Unlocking iron metal as a cathode for sustainable Li-ion batteries by an anion solid solution.

Traditional cathode chemistry of Li-ion batteries relies on the transport of Li-ions within the solid structures, with the transition metal ions and anions acting as the static components. Here, we demonstrate that a solid solution of F- and PO43- facilitates the reversible conversion of a fine mixture of iron powder, LiF, and Li3PO4 into iron salts. Notably, in its fully lithiated state, we use commercial iron metal powder in this cathode, departing from electrodes that begin with iron salts, such as FeF3. Our results show that Fe-cations and anions of F- and PO43- act as charge carriers in addition to Li-ions during the conversion from iron metal to a solid solution of iron salts. This composite electrode delivers a reversible capacity of up to 368 mAh/g and a specific energy of 940 Wh/kg. Our study underscores the potential of amorphous composites comprising lithium salts as high-energy battery electrodes.

Reducing Gases Triggered Cathode Surface Reconstruction for Stable Cathode-Electrolyte Interface in Practical All-Solid-State Lithium Batteries.

The interfacial compatibility between cathodes and sulfide solid-electrolytes (SEs) is a critical limiting factor of electrochemical performance in all-solid-state lithium-ion batteries (ASSLBs). This work presents a gas-solid interface reduction reaction (GSIRR), aiming to mitigate the reactivity of surface oxygen by inducing a surface reconstruction layer (SRL) . The application of a SRL, CoO/Li2 CO3 , onto LiCoO2 (LCO) cathode results in impressive outcomes, including high capacity (149.7 mAh g-1 ), remarkable cyclability (retention of 84.63% over 400 cycles at 0.2 C), outstanding rate capability (86.1 mAh g-1 at 2 C), and exceptional stability in high-loading cathode (28.97 and 23.45 mg cm-2 ) within ASSLBs. Furthermore, the SRL CoO/Li2 CO3 enhances the interfacial stability between LCO and Li10 GeP2 S12 as well as Li3 PS4 SEs. Significantly, the experiments suggest that the GSIRR mechanism can be broadly applied, not only to LCO cathodes but also to LiNi0.8 Co0.1 Mn0.1 O2 cathodes and other reducing gases such as H2 S and CO, indicating its practical universality. This study highlights the significant influence of the surface chemistry of the oxide cathode on interfacial compatibility, and introduces a surface reconstruction strategy based on the GSIRR process as a promising avenue for designing enhanced ASSLBs.

Revealing the effect of LiOH on forming a SEI using a Co magnetic "probe".

The solid-electrolyte-interphase (SEI) plays a critical role in lithium-ion batteries (LIBs) because of its important influence on electrochemical performance, such as cycle stability, coulombic efficiency, etc. Although LiOH has been recognized as a key component of the SEI, its influence on the SEI and electrochemical performance has not been well clarified due to the difficulty in precisely controlling the LiOH content and characterize the detailed interface reactions. Here, a gradual change of LiOH content is realized by different reduction schemes among Co(OH)2, CoOOH and CoO. With reduced Co nanoparticles as magnetic "probes", SEI characterization is achieved by operando magnetometry. By combining comprehensive characterization and theoretical calculations, it is verified that LiOH leads to a composition transformation from lithium ethylene di-carbonate (LEDC) to lithium ethylene mono-carbonate (LEMC) in the SEI and ultimately results in capacity decay. This work unfolds the detailed SEI reaction scenario involving LiOH, provides new insights into the influence of SEI composition, and has value for the co-development between the electrode materials and electrolyte.

Decoupling the roles of Ni and Co in anionic redox activity of Li-rich NMC cathodes.

