Structural design strategies of polymer binders for Silicon-based anodes in lithium-ion batteries

Abstract

Silicon (Si) anodes have emerged as promising candidates for next-generation lithium-ion batteries owing to their high theoretical capacity. However, their practical application is hindered by severe volume expansion and unstable electrode interfaces during cycling. Polymer binders play a critical role in mitigating these issues by maintaining electrode integrity and enhancing interfacial stability. This review provides a systematic classification of polymer binders for Si-based anodes according to their binding mechanisms, including covalent, hydrogen-bonding, and supramolecular interactions. The discussion emphasizes how structural configurations, such as linear, branched, and cross-linked architectures, affect mechanical resilience, adhesion strength, and compatibility with high-loading electrodes. Recent advances in multifunctional and dynamic cross-linked binders are highlighted, with particular focus on strategies to accommodate large volume changes and suppress interfacial degradation. In addition, a comparative analysis of advantages and limitations for various binder systems is provided, along with perspectives on future development trends. This work aims to guide the rational design of polymer binders for achieving stable, high-energy-density Si-based anodes.

Keywords

Polymeric binder / Si anode / binder-electrode interaction / evolution

References

[1] Jung HW,Lee JT.Sustainable and robust biomass-based binder for silicon anodes in lithium-ion batteries: cross-linked sodium alginate and chondroitin sulfate.Sci Technol Adv Mater2025;26:2523243 PMCID:PMC12284990

[2] Park S,Lee J.Architecting sturdy Si/graphite composite with lubricative graphene nanoplatelets for high-density electrodes.Small2025;21:e2404949

[3] Zeng X,Huang F,Liu L.A novel gelatin binder with helical crosslinked network for high-performance Si anodes in lithium-ion batteries.Small2024;20:e2403754

[4] Kang D,Chae S,Ko M.Efficient recycling of spent LiCoO₂ cathodes via confined pore-assisted simplified direct carbothermic reduction without external reducing agents.Energy Environ Mater2025;9:e70037

[5] Samridh A,John B,Devassia MT.Sustainable binder system: cross-linked tamarind gum-polyacrylic acid for silicon-graphite anodes in future lithium-ion batteries.Energy Technol2025;13:2401837

[6] Han SA,Kim J.3D pathways enabling highly-efficient lithium reservoir for fast-charging batteries.Small2024;20:e2310201

[7] Suh JH,Yang SY.Toward fast-charging and dendritic-free Li growth on natural graphite through intercalation/conversion on MoS₂ nanosheets.Adv Mater2025;37:e2414117

[8] Feng J,Amzil S.Slurry additive approach enables a mechanically robust binder for silicon-carbon anodes in lithium-ion batteries.ACS Appl Mater Interfaces2025;17:18339-50

[9] Xiang Y,Deng J,Nazir MA.Spiderweb-like three-dimensional cross-linked AGE binder for high performance silicon-based lithium battery.ACS Appl Energy Mater2025;8:2973-81

[10] Li X,Rajapaske G.A rigid-flexible network binder with multiple hydrogen bond interactions for high-performance silicon anodes.ACS Appl Energy Mater2025;8:5199-208

[11] Jolley MJ,Jenkins C.Exploration of high and low molecular weight polyacrylic acids and sodium polyacrylates as potential binder system for use in silicon graphite anodes.ACS Appl Energy Mater2025;8:1647-60 PMCID:PMC11815634

[12] Kim J,Lim EY.Stress-dissipative elastic waterborne polyurethane binders for silicon anodes with high structural integrity in lithium-ion batteries.ACS Appl Energy Mater2024;7:1629-39

[13] Sun C,Mu P.Covalently cross-linked chemistry of a three-dimensional network binder at limited dosage enables practical Si/C composite electrode applications.ACS Nano2024;18:2475-84

[14] Lee T,Na H.Cross-linked poly(vinyl alcohol)-malonic acid water-soluble binder for high-performance silicon anodes in lithium-ion batteries.ACS Appl Energy Mater2025;8:332-42

[15] Liu H,Li S,Nan J.A Temperature-controlled chemoswitching aqueous binder and in situ binding strategy for stabilizing SiO_x anodes of lithium-ion batteries.ACS Sustain Chem Eng2024;12:17855-68

