Semi-Interpenetrating Polymer Network Electrolytes Based on a Spiro-Twisted Benzoxazine for All-Solid-State Lithium-Ion Batteries

Lee, Jen‐Yu; Yu, Tsung-Yu; Chung, Pei-Hsuan; Lee, Wen‐Ya; Yeh, Shih-Chieh; Wu, Nae‐Lih; Jeng, Ru‐Jong

doi:10.1021/acsaem.0c03222

Cited by 16 publications

(22 citation statements)

References 98 publications

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“…The lithium dendrite growth made the overpotential happen and the noise form. This phenomenon can be observed in the charge curve, as reported in the literature. − In addition, the charge–discharge profile, as shown in Figure S7, was assembled by the PEO/LiTFSI (over 250 μm) with the spacer. The charge–discharge profile of the LFP|(PEO/LiTFSI)|Li cell with the thin-film electrolyte (150 μm) without spacer is shown in Figure S8.…”

Section: Resultssupporting

confidence: 70%

Tough Polymer Electrolyte with an Intrinsically Stabilized Interface with Li Metal for All-Solid-State Lithium-Ion Batteries

et al. 2021

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A high-performance solid polymer electrolyte (SPE) membrane that simultaneously addresses the issues of enhanced toughness and Li-dendrite mitigation for all-solid-state Li-ion batteries (ASSLIBs) is demonstrated. The membrane has a sandwiched structure consisting of a center poly(ethylene oxide)/ lithium bis(trifluoromethanesulfonyl) imide (PEO/LiTFSI) electrolyte matrix laminated on both sides with electrospun high-polarity β-phase poly(vinylidene fluoride-co-hexafluoropropylene) (β-PVDF-HFP) nanofibers. The nanofiber layers impart remarkable enhancement in both mechanical and electrochemical properties of the SPE, including a 20-fold increase in tensile strength and a 48-fold increase in toughness, along with up to 4-fold enhancement in Li-ionic conductivity. Moreover, the highly polar fluorinated nanofiber cladding layers enable a stable Li-plating/ stripping interface on the Li anode to efficiently mitigate dendrite formation, while improving the electrochemical interfacial stability with the cathode. In a Li|SPE|Li symmetric cell, the use of the sandwiched SPE is demonstrated to improve the cycle stability from short-circuiting at 144 h for a pristine PEO/LiTFSI membrane to no short-circuiting even up to 3600 h (1800 Liplating-stripping cycles). In an example of LiFePO 4 |SPE|Li ASSLIBs, using the sandwiched membrane enables substantial reduction irreversible capacity upon charging to the high-voltage end and more than 80% capacity retention for over 1600 h. This work presents a feasible and facile design for an SPE for high-performance ASSLIBs.

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Section: Resultssupporting

confidence: 70%

Tough Polymer Electrolyte with an Intrinsically Stabilized Interface with Li Metal for All-Solid-State Lithium-Ion Batteries

et al. 2021

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“…TSBZBC and TSBZBN ( Scheme 1 ) were synthesized in a manner similar to that described in our previous work [ 29 ]. BPA conversion in methanesulfonic acid (135 °C, 4 h) was performed to obtain the spiro-twist compound 3,3,3′,3′-tetramethyl-1,1′-spirobisindane-6,6′-diol (TSD).…”

Section: Methodsmentioning

confidence: 99%

“…Several attempts have been made to obtain amorphous polyether matrices with adequate mechanical properties to facilitate their use in practical applications. For instance, researchers have used materials such as plasticizers [ 19 , 20 ], organic fillers [ 21 , 22 , 23 ], comb polymers [ 24 , 25 ], and interpenetrating polymer networks (IPNs) [ 26 , 27 , 28 , 29 ] as well as methods such as copolymerization [ 30 , 31 ] and cross-linking [ 32 , 33 , 34 ] to reduce the glass transition temperature and crystallinity of polymers. Cross-linked polymer networks effectively improve the mechanical properties and stability of SPEs.…”

Section: Introductionmentioning

confidence: 99%

“…In our previous work [ 29 ], the design of the semi-interpenetrating polymer network (s-IPN) structure in the PEO matrix by using the hexanol group containing spiro-twisted cross-linkable benzoxazine cross-linking agent TSBZ6D have preliminarily enhanced the mechanical property and the electrochemical stabilities. These SPEs were called PTx and the x was represented to the weight percentage of the TSBZ6D in the polymer matrix.…”

Section: Introductionmentioning

confidence: 99%

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Spiro-Twisted Benzoxazine Derivatives Bearing Nitrile Group for All-Solid-State Polymer Electrolytes in Lithium Batteries

