scholarly journals Study of the Segmental Dynamics and Ion Transport of Solid Polymer Electrolytes in the Semi-crystalline State

2021 ◽  
Vol 8 ◽  
Author(s):  
Xi Chelsea Chen ◽  
Robert L. Sacci ◽  
Naresh C. Osti ◽  
Madhusudan Tyagi ◽  
Yangyang Wang ◽  
...  

Solid polymer electrolytes are promising in fulfilling the requirements for a stable lithium metal anode toward higher energy and power densities. In this work, we investigate the segmental dynamics, ionic conductivity, and crystallinity of a polymer electrolyte consisting of poly(ethylene oxide) (PEO) and lithium triflate salt, in the semi-crystalline state. Using quasi-elastic neutron scattering, the segmental dynamics of PEO chains confined between the crystalline lamellae is quantified, using Cole–Cole analysis. We show that the structural relaxation time, τ0, of PEO equilibrated near room temperature is six-fold longer than the same sample that had just cooled down to room temperature. This corresponds to a three-fold smaller ionic conductivity in the equilibrated condition. This work reveals that the segmental dynamics of semi-crystalline polymer electrolytes is very sensitive to thermal history. We demonstrate that quasi-elastic neutron scattering can be used to characterize the ion transport and segmental dynamics in the semi-crystalline state.

2021 ◽  
Vol 9 ◽  
Author(s):  
Benxin Jing ◽  
Xiaofeng Wang ◽  
Yi Shi ◽  
Yingxi Zhu ◽  
Haifeng Gao ◽  
...  

Polyethylene oxide (PEO)-based polymers are commonly studied for use as a solid polymer electrolyte for rechargeable Li-ion batteries; however, simultaneously achieving sufficient mechanical integrity and ionic conductivity has been a challenge. To address this problem, a customized polymer architecture is demonstrated wherein PEO bottle-brush arms are hyperbranched into a star architecture and then functionalized with end-grafted, linear PEO chains. The hierarchical architecture is designed to minimize crystallinity and therefore enhance ion transport via hyperbranching, while simultaneously addressing the need for mechanical integrity via the grafting of long, PEO chains (Mn = 10,000). The polymers are doped with lithium bis(trifluoromethane) sulfonimide (LiTFSI), creating hierarchically hyperbranched (HB) solid polymer electrolytes. Compared to electrolytes prepared with linear PEO of equivalent molecular weight, the HB PEO electrolytes increase the room temperature ionic conductivity from ∼2.5 × 10–6 to 2.5 × 10−5 S/cm. The conductivity increases by an additional 50% by increasing the block length of the linear PEO in the bottle brush arms from Mn = 1,000 to 2,000. The mechanical properties are improved by end-grafting linear PEO (Mn = 10,000) onto the terminal groups of the HB PEO bottle-brush. Specifically, the Young’s modulus increases by two orders of magnitude to a level comparable to commercial PEO films, while only reducing the conductivity by 50% below the HB electrolyte without grafted PEO. This study addresses the trade-off between ion conductivity and mechanical properties, and shows that while significant improvements can be made to the mechanical properties with hierarchical grafting of long, linear chains, only modest gains are made in the room temperature conductivity.


2020 ◽  
Vol 20 (2) ◽  
Author(s):  
Qolby Sabrina ◽  
Titik Lestariningsih ◽  
Christin Rina Ratri ◽  
Achmad Subhan

Solid polymer electrolyte (SPE) appropriate to solve packaging leakage and expansion volume in lithium-ion battery systems. Evaluation of electrochemical performance of SPE consisted of mixture lithium salt, solid plasticizer, and polymer precursor with different ratio. Impedance spectroscopy was used to investigate ionic conduction and dielectric response lithium bis(trifluoromethane)sulfony imide (LiTFSI) salt, and additive succinonitrile (SCN) plasticizer. The result showing enhanced high ionic conductivity. In half-cell configurations, wide electrochemical stability window of the SPE has been tested. Have stability window at room temperature, indicating great potential of SPE for application in lithium ion batteries. Additive SCN contribute to forming pores that make it easier for the li ion to move from the anode to the cathode and vice versa for better perform SPE. Pore of SPE has been charaterization with FE-SEM. Additive 5% w.t SCN shows the best ionic conductivity with 4.2 volt wide stability window and pretty much invisible pores.


2019 ◽  
Vol 4 (2) ◽  
pp. 379-385 ◽  
Author(s):  
X. Chelsea Chen ◽  
Robert L. Sacci ◽  
Naresh C. Osti ◽  
Madhusudan Tyagi ◽  
Yangyang Wang ◽  
...  

This work elucidates the effects of Li+ conducting ceramic on the segmental dynamics and ionic conductivity of polymer electrolyte using quasi-elastic neutron scattering.


2020 ◽  
Vol 4 (3) ◽  
pp. 44
Author(s):  
Xinyi Mei ◽  
Wendy Zhao ◽  
Qiang Ma ◽  
Zheng Yue ◽  
Hamza Dunya ◽  
...  