[16] Yoon J,Kim H,Jin HJ.Polymeric binder design for sustainable lithium-ion battery chemistry.Polymers2024;16:254 PMCID:PMC10821008

[17] Tan W,Chen M.Bio-based adenine-derived polyimide as a dual-functional binder for the silicon anode in lithium-ion batteries.ACS Appl Energy Mater2023;6:10723-33

[18] Kang Y,Yin J.Structurally adaptive branched polyimide binder with synergistic elastic buffering and ionic transport for long-term stability of silicon anodes.Small2025;e07023

[19] Lee J,Han SA.Everlasting living and breathing gyroid 3D network in Si@SiO_x/C nanoarchitecture for lithium ion battery.ACS Nano2019;13:9607-19

[20] Han D,Son J.Molecular engineering of coacervate network binders for stable silicon-based anodes in lithium-ion batteries.Adv Funct Mater2025:e09445

[21] Wang W,Chen X,Wang G.Aqueous binder with self-emulsifying characteristics for practical Si/C anode in lithium-ion batteries.Chemistry2025;31:e202403924

[22] He Y,Zhang Y,Chu PK.High-toughness and hierarchical stress-dissipating binder based on physicochemical dual-cross-linking for high-performance silicon anodes.ACS Appl Mater Interfaces2025;17:21206-14

[23] Sun Z,Yang C.N-type polyoxadiazole conductive polymer binders derived high-performance silicon anodes enabled by crosslinking metal cations.ACS Appl Mater Interfaces2023;15:12946-56

[24] Xiao H,Wu S.Cross-linked γ-polyglutamic acid as an aqueous SiO_x anode binder for long-term lithium-ion batteries.ACS Appl Mater Interfaces2022;14:18625-33

[25] Zhang Z,Li Y.Highly ion-conductive Si anode binder with optimized tensile strength and large deformation for lithium-ion batteries.ACS Appl Mater Interfaces2025;17:43034-47

[26] He T,Zhang H.Self-healing SA@borax binder for in situ tuning of the solid electrolyte interfaces for silicon anodes.ACS Sustain Chem Eng2025;13:4093-107

[27] Ai W,Wang Q.Stable silicon anodes enabled by innovative biobased binder with cross-linking network in lithium-ion batteries.Langmuir2025;41:9469-79

[28] Kang Y,Han J,Kim T.Poly(acrylic acid) grafted with a boronic ester and dopamine as a self-healable and highly adhesive aqueous binder for Si anodes.ACS Appl Energy Mater2024;7:2436-50

[29] Xu M,Yan Z.A fast self-healing binder for highly stable SiO_x anodes in lithium-ion batteries.ACS Appl Mater Interfaces2024;16:55353-61

[30] Kim S,Han JH,Min K.A polysaccharide binder with carbon quantum dots for improved flexibility of Si anodes in lithium-ion batteries.ACS Appl Energy Mater2024;7:9806-15

[31] Yang L,Zheng W.Advanced binder design for high-performance silicon anodes.Energy Storage Mater2024;72:103766

[32] Shen J,Mei Y.Multidimensional branched composite binder via covalent grafting for high-performance silicon-based anodes.J Phys Chem C2023;127:14613-22

[33] Preman AN,Choi S.Self-healable poly(acrylic acid) binder toward optimized electrochemical performance for silicon anodes: importance of balanced properties.ACS Appl Energy Mater2024;7:749-59

[34] Zhang B,Xie H.Cross-linking chemistry enables robust conductive polymeric network for high-performance silicon microparticle anodes in lithium-ion batteries.J Power Sources2023;556:232495

[35] Guo S,Li Y.SiO₂-enhanced structural stability and strong adhesion with a new binder of konjac glucomannan enables stable cycling of silicon anodes for lithium-ion batteries.Adv Energy Mater2018;8:1800434

[36] Shang Y,Ma T,Jiang Y.Suppression strategies for Si anode volume expansion in Li-ion batteries based on structure design and modification: a review.ACS Appl Mater Interfaces2025;17:31730-53

