形貌遗传法制备碳包覆棒状Li_3VO_4锂离子电池负极材料（英文）
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摘要
Li_3VO_4作为一种能够应用到储能装置上的脱嵌型负极材料展现了巨大的应用潜力.形貌调控和表面修饰是提升Li_3VO_4电化学性能非常有效的方法.本文通过一种形貌遗传法制备了碳包覆的棒状Li_3VO_4. SEM和TEM结果表明这种碳包覆棒状Li_3VO_4材料的长度约为400–800 nm,直径约为200–400 nm. XRD和XPS结果证明碳包覆棒状Li_3VO_4仍然是正交相,其中V的价态为+5.由于其独特的核壳结构,它的电子和锂离子的传输能力都有较大的提升.因此,碳包覆棒状Li_3VO_4展现出优异的电化学性能,在0.2, 1, 2, 5和10 C的电流密度下分别有460, 438, 416, 359和310 mA h g~(-1)的可逆容量,在0.2和5 C的电流密度下循环300圈后仍然具有440和313 mA h g~(-1)的可逆容量.
Li_3VO_4 shows great potential as an intercalation/de-intercalation type anode material for energy-storage devices. Morphology tailoring and surface modification are effective to enhance its lithium storage performance. In this work, we fabricate carbon coated Li_3VO_4(C@LVO) rods by a facile morphology inheritance route. The as-prepared C@LVO rods are 400–800 nm in length and 200–400 nm in diameter,and orthorhombic phase with V~(5+). The unique core-shell rods structure greatly improves the transport ability of electrons and Li~+. Such C@LVO submicron-rods as anode materials exhibit excellent rate capability(a reversible capability of 460,438, 416, 359 and 310 m A h g~(-1) at 0.2, 1, 2, 5 and 10 C, respectively) and a high stable capacity of 440 and 313 m A h g~(-1) up to 300 cycles at 0.2 and 5 C, respectively.
Li_3VO_4 shows great potential as an intercalation/de-intercalation type anode material for energy-storage devices. Morphology tailoring and surface modification are effective to enhance its lithium storage performance. In this work, we fabricate carbon coated Li_3VO_4(C@LVO) rods by a facile morphology inheritance route. The as-prepared C@LVO rods are 400–800 nm in length and 200–400 nm in diameter,and orthorhombic phase with V~(5+). The unique core-shell rods structure greatly improves the transport ability of electrons and Li~+. Such C@LVO submicron-rods as anode materials exhibit excellent rate capability(a reversible capability of 460,438, 416, 359 and 310 m A h g~(-1) at 0.2, 1, 2, 5 and 10 C, respectively) and a high stable capacity of 440 and 313 m A h g~(-1) up to 300 cycles at 0.2 and 5 C, respectively.
