Self-Healing Systems in Silicon Anodes for Li-Ion Batteries

Abstract

Self-healing is the capability of materials to repair themselves after the damage has occurred, usually through the interaction between molecules or chains. Physical and chemical processes are applied for the preparation of self-healing systems. There are different approaches for these systems, such as heterogeneous systems, shape memory effects, hydrogen bonding or covalent-bond interaction, diffusion, and flow dynamics. Self-healing mechanisms can occur in particular through heat and light exposure or through reconnection without a direct effect. The applications of these systems display an increasing trend in both the R&D and industry sectors. Moreover, self-healing systems and their energy storage applications are currently gaining great importance. This review aims to provide general information on recent developments in self-healing materials and their battery applications given the critical importance of self-healing systems for lithium-ion batteries (LIBs). In the first part of the review, an introduction about self-healing mechanisms and design strategies for self-healing materials is given. Then, selected important healing materials in the literature for the anodes of LIBs are mentioned in the second part. The results and future perspectives are stated in the conclusion section.

Keywords: energy storage; lithium-ion batteries; polymers; self-healing; silicon anodes.

Figure 1

Self-healing systems. Reprinted with permission from ref. [7]. Copyright 2012 Elsevier.

Figure 2

Intrinsically capsulated self-healing systems. Reprinted with permission from ref. [17]. Copyright 2009 Wiley.

Figure 3

(a). Mechanism of the self-healing polymer, reprinted with permission from ref. [62], copyright 2015, Advanced Energy Materials. (b). Scheme of the self-healing electrode with a homogenous distribution of silicon microparticles and self-healing polymer with hydrogen bond. Reprinted with permission from ref. [63], copyright 2018, Royal Society of Chemistry. (c). Scheme of silicon anode with self-healing polymer and SEM images of silicon anode with self-healing polymer coating, reprinted with permission from ref. [62], copyright 2015, Advanced Energy Materials.

Figure 4

(a). The mechanism of the synthesis of self-healing polymers. Reprinted with permission from ref. [29], copyright 2016, ACS Applied Materials & Interfaces. (b). Structure of PAA–UPy binder and dimers bottomed on quadruple hydrogen bond and the illustration of the large volume expansion of silicon particles, reprinted with permission from ref. [40], copyright 2018, Advanced Science News. (c). Mechanism with CMC binder crosslinked CMC–PAA binder, and self-healing CMC–CPAM binder, reprinted with permission from ref. [59], copyright 2020, Elsevier. (d). Synthesis mechanism of the carboxylic acid functional self-healing polymer, from ref. [65], copyright 2019, Advanced Materials. (e). Scheme of silicon anode with ultrasonic assisted by PEDOT:PSS binder self-healing conductive hydrogel binder, reprinted with permission from ref. [35], copyright 2020, Elsevier. (f). Synthesis of alginic acid and acrylamide-based dual-crosslinking polymers, from ref. [66], copyright 2019, Journal of Power Sources. (g). C-chitosan/Si nanoparticles surface structure and the capacity–cycle graph of silicon anode with CMC, C-chitosan, and alginate, reprinted with permission from ref. [64], copyright 2014, Journal of Power Source.

Figure 5

(a). A capillary cell with (b). its conceptual picture. (c). Magnified view of the surface near Ga electrode before lithiation and (d). after partial lithiation. Reprinted with permission from ref. [73], copyright 2011, Elsevier.

Figure 6

(a). Morphology of liquid metal–silicon electrode before the cycle, after the 200th cycle, and after the 1500th cycle. (b). Capacity–cycle graph of liquid metal anode and Si anode cycled using different current densities for 500 cycles; Nyquist graph of the liquid metal anode, liquid metal–silicon anode, and silicon anode. Reprinted with permission from ref. [48], copyright 2018, Elsevier.

Figure 7

(a). Scheme of coordinate bonds between alginate chains and calcium cations, reprinted with permission from ref. [74], copyright 2014, Elsevier. (b). Self-healing illustration of Ca–alginate–silicon anode during cycling, reprinted with permission from ref. [75], copyright 2014, Elsevier. (c). Scheme of silicon–self-healing binder over Fe⁺³/cathecol–based bond cleave and rearrangement type (metal–ligand complex) healing system, reprinted with permission from ref. [76], copyright 2019, Advanced Materials.

Figure 8

The mechanism of dynamic crosslinking for silicon nanoparticle anodes by engaging host–guest interactions between hyperbranched βcyclodextrin polymer and a dendritic-gallic-acid-derived supramolecular crosslinker incorporating six adamantane units. Reprinted with permission from ref. [78], copyright 2015, American Chemical Society.

Figure 9

Chemical structures of polymers and synthesis of lithium 2-methyl-2-(4-vinylbenzyl) malonate from Meldrum’s acid, reprinted with permission from ref. [79], copyright 2014, Advanced Materials.

Figure 10

(a). The chemical structure of PAA-PBI, reprinted with permission from ref. [81], copyright 2015, American Chemical Society. (b). Self-healing interaction with silicon and binder, reprinted with permission from ref. [15], copyright 2018, Elsevier. (c). The interactions between binder, silicon particles, and CB and the structure of reDNA/alginate, reprinted with permission from ref. [82], copyright 2018, Advanced Materials.

Figure 11

(a). Synthesis of a crosslinking catechol-rich network, reprinted with permission from ref. [98], copyright 2019, American Chemical Society. (b). The self-healing process between glycol chitosan and oxidized alginate (OSA) and schematic comparison of GCS-I-OSA binder and traditional binder, reprinted with permission from ref. [34], copyright 2020, Elsevier.

Figure 11

(a). Synthesis of a crosslinking catechol-rich network, reprinted with permission from ref. [98], copyright 2019, American Chemical Society. (b). The self-healing process between glycol chitosan and oxidized alginate (OSA) and schematic comparison of GCS-I-OSA binder and traditional binder, reprinted with permission from ref. [34], copyright 2020, Elsevier.

Figure 12

Cycle–capacity of the different types silicon electrodes and the interactions between Si nanoparticles and PAA binder, reprinted with permission from ref. [99], copyright 2019, American Chemical Society.

Figure 13

(a). The BFPU polymer that has different functionalities, from ionic conductivity and mechanical durability to self-healable S-S bonds (b). Silicon electrode with PAA–BFPU binder, reprinted with permission from ref. [101], copyright 2021, Advanced Materials.

Figure 14

(a). Diels-Alder chemistry in silicon anode with self-healing binder (b). The comparison of cycle-capacity among binders, reprinted with permission from ref. [22], copyright 2021, Advanced Materials.