High-voltage Batteries Research Articles

High-Voltage Single-Ion Covalent Organic Framework Electrolytes Enabled by Nitrile Migration Ladders for Lithium Metal Batteries.

The poor electrochemical stability window and low ionic conductivity in solid-state electrolytes hinder the development of safe, high-voltage, and energy-dense lithium metal batteries. Herein, taking advantage of the unique electronic effect of nitrile groups, we designed a novel azanide-based single-ion covalent organic framework (CN-iCOF) structure that possesses effective Li+ transport and high-voltage stability in lithium metal batteries. Density functional theory (DFT) calculations and molecular dynamics (MD) revealed that electron-withdrawing nitrile groups not only resulted in an ultralow HOMO energy orbital but also enhanced Li+ dissociation through charge delocalization, leading to a high tLi+ of 0.93 and remarkable oxidative stability up to 5.6 V (vs. Li+/Li) simultaneously. Moreover, cyanation leveraging Strecker reaction transformed reversible imine-linkage to a stable sp3-carbon-containing azanide anion, which facilitated contorted alignment of transport "ladders" along the one-dimensional anionic channels and the ionic conductivity could reach 1.33×10-5 S cm-1 at ambient temperature without any additives. As a result, CN-iCOF allowed operation of solid-state lithium metal batteries with high-voltage cathodes such as LiNi0.8Mn0.1Co0.1O2 (NCM811), demonstrating stable lithium deposition up to 1,100 h and reversible battery cycling at ambient temperature up to 4.5 V, shedding light on the importance of discovering new functionality for forthcoming high-performance batteries.

Issues of ensuring the resistance of high-voltage solar arrays of spacecraft to the effects of secondary arc discharges

We have considered the issues of ensuring the resistance of high-voltage solar battery (SB) of spacecraft to the effects of secondary arc discharges. Research in this area has been going on for more than 50 years, but the answer to all the questions has not yet been found. First of all, this is due to the complexity of the electrophysical processes occurring on the surface of the spacecraft in space and in laboratory conditions. The second reason is the random nature of secondary vacuum arc discharges, which requires the use of special test methods to confirm the effectiveness and reliability of selected design and technological solutions. Tests in conditions close to full-scale conditions do not allow us to solve this problem. We have given a retrospective review of publications on the physical features of secondary arcs arising on SB of spacecraft, the mechanisms of their initiation, experimental research and testing methods. We paid considerable attention to the issues of the occurrence of secondary arc discharges SB of the spacecraft in the conditions of ionospheric plasma and plasma generated by electric propulsion thrusters. We have shown that despite the large amount of accumulated data and knowledge, the transition from low-voltage SB to high-voltage SB remains a difficult scientific and technical problem, which requires additional research to solve. In addition, it is already necessary to start training personnel who possess a wide range of knowledge and are able to work on this topic. To do this, it seems advisable to organize sectoral research, as well as the allocation of targeted funds for the training of highly qualified specialists and their independent research. This approach will make it possible to solve the problem of creating high-voltage SB in the shortest possible time and prepare personnel for the development of this technology.

Open-framework indium hexacyanoferrate for high-voltage and coaxially-fibrous aqueous K//Zn battery

The design of eco-friendly fibrous aqueous rechargeable Zn-based batteries is important for the advancement of flexible electronics. But it is still remains extremely difficult to develop high-voltage fibrous Zn-based batteries on a single-fiber architecture that directly influence their energy density. Furthermore, the sluggish Zn2+ diffusion kinetics and tough electrostatic interaction seriously astrict to further move ahead for the Zn-based batteries. Herein, we demonstrate a high-voltage coaxially-fibrous aqueous rechargeable (CFAR) K//Zn battery based on open-framework indium hexacyanoferrate (InHCF) cathode. The resultant assembled CFAR K//Zn battery provides an eminent voltage of 1.70 V and a superhigh energy density of 197.88 mWh cm-3 at 170.4 mW cm-3. More importantly, our assembled CFAR K//Zn battery exhibits excellent mechanical steadiness with the capacity retention of 92.7 % by following bending at 90° for 4000 times. Therefore, the design of the new-style architecture in high-voltage CFAR K//Zn batteries provides a fresh strategy for economic, reliable, and high-energy-density wearable energy-storage devices.

Anchored Weakly-Solvated Electrolytes for High-Voltage and Low-Temperature Lithium-ion Batteries.

