High Cut-off Voltage Research Articles

Regulating Non-Equilibrium Solvation Structure in Locally Concentrated Ionic Liquid Electrolytes for Wide-Temperature and High-Voltage Lithium Metal Batteries.

The development of high-voltage lithium metal batteries (LMBs) encounters significant challenges due to aggressive electrode chemistry. Recently, locally concentrated ionic liquid electrolytes (LCILEs) have garnered attention for their exceptional stability with both Li anodes and high-voltage cathodes. However, there remains a limited understanding of how diluents in LCILEs affect the thermodynamic stability of the solvation structure and transportation dynamics of Li+ ions. Herein, we propose a wide-temperature LCILEs with 1,3-dichloropropane (DCP13) diluent to construct a non-equilibrium solvation structure under external electric field, wherein the DCP13 diluent enters the Li+ ion solvation sheath to enhance Li+ ion transport and suppress oxidative side reactions at high-nickel cathode (LiNi0.9Co0.05Mn0.05O2, NCM90). Consequently, a Li/NCM90 cell utilizing this LCILE achieves a high capacity retention of 94 % after 240 cycles at 4.3 V, also operates stably at high cut-off voltages from 4.4 V to 4.6 V and over a wide temperature range from -20 °C to 60 °C. Additionally, an Ah-level pouch cell with this LCILE simultaneously achieves high-energy-density and stable cycling, manifesting the practical feasibility. This work redefines the role of diluents in LCILEs, providing inspiration for electrolyte design in developing high-energy-density batteries.

Surface Engineering via Rare Earth Oxide Composite Coating to Enhance the High-Voltage Stability of the LiCoO2 Cathode.

The commercial application of high-voltage LiCoO2 (LCO) faces significant challenges due to rapid capacity decay, primarily attributed to an unstable interface and structure at deeply delithiated states. Herein, a unique rare earth oxide composite coating comprising La2O3, Y2O3, and LaYO3 has been prepared to stabilize LCO at high voltage. The synergistic effect between these rare earth oxides significantly reinforces the protective capabilities of the coating, effectively enhancing the interfacial/structural stability of LCO. When tested at 4.6 V, the coated LCO exhibits an excellent capacity retention of 94.4% after 300 cycles at 1 C. Even after an ultralong charge/discharge test of 700 cycles at 2 C, the coated LCO retains 85.2% of its initial specific capacity, which significantly outperforms the uncoated LCO (6.3%). Moreover, the coated LCO shows enhanced cycling performance at a high temperature of 45 °C, owing to the outstanding thermal stability of the La-Y-O composite. Additionally, the superior cycling stability of the coated LCO at 4.7 V, compared to the uncoated LCO, demonstrated the promising potential of the La-Y-O composite coating in improving electrochemical performance of LCO at higher cutoff voltages. These findings highlight an efficacious strategy to enhance the interfacial/structural stability of high-voltage LCO using rare earth oxides.

Reversible silicon anodes enabled by fluorinated inorganic-organic hybrid coating

Silicon anodes deliver batteries with energy densities much higher than those based on today’s dominant graphite anodes. However, they commonly exhibit huge volume variations and unfavorable interface stability, causing a gradually diminishing capacity on extended cycling. Most Si-based batteries consisting Si/C composites in industry can only use a very limited amount of Si (<30 % by weight). Exploiting molecular layer deposition (MLD) technique, a fluorine-rich flexible inorganic–organic hybrid alucone (AlFHQ) shell is controllably deposited onto Si electrodes. Employing ex situ XPS and AFM, the AlFHQ film presents reversible electrochemical evolutions in terms of composition and morphology. The interactions the between Li+ and −O−2,3,5,6-fluorobenzene functional groups help to construct a mechanically-chemically robust LiF-rich hybrid solid electrolyte interphase (SEI) on Si anode, delivering enhanced interfacial stability and integrity of electrode. An optimized coating thickness (≈5 nm) for interfacial stabilization and Li+ transport kinetics is demonstrated, namely, Si@AlFHQ-20. The reported fluorine-rich hybrid modification technique endows (a), stable cycling of Si anode (≈3.8 mAh cm−2) with an ultrahigh initial Coulombic efficiency (ICE) of 92.3 %; (b), enhanced rate capability of 1468 mAh/g at 2.0 A g−1 and good cycling performance; and (c), overall cell (Si@AlFHQ-20//LiCoO2@Al2O3) operational stability for more than 100 cycles under stringent cathode conditions (2.68 mAh cm−2, high cutoff voltage at 4.55 V).

