Small Angle X-Ray Scattering Data

Figure 2.23 Small Angle X-ray Scattering (SAXS) profiles of scattering angle

intensity as a function of wavevector (q) for (70PEOX0.34)(34PE0.35)(5PEG0.31) electrolyte. 0.01 0.1 1 -0.005 0 0.005 0.01 0.015 0.02 In te n si ty q (Å-1)

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(47) The reaction mixture for polymer casting also contained hydrogenation catalyst (Crabtree's catalyst) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) ([EO]:[Li] = 18:1). The activity of the Grubbs G2 catalyst in the presence of TFSI anion and Crabtree's catalyst was confirmed by control experiments. COE was copolymerized with PEG-grafted COE using Grubbs' G2 catalyst in the presence and absence of additives to obtain copolymers, and the number average molecular weights (Mns) of these polymers were determined using GPC. The activity of the Grubbs' G2 catalyst was found to be comparable with

or without the presence of additives. See Experimental Section for more details.

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CHAPTER 3

Binary Salt-Doped Tetraphenylborate Tethered Li-Ion Conducting Ionomers: Synthesis, Characterization, and Applications for Lithium Metal Batteries

CHAPTER 3

Binary Salt-Doped Tetraphenylborate Tethered Li-Ion Conducting Ionomers: Synthesis, Characterization, and Applications for Lithium Metal Batteries

3.1 Abstract

We report a new class of ‘binary salt-doped single-ion conductor (mixed SIC)’ electrolytes for Li-ion conduction. These mixed SICs were synthesized using ring opening metathesis polymerization chemistry and evaluated as electrolytes for lithium battery applications. A weakly coordinating tetraphenylborate anion was covalently attached to a rigid polyethylene backbone in a polyethylene/poly(ethylene oxide) (PE/PEO) cross-linked polymer, and further doped with a binary lithium salt (LiBPh4) to develop these mixed SICs. A systematic investigation of the effect of different fractions of immobilized borate anions on the thermal properties, electrochemical stability, and ionic conductivities of the electrolytes is reported. At similar Li+ ion concentration, the increase in binary salt content in the mixed SIC system led to a significant increase in ionic conductivity values. However, the electrochemical stability of the single-ion electrolyte was observed to decrease upon doping with the binary lithium salt. The results reported in this study demonstrate that these modular mixed SICs are an interesting platform to obtain high ionic conductivities and tunable electrochemical stabilities.

3.2 Introduction

Reducing greenhouse gas emissions and achieving a sustainable energy supply have been long-standing goals for mankind. Rechargeable batteries are considered an excellent means of storing and supplying large amounts of energy for sustainable transportation options, like electric vehicles and hybrid-electric vehicles, and grid energy storage applications.1-3 Li-ion batteries (LIBs) have gained notable attention for automotive applications due to their high energy density compared to other battery technologies.4-6 However, the inherent flammability of their liquid electrolyte components raises safety concerns. In contrast to liquid electrolytes, solid polymer electrolytes (SPEs) are less flammable and therefore considered to be safer alternatives to their liquid counterparts in LIBs.7 Additionally, these SPEs allow the miniaturization of devices, allowing higher energy density values. However, like the liquid electrolytes, most of the lithium salt-doped SPEs have low lithium-ion transference numbers (tLi+), unacceptably low ionic conductivities at room temperature, and unsatisfactory electrochemical performance.8,9

The poor electrochemical performance is proposed to arise from the ionic concentration gradients within the cell, which produce physical and chemical changes at the electrode/electrolyte interface that lead to high internal and interfacial resistance (Figure 3.1a).10

Single-ion conductors (SICs), in which anions are tethered to the polymer backbone have long been proposed as an ideal candidate to achieve superior battery performance (Figure 3.1b).8 Single-ion conductors offer number of advantages, such as tLi+ approaching unity and the absence of concentration polarization effects.9,11 Despite these attractive features, their practical applications are limited due to low

Figure 3.1 Li-ion conduction during charge in polymer electrolytes. a) Polymer

electrolytes containing mobile anions. b) Single-ion conductors with anions covalently bound to the polymer.

