Sodium carboxymethyl cellulose (CMC) and polyacrylic acid (PAA) are state-of-the-art binders in aqueous-processed anodes for lithium-ion batteries. Binders act as dispersing agents and rheology modifiers in aqueous slurries, while also providing mechanical integrity of dry electrodes during battery fabrication and operation. However, despite their low concentration, they may have detrimental effects on the conductivity and electrochemical performance of batteries, for example, due to their adsorption on active material particles, which is supposed to limit Li+ insertion and extraction, but also affect electrode microstructure and adhesion to the current collector. Here, a commercially available, cross-linked acrylate binder (Carbopol® Ultrez10, x-PAA) with high thickening efficiency is applied for graphite anodes. At lower polymer content, anode slurries based on x-PAA exhibit high-shear viscosities similar to those of the CMC reference and provide a yield stress, which is advantageous for slurry stability. Furthermore, SBR content could be reduced without loss of adhesion strength compared to the CMC reference, since x-PAA does not adsorb onto graphite. Thus, the total binder content could be lowered by about 40% in comparison to reference anodes comprising CMC. The substantial reduction in total binder amount resulted in slightly lower long-term stability compared to the reference cell including CMC. Cells incorporating x-PAA, however, outperformed references under fast-charging conditions (up to 5C) presumably since x-PAA does not adsorb on graphite, thus enabling more effective Li+ insertion and extraction. Further refinement of crosslinking microstructure may enable fabrication of electrodes with higher energy density and higher capacity retention during cycling, irrespective of cycling rate.
| [1] |
A. Guerfi, M. Kaneko, M. Petitclerc, M. Mori, and K. Zaghib, “LiFePO4 Water-Soluble Binder Electrode for Li-Ion Batteries,” Journal of Power Sources163 (2007): 1047-1052, https://doi.org/10.1016/j.jpowsour.2006.09.067.
|
| [2] |
J.-H. Lee, J.-S. Kim, Y. C. Kim, et al., “Effect of Carboxymethyl Cellulose on Aqueous Processing of LiFePO4 Cathodes and Their Electrochemical Performance,” Electrochemical and Solid-State Letters11 (2008): A175, https://doi.org/10.1149/1.2966286.
|
| [3] |
A. Cholewinski, P. Si, M. Uceda, M. Pope, and B. Zhao, “Polymer Binders: Characterization and Development Toward Aqueous Electrode Fabrication for Sustainability,” Polymers13 (2021): 631, https://doi.org/10.3390/polym13040631.
|
| [4] |
B. Lestriez, “Functions of Polymers in Composite Electrodes of Lithium Ion Batteries,” Comptes Rendus Chimie13 (2010): 1341-1350, https://doi.org/10.1016/j.crci.2010.01.018.
|
| [5] |
N. Loeffler, T. Kopel, G.-T. Kim, and S. Passerini, “Polyurethane Binder for Aqueous Processing of Li-Ion Battery Electrodes,” Journal of the Electrochemical Society162 (2015): A2692-A2698, https://doi.org/10.1149/2.0641514jes.
|
| [6] |
R. Gordon, R. Orias, and N. Willenbacher, “Effect of Carboxymethyl Cellulose on the Flow Behavior of Lithium-Ion Battery Anode Slurries and the Electrical as Well as Mechanical Properties of Corresponding Dry Layers,” Journal of Materials Science55 (2020): 15867-15881, https://doi.org/10.1007/s10853-020-05122-3.
|
| [7] |
M. J. Jolley, T. S. Pathan, C. Jenkins, and M. J. Loveridge, “Exploration of High and Low Molecular Weight Polyacrylic Acids and Sodium Polyacrylates as Potential Binder System for Use in Silicon Graphite Anodes,” ACS Applied Energy Materials8 (2025): 1647-1660, https://doi.org/10.1021/acsaem.4c02672.
