Cathode Electrolyte Interphase Research Articles

Boron- and calcium-interspersed cathode-electrolyte interphases on Ni-rich layered oxide cathodes for advanced performance lithium-ion batteries

Although Ni-rich layered oxides (Ni-rich NCM) have become the preferred cathode materials in the electric vehicle market, their unsustainable cycling behavior arising from the extremely high reactivity at the interface has become a formidable challenge. To alleviate this problem, we propose modifying the cathode-electrolyte interphase (CEI) of Ni-rich L-NCM cathodes by incorporating B/Ca functional groups. Dual-functionalized CEI layers are prepared by heating boric acid (H3BO3) and calcium oxide (CaO) in a one-step process. Islands of B- and Ca-functionalized CEI layer are observed at the Ni-rich L-NCM cathode, and the thickness is controlled to approximately 2.4 nm. The B-functional group not only lowers the concentration of residual lithium but also compensates for the longer Li+ migration distance by providing a desirable pathway based on ion-hopping sites. The Ca functional groups increase the mechanical rigidity of the Ni-rich L-NCM cathode, which inhibits the appearance of microcracks. In terms of its cycling behavior, the capacity retention of the cell with the B/Ca-incorporated Ni-rich L-NCM cathode improves markedly (72.4%), whereas the bare Ni-rich L-NCM material only retains 44.3% of its capacity after 100 cycles.

Long‐Life High‐Voltage Sodium‐Ion Batteries Enabled by Electrolytes with Cooperative Na+‐Solvation

AbstractStabilizing the electrode interphases is urgently required to enhance the lifetime of high‐voltage sodium‐ion batteries (SIBs). However, the continuous anode solid–electrolyte interphase (SEI) growth associated with electron leakage and the fragile cathode–electrolyte interphase (CEI) lead to capacity fade at high voltage; and yet the solvation‐interphase‐performance relationship is inadequately addressed. Herein, a cooperative Na+‐solvation strategy is reported to stabilize the interphases by a holistic design of electrolytes combining soft and moderate co‐solvents. The rationally regulated Na+‐solvation leads to CEI/SEI with the desired thickness and component stability. As such, remarkable cycling stability is achieved for 4.3‐V Na3V2O2(PO4)2F (NVOPF) cathodes with 83.3% capacity retention over 3000 cycles at 1 C, significantly outperforming the carbonate counterpart (41.6% capacity retention). Meanwhile, the restrained SEI growth via reducing the formation of electron‐leaking Na2CO3 stabilizes the long‐term cycling of the hard carbon (HC) anode. The assembled NVOPF||HC full cells achieve superior rate capability (up to 15 C) and stable cycling stability over 500 cycles. The demonstrated engineering of electrolyte chemistry, Na+‐solvation, and interphase structure/component contributes toward the rational establishment of design rules for high‐voltage SIBs and possibly other similar chemistries.

Low‐Strain and High‐Energy KVPO4F Cathode with Multifunctional Stabilizer for Advanced Potassium‐Ion Batteries

KVPO4F with excellent structural stability and high operating voltage has been identified as a promising cathode for potassium‐ion batteries (PIBs), but limits in sluggish ion transport and severe volume change cause insufficient potassium storage capability. Here, a high‐energy and low‐strain KVPO4F composite cathode assisted by multifunctional K2C4O4 electrode stabilizer is exquisitely designed. Systematical electrochemical investigations demonstrate that this composite cathode can deliver a remarkable energy density up to 530 Wh kg−1 with 142.7 mAh g−1 of reversible capacity at 25 mA g−1, outstanding rate capability of 70.6 mAh g−1 at 1000 mA g−1, and decent cycling stability. Furthermore, slight volume change (~5%) and increased interfacial stability with thin and even cathode–electrolyte interphase can be observed through in situ and ex situ characterizations, which are attributed to the synergistic effect from in situ potassium compensation and carbon deposition through self‐sacrificing K2C4O4 additive. Moreover, potassium‐ion full cells manifest significant improvement in energy density and cycling stability. This work demonstrates a positive impact of K2C4O4 additive on the comprehensive electrochemical enhancement, especially the activation of high‐voltage plateau capacity and provides an efficient strategy to enlighten the design of other high‐voltage cathodes for advanced high‐energy batteries.

