Enhancing the polymer electrolyte–Li metal interface on high-voltage solid-state batteries with Li-based additives inspired by the surface chemistry of Li7La3Zr2O12

Orue, Ander; Arrese-Igor, Mikel; Cid, Rosalía; Judez, Xabier; Gómez, Nuria; Amo, Juan Miguel López del; Manalastas, William; Srinivasan, Madhavi; Rojviriya, Catleya; Armand, Michel; Aguesse, Frédéric; López-Aranguren, Pedro

doi:10.1039/d1ta08362g

Cited by 15 publications

(13 citation statements)

References 56 publications

(71 reference statements)

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“…This effect has been observed with several types of fillers, namely "passive" fillers such as SiO 2 , [114] ZrO 2 , [115] and Al 2 O 3 , [116] lithium-conductive fillers, [81] such as Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP), [41,117] garnets (e.g. Li 7 La 3 Zr 2 O 12 -LLZO and Li 7-x La 3 Zr 2-x Ta x O 12 -LLZTO), [118][119][120][121][122][123][124][125][126] argyrodites (Li 6 PS 5 Cl), [127] perovskites (e.g. Li 3/8 Sr 7/16 Ta 3/4 Zr 1/4 O 3 -LSTZ), [128] and cationic metal-organic frameworks (such as D-UiO-66-NH 2 ).…”

Section: Composite Polymer Electrolytesmentioning

confidence: 99%

Are Polymer‐Based Electrolytes Ready for High‐Voltage Lithium Battery Applications? An Overview of Degradation Mechanisms and Battery Performance

Martínez

Boaretto

Naylor

et al. 2022

Advanced Energy Materials

120

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High‐voltage lithium polymer cells are considered an attractive technology that could out‐perform commercial lithium‐ion batteries in terms of safety, processability, and energy density. Although significant progress has been achieved in the development of polymer electrolytes for high‐voltage applications (> 4 V), the cell performance containing these materials still encounters certain challenges. One of the major limitations is posed by poor cyclability, which is affected by the low oxidative stability of standard polyether‐based polymer electrolytes. In addition, the high reactivity and structural instability of certain common high‐voltage cathode chemistries further aggravate the challenges. In this review, the oxidative stability of polymer electrolytes is comprehensively discussed, along with the key sources of cell degradation, and provides an overview of the fundamental strategies adopted for enhancing their cyclability. In this regard, a statistical analysis of the cell performance is provided by analyzing 186 publications reported in the last 17 years, to demonstrate the gap between the state‐of‐the‐art and the requirements for high‐energy density cells. Furthermore, the essential characterization techniques employed in prior research investigating the degradation of these systems are discussed to highlight their prospects and limitations. Based on the derived conclusions, new targets and guidelines are proposed for further research.

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Section: Composite Polymer Electrolytesmentioning

confidence: 99%

Are Polymer‐Based Electrolytes Ready for High‐Voltage Lithium Battery Applications? An Overview of Degradation Mechanisms and Battery Performance

Martínez

Boaretto

Naylor

et al. 2022

Advanced Energy Materials

120

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“…There are likely two main causes of the poor performance of all-PEO-based cells (Figure a,b): first, the parasitic reactions from the TFSI – counterion (driven by the low T Li + value of LiTFSI) seem to limit the charge cutoff voltage to 3.9 V (Figure a), and second, the degradation of PEO above this potential leading to an increase in the Ohmic drop (Figure b). The reaction between TFSI – anions and Li metal has been widely discussed in the literature, comprising a wide range of mechanisms. − Golozar et al showed the accumulation of TFSI – in the vicinity of damaged Li-metal regions . They suggested a gradual decomposition of LiTFSI by multiple reduction steps, forming subunits such as Li x CNF 3 and Li y SO x through the reduction of the anion.…”

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confidence: 99%

Toward High-Voltage Solid-State Li-Metal Batteries with Double-Layer Polymer Electrolytes

et al. 2022

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Solid polymer electrolyte batteries with a Li-metal anode and high-voltage active materials hold promising prospects to increase the energy density and improve the safety of conventional Li-ion batteries. An adequate choice of the polymers used for the cathode (catholyte) and for the separator (electrolyte) to create a sufficient energy gap and improve the chemical compatibility at both the positive electrode and Li-metal anode is required. The present work highlights the advantages of the double-layer polymer electrolyte approach in cells with a LiNi x Mn y Co z O2 active material, a poly(propylene carbonate) (PPC) catholyte, and a poly(ethylene oxide) (PEO) electrolyte. Replacing PEO in the catholyte with PPC results in a remarkably improved cycling performance. In addition, the higher lithium transference number of electrolytes with single lithium ion conductors leads to a smooth cycling of solid-state batteries. Cells with 1 mAh cm–2 deliver 160 mAh g–1, with a capacity retention above 80% over 80 cycles and a Coulombic efficiency close to 100%.