room temperature ionic conductivity (<10−4 S/cm at 25 °C). Ionic conductivity of the SICs is strongly influenced by the nature of the anions tethered to the polymer backbone. Numerous anions such as carboxylate,12 alkyl sulfonate,13,14 bis(allylmalonato)borate,15-17 and trifluoromethylsulfonimide18-22 have been anchored to the polymer backbone to obtain Li+ conducting polyelectrolytes. To increase the Li+ ion mobility and improve the battery performance, current research efforts are focused on developing new anions, which facilitate better delocalization of negative charge, decrease the ion-pair dissociation energy and thus increase the concentration of mobile Li+ ions. Theoretical calculations have suggested that trifluoromethylsulfonimide (N(SO2CF3)2−; TFSI) and tetraphenylborate (BPh4−; TPB) anions have relatively low ion-dissociation energy.23 While a variety of TFSI tethered single-ion electrolytes have been investigated in the literature,18-22 only few SIC reports have examined the effect of covalently bound BPh4− anions on the electrolyte’s properties.24,25 Moreover, TFSI anions are known to corrode the aluminum current collector in a lithium based battery device.26 We were interested in exploring the effect

Disadvantages

- Anion accumulation near the anode - tLi+ < 0.5 A N O D E C A T H O D E

Bulky non-coordinating anion Li cation

Advantages

- Minimal concentration polarization effects - tLi+ ~ 1

a) Mobile anions b) Anions covalently bound to polymer

C A T H O D E A N O D E

of weakly coordinating BPh4− anion in the SIC electrolyte because of their non-toxic and hydrolytically stable nature.27 Previously, Colby and co-workers reported TPB containing SICs in which the BPh4− anions were tethered on a low Tg polysiloxane backbone.24,25 Although these poly(ethylene glycol) (PEG; Mn 600 Da)-doped and TPB tethered polysiloxane ionomers exhibited reasonable ionic conductivity at ambient temperature (10−5.2 S/cm for the 70 wt% PEG-doped composition at 25 °C),24 the mechanical properties of the polysiloxane ionomers are expected to be extremely poor, preventing their use as a separator in a battery device. In contrast to the previously reported ionomers, we aimed to tether these weakly coordinating BPh4− anions on a mechanically rigid polyethylene (PE) backbone in a polyethylene/poly(ethylene oxide) (PE/PEO) framework. The specific PE/PEO framework used in the study was also selected based on their unprecedented lithium dendrite growth resistance in high energy Li-metal batteries (LMB) reported in our previous study.28

Recently, Tikekar et al. proposed a theoretical model, which suggests that the lifetime of a LMB may be improved by use of a mixed conducting system, e.g. doping of a single-ion conducting electrolyte containing immobilized anions with a free lithium salt.29 Significantly, their calculations predicts that the presence of even a low fraction of immobilized anions (10%) should decrease the potential at the electrode/electrolyte interface, and thereby increase the stability of lithium electrodeposits compared to conventional liquid electrolytes. Inspired by this theory, we sought to develop binary lithium salt-doped single-ion conductors with variable fractions of immobilized anions. Beyond the benefits anticipated from the theory, we

anticipate that in these binary lithium salt-doped polyelectrolytes, the immobilized anions would serve to decrease the detrimental ionic concentration gradients, and the free lithium salt would increase the conductivity of the electrolyte.

Although there have been previous reports on lithium-ion conducting SICs, none of these SIC electrolytes have been doped with a binary lithium salt. Our specific interest in this first study is two-fold. First, to quantify and study the effect of different fractions of immobilized anion on the electrochemical properties of the polymer electrolyte. And, second to evaluate the effect of the binary salt content in the electrolyte on ionic conductivity and electrochemical stability of the SICs. We prepared a series of binary salt-doped SICs containing varying fractions of covalently bound anions to the polymer backbone. Tetraphenylborate anions were selected due to their weakly coordinating nature,27 and were immobilized on the mechanically rigid polyethylene backbone. A binary lithium salt, namely lithium tetraphenylborate (LiBPh4) was also added during the preparation of these electrolyte formulations. These ionomers were synthesized using ring opening metathesis chemistry and further tested as Li-ion conducting electrolytes for LMB applications.

3.3 Results and Discussion