Shuttle Balance between Lithiophilic Functionalities Substituted on Conjugated Polymers to Improve Lithium-Ion Diffusion and Cycling Stability of Batteries,Macromolecules

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Shuttle Balance between Lithiophilic Functionalities Substituted on Conjugated Polymers to Improve Lithium-Ion Diffusion and Cycling Stability of Batteries
Macromolecules ( IF 5.1 ) Pub Date : 2024-08-15 , DOI: 10.1021/acs.macromol.4c01036
Radhakisan Kargude _{1,

2} , Bharathkumar H. Javaregowda _{1,

2} , Sathishkumar Palani ₁ , Anup K. Singh _{1,

2} , Kothandam Krishnamoorthy _{1,

2}

Affiliation

Herein, we report the design and synthesis of i-Indigo and trans-1,2-di(2-thienyl)ethylene (TVT) comprising copolymers with various side chains that are used as anode-cum-binder in Li-ion batteries. The TVT disrupts the crystallinity, and the i-Indigo renders the handle for unsymmetrical substitution. Polymer P1 comprises alkyl chains on i-Indigo, whereas P2 comprises an alkyl chain and a chain with a urethane moiety as another side chain. Polymer P3 comprises i-Indigo with a urethane moiety and triethylene glycol as side chains. The i-Indigo in P4 is substituted with triethylene glycol and alkyl chains as side chains. These polymers were found to be amorphous with π–π stacking due to the extremely small torsional angle imparted by TVT moieties. All of these polymers showed comparable specific capacity while used as an anode in Li-ion batteries due to the presence of a common conjugated backbone. However, the battery metrics varied significantly while the current density of the batteries varied between 0.1 and 2.0 A g^–1. P1 and P2 showed a very close recovery of specific capacity at 0.1 A g^–1 before and after various current densities. However, polymers P3 and P4 did not recover from the specific capacity fading due to the presence of triethylene glycol side chain that degraded. Polymer P2 with an alkyl side chain and a chain with a urethane moiety showed stable performance over 2000 charge–discharge cycles. Contrary to this, the stability of polymers with triethylene glycol side chains decreased over 2000 charge–discharge cycles. Polymer P2 with a urethane side chain also showed improved Li-ion diffusion because the urethane moiety facilitated better Li-ion transport.

中文翻译：

取代共轭聚合物的亲锂官能团之间的穿梭平衡以改善锂离子扩散和电池的循环稳定性

在此，我们报告了i -Indigo和反式-1,2-二(2-噻吩基)乙烯(TVT)的设计和合成，其包含具有各种侧链的共聚物，用作锂离子电池中的阳极兼粘合剂。 TVT 会破坏结晶度， i -Indigo 则为不对称取代提供了把柄。聚合物P1包含异靛蓝上的烷基链，而P2包含烷基链和具有氨基甲酸酯部分作为另一侧链的链。聚合物P3包含具有氨基甲酸酯部分和三甘醇作为侧链的i -Indigo。 P4中的异靛蓝被三乙二醇和烷基链作为侧链取代。由于 TVT 部分赋予的扭转角极小，这些聚合物被发现是无定形的，具有 π-π 堆积。由于存在共同的共轭主链，所有这些聚合物在用作锂离子电池阳极时都表现出相当的比容量。然而，当电池的电流密度在 0.1 至 2.0 A g ^–1之间变化时，电池指标变化很大。 P1和P2在不同电流密度之前和之后在 0.1 A g ^–1处表现出非常接近的比容量恢复。然而，由于存在降解的三甘醇侧链，聚合物P3和P4没有从比容量衰减中恢复。具有烷基侧链和具有氨基甲酸酯部分的链的聚合物P2在2000次充放电循环中表现出稳定的性能。与此相反，具有三甘醇侧链的聚合物的稳定性在超过 2000 次充放电循环后下降。具有氨基甲酸酯侧链的聚合物P2也表现出改善的锂离子扩散，因为氨基甲酸酯部分有利于更好的锂离子传输。

更新日期：2024-08-15

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