[37] Tatara R,Yamazaki S.Impact of maturation on Si-based negative electrodes for LIBs: contributions of binder migration and Cu corrosion.J Electrochem Soc2025;172:030519

[38] Xiao Y,Li T.Multifunctional cross-linking composite binder enables the stable performance of Si-based anodes for high-energy-density lithium-ion batteries.ACS Appl Mater Interfaces2024;16:41036-47

[39] Sun B,Liu J.Neural network inspired binder enables fast Li-ion transport and high stress adaptation for Si anode.Nano Lett2024;24:7662-71

[40] Wu F,Yang Z.Highly stable silicon anode enabled by a water-soluble tannic acid functionalized dual-network binder.ACS Appl Mater Interfaces2024;16:23396-405

[41] Long J,Liao H,Dou H.In Situ prepared three-dimensional covalent and hydrogen bond synergistic binder to boost the performance of SiO_x anodes for lithium-ion batteries.ACS Appl Mater Interfaces2023;15:10726-34

[42] Wu Z,Li S.Damage-tolerant and self-repairing web-like borate type binder enable stable operation of efficient Si-based anodes.Small2024;20:e2401345

[43] Ba Z,Xu K.Dual cross-linked poly(ether imide)/poly(vinyl alcohol) network binder with improved stability for silicon based anodes in lithium-ion batteries.ACS Appl Mater Interfaces2025;17:20197-208

[44] Jin JH,Kim JH.Graphene-assisted interfacial engineering to develop binder- and dispersant-free cast Si Alloy/nanocarbon anodes for high-performance Li-ion batteries.Adv Funct Mater2025;35:e11352

[45] An W,Mei S.Scalable synthesis of ant-nest-like bulk porous silicon for high-performance lithium-ion battery anodes.Nat Commun2019;10:1447 PMCID:PMC6441089

[46] Kwon TW,Coskun A.The emerging era of supramolecular polymeric binders in silicon anodes.Chem Soc Rev2018;47:2145-64

[47] Choi S,Coskun A.Highly elastic binders integrating polyrotaxanes for silicon microparticle anodes in lithium ion batteries.Science2017;357:279-83

[48] Mun J,Park MS.Paving the way for next-generation all-solid-state batteries: dry electrode technology.Adv Mater2025;37:e2506123

[49] Salehabadi M,Werner-Zwanziger U.Citric acid as a small molecule binder for Si-based Li-ion battery anode materials.J Electrochem Soc2025;172:020520

[50] Oh H,Shin H.Stable performance for pouch-type all-solid-state batteries enabled by current collector with optimized primer layer.Mater Sci Eng R Rep2025;164:100970

[51] Kim T,Kim H.New suggestion of highly durable electrode design for ordered mesoporous Ni-Mn binary transition metal oxide anode material in lithium-ion batteries.Small2025;21:e2406243

[52] Chen H,Hencz L.Exploring chemical, mechanical, and electrical functionalities of binders for advanced energy-storage devices.Chem Rev2018;118:8936-82

[53] Shen H,Chen Z,Chao D.Application and development of silicon anode binders for lithium-ion batteries.Materials2023;16:4266 PMCID:PMC10301976

[54] Yang Y,Zhang Y.Towards efficient binders for silicon based lithium-ion battery anodes.Chem Eng J2021;406:126807

[55] Kwon T,Coskun A.Prospect for supramolecular chemistry in high-energy-density rechargeable batteries.Joule2019;3:662-82

[56] Lee J,Kim JH.Stabilizing Li-metal host anode with LiF-rich solid electrolyte interphase.Nano Converg2021;8:18 PMCID:PMC8200894

[57] An Y,Liu C,Feng J.One-step, vacuum-assisted construction of micrometer-sized nanoporous silicon confined by uniform two-dimensional N-doped carbon toward advanced Li ion and MXene-based Li metal batteries.ACS Nano2022;16:4560-77

[58] Browning KL,Doucet M,Kim JR.The study of the binder poly(acrylic acid) and its role in concomitant solid-electrolyte interphase formation on Si anodes.ACS Appl Mater Interfaces2020;12:10018-30

[59] Hu Z,Lv M.Bio-inspired toughening elastomer as an innovative self-healing binder for Si-based electrode.Adv Energy Mater2025;15:2501991

