A sulfur-containing polymer-plasticized poly(ethylene oxide)-based electrolyte enables highly effective lithium dendrite suppression

Chen, Zhenying; Li, Jingyan; Qiu, Feng; Lu, Chenbao; Zhuang, Xiaodong; Zhuang, Xiaodong

doi:10.1039/d2ta03042j

“…The 0.5 %CNF-COF@PEO electrolyte exhibits a much higher t Li + of 0.81 (Figure 3e) relative to the PEO counterpart (0.22) (Figure S11) and even surpassing most reported PEO-based solid electrolytes involving different functional fillers under comparable conditions. [6,20,21,[23][24][25][47][48][49] As indicated in Figure S3 and S12, at 30 °C, the ionic conductivity and t Li + of the 0.5 %CNF-COF@PEO SPE are 2.65×10 À 5 S cm À 1 and 0.37, higher than 0.5 %CNF-COP@PEO SPE (1.90×10 À 5 S cm À 1 and 0.33), indicating the promoting role of crystalline structure, while 0.5 %CNF-COP@PEO SPE outperforms 0.5 %F-COP @PEO SPE (1.16×10 À 5 S cm À 1 , 0.22) and 0.5 %CN-COP@-PEO SPE (1.46×10 À 5 S cm À 1 , 0.27), implying the key role of -CN and F dual-decoration in Li ion conduction, consistent with the theoretical prediction. Similar trends are also observed in term of the ionic conductivity at 60 °C: CNF-COF@PEO > CNF-COP@PEO > CN-COP@PEO > F-COP@PEO > COP@PEO (Figure S4).…”

Section: Resultsmentioning

confidence: 99%

“…Such cycling performance metric surpasses almost all literature-reported results using various PEO-based SPE under comparable conditions (Figure 6f). [6,20,21,23,25,48,49,53] Notably, at a higher LFP loading of 4.9 mg cm À 2 , the Li/0.5 %CNF-COF@PEO SPE/LiFePO 4 cell yields an initial capacity of 137.2 mAh g À 1 at 0.2 C with impressive capacity retention of 97.2 % over 500 cycles (Figure 6h). At 50 °C, the 0.5wt %CNF-COP@PEO SPE equipped battery can also perform well and deliver the initial discharge capacity of 89 mAh g À 1 at 2 C with a large retention of 98.8 % after 260 cycles (Figure S27).…”

Section: Methodsmentioning

confidence: 99%

Multipolar Conjugated Polymer Framework Derived Ionic Sieves via Electronic Modulation for Long‐Life All‐Solid‐State Li Batteries

Yang,

Fang,

Li

et al. 2024

Angewandte Chemie

0

View full text Add to dashboard Cite

Here, we build a tunable multipolar conjugated polymer framework platform via pore wall chemistry to probe the role of electronic structure engineering in improving the Li+ conduction by theoretical studies. Guided by theoretical prediction, we develop a new cyano‐vinylene‐linked multipolar polymer framework namely CNF‐COF, acting as efficient ion sieves to modify polymer electrolytes for long‐lifespan all‐solid‐state (ASS) Li metal batteries. The cyano and fluorine groups dual‐decoration in CNF‐COF favorably regulates the electronic structure via multipolar donor‐acceptor electronic effects to afford proper energy band structure and abundant electron‐rich sites for enhanced anti‐oxidative ability, facilitated ion‐pair dissociation and suppressed anion movements. Thus, the CNF‐COF incorporation into poly (ethylene oxide) (PEO) electrolytes not only renders selective rapid Li+ conduction but also facilitates the Li dendrite suppression. Specifically, the constructed composite electrolyte with an ultralow CNF‐COF content of only 0.5 wt% is endowed with a high ionic conductivity of 0.634 mS cm‐1 at 60 °C and a large Li+ transference number of 0.81. As such, the Li symmetric cell delivers stable Li plating/stripping over 1400 h. Impressively, t he assembled ASS Li battery under 60 °C allows for stable cycling over 2000 cycles at 1 C and over 1000 cycles even at 2 C.

show abstract

“…The 0.5 %CNF-COF@PEO electrolyte exhibits a much higher t Li + of 0.81 (Figure 3e) relative to the PEO counterpart (0.22) (Figure S11) and even surpassing most reported PEO-based solid electrolytes involving different functional fillers under comparable conditions. [6,20,21,[23][24][25][47][48][49] As indicated in Figure S3 and S12, at 30 °C, the ionic conductivity and t Li + of the 0.5 %CNF-COF@PEO SPE are 2.65×10 À 5 S cm À 1 and 0.37, higher than 0.5 %CNF-COP@PEO SPE (1.90×10 À 5 S cm À 1 and 0.33), indicating the promoting role of crystalline structure, while 0.5 %CNF-COP@PEO SPE outperforms 0.5 %F-COP @PEO SPE (1.16×10 À 5 S cm À 1 , 0.22) and 0.5 %CN-COP@-PEO SPE (1.46×10 À 5 S cm À 1 , 0.27), implying the key role of -CN and F dual-decoration in Li ion conduction, consistent with the theoretical prediction. Similar trends are also observed in term of the ionic conductivity at 60 °C: CNF-COF@PEO > CNF-COP@PEO > CN-COP@PEO > F-COP@PEO > COP@PEO (Figure S4).…”