|
| [8] |
T. Mori and K. Kitamura, “Effect of Adsorption Behaviour of Polyelectrolytes on Fluidity and Packing Ability of Aqueous Graphite Slurries,” Advanced Powder Technology28 (2017): 280-287, https://doi.org/10.1016/j.apt.2016.10.005.
|
| [9] |
W. J. Chang, G. H. Lee, Y. J. Cheon, et al., “Direct Observation of Carboxymethyl Cellulose and Styrene–Butadiene Rubber Binder Distribution in Practical Graphite Anodes for Li-Ion Batteries,” ACS Applied Materials & Interfaces11 (2019): 41330-41337, https://doi.org/10.1021/acsami.9b13803.
|
| [10] |
T. Kwon, J. W. Choi, and A. Coskun, “The Emerging Era of Supramolecular Polymeric Binders in Silicon Anodes,” Chemical Society Reviews47 (2018): 2145-2164, https://doi.org/10.1039/c7cs00858a.
|
| [11] |
J. H. Lee, U. Paik, V. A. Hackley, and Y. M. Choi, “Effect of Carboxymethyl Cellulose on Aqueous Processing of Natural Graphite Negative Electrodes and Their Electrochemical Performance for Lithium Batteries,” Journal of the Electrochemical Society152, no. 9 (2005): A1763, https://doi.org/10.1149/1.1979214.
|
| [12] |
X. Qi, W. Song, and J. Shi, “Density Functional Theory Study the Effects of Oxygen-Containing Functional Groups on Oxygen Molecules and Oxygen Atoms Adsorbed on Carbonaceous Materials,” PLoS One12 (2017): e0173864, https://doi.org/10.1371/journal.pone.0173864.
|
| [13] |
A. Magasinski, B. Zdyrko, I. Kovalenko, et al., “Toward Efficient Binders for Li-Ion Battery Si-Based Anodes: Polyacrylic Acid,” ACS Applied Materials & Interfaces2 (2010): 3004-3010, https://doi.org/10.1021/am100871y.
|
| [14] |
D. Mazouzi, Z. Karkar, C. Reale Hernandez, et al., “Critical Roles of Binders and Formulation At Multiscales of Silicon-Based Composite Electrodes,” Journal of Power Sources280 (2015): 533-549, https://doi.org/10.1016/j.jpowsour.2015.01.140.
|
| [15] |
K. Hofmann and N. Willenbacher, “How Carboxymethylcellulose Adsorption and Porous Active Material Particles Diminish the Adhesion of Graphite-Silicon Anodes in Lithium-Ion Batteries,” Energy Materials5 (2025): 500092, https://doi.org/10.20517/energymater.2024.281.
|
| [16] |
D. G. Mintis and V. G. Mavrantzas, “Effect of pH and Molecular Length on the Structure and Dynamics of Short Poly(Acrylic Acid) in Dilute Solution: Detailed Molecular Dynamics Study,” Journal of Physical Chemistry B123 (2019): 4204-4219, https://doi.org/10.1021/acs.jpcb.9b01696.
|
| [17] |
D. Martins, F. Dourado, and M. Gama, “Effect of Ionic Strength, pH and Temperature on the Behaviour of Re-Dispersed BC:CMC - A Comparative Study With Xanthan Gum,” Food Hydrocolloids135 (2023): 108163, https://doi.org/10.1016/j.foodhyd.2022.108163.
|
| [18] |
S. Kobayashi and K. Müllen, Encyclopedia of Polymeric Nanomaterials (Springer Berlin Heidelberg, 2015), https://doi.org/10.1007/978-3-642-29648-2.
|
| [19] |
W. Kam, C.-W. Liew, J. Y. Lim, and S. Ramesh, “Electrical, Structural, and Thermal Studies of Antimony Trioxide-Doped Poly(Acrylic Acid)-Based Composite Polymer Electrolytes,” Ionics20 (2014): 665-674, https://doi.org/10.1007/s11581-013-1012-0.