Three new crosslinked polystyrene nanoparticles covalently attached with low lattice energy lithium salt moieties were synthesized: poly(styrene lithium trifluoromethane sulphonyl imide) (PSTFSILi), poly(styrene lithium benzene sulphonyl imide) (PSPhSILi), and poly(styrene lithium sulfonyl-1,3-dithiane-1,1,3,3-tetraoxide) (PSDTTOLi). A series of solid polymer electrolytes (SPEs) were formulated by mixing these lithium salts with high molecular weight poly(ethylene oxide), poly(ethylene glycol dimethyl ether), and lithium bis(fluorosulfonyl)imide. The crosslinked nano-sized polymer salts improved film strength and decreased the glass transition temperature (Tg) of the polymer electrolyte membranes. An enhancement in both ionic conductivity and thermal stability was observed. For example, the SPE film containing PSTFSILi displayed ionic conductivity of 7.52 × 10−5 S cm−1 at room temperature and 3.0 × 10−3 S cm−1 at 70 °C, while the SPE film containing PSDTTOLi showed an even better performance of 1.54 × 10−4 S cm−1 at room temperature and 3.23 × 10−3 S cm−1 at 70 °C.


Author(s):  
Pranav Utpalla ◽  
Sandeep Kumar Sharma ◽  
S. K. Deshpande ◽  
Jitendra Bahadur ◽  
Debasis Sen ◽  
...  

Limited ionic conductivity of polymer electrolytes is a major issue in their industrial application. Enhancement in ionic conductivity in Poly (ethylene oxide), PEO, based electrolyte have been achieved by loading...


2020 ◽  
Vol 53 (7) ◽  
pp. 2406-2411 ◽  
Author(s):  
Katrina Irene S. Mongcopa ◽  
Daniel A. Gribble ◽  
Whitney S. Loo ◽  
Madhusudan Tyagi ◽  
Scott A. Mullin ◽  
...  

2008 ◽  
Vol 73 (12) ◽  
pp. 1777-1798 ◽  
Author(s):  
Olt E. Geiculescu ◽  
Rama V. Rajagopal ◽  
Emilia C. Mladin ◽  
Stephen E. Creager ◽  
Darryl D. Desmarteau

The present work consists of a series of studies with regard to the structure and charge transport in solid polymer electrolytes (SPE) prepared using various new bis(trifluoromethanesulfonyl)imide (TFSI)-based dianionic dilithium salts in crosslinked low-molecular-weight poly(ethylene glycol). Some of the thermal properties (glass transition temperature, differential molar heat capacity) and ionic conductivities were determined for both diluted (EO/Li = 30:1) and concentrated (EO/Li = 10:1) SPEs. Trends in ionic conductivity of the new SPEs with respect to anion structure revealed that while for the dilute electrolytes ionic conductivity is generally rising with increased length of the perfluoroalkylene linking group in the dianions, for the concentrated electrolytes the trend is reversed with respect to dianion length. This behavior could be the result of a combination of two factors: on one hand a decrease in dianion basicity that results in diminished ion pairing and an enhancement in the number of charge carriers with increasing fluorine anion content, thereby increasing ionic conductivity while on the other hand the increasing anion size and concentration produce an increase in the friction/entanglements of the polymeric segments which lowers even more the reduced segmental motion of the crosslinked polymer and decrease the dianion contribution to the overall ionic conductivity. DFT modeling of the same TFSI-based dianionic dilithium salts reveals that the reason for the trend observed is due to the variation in ion dissociation enthalpy, derived from minimum-energy structures, with respect to perfluoroalkylene chain length.


2020 ◽  
pp. 152808372097062
Author(s):  
Muhammad Yameen Solangi ◽  
Umair Aftab ◽  
Muhammad Ishaque ◽  
Aqeel Bhutto ◽  
Ayman Nafady ◽  
...  

Solid polymer electrolytes (SPEs) are the best choice to replace liquid electrolytes in supercapacitors, fuel cells, solar cells and batteries. The main challenge in this filed is the ionic conductivity and thermal stability of SPEs which is still not up to mark, therefore more investigations are needed to address these issues. In this study, PVA/salt based SPEs was fabricated using both solution cast and electro-spinning methods to probe the effect of different salts such as (NaCl, KCl and KI) and their concentrations on the ionic conductivity. Scanning electron microscopy (SEM) x and Fourier Transform Infra-Red (FTIR) have been employed to study the morphology as well as the different functional groups of SPEs, respectively. It was noted that small addition of NaCl, KCl and KI salts in SPEs dramatically increased the ionic conductivity to 5.95×10−6, 5.31×10−6 and 4.83×10−6 S/cm, respectively. Importantly, the SPEs obtained with NaCl via electro-spinning have higher ionic conductivity (5.95×10−6 S/cm) than their casted SPEs (1.87×10−6 S/cm). Thermal stability was also studied at two different temperatures i.e. 80 °C and 100 °C. The weight loss percentage of electrospun SPEs have zero percent weight loss than the solution based SPEs. The combined results clearly indicated that the nature of salt, concentration and fabrication process play a vital role in the ionic conductivity. Also, the NaCl salt with low molecular weight at low concentrations shows an enhanced ionic conductivity.


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