Sb-anchoring single-crystal engineering enables ultra-high-Ni layered oxides with high-voltage tolerance and long-cycle stability

Ni-rich layered oxides are promising cathodes for Li-ion batteries, but the inherent structural defects result in severe surface/bulk degradation during long cycling, especially at high cutoff voltage. Herein we propose a Sb-anchoring single-crystalline engineering to enhance the microstructural and electrochemical stability of ultra-high-Ni layered oxides, where the surface-enriched Sb doping inhibits Li-Ni mixing, suppressing the undesired layered to mixed/rock-salt phase transformation; the bulk-doped Sb rivets into Ni sites, reinforcing the bulk phase stability; the single-crystal endows enhanced crack resistance and reduced surface area, preventing surface parasitic reactions and the subsequent proliferation of cathode electrolyte interfaces. In-situ XRD reveals an essential correlation between cycle stability and phase reversibility, whereas Sb doping into both surface and bulk structures showcases a continuous anchoring effect, largely enhancing the phase transformation reversibility. DFT calculations prove a high oxidation tolerance, as Ni2+ diffusion barrier is higher than the pure cathode. A representative Li(Ni0.9Co0.05Mn0.05)0.99Sb0.01O2 cathode exhibits a high-voltage up to 4.6V, and a Li(Ni0.9Co0.05Mn0.05)0.99Sb0.01O2//graphite full-cell demonstrates an ultra-high capacity retention of 93.4% after 1000 cycles at 1C in 3.0−4.2V. This simple and efficient cathode engineering will promote the promising application of Ni-rich layered oxides in high-energy Li-ion batteries.

Study on the impact of cutoff voltage on structural and electrochemical stability of sodium-ion layered cathodes

NaNi1/3Fe1/3Mn1/3O2 is recognized for its relatively high theoretical specific capacity and operating voltage, rendering it a sodium-ion cathode material with significant commercial potential. A higher cutoff voltage typically enables more sodium ion deintercalation, thereby achieving higher capacity. However, this increased deintercalation can introduce challenges such as structural instability and side reactions with the electrolyte, leading to electrochemical performance degradation. This study focuses on the migration process of transition metal ions under conditions of high charging cutoff voltage and high sodium removal. At a voltage of 4.3 V, the migration of Ni ions facilitates more charge compensation but is accompanied by irreversible Ni migration, inducing an irreversible phase transition to the O’ phase. Conversely, at a cutoff voltage of 4.1 V, the P3 and O3 phases with high sodium removal demonstrate excellent cycling stability. The specific capacities before and after 150 cycles (at 0.5C) are 142.3 and 113.7 mAh/g, respectively, indicating a tolerable internal structural stress within these high sodium removal phases. This contrasts with the differentiated internal structural stresses generated by the P3, O3, and O’ phases during phase transitions at a cutoff voltage of 4.3 V. The research underscores the importance of regulating reversible crystal phases within the tolerance range of internal stress and avoiding irreversible crystal phases to enhance the cycling stability of cathode materials. These findings provide crucial insights for optimizing NNFMO cathode materials and hold significant implications for the design of high-performance, long-life sodium-ion batteries.