Li[LixNiyMnzCo1-x-y-z]O2 (lithium-rich NMCs) are benchmark cathode materials receiving considerable attention due to the abnormally high capacities resulting from their anionic redox chemistry. Although their anionic redox mechanisms have been much investigated, the roles of cationic redox processes remain underexplored, hindering further performance improvement. Here we decoupled the effects of nickel and cobalt in lithium-rich NMCs via a comprehensive study of two typical compounds, Li1.2Ni0.2Mn0.6O2 and Li1.2Co0.4Mn0.4O2. We discovered that both Ni3+/4+ and Co4+, generated during cationic redox processes, are actually intermediate species for triggering oxygen redox through a ligand-to-metal charge-transfer process. However, cobalt is better than nickel in mediating the kinetics of ligand-to-metal charge transfer by favouring more transition metal migration, leading to less cationic redox but more oxygen redox, more O2 release, poorer cycling performance and more severe voltage decay. Our work highlights a compositional optimization pathway for lithium-rich NMCs by deviating from using cobalt to using nickel, providing valuable guidelines for future high-capacity cathode design.

Li2 MnO3 : A Catalyst for a Liquid Cl2 Electrode in Low-Temperature Aqueous Batteries.

Li2 MnO3 has been contemplated as a high-capacity cathode candidate for Li-ion batteries; however, it evolves oxygen during battery charging under ambient conditions, which hinders a reversible reaction. However, it is unclear if this irreversible process still holds under subambient conditions. Here, the low-temperature electrochemical properties of Li2 MnO3 in an aqueous LiCl electrolyte are evaluated and a reversible discharge capacity of 302 mAh g-1 at a potential of 1.0 V versus Ag/AgCl at -78 °C with good rate capability and stable cycling performance, in sharp contrast to the findings in a typical Li2 MnO3 cell cycled at room temperature, is observed. However, the results reveal that the capacity does not originate from the reversible oxygen oxidation in Li2 MnO3 but the reversible Cl2 (l)/Cl- (aq.) redox from the electrolyte. The results demonstrate the good catalytic properties of Li2 MnO3 to promote the Cl2 /Cl- redox at low temperatures.

LiMgPO4 -Coating-Induced Phosphate Shell and Bulk Mg-Doping Enables Stable Ultra-High-Voltage Cycling of LiCoO2 Cathode.

Stable cycling of LiCoO2 (LCO) cathode at high voltage is extremely challenging due to the notable structural instability in deeply delithiated states. Here, using the sol-gel coating method, LCO materials (LMP-LCO) are obtained with bulk Mg-doping and surface LiMgPO4 /Li3 PO4 (LMP/LPO) coating. The experimental results suggest that the simultaneous modification in the bulk and at the surface is demonstrated to be highly effective in improving the high-voltage performance of LCO. LMP-LCO cathodes deliver 149.8 mAh g-1 @4.60 V and 146.1 mAh g-1 @4.65 V after 200 cycles at 1 C. For higher cut-off voltages, 4.70 and 4.80 V, LMP-LCO cathodes still achieve 144.9 mAh g-1 after 150 cycles and 136.8 mAh g-1 after 100 cycles at 1 C, respectively. Bulk Mg-dopants enhance the ionicity of CoO bond by tailoring the band centers of Co 3d and O 2p, promoting stable redox on O2- , and thus enhancing stable cycling at high cut-off voltages. Meanwhile, LMP/LPO surface coating suppresses detrimental surface side reactions while allowing facile Li-ion diffusion. The mechanism of high-voltage cycling stability is investigated by combining experimental characterizations and theoretical calculations. This study proposes a strategy of surface-to-bulk simultaneous modification to achieve superior structural stability at high voltages.

Stacking Faults Inducing Oxygen Anion Activities in Li2 MnO3.

Controllable anionic redox for a transformational increase in the energy density is the pursuit of next generation Li-ion battery cathode materials. Its activation mechanism is coupled with the local coordination environment around O, which posts experimental challenges for control. Here, the tuning capability of anionic redox is shown by varying O local environment via experimentally controlling the density of stacking faults in Li2 MnO3 , the parent compound of Li-rich oxides. By combining computational analysis and spectroscopic study, it is quantitatively revealed that more stacking faults can trigger smaller LiOLi bond angles and larger LiO bond distance in local Li-rich environments and subsequently activate oxygen redox reactivity, which in turn enhances the reactivity of Mn upon the following reduction process. This study highlights the critical role of local structure environment in tuning the anionic reactivity, which provides guidance in designing high-capacity layered cathodes by appropriately adjusting stacking faults.