|
| [20] |
J. Wang, Q. Zheng, M. Fang, S. Ko, Y. Yamada, and A. Yamada, “Concentrated Electrolytes Widen the Operating Temperature Range of Lithium-Ion Batteries,” Advancement of Science8 (2021): 2101646, https://doi.org/10.1002/advs.202101646.
|
| [21] |
R. Xie, A. R. Weisen, Y. Lee, et al., “Glass Transition Temperature From the Chemical Structure of Conjugated Polymers,” Nature Communications11 (2020): 893, https://doi.org/10.1038/s41467-020-14656-8.
|
| [22] |
K. Hofmann, A. D. Hegde, X. Liu-Theato, R. Gordon, A. Smith, and N. Willenbacher, “Effect of Mechanical Properties on Processing Behavior and Electrochemical Performance of Aqueous Processed Graphite Anodes for Lithium-Ion Batteries,” Journal of Power Sources593 (2024): 233996, https://doi.org/10.1016/j.jpowsour.2023.233996.
|
| [23] |
R. Kasinathan, M. Marinaro, P. Axmann, and M. Wohlfahrt–Mehrens, “Influence of the Molecular Weight of Poly-Acrylic Acid Binder on Performance of Si-Alloy/Graphite Composite Anodes for Lithium-Ion Batteries,” Energy Technology6 (2018): 2256-2263, https://doi.org/10.1002/ente.201800302.
|
| [24] |
P. Parikh, M. Sina, A. Banerjee, et al., “Role of Polyacrylic Acid (PAA) Binder on the Solid Electrolyte Interphase in Silicon Anodes,” Chemistry of Materials31 (2019): 2535-2544, https://doi.org/10.1021/acs.chemmater.8b05020.
|
| [25] |
C. Li, T. Shi, H. Yoshitake, and H. Wang, “Improved Performance in Micron-Sized Silicon Anodes by In Situ Polymerization of Acrylic Acid-Based Slurry,” Journal of Materials Chemistry A4 (2016): 16982-16991, https://doi.org/10.1039/C6TA05650D.
|
| [26] |
W. Yi, T. Zhao, D. Li, et al., “Research Progress of Polyacrylate Binders for Silicon-Based Anodes In Lithium-Ion Batteries,” Chemistry – A European Journal31 (2025): e202500321, https://doi.org/10.1002/chem.202500321.
|
| [27] |
L. Wei, C. Chen, Z. Hou, and H. Wei, “Poly (Acrylic Acid Sodium) Grafted Carboxymethyl Cellulose as a High Performance Polymer Binder for Silicon Anode in Lithium Ion Batteries,” Scientific Reports6 (2016): 19583, https://doi.org/10.1038/srep19583.
|
| [28] |
Q. Huang, C. Wan, M. Loveridge, and R. Bhagat, “Partially Neutralized Polyacrylic Acid/Poly(Vinyl Alcohol) Blends as Effective Binders for High-Performance Silicon Anodes in Lithium-Ion Batteries,” ACS Applied Energy Materials1 (2018): 6890-6898, https://doi.org/10.1021/acsaem.8b01277.
|
| [29] |
Y. Gao, X. Qiu, X. Wang, et al., “Chitosan- g -Poly(Acrylic Acid) Copolymer and Its Sodium Salt as Stabilized Aqueous Binders for Silicon Anodes in Lithium-Ion Batteries,” ACS Sustainable Chemistry & Engineering7 (2019): 16274-16283, https://doi.org/10.1021/acssuschemeng.9b03307.
|
| [30] |
X. Zhao, C.-H. Yim, N. Du, and Y. Abu-Lebdeh, “Crosslinked Chitosan Networks as Binders for Silicon/Graphite Composite Electrodes in Li-Ion Batteries,” Journal of the Electrochemical Society165 (2018): A1110-A1121, https://doi.org/10.1149/2.114805jes.