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“…However, Ranque et al showed that a LiOH shell surrounding LLZO facilitated Li + -ion transfer between PEO and LLZO in a CSE, demonstrating that LiOH might not deter ion transport . Importantly, Orue et al similarly found that LiOH enhances the cyclability of CSEs by promoting a LiF-rich interface and a wide voltage window …”

Section: Introductionmentioning

confidence: 99%

“…Inorganic-derived species are considered beneficial to the SEI in liquid-based batteries because they transport Li + but insulate the electrolyte from electrons . Similarly, SEI and interfacial chemistry can be important in SSBs and can be adjusted by the strategic use of additives that affect the SEI such as LiF, LiNO 3 , Al 2 O 3 , and LiOH. ,,,− Such additives can promote the growth of a more stable, inorganic-rich SEI. The SEI at the Li 0 anode in SSBs has been shown to contain lithium hydroxide (LiOH), lithium carbonate (Li 2 CO 3 ), and some lithium fluoride (LiF), but how the choice of additives controls the composition of the SEI and how the inorganic compounds stabilize the interfaces is not fully understood .…”

Section: Introductionmentioning

confidence: 99%

“…22 Importantly, Orue et al similarly found that LiOH enhances the cyclability of CSEs by promoting a LiF-rich interface and a wide voltage window. 12 We present a method for synthesizing Li 3 N−LiOH core− shell particles and show that the LiOH shell passivates the Li 3 N particles, inhibiting Li 3 N from reacting with both electrodes and other electrolyte components. We investigate the electrochemical properties of the electrolytes, Li−Li symmetric cell cycling, and full cell performance with lithium iron phosphate (LFP) cathodes.…”

Section: ■ Introductionmentioning

confidence: 99%

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Investigating the Cyclability and Stability at the Interfaces of Composite Solid Electrolytes in Li Metal Batteries

Holmes

Liu

Zhang

et al. 2022

ACS Appl. Mater. Interfaces

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Despite the fact that much work has been dedicated to finding the ideal additive for composite solid electrolytes (CSEs) for lithium-based solid-state batteries, little is known about the properties of a CSE that enable stable cycling with a lithium metal anode. In this work, we use three CSEs based on lithium nitride (Li 3 N), a fast lithium-ion conductor, and lithium hydroxide (LiOH) to investigate the properties and interfacial interactions that impact the cyclability of CSEs. We present a method for stabilizing Li 3 N with a shell of LiOH, and we incorporate Li 3 N, core−shell particles, and LiOH into CSEs using polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imide. Through improved interfacial chemistry, CSEs with core−shell particles have superior electrochemical cycling performance compared to those with unprotected Li 3 N in symmetric Li−Li cells. This CSE features a high ionic conductivity of 0.66 mS cm −1 at 60 °C, a high critical current density of 1.2 mA cm −2 , and a wide voltage window of 0−5.1 V. Full cells with the core−shell CSE and lithium iron phosphate cathodes exhibit stable cycling and high reversible specific capacities in cells as high as 2.5 mAh cm −2 . We report that the improved ionic conductivity and amorphous PEO content have a limited effect on the solid-state electrolyte performance, while improving the electrolyte−Li metal anode interface is key to cycling longevity.

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Enhancing the polymer electrolyte–Li metal interface on high-voltage solid-state batteries with Li-based additives inspired by the surface chemistry of Li₇La₃Zr₂O₁₂

Abstract: High-voltage Li metal solid-state batteries are in the spotlight of high energy and power density devices for the next generation of batteries. However, the lack of robust solid-electrolyte interfaces (SEI)...

Cited by 15 publications

References 56 publications

Are Polymer‐Based Electrolytes Ready for High‐Voltage Lithium Battery Applications? An Overview of Degradation Mechanisms and Battery Performance

Are Polymer‐Based Electrolytes Ready for High‐Voltage Lithium Battery Applications? An Overview of Degradation Mechanisms and Battery Performance

Toward High-Voltage Solid-State Li-Metal Batteries with Double-Layer Polymer Electrolytes

Investigating the Cyclability and Stability at the Interfaces of Composite Solid Electrolytes in Li Metal Batteries

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