Double additive electrolyte solvation engineering to achieve long cycle and high capacity sodium-ion battery

Sodium-ion batteries are a promising energy storage system due to their rich sodium resources and many other advantages. However, its development is severely hampered by the electrolyte's low compatibility with the electrode contact. Herein, we propose a solvation control strategy with ethoxy (pentafluoro) cyclotriphosphazene (PFPN) and NaClO4 double additives to reconstruct the solvation structure of sodium ions in electrolytes. This enables the electrolyte to form a dense and stable solid electrolyte interlayer (SEI) and double-layer cathode electrolyte interphase (CEI) on the surface of the electrode material to achieve long-cycle and high-capacity sodium-ion batteries. PFPN can form a stable SEI rich in inorganic components at the anode interface. ClO4- can first reach the cathode surface to create a NaCl and polymer-like chain CEI with sodium ions and solvents, and then the PFPN derivatives are migrated to the cathode surface to open the ring and decompose, thus forming a double-layer stable CEI. Therefore, the PEDN electrolyte can simultaneously improve the interface stability of the battery's cathode and anode solid electrolyte. Hence, the capacity retention rate of the 4.5 Ah Na3Fe2(PO4)P2O7 (NFP)||hard carbon (HC) pouch cell after 2500 cycles at 1C is 88.26%.

Multifunctional Additive Enables a "5H" PEO Solid Electrolyte for High-Performance Lithium Metal Batteries.

The solid-state battery with a lithium metal anode is a promising candidate for next-generation batteries with improved energy density and safety. However, the current polymer electrolytes still cannot fulfill the demands of solid-state batteries. In this work, we propose a "5H" poly(ethylene oxide) (PEO) electrolyte via introducing a multifunctional additive of tris(pentafluorophenyl)borane (TPFPB) for high-performance lithium metal batteries. The addition of TPFPB improves the ionic conductivity from 6.08 × 10-5 to 1.54 × 10-4 S cm-1 via reducing the crystallinity of the PEO electrolyte and enhances the lithium-ion transference number from 0.19 to 0.53 via anion trapping due to its Lewis acid nature. Furthermore, the fluorine and boron segments from TPFPB can optimize the composition of the solid-electrolyte interphase and cathode-electrolyte interphase, providing a high electrochemical stability window over 4.6 V of the PEO electrolyte along with significantly improved interface stability. At last, TPFPB can ensure improved safety through a self-extinguishing effect. As a result, the "5H" electrolyte enables the Li/Li symmetric cells to achieve a stable cycle over 2200 h at the current density of 0.2 mA cm-2 with a capacity of 0.2 mA h cm-2; the LiFePO4/Li full cells with a high LFP loading of 8 mg cm-2 exhibits decay-free capacity of 140 mA h g-1 (99% capacity retention) after 100 cycles; and the NCM811/Li cells exhibit a high capacity of 160 mA h g-1 after 50 cycles at 0.5 C. This work presents an innovative approach to utilizing a "5H" electrolyte for high-performance solid-state lithium batteries.

LiF/Li3N-Rich Electrode-Electrolyte Interfaces Enabled by Multi-Functional Electrolyte Additive to Achieve High-Performance Li/LiNi0.8Co0.1Mn0.1O2 Batteries.

