高比容量的硅/碳材料在嵌锂-脱锂过程中,Si的大体积膨胀容易引起电极粉碎和脱落问题,最终导致循环性能衰减和电池寿命缩短,通过设计新型硅/碳材料粘结剂可以有效提升电池循环性能。利用戊二醛(GA)的双醛基团与聚乙烯亚胺(PEI)和多巴胺(DPA)的胺基能发生反应生成亚胺键(—CN—)的原理,制备三维网状结构的粘结剂(PEI-GA-DPA),并用于高比容量的硅碳负极材料的性能研究。与纯PEI和商业化PVDF粘结剂对比,研究PEI-GA-DPA粘结剂的粘结性能和循环性能。结果表明:当PEI∶GA∶DPA的质量比为90∶0.2∶9.8时,制备的Si/C@PEI-GA-DPA电极的平均剥离强度为3.28N,高于Si/C@PVDF电极(1.43N)和Si/C@PEI电极(1.33N)。在0.5C电流密度循环100圈,Si/C@PEI-GA-DPA-2电池的充电比容量为540.8mAh/g,优于Si/C@PVDF电池(489.6mAh/g)和Si/C@PEI电池(412.0mAh/g)。因此,通过亚胺键的生成制备的粘结剂PEI-GA-DPA具有更优异的粘结力,能显著提升Si/C电极的循环性能。
During the lithiation and de-lithiation process of high specific capacity Si/C materials,the drastic volume changes of Si can cause electrode pulverization and delamination,ultimately causing the degradation of cycling performance and shortened battery lifespan.Battery cycling performance can be effectively enhanced by designing novel Si/C binders.In this paper,a three-dimensional network structure binder (PEI-GA-DPA) was prepared by forming the imine bond (—CN—) between the aldehyde groups (—CHO) of glutaraldehyde (GA) and the amine groups (—NH2) of poly-ethyleneimine (PEI) and dopamine (DPA).It was used for the performance study of Si/C anode materials with high specific capacity.The adhesion and cycling performance of the PEI-GA-DPA binder were studied and compared with pure PEI and commercial PVDF binders.The results showed that when the mass ratio of PEI∶GA∶DPA was 90∶0.2∶9.8,the designed Si/C@ PEI-GA-DPA electrode displayed the average peeling strength of 3.28N,which was higher than that of Si/C@PVDF electrode (1.43N) and Si/C@PEI (1.33N).after 100 cycles at 0.5C,the Si/C@PEI-GA-DPA-2 electrode exhibited a charging specific capacity of 540.8mAh/g,which was superior to that of Si/C@PVDF cell(489.6mAh/g) and Si/C@PEI (412.0mAh/g).The PEI-GA-DPA binder prepared by the generation of imine bonds possessed superior bonding strength and could significantly improve the cycling performance of Si/C electrodes.
[1] Hu L,Zhang X,Li B,et al.Design of high-energy-dissipation,deformable binder for high-areal-capacity silicon anode in lithium-ion batteries[J].Chemical Engineering Journal,2021,420:129991.
[2] Rajeev K K,Nam J,Jang W,et al.Polysaccharide-based self-healing polymer binder via Schiff base chemistry for high-performance silicon anodes in lithium-ion batteries[J].Electrochimica Acta,2021,384:138364.
[3] 邓攀,陈程,张灵志.聚乙烯亚胺/聚丙烯酰胺复合交联型水性粘结剂在锂离子电池Si/C负极中的应用[J].高分子学报,2021,52(11):1473-1480.
[4] Su X,Wu Q,Li J,et al.Silicon-based nanomaterials for lithium-ion batteries:a review[J].Advanced Energy Materials,2014,4:1300882.
[5] Li P,Kim H,Myung S T,et al.Diverting exploration of silicon anode into practical way:a review focused on silicon-graphite composite for lithium ion batteries[J].Energy Storage Materials,2021,35:550-576.
[6] Wu H,Cui Y.Designing nanostructured Si anodes for high energy lithium ion batteries[J].Nano Today,2012,7:414-429.
[7] 高嘉祺,高银红,姜敏,等.硅碳负极材料的维度设计、制备及在锂离子电池中的应用[J].化工新型材料,2024,52(5):10-15.
[8] Yang F,Deng P,He H,et al.Rapid Joule heating-induced welding of silicon and graphene for enhanced lithium-ion battery anodes[J].Chemical Engineering Journal,2024,494:152828.