Near-surface reconstruction strategy stabilizing high-voltage redox reactions in single crystal Li-rich Mn-based oxides

Li-rich Mn-based oxides (LRMO) greatly increase its output energy density due to its additional oxygen redox activity. However, the inherent oxygen loss and irreversible phase transition induce low initial coulombic efficiency and serious voltage decay, further seriously impeding its industrial application. Herein, a near-surface in-situ reconstruction strategy has been proposed, which constructs the oxygen vacancies and spinel phase coating on the surface of single-crystal Li-rich Mn-based oxide (SC-LRMO) concurrently to improve Li+ storage performance via the oxalic acid induction method. Intensive exploration based on structure characterizations demonstrates that such a near-surface in-situ reconstruction strategy not only accelerates the transmission of Li+, but also stabilizes high-voltage redox reactions by trapping the escaping On− within the newly formed spinel phase coating. Impressively, the modified sample exhibit 91.1% capacity retention ratio after 300 cycles, superior to the SC-LRMO (74.5% capacity retention ratio after 300 cycles). Additionally, even at a high cut-off voltage of 5 V, the acid etched sample exhibits significantly enhanced cycling stability, delivering 200 mAh g−1 with a 94% capacity retention ratio after 300 cycles. This surface self-reconstruction strategy provides profound insights into regulating the surface structure of LRMO for high-energy-density lithium-ion batteries.

Regulating interfacial reactions via quasi-solid polymer electrolyte to enable high-voltage lithium metal batteries

Sulfolane (SUL), known for its low cost, environmental friendliness, and high voltage tolerance, stands out as a promising polar solvent for lithium (Li) metal batteries with high energy density. However, its long-term stability with Li metal is compromised due to its inherently low reduction resistance. To address this issue, we introduce a novel electrolyte strategy, where the reactive SUL is encapsulated within a fluorinated polymer framework formed through in-situ thermal polymerization. The polymer network’s specific structure interacts with SUL, effectively mitigating its electrochemical degradation on the Li metal anode and the NCM811 cathode, thus enhancing electrode stability. This approach not only extends the Li+ plating/stripping reversibility for over 1,000 h at a current density of 0.3 mA cm−2, but also delivers outstanding performance in NCM811||Li batteries, achieving a capacity retention of 78.56 % after 1,000 cycles at 30 °C and 87.14 % after 100 cycles at 60 °C under a high cutoff voltage of 4.5 V.

Durable high voltage solid-state sodium batteries with Pseudocapacitive P2 layered oxide cathode

Solid-state sodium batteries (SSBs) have attracted great interests due to their high energy density, good safety and low cost, but their performance including operation voltage, cycling stability and rate capability are far from satisfactory. In this study, a P2-Na0.68Li0.10Ni0.25Mn0.63Ca0.01Ti0.01O2 (NM-L10CT) layered cathode material were successfully fabricated, which possesses a high pseudocapacitance over 92 %, low volume strain of 0.8 %, high Na-ion diffusion coefficient and very good reversibility of anionic redox reaction. Moreover, room temperature solid-state sodium batteries with NM-L10CT and Na3Zr2Si2PO12 (NZSP) solid electrolyte are demonstrated, displaying much improved structural stability and cycling performance compared with that in liquid electrolyte batteries. The NM-L10CT/NZSP/Na SSBs exhibit very excellent electrochemical performance under high cut-off voltage, with high retention rates of 81.2 % after 500 cycles (2.0–4.2 V) and 74.2 % after 300 cycles (2.0–4.3 V), respectively. It has an outstanding rate performance with a high capacity of 115.4 mAh g-1 at 1 C and 74.5 mAh g-1 even at 10 C rate. This is due to the significantly reduced interface resistance and improved structural stability in solid state. This work demonstrates the successful application of high voltage layered cathode in SSBs and provides the insightful understanding of such material in liquid electrolyte and solid state battery.

Chemically Bonded Biphase Coating of Ni-Rich Layered Oxides with Enhanced High-Voltage Tolerance and Long-Cycle Stability.

