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Polymer Binders: Characterization and Development Toward Aqueous Electrode Fabrication for Sustainability

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Polymer Binders: Characterization and Development Toward Aqueous Electrode Fabrication for Sustainability polymers Review Polymer Binders: Characterization and Development toward Aqueous Electrode Fabrication for Sustainability Aleksander Cholewinski, Pengxiang Si, Marianna Uceda, Michael Pope and Boxin Zhao * Department of Chemical Engineering, Waterloo Institute for Nanotechnology, Institute for Polymer Research, Centre for Bioengineering and Biotechnology, University of Waterloo, Waterloo, ON N2L 3G1, Canada; [email protected] (A.C.); [email protected] (P.S.); [email protected] (M.U.); [email protected] (M.P.) * Correspondence: [email protected] Abstract: Binders play an important role in electrode processing for energy storage systems. While conventional binders often require hazardous and costly organic solvents, there has been increasing development toward greener and less expensive binders, with a focus on those that can be processed in aqueous conditions. Due to their functional groups, many of these aqueous binders offer further beneficial properties, such as higher adhesion to withstand the large volume changes of several high- capacity electrode materials. In this review, we first discuss the roles of binders in the construction of electrodes, particularly for energy storage systems, summarize typical binder characterization techniques, and then highlight the recent advances on aqueous binder systems, aiming to provide a stepping stone for the development of polymer binders with better sustainability and improved functionalities. Citation: Cholewinski, A.; Si, P.; Keywords: binder; energy storage; lithium ion battery; aqueous electrode; carboxymethylcellulose; Uceda, M.; Pope, M.; Zhao, B. battery characterization Polymer Binders: Characterization and Development toward Aqueous Electrode Fabrication for Sustainability. Polymers 2021, 13, 631. 1. Introduction: Binders and Electrodes for Energy Storage Systems https://doi.org/10.3390/ Electrochemical energy storage systems, such as batteries, play an important role polym13040631 together with renewable energy sources for creating a greener and more sustainable future. When developing new solutions and improving battery performance, the primary focus has Academic Editor: Dan Rosu been toward electrode active materials and electrolytes. Binders, on the other hand, have received comparatively little attention, although recent reviews have begun to highlight Received: 1 February 2021 Accepted: 18 February 2021 their importance, especially in high-capacity battery systems [1–4]. While they only make Published: 20 February 2021 up a small portion of the electrode material (typically 2–5% of the mass in commercial electrodes), binders play multiple important roles in battery performance. First, they Publisher’s Note: MDPI stays neutral help to disperse the other components in solvent during the fabrication process (with with regard to jurisdictional claims in some also acting as a thickener), enabling a homogeneous distribution [5,6]. Second, they published maps and institutional affil- hold together the various components of energy storage devices, including the active iations. components, any conductive additive, and the current collector, ensuring all these pieces are kept in contact [1,7] (Figure1a shows a schematic for a composite electrode with binder interacting with the various components). Through chemical or physical interactions, the binder bridges these separate components, keeping them together and ensuring mechanical integrity of the electrode without significantly impacting electronic or ionic conductivity. Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. Third, they often act as an interface between the electrode and electrolyte. In this role, they This article is an open access article can protect the electrode from corrosion or the electrolyte from depletion while facilitating distributed under the terms and ion transport across this interface [8,9]. conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/). Polymers 2021, 13, 631. https://doi.org/10.3390/polym13040631 https://www.mdpi.com/journal/polymers Polymers 2021, 13, x FOR PEER REVIEW 2 of 21 batteries (LIB) consist of an anode and cathode separated via a porous membrane separa‐ tor and/or electrolyte (which may be liquid or solid). The electrodes and electrolyte are enclosed within a protective casing and are externally connected through circuitry. A sim‐ plified cell schematic can be seen in Figure 1b where lithium cobalt oxide (LiCoO2) and graphite are the active materials used in the cathode and anode, respectively. In this sys‐ tem, the cathode is composed of layered materials with freely moving lithium ions