Armor‐like Inorganic‐rich Cathode Electrolyte Interphase Enabled by the Pentafluorophenylboronic Acid Additive for High‐voltage Li||NCM622 Batteries

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(22)

Published: March 17, 2023

Lithium metal batteries (LMBs) comprising Li anode and high-voltage nickel-rich cathode could potentially realize high capacity power density. However, suitable electrolytes to tolerate the oxidation on at cut-off voltage are urgently needed. Herein, we present an armor-like inorganic-rich electrolyte interphase (CEI) strategy for exploring oxidation-resistant sustaining 4.8 V Li||LiNi0.6 Co0.2 Mn0.2 O2 (NCM622) with pentafluorophenylboronic acid (PFPBA) as additive. In such CEI, armored lithium borate surrounded by CEI up-layer represses dissolution of inner moieties also improves Li+ conductivity while abundant LiF is distributed over whole enhance mechanical stability compared polymer moieties. With robust conductive Li||NCM622 battery delivered excellent 4.6 91.2 % retention after 400 cycles. The cycling performance was obtained even voltage.

Language: Английский

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Amide‐Functional, Li₃N/LiF‐Rich Heterostructured Electrode Electrolyte Interphases for 4.6 V Li||LiCoO₂ Batteries

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(15)

Published: March 4, 2023

Abstract Enhancing the charge cut‐off voltage of LiCoO 2 at 4.6 V can improve battery density, however, structural instability is a critical challenge (e.g., electrolyte decomposition, Co dissolution, and phase transition). Here, robust electrode interphases (EEIs) with high Li + conductivity offered by polar amide groups 3 N/LiF heterostructure constructed. 3‐(trifluoromethyl) phenyl isocyanate (3‐TPIC) rationally designed as an additive for sustaining Li||LiCoO such CEI, which effectively address instability. The group achieve de‐solvation increase transport. in cathode interphase (CEI) speed up insertion/extraction improving Coulombic efficiency weakening polarization V. In addition, solid (SEI) similar structure on anode surface contributes to uniform deposition suppressing dendrite growth. As expected, batteries superior EEIs deliver excellent electrochemical performance.

Language: Английский

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Multifunctional Additives to Realize Dendrite‐Free Lithium Deposition in Carbonate Electrolytes toward Low‐Temperature Li Metal Batteries

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(27)

Published: April 25, 2024

Abstract Li metal is recognized as one of the most promising anode candidates for next‐generation high specific energy batteries. However, fragile solid electrolyte interface (SEI) and heterogeneous plating/stripping in carbonate severely encumber its practical application. Here, heptafluorobutyramide (HFT) lithium nitrate (LiNO 3 ) are proposed to synergistically construct a robust SEI layer with excellent + transport kinetics. The HFT can promote dissolution LiNO due strong cooperation. results theoretical calculations, situ Raman X‐ray photoelectron spectroscopy deep Ar‐ion etching demonstrate that NO − will be preferentially reduced N/LiF‐rich composite structure on surface metal. Particularly, after addition additives, first solvent shell converted from solvent‐dominated anion‐dominated structure, thus significantly lower Li‐ion desolvation barrier presented. Consequently, Coulombic efficiency (CE) Li||Cu half cells using designed reach 97.1%. full matched LiFePO 4 LiNi 0.8 Co 0.1 Mn O 2 (NCM 811) deliver high‐capacity retention over 100% at −20°C. This work provides an effective strategy regulation solvation construction high‐performance

Language: Английский

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Transesterification Induced Multifunctional Additives Enable High‐Performance Lithium Metal Batteries

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)

Published: March 11, 2024

Abstract The electrolyte chemistry is crucially important for promoting the practical application of lithium metal batteries (LMBs). Here, we demonstrate first time that 1,3‐dimethylimidazolium dimethyl phosphate (DIDP) and trimethylsilyl trifluoroacetate (TMSF) can undergo in situ transesterification carbonate to generate (DTMSP) (DITFA) as multifunctional additives LMBs. H 2 O HF be removed by Si−O group DTMSP improve moisture resistance stability cathode. Furthermore, dissolution nitrate (LiNO 3 ) promoted anion (TFA − DITFA, thereby optimizing solvation structure transport kinetics Li + . More importantly, both DITFA tend preferential redox decomposition due low lowest unoccupied molecular orbital (LUMO) high highest occupied (HOMO). Consequently, a thin robust layer rich P/N/Si on cathode an inorganic‐rich (e.g. N/Li P) anode constructed superior electrochemical performances are achieved. This artificial strategy introduce favorable paves efficient ingenious route high‐performance

Language: Английский

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Constructing Matching Cathode–Anode Interphases with Improved Chemo-mechanical Stability for High-Energy Batteries