LiPF6-based carbonate electrolytes have been extensively employed in commercial Li-ion batteries, but they face numerous interfacial stability challenges while applicating in high-energy-density lithium-metal batteries (LMBs). Herein, this work proposes N-succinimidyl trifluoroacetate (NST) as a multifunctional electrolyte additive to address these challenges. NST additive could optimize Li+ solvation structure and eliminate HF/H2O in the electrolyte, and preferentially be decomposed on the Ni-rich cathode (LiNi0.8Co0.1Mn0.1O2, NCM811) to generate LiF/Li3N-rich cathode-electrolyte interphase (CEI) with high conductivity. The synergistic effect reduces the electrolyte decomposition and inhibits the transition metal (TM) dissolution. Meanwhile, NST promotes the creation of solid electrolyte interphase (SEI) rich in inorganics on the Li metal anode (LMA), which restrains the growth of Li dendrites, minimizes parasitic reactions, and fosters rapid Li+ transport. As a result, compared with the reference, the Li/LiNi0.8Co0.1Mn0.1O2 cell with 1.0 wt.% NST exhibits higher capacity retention after 200 cycles at 1C (86.4% vs. 64.8%) and better rate performance, even at 9C. In the presence of NST, the Li/Li symmetrical cell shows a super-stable cyclic performance beyond 500 h at 0.5 mA cm-2/0.5 mAh cm-2. These unique features of NST are a promising solution for addressing the interfacial deterioration issue of high-capacity Ni-rich cathodes paired with LMA.

Anion-mediated interphase construction enabling high-voltage solid-state lithium metal batteries

Enhancing the interphase stability of polymer electrolytes with high-voltage cathodes is crucial for the development of high-energy-density lithium metal batteries (LMBs), especially in wearable devices area. Herein, lithium difluorophosphate (LiDFP) is incorporated into the solid polymer electrolyte of poly(ethylene oxide) (PEO) to enhance the formation of a robust cathode-electrolyte interphase (CEI) in high-voltage LiCoO2 LMBs. Through combining electrochemical measurements, spectroscopic techniques and theoretical calculations, the underlying modification mechanism is revealed. Due to its stronger anionic coordination with both polymer electrolyte chain and proton, and more oxidation-active resultant anion-coordinated polymer compared with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiDFP suppresses the formation of the strong acid HTFSI deriving from the deprotonated process of the terminal O-H group thus avoiding the further oxidative attack to the polymeric framework. Furthermore, under the synergetic decomposition of HDFP intermediate, the polymer-derived radical helps to reconstruct a chemo-mechanically stable and Li-conductive CEI layer, which consists of abundant LiF/Li3PO4/LixPOyFz inorganic species distributed in lithiated organic macromolecules. The in-situ constructed CEI effectively passivates catalytic sites on LiCoO2 directly against PEO, resulting in well-maintained layered structure during high-voltage cycling. The proposed interphasial chemistry that regulates CEI formation provides directive knowledge of electrolyte optimization for high-voltage solid-state batteries.

Tailoring Solvation Solvent in Localized High-Concentration Electrolytes for Lithium||Sulfurized Polyacrylonitrile.

Sulfurized polyacrylonitrile (SPAN) is a promising cathode material for lithium-sulfur (Li-S) batteries due to its significantly reduced polysulfide (PS) dissolution compared to that of elemental S cathodes. Although conventional carbonate-based electrolytes are stable with SPAN electrodes, they are unstable with Li metal anodes. Recently, localized high-concentration electrolytes (LHCEs) have been developed to improve the stability of Li anodes. Here, we report a new strategy to further improve the performance of Li||SPAN batteries by replacing the conventional solvating solvent 1,2-dimethoxyethane (DME) in LHCEs with a new solvating solvent, 1,2-diethoxyethane (DEE). The new optimal DEE-LHCE exhibits less reactivity against Li2S2, alleviates PS dissolution, forms a better cathode-electrolyte interphase layer on the SPAN cathode, and enhances SPAN structural reversibility even at elevated temperatures (45 °C). Compared to DME-LHCE, DEE-LHCE with the same salt and diluent leads to better performance in Li||SPAN batteries (with 82.9% capacity retention after 300 cycles at 45 °C), preservation of the SPAN cathode structure, and suppression of volume change of the Li metal anode. A similar strategy on tailoring the solvating solvents in LHCEs can also be used in other rechargeable batteries to improve their electrochemical performances.

Development of the ReaxFF Reactive Force Field for Li/Mn/O Battery Technology with Application to Design a Self-Healing Cathode Electrolyte Interphase

Development of the ReaxFF Reactive Force Field for Li/Mn/O Battery Technology with Application to Design a Self-Healing Cathode Electrolyte Interphase

Concerted Effect of Ion- and Electron-Conductive Additives on the Electrochemical and Thermal Performances of the LiNi0.8Co0.1Mn0.1O2 Cathode Material Synthesized by a Taylor-Flow Reactor for Lithium-Ion Batteries.

