains. Three LiCoO2 polymorphs are formed from the close-packed CoO2 layers, which consist of edge-shared CoO6 octahedra, whereas the oxide-ion stacking is different: cubic in the O3-phase, cubic/hexagonal in the O2-phase, and alternate O3 and O2 in the O4-phase. Structural analysis using the DIFFaX program suggests that the O4-phase consists of approximately 30% of O12-domains, while stacking faults are not evidenced for O2-phase. The results suggest that a nucleation process for Na/Li ion-exchange kinetically dominates a growth process of ideal O4-domains because the presence of CoO2-Li-CoO2 blocks as O3-domains could be expected to prevent through-plane interaction of Na layers. Electrochemical behavior and structural transition processes for three LiCoO2 polymorphs are compared in Li cells. A new phase, OT(#)4-type Li0.5CoO2, is first isolated as an intergrowth phase of O3- and T(#)2-Li0.5CoO2. However, some deviations from ideal behavior as the O2/O3-intergrowth phase are also noted, presumably because of the existence of stacking faults.

Anion-Induced Interfacial Liquid Layers on LiCoO2 in Salt-in-Water Lithium-Ion Batteries.

The incompatibility of lithium intercalation electrodes with water has impeded the development of aqueous Li-ion batteries. The key challenge is protons which are generated by water dissociation and deform the electrode structures through intercalation. Distinct from previous approaches utilizing large amounts of electrolyte salts or artificial solid-protective films, we developed liquid-phase protective layers on LiCoO2 (LCO) using a moderate concentration of 0.5∼3 mol kg-1 lithium sulfate. Sulfate ion strengthened the hydrogen-bond network and easily formed ion pairs with Li+, showing strong kosmotropic and hard base characteristics. Our quantum mechanics/molecular mechanics (QM/MM) simulations revealed that sulfate ion paired with Li+ helped stabilize the LCO surface and reduced the density of free water in the interface region below the point of zero charge (PZC) potential. In addition, in situ electrochemical surface-enhanced infrared absorption spectroscopy (SEIRAS) proved the appearance of inner-sphere sulfate complexes above the PZC potential, serving as the protective layers of LCO. The role of anions in stabilizing LCO was correlated with kosmotropic strength (sulfate > nitrate > perchlorate > bistriflimide (TFSI-)) and explained better galvanostatic cyclability in LCO cells.

Study on the reversible electrode reaction of Na(1-x)Ni(0.5)Mn(0.5)O2 for a rechargeable sodium-ion battery.

Layered NaNi(0.5)Mn(0.5)O(2) (space group: R ̅3m), having an O3-type (α-NaFeO(2) type) structure according to the Delmas' notation, is prepared by a solid-state method. The electrochemical reactivity of NaNi(0.5)Mn(0.5)O(2) is examined in an aprotic sodium cell at room temperature. The NaNi(0.5)Mn(0.5)O(2) electrodes can deliver ca. 105-125 mAh g(-1) at rates of 240-4.8 mA g(-1) in the voltage range of 2.2-3.8 V and show 75% of the initial reversible capacity after 50 charge/discharge cycling tests. In the voltage range of 2.2-4.5 V, a higher reversible capacity of 185 mAh g(-1) is achieved; however, its reversibility is insufficient because of the significant expansion of interslab space by charging to 4.5 V versus sodium. The reversbility is improved by adding fluoroethylene carbonate into the electrolyte solution. The structural transition mechanism of Na(1-x)Ni(0.5)Mn(0.5)O(2) is also examined by an ex situ X-ray diffraction method combined with X-ray absorption spectroscopy (XAS). The staking sequence of the [Ni(0.5)Mn(0.5)]O(2) slabs changes progressively as sodium ions are extracted from the crystal lattice. It is observed that the original O3 phase transforms into the O'3, P3, P'3, and P3" phases during sodium extraction. XAS measurement proves that NaNi(0.5)Mn(0.5)O(2) consists of divalent nickel and tetravalent manganese ions. As sodium ions are extracted from the oxide to form Na(1-x)Ni(0.5)Mn(0.5)O(2), nickel ions are oxidized to the trivalent state, while the manganese ions are electrochemically inactive as the tetravalent state.

Unexpectedly Large Contribution of Oxygen to Charge Compensation Triggered by Structural Disordering: Detailed Experimental and Theoretical Study on a Li3NbO4-NiO Binary System.

Dependence on lithium-ion batteries for automobile applications is rapidly increasing. The emerging use of anionic redox can boost the energy density of batteries, but the fundamental origin of anionic redox is still under debate. Moreover, to realize anionic redox, many reported electrode materials rely on manganese ions through π-type interactions with oxygen. Here, through a systematic experimental and theoretical study on a binary system of Li3NbO4-NiO, we demonstrate for the first time the unexpectedly large contribution of oxygen to charge compensation for electrochemical oxidation in Ni-based materials. In general, for Ni-based materials, e.g., LiNiO2, charge compensation is achieved mainly by Ni oxidation, with a lower contribution from oxygen. In contrast, for Li3NbO4-NiO, oxygen-based charge compensation is triggered by structural disordering and σ-type interactions with nickel ions, which are associated with a unique environment for oxygen, i.e., a linear Ni-O-Ni configuration in the disordered system. Reversible anionic redox with a small hysteretic behavior was achieved for LiNi2/3Nb1/3O2 with a cation-disordered Li/Ni arrangement. Further Li enrichment in the structure destabilizes anionic redox and leads to irreversible oxygen loss due to the disappearance of the linear Ni-O-Ni configuration and the formation of unstable Ni ions with high oxidation states. On the basis of these results, we discuss the possibility of using σ-type interactions for anionic redox to design advanced electrode materials for high-energy lithium-ion batteries.