Tailoring hard carbon interfaces in carbonate-based electrolytes for sodium-ion hybrid capacitors

Abstract

The poor rate performance of hard carbon (HC) in carbonate electrolytes limits its applicability in hybrid capacitors, primarily due to the low working potential and the slow Na⁺ transport kinetics within the potential plateau region. The slow desolvation of Na⁺ at the electrode surface and sluggish transport of Na⁺ through the solid electrolyte interface are the critical factors contributing to this issue. In this study, Co₃O₄ nanoparticles are uniformly self-grown on the HC surface to modulate the surface chemistry of HC. The introduction of Co₃O₄ not only facilitates the desolvation of Na⁺ and reduces internal resistance, but also provides additional active sites for Na⁺ storage as an active material. As a result of these dual effects, HC125@Co₃O₄ (a composite with an optimal Co₃O₄ loading on HC surfaces) exhibits superior rate performance and reversible capacity compared to pure HC. The sodium-ion hybrid capacitor assembled with the HC125@Co₃O₄ anode and activated carbon cathode demonstrates high energy density (129.5 Wh kg^-1 at 583 W kg^-1) and high power density (26.5 Wh kg^-1 at 11,650 W kg^-1), along with excellent long-time cycling stability. This study offers an effective solution to the poor rate performance and slow kinetics of HC in carbonate-based electrolytes, addressing the issue from the perspective of the electrode-electrolyte interface.

Keywords

Hard carbon / Co₃O₄ / solvated structure / sodium ion / hybrid capacitors

References

[1] Simon P,Dunn B.Where do batteries end and supercapacitors begin?.Science2014;343:1210-1

[2] Dong S,Wu Y,Dong X.Lithium-ion and sodium-ion hybrid capacitors: from insertion-type materials design to devices construction.Adv Funct Mater2021;31:2100455

[3] Raza W,Raza N.Recent advancements in supercapacitor technology.Nano Energy2018;52:441-73

[4] Yuan X,Zhang S.An aqueous rechargeable Al-ion battery based on cobalt hexacyanoferrate and Al metal.Adv Energy Mater2024;14:2302712

[5] Wang H,Chao D,Fan HJ.Nonaqueous hybrid lithium-ion and sodium-ion capacitors.Adv Mater2017;29:1702093

[6] Eshetu GG,Armand M.Electrolytes and interphases in sodium-based rechargeable batteries: recent advances and perspectives.Adv Energy Mater2020;10:2000093

[7] Ponrouch A,Boschin A,Johansson P.Non-aqueous electrolytes for sodium-ion batteries.J Mater Chem A2015;3:22-42

[8] Jónsson E.Modern battery electrolytes: ion-ion interactions in Li⁺/Na⁺ conductors from DFT calculations.Phys Chem Chem Phys2012;14:10774-9

[9] Okoshi M,Yamada A.Theoretical analysis on de-solvation of lithium, sodium, and magnesium cations to organic electrolyte solvents.J Electrochem Soc2013;160:A2160-5

[10] Lu Z,Ji Y.Modulating the graphitic domains of hard carbons via tuning resin crosslinking degree to achieve high rate and stable sodium storage.Energy Mater2024;4:400038

[11] Wang Z,Bai Y.Probing the energy storage mechanism of quasi-metallic na in hard carbon for sodium-ion batteries.Adv Energy Mater2021;11:2003854

[12] Sun N,Xu B.Understanding of sodium storage mechanism in hard carbons: ongoing development under debate.Adv Energy Mater2022;12:2200715

[13] Bouibes A,Fujie T,Komaba S.Concentration effect of fluoroethylene carbonate on the formation of solid electrolyte interphase layer in sodium-ion batteries.ACS Appl Mater Interfaces2018;10:28525-32

[14] Xia H,Qu G.Evolution of a solid electrolyte interphase enabled by FeN_X/C catalysts for sodium-ion storage.Energy Environ Sci2022;15:771-9

[15] Yi X,Zhong J.Unraveling the mechanism of different kinetics performance between ether and carbonate ester electrolytes in hard carbon electrode.Adv Funct Mater2022;32:2209523

[16] Yang J,Li Q.Improved low-temperature performance of rocking-chair sodium-ion hybrid capacitor by mitigating the de-solvation energy and interphase resistance.Adv Funct Mater2022;32:2200566

[17] Yan L,Wang J.Revisiting electrolyte kinetics differences in sodium ion battery: are esters really inferior to ethers?.Energy Environ Mater2023;6:e12523

[18] Kang HJ,Im WB.Molecular cooperative assembly-mediated synthesis of ultra-high-performance hard carbon anodes for dual-carbon sodium hybrid capacitors.ACS Nano2019;13:11935-46

[19] Wang C,Li B.Pseudocapacitive porous hard carbon anode with controllable pyridinic nitrogen and thiophene sulfur co-doping for high-power dual-carbon sodium ion hybrid capacitors.J Mater Chem A2021;9:20483-92

[20] Wang E,Guo YJ.Mitigating electron leakage of solid electrolyte interface for stable sodium-ion batteries.Angew Chem Int Ed2023;62:e202216354

[21] Lv Z,Hou X.Solvation structure and solid electrolyte interface engineering for excellent Na⁺ storage performances of hard carbon with the ether-based electrolytes.Chem Eng J2022;430:133143

