Hybrid CoMoO₃/CoMoO₄ nanorods for enhanced lithium-ion battery performance

Abstract

Electrode materials that rely on conversion reactions for lithium-ion batteries (LIBs) possess high energy densities. However, a key issue in their design is bolstering their stability and minimizing volume variations during lithiation and delithiation. Herein, an effective strategy was devised to fulfill the fully reversible conversion reaction for lithium storage in CoMoO₄ through the hybridization of CoMoO₃. CoMoO₃/CoMoO₄ with a nanorod structure was synthesized via one-step annealing treatment after a solvothermal process. In such a structure, the CoMoO₃/CoMoO₄ nanorod can considerably boost mechanical robustness and offer ample space to counteract volume fluctuations throughout successive cycles owing to the cooperative interaction between CoMoO₃ and CoMoO₄. CoMoO₃/CoMoO₄ exhibited superior lithium-storage capacity (919.6 mAh/g at 0.1 A/g after 200 cycles) and cycling stability (683.4 mAh/g at 1 A/g after 600 cycles). CoMoO₃/CoMoO₄ showed a high potential as an anode material for LIBs.

Keywords

anode / CoMoO₃/CoMoO₄ / nanorod structure / hybrid material / electrode materials / conversion reaction-type / lithium-ion batteries

References

[1] PoizotP, LaruelleS, GrugeonS, DupontL, TarasconJM. Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries. Nature, 2000, 4076803496

[2] LuY, YuL, LouXW. Nanostructured conversion-type anode materials for advanced lithium-ion batteries. Chem, 2018, 45972

[3] G.S. Xu, M.X. Jiang, J.L. Li, et al., Machine learning-accelerated discovery and design of electrode materials and electrolytes for lithium ion batteries, Energy Storage Mater., 72(2024), art. No. 103710.

[4] YuSH, LeeSH, LeeDJ, SungYE, HyeonT. Conversion reaction-based oxide nanomaterials for lithium ion battery anodes. Small, 2016, 12162146

[5] ZhangD, ZhangCY, ZhengX, et al.. Facile synthesis of the Mn₃O₄ polyhedron grown on N-doped honeycomb carbon as high-performance negative material for lithium-ion batteries. Int. J. Miner. Metall. Mater., 2023, 3061152

[6] EbnerM, MaroneF, StampanoniM, WoodV. Visualization and quantification of electrochemical and mechanical degradation in Li ion batteries. Science, 2013, 3426159716

[7] SengKH, ParkMH, GuoZP, LiuHK, ChoJ. Catalytic role of Ge in highly reversible GeO₂/Ge/C nanocomposite anode material for lithium batteries. Nano Lett., 2013, 1331230

[8] Z.H. Yang, C.C. Weng, X.Y. Gao, et al., In situ construction of Sn-based metal–organic frameworks on MXene achieving fast electron transfer for rapid lithium storage, Chem. Eng. J., 486(2024), art. No. 150299.

[9] CaoKZ, WangST, HeYN, MaJH, YueZW, LiuHQ. Constructing Al@C–Sn pellet anode without passivation layer for lithium-ion battery. Int. J. Miner. Metall. Mater., 2024, 313552

[10] WangDH, KouR, ChoiD, et al.. Ternary self-assembly of ordered metal oxide–graphene nanocomposites for electrochemical energy storage. ACS Nano, 2010, 431587

[11] YuJ, WangYL, MouLH, FangDL, ChenSM, ZhangSJ. Nature-inspired 2D-mosaic 3D-gradient mesoporous framework: Bimetal oxide dual-composite strategy toward ultrastable and high-capacity lithium storage. ACS Nano, 2018, 1222035

[12] HouXY, XueS, LiuMT, ShangXN, FuYJ, HeDY. Hollow irregular octahedra-like NiCo₂O₄ cages composed of mesoporous nanosheets as a superior anode material for lithiumion batteries. Chem. Eng. J., 2018, 35029

[13] LiJF, HanL, ZhangXJ, et al.. Sb₂O₅/Co-containing carbon polyhedra as anode material for high-performance lithium-ion batteries. Chem. Eng. J., 2019, 370800

