A Lithium Polyacrylate-based High-performance Composite Binder for Graphite Anode

doi:10.6023/A24050160

Abstract

Lithium polyacrylate (LiPAA) is widely used as a binder for lithium-ion battery anodes due to its high ionic conductivity and good chemical stability. However, LiPAA has disadvantages such as low viscosity and high hardness, resulting in the adhesive performance, flexibility and processability of the anode becoming an issue when LiPAA is used as a binder. In this paper, a composite formula was developed by integrating LiPAA with other polymers, including carboxymethyl cellulose (CMC) or Xanthan gum (XG) to tune the viscosity, sodium hyaluronate (HA) to reduce the brittleness, and benzene butadiene rubber (SBR) to improve the stripping strength. On this basis, two LiPAA-based composite binders (LiPAA-CMC-HA-SBR and LiPAA-XG-HA-SBR) were developed. Compared with the commercial anode binder (CMC-SBR), the two LiPAA-based composite binders both demonstrate well-tuned bonding strength and flexibility; more importantly, they also can significantly improve the interfacial affinity between the graphite particles, the conductive agent and the electrolyte, which hence promotes the diffusion kinetics of lithium ions at the electrode/electrolyte interface and thus improves the electrochemical performance of the graphite anode. At the current density of 0.5 C, after 150 cycles, the graphite anode prepared with our two composite binders displayed a capacity of 209 mAh•g⁻¹ and 191 mAh•g⁻¹, respectively, which was much higher than the graphite anode prepared with the commercial CMC-SBR binder (which is 108 mAh•g⁻¹). The graphite anode prepared with our binder also demonstrates much higher rate capability and better cycling stability compared to the control. Characterizations of the cycled anode reveal that, in the anode prepared with our binders, a much more homogeneous distribution of the conductive carbon and the graphite particles was observed, and a solid electrolyte interphase (SEI) with a higher fraction of LiF was formed. In addition, in the commercial CMC-SBR formula, a mass fraction of SBR up to 50% is required; in comparison, in our two LiPAA-based formulations, only a small fraction of SBR is employed yet which can still maintain the integrity of the anode sheet. It is worth noting that, at a low binder content (≈3%) and high active material load (≈95%), the graphite anode elec trode prepared by these two composite binders can still maintain remarkable mechanical strength, and it also demonstrates excellent electrochemical performance, showing the promising industrialization potential of such LiPAA-based composite binders.

Key words: lithium-ion battery, graphite anode, composite binder, lithium polyacrylate

Cite this article

Kungui Zheng, Junke Liu, Yiyang Hu, Zuwei Yin, Yao Zhou, Juntao Li, Shigang Sun. A Lithium Polyacrylate-based High-performance Composite Binder for Graphite Anode[J]. Acta Chimica Sinica, 2024, 82(8): 833-842.

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Fig. & Tab. 9

Figure 1. The molecular structure of the binders selected in this work: (a) lithium polyacrylate (LiPAA); (b) sodium carboxymethyl cellulose (CMC); (c) xanthan gum (XG); (d) sodium hyaluronate (HA); (e) styrene-butadiene rubber (SBR)

Figure 2. (a) Viscosity test results of 2% solutions of different binders; (b) electronic photographs of commercial CMC-SBR binders and LiPAA-based composite binders solutions after stand 24 h; (c) stress-strain profiles of films with different binders; (d) nanoindentation and corresponding modulus and hardness

Figure 3. Bending test results of anode sheets and films prepared with different binders

Figure 4. (a) Peel strength profiles of different binders; (b) peel strength of different binders; (c, d) infrared spectra of different binders; (e) change rate of electrode thickness of graphite anode prepared with different binders after lithium insertion to 0.01 V; (f) the change rate of electrode thickness of graphite anode prepared with different binders after soaking in electrolyte for 5 d

Figure 5. Contact angle between graphite anode sheet prepared with different binders and electrolyte: (a) CMC-SBR; (b) LiPAA-CMC-HA-SBR; (c) LiPAA-XG-HA-SBR; (d) electrochemical impedance spectra of batteries assembled with graphite anode of different binders before cycling and fitting results of charge transfer impedance (Rct)

Figure 6. (a) LSV curve of copper foil coated with different binders; (b) cycle performance of batteries with different graphite anodes; (c) rate performance; (d) charge and discharge curve at 1 C; (e) charge and discharge curve at 2 C and (f) cyclic voltammetry curve

Figure 7. (a) Electrochemical impedance spectra of batteries with graphite anode with different binders after 10 cycles; (b) the relevant Zre-ω-1/2 plot and (c) the resulting Warburg factor

Figure 8. SEM images of graphite anode prepared with different binders before (a, b) cycle and after (c) 10 cycles

Figure 9. Fine XPS spectra of different graphite anodes after 10 cycles: (a) C 1s; (b) F 1s; (c) the atomic fraction of C and F on the electrode surface and after etching up to 50 nm

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