skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: The Promise of 3D Printed Solid Polymer Electrolytes for Developing Sustainable Batteries: A Techno-Commercial Perspective
The year 1975 can be claimed to be the year of inception for the research and development of solid polymer electrolytes (SPEs) for Lithium-Ion Batteries (LIB), when the ionic conductivity of polyethylene oxide–alkaline metal ion complex was found by Peter Wright from the University of Sheffield. However, SPE research has undergone a leapfrog development, with conductivity values improving from 1 × 10–7 S·cm−1 to 1 × 10– 1 S·cm−1. The seed of development of SPEs spurs from the need for introducing design freedom to battery structures as well as the need for leak-proof electrolytes, greater operational safety, higher energy density, and other considerations. While the benefits of SPEs are evident, poor interfacial contact is a major factor limiting their application. This review presents the history of SPEs and shows how the additive manufacturing (AM) could prove beneficial for the improvement of performance and the functional implementation of SPEs. While the article articulates a technical review of additively manufactured SPEs, it also provides a lab-to-market perspective that could aid in shaping the future of green technology in energy storage. It also aims to provide an overall picture about the evolution and diversity of research advances in the development of greener SPEs through AM technology.  more » « less
Award ID(s):
2214006
PAR ID:
10518148
Author(s) / Creator(s):
; ; ; ; ; ;
Publisher / Repository:
Springer
Date Published:
Journal Name:
International Journal of Precision Engineering and Manufacturing-Green Technology
Volume:
11
Issue:
1
ISSN:
2288-6206
Page Range / eLocation ID:
321 to 352
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Improving the total ionic conductivity (σ) of solid polymer electrolytes (SPEs) is critical to the development of solid–state sodium (Na) batteries. In this work, we investigate the effect of two–dimensional (2D), dual–Lewis hexagonal boron nitride (h–BN) filler on polymer structure and ion transport properties of P(EO)24:Na+ and P(EO)4:Na+ mixtures of poly (ethylene oxide) (PEO)–bis (fluorosulfonylimide) (NaFSI). Below the critical percolation concentration threshold for the h–BN flakes, x–ray diffraction (XRD) and differential scanning calorimetry (DSC) studies show that an increase in h–BN concentration initially induces an increase in PEO crystallinity followed by a decrease due to competing effects between heterogeneous nucleation of PEO lamellae and its spherulitic confinement, respectively. Raman spectroscopy reveals that h–BN improves NaFSI dissociation in the semi–dilute SPEs which is supported by density functional theory (DFT) calculations. Our calculations suggest that PEO can almost fully dissociate an NaFSI molecule with a coordination number of 6. We propose an h–BN–‘assisted’ mechanism to explain this observation, wherein h–BN aids PEO in better matching the dissociation energy of the NaFSI salt by virtue of its dual–Lewis surface chemistry. A corresponding 4x increase in σ is observed for the P(EO)24:Na+ SPEs using electrochemical impedance spectroscopy (EIS). The P(EO)4:Na+ SPEs do not show this increase likely due to a significantly different local solvation environment wherein contact ion pairs (CIPs) and aggregates (AGGs) dominate. Our findings highlight the role of filler chemistry in the design and development of composite solid polymer electrolytes for Na batteries. 
    more » « less
  2. Abstract This present study illustrates the synthesis and preparation of polyoxanorbornene‐based bottlebrush polymers with poly(ethylene oxide) (PEO) side chains by ring‐opening metathesis polymerization for solid polymer electrolytes (SPE). In addition to the conductive PEO side chains, the polyoxanorbornene backbones may act as another ion conductor to further promote Li‐ion movement within the SPE matrix. These results suggest that these bottlebrush polymer electrolytes provide impressively high ionic conductivity of 7.12 × 10−4S cm−1at room temperature and excellent electrochemical performance, including high‐rate capabilities and cycling stability when paired with a Li metal anode and a LiFePO4cathode. The new design paradigm, which has dual ionic conductive pathways, provides an unexplored avenue for inventing new SPEs and emphasizes the importance of molecular engineering to develop highly stable and conductive polymer electrolytes for lithium‐metal batteries (LMB). 
    more » « less
  3. The development of the multivalent electrolytes is a critical component to advance polyvalent energy storage technology. In this work, a new and simple nonaqueous zinc electrolyte is developed and investigated where a secondary amine is introduced as a cosolvent. The addition of dimethylamine (DMA) as a cosolvent in THF facilitates the solubilization of Zinc (II) bis(trifluoromethanesulfonyl)imde (Zn(TFSI)2) and results in a homogeneous electrolyte with reversible plating of zinc achieved at high coulombic efficiencies. The electrochemical properties of the developed electrolyte and the effects of the cosolvent and salt concentrations are systematically investigated. It was found that increasing the ratio of the cosolvent DMA in THF for a Zn(TFSI)2electrolyte leads to more facile kinetics, better ion solubilization, and higher ion mobility evidenced by up a significant increase in conductivity as well as the plating/stripping current densities. Increased Zn(TFSI)2salt concentration in a 2.0 M DMA in THF solvent mixture not only leads to a higher current density and conductivity, but also a higher molar conductivity due to a redissociation mechanism. The findings in this study are relevant and important to further understand and characterize multivalent electrolytes from a simple and effective electrolyte design strategy. 
    more » « less
  4. null (Ed.)
    To improve the energy density of lithium-ion batteries, the development of advanced electrolytes with enhanced transport properties is highly important. Here, we show that by confining the conventional electrolyte (1 M LiPF6 in EC-DEC) in a microporous polymer network, the cation transference number increases to 0.79 while maintaining an ionic conductivity on the order of 10−3 S cm−1. By comparison, a non-porous, condensed polymer electrolyte of the same chemistry has a lower transference number and conductivity, of 0.65 and 7.6 × 10−4 S cm−1, respectively. Within Li-metal/LiFePO4 cells, the improved transport properties of the porous polymer electrolyte enable substantial performance enhancements compared to a commercial separator in terms of rate capability, capacity retention, active material utilization, and efficiency. These results highlight the importance of polymer electrolyte structure–performance property relationships and help guide the future engineering of better materials. 
    more » « less
  5. null (Ed.)
    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 ( M n = 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 M n = 1,000 to 2,000. The mechanical properties are improved by end-grafting linear PEO ( M n = 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. 
    more » « less