[14] LeyzerovichNN, BramnikKG, BuhrmesterT, EhrenbergH, FuessH. Electrochemical intercalation of lithium in ternary metal molybdates MMoO₄ (M: Cu, Zn, Ni and Fe). J. Power Sources, 2004, 1271–276

[15] YuH, GuanC, RuiXH, et al.. Hierarchically porous three-dimensional electrodes of CoMoO₄ and ZnCo₂O₄ and their high anode performance for lithium ion batteries. Nanoscale, 2014, 61810556

[16] WengCC, HuangSM, LuT, et al.. NiM (Sb, Sn)/N-doped hollow carbon tube as high-rate and high-capacity anode for lithium-ion batteries. J. Colloid Interface Sci., 2023, 652208

[17] XiaoW, ChenJS, LiCM, XuR, LouXW. Synthesis, characterization, and lithium storage capability of AMoO₄ (A = Ni, Co) nanorods. Chem. Mater., 2010, 223746

[18] LiJB, YanD, HouSJ, et al.. Metal-organic frameworks derived yolk–shell ZnO/NiO microspheres as high-performance anode materials for lithium-ion batteries. Chem. Eng. J., 2018, 335579

[19] TangK, FarooqiSA, WangXF, YanCL. Recent progress on molybdenum oxides for rechargeable batteries. ChemSusChem, 2019, 124755

[20] WangLJ, CuiXH, GongLL, et al.. Synthesis of porous CoMoO₄ nanorods as a bifunctional cathode catalyst for a Li–O₂ battery and superior anode for a Li-ion battery. Nanoscale, 2017, 9113898

[21] YuJ, WeiYB, MengBC, et al.. Homogeneous distributed natural pyrite-derived composite induced by modified graphite as high-performance lithium-ion batteries anode. Int. J. Miner. Metall. Mater., 2023, 3071353

[22] LiZL, YangYZ, WangJ, YangZ, ZhaoHL. Sandwich-like structure C/SiO_x@graphene anode material with high electrochemical performance for lithium ion batteries. Int. J. Miner. Metall. Mater., 2022, 29111947

[23] ZhengZH, XieMZ, YuGQ, et al.. Preparation of lithiumion battery anode materials from graphitized spent carbon cathode derived from aluminum electrolysis. Int. J. Miner. Metall. Mater., 2024, 31112466

[24] W.X. Liu, T. Xie, X.W. Wang, et al., Diffusion of carbon quantum dots on lithium liquid metal for artificial SEI, Adv. Funct. Mater., 34(2024), No. 52, art. No. 2410843.

[25] ChenYP, LiuBR, JiangW, et al.. Coaxial three-dimensional CoMoO₄ nanowire arrays with conductive coating on carbon cloth for high-performance lithium ion battery anode. J. Power Sources, 2015, 300132

[26] YaoJY, GongYJ, YangSB, et al.. CoMoO₄ nanoparticles anchored on reduced graphene oxide nanocomposites as anodes for long-life lithium-ion batteries. ACS Appl. Mater. Interfaces, 2014, 62220414

[27] ZhuYL, WangYX, GaoC, ZhaoWN, WangXB, WuMB. CoMoO₄–N-doped carbon hybrid nanoparticles loaded on a petroleum asphalt-based porous carbon for lithium storage. New Carbon Mater., 2020, 354358

[28] LiLX, DongGS, ZhaoH, et al.. Coral-like CoMoO₄ hierarchical structure uniformly encapsulated by graphene-like N-doped carbon network as an anode for high-performance lithium-ion batteries. J. Colloid Interface Sci., 2021, 58611

[29] XiaoY, HwangJY, SunYK. Micro-intertexture carbon-free iron sulfides as advanced high tap density anodes for rechargeable batteries. ACS Appl. Mater. Interfaces, 2017, 94539416

[30] WangW, QinJW, YinZG, CaoMH. Achieving fully reversible conversion in MoO₃ for lithium ion batteries by rational introduction of CoMoO₄. ACS Nano, 2016, 101110106

[31] ChenYY, WangY, ShenXP, et al.. Cyanide–metal framework derived CoMoO₄/Co₃O₄ hollow porous octahedrons as advanced anodes for high performance lithium ion batteries. J. Mater. Chem. A, 2018, 631048

[32] JiangMX, ZhangYJ, YangZH, et al.. A data-driven interpretable method to predict capacities of metal ion doped TiO₂ anode materials for lithium-ion batteries using machine learning classifiers. Inorg. Chem. Front., 2023, 10226646

[33] C.C. Weng, L. Ma, B.F. Wang, et al., Single-solvent ionic liquid strategy achieving wide-temperature and ultra-high cut-off voltage for lithium metal batteries, Energy Storage Mater., 71(2024), art. No. 103584.

