Electrochemical polymerization of reactive monomers on metallic surfaces is a well-established method to fabricate functional polymer thin films for protecting metals [10] and electronic devices, including sensors.[120]] The approach offers several advantages over other polymerization techniques that may also be used to create coatings on metals: (i) It combine polymer synthesis with thin film formation; (ii) It eliminates the need for exogenous oxidants to initiate the polymerization; and (iii) important properties of the membrane, including its thickness, morphology, and porosity are controlled by transport processes in the film itself [121]. Although the method has not been previously studied to protect reactive alkali metals for battery applications, it is well suited to this application because the transport processes that controll film
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thickness and morphology are related to those that controll access of ions to/from the metal surface during charge/discharge processes in a battery. Figure 34A is a schematic representation of the process, showing how it can be used to create an ionic polymer membrane on the surface of a sodium anode. The polymerization reaction is believed to progress via the usual steps (initiation, propagation, and termination) that govern free radical polymerization processes. Initiation occurs during charging, wherein the unsaturated ionic liquid monomers accept electrons to form reactive radical species. These species react with monomers to increase the size of the radicals, propagating the polymerization process and creating a thin, porous film in conformal contact with the electrode. Termination requires collision of two growing radicals or collision between a radical species and solvent molecule; here we eliminate the latter possibility by performing the reaction in the pure liquid IL monomer.
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Figure 34: Formation of polymeric ionic liquid film. A. A schematic drawing of the polymeric ionic liquid film formation on the electrode. The cations bearing unsaturated compound accept electrons from the electrode during charging and form free radicals. These radicals will initiate and propagate the polymerization process and form polymer film on the electrode surface. B. SEM, EDS mapping and C. AFM height image of the stainless-steel electrode covered by the polymeric film formed by 1,3-diallyl imidazolium perchlorate (DAIM) under constant current of 1 mA/cm2 (Scale bar: 20 µm). D, E, Amplitude and the relevant 3-D height AFM images of the same film covered on the stainless-steel electrode in B and C.
The molecular structure of the IL monomer was found to be an important factor in regulating the structure and morphology of the electrodeposited polymer membrane as well as the degree of polymerization achieved.[122, 123] This opens opportunities for development of new task-specific IL monomers for the intended purpose. Ohno has argued that polymerization of IL molecules may result in degradation of properties of the monomers, including ionic conductivity, due to elevation
20 15 10 5 0 µm 20 15 10 5 0 µm 62 61 60 59 58 nm A B D C E 20 15 10 5 0 µm 20 15 10 5 0 µm 100 90 80 70 nm
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of the glass transition temperature and reduced number of mobile ions after covalent bonding of the component ions.[124, 125] In order to achieve optimized adhesion and ionic conductivity, different functional imidazolium cation- based ionic liquid monomers bearing allyl or vinyl group and perchlorate anion, namely 1-allyl-3-methylimidazolium perchlorate (AMIM), 1,3-diallyl imidazolium perchlorate (DAIM), 1-allyl-3-vinyl imidazolium perchlorate (AVIM) were synthesized, and their electroinitiated polymerization process on the electrode surface was investigated. To characterize the polymeric film formed on the electrode, the monomers were dropped on a polypropylene separator sandwiched by two stainless steel electrodes in a coin cell. A constant current of 1 mA/cm2 was applied to the cells to initiate polymerization until the voltage goes diverging with no current passing through the cell (see Figure. 35), at which point the electrodes are probably covered by the films and completely insulated. The morphology of the polymer film was examined by scanning electron microscopy (SEM) as shown in Figure 34B and Figure 36. Both DAIM and AVIM monomers are able to be polymerized by charges with good adhesion and contact to the stainless-steel electrode, while AMIM barely forms a film on the surface dues to limited unsaturated components. A uniform thin, membrane was found to cover the rough and scratched surface of the stainless-steel electrode by polymerizing DAIM monomer. The surface topography of the film formed by DAIM was further characterized by atomic force microscopy (AFM) in tapping mode. Figure 34C represents a smooth and uniform height/topography image of the DAIM film on the stainless steel, which is comparable with the SEM image. To assess the thickness of the film formed on the electrode, a scratch was made to expose the stainless steel and allow measurement of the height from the stainless steel surface to
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the upper polymer, giving a thickness of ~80 nm (Fig 34D and Fig 37).[126]
Figure 35: Voltage (A) and Current (B) -time profile during the electroinitiated polymerization process for the neat ionic liquid monomer in a coin cell with stainless steel electrode.
Figure 36: SEM images of the A neat stainless steel electrode, B, stainless steel electrode covered by polymerizing 1-allyl-3-methylimidazolium perchlorate (AMIM), C, stainless steel electrode covered by the polymeric film formed by 1-allyl-3-vinyl imidazolium perchlorate (AVIM) under a constant current of 1 mA/cm2 (scale bar: 20 µm).
B A
A B
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Figure 37: A. AFM phase image of stainless steel electrode covered by the polymeric film formed by 1,3-diallyl imidazolium perchlorate (DAIM). B AFM height image and the corresponding height profile (C) along the red line of the same material in A.
The molecular weight (Mw) and polydispersity index (PDI) of the electropolymerized IL films were determined by means of gel permeation chromatography (GPC) and the results are reported in Table 4. Under the conditions studied here, AMIM forms oligomers (possibly due to the limited unsaturated double bonds), while DAIM and AVIM monomers were capable of forming large molecular weight polymer films, consistent with the film morphologies characterized by SEM. Due to the existence of sp2 hybridized vinyl group in AVIM, this monomer is very reactive and self-polymeriable in the presence an initiating moiety,[127] leading to much larger Mw, denser memebrane films than produced by electropolymerization of DAIM. Thus, while membranes formed by DAIM are rubber-like with softer consistency and more open morphologies, those based on AVIM have molecular weight about twice as large and less open morphologies. Based on the
20 15 10 5 0 µm 20 15 10 5 0 µm 121 120 119 118 117 116 115 Deg A C B
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morphology and stability of the film formed, DAIM was selected for more indept studies. To create membranes suitable for electrochemical studies, DAIM monomer was used as additives in liquid electrolytes to form optimized passivation membranes in a variety of configurations on sodium metal anodes. For brevity, we here focus on membranes created in-situ on metallic sodium using 20 wt% of the IL monomer as an additive in an electrolyte comprised of 1 M sodium perchlorate in ethylene carbonate/properlynee carbonate (EC/PC-NaClO4). The effect of the resultant coatings on stability of sodium metal metal anode is discussed in detail in the following sections of the paper.
Table 4: Molecular weight and polydispersity index of the electroinitiated polymer IL film analyzed by Gel permeation chromatography (GPC) in dimethylformamide.
Ionic Liquid Monomer Mw [g/mol] PDI
AMIM 896 1.024
DAIM 58540 1.546
AVIM 122100 1.248