To address the issue that a single coating agent cannot simultaneously enhance Li+-ion transport and electronic conductivity of Ni-rich cathode materials with surface modification, in the present study, we first successfully synthesized a LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode material by a Taylor-flow reactor followed by surface coating with Li-BTJ and dispersion of vapor-grown carbon fibers treated with polydopamine (PDA-VGCF) filler in the composite slurry. The Li-BTJ hybrid oligomer coating can suppress side reactions and enhance ionic conductivity, and the PDA-VGCFs filler can increase electronic conductivity. As a result of the synergistic effect of the dual conducting agents, the cells based on the modified NCM811 electrodes deliver superior cycling stability and rate capability, as compared to the bare NCM811 electrode. The CR2032 coin-type cells with the NCM811@Li-BTJ + PDA-VGCF electrode retain a discharge specific capacity of ∼92.2% at 1C after 200 cycles between 2.8 and 4.3 V (vs Li/Li+), while bare NCM811 retains only 84.0%. Moreover, the NCM811@Li-BTJ + PDA-VGCF electrode-based cells reduced the total heat (Qt) by ca. 7.0% at 35 °C over the bare electrode. Remarkably, the Li-BTJ hybrid oligomer coating on the surface of the NCM811 active particles acts as an artificial cathode electrolyte interphase (ACEI) layer, mitigating irreversible surface phase transformation of the layered NCM811 cathode and facilitating Li+ ion transport. Meanwhile, the fiber-shaped PDA-VGCF filler significantly reduced microcrack propagation during cycling and promoted the electronic conductance of the NCM811-based electrode. Generally, enlightened with the current experimental findings, the concerted ion and electron conductive agents significantly enhanced the Ni-rich cathode-based cell performance, which is a promising strategy to apply to other Ni-rich cathode materials for lithium-ion batteries.

Self-repaired cathode electrolyte interphase to stabilize the high-nickel cathode interface by a sustained-release multifunctional electrolyte additive

Increasing the nickel content in high-nickel LiNixCoyMn1-x-yO2 cathode materials (NCM) can boost their energy density. However, the consequence of rising Ni content in NCM consists in the heightened stress buildup, intensified irreversible phase transition and severe electrolyte decomposition, and consequently accelerating the battery’s degradation. In the current study, we have revealed that the 4-fluoro-N, N dimethylbenzenesulfonamide (FBSN) as an electrolyte additive can refrain the typical dehydrogenation of EC. Furthermore, a continuously repaired cathode electrolyte interphase (CEI) is designed elaborately on LiNi0.9Co0.05Mn0.05O2 (NCM90) surface by employing the FBSN as a sustained-release electrolyte additive to enhance cycling stability of NCM90||Li cells. This CEI, composed of high mechanical strength LiF and benzene ring skeleton, along with conductive Li+ moieties (S-rich and N-rich species), can be effectively self-repaired in time when damaged, reduce the interaction between the NCM90 and sensitive electrolyte, and mitigate the devastation to the NCM90 cathode surface. As a result, the NCM90||Li cells with 2 % FBSN-containing electrolyte delivers a capacity retention of 90.2 % after 200 cycles at 1C, and 83.1 % after 200 cycles even at higher voltage of 4.5 V, superior than that of Base electrolyte (70.0 % at 4.3 V and 68.0 % at 4.5 V). This study provides an engaging approach to design electrolytes for high-nickel cathodes by autonomously interfacial repair.

