Experimental evaluation of thermolysis-driven gas emissions from LiPF6-carbonate electrolyte used in lithium-ion batteries

Liao, Zhenghai; Zhang, Shen; Zhao, Yikun; Qiu, Zongjia; Li, Kang; Han, Dong; Zhang, Guoqiang; Habetler, T.G.

doi:10.1016/j.jechem.2020.01.030

Cited by 28 publications

(5 citation statements)

References 42 publications

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“…The recovered 1.0 POS-LN83 cathode revealed surface coverage that was attributed to electrolyte decomposition; however, its surface was much cleaner than the surface of the recovered P-LN83 cathode. The TEM images also showed that the recovered P-LN83 cathode had an irregular surface morphology (considered to be evidence of electrolyte decomposition) when compared to the cycled 1.0 POS-LN83 cathode. − The degree of electrolyte decomposition was also estimated by analyzing the internal pressure of the cell because decomposition of electrolytes always involves gas formation within the cell. − The pressure behaviors were confirmed using homemade pressure-monitoring cells charged to 4.3 V (vs Li/Li + ) at high temperature (Figure S5). The internal pressure of the POS-modified LN83 cathode reached 15.84 kPa, whereas the pressure of the P-LN83 cathode rapidly increased to 21.53 kPa, or a 1.4-fold higher pressure.…”

Section: Resultsmentioning

confidence: 96%

Edge-Protected Ni-Enriched LiNi_xCo_yMn_zO₂ Cathode Materials by Interface Modification with a Si- and F-Functionalized Surface Modifier

Ahn

Lee

Kim

et al. 2023

ACS Sustainable Chem. Eng.

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Many advances made in recent years have highlighted Ni-enriched nickel, cobalt, manganese (NCM) material as a prospective positive electrode material for lithium-ion batteries. However, prolonged cycling is limited by several critical issues, including surface instability, gas generation, and transitional metal dissolution upon cycling. Here, we propose a simple interfacial modification approach that uses 1H,1H,2H,2H-perfluorooctyltriethoxysilane (POS) as a coating precursor to improve surface stability. A one-step thermal heat treatment creates bifunctional cathode electrolyte interphase (CEI) layers from F- and Si-functionalized POS, especially at the edge sites of the Ni-enriched NCM cathode, where serious undesired reactions occur during cycling. The POS-modified Ni-enriched NCM cathode exhibits improved cycling retention compared to the unmodified Ni-enriched NCM cathode because parasitic reactions are well suppressed upon cycling. Systematic analyses show an apparent inhibition of electrolyte decomposition in the POS-modified Ni-enriched NCM cathode due to the effective protection of the active edge sites by the artificial POS-derived CEI layers. The dissolution of metal components is also greatly decreased because the Si-functional groups that develop on the POS-derived CEI layers selectively scavenge F– species formed by electrolyte decomposition.

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Section: Resultsmentioning

confidence: 96%

Edge-Protected Ni-Enriched LiNi_xCo_yMn_zO₂ Cathode Materials by Interface Modification with a Si- and F-Functionalized Surface Modifier

Ahn

Lee

Kim

et al. 2023

ACS Sustainable Chem. Eng.

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“…Radicals, such as PF 6 ·, in electrolytes are known to accelerate electrolyte decomposition through radical chain reaction. [ 26 ] Therefore, we believe that these radicals were scavenged on the BTO surface, leading to mitigating electrolyte decomposition.…”

Section: Resultsmentioning

confidence: 99%

Electrochemically Active Red P/BaTiO₃‐Based Protective Layers Suppressing Li Dendrite Growth for Li Metal Batteries