Electrolytes endowed with high oxidation/reduction interfacial stability, fast Li-ion desolvation process and decent ionic conductivity over wide temperature region are known critical for low temperature and fast-charging performance of energy-dense batteries, yet these characteristics are rarely satisfied simultaneously. Here, we report anchored weakly-solvated electrolytes (AWSEs), that are designed by extending the chain length of polyoxymethylene ether electrolyte solvent, can achieve the above merits at moderate salt concentrations. The -O-CH2-O- segment in solvent enables the weak four-membered ring Li+ coordination structure and the increased number of segments can anchor the solvent by Li+ without largely sacrificing the ionic dissociation ability. Therefore, the single salt/single solvent AWSEs enable solvent co-intercalation-free behavior towards graphite (Gr) anode and high oxidation stability towards high-nickel cathode (LiNi0.8Co0.1Mn0.1O2-NCM811), as well as the formation of inorganic rich electrode/electrolyte interphase on both of them due to the anion-rich solvation shells. The capacity retention of Gr||NCM811 Ah-class pouch cell can reach 70.85 % for 1000 cycles at room-temperature and 75.86 % for 400 cycles at -20 °C. This work points out a promising path toward the molecular design of electrolyte solvents for high-energy/power battery systems that are adaptive for extreme conditions.

Boosting High-Voltage Practical Lithium Metal Batteries with Tailored Additives

HighlightsFGN-182 electrolytes exhibit highly reversible Li plating/stripping with an average Coulombic efficiency reaching up to 99.56% determined from Auerbach’s test.The gas-evolution process of LiNO3 in high-voltage lithium cobalt oxide (LCO) cathodes is revealed by in situ differential electrochemical mass spectrometry.Pouch cells equipped with high-loading LCO (3 mAh cm−2) cathodes, ultrathin Li chips (25 μm), and lean electrolytes (5 g Ah−1) using optimized electrolyte (FGN-182 + 1%HTCN) demonstrate outstanding cycling performance.

Acetonitrile-Based Local High-Concentration Electrolytes for Advanced Lithium Metal Batteries.

Acetonitrile (AN) is a compelling electrolyte solvent for high-voltage and fast-charging batteries, but its reductive instability makes it incompatible with lithium metal anodes (LMAs). Herein, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) is used as the diluent to build an AN-based local high-concentration electrolyte (LHCE) to realize dense, dendrite-free, and stable LMAs. Such LHCE exhibits an exceptional electrochemical stability window close to 6V (vs Li+/Li), excellent wettability, and promising flame retardancy. Compared to a baseline carbonate-based electrolyte, its electrochemical performance is prominent: the overpotential of lithium nucleation is minimal (only 24mV), the average half-cell coulombic efficiency (CE) reaches 99.5% at 0.5mAcm-2, and its practicality in full cells with LiFePO4 (LFP) and LiNi0.8Co0.1Mn0.1O2 (NCM811) cathodes is also demonstrated. Compounding factors are identified to decipher the superiority of the AN-based LHCE. From the respect of solvation structures, both the elimination of free AN molecule and the diluent separation would contribute to prevention of anodic AN decomposition. Based on cryogenic electron microscopy (Cryo-EM) characterization and theoretical simulations results, the produced solid-electrolyte interphase (SEI) layer is uniform and compact. Thus, this work demonstrates a successful application of AN-based electrolytes in LMAs-traditionally deemed impractical-via the combined regulation of solvation and SEI structures.

High-voltage and dendrite-free zinc-iodine flow battery

Zn-I2 flow batteries, with a standard voltage of 1.29 V based on the redox potential gap between the Zn2+-negolyte (−0.76 vs. SHE) and I2-posolyte (0.53 vs. SHE), are gaining attention for their safety, sustainability, and environmental-friendliness. However, the significant growth of Zn dendrites and the formation of dead Zn generally prevent them from being cycled at high current density (>80 mA cm−2). In addition, the crossover of Zn2+ across cation-exchange-membrane also limits their cycle stability. Herein, we propose a chelated Zn(P2O7)26- (donated as Zn(PPi)26-) negolyte, which facilitates dendrite-free Zn plating and effectively prevents Zn2+ crossover. Remarkably, the utilization of chelated Zn(PPi)26- as a negolyte shifts the Zn2+/Zn plating/stripping potential to −1.08 V (vs. SHE), increasing cell voltage to 1.61 V. Such high voltage Zn-I2 flow battery shows a promising stability over 250 cycles at a high current density of 200 mA cm−2, and a high power density up to 606.5 mW cm−2.

Regulating the Solvation Structure in Polymer Electrolytes for High-Voltage Lithium Metal Batteries.