Unveiling the High-valence Oxygen Degradation Across the Delithiated Cathode Surface.

Charge compensation on anionic redox reaction (ARR) has been promising to realize extra capacity beyond transition metal redox in battery cathodes. The practical development of ARR capacity has been hindered by high-valence oxygen instability, particularly at cathode surfaces. However, the direct probe of surface oxygen behavior has been challenging. Here, the electronic states of surface oxygen are investigated by combining mapping of resonant Auger electronic spectroscopy (mRAS) and ambient pressure X-ray photoelectron spectroscopy (APXPS) on a model LiCoO2 cathode. The mRAS verified that no high-valence oxygen can sustain at cathode surfaces, while APXPS proves that cathode electrolyte interphase (CEI) layer evolves and oxidizes upon oxygen gas contact. This work provides valuable insights into the high-valence oxygen degradation mode across the interface. Oxygen stabilization from surface architecture is proven a prerequisite to the practical development of ARR active cathodes.

Controlled Experiments and Optimized Theory of Absorption Spectra of Li Metal and Salts.

Investigation of Li metal and ionic compounds through experimental and theoretical spectroscopy has been of tremendous interest due to their prospective applications in Li-metal and Li-ion batteries. Li K-edge soft X-ray absorption spectroscopy (sXAS) provides the most direct spectroscopic characterization; unfortunately, due to the low core-level energy and the highly reactive surface, Li-K sXAS of Li metal has been extremely challenging, as evidenced by many controversial reports. Here, through controlled and ultra-high energy resolution experiments of two kinds of in situ prepared samples, we report the intrinsic Li-K sXAS of Li-metal that displays a prominent leading peak that has not been revealed before. Furthermore, theoretical simulations show that, due to the low number of valence electrons in Li, the Li-K sXAS is strongly affected by the response of the valence electrons to the core hole. We successfully reproduce the Li-K sXAS by state-of-the-art calculations with considerations of a number of relevant parameters such as temperature, energy resolution, and, especially, contributions from transitions which are forbidden in the single-particle treatment. Such a comparative experimental and theoretical investigation is further extended to a series of Li ionic compounds, which highlight the importance of considering the total and single-particle energies for obtaining an accurate alignment of the spectra. Our work provides the first reliable Li-K sXAS of the Li metal surface with advanced theoretical calculations. The experimental and theoretical results provide a critical benchmark for studying Li chemistry in both metallic and ionic states.

Layered-rocksalt intergrown cathode for high-capacity zero-strain battery operation.

The dependence on lithium-ion batteries leads to a pressing demand for advanced cathode materials. We demonstrate a new concept of layered-rocksalt intergrown structure that harnesses the combined figures of merit from each phase, including high capacity of layered and rocksalt phases, good kinetics of layered oxide and structural advantage of rocksalt. Based on this concept, lithium nickel ruthenium oxide of a main layered structure (R[Formula: see text]m) with intergrown rocksalt (Fm[Formula: see text]m) is developed, which delivers a high capacity with good rate performance. The interwoven rocksalt structure successfully prevents the anisotropic structural change that is typical for layered oxide, enabling a nearly zero-strain operation upon high-capacity cycling. Furthermore, a design principle is successfully extrapolated and experimentally verified in a series of compositions. Here, we show the success of such layered-rocksalt intergrown structure exemplifies a new battery electrode design concept and opens up a vast space of compositions to develop high-performance intergrown cathode materials.

Full Energy Range Resonant Inelastic X-ray Scattering of O2 and CO2: Direct Comparison with Oxygen Redox State in Batteries.