|
| [31] |
L. Zhu, F. Du, Y. Zhuang, et al., “Effect of Crosslinking Binders on Li-Storage Behavior of Silicon Particles as Anodes for Lithium Ion Batteries,” Journal of Electroanalytical Chemistry845 (2019): 22-30, https://doi.org/10.1016/j.jelechem.2019.05.019.
|
| [32] |
H. Zhong, J. He, and L. Zhang, “Crosslinkable Aqueous Binders Containing Arabic Gum-Grafted-Poly (Acrylic Acid) and Branched Polyols for Si Anode of Lithium-Ion Batteries,” Polymer215 (2021): 123377, https://doi.org/10.1016/j.polymer.2020.123377.
|
| [33] |
A. N. Preman, S. Aswale, T. T. Salunkhe, et al., “Better Together: Integrating Adhesion and Ion Conductivity in Composite Binders for High-Performance Silicon Anodes,” Journal of Materials Chemistry A13 (2025): 8355-8367, https://doi.org/10.1039/D4TA07078J.
|
| [34] |
D. Jeong, J. Yook, D. S. Kwon, J. Shim, and J. C. Lee, “Interweaving Elastic and Hydrogen Bond-Forming Polymers Into Highly Tough and Stress-Relaxable Binders for High-Performance Silicon Anode in Lithium-Ion Batteries,” Advanced Science10 (2023): 2302027, https://doi.org/10.1002/advs.202302027.
|
| [35] |
C. Wang, S. Wu, and J. Weng, “Integrating With a Tough Framework and Efficient Self-Healing Behavior Based on a Flexible Polymer Skeleton for Si Anode Binders in Lithium-Ion Cells,” Journal of Energy Storage80 (2024): 110314, https://doi.org/10.1016/j.est.2023.110314.
|
| [36] |
P. Lv, H. Liu, Z. Cui, et al., “Covalently Cross-Linked Waterborne Polyurethane Acrylate Network Binder for Low-Expansion Silicon/Carbon Anode,” Journal of Power Sources655 (2025): 237985, https://doi.org/10.1016/j.jpowsour.2025.237985.
|
| [37] |
C. Oelschlaeger, J. Marten, F. Péridont, and N. Willenbacher, “Imaging of the Microstructure of Carbopol Dispersions and Correlation With Their Macroelasticity: A Micro- and Macrorheological Study,” Journal of Rheology66 (2022): 749-760, https://doi.org/10.1122/8.0000452.
|
| [38] |
L. Baudonnet, J. L. Grossiord, and F. Rodriguez, “Effect of Dispersion Stirring Speed on the Particle Size Distribution and Rheological Properties of Three Carbomers,” Journal of Dispersion Science and Technology25 (2004): 183-192, https://doi.org/10.1081/DIS-120030665.
|
| [39] |
A. Kowalczyk, C. Oelschlaeger, and N. Willenbacher, “Visualization of Micro-Scale Inhomogeneities in Acrylic Thickener Solutions: A Multiple Particle Tracking Study,” Polymer58 (2015): 170-179, https://doi.org/10.1016/j.polymer.2014.12.041.
|
| [40] |
J. H. Park, S. H. Kim, and K. H. Ahn, “Role of Carboxymethyl Cellulose Binder and Its Effect on the Preparation Process of Anode Slurries for Li-Ion Batteries,” Colloids and Surfaces, A: Physicochemical and Engineering Aspects664 (2023): 131130, https://doi.org/10.1016/j.colsurfa.2023.131130.
|
| [41] |
J.-H. Lee, U. Paik, V. A. Hackley, and Y.-M. Choic, “Effect of Carboxymethyl Cellulose on Aqueous Processing,” Journal of the Electrochemical Society152 (2005): A1763, https://doi.org/10.1149/1.1979214.
|
| [42] |
J. H. Park, S. H. Kim, and K. H. Ahn, “Role of Carboxymethyl Cellulose Binder and Its Effect on the Preparation Process of Anode Slurries for Li-Ion Batteries,” Colloids and Surfaces, A: Physicochemical and Engineering Aspects664 (2023): 131130, https://doi.org/10.1016/j.colsurfa.2023.131130.