Solid polymer electrolytes are promising electrolytes for safe and high-energy-density lithium metal batteries. However, traditional ether-based polymer electrolytes are limited by their low lithium-ion conductivity and narrow electrochemical window because of the well-defined and intimated Li+-oxygen binding topologies in the solvation structure. Herein, we proposed a new strategy to reduce the Li+-polymer interaction and strengthen the anion-polymer interaction by combining strong Li+-O (ether) interactions, weak Li+-O (ester) interactions with steric hindrance in polymer electrolytes. In this way, a polymer electrolyte with a high lithium ion transference number (0.80) and anion-rich solvation structure is obtained. This polymer electrolyte possesses a wide electrochemical window (5.5 V versus Li/Li+) and compatibility with both Li metal anode and high-voltage NCM cathode. Li||LiNi0.5Co0.2Mn0.3O2 full cells with middle-high active material areal loading (~7.5 mg cm-2) can stably cycle at 4.5 V. This work provides new insight into the design of polymer electrolytes for high-energy-density lithium metal batteries through the regulation of ion-dipole interactions.

Recycled micro-sized silicon anode for high-voltage lithium-ion batteries

Recycled micro-sized silicon anode for high-voltage lithium-ion batteries

Maleic Anhydride and (Ethoxy)pentafluorocyclotriphosphazene as Electrolyte Additives for High-Voltage LiCoO2/Si-Graphite Lithium-Ion Batteries.

Anhydride additives including maleic anhydride and succinic anhydride are initially selected as additives in the commercial electrolytes for high-voltage lithium-ion batteries with a Si-based anode. The introduction of (ethoxy)pentafluorocyclotriphosphazene as a flame retardant realizes the nonflammability of electrolytes, and the conductivity of electrolytes exceeds 10 mS cm-1 at 25 °C. Maleic anhydride and (ethoxy)pentafluorocyclotriphosphazene jointly contribute to the exceptional performances of 4.45 V LiCoO2/Si-graphite pouch cells at 25 °C. The capacity retention at 1C of 300 cycles reaches 78%, and the discharge capacity ratio of 6C/1C is approximately 83%. These results suggest that this nonflammable electrolyte has good application prospect. Scanning electron microscopy and X-ray photoelectron spectroscopy measurements are implemented to analyze the interface properties of electrodes.

Molecular-docking electrolytes enable high-voltage lithium battery chemistries.

Ideal rechargeable lithium battery electrolytes should promote the Faradaic reaction near the electrode surface while mitigating undesired side reactions. Yet, conventional electrolytes usually show sluggish kinetics and severe degradation due to their high desolvation energy and poor compatibility. Here we propose an electrolyte design strategy that overcomes the limitations associated with Li salt dissociation in non-coordinating solvents to enable fast, stable Li chemistries. The non-coordinating solvents are activated through favourable hydrogen bond interactions, specifically Fδ--Hδ+ or Hδ+-Oδ-, when blended with fluorinated benzenes or halide alkane compounds. These intermolecular interactions enable a dynamic Li+-solvent coordination process, thereby promoting the fast Li+ reaction kinetics and suppressing electrode side reactions. Utilizing this molecular-docking electrolyte design strategy, we have developed 25 electrolytes that demonstrate high Li plating/stripping Coulombic efficiencies and promising capacity retentions in both full cells and pouch cells. This work supports the use of the molecular-docking solvation mechanism for designing electrolytes with fast Li+ kinetics for high-voltage Li batteries.

Revolutionizing multifunctional electrolyte additive design and synthesis for high-voltage nickel-rich batteries in diverse climates

The high-voltage LiNi0.6Co0.2Mn0.2O2 (NCM622) cathode presents a promising avenue for advancing the energy density of lithium-ion batteries. Nevertheless, current limitations primarily arise from electrolyte systems unable to meet stringent criteria, including stable performance under elevated temperatures and efficient discharge at low temperatures. In this study, we address these challenges by designing a molecular structure incorporating boron oxygen functional groups, phenyl-, and fluorine moieties to simultaneously enhance ion conductivity and thermal stability under extreme voltages. A multifunctional electrolyte additive, 3, 4, 5-trifluorophenylboronic anhydride (TFPBA), has been successfully developed via synthesis. TFPBA plays a pivotal role in promoting the formation of a hierarchical cathode electrolyte interphase (CEI) through its preferential decomposition and oxidation processes. This CEI features a mechanically stable inner layer enriched with fluorophenyl- groups, crucial for high-temperature cycling, alongside an outer layer concentrated with BxOyFz complexes that significantly improve Li+ conductivity, ensuring superior performance under low-temperature conditions and at elevated rates. Moreover, TFPBA acts as an HF scavenger within the electrolyte, mitigating corrosive effects on the cathode surface, thereby curtailing CEI reformation and the transition metal dissolution. The Li/NCM622 half cells with TFPBA exhibit impressive capacity retention rates of 92.58%, 80.09%, and 81.77% after extensive cycling at temperatures of −20 °C, 25 °C, and 55 °C, respectively. Moreover, NCM622/graphite full cells with TFPBA achieve a remarkable capacity retention of 97.97% after 150 cycles at room temperature. Our findings highlight the exceptional electrochemical performance of NCM622 cathodes at elevated voltages across a wide temperature range, providing valuable insights for the development of advanced electrolytes in high-demand applications.