引文
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4 Assat G,Tarascon JM.Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries.Nat Energy,2018,3:373-386
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11 Zhou L,Yi Z,Lyu F,et al.Facile one-pot fabrication ofα-Fe2O3nano-coffee beans by etching along[001]direction for high lithium storage.Sci China Mater,2017,60:1187-1195
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18 Ni S,Lv X,Zhang J,et al.The electrochemical performance of lithium vanadate/natural graphite composite material as anode for lithium ion batteries.Electrochim Acta,2014,145:327-334
19 Shen L,Chen S,Maier J,et al.Carbon-coated Li3VO4spheres as constituents of an advanced anode material for high-rate long-life lithium-ion batteries.Adv Mater,2017,29:1701571
20 Yang G,Zhang B,Feng J,et al.Morphology controlled lithium storage in Li3VO4anodes.J Mater Chem A,2018,6:456-463
21 Ni S,Zhang J,Ma J,et al.Superior electrochemical performance of Li3VO4/N-doped C as an anode for Li-ion batteries.J Mater Chem A,2015,3:17951-17955
22 Yang Y,Li J,He X,et al.A facile spray drying route for mesoporous Li3VO4/C hollow spheres as an anode for long life lithium ion batteries.J Mater Chem A,2016,4:7165-7168
23 Mu C,Lei K,Li H,et al.Enhanced conductivity and structure stability of Ti4+doped Li3VO4as anodes for lithium-ion batteries.JPhys Chem C,2017,121:26196-26201
24 Zhang C,Liu C,Nan X,et al.Hollow-cuboid Li3VO4/C as highperformance anodes for lithium-ion batteries.ACS Appl Mater Interfaces,2016,8:680-688
25 Shen L,Lv H,Chen S,et al.Peapod-like Li3VO4/N-doped carbon nanowires with pseudocapacitive properties as advanced materials for high-energy lithium-ion capacitors.Adv Mater,2017,29:1700142
26 Zheng YZ,Ding H,Uchaker E,et al.Nickel-mediated polyol synthesis of hierarchical V2O5hollow microspheres with enhanced lithium storage properties.J Mater Chem A,2015,3:1979-1985
27 Ragupathy P,Shivakumara S,Vasan HN,et al.Preparation of nanostrip V2O5by the polyol method and its electrochemical characterization as cathode material for rechargeable lithium batteries.J Phys Chem C,2008,112:16700-16707
28 Zeng L,Pan A,Liang S,et al.Novel synthesis of V2O5hollow microspheres for lithium ion batteries.Sci China Mater,2016,59:567-573
29 Wang H,Ma D,Huang Y,et al.Electrospun V2O5nanostructures with controllable morphology as high-performance cathode materials for lithium-ion batteries.Chem Eur J,2012,18:8987-8993
30 Yue Y,Liang H.Micro-and nano-structured vanadium pentoxide(V2O5)for electrodes of lithium-ion batteries.Adv Energy Mater,2017,7:1602545
31 Deng Z,Tang F,Chen D,et al.A simple solution route to singlecrystalline Sb2O3nanowires with rectangular cross sections.J Phys Chem B,2006,110:18225-18230
32 Deng Z,Chen D,Tang F,et al.Orientated attachment assisted selfassembly of Sb2O3nanorods and nanowires:end-to-end versus side-by-side.J Phys Chem C,2007,111:5325-5330
33 Uchaker E,Zhou N,Li Y,et al.Polyol-mediated solvothermal synthesis and electrochemical performance of nanostructured V2O5hollow microspheres.J Phys Chem C,2013,117:1621-1626
34 Liu Y,Uchaker E,Zhou N,et al.Facile synthesis of nanostructured vanadium oxide as cathode materials for efficient Li-ion batteries.JMater Chem,2012,22:24439-24445
35 Liu J,Lu PJ,Liang S,et al.Ultrathin Li3VO4nanoribbon/graphene sandwich-like nanostructures with ultrahigh lithium ion storage properties.Nano Energy,2015,12:709-724
36 Li Q,Wei Q,Sheng J,et al.Mesoporous Li3VO4/C submicronellipsoids supported on reduced graphene oxide as practical anode for high-power lithium-ion batteries.Adv Sci,2015,2:1500284
37 Li S,Wang T,Zhu W,et al.Controllable synthesis of uniform mesoporous H-Nb2O5/rGO nanocomposites for advanced lithium ion hybrid supercapacitors.J Mater Chem A,2019,7:693-703