[9] Zhang L,Wang C,Dou Y,et al.A Yolk-Shell structured silicon anode with superior conductivity and high tap density for full lithium-ion batteries[J].Angewandte Chemie International Edition,2019,58:8824-8828.
[10] Li Z,Wan Z,Zeng X,et al.A robust network binder via localized linking by small molecules for high-areal-capacity silicon anodes in lithium-ion batteries[J].Nano Energy,2021,79:105430.
[11] Kovalenko I,Zdyrko B,Magasinski A,et al.A major constituent of brown algae for use in high-capacity Li-ion batteries[J].Science,2011,334:75-79.
[12] Ryou M H,Kim J,Lee I,et al.Mussel-inspired adhesive binders for high-performance silicon nanoparticle anodes in lithium-ion batteries[J].Advanced Materials,2013,25:1571-1576.
[13] Gao H,Zhou W,Jang J H,et al.Cross-linked chitosan as a polymer network binder for an antimony anode in sodium-ion batteries[J].Advanced Energy Materials,2016,6:1502130.
[14] Sun X,Lin X,Dong F,et al.Advanced-design cross-linked binder enables high-performance silicon-based anodes through in-situ crosslinking based on sodium carboxymethyl cellulose and poly-lysine[J].International Journal of Biological Macromolecules,2024,274:133050.
[15] Zhang D,Ouyang Y,Wang Y,et al.A gradient-distributed binder with high energy dissipation for stable silicon anode[J].Journal of Colloid and Interface Science,2024,673:312-320.
[16] Chen J,Li Y,Wu X,et al.Dynamic hydrogen bond cross-linking binder with self-healing chemistry enables high-performance silicon anode in lithium-ion batteries[J].Journal of Colloid and Interface Science,2024,657:893-902.
[17] He J,Zhang L.Polyvinyl alcohol grafted poly(acrylic acid) as water-soluble binder with enhanced adhesion capability and electrochemical performances for Si anode[J].Journal of Alloys and Compounds,2018,763:228-240.
[18] Chuang Y P,Lin Y L,Wang C C,et al.Dual cross-linked polymer networks derived from the hyperbranched poly(ethyleneimine) and poly(acrylic acid) as efficient binders for silicon anodes in lithium-ion batteries[J].ACS Applied Energy Materials,2021,4:1583-1592.
[19] Gendensuren B,Oh E S.Dual-crosslinked network binder of alginate with polyacrylamide for silicon/graphite anodes of lithium ion battery[J].Journal of Power Sources,2018,384:379-386.
[20] Lee S H,Lee J H,Nam D H,et al.Epoxidized natural rubber/chitosan network binder for silicon anode in lithium-ion battery[J].ACS Applied Materials & Interfaces,2018,10:16449-16457.
[21] Liu Y,Tai Z,Zhou T,et al.An all-integrated anode via interlinked chemical bonding between double-Shelled-Yolk-structured silicon and binder for lithium-ion batteries[J].Advanced Materials,2017,29:1703028.
[22] Sun B,Jiao X,Liu J,et al.Neural network inspired binder enables fast Li-ion transport and high stress adaptation for Si anode[J].Nano Letters,2024,24:7662-7671.
[23] Cao Z,Zheng X,Huang W,et al.Dynamic bonded supramolecular binder enables high-performance silicon anodes in lithium-ion batteries[J].Journal of Power Sources,2020,463:228208.
[24] Chen C,Chen F,Liu L,et al.Cross-linked hyperbranched polyethylenimine as an efficient multidimensional binder for silicon anodes in lithium-ion batteries[J].Electrochimica Acta,2019,326:134964.
[25] 朱康帅.自修复聚乙烯亚胺作为锂硫电池粘结剂的研究[D].哈尔滨:哈尔滨工业大学,2021.
[26] Chen C,Lee S H,Cho M,et al.Cross-linked chitosan as an efficient binder for Si anode of Li-ion batteries[J].ACS Applied Materials & Interfaces,2016,8:2658-2665.
[27] Jeong Y K,Choi J W.Mussel-inspired self-healing metallopolymers for silicon nanoparticle anodes[J].ACS Nano,2019,13:8364-8373.
[28] Wang Z,Huang T,Liu Z,et al.Dopamine-modified carboxymethyl cellulose as an improved aqueous binder for silicon anodes in lithium-ion batteries[J].Electrochimica Acta,2021,389:138806.
基金资助
福建省科技创新重点项目(2022G02020);福建省自然科学基金项目(2023J011054);福建省大学生创新创业项目(S202410397040);武夷学院教研教改项目(KC2024004SC)
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