Stabilizing the crystalline structure and surface chemistry of Ni-rich layered oxides is critical for enhancing their capacity output and cycle life at a high cutoff voltage. Herein, we adopted a simple one-step solid-state method by directly sintering the Ni0.9Co0.1(OH)2 precursor with LiOH and Ta2O5, to simultaneously achieve the bulk material synthesis of LiNi0.9Co0.1O2 and in situ construction of a rock-salt Ta-doped interphase and an amorphous LiTaO3 outer layer, forming a chemically bonded surface biphase coating on LiNi0.9Co0.1O2. Such a cathode architectural design has been demonstrated with superior advantages: (1) eliminating surface residual alkali, (2) strengthening the layered oxygen lattice, (3) suppressing bulk-phase transformation, and (4) facilitating Li-ion transport. The obtained cathode exhibits excellent electrochemical performance, including a high initial reversible capacity of 180.3 mAh g-1 at 1.0 C with 85.5% retention after 300 cycles (2.8-4.35 V) and a high initial reversible capacity of 182.5 mAh g-1 at 0.2 C with 87.6% retention after 100 cycles (2.8-4.5 V). Notably, this facile and scalable electrode engineering makes Ni-rich layered oxides promising for practical applications.

Al Impurity Upcycled High-Voltage Cathodes from Spent LiCoO2 Batteries.

Al impurity is among the most likely components to enter the spent lithium-ion battery (LIB) cathode powder due to the strong adhesion between the cathode material and the Al current collector. However, high-value metal elements tend to be lost during the deep removal of Al impurities to obtain high-purity metal salt products in the conventional hydrometallurgical process. In this work, the harmful Al impurity is designed as a beneficial ingredient to upcycle high-voltage LiCoO2 by incorporating robust Al-O covalent bonds into the bulk of the cathode assisted with Ti modification. Benefiting from the strong Al-O and Ti-O bonds in the bulk, the irreversible phase transitions of the upcycled R-LCO-AT have been significantly suppressed at high voltages, as revealed by in situ XRD. Moreover, a Li+-conductive Li2TiO3 protective layer is constructed on the surface of R-LCO-AT by pinning slow-diffusion Ti on the grain boundaries, resulting in improved Li+ diffusion kinetics and restrained interface side reactions. Consequently, the cycle stability and rate performance of R-LCO-AT were significantly enhanced at a high cutoff voltage of 4.6 V, with a discharge capacity of 189.5 mAhg-1 at 1 C and capacity retention of 92.9% over 100 cycles at 4.6 V. This study utilizes the detrimental impurity element to upcycle high-voltage LCO cathodes through an elaborate bulk/surface structural design, offering a strategy for the high-value utilization of spent LIBs.