Synergistic Effects of Bisalt Additives in High-Voltage Rechargeable Lithium Batteries.

The stability of high-energy-density lithium metal batteries (LMBs) heavily relies on the composition of the solid electrolyte interphase (SEI) formed on lithium metal anodes. In this study, the inorganic-rich SEI layer was achieved by incorporating bisalts additives into carbonate-based electrolytes. Within this SEI layer, the presence of LiF, polythionate, and Li3N was observed, generated by combining 1.0 м lithium bis(trifluoromethanesulfonyl)imide in ethylene carbonate: ethyl methyl carbonate:dimethyl carbonate in a 1 : 1 : 1 volume ratio, with the addition of 2 wt% lithium difluorophosphate and 2 wt% lithium difluoro(oxalato)borate additives (EL-DO). Furthermore, this formulation effectively mitigated corrosion of aluminum current collectors. EL-DO exhibited outstanding performance, including an average coulombic efficiency of 98.2 % in Li||Cu cells and a stable discharge capacity of approximately 162 mAh g-1 after 200 cycles in a Li||LiNi0.8Co0.1Mn0.1O2 (NCM811) configuration. Moreover, EL-DO displayed the potential to enhance the performance not only of LMBs but also of lithium-ion batteries. In the case of Gr||NCM811 cell using EL-DO, it consistently maintained high discharge capacities, even achieving around 135 mAh g-1 after the 100th cycle, surpassing the performance of other electrolytes. This study underscores the synergistic impact of bisalts additives in elevating the performance of lithium batteries.

Double-network gel electrolyte with high electrolyte retention for flexible high-voltage Zn-air batteries

The zinc-air battery (ZAB) exhibits promising potential for application in wearable devices due to its high energy density, low cost, and safety features. However, the semi-open structure of ZAB accelerates the evaporation of battery electrolytes and poses a potential risk of leakage. Herein, a novel polyacrylamide-co-sodium p-benzenesulfonate and carboxymethyl cellulose (PAS-CMC) double-network gel electrolyte was synthesized and utilized in a flexible ZAB. The prepared PAS-CMC exhibits exceptional electrical conductivity (315.53 mS cm−1), mechanical properties, as well as electrolyte retention capacity. The ZAB assembled by alkaline PAS-CMC exhibits remarkable stability during circulation for over 120 h. Compared with the traditional alkaline PAS-CMC electrolyte, the open-circuit voltage (2.03 V), operating voltage (1.90 V) and power density (164.3 mW cm−2) of the ZAB assembled by the acid-alkaline PAS-CMC prepared by the “sandwich” strategy have been significantly improved, showing excellent flexibility under various bending conditions without any degradation in performance. Furthermore, the interaction mechanisms between PAS-CMC/H2O and PAS-CMC/Zn were further elucidated by DFT calculation, thereby establishing a theoretical foundation for high-voltage flexible ZAB.

High-voltage aqueous zinc-ion batteries with conversion-type anode and modified electrolyte.

High-voltage aqueous zinc-ion batteries with conversion-type anode and modified electrolyte.

Enhanced electrochemical performance of a cost-effective Sm2O3-coated spinel LiNi0.5Mn1.5O4 cathode for high-voltage lithium-ion batteries

Spinel LiNi0.5Mn1.5O4 (LNMO) has gained significant attention as a promising cathode material for lithium-ion batteries due to its high working voltage (>4.7 V) and energy density. However, challenges such as electrolyte decomposition-induced material interface erosion and transition metal dissolution under high operating voltage hinder its commercial use. In this study, a thin and uniform Sm2O3 layer has been successfully deposited on the surface of LNMO using a wet chemical method. A comprehensive investigation of surface morphology, crystal structure, and electrochemical performance of the modified LNMO is conducted. The results demonstrate that the Sm2O3 surface modification acts as a robust multifunctional protective layer, effectively shielding against hydrofluoric acid-induced chemical attack and enhancing the migration efficiency of lithium ions. Notably, the capacity retention rate of LNMO@Sm2O3 (3 wt%) remains up to 88 % after 280 cycles, significantly surpassing the uncoated counterpart. The coated material exhibits a capacity of 114 mAh g−1 even under 10 C rate conditions. Moreover, the AC impedance values and manganese dissolution of the modified material in the organic electrolyte are considerably lower than those of the uncoated counterpart. Theoretical calculations strongly support the experimental findings, revealing higher Mn vacancy formation energy and density of states at the Fermi energy level for the Sm2O3-modified electrodes. This research contributes to the field of surface modification and paves the way for further enhancements in the electrochemical performance of other high-voltage manganese-based lithium-ion batteries (LIBs).