ACS Nano, Journal Year: 2024, Volume and Issue: 18(8), P. 6600 - 6611

Published: Feb. 14, 2024

Coupling Ni-rich layered oxide cathodes with Si-based anodes is one of the most promising strategies to realize high-energy-density Li-ion batteries. However, unstable interfaces on both cathode and anode sides cause continuous parasitic reactions, resulting in structural degradation capacity fading full cells. Herein, lithium tetrafluoro(oxalato) phosphate synthesized applied as a multifunctional electrolyte additive mitigate irreversible volume swing SiOx suppress undesirable interfacial evolution LiNi0.83Co0.12Mn0.05O2 (NCM) simultaneously, improved cycle life. Benefiting from its desirable redox thermodynamics kinetics, molecularly tailored facilitates matching interphases consisting LiF, Li3PO4, P-containing macromolecular polymer NCM anode, respectively, modulating chemo-mechanical stability well charge transfer kinetics. More encouragingly, proposed strategy enables 4.4 V 21700 cylindrical batteries (5 Ah) excellent cycling (92.9% retention after 300 cycles) under practical conditions. The key finding points out fresh perspective optimization for battery systems.

Language: Английский

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Lithium Superionic Conductive Nanofiber-Reinforcing High-Performance Polymer Electrolytes for Solid-State Batteries

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(17), P. 11897 - 11905

Published: March 28, 2024

Although composite solid-state electrolytes (CSEs) are considered promising ionic conductors for high-energy lithium metal batteries, their unsatisfactory conductivity, low mechanical strength, poor thermal stability, and narrow voltage window limit practical applications. We have prepared a new superionic conductor (Li-HA-F) with an ultralong nanofiber structure ultrahigh room-temperature conductivity (12.6 mS cm–1). When it is directly coupled typical poly(ethylene oxide)-based solid electrolyte, the Li-HA-F nanofibers endow resulting CSE high (4.0 × 10–4 S cm–1 at 30 °C), large Li+ transference number (0.66), wide (5.2 V). Detailed experiments theoretical calculations reveal that supplies continuous dual-conductive pathways results in stable LiF-rich interfaces, leading to its excellent performance. Moreover, nanofiber-reinforced exhibits good heat/flame resistance flexibility, breaking strength (9.66 MPa). As result, Li/Li half cells fabricated exhibit stability over 2000 h critical current density of 1.4 mA cm–2. Furthermore, LiFePO4/Li-HA-F CSE/Li LiNi0.8Co0.1Mn0.1O2/Li-HA-F batteries deliver reversible capacities temperature range cycling

Language: Английский

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Application of a cost-effective boron-based electrolyte additive in high-voltage lithium metal battery

Journal of Energy Storage, Journal Year: 2025, Volume and Issue: 112, P. 115596 - 115596

Published: Jan. 30, 2025

Language: Английский

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Interfacially-localized high-concentration electrolytes for high-performance rechargeable aqueous lithium-ion batteries

EES batteries., Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Interfacially-localized high-concentration electrolytes were developed using an anionic surfactant and a magnesium( ii ) salt to achieve selective Li ion transport, high electrochemical stability superior SEI formation in aqueous electrolytes.

Language: Английский

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Stable Non‐flammable Phosphate Electrolyte for Lithium Metal Batteries via Solvation Regulation by the Additive

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(30)

Published: April 26, 2023

Abstract The application of lithium metal batteries (LMBs) is impeded by safety concerns. Employing non‐flammable electrolytes can improve battery reliability while the cost and performance deterioration limit their popularization. Herein, a high‐performance electrolyte designed, 1.5 m LiTFSI in propylene carbonate (PC)/triethyl phosphate (TEP) (4:1 vol.) with 4‐nitrophenyl trifluoroacetate (TFANP) as additive, which facilitate construction LiF‐rich solid interphase (SEI) on Li anode surface cathode (CEI) through its prioritized decomposition. In TFANP‐containing electrolyte, decreased TEP coordination number solvation sheath relieves adverse effect active both SEI CEI for suppressing growth dendrites reducing continuous consumption. Thus, Li||LiNi 0.6 Co 0.2 Mn O 2 such an deliver 132 mAh g −1 after 150 cycles high coulombic efficiency (99.5%) superior rate (110 at 5 C, 1 C = 200 mA ). This work provides new additive insight reliable LMBs.

Language: Английский

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Conductive Li⁺ Moieties‐Rich Cathode Electrolyte Interphase with Electrolyte Additive for 4.6 V Well‐Cycled Li||LiCoO₂ Batteries

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(20)

Published: April 7, 2023

Abstract Increasing the cut‐off voltage of cathodes can improve energy density Li||LiCoO 2 batteries. However, electrolyte and cathode suffer from oxidation deterioration at high voltage, respectively, which lead to rapid battery degradation. Herein, a uniform, highly Li + conductive interphase (CEI) is constructed by using bis‐(benzenesulfonyl)imide (BBSI) as an additive stabilize batteries 4.6 with superior cycling high‐rate performance. Such CEI comprised LiF moieties (e.g., S 3 N), migration, alleviate degradation, other secondary degradation factors caused uneven local intercalation/deintercalation. As expected, 1% BBSI‐containing sustain 81.30% initial capacity after 300 cycles 0.5C, 88.27% even 500 2C/3C.

Language: Английский

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