Stable electrode–electrolyte interfaces constructed by fluorine- and nitrogen-donating ionic additives for high-performance lithium metal batteries

Kim, Saehun; Park, Sung O; Lee, Min Young; Lee, Jeong-A; Kristanto, Imanuel; Lee, Tae Kyung; Hwang, Daeyeon; Kim, Ju‐Young; Wi, Tae‐Ung; Lee, Hyun‐Wook; Kwak, Sang Kyu; Choi, Nam‐Soon

doi:10.1016/j.ensm.2021.10.031

Cited by 88 publications

(50 citation statements)

References 79 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Figure 5i exhibits the Ragone plot of the NCM811|MS|PE|Ag 2 S|Li prototype in comparison with previously reported NCM811|Li cell models, all values were calculated based on the mass of electrode material. [ 21,44–50 ] The NCM811|Li cell with MS|PE|Ag 2 S separator shows the highest power output of 2040 W kg −1 with the energy density of 408 Wh kg −1 at 5 C, which surpass the most values of the previously reported NCM811|Li metal batteries. Furthermore, the cycling stability of cell assembled with MS|PE|Ag 2 S separators is also superior to most previously reported metal batteries with other modified separators under lean electrolyte condition (Table S4, Supporting Information).…”

Section: Resultsmentioning

confidence: 91%

Boosting the Temperature Adaptability of Lithium Metal Batteries via a Moisture/Acid‐Purified, Ion‐Diffusion Accelerated Separator

Zhang

Liu

Gan

et al. 2022

Advanced Energy Materials

View full text Add to dashboard Cite

solutions, explorative studies of the electro-redox couples, with the concurrent high retrievable capacity, enlarged nominal voltage gap, and rapid reaction kinetics, hold the key to promote the energy-dense battery construction at the extreme power output. [1] For the lithium ion batteries, the energy densities of traditional formats (LiCoO 2 /LiFePO 4 cathodes and graphite anodes) have approached their theoretical limits. [2] Alternatively, the unit cell prototyping of the high-capacity Li metal anode with the nickel-rich cathode can achieve the enhanced level of energy densities at the device level. [3,4] When soaking this electrode couples in the conventional carbonate-based electrolytes, however, the Fermi-energy incompatibility at the multiscale interface would cause the uncontrollable dendrite growth on the metallic foil and cathode structure collapse upon the high-voltage cycling. [5] Therefore, the reliable operation of the energy-dense battery necessitates the harmony balance of the enlarged voltage gap and the interfacial stability at multiple scales, yet still remains challenging.As the most attractive cathode type of the practical relevance, nickel-rich (Ni content >0.8) layered oxides exhibit the merits of the large specific capacity (>200 mAh g −1 ), environmental benignity and relative lower cost as compared to the LiCoO 2 cathode. Despite of the dominant nickel occupancy in the layered oxides for elevating the Li storage sites, the increased nickel ratio adversely deteriorates the cycle performance. The transition metal (TM) layer of the oxide structure at the highvoltage charged states would oxidize the carbonate solvents in the presence of moisture, leading to serious self-discharge rates upon the high-temperature storage. [6] Additionally, the hydrofluoric acid (HF) formed by the decomposition of the lithium hexafluorophosphate (LiPF 6 ) salt aggravates the TM ions (Co 2+ , Ni 2+ , and Mn 2+ ) dissolution and structural collapse of the layered cathode, meanwhile the TM species would deposit on the anode surface and degrade the solid electrolyte interface (SEI). [7] So far, a plethora of mitigation strategies were implemented to insulate the direct contact of the oxide particles with the electrolyte, for instance the exquisite coatings with The reliable operation of Li metal batteries suffers from cathode collapse due to high-voltage cycling, interfacial reactivity of the Li deposits, self-discharge at the elevated temperatures, as well as the power output deterioration in low-temperature scenarios. In contrast to the individual electrode optimization, herein, a hetero-layered separator with an asymmetric functional coating on polyethylene is proposed in response to the aforementioned issues: On the face-to-cathode side, the hybrid layer of the molecular sieve and sulfonated melamine formaldehyde can scavenge the hydrofluoric acid and moisture residues from the carbonate electrolyte, maintaining the cathode robustness in both the high-voltage cycling or high-temperature storage scenarios; while...

show abstract

Section: Resultsmentioning

confidence: 91%

Boosting the Temperature Adaptability of Lithium Metal Batteries via a Moisture/Acid‐Purified, Ion‐Diffusion Accelerated Separator