[22] Yang J,Guo Z.Synergetic modulation on solvation structure and electrode interface to achieve lithium-ion batteries cycled at ultra-low temperature.Chem Eng J2023;473:145455

[23] Shen C,Jin T,Jiao L.Tailoring the surface chemistry of hard carbon towards high-efficiency sodium ion storage.Nanoscale2022;14:8959-66

[24] Lee CR,Leem HJ.Surface work function-induced thermally vulnerable solid electrolyte interphase formation on the negative electrode for lithium-ion batteries.Adv Energy Mater2024;14:2302906

[25] Tu S,Zhang Y.Fast-charging capability of graphite-based lithium-ion batteries enabled by Li₃P-based crystalline solid-electrolyte interphase.Nat Energy2023;8:1365-74

[26] Huo J,Yang H,Fang Y.Ultrasmall TiO₂/C nanoparticles with oxygen vacancy-enriched as an anode material for advanced Li-ion hybrid capacitors.J Energy Storage2024;89:111586

[27] Peng Y,Li Y,Zhang C.Embedding Co₃O₄ nanoparticles in three-dimensionally ordered macro-/mesoporous TiO₂ for Li-ion hybrid capacitor.J Colloid Interface Sci2021;596:130-8

[28] Jiang Y,Dong J.Mo₂C nanoparticles embedded in carbon nanowires with surface pseudocapacitance enables high-energy and high-power sodium ion capacitors.Small2022;18:e2200805

[29] Yang Y,Wang X,Yu J.In-situ evolution of CoS/C hollow nanocubes from metal-organic frameworks for sodium-ion hybrid capacitors.Chem Eng J2023;455:140610

[30] Dong Y,Yin L.A facile route to controlled synthesis of Co₃O₄ nanoparticles and their environmental catalytic properties.Nanotechnology2007;18:435602

[31] Huang S,Xu G.Hollow Co₃O₄@N-doped carbon nanocrystals anchored on carbon nanotubes for freestanding anode with superior Li/Na storage performance.Chem Eng J2021;415:128861

[32] Yin X,Wang N.Facile fabrication of a series of Cu-doped Co₃O₄ with controlled morphology for alkali metal-ion batteries.Colloids Surf A2023;656:130459

[33] Ma M,Xu C.Engineering solid electrolyte interface at nano-scale for high-performance hard carbon in sodium-ion batteries.Adv Funct Mater2021;31:2100278

[34] Liu M,Gong Y.Interfacial-catalysis-enabled layered and inorganic-rich SEI on hard carbon anodes in ester electrolytes for sodium-ion batteries.Adv Mater2023;35:e2300002

[35] Song G,Su F.Boosting the low-temperature performance for Li-ion batteries in LiPF₆-based local high-concentration electrolyte.ACS Energy Lett2023;8:1336-43

[36] Lu Z,Yang H.Step-by-step desolvation enables high-rate and ultra-stable sodium storage in hard carbon anodes.Proc Natl Acad Sci USA2022;119:e2210203119 PMCID:PMC9546550

[37] Huang X,Wang Q.Acceleration of interfacial kinetics induced by regulation of Li⁺ desolvation process in lithium metal-based batteries.J Power Sources2024;592:233884

[38] Yang G,Ruther RE.Electrolyte solvation structure at solid-liquid interface probed by nanogap surface-enhanced raman spectroscopy.ACS Nano2018;12:10159-70

[39] Cai T,Cao Z.Electrolyte additive-controlled interfacial models enabling stable antimony anodes for lithium-ion batteries.J Phys Chem C2022;126:20302-13

[40] Umesh B,Hernandha RFH.Moderate-concentration fluorinated electrolyte for high-energy-density Si//LiNi_0.8Co_0.1Mn_0.1O₂ batteries.ACS Sustain Chem Eng2020;8:16252-61

[41] Hai F,Guo J.Indirect regulation of solvation structure in all-fluorinated electrolyte by introducing carboxylate for stable 5 V battery.Chem Eng J2023;472:144993

[42] Pham TD,Nguyen HD,Lee K.Enhanced performances of lithium metal batteries by synergistic effect of low concentration bisalt electrolyte.J Mater Chem A2022;10:12035-46

[43] Li W,Song K.Binder-induced ultrathin SEI for defect-passivated hard carbon enables highly reversible sodium-ion storage.Adv Energy Mater2023;13:2300648

[44] Spotte-smith EWC,Patel HD,Persson KA.Elementary decomposition mechanisms of lithium hexafluorophosphate in battery electrolytes and interphases.ACS Energy Lett2023;8:347-55

[45] Li Z,Bi C.Construction of organic-rich solid electrolyte interphase for long-cycling lithium-sulfur batteries.Adv Funct Mater2024;34:2304541

[46] Lu Y,Liu S.Tuning the Li⁺ solvation structure by a "bulky coordinating" strategy enables nonflammable electrolyte for ultrahigh voltage lithium metal batteries.ACS Nano2023;17:9586-99

[47] Eshetu GG,Hekmatfar M.Impact of the electrolyte salt anion on the solid electrolyte interphase formation in sodium ion batteries.Nano Energy2019;55:327-40

[48] Luo D,Guo Q.Surface-dominated sodium storage towards high capacity and ultrastable anode material for sodium-ion batteries.Adv Funct Mater2018;28:1805371