[60] Chen W,Jiang J,Li L.Effect of binder types on performance of spherical and flaky silicon electrodes.J Solid State Electrochem2025;29:2623-37

[61] Li K,Qiao S.Fatigue resistant polyimide binders for high-performance SiO_x/C anodes in lithium-ion batteries.ACS Appl Polym Mater2025;7:278-86

[62] Magasinski A,Kovalenko I.Toward efficient binders for Li-ion battery Si-based anodes: polyacrylic acid.ACS Appl Mater Interfaces2010;2:3004-10

[63] Wang Y,Meng Y.Fluorine chemistry in rechargeable batteries: challenges, progress, and perspectives.Chem Rev2024;124:3494-589

[64] Choi N,Lee Y.Recent progress on polymeric binders for silicon anodes in lithium-ion batteries.J Electrochem Sci Technol2015;6:35-49

[65] Liu Y,Jiang R,Jin Z.A review of existing and emerging binders for silicon anodic Li-ion batteries.Nano Res2023;16:6736-52

[66] Vogl US,Weber AZ,Kostecki R.Mechanism of interactions between CMC binder and Si single crystal facets.Langmuir2014;30:10299-307

[67] Rajeev K,Nam J,Mun J.Chitosan-grafted-polyaniline copolymer as an electrically conductive and mechanically stable binder for high-performance Si anodes in Li-ion batteries.Electrochim Acta2020;333:135532

[68] Chai L,Zhang L,Zhang L.Chitosan, a new and environmental benign electrode binder for use with graphite anode in lithium-ion batteries.Electrochim Acta2013;105:378-83

[69] Kovalenko I,Magasinski A.A major constituent of brown algae for use in high-capacity Li-ion batteries.Science2011;334:75-9

[70] Kim SW.k R, Kang Y, et al. Oxidized λ-carrageenan as an aqueous silicon-anode polymer binder with reduced viscosity for lithium-ion batteries.ACS Sustain Chem Eng2024;12:16041-51

[71] Jang W.K. R, Thorat GM, Kim S, Kang Y, Kim T. Lambda carrageenan as a water-soluble binder for silicon anodes in lithium-ion batteries.ACS Sustain Chem Eng2022;10:12620-9

[72] Lee SH,Nam DH.Epoxidized natural rubber/chitosan network binder for silicon anode in lithium-ion battery.ACS Appl Mater Interfaces2018;10:16449-57

[73] Ko M,Ma J.Scalable synthesis of silicon-nanolayer-embedded graphite for high-energy lithium-ion batteries.Nat Energy2016;1:16113

[74] Ryou MH,Lee I.Mussel-inspired adhesive binders for high-performance silicon nanoparticle anodes in lithium-ion batteries.Adv Mater2013;25:1571-6

[75] Zhang Q,Zhang M,Yuan S.A highly efficient silicone-modified polyamide acid binder for silicon-based anode in lithium-ion batteries.ACS Appl Energy Mater2021;4:7209-18

[76] Wang X,Zhang Y.Highly elastic block copolymer binders for silicon anodes in lithium-ion batteries.ACS Appl Mater Interfaces2020;12:38132-9

[77] Jiang H,Yasmin S.Deconvoluting slurry rheology from binder performance in Si-based anodes.J Electrochem Soc2023;170:120522

[78] Jagodziński K,Casado N.Poly(ethylene-alt-maleic acid)-based binders for silicon anodes.ACS Appl Polym Mater2025;7:2973-85 PMCID:PMC11915192

[79] Chen J,Wu X.Dynamic hydrogen bond cross-linking binder with self-healing chemistry enables high-performance silicon anode in lithium-ion batteries.J Colloid Interface Sci2024;657:893-902

[80] Parikh P,Banerjee A.Role of polyacrylic acid (PAA) binder on the solid electrolyte interphase in silicon anodes.Chem Mater2019;31:2535-44

[81] Rahaman M,Mustafa A.A review of heat treatment on polyacrylonitrile fiber.Polym Degrad Stab2007;92:1421-32

[82] Hwang SS,Park H,Cho CG.Effect of the heat treatment on the dimensional stability of Si electrodes with PVDF binder.Electrochim Acta2016;211:356-63