The evolving oxygen state plays key roles in the performance and stability of high-energy batteries involving oxygen redox reactions. Here, high-efficiency full energy range O-K mapping of resonant inelastic X-ray scattering (mRIXS) was collected from O2 (O0) and CO2 (O2- with strong covalency) molecules and compared directly with Li2O2 (O-) and the oxidized oxygen state in representative Na/Li-ion battery electrodes. Our results confirm again that the critical mRIXS feature around the 523.7 eV emission energy is from intrinsically oxidized oxygen, but not from the highly covalent oxygen state (CO2). The comparison of the mRIXS profile of the four different oxygen states, i.e., O2-, O-, On- (0 < n < 2), and O0, reveals that oxygen redox states in batteries have distinct widths and positions along the excitation energy compared with Li2O2 and O2. The nature of the oxidized oxygen state in oxide electrodes is thus beyond a simple molecular configuration of either peroxide or O2.

Dissociate lattice oxygen redox reactions from capacity and voltage drops of battery electrodes.

The oxygen redox (OR) activity is conventionally considered detrimental to the stability and kinetics of batteries. However, OR reactions are often confused by irreversible oxygen oxidation. Here, based on high-efficiency mapping of resonant inelastic x-ray scattering of both the transition metal and oxygen, we distinguish the lattice OR in Na0.6[Li0.2Mn0.8]O2 and compare it with Na2/3[Mg1/3Mn2/3]O2. Both systems display strong lattice OR activities but with distinct electrochemical stability. The comparison shows that the substantial capacity drop in Na0.6[Li0.2Mn0.8]O2 stems from non-lattice oxygen oxidations, and its voltage decay from an increasing Mn redox contribution upon cycling, contrasting those in Na2/3[Mg1/3Mn2/3]O2. We conclude that lattice OR is not the ringleader of the stability issue. Instead, irreversible oxygen oxidation and the changing cationic reactions lead to the capacity and voltage fade. We argue that lattice OR and other oxygen activities should/could be studied and treated separately to achieve viable OR-based electrodes.

Mechanism of Exact Transition between Cationic and Anionic Redox Activities in Cathode Material Li2FeSiO4.

The discovery of anion redox activity is promising for boosting the capacity of lithium ion battery (LIB) cathodes. However, fundamental understanding of the mechanisms that trigger the anionic redox is still lacking. Here, using hybrid density functional study combined with experimental soft X-ray absorption spectroscopy (sXAS) measurements, we unambiguously proved that Li(2- x)FeSiO4 performs sequent cationic and anionic redox activity through delithiation. Specifically, Fe2+ is oxidized to Fe3+ during the first Li ion extraction per formula unit (f.u.), while the second Li ion extraction triggered the oxygen redox exclusively. Cationic and anionic redox result in electron and hole polaron states, respectively, explaining the poor conductivity of Li(2- x)FeSiO4 noted by previous experiments. In contrast, other cathode materials in this family exhibit diversity of the redox process. Li2MnSiO4 shows double cationic redox (Mn2+-Mn4+) during the whole delithiation, while Li2CoSiO4 shows simultaneous cationic and anionic redox. The present finding not only provides new insights into the oxygen redox activity in polyanionic compounds for rechargeable batteries but also sheds light on the future design of high-capacity rechargeable batteries.

Spectroscopic Signature of Oxidized Oxygen States in Peroxides.

Recent debates on the oxygen redox behaviors in battery electrodes have triggered a pressing demand for the reliable detection and understanding of nondivalent oxygen states beyond conventional absorption spectroscopy. Here, enabled by high-efficiency mapping of resonant inelastic X-ray scattering (mRIXS) coupled with first-principles calculations, we report distinct mRIXS features of the oxygen states in Li2O, Li2CO3, and especially, Li2O2, which are successfully reproduced and interpreted theoretically. mRIXS signals are dominated by valence-band decays in Li2O and Li2CO3. However, the oxidized oxygen in Li2O2 leads to partially unoccupied O-2p states that yield a specific intraband excitonic feature in mRIXS. Such a feature displays a specific emission energy in mRIXS, which disentangles the oxidized oxygen states from the dominating transition-metal/oxygen hybridization features in absorption spectroscopy, thus providing critical hints for both detecting and understanding the oxygen redox reactions in transition-metal oxide based battery materials.

Photocharging and Band Gap Narrowing Effects on the Performance of Plasmonic Photoelectrodes in Dye-Sensitized Solar Cells.