Zhang

Liu

Gan

et al. 2022

Advanced Energy Materials

View full text Add to dashboard Cite

show abstract

“…Furthermore, the Young’s modulus of the SEI formed by STD+2% LiDFBOP comes up to a high value of 10.3 GPa, which is five times as great as the value of the STD (Figure c, d). This difference is directly related to the changing composition, where the STD+2% LiDFBOP electrolyte can form a dense SEI film rich in inorganics as well as organics containing P and F atoms by the contributions of DFBOP – , whereas there are abundant organic materials in the SEI established in the STD electrolyte owing to the prior reduction of the ethylene carbonate (Figure e, f) …”

Section: Resultsmentioning

confidence: 99%

Improving Toleration of Volume Expansion of Silicon-Based Anode by Constructing a Flexible Solid-Electrolyte Interface Film via Lithium Difluoro(bisoxalato) Phosphate Electrolyte Additive

Wang

Zhang

et al. 2022

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

The silicon (Si) anode is considered one of the most promising candidates among many novel anode materials in lithium-ion batteries owing to its high theoretical capacity and earth abundancy. Nonetheless, a large volume expansion of Si particles appears with cycling, prompting unceasing breakage/reformation of the solid-electrolyte interface (SEI) and fast capacity degradation in traditional electrolytes. For the purpose of tolerating volume expansion for the Si anode, lithium difluoro(bisoxalato) phosphate (LiDFBOP) was adopted in the standard (STD) electrolyte based on LiPF6. Density functional theory (DFT) calculations, Young’s modulus from atomic force microscopy, potential-resolved in situ electrochemical impedance spectroscopy (PRI-EIS) measurement, and other characterizations proved that the formed SEI can inhibit volume expansion of a Si@Graphite@C anode. In the STD+2% LiDFBOP electrolyte, the solvation structure of Li(EC)2(PF6)1(DFBOP)1 is more likely to be produced, and this kind of solvation structure has stronger reducibility and easily participates in SEI formation. The 2% LiDFBOP additive increases the inorganic LiF component of SEI, which yields great advantages in regulating the uniform diffusion of Li+ ions passing through the SEI. Besides, the organics containing P and F atoms are also abundant in SEI, which has greater flexibility and can tolerate volume expansion of the Si@Graphite@C anode. Therefore, the STD+2% LiDFBOP electrolyte can improve the electrochemical performances of Si@Graphite@C/Li half-cells. This work has practical implications not only for the molecular design of novel lithium salt but also for the constructions of SEI and electrolyte systems compatible with the Si@Graphite@C anode.

show abstract

“…32,33 The N 1s spectrum shows that two peaks at 398.4 eV and 401.1 eV re ect the composition of Li 2 N-SO 2 − and Li 3 N after cycling. 34 In contrast, the Li metal exhibits no obvious Li 3 N before cycling (Fig. 4f).…”

Section: Anode Interface Compatibilitymentioning

confidence: 97%

Polyfluorinated Crosslinker-based Solid Polymer Electrolytes for Long-Cycling 4.5 V Lithium Metal Batteries

Tang

Chen

et al. 2022

Preprint

View full text Add to dashboard Cite

Solid polymer electrolytes (SPEs), which are favorable to form intimate interfacial contacts with electrodes, are promising electrolyte of choice for long-cycling lithium metal batteries (LMBs). However, typical SPEs with easily oxidized oxygen-bearing polar groups exhibit narrow electrochemical stability window (ESW), making it impractical to increase specific capacity and energy density of SPE based LMBs with charging cut-off voltage of 4.5 V or higher. Here, a polyfluorinated crosslinker has been applied to enhance oxidation resistance of SPEs via inductive electron-withdrawing effect of polyfluorinated segments transmitted through crosslinked networks. As a result, polyfluorinated crosslinked SPE exhibits a wide ESW, and the Li|SPE|LiNi0.5Co0.2Mn0.3O2 cell with a cutoff voltage of 4.5 V delivers a high discharge specific capacity of ~ 164.19 mAh g− 1 at 0.5 C and capacity retention of ~ 90% after 200 cycles. This work opens a new direction in developing SPEs for long-cycling high-voltage LMBs by using polyfluorinated crosslinking strategy.

show abstract

Stable electrode–electrolyte interfaces constructed by fluorine- and nitrogen-donating ionic additives for high-performance lithium metal batteries

Cited by 88 publications

References 79 publications

Boosting the Temperature Adaptability of Lithium Metal Batteries via a Moisture/Acid‐Purified, Ion‐Diffusion Accelerated Separator

Boosting the Temperature Adaptability of Lithium Metal Batteries via a Moisture/Acid‐Purified, Ion‐Diffusion Accelerated Separator

Improving Toleration of Volume Expansion of Silicon-Based Anode by Constructing a Flexible Solid-Electrolyte Interface Film via Lithium Difluoro(bisoxalato) Phosphate Electrolyte Additive

Polyfluorinated Crosslinker-based Solid Polymer Electrolytes for Long-Cycling 4.5 V Lithium Metal Batteries

Contact Info

Product

Resources

About