[83] Liu D,Tan R.Novel conductive binder for high-performance silicon anodes in lithium ion batteries.Nano Energy2017;36:206-12

[84] Li J,Lu Y.Water soluble binder, an electrochemical performance booster for electrode materials with high energy density.Adv Energy Mater2017;7:1701185

[85] Yoon J,Cho S.Microbial-copolyester-based eco-friendly binder for lithium-ion battery electrodes.ACS Appl Polym Mater2023;5:1199-207

[86] Luo L,Zhang H.Comprehensive understanding of high polar polyacrylonitrile as an effective binder for Li-ion battery nano-Si anodes.ACS Appl Mater Interfaces2016;8:8154-61

[87] Umirov N,Park G,Lee KJ.Novel silane-treated polyacrylonitrile as a promising negative electrode binder for LIBs.J Alloys Compd2020;815:152481

[88] Yang J,Li B.Zwitterionic polymer binder networks with structural locking and ionic regulation functions for high performance silicon anodes.ACS Appl Mater Interfaces2024;16:70544-54

[89] He J.Polyvinyl alcohol grafted poly (acrylic acid) as water-soluble binder with enhanced adhesion capability and electrochemical performances for Si anode.J Alloys Compd2018;763:228-40

[90] Jolley MJ,Wemyss AM.Development and application of a poly(acrylic acid)-grafted styrene-butadiene rubber as a binder system for silicon-graphite anodes in Li-ion batteries.ACS Appl Energy Mater2023;6:496-507

[91] He J,Zhong H.Enhanced adhesion and electrochemical performance of Si anodes with gum arabic grafted poly(acrylic acid) as a water-soluble binder.Polym Int2021;70:1668-79

[92] Yang C,Chen F.Highly elastic hyperbranched polymer binder for silicon anodes in lithium-ion batteries.Electrochim Acta2023;442:141805

[93] Chuang Y,Wang C.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.ACS Appl Energy Mater2021;4:1583-92

[94] Gendensuren B.Dual-crosslinked network binder of alginate with polyacrylamide for silicon/graphite anodes of lithium ion battery.J Power Sources2018;384:379-86

[95] Song J,Yi R.Interpenetrated gel polymer binder for high-performance silicon anodes in lithium-ion batteries.Adv Funct Mater2014;24:5904-10

[96] Lou X,Zhao L,Zhang H.Cross-linked multifunctional binder in situ tuning solid electrolyte interface for silicon anodes in lithium ion batteries.Sci Rep2023;13:18560 PMCID:PMC10613629

[97] Kwon TW,Deniz E,Choi JW.Dynamic cross-linking of polymeric binders based on host-guest interactions for silicon anodes in lithium ion batteries.ACS Nano2015;9:11317-24

[98] Zhang J,Zhang W.A cycling robust network binder for high performance Si-based negative electrodes for lithium-ion batteries.J Colloid Interface Sci2020;578:452-60

[99] Kang E,Kim S,Cho KY.A tough and self-healable semi-IPN hydrogel binder based on multiple dynamic bonds for Si anodes in lithium-ion batteries.ACS Appl Mater Interfaces2025;17:30054-66

[100] Zhang J,Zhao Y.A multifunctional supramolecular polymer binder with hard/soft phase interaction for Si-based lithium-ion batteries.Nano Energy2024;125:109573

[101] Boorboor Ajdari F,Molaei Aghdam A.Silicon solid state battery: the solid-state compatibility, particle size, and carbon compositing for high energy density.Adv Funct Mater2024;34:2314822

[102] Sun Z,Chen H.Building better solid-state batteries with silicon-based anodes.Interd Mater2023;2:635-63

[103] Nelson DL,Pyo J.Fracture dynamics in silicon anode solid-state batteries.ACS Energy Lett2024;9:6085-95 PMCID:PMC11650773

[104] Grill J.Cation conducting binders: from liquid to solid-state batteries.ACS Energy Lett2024;9:4465-74

[105] Hong S,Kim U.All-solid-state lithium batteries: Li⁺-conducting ionomer binder for dry-processed composite cathodes.ACS Energy Lett2022;7:1092-100