The incorporation of plasmonic nanostructures in active electrodes has become one of the most attractive ways to enhance the photoconversion efficiency (PCE) of dye-sensitized solar cells (DSSCs). Although an enhancement of PCE because of the incorporation of plasmonic nanostructures of different sizes, either bare or coated, has been demonstrated, the fundamental mechanisms associated to such enhancement are still unclear. Besides, the photocurrent enhancement of plasmonic DSSCs is frequently associated to the strong surface plasmon resonance (SPR) absorption of metal nanoparticles. In this work, through oxygen K-edge soft X-ray absorption and emission spectroscopies of plasmonic electrodes and electrodynamical characterization of the fabricated cells, we demonstrate a band gap narrowing and photocharging effect on the plasmonic electrodes that definitely contribute to the PCE enhancement in plasmonic DSSCs. The incorporation of bare metal nanoparticles in active metal-oxide semiconductor electrodes such as TiO2 in optimum concentration causes an upward shift of its valence band edge, reducing its effective band gap energy and enhancing the short-circuit current of DSSCs. On the other hand, small perturbation-based stepped light-induced transient measurements of photovoltage and photocurrent of the operating DSSCs revealed an upward shift of quasi-Fermi level of photoelectrodes because of the photocharging effect induced by the incorporated metal nanoparticles. The upward shift of the quasi-Fermi level causes an increase in open-circuit voltage ( VOC), nullifying the effect of band gap reduction. The short-circuit photocurrent enhancement was controlled by the band gap narrowing, screening the SPR contribution. The results presented in this work not only clarify the contribution of SPR absorption in plasmonic DSSCs, but also highlight the importance of considering the corrections in the effective base voltage because of the quasi-Fermi level band shift during the estimation of the transport and recombination parameters of an assembled DSSC.

Elemental-sensitive Detection of the Chemistry in Batteries through Soft X-ray Absorption Spectroscopy and Resonant Inelastic X-ray Scattering.

Energy storage has become more and more a limiting factor of today's sustainable energy applications, including electric vehicles and green electric grid based on volatile solar and wind sources. The pressing demand of developing high-performance electrochemical energy storage solutions, i.e., batteries, relies on both fundamental understanding and practical developments from both the academy and industry. The formidable challenge of developing successful battery technology stems from the different requirements for different energy-storage applications. Energy density, power, stability, safety, and cost parameters all have to be balanced in batteries to meet the requirements of different applications. Therefore, multiple battery technologies based on different materials and mechanisms need to be developed and optimized. Incisive tools that could directly probe the chemical reactions in various battery materials are becoming critical to advance the field beyond its conventional trial-and-error approach. Here, we present detailed protocols for soft X-ray absorption spectroscopy (sXAS), soft X-ray emission spectroscopy (sXES), and resonant inelastic X-ray scattering (RIXS) experiments, which are inherently elemental-sensitive probes of the transition-metal 3d and anion 2p states in battery compounds. We provide the details on the experimental techniques and demonstrations revealing the key chemical states in battery materials through these soft X-ray spectroscopy techniques.

Breathing and oscillating growth of solid-electrolyte-interphase upon electrochemical cycling.

We report the first direct experimental evidence of the dynamic behavior of the solid-electrolyte-interphase (SEI) on copper electrodes upon electrochemical cycling. Synchrotron-based soft X-ray absorption spectroscopy (sXAS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) consistently show that both the chemical composition and the thickness of the SEI change with electrochemical potential throughout the slow formation process. In particular, sXAS results show that the nascent carbonate species in SEI show redox reversibility and decompose during the delithiation (oxidation) process, which leads to a significant shrinking of the SEI thickness as confirmed by TOF-SIMS. Meanwhile, the carbonates also matures and become more and more inactive at every lithiation (reduction) process. These experimental observations reveal unambiguously that SEI formation is much more complicated than a simple and monotonous deposition of electrolyte decomposition product; instead, it could be an oscillating process with a breathing growth.

How Solid-Electrolyte Interphase Forms in Aqueous Electrolytes.