Designing Novel Solvents for High Voltage Li-Ion Batteries

The pursuit of higher energy density in lithium-ion batteries has led to the development of new cathode materials that can operate at elevated voltages and provide increased specific capacities. [1-2] One such class of materials is the nickel-rich layered oxide cathodes known as LiNixMnyCozO2 (NMC). These cathodes offer high specific capacities and demonstrate electrochemical stability at high cutoff voltages, making them promising candidates for advanced lithium-ion batteries. [3-4] However, NMC cathodes face a significant challenge in the form of capacity fading during cycling. This issue primarily arises from the voltage instability of the conventional carbonate-based electrolytes used in lithium-ion batteries, which are typically designed for the 4-V lithium-ion chemistry. [5-6] As a result, researchers and scientists have directed extensive efforts toward developing new and improved electrolyte systems that can withstand the high voltage requirements of NMC cathodes and other high-energy applications. [7-8]Designing and synthesizing new molecules for use as electrolyte solvents in lithium-ion batteries is indeed a complex and challenging task. Researchers often focus on optimizing one specific property, which can lead to the development of molecules that excel in that aspect while potentially overlooking other crucial features that are necessary for stable battery cycling. For example, the development of α-fluorinated sulfones as electrolyte solvents was driven by their exceptional anodic stability. [9] This stability is achieved by introducing strong electron-withdrawing trifluoromethyl groups directly attached to the sulfonyl group. However, while this electron-withdrawing effect enhances anodic stability, it can also significantly increase the reduction potential of α-fluorinated sulfones. This heightened reduction potential renders them unstable when used with graphite anodes, highlighting the delicate balance required in designing electrolyte solvents that perform well across various aspects of battery operation.In this presentation, we embraced the concept of a "golden middle way" when designing and synthesizing new electrolyte solvents. The recently developed β-fluorinated sulfone, TFPMS, doesn't claim to be the best in any single property, but it strikes a balance across various key characteristics. This equilibrium has proven to be highly effective in ensuring the long-term stability of high-voltage graphite||NMC622 full cells. Positioned at the β site of the sulfone molecule, the strong electron-withdrawing trifluoromethyl group renders β-fluorinated sulfone sufficiently stable against the high-voltage NMC622 cathode, even if it possesses a slightly lower oxidation potential compared to its α-fluorinated counterparts. Furthermore, its reduction potential is lower than that of α-fluorinated sulfone, making it considerably more stable when paired with the graphite anode. While it may not possess the same high lithium solvating power as the typical sulfone (EMS), the lithium solvating capacity of β-fluorinated sulfone falls somewhere in between, mitigating transition metal dissolution and deposition in the graphite||NMC622 full cell that utilizes a β-fluorinated sulfone-based electrolyte. As a result, the full cell equipped with TFPMS-based electrolyte demonstrates superior cycling performance, with a significantly higher average capacity than cells using regular sulfone or α-fluorinated sulfone-based electrolytes. In summary, our approach exemplifies the successful application of the "golden middle way" in designing and synthesizing new electrolyte solvents.Reference: Santhanam, R.; Rambabu, B., Power Sources 2010, 195, 5442.Lin, F.; Markus, I. M.; Nordlund, D.; Weng, T.-C.; Asta, M. D.; Xin, H. L.; Doeff, M. M., Commun. 2014, 5, 3529.Li, W.; Song, B.; Manthiram, A., Chemical Society Reviews 2017, 46 (10), 3006.Xu, J.; Lin, F.; Doeff, M. M.; Tong, W., Journal of Materials Chemistry A 2017, 5 (3), 874.Xia, J.; Petibon, R.; Xiong, D.; Ma, L.; Dahn, J., Journal of Power Sources 2016, 328, 124.Chen, S.; Wen, K.; Fan, J.; Bando, Y.; Golberg, D., Journal of Materials Chemistry A 2018, 6 (25), 11631.Zheng, J.; Lochala, J. A.; Kwok, A.; Deng, Z. D.; Xiao, J., Advanced Science 2017, 4 (8), 1700032.Yamada, Y.; Wang, J.; Ko, S.; Watanabe, E.; Yamada, A., Nature Energy 2019, 4 (4), 269.Su, C.-C.; He, M.; Redfern, P. C.; Curtiss, L. A.; Shkrob, I. A.; Zhang, Z., Environ. Sci. 2017, 10 (4), 900.

(Invited) Deciphering the Interfacial Chemistry and Degradation Pathway of Layered Cathode Materials

Cathode materials such as layered oxides play a crucial role in determining batteries' energy density and safety. LiNixMnyCozO2 (NMC), as the dominating cathode, has been successfully commercialized for many years. In addition, there is a consensus that integrating NMC cathodes into all-solid-state batteries (ASSBs) is an effective way to achieve high energy densities. However, NMC cathodes are still facing many challenges, particularly, during the perusing of the high Ni concentration and high cut-off voltages. In the presentation, we will discuss the interface degradation of the NMC cathode at multiple length scales. By comprehensive imaging and spectroscopic techniques, we could bridge the degradation phenomenon from the electrode scale to the atomic scale. We will present the challenges of characterizing the surface properties of the cycled layered cathode and summarize our strategies that can enhance the surface stability of NMCs. Our fundamental understanding will inform the design principles at multiple length scales in batteries. Shifting our focus to solid-state batteries (SSBs), there is a growing body of research on SSBs incorporating NMC cathodes and argyrodite solid electrolytes (SEs). However, these advanced ASSBs face significant challenges in terms of low initial Coulombic efficiency and rapid capacity degradation. Therefore, we also try to understand the interfacial degradation mechanisms in composite SE-NMC cathodes in this talk.

