Design and modification progress of binders for silicon-based anodes of lithium-ion batteries
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摘要: 发展锂离子电池是缓解当前能源和环境问题的有力措施，但其能量密度已无法满足未来储能装置的高要求。发展高比能量型锂离子电池必须从提高电极材料的性能入手。硅基材料具有容量高、成本低、平台电压低等优点，被认为是最具潜力的负极材料。然而，该类材料在充放电过程中会发生巨大的体积变化(300%)，导致电池容量下降严重甚至失效。近年来，研究者们开始着眼于通过对电极中的粘结剂进行结构设计和复合改性来提升硅基负极的性能，并取得了显著的效果。基于硅基负极目前存在的问题，总结了适用于硅基负极的粘结剂类型，并从粘结剂分子链结构设计和增强电极微粒间作用力这两个方面综述了近年来硅基负极中粘结剂的设计改性进展，最终展望了硅基负极用粘结剂的发展趋势和未来前景。Abstract: Developing lithium-ion batteries (LIBs) is a powerful measure to alleviate current energy and environmental problems, but their energy density can no longer meet the high requirements of future energy storage devices. The development of LIBs with high energy density must start from improving the performance of electrode materials. Silicon-based materials have the advantages of high capacity, low cost, and low platform voltage, and are considered to be the most promising anode materials. However, this type of material would undergo a huge volume change (300%) during charging and discharging processes, resulting in serious capacity decline or even failure. In recent years, researchers have begun to focus on improving the performance of silicon-based anodes through structural design and composite modification of the binder in the electrode, and significant results have been achieved. In this paper, the existing problems of silicon-based anodes were briefly introduced, and the types of the binders suitable for silicon-based anodes were summarized. The progress in the design and modification of the binders in silicon-based anodes in recent years was reviewed from the aspects of molecular chain structure design of the binders and enhancement of inter particle force in the electrode. Finally, the development trend and future prospect of the binders for silicon-based anodes were prospected.
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Key words:
- batteries /
- anodes /
- silicon /
- lithium ions /
- binders /
- energy /
- environmental
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图 2 <100>、<110>、<111>方向的膨胀和裂纹行为的统计分析和无定形硅纳米管阵列嵌锂后形态[16]
Figure 2. Statistical analysis on the expansion and fracture behavior of the <100>, <110>, <111>, and amorphous silicon nanotubes after full lithiation[16]((a) Schematics of the cross-sectional shape and fracture angles of nanotubes; (b) Variations of wall thickness; (c) Cross-sectional area and hollow area; (d) Height; (e) Volume of Si nanotubes)
图 3 <100> (a)、<110> (b)、<111> (c) 纳米管阵列嵌锂后裂纹的角度分布；径向应力分布示意图 (d)；应力积累与嵌锂时间关系曲线(e)；<111>纳米管阵列不同角度应力积累与嵌锂时间关系曲线(f)；不同角度应力积累的径向分布曲线 (g)；嵌锂后的应力积累和裂纹比率与内径(h)；管厚(i)和厚度/外径 (j) 之间的关系曲线[16]
Figure 3. <100> (a), <110> (b), <111> (c), the angular distribution of the crack after the nanotube array is lithium-inserted, and the schematic diagram of the radial stress distribution (d) , Stress accumulation and lithium insertion time relationship curve (e), <111>Nanotube array different angle stress accumulation and lithium insertion time relationship curve (f), different angle stress accumulation radial distribution curve (g), after lithium insertion The relationship between stress accumulation and crack ratio and inner diameter (h), tube thickness (i) and thickness/outer diameter (j)[16]
图 4 体电解质界面(SEI)膜的可视化3D成像，其中不同颜色箭头代表着不同的反应路径：路径1为室温且无电解液添加剂的充放电过程，路径2为55℃且无电解液添加剂的充放电过程，路径3为室温且有电解液添加剂的充放电过程[17]
Figure 4. 3D visual imaging of solid electrolyte interface (SEI) film, in which different color arrows represent different reaction paths: Path 1 is the charge and discharge process at room temperature without electrolyte additive, path 2 is the charge and discharge process at 55℃ without electrolyte additive, path 3 is the charge and discharge process at room temperature with electrolyte additive[17]
图 6 预先设计裂纹的光学显微镜图像[40]
Figure 6. Optical microscopy image of predesigned crack[40]((a)-(c)) Prepared and after 1.5 and 3 h on pyrimidone (Upy)-polyethylene glycol (PEG)-Si-15 electrode; (d)-(f), (g)-(i) Prepared and after 13 and 25 h on Upy-PEG-Si-15 and polyacrylic acid (PAA)-Si-15 electrode, respectively; (j) Proposed mechanism for self-healing of Upy-PEG binders)
图 7 黏结机制示意图[14]
Figure 7. Schematic illustration of the binding mechanism[14]((a) Diffusion/penetrating process during electrode preparation; (b) Formation of mechanical interlocking during the drying process; (c) Interfacial bonding forces include intermolecular forces and chemical bonds; (d) Polymer states in a bonding system: Bonded polymer, fixed polymer, and excessive polymer)
图 8 提出的用于SiMP阳极的PR-PAA粘结剂的应力耗散机制[43]
Figure 8. Proposed stress dissipation mechanism of PR-PAA binder for SiMP anodes[43]((a) Pulley principle to lower the force in lifting an object; (b) Graphical representation of the operation of PR-PAA binder to dissipate the stress during repeated volume changes of SiMPs, together with chemical structures of polyrotaxane and PAA; (c) Schematic illustration of the pulverization of the PAA-SiMP electrode during cycling and its consequent SEI layer growth)
图 9 以自固化PAA-Upy聚合物为粘结剂的硅阳极充放电过程示意图[49]
Figure 9. Schematic illustration of the charge–discharge process of silicon anodes using self-healable PAA-Upy polymer as binder[49]((a) Chemical structure of PAA-Upy supramolecular polymer; (b) Upy-Upy dimers could reversibly break and reform based on quadruple hydrogen bonding; (c) Large volume expansion of silicon particles during the charge process results in the dissociation of the noncovalent crosslinking of Upy dimers, and these crosslinking networks can be rebuilt when the battery undergoes delithiation process even after many cycles due to the reversibility of quadruple hydrogen bonding)
图 10 海藻酸盐(Alg) (a) 和β-CDp (b) 粘合剂的结构式和示意图；硅(球)在锂化/脱锂过程中SiAlg (c) 和Siβ-CDp (d) 的粘结剂变化示意图[50]
Figure 10. Structural formulas and graphical representations of the Alginate (Alg) (a) and β-CD polymer (β-CDp) (b) binders; Schematic representations of Si-binder configurations for SiAlg (c) and Siβ-CDp (d) during lithiation/delithiation of Si (sphere)[50]
图 11 NaPAA与羧甲基纤维素基聚合物(CMC)主链共价接枝的合成方案 (a)、NaPAA-g-CMC粘合剂适应循环过程中Si颗粒体积变化的可能机制 (b)[52]
Figure 11. Synthetic scheme for covalent graft of NaPAA onto carboxymethyl cellulose (CMC) backbone (a), possible working mechanism of NaPAA-g-CMC binder to accommodate the lager volume change of Si particles during cycling (b)[52]
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