[34] ChenJ, RaoAM, GaoCT, et al.. Phase-transition-free rivets for layered oxide potassium cathodes. Nano Res., 2024, 17119671

[35] J.K. Wang, T.H. Yao, L.L. Wang, Z.Y. Wang, Z.D. Wang, and H.K. Wang, Structural engineering of CoMoO₃ nanosheets on cage-like carbon nanoflakes toward enhanced lithium storage performance, J. Alloy. Compd., 926(2022), art. No. 166871.

[36] MarkaSK, PetnikotaS, SrikanthVVSS, ReddyMV, AdamsS, ChowdariBVR. Co₂Mo₃O₈/reduced graphene oxide composite: Synthesis, characterization, and its role as a prospective anode material in lithium ion batteries. RSC Adv., 2016, 66055167

[37] XieLF, ChenT, ChanHC, ShuYJ, GaoQS. Hydrogen doping into MoO₃ supports toward modulated metal-support interactions and efficient furfural hydrogenation on iridium nanocatalysts. Chem. Asian J., 2018, 136641

[38] LiuZ, ZhanCH, PengLK, et al.. A CoMoO₄–Co₂Mo₃O₈ heterostructure with valence-rich molybdenum for a high-performance hydrogen evolution reaction in alkaline solution. J. Mater. Chem. A, 2019, 72816761

[39] SmithGW, IbersJA. The crystal structure of cobalt molybdate CoMoO₄. Acta Crystallogr., 1965, 192269

[40] LeiL, FangLM, ZhaiLF, WangR, SunM. Anodic oxidation-assisted O₂ oxidation of phenol catalyzed by Fe₃O₄ at low voltage. Electrochim. Acta, 2018, 261394

[41] RodriguezJA, KimJY, HansonJC, BritoJL. Reduction of CoMoO₄ and NiMoO₄: In situ time-resolved XRD studies. Catal. Lett., 2002, 821103

[42] LiM, XuSH, CherryC, et al.. Hierarchical 3-dimensional CoMoO4 nanoflakes on a macroporous electrically conductive network with superior electrochemical performance. J. Mater. Chem. A, 2015, 32613776

[43] BaskarS, MeyrickD, RamakrishnanKS, MinakshiM. Facile and large scale combustion synthesis of α-CoMoO₄: Mimics the redox behavior of a battery in aqueous hybrid device. Chem. Eng. J., 2014, 253502

[44] XuJ, GuSZ, FanL, XuP, LuBG. Electrospun lotus root-like CoMoO₄@graphene nanofibers as high-performance anode for lithium ion batteries. Electrochim. Acta, 2016, 196125

[45] DamDT, HuangT, LeeJM. Ultra-small and low crystalline CoMoO₄ nanorods for electrochemical capacitors. Sustainable Energy Fuels, 2017, 12324

[46] XuR, LinJM, WuJH, et al.. Hydrothermal synthesis of CoMoO₄/Co₉S₈ nanorod arrays on nickel foam for high-performance asymmetric supercapacitors with high energy density. Electrochim. Acta, 2017, 252470

[47] OuYQ, TianWQ, LiuL, ZhangYH, XiaoP. Bimetallic Co₂Mo₃O₈ suboxides coupled with conductive cobalt nanowires for efficient and durable hydrogen evolution in alkaline electrolyte. J. Mater. Chem. A, 2018, 6125217

[48] LiYQ, XuHB, HuangHY, WangC, GaoLG, MaTL. One-dimensional MoO₂–Co₂Mo₃O₈@C nanorods: A novel and highly efficient oxygen evolution reaction catalyst derived from metal–organic framework composites. Chem. Commun., 2018, 54222739