Regulations of Bulk and Interfacial Chemistry of Mn-Based Cathode Materials for Sodium Ion Batteries

Sodium ion batteries (SIBs) show the great potential to achieve large-scale energy storage due to their low cost and good safety as well as abundant resources of sodium. Among the cathode materials for SIBs, manganese-based layered oxides with adjustable structure have been attached great interest for the high energy density and low-cost SIBs. . Particularly, P2-type Mn-based materials exhibit anionic redox during charge and discharge processes, which can not only elevate the battery potential but also provide extra capacity, drastically boosting the energy density of the batteries. However, the irreversible phase transition, Jahn-Teller effect of manganese and interphase degradation at high charge cutoff voltage during anionic redox largely affect the cyclic stability of the cathodes. Therefore, it is essential to develop effective strategies to regulate the structural and interfacial chemistry for suppressing the phase transition and voltage hysteresis as well as increasing the cycle life of cathode materials. In this work, various electrochemical inert/active elements have been introduced into Mn-based P2 type cathode materials for regulating the electronic structure of the cathodes to promote more anionic redox and improve the structural stability. In addition, a new type of ionic liquid is introduced to build a stable interphase and improve the high voltage stability of the cathode material. Multi-model synchrotron-based X-ray characterization techniques combined with first-principles calculation are used to reveal the effectiveness of different strategies on the electrochemical properties of SIBs. The results provide valuable information for the development of high-performance cathode materials. Acknowledgement This work at Shanghai Jiao Tong University was financially supported by the National Natural Science Foundation of China (No. 22209106).

Slightly Li-enriched chemistry enabling super stable LiNi0.5Mn0.5O2 cathodes under extreme conditions.

High voltage/high temperature operation aggravates the risk of capacity attenuation and thermal runaway of layered oxide cathodes due to crystal degradation and interfacial instability. A combined strategy of bulk regulation and surface chemistry design is crucial to handle these issues. Here, we present a simultaneous Li2WO4-coated and gradient W-doped 0.98LiNi0.5Mn0.5O2·0.02Li2WO4 cathode through modulating the content of the exotic dopant and stoichiometric lithium salt during lithiation calcination. Benefiting from the slightly Li-enriched chemistry induced by the hetero-epitaxially grown Li2WO4 surface, the 0.98LiNi0.5Mn0.5O2·0.02Li2WO4 cathode demonstrates superior electrochemical performance to W-doped LiNi0.49Mn0.49W0.02O2 and WO3 coated 0.98LiNi0.5Mn0.5O2·0.02WO3 cathodes without a Li-enriched phase. Specifically, when cycled in the potential range of 2.7-4.5 V at 30 °C, the 0.98LiNi0.5Mn0.5O2·0.02Li2WO4 cathode possesses a high discharge capacity of 199.2 and 156.5 mA h g-1 at 0.1 and 5C and a capacity retention of 92.88% after 300 cycles at 1C. Even at a high cut-off voltage of 4.6 V, it still retains a capacity retention of 91.15% after 200 cycles at 1C and 30 °C. Compared with LiNi0.5Mn0.5O2, the enhanced performance of 0.98LiNi0.5Mn0.5O2·0.02Li2WO4 can be attributed to its robust bulk and stable interface, inhibited lattice oxygen release, and improved Li+ transport kinetics. Our work emphasizes the significance of the slightly Li-enriched chemistry and bulk modulation strategy in stabilizing cathodes and hence unlocks vast possibilities for future cathode design.

Interface engineering enabling non-corrosive sulfonimide salt for 4.4 V class lithium batteries

Lithium bis(trifluoromethanesulphonyl)imide (LiTFSI) with outstanding electrochemical and thermal stability has promising applications in electrolytes for lithium batteries. However, a low concentration of the sulfonimide salt electrolyte can corrode a commonly used aluminum (Al) current collector, posing a perennial conundrum that hinders its wide application. In this work, we find that pure H2O as an additive in the 1 M LiTFSI electrolyte effectively protects the Al current collector from corrosion by TFSI−. The interface engineering by specific adsorption of H2O plays a pivotal role in regulating the structure of the electrical double layer on the Al foil surface, blocking the interaction of TFSI− with Al. Meanwhile, hydrogen bonds are verified between H2O and TFSI−, weakening the attack of TFSI− on the Al collector and improving the Li+ conductivity. The mechanism has been confirmed by theoretical calculations and a variety of characterizations. Benefiting from the addition of H2O, the lithium batteries exhibit excellent cycling performance at a high cut-off voltage of 4.4 V even at −20 °C and a 3 Ah pouch full cell shows long cycling performance. The results demonstrate the high compatibility of the H2O-added electrolyte with high voltage cathode, lithium metal and graphite anodes. This work introduces a strategy for the utilization of sulfonimide salt at high voltage and wide temperature even at a low concentration.