[106] Shin DO,Jung S.Electrolyte-free graphite electrode with enhanced interfacial conduction using Li⁺-conductive binder for high-performance all-solid-state batteries.Energy Storage Mater2022;49:481-92

[107] Boaretto N,Lindberg S.Hybrid ceramic polymer electrolytes enabling long cycling in practical 1 Ah-class high-voltage solid-state batteries with Li metal anode.Adv Funct Mater2024;34:2404564

[108] Shi Y,Yu G.Material and structural design of novel binder systems for high-energy, high-power lithium-ion batteries.Acc Chem Res2017;50:2642-52

[109] Qin T,Li Q,Li H.Design of functional binders for high-specific-energy lithium-ion batteries: from molecular structure to electrode properties.Ind Chem Mater2024;2:191-225

[110] Lestriez B,Sandu I,Guyomard D.On the binding mechanism of CMC in Si negative electrodes for Li-ion batteries.Electrochem Commun2007;9:2801-6

[111] Li M,Chen Z.30 years of lithium-ion batteries.Adv Mater2018;30:e1800561

[112] Ling M,Zhao H.Dual-functional gum arabic binder for silicon anodes in lithium ion batteries.Nano Energy2015;12:178-85

[113] Liu J,Zhang T,Huang L.A robust ion-conductive biopolymer as a binder for Si anodes of lithium-ion batteries.Adv Funct Mater2015;25:3599-605

[114] Li J,Obrovac MN,Dahn JR.Effect of heat treatment on Si electrodes using polyvinylidene fluoride binder.J Electrochem Soc2008;155:A234

[115] Park H,Oh E.Effect of high adhesive polyvinyl alcohol binder on the anodes of lithium ion batteries.Electrochem Commun2011;13:1051-3

[116] Kim JS,Cho KY,Lim J.Effect of polyimide binder on electrochemical characteristics of surface-modified silicon anode for lithium ion batteries.J Power Sources2013;244:521-6

[117] Koo B,Cho Y,Choi NS.A highly cross-linked polymeric binder for high-performance silicon negative electrodes in lithium ion batteries.Angew Chem Int Ed2012;51:8762-7

[118] Li K,Zhang X.Dual-function polyimide binders containing benzimidazole/benzoxazole moieties for high-performance SiO_x/C anodes in lithium-ion batteries.ACS Appl Polym Mater2025;7:7267-74

[119] Jeong YK,Lee I,Coskun A.Hyperbranched β-cyclodextrin polymer as an effective multidimensional binder for silicon anodes in lithium rechargeable batteries.Nano Lett2014;14:864-70

[120] Shi Z,Robertson LA.Restorable neutralization of poly(acrylic acid) binders toward balanced processing properties and cycling performance for silicon anodes in lithium-ion batteries.ACS Appl Mater Interfaces2020;12:57932-40

[121] Zhong H,Zhang L.Crosslinkable aqueous binders containing Arabic gum-grafted-poly (acrylic acid) and branched polyols for Si anode of lithium-ion batteries.Polymer2021;215:123377

[122] Hu YY,Zhang SJ.Li_0.5PAA domains filled in porous sodium alginate skeleton: a 3D bicontinuous composite network binder to stabilize micro-silicon anode for high-performance lithium ion battery.Electrochim Acta2021;386:138361

[123] Kim J,Cho Y.Zn²⁺-imidazole coordination crosslinks for elastic polymeric binders in high-capacity silicon electrodes.Adv Sci2021;8:2004290 PMCID:PMC8097348

[124] Zhao Y,Li S.Advances of polymer binders for silicon-based anodes in high energy density lithium-ion batteries.InfoMat2021;3:460-501

[125] Wu C.Distribution uniformity of water-based binders in Si anodes and the distribution effects on cell performance.ACS Sustain Chem Eng2020;8:6868-76

[126] Liu J,Wu ZY.A high-performance alginate hydrogel binder for the Si/C anode of a Li-ion battery.Chem Commun2014;50:6386-9

[127] Peng B,Ji M.Low-cost and multifunctional copolymer binder for stabilizing high-capacity Si/C composite anodes in practical lithium-ion batteries.ACS Appl Energy Mater2025;8:5403-13