|
| [43] |
J. Mewis and N. J. Wagner, Colloidal Suspension Rheology (Cambridge University Press, 2011), https://doi.org/10.1017/CBO9780511977978.
|
| [44] |
K. Dyhr and N. Willenbacher, “Formulating Graphite-Filled PU Dispersions With Extended Shelf Life Using the Capillary Suspension Concept,” Colloids and Interfaces9 (2025): 26, https://doi.org/10.3390/colloids9030026.
|
| [45] |
N. J. Balmforth, I. A. Frigaard, and G. Ovarlez, “Yielding to Stress: Recent Developments in Viscoplastic Fluid Mechanics,” Annual Review of Fluid Mechanics46 (2014): 121-146, https://doi.org/10.1146/annurev-fluid-010313-141424.
|
| [46] |
A. N. Beris, J. A. Tsamopoulos, R. C. Armstrong, and R. A. Brown, “Creeping Motion of a Sphere Through a Bingham Plastic,” Journal of Fluid Mechanics158 (1985): 219-244, https://doi.org/10.1017/S0022112085002622.
|
| [47] |
B. Bitsch, J. Dittmann, M. Schmitt, P. Scharfer, W. Schabel, and N. Willenbacher, “A Novel Slurry Concept for the Fabrication of Lithium-Ion Battery Electrodes With Beneficial Properties,” Journal of Power Sources265 (2014): 81-90, https://doi.org/10.1016/j.jpowsour.2014.04.115.
|
| [48] |
B. G. Westphal and A. Kwade, “Critical Electrode Properties and Drying Conditions Causing Component Segregation in Graphitic Anodes for Lithium-Ion Batteries,” Journal of Energy Storage18 (2018): 509-517, https://doi.org/10.1016/j.est.2018.06.009.
|
| [49] |
B. Westphal, H. Bockholt, T. Günther, W. Haselrieder, and A. Kwade, “Influence of Convective Drying Parameters on Electrode Performance and Physical Electrode Properties,” ECS Transactions64 (2015): 57-68, https://doi.org/10.1149/06422.0057ecst.
|
| [50] |
J. Kumberg, W. Bauer, J. Schmatz, et al., “Reduced Drying Time of Anodes for Lithium-Ion Batteries Through Simultaneous Multilayer Coating,” Energy Technology9 (2021): 2100367, https://doi.org/10.1002/ente.202100367.
|
| [51] |
A. Smith, P. Stüble, L. Leuthner, A. Hofmann, F. Jeschull, and L. Mereacre, “Potential and Limitations of Research Battery Cell Types for Electrochemical Data Acquisition,” Batter. Supercaps6 (2023): e202300080, https://doi.org/10.1002/batt.202300080.
|
| [52] |
R. Tian, S.-H. Park, P. J. King, et al., “Quantifying the Factors Limiting Rate Performance in Battery Electrodes,” Nature Communications10 (2019): 1933, https://doi.org/10.1038/s41467-019-09792-9.
|
| [53] |
R. Gordon and A. Smith, “Towards More Realistic Li-Ion Battery Safety Tests Based on Li-Plating as Internal Cell Error,” Journal of Energy Storage72 (2023): 108200, https://doi.org/10.1016/j.est.2023.108200.
|
| [54] |
K. Ui, D. Fujii, Y. Niwata, et al., “Analysis of Solid Electrolyte Interface Formation Reaction and Surface Deposit of Natural Graphite Negative Electrode Employing Polyacrylic Acid as a Binder,” Journal of Power Sources247 (2014): 981-990, https://doi.org/10.1016/j.jpowsour.2013.08.083.
|
RIGHTS & PERMISSIONS
2025 The Author(s). Battery Energy published by Xijing University and John Wiley & Sons Australia, Ltd.
PDF