Achieving thermodynamic stability of single-crystal ultrahigh-nickel cathodes via an alcohol-assisted mechanical fusion

Elevating the operating voltage is an effective approach to improve the reversible capacity of ultra-high nickel layered oxide cathode LiNixCoyMnzO2 (NCM, x ≥ 0.8) and solve the “range anxiety” confusion of electric vehicles. However, the undesirable surface reconstruction induced by the high cut-off voltage has a fatal impact on the thermodynamic stability of the material, inevitably leading to fast capacity degradation. Herein, a mechanical fusion aided by alcohol is suggested to create a stable olivine structure for the single-crystal (SC) ultrahigh-nickel cathode LiNi0.92Co0.04Mn0.04O2. The addition of nanoparticles effectively bridges the void of SC-NCM, builds an ideal particle grading, and significantly raises the cost efficiency, as well as promotes the cycling stability and safety of the full cell. Remarkably, the layered/olivine mixture forms a perfect shield by lowering the surface area between the NCM cathode and electrolyte, hence mitigating side reactions and contributing to an incredibly thin and stable cathode/electrolyte interface. Furthermore, the thermodynamic stability of highly delithiated NCM is improved, as both the particle cracks and structural degradation are simultaneously postponed. Consequently, the maximum temperature of the single-crystal LiNi0.92Co0.04Mn0.04O2@LiFePO4‖graphite pouch full cell is dramatically reduced from 599.4 to 351.4 °C, and the full cell achieves 88.2% capacity retention after 800 cycles, demonstrating excellent thermal stability and cycling stability. This facile strategy provides a feasible technical reference for further exploiting the ultrahigh-capacity, high-safety, and long-life Ni-rich cathode for commercial application of lithium-ion batteries (LIBs).

Na+ orientates Jahn-Teller effect to tune Li+ diffusion pathway and kinetics for Single-Crystal Ni-rich LiNixCoyMn1-x-yO2 cathode materials

Single-crystallization is an effective strategy for enhancing both capacity and stability of Ni-rich LiNi1-x-yCoxMnyO2 (NCM) cathode materials, especially at high cut-off voltages. However, the kinetics limitation of solid-phase Li+ diffusion is a major concern because of the long diffusion path in large single-crystal particles. To address this issue, we synthesize a Na-doped single-crystal LiNi0.82Co0.125Mn0.055O2 (NCM-Na) cathode material by a facile mixed-molten-salt sintering process. Na+ is revealed to be uniformly doped at the Li+ lattice sites within the entire single-crystal particles. This Na+ doping effectively enhances the dynamics of Li+ transport in the layered oxide phases. The NCM-Na material with 2 at.% Na doping shows a Li+ diffusion coefficient up to more than 8 times higher than pristine NCM. In-situ X-ray diffraction and finite element analysis demonstrate significantly facilitated H1-H2-H3 phase transition in NCM-Na materials, compared with the severe phase separation phenomenon in NCM counterpart, hoisting their rate capacity and structure stability. Thus, the NCM-Na material achieves a superior reversible capacity of 177.7 mAh/g at 5C, and a capacity retention of 94.4 % after 100 cycles at 0.5C at a high cut-off voltage of 4.5 V. By density function theory calculations, we reveal that Na+ doping can selectively stabilize the surrounding Li+ at the second farthest hexagonal vertexes by tuning the orientation of the Jahn-Teller effect of Ni3+. These Li+ ions frame a high-speed pathway for preferential Li+ diffusion, which promotes the Li+ diffusion kinetics even in highly delithiated states. Our findings provide insights into the Na+ doping mechanism and present a low-cost, highly efficient, and scalable method to enhance the performance of single-crystal Ni-rich NCM materials.