that travel between the anode and cathode during charge/discharge. The ions will move within the layered material where the storage of lithium ions is enabled via reduction/oxidation of the transition metal (in this case, Co4+/Co3+). The electrodes themselves are comprised of active, conductive, and binding materials cast onto a metallic current collector. The con‐ ductive material compensates for the poor electronic conductivity, thereby facilitating charge transfer and improving electrode kinetics. Binders interact with many of these Polymers 2021, 13components,, 631 each of which add requirements to maintain the stability and performance 2 of 20 of the cell. Figure 1.FigureSchematic 1. Schematic for (a) a composite for (a) a composite electrode including electrode the including active material, the active conductive material, additive, conductive and addi polymeric‐ binder; (b) a fulltive, lithium-ion and polymeric battery binder; (LIB) with (b) LiCoOa full lithium2 used as‐ion the battery active (LIB) material with for LiCoO the cathode2 used as and the graphite active ma anode‐ during dischargeterial (with for reactions the cathode shown and occurring graphite within anode a crystalliteduring discharge of active (with material). reactions shown occurring within a crystallite of active material). With all the roles that binders play in an electrode (and the overall battery), there The batteryare structure many different highlights properties the importance that are desirable of several in properties a good binder. for polymer To better understand binders, which arethese summarized desired properties, in Figure it is 2. useful Mechanical to examine properties, the structure which of ainclude typical battery.the Lithium- stiffness, toughness,ion batteriesand hardness (LIB) consistof the binder of an anodeas well and as its cathode adhesion separated to the viaother a porous com‐ membrane ponents, are importantseparator for and/or the electrode electrolyte to (whichwithstand may the be liquid forces or that solid). result The from electrodes the ex and‐ electrolyte pansion and contractionare enclosed of withinactive amaterials protective during casing andcharge/discharge are externally connectedcycles. Thermal through circuitry. A simplified cell schematic can be seen in Figure1b where lithium cobalt oxide (LiCoO ) properties, particularly thermal stability, are also important, both for the high tempera‐ 2 and graphite are the active materials used in the cathode and anode, respectively. In this tures commonly used for curing and drying in electrode fabrication as well as for the op‐ system, the cathode is composed of layered materials with freely moving lithium ions that eration of the final device in various conditions. Similarly, chemical and electrochemical travel between the anode and cathode during charge/discharge. The ions will move within stability are essentialthe layered binder material properties where to the allow storage them of to lithium function ions for is enabled long periods via reduction/oxidation and over numerous ofcycles the transition without metaldegradation (in this case,of the Co 4+energy/Co3+ ).storage The electrodes system. themselvesThe binder are comprised should not reactof with active, any conductive, other components and binding or intermediates materials cast formed onto a metallicduring operation current collector. The and should remainconductive stable at material the high compensates and low potentials for the poor experienced electronic by conductivity, the cathode thereby and facilitating anode, respectively.charge Good transfer dispersive and improving capabilities electrode are also kinetics.extremely Binders helpful interact for binders with to many of these possess and can components,help evenly eachdistribute of which the add other requirements components to maintain during fabrication. the stability andThese performance of depend on propertiesthe cell. of the polymer chains, including the presence of charges, their den‐ sity, and chain flexibility,The batterywhich all structure play a highlightsrole in the theelectrostatic importance repulsion of several and properties resisting for polymer depletion flocculationbinders, [6,10]. which While are not summarized necessary, in binders Figure 2would. Mechanical ideally properties,support electrical which include the and ionic conductivitystiffness, in toughness,the energy and storage hardness device. of the Electrical binder asconductivity well as its adhesion can primarily to the other compo- nents, are important for the electrode to withstand the forces that result from the expansion and contraction of active materials during charge/discharge cycles. Thermal properties, particularly thermal stability, are also important, both for the high temperatures commonly used for curing and drying in electrode fabrication
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