High-Concentrated Binary-Salt Ether Electrolytes for High-Voltage Lithium Metal Batteries with Ni-Rich Cathode.

The incompatibility of ether electrolytes with a cathode dramatically limits its application in high-voltage Li metal batteries. Herein, we report a new highly concentrated binary salt ether-based electrolyte (HCBE, 1.25 M LiTFSI + 2.5 M LiFSI in DME) that enables stable cycling of high-voltage lithium metal batteries with the Ni-rich (NCM83, LiNi0.83Co0.12Mn0.05O2) cathode. Experimental characterizations and density functional theory (DFT) calculations reveal the special solvation structure in HCBE. A solvation structure rich in aggregates (AGGs) can effectively broaden the electrochemical window of the ether electrolyte. The anions in HCBE preferentially decompose under high voltage, forming a CEI film rich in inorganic components to protect the electrolyte from degradation. Thus, the high-energy-density Li||NCM83 cell has a capacity retention of ≈95% after 150 cycles. Significantly, the cells in HCBE have a high and stable average Coulombic efficiency of over 99.9%, much larger than that of 1 M LiPF6 + EC + EMC + DMC (99%). The result emphasizes that the anionic-driven formation of a cathode electrolyte interface (CEI) can reduce the number of interface side reactions and effectively protect the cathode. Furthermore, the Coulombic efficiency of Li||Cu using the HCBE is 98.5%, underscoring the advantages of using ether-based electrolytes. This work offers novel insights and approaches for the design of high-performance electrolytes for lithium metal batteries.

H-Transfer Mediated Self-Enhanced Interphase for High-Voltage Lithium-Ion Batteries

H-Transfer Mediated Self-Enhanced Interphase for High-Voltage Lithium-Ion Batteries

Ion-dipole regulation based on bidentate solvent for stabilizing high-voltage lithium metal batteries

The poor compatibility of ester electrolytes with lithium metal anode severely limits its use in high voltage lithium metal batteries (LMBs). In this work, a bidentate solvent 1,2-diethoxyethane (DEE) is introduced into ester electrolyte to regulate the ion-dipole interactions to enhance the solubility of LiNO3, which enables compatibility with Li anode and maintains the high voltage cathode stability. In the designed electrolyte, the steric effect of DEE facilitates the participation of NO3– and PF6− anions in the Li+ solvation structure, thus promoting the generation of inorganic-rich solid electrolyte interphase (SEI). And the low viscosity of DEE also ensures that the ester electrolyte poses good interfacial wettability. As a result, our designed electrolyte enables the high-loading Li||NCM622 and Li||NCM811 (∼3 mA h cm−2) full cells to achieve stable cycling over 200 cycles, 8 times longer than that of a conventional ester electrolyte. This work suggests that regulation of intermolecular interactions in conventional ester electrolytes is a scalable and effective approach to achieve excellent electrochemical performance of LMBs.

Electronic structure and delithiation mechanism of vanadium and nickel doped Li2MnPO4F cathode material for lithium-ion batteries

This study calculates the energy band structure and density of states of Lithium manganese fluorophosphate (Li2MnPO4F, a lithium transition metal phosphate compounds) using the first-principles plane-wave pseudopotential approach within the density-functional theory. The model of Li2M0.5Mn0.5PO4F (M = V, Ni) with transition metal doped Mn sites is constructed by using the CASTEP module. The calculation findings indicate that the transition metal doping can regulate the energy band structure of the intrinsic system, and Li2MnPO4F makes the band gap decrease, and the volume increase with the Li ions of being deintercalated, and the electrons can be readily stimulated from the valence band to the conduction band. The findings indicate that Li2MnPO4F is a favorable cathode material for high-voltage lithium ion batteries (LIBs). The introduction of vanadium (V) and nickel (Ni) doping reduces the band gap, facilitating an easier excitation of electrons from the valence band to the conduction band. This study provides a theoretical study of new cathode materials for high performance LIBs.