Kwon

Ha²,

Kim

et al. 2020

Adv Materials Inter

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distance of state-of-the-art electric vehicles powered by lithium ion batteries is ≈200 km per charging for 20 min, which is significantly lower than gasoline vehicles. Therefore, it is essential to increase the energy density of lithium ion batteries for extending driving distance. Unfortunately, the energy density of lithium ion batteries has almost reached the theoretical value, when assuming that layered oxides and carbons are used as cathode and anode materials, respectively. [2] This is attributed to the limitation of intercalation chemistry of lithium ion batteries. In this connection, lithium metal has been considered one of promising anode materials because of its high theoretical specific capacity (3860 mA h g −1). Furthermore, since the use of lithium metal anodes is essential for lithium-sulfur and lithium-oxygen batteries containing Li-free cathodes, it is necessary to develop Li metal anodes. [3] Li metal is fascinating in terms of energy density, but some electrochemical properties of current Li metal are unsatisfactory. First of all, most liquid electrolytes are so highly unstable against Li metal that Li metal gives rise to irreversible electrochemical decomposition of electrolytes, eventually leading to poor Coulombic efficiency. [4] In addition, Li metal grows in the form of dendrites during a plating process. Li dendrites are able to penetrate through a porous separator, resulting in the internal short-circuit of cells and cell explosion. [5] Moreover, porous deactivated layers, which form from the accumulation of "dead Li," on the Li metal surface thicken gradually during cycling. As a result, the mass transport of Li + ions is interrupted near the Li metal surface and cell polarization increases substantially during cycling. [6] To overcome these challenging issues, a lot of promising strategies have been introduced, including (i) electrolyte additives, [7] (ii) artificial solid electrolyte interphase (SEI) layers through chemical and physical treatments, [8] and (iii) guiding uniform Li plating through lithiophilic hosts and confining Li metal in three-dimensional structures. [9] In particular, physical protective layers have been intensively explored as one of artificial SEI layers to stabilize Li metal. Various physical protective layers were prepared using organic polymers, [10] inorganic Li metal has been considered a promising anode for high-energy density batteries because of its high specific capacity. However, uncontrolled Li dendrite growth and severe electrolyte decomposition are detrimental obstacles hindering the practical applications of lithium metal batteries. Herein, electrochemically active red P-based protective layers are introduced to suppress Li dendrite growth during cycling. Red P particles confined in the protective layer react with Li dendrites, forming Li 3 P, as Li dendrites are penetrating through the protective layer. As a result, Li metal is no longer plated on the Li 3 P surface because Li 3 P is electrically insulating, eventually leading to suppressing Li de...

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“…In the electrolyte without EC or FEC, the reduction products of DMC contribute to the outer layer of the SEI, which are simple molecules including gaseous CO and CH 3 CH 3 and solid CH 3 OLi and Li 2 CO 3 (Figure S4). , The gaseous products interfere with the formation of the SEI, while the small molecules in solid products cannot interconnect with each other, accounting for the ineffective protection of the SEI (Figure c), poor cycling stability (Figure a), and large interface resistance (Figure d,e) for the graphite anode in the electrolyte without EC or FEC.…”

Section: Resultsmentioning

confidence: 99%

Insight into the Role of Fluoroethylene Carbonate in Solid Electrolyte Interphase Construction for Graphite Anodes of Lithium-Ion Batteries

Huang,

Chen,

Zhan

et al. 2024

J. Phys. Chem. C

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The role that fluoroethylene carbonate (FEC) plays in the construction of the solid electrolyte interphase (SEI) on graphite anodes of lithium-ion batteries is understood by theoretical calculations combined with electrochemical measurements and spectral characterizations. It is found that FEC is different from ethylene carbonate (EC), although they have a similar structure. FEC presents a stronger ability than EC to combine with PF6 –, which is helpful for the reduction of LiPF6 to construct a LiF-rich inner layer of SEI. Additionally, FEC has a more negative electron affinity than EC, which makes it much easier to reduce, resulting in F-containing polymers that contribute to the outer layer of SEI. Consequently, the FEC-constructed SEI endows the graphite anode with excellent cycling stability.

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Experimental evaluation of thermolysis-driven gas emissions from LiPF6-carbonate electrolyte used in lithium-ion batteries

Cited by 28 publications

References 42 publications

Edge-Protected Ni-Enriched LiNi_xCo_yMn_zO₂ Cathode Materials by Interface Modification with a Si- and F-Functionalized Surface Modifier

Edge-Protected Ni-Enriched LiNi_xCo_yMn_zO₂ Cathode Materials by Interface Modification with a Si- and F-Functionalized Surface Modifier

Electrochemically Active Red P/BaTiO₃‐Based Protective Layers Suppressing Li Dendrite Growth for Li Metal Batteries

Insight into the Role of Fluoroethylene Carbonate in Solid Electrolyte Interphase Construction for Graphite Anodes of Lithium-Ion Batteries

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Experimental evaluation of thermolysis-driven gas emissions from LiPF6-carbonate electrolyte used in lithium-ion batteries

Cited by 28 publications

References 42 publications

Edge-Protected Ni-Enriched LiNixCoyMnzO2 Cathode Materials by Interface Modification with a Si- and F-Functionalized Surface Modifier

Edge-Protected Ni-Enriched LiNixCoyMnzO2 Cathode Materials by Interface Modification with a Si- and F-Functionalized Surface Modifier

Electrochemically Active Red P/BaTiO3‐Based Protective Layers Suppressing Li Dendrite Growth for Li Metal Batteries

Insight into the Role of Fluoroethylene Carbonate in Solid Electrolyte Interphase Construction for Graphite Anodes of Lithium-Ion Batteries

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Edge-Protected Ni-Enriched LiNi_xCo_yMn_zO₂ Cathode Materials by Interface Modification with a Si- and F-Functionalized Surface Modifier

Edge-Protected Ni-Enriched LiNi_xCo_yMn_zO₂ Cathode Materials by Interface Modification with a Si- and F-Functionalized Surface Modifier

Electrochemically Active Red P/BaTiO₃‐Based Protective Layers Suppressing Li Dendrite Growth for Li Metal Batteries