Section: Methodsmentioning

confidence: 99%

“…Such cycling performance metric surpasses almost all literature-reported results using various PEO-based SPE under comparable conditions (Figure 6f). [6,20,21,23,25,48,49,53] Notably, at a higher LFP loading of 4.9 mg cm À 2 , the Li/0.5 %CNF-COF@PEO SPE/LiFePO 4 cell yields an initial capacity of 137.2 mAh g À 1 at 0.2 C with impressive capacity retention of 97.2 % over 500 cycles (Figure 6h). At 50 °C, the 0.5wt %CNF-COP@PEO SPE equipped battery can also perform well and deliver the initial discharge capacity of 89 mAh g À 1 at 2 C with a large retention of 98.8 % after 260 cycles (Figure S27).…”

Section: Angewandte Chemiementioning

confidence: 99%

Multipolar Conjugated Polymer Framework Derived Ionic Sieves via Electronic Modulation for Long‐Life All‐Solid‐State Li Batteries

Yang,

Fang,

Li

et al. 2024

Angew Chem Int Ed

0

View full text Add to dashboard Cite

Here, we build a tunable multipolar conjugated polymer framework platform via pore wall chemistry to probe the role of electronic structure engineering in improving the Li+ conduction by theoretical studies. Guided by theoretical prediction, we develop a new cyano‐vinylene‐linked multipolar polymer framework namely CNF‐COF, acting as efficient ion sieves to modify polymer electrolytes for long‐lifespan all‐solid‐state (ASS) Li metal batteries. The cyano and fluorine groups dual‐decoration in CNF‐COF favorably regulates the electronic structure via multipolar donor‐acceptor electronic effects to afford proper energy band structure and abundant electron‐rich sites for enhanced anti‐oxidative ability, facilitated ion‐pair dissociation and suppressed anion movements. Thus, the CNF‐COF incorporation into poly (ethylene oxide) (PEO) electrolytes not only renders selective rapid Li+ conduction but also facilitates the Li dendrite suppression. Specifically, the constructed composite electrolyte with an ultralow CNF‐COF content of only 0.5 wt% is endowed with a high ionic conductivity of 0.634 mS cm‐1 at 60 °C and a large Li+ transference number of 0.81. As such, the Li symmetric cell delivers stable Li plating/stripping over 1400 h. Impressively, t he assembled ASS Li battery under 60 °C allows for stable cycling over 2000 cycles at 1 C and over 1000 cycles even at 2 C.

show abstract

“…Numerous strategies have been explored to improve the ionic conductivity of PEO-based polymer electrolytes. The most frequently reported methods include some simpler techniques like the introduction of inorganic fillers, , addition of various additives, plasticizers, plastic crystals, porous frameworks, , and other complicated methods like copolymerization, , cross-linking, , etc. The incorporation of inorganic nanoparticles or porous metal–organic frameworks (MOFs) as fillers into the polymer matrix is successful in improving the ionic conductivity of the solid polymer electrolyte to a certain extent .…”

Section: Introductionmentioning

confidence: 99%

Solid Polymer Electrolyte Based on an Ionically Conducting Unique Organic Polymer Framework for All-Solid-State Lithium Batteries

Bandyopadhyay

¹

,

Gupta

²

,

Joshi

³

et al. 2023

ACS Appl. Energy Mater.

View full text Add to dashboard Cite

Solid polymer electrolytes (SPEs) are regarded as a potential candidate for the development of all-solid-state lithium batteries minus the safety issues related to their liquid counterparts. Poly(ethylene oxide) (PEO)-based SPEs with strong capability to dissolve lithium salts have found extensive application in lithium batteries. However, the crystalline nature and propensity of lithium dendrite growth in such SPEs have led to the search for preemptive alternatives like the incorporation of inorganic nanoparticles or porous frameworks as fillers in the polymer matrix. Herein, a unique organic polymer framework (OPF) was synthesized by the Suzuki–Miyaura coupling reaction between 2,5-dibromo-3-(2-(2-(2-ethoxyethoxy)ethoxy)ethyl)thiophene and triazine-phenyl boronic acid. Interestingly, the incorporation of long ethylene glycol side chains in the polymer framework resulted in the amorphous nature of the OPF. Impressively, the percentage of crystallinity of PEO reduced significantly to only 30% in OPF-incorporated PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) composites. Further, the side chains present in a multidirectional manner acted as an interfacial compatibilizer aiding the homogeneous distribution of OPF in the PEO matrix. The SPE showed significantly improved ionic conductivity compared to the pristine samples (9.61 × 10–3 S cm–1 at 55 °C) and a lithium-ion transference number of 0.53. The performance of such SPE was further evaluated by assembling Li/LiFePO4 (LFP) coin cells, showing a stable discharge capacity of 130 mAh g–1 at 0.2C after 200 cycles. This work provides an interesting concept for building a unique type of homogeneous OPF/PEO-based composite SPE film that can be utilized as a desirable material in solid electrolytes for lithium battery applications.

show abstract

A sulfur-containing polymer-plasticized poly(ethylene oxide)-based electrolyte enables highly effective lithium dendrite suppression

Abstract: Herein, a multifunctional S-containing polymer filler to enhance PEO-based composite polymer electrolyte is reported.

Cited by 6 publications

References 47 publications

Multipolar Conjugated Polymer Framework Derived Ionic Sieves via Electronic Modulation for Long‐Life All‐Solid‐State Li Batteries

Multipolar Conjugated Polymer Framework Derived Ionic Sieves via Electronic Modulation for Long‐Life All‐Solid‐State Li Batteries

Multipolar Conjugated Polymer Framework Derived Ionic Sieves via Electronic Modulation for Long‐Life All‐Solid‐State Li Batteries

Solid Polymer Electrolyte Based on an Ionically Conducting Unique Organic Polymer Framework for All-Solid-State Lithium Batteries

Contact Info

Product

Resources

About