Controllable synthesis of carbon supported cobalt monoxide anode and high-voltage lithium cobalt oxide cathode with enhanced lithium-ion storage

Natural macromolecule amylose (AM) is employed to deoxygenate few-layered graphene oxide (GO) and modulate the surface interaction between GO sheets and Co2+ ions under mild hydrothermal conditions. The obtained Co2+ ions and AM molecule jointly decorated reduced graphene oxide (Co-AM/RGO) sample is further utilized to synthesize both anode and cathode materials with controlled microstructures. To synthesize anode material, the Co-AM/RGO can be directly converted to a hierarchical AM pyrolyzed carbon and RGO supported cobalt monoxide nanocomposite (CoO@AMC/RGO) after a simple inert gas protected thermal treatment. To synthesize cathode material, a carbon coated nano-sized lithium cobalt oxide sample (LiCoO2/C, LCO/C) can be obtained after a solid-state reaction in air by mixing lithium salt with the Co-AM/RGO. The CoO and LCO nanocrystals with significantly controlled sizes are well dispersed in the carbon matrices. The CoO@AMC/RGO anode shows a high reversible capacity of 785.25 mAh·g−1 after 500 cycles at 200 mA·g−1 and 608.25 mAh·g−1 after 700 cycles at 1000 mA·g−1, while the LCO/C cathode delivers a superior reversible capacity of 140.91 mAh·g−1 after 1000 cycles at 1000 mA·g−1 with a high cut-off voltage of 4.6 V. This work provides a new perspective for controllable engineering of electrode materials with enhanced lithium-ion storage performances.

Constructing An Oxyhalide Interface for 4.8 V‐Tolerant High‐Nickel Cathodes in All‐Solid‐State Lithium‐Ion Batteries

AbstractAll‐solid‐state lithium batteries (ASSBs) have received increasing attentions as one promising candidate for the next‐generation energy storage devices. Among various solid electrolytes, sulfide‐based ASSBs combined with layered oxide cathodes have emerged due to the high energy density and safety performance, even at high‐voltage conditions. However, the interface compatibility issues remain to be solved at the interface between the oxide cathode and sulfide electrolyte. To circumvent this issue, we propose a simple but effective approach to magic the adverse surface alkali into a uniform oxyhalide coating on LiNi0.8Co0.1Mn0.1O2 (NCM811) via a controllable gas‐solid reaction. Due to the enhancement of the close contact at interface, the ASSBs exhibit improved kinetic performance across a broad temperature range, especially at the freezing point. Besides, owing to the high‐voltage tolerance of the protective layer, ASSBs demonstrate excellent cyclic stability under high cutoff voltages (500 cycles~94.0 % at 4.5 V, 200 cycles~80.4 % at 4.8 V). This work provides insights into using a high voltage stable oxyhalide coating strategy to enhance the development of high energy density ASSBs.

Constructing An Oxyhalide Interface for 4.8 V-Tolerant High-Nickel Cathodes in All-Solid-State Lithium-Ion Batteries.

All-solid-state lithium batteries (ASSBs) have received increasing attentions as one promising candidate for the next-generation energy storage devices. Among various solid electrolytes, sulfide-based ASSBs combined with layered oxide cathodes have emerged due to the high energy density and safety performance, even at high-voltage conditions. However, the interface compatibility issues remain to be solved at the interface between the oxide cathode and sulfide electrolyte. To circumvent this issue, we propose a simple but effective approach to magic the adverse surface alkali into a uniform oxyhalide coating on LiNi0.8Co0.1Mn0.1O2 (NCM811) via a controllable gas-solid reaction. Due to the enhancement of the close contact at interface, the ASSBs exhibit improved kinetic performance across a broad temperature range, especially at the freezing point. Besides, owing to the high-voltage tolerance of the protective layer, ASSBs demonstrate excellent cyclic stability under high cutoff voltages (500 cycles~94.0 % at 4.5 V, 200 cycles~80.4 % at 4.8 V). This work provides insights into using a high voltage stable oxyhalide coating strategy to enhance the development of high energy density ASSBs.