Solid-electrolyte interphase (SEI) is the key component that enables all advanced electrochemical devices, the best representative of which is Li-ion battery (LIB). It kinetically stabilizes electrolytes at potentials far beyond their thermodynamic stability limits, so that cell reactions could proceed reversibly. Its ad hoc chemistry and formation mechanism has been a topic under intensive investigation since the first commercialization of LIB 25 years ago. Traditionally SEI can only be formed in nonaqueous electrolytes. However, recent efforts successfully transplanted this concept into aqueous media, leading to significant expansion in the electrochemical stability window of aqueous electrolytes from 1.23 V to beyond 4.0 V. This not only made it possible to construct a series of high voltage/energy density aqueous LIBs with unprecedented safety, but also brought high flexibility and even "open configurations" that have been hitherto unavailable for any LIB chemistries. While this new class of aqueous electrolytes has been successfully demonstrated to support diversified battery chemistries, the chemistry and formation mechanism of the key component, an aqueous SEI, has remained virtually unknown. In this work, combining various spectroscopic, electrochemical and computational techniques, we rigorously examined this new interphase, and comprehensively characterized its chemical composition, microstructure and stability in battery environment. A dynamic picture obtained reveals how a dense and protective interphase forms on anode surface under competitive decompositions of salt anion, dissolved ambient gases and water molecule. By establishing basic laws governing the successful formation of an aqueous SEI, the in-depth understanding presented in this work will assist the efforts in tailor-designing better interphases that enable more energetic chemistries operating farther away from equilibria in aqueous media.

Modification of Transition-Metal Redox by Interstitial Water in Hexacyanometalate Electrodes for Sodium-Ion Batteries.

A sodium-ion battery (SIB) solution is attractive for grid-scale electrical energy storage. Low-cost hexacyanometalate is a promising electrode material for SIBs because of its easy synthesis and open framework. Most hexacyanometalate-based SIBs work with aqueous electrolyte, and interstitial water in the material has been found to strongly affect the electrochemical profile, but the mechanism remains elusive. Here we provide a comparative study of the transition-metal redox in hexacyanometalate electrodes with and without interstitial water based on soft X-ray absorption spectroscopy and theoretical calculations. We found distinct transition-metal redox sequences in hydrated and anhydrated NaxMnFe(CN)6·zH2O. The Fe and Mn redox in hydrated electrodes are separated and are at different potentials, leading to two voltage plateaus. On the contrary, mixed Fe and Mn redox in the same potential range is found in the anhydrated system. This work reveals for the first time how transition-metal redox in batteries is strongly affected by interstitial molecules that are seemingly spectators. The results suggest a fundamental mechanism based on three competing factors that determine the transition-metal redox potentials. Because most hexacyanometalate electrodes contain water, this work directly reveals the mechanism of how interstitial molecules could define the electrochemical profile, especially for electrodes based on transition-metal redox with well-defined spin states.

Role of Superexchange Interaction on Tuning of Ni/Li Disordering in Layered Li(NixMnyCoz)O2.

Ni/Li exchange (disordering) usually happens in layered Li(NixMnyCoz)O2 (NMC) materials and affects the performance of the material in lithium-ion batteries. Most of previous studies attributed this phenomenon to the similar size of Ni2+ and Li+, which implies that Ni2+ should be more favorable than Ni3+ to be located at Li 3b sites in the Li slab. However, this theory cannot explain why in Ni-rich NMC materials where most Ni cations are Ni3+, Ni/Li exchange happens even more frequently. Using extensive ab initio calculations combined with experiments, here we report that a superexchange interaction between transition metals plays a dominating role in tuning the Ni/Li disordering in NMC materials. Under this scheme, we also propose a new charge compensation mechanism that describes that after Ni3+/Li exchange the nearest Co3+ transforms to Co4+ in Ni-rich NMC materials. On the basis of this theory, the existence of Co4+ in the initial Ni-rich NMC samples was predicted for the first time, which was further confirmed by our synchrotron-based soft X-ray absorption spectroscopy.