Lee

Yeh

et al. 2022

Polymers

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In this study, two nitrile-functionalized spiro-twisted benzoxazine monomers, namely 2,2′-((6,6,6′,6′-tetramethyl-6,6′,7,7′-tetrahydro-2H,2′H-8,8′-spirobi[indeno[5,6-e][1,3]oxazin]-3,3′(4H,4′H)-diyl)bis(4,1-phenylene))diacetonitrile (TSBZBC) and 4,4′-(6,6,6′,6′-tetramethyl-6,6′,7,7′-tetrahydro-2H,2′H-8,8′-spirobi[indeno[5,6-e][1,3]oxazin]-3,3′(4H,4′H)-diyl)dibenzonitrile (TSBZBN) were successfully developed as cross-linkable precursors. In addition, the incorporation of the nitrile group by covalent bonding onto the crosslinked spiro-twisted molecular chains improve the miscibility of SPE membranes with lithium salts while maintaining good mechanical properties. Owing to the presence of a high fractional free volume of spiro-twisted matrix, the –CN groups would have more space for rotation and vibration to assist lithium migration, especially for the benzyl cyanide-containing SPE. When combined with poly (ethylene oxide) (PEO) electrolytes, a new type of CN-containing semi-interpenetrating polymer networks for solid polymer electrolytes (SPEs) were prepared. The PEO-TSBZBC and PEO-TSBZBN composite SPEs (with 20 wt% crosslinked structure in the polymer) are denoted as the BC20 and BN20, respectively. The BC20 sample exhibited an ionic conductivity (σ) of 3.23 × 10−4 S cm−1 at 80 °C and a Li+ ion transference number of 0.187. The LiFePO4 (LFP)|BC20|Li sample exhibited a satisfactory charge–discharge capacity of 163.6 mAh g−1 at 0.1 C (with approximately 100% coulombic efficiency). Furthermore, the Li|BC20|Li cell was more stable during the Li plating/stripping process than the Li|BN20|Li and Li|PEO|Li samples. The Li|BC20|Li symmetric cell could be cycled continuously for more than 2700 h without short-circuiting. In addition, the specific capacity of the LFP|BC20|Li cell retained 87% of the original value after 50 cycles.

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“…Therefore, several versatile SPEs were developed to solve these problems, such as composited polymer electrolytes [15,16], biosource-derived electrolytes [17,18], UV-cured electrolytes [19][20][21], and thermal crosslinked electrolytes [22,23]. Among these SPEs, the incorporation of a crosslinking network in the polymer matrix is one of the useful methods to block lithium dendrite crossover to the opposite electrode [24,25]. Primary amines containing precursors, especially Jeffamine, are of great interest for obtaining crosslinking networks in robust SPE matrices.…”

Section: Introductionmentioning

confidence: 99%

Epoxy-Based Interlocking Membranes for All Solid-State Lithium Ion Batteries: The Effects of Amine Curing Agents on Electrochemical Properties

Yeh

Lee

et al. 2021

Polymers

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In this study, a series of crosslinked membranes were prepared as solid polymer electrolytes (SPEs) for all-solid-state lithium ion batteries (ASSLIBs). An epoxy-containing copolymer (glycidyl methacrylate-co-poly(ethylene glycol) methyl ether methacrylate, PGA) and two amine curing agents, linear Jeffamine ED2003 and hyperbranched polyethyleneimine (PEI), were utilized to prepare SPEs with various crosslinking degrees. The PGA/polyethylene oxide (PEO) blends were cured by ED2003 and PEI to obtain slightly and heavily crosslinked structures, respectively. For further optimizing the interfacial and the electrochemical properties, an interlocking bilayer membrane based on overlapping and subsequent curing of PGA/PEO/ED2003 and PEO/PEI layers was developed. The presence of this amino/epoxy network can inhibit PEO crystallinity and maintain the dimensional stability of membranes. For the slightly crosslinked PGA/PEO/ED2003 membrane, an ionic conductivity of 5.61 × 10−4 S cm−1 and a lithium ion transference number (tLi+) of 0.43 were obtained, along with a specific capacity of 156 mAh g−1 (0.05 C) acquired from an assembled half-cell battery. However, the capacity retention retained only 54% after 100 cycles (0.2 C, 80 °C), possibly because the PEO-based electrolyte was inclined to recrystallize after long term thermal treatment. On the other hand, the highly crosslinked PGA/PEO/PEI membrane exhibited a similar ionic conductivity of 3.44 × 10−4 S cm−1 and a tLi+ of 0.52. Yet, poor interfacial adhesion between the membrane and the cathode brought about a low specific capacity of 48 mAh g−1. For the reinforced interlocking bilayer membrane, an ionic conductivity of 3.24 × 10−4 S cm−1 and a tLi+ of 0.42 could be achieved. Moreover, the capacity retention reached as high as 80% after 100 cycles (0.2 C, 80 °C). This is because the presence of the epoxy-based interlocking bilayer structure can block the pathway of lithium dendrite puncture effectively. We demonstrate that the unique interlocking bilayer structure is capable of offering a new approach to fabricate a robust SPE for ASSLIBs.

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Semi-Interpenetrating Polymer Network Electrolytes Based on a Spiro-Twisted Benzoxazine for All-Solid-State Lithium-Ion Batteries

Cited by 16 publications

References 98 publications

Tough Polymer Electrolyte with an Intrinsically Stabilized Interface with Li Metal for All-Solid-State Lithium-Ion Batteries

Tough Polymer Electrolyte with an Intrinsically Stabilized Interface with Li Metal for All-Solid-State Lithium-Ion Batteries

Spiro-Twisted Benzoxazine Derivatives Bearing Nitrile Group for All-Solid-State Polymer Electrolytes in Lithium Batteries

Epoxy-Based Interlocking Membranes for All Solid-State Lithium Ion Batteries: The Effects of Amine Curing Agents on Electrochemical Properties

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