[49] YuMQ, JiangLX, YangHG. Ultrathin nanosheets constructed CoMoO₄ porous flowers with high activity for electrocatalytic oxygen evolution. Chem. Commun., 2015, 517614361

[50] JasieniakJJ, TreatND, McNeillCR, de VillersBJT, GasperaED, ChabinycML. Interfacial characteristics of efficient bulk heterojunction solar cells fabricated on MoO_x anode interlayers. Adv. Mater., 2016, 28203944

[51] CherianCT, ReddyMV, HaurSC, ChowdariBVR. Interconnected network of CoMoO₄ submicrometer particles as high capacity anode material for lithium ion batteries. ACS Appl. Mater. Interfaces, 2013, 53918

[52] WuX, XiongXY, YuanB, LiuJ, HuRZ. Understanding the phenomenon of capacity increasing along cycles: In the case of an ultralong-life and high-rate SnSe–Mo–C anode for lithium storage. J. Energy Chem., 2022, 72133

[53] BrezesinskiT, WangJ, TolbertSH, DunnB. Ordered mesoporous alpha-MoO₃ with iso-oriented nanocrystalline walls for thin-film pseudocapacitors. Nat. Mater., 2010, 92146

[54] AugustynV, ComeJ, LoweMA, et al.. High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance. Nat. Mater., 2013, 126518

[55] J.B. Cook, H.S. Kim, Y. Yan, et al., Mesoporous MoS₂ as a transition metal dichalcogenide exhibiting pseudocapacitive Li and Na-ion charge storage, Adv. Energy Mater., 6(2016), No. 9, art. No. 1501937.

[56] LiJB, YanD, HouSJ, LuT, YaoYF, PanLK. Metalorganic frameworks converted flower-like hybrid with Co₃O₄ nanoparticles decorated on nitrogen-doped carbon sheets for boosted lithium storage performance. Chem. Eng. J., 2018, 354172

[57] J.B. Li, Z.B. Ding, J.L. Li, C.Y. Wang, L.K. Pan, and G.X. Wang, Synergistic coupling of NiS_1.03 nanoparticle with S-doped reduced graphene oxide for enhanced lithium and sodium storage, Chem. Eng. J., 407(2021), art. No. 127199.

[58] KimHS, CookJB, LinH, et al.. Oxygen vacancies enhance pseudocapacitive charge storage properties of MoO_3−x. Nat. Mater., 2017, 164454

[59] M. Salanne, B. Rotenberg, K. Naoi, et al., Efficient storage mechanisms for building better supercapacitors, Nat. Energy, 1(2016), art. No. 16070.

[60] LiJB, YanD, HouSJ, et al.. Improved sodium-ion storage performance of Ti₃C₂T_x MXenes by sulfur doping. J. Mater. Chem. A, 2018, 631234

[61] J.F. Li, L. Han, X.L. Zhang, et al., Multi-role TiO₂ layer coated carbon@few-layered MoS₂ nanotubes for durable lithium storage, Chem. Eng. J., 406(2021), art. No. 126873.

[62] LiJB, DingZB, PanLK, LiJL, WangCY, WangGX. Facile self-templating synthesis of layered carbon with N, S dual doping for highly efficient sodium storage. Carbon, 2021, 17331

[63] LeiHP, WeiTW, TuJG, JiaoSQ. Core–shell mesoporous carbon hollow spheres as Se hosts for advanced Al–Se batteries. Int. J. Miner. Metall. Mater., 2024, 315899

[64] E.J.F. Dickinson and A.J. Wain, The Butler–Volmer equation in electrochemical theory: Origins, value, and practical application, J. Electroanal. Chem., 872(2020), art. No. 114145.

[65] YanD, YuCY, ZhangXJ, et al.. Enhanced electrochemical performances of anatase TiO₂ nanotubes by synergetic doping of Ni and N for sodium-ion batteries. Electrochim. Acta, 2017, 254130

[66] LiJB, LiJL, YanD, et al.. Design of pomegranate-like clusters with NiS2 nanoparticles anchored on nitrogen-doped porous carbon for improved sodium ion storage performance. J. Mater. Chem. A, 2018, 6156595

RIGHTS & PERMISSIONS

University of Science and Technology Beijing