Reconstructing Inorganic‐Rich Interphases by Nonflammable Electrolytes for High‐Voltage and Low‐Temperature LiNi0.5Mn1.5O4 Cathodes

AbstractCobalt‐free and spinel LiNi0.5Mn1.5O4 (LNMO) cathodes commonly suffer from undesirable solvent decomposition, serious transition‐metal dissolution, and unstable cathode electrolyte interphase (CEI) layers, incurring rapid capacity decay at high voltages and low temperatures. Herein, these issues are well addressed by utilizing fluorinated solvents with a low coordination number and ethyl propionate with a low melting point. A Li2CO3/LiF‐rich heterostructured CEI layer, which possesses good electron blocking capability of LiF, fast Li+ transport kinetics of Li2CO3 and good mechanical stability, is generated by the synergistic decomposition of hybrid solvents. The robust, homogeneous, and well‐balanced CEI layers subsequently prevent catalyzed parasitic side reactions, prohibit transition‐metal dissolution, and ensure fast interfacial reaction kinetics crossover to the LNMO cathode, thus improving its cycling stability. Consequently, the LNMO cathode delivers a high‐capacity retention of 95.8% over 500 cycles at 25 °C and 97.5% after 180 cycles at −20 °C. This work provides an encouraging alternative to design the high‐voltage and low‐temperature electrolyte for pushing the ongoing research to stabilize Co‐free LNMO materials toward practical applications.

Stabilizing Interfacial Behaviors of Ni‐rich Cathodes by Upcycling of Oyster Shells Waste

AbstractLayered lithium oxides (LNCM), with over 60% Ni, are promising cathode materials for electric vehicles due to their high capacity. however, reliable cycling retention cannot easily achieved owing to the instability of the interface. Here, recycled oyster shell (OS) is employed as an efficient precursor for the surface modification of LNCM cathodes; subsequently, Ca‐based artificial cathode–electrolyte interphases (CEI) are obtained at the LNCM interfaces through a simple calcination process. When the pulverized OS is calcined with LNCM cathode materials at elevated temperatures, CaCO3 is converted to CaO via thermal decomposition at the LNCM interface, which effectively protects the unstable interface. Microscopic analyses indicate the nanodomain island‐type CEI layers embedded after OS calcination. The OS‐coated LNCM cathode materials increase the cycling retention after 100 cycles (93.8% vs. 62.7%) and decrease the internal cell pressure by preventing electrolyte decomposition. Incorporating Ca into the LNCM cathode materials also inhibits microcrack formation because of the improvement in particle hardness and the remarkable decrease in the irreversible dissolution of transition metals from LNCM cathodes, considering that Ca plays a crucial role in scavenging fluoride species. Consequently, recycling OS as a functional LNCM precursor is an innovative approach for enhanced cycling retention.

Enhanced performance of lithium metal batteries via cyclic fluorinated ether based electrolytes

To address the challenges associated with applying high-voltage cathodes in lithium metal batteries (LMBs) there is a need for new electrolytes enabling stable interphases at both electrodes. Here we attack this by using a dioxolane-derived cyclic fluorinated ether, 2,2-bis(trifluoromethyl)-1,3-dioxolane (BTFD), as a fluorinated diluent to a 1,2-dimethoxyethane (DME) based electrolyte. The cells using the resulting BTFD-based electrolytes exhibit higher Coulombic efficiencies for lithium stripping and plating as compared to those using the non-fluorinated ether-based electrolyte. This originates from the reduced formation of ‘dead Li’ at the anode, as shown by using electrochemical impedance spectroscopy (EIS). In practice, the BTFD-based electrolytes are shown to improve the performance of Li||NMC cells, which is due to the formation of a predominantly inorganic cathode electrolyte interphase (CEI) that suppresses the cathode degradation during cycling. We used X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM) to characterize the CEIs’ overall composition and structure. To obtain more details on the CEI speciation, Raman and nuclear magnetic resonance (NMR) spectroscopies were employed, assisted by molecular level computations. Overall, we demonstrate how the very design of the electrolyte composition influences the performance of LMBs.

Reconstruction of solvation structure at the cathode-electrolyte interface via partial de-solvation in a metal-organic framework

The formation of cathode-electrolyte interphase (CEI) is closely related to the solvation structure in direct contact with the cathode. The de-solvated solvent molecules are subject to the attack of highly catalytic transition metal ions in the cathode materials (such as Ni-rich LiNi0.8Co0.1Mn0.1O2, Ni-rich NCM), especially at high voltage or high temperature, leading to the poor CEI structure that accelerates the deterioration of rechargeable batteries. Considerable strategies have been proposed to solve this issue. Herein, we have constructed a porous Mg-MOF buffer layer on the surface of Ni-rich NCM, which not only greatly reduces the contact between solvent molecules and cathodes to alleviate the extensive interface reactions, but also promote the de-solvation of Li+ solvation structure through strong affinity between solvents and Mg2+. The partially de-solvated structure induces the anion to participate in the solvation structure and contributes to the formation of a uniform LiF-rich CEI with superior mechanical integrity and chemical stability. Therefore, the NCM with Mg-MOF buffer layer exhibits improved cycling stability at both elevated temperature of 45 °C and high voltage of 4.5 V with lithium as anode. Moreover, the modified NCM/graphite full cells also deliver ultra-stable rechargeable capability with a remarkable capacity retention of 87.3% over 1000 cycles as compared to the only 21.7% of pristine NCM based cells.

Hybrid ion/electron interfacial regulation stabilizes the cobalt/oxygen redox of ultrahigh-voltage lithium cobalt oxide for fast-charging cyclability

High-voltage and fast-charging LiCoO2 (LCO) is key to high-energy/power-density Li-ion batteries. However, unstable surface structure and unfavorable electronic/ionic conductivity severely hinder its high-voltage fast-charging cyclability. Here, we construct a Li/Na-B-Mg-Si-O-F-rich mixed ion/electron interface network on the 4.65 V LCO electrode to enhance its rate capability and long-term cycling stability. Specifically, the resulting artificial hybrid conductive network enhances the reversible conversion of Co3+/4+/O2−/n− redox by the interfacial ion–electron cooperation and suppresses interface side reactions, inducing an ultrathin yet compact cathode electrolyte interphase. Simultaneously, the derived near-surface Na+/Mg2+/Si4+-pillared local intercalation structure greatly promotes the Li+ diffusion around the 4.55 V phase transition and stabilizes the cathode interface. Finally, excellent 3 C (1 C = 274 mA g−1) fast charging performance is demonstrated with 73.8% capacity retention over 1000 cycles. Our findings shed new insights to the fundamental mechanism of interfacial ion/electron synergy in stabilizing and enhancing fast-charging cathode materials.

A Highly-Fluorinated Lithium Borate Main Salt Empowering Stable Lithium Metal Batteries.

Traditional lithium salts are difficult to meet practical application demand of lithium metal batteries (LMBs) under high voltages and temperatures. LiPF6, as the most commonly used lithium salt, still suffers from notorious moisture sensitivity and inferior thermal stability under those conditions. Here, we synthesize a lithium salt of lithium perfluoropinacolatoborate (LiFPB) comprising highly-fluorinated and borate functional groups to address the above issues. It is demonstrated that the LiFPB shows superior thermal and electrochemical stability without any HF generation under high temperatures and voltages. In addition, the LiFPB can form a protective outer-organic and inner-inorganic rich cathode electrolyte interphase on LiCoO2 (LCO) surface. Simultaneously, the FPB- anions tend to integrate into lithium ion solvation structure to form a favorable fast-ion conductive LiBxOy based solid electrolyte interphase on lithium (Li) anode. All these fantastic features of LiFPB endow LCO (1.9 mAh cm-2)/Li metal cells excellent cycling under both high voltages and temperatures (e.g., 80 % capacity retention after 260 cycles at 60 °C and 4.45 V), and even at an extremely elevated temperature of 100 °C. This work emphasizes the important role of salt anions in determining the electrochemical performance of LMBs at both high temperature and voltage conditions.

A Highly‐Fluorinated Lithium Borate Main Salt Empowering Stable Lithium Metal Batteries

AbstractTraditional lithium salts are difficult to meet practical application demand of lithium metal batteries (LMBs) under high voltages and temperatures. LiPF6, as the most commonly used lithium salt, still suffers from notorious moisture sensitivity and inferior thermal stability under those conditions. Here, we synthesize a lithium salt of lithium perfluoropinacolatoborate (LiFPB) comprising highly‐fluorinated and borate functional groups to address the above issues. It is demonstrated that the LiFPB shows superior thermal and electrochemical stability without any HF generation under high temperatures and voltages. In addition, the LiFPB can form a protective outer‐organic and inner‐inorganic rich cathode electrolyte interphase on LiCoO2 (LCO) surface. Simultaneously, the FPB− anions tend to integrate into lithium ion solvation structure to form a favorable fast‐ion conductive LiBxOy based solid electrolyte interphase on lithium (Li) anode. All these fantastic features of LiFPB endow LCO (1.9 mAh cm−2)/Li metal cells excellent cycling under both high voltages and temperatures (e.g., 80 % capacity retention after 260 cycles at 60 °C and 4.45 V), and even at an extremely elevated temperature of 100 °C. This work emphasizes the important role of salt anions in determining the electrochemical performance of LMBs at both high temperature and voltage conditions.

Bismuth-doping boosting Na+ diffusion kinetics of layered oxide cathode with radially oriented {010} active lattice facet for sodium-ion batteries.

O3-type layered oxide cathodes (NaxTMO2) for sodium-ion batteries (SIBs) have attracted significant attention as one of the most promising potential candidates for practical energy storage applications. The poor Na+ diffusion kinetics is, however, one of the major obstacles to advancing large-scale practical application. Herein, we report bismuth-doped O3-NaNi0.5Mn0.5O2 (NMB) microspheres consisting of unique primary nanoplatelets with the radially oriented {010} active lattice facets. The NMB combines the advantages of the oriented and exposed electrochemical active planes for direct paths of Na+ diffusion, and the thick primary nanoplatelets for less surface parasitic reactions with the electrolyte. Consequently, the NMB cathode exhibits a long-term stability with an excellent capacity retention of 72.5% at 1C after 300 cycles and an enhanced rate capability at a 0.1C to 10C rate (1C = 240 mA g-1). Furthermore, the enhancement is elucidated by the small volume change, thin cathode-electrolyte-interphase (CEI) layer, and rapid Na+ diffusion kinetics. In particular, the radial orientation-based Bi-doping strategy is demonstrated to be effective at boosting electrochemical performance in other layered oxides (such as Bi-doped NaNi0.45Mn0.45Ti0.1O2 and NaNi1/3Fe1/3Mn1/3O2). The results provide a promising strategy of utilizing the advantages of the oriented active facets of primary platelets and secondary particles to develop high-rate layered oxide cathodes for SIBs.

Role of Salt Concentration in Stabilizing Charged Ni-Rich Cathode Interfaces in Li-Ion Batteries.

The cathode-electrolyte interphase (CEI) in Li-ion batteries plays a key role in suppressing undesired side reactions while facilitating Li-ion transport. Ni-rich layered cathode materials offer improved energy densities, but their high interfacial reactivities can negatively impact the cycle life and rate performance. Here we investigate the role of electrolyte salt concentration, specifically LiPF6 (0.5-5 m), in altering the interfacial reactivity of charged LiN0.8Mn0.1Co0.1O2 (NMC811) cathodes in standard carbonate-based electrolytes (EC/EMC vol %/vol % 3:7). Extended potential holds of NMC811/Li4Ti5O12 (LTO) cells reveal that the parasitic electrolyte oxidation currents observed are strongly dependent on the electrolyte salt concentration. X-ray photoelectron and absorption spectroscopy (XPS/XAS) reveal that a thicker LixPOyFz-/LiF-rich CEI is formed in the higher concentration electrolytes. This suppresses reactions with solvent molecules resulting in a thinner, or less-dense, reduced surface layer (RSL) with lower charge transfer resistance and lower oxidation currents at high potentials. The thicker CEI also limits access of acidic species to the RSL suppressing transition-metal dissolution into the electrolyte, as confirmed by nuclear magnetic resonance (NMR) spectroscopy and inductively coupled plasma optical emission spectroscopy (ICP-OES). This provides insight into the main degradation processes occurring at Ni-rich cathode interfaces in contact with carbonate-based electrolytes and how electrolyte formulation can help to mitigate these.