38 Di Noto V,Negro E,Polizzi S,et al.Synthesis,studies and fuel cell performance of“core-shell”electrocatalysts for oxygen reduction reaction based on a PtNixcarbon nitride“shell”and a pyrolyzed polyketone nanoball“core”.Int J Hydrogen Energy,2014,39:2812-2827
39 Sathiya M,Prakash AS,Ramesha K,et al.V2O5-anchored carbon nanotubes for enhanced electrochemical energy storage.J Am Chem Soc,2011,133:16291-16299
40 Cai Z,Xu L,Yan M,et al.Manganese oxide/carbon yolk-shell nanorod anodes for high capacity lithium batteries.Nano Lett,2015,15:738-744
41 Qin R,Shao G,Hou J,et al.One-pot synthesis of Li3VO4@C nanofibers by electrospinning with enhanced electrochemical performance for lithium-ion batteries.Sci Bull,2017,62:1081-1088
42 Glushenkov AM,Stukachev VI,Hassan MF,et al.A novel approach for real mass transformation from V2O5particles to nanorods.Cryst Growth Des,2008,8:3661-3665
43 Zhang LL,Li Y,Peng G,et al.High-performance Li3V2(PO4)3/Ccathode materials prepared via a sol-gel route with double carbon sources.J Alloys Compd,2012,513:414-419
44 Tartaj P,Amarilla JM,Vazquez-Santos MB.Aerosol-assisted synthesis of colloidal aggregates with different morphology:Toward the electrochemical optimization of Li3VO4battery anodes using scalable routes.Chem Mater,2016,28:986-993
45 Hu S,Song Y,Yuan S,et al.A hierarchical structure of carboncoated Li3VO4nanoparticles embedded in expanded graphite for high performance lithium ion battery.J Power Sources,2016,303:333-339
46 Liu H,Hu P,Yu Q,et al.Boosting the deep discharging/charging lithium storage performances of Li3VO4through double-carbon decoration.ACS Appl Mater Interfaces,2018,10:23938-23944
47 Xia L,Wang S,Liu G,et al.Flexible SnO2/N-doped carbon nanofiber films as integrated electrodes for lithium-ion batteries with superior rate capacity and long cycle life.Small,2016,12:853-859
48 Wang G,Xie J,Wu C,et al.Submicron lithium nickel manganese oxide spinel with long cycling stability and high rate performance prepared by a facile route.J Power Sources,2014,265:118-124
49 Cheng F,Wang H,Zhu Z,et al.Porous LiMn2O4nanorods with durable high-rate capability for rechargeable Li-ion batteries.Energy Environ Sci,2011,4:3668-3675
50 Lou XW,Li CM,Archer LA.Designed synthesis of coaxial SnO2@carbon hollow nanospheres for highly reversible lithium storage.Adv Mater,2009,21:2536-2539
51 Ko JS,Doan-Nguyen VVT,Kim HS,et al.High-rate capability of Na2FePO4F nanoparticles by enhancing surface carbon functionality for Na-ion batteries.J Mater Chem A,2017,5:18707-18715
52 Yang C,Tang Y,Tian Y,et al.Achieving of flexible,free-standing,ultracompact delaminated titanium carbide films for high volumetric performance and heat-resistant symmetric supercapacitors.Adv Funct Mater,2018,28:1705487
53 Brezesinski T,Wang J,Tolbert SH,et al.Ordered mesoporousα-MoO3with iso-oriented nanocrystalline walls for thin-film pseudocapacitors.Nat Mater,2010,9:146-151
54 Lou S,Cheng X,Wang L,et al.High-rate capability of threedimensionally ordered macroporous t-Nb2O5through Li+intercalation pseudocapacitance.J Power Sources,2017,361:80-86
55 Lou S,Cheng X,Gao J,et al.Pseudocapacitive Li+intercalation in porous Ti2Nb10O29nanospheres enables ultra-fast lithium storage.Energy Storage Mater,2018,11:57-66
56 Lou S,Cheng X,Zhao Y,et al.Superior performance of ordered macroporous TiNb2O7anodes for lithium ion batteries:Understanding from the structural and pseudocapacitive insights on achieving high rate capability.Nano Energy,2017,34:15-25
57 Zhao C,Yu C,Zhang M,et al.Ultrafine MoO2-carbon microstructures enable ultralong-life power-type sodium ion storage by enhanced pseudocapacitance.Adv Energy Mater,2017,7:1602880
58 Fan X,Tang X,Ma D,et al.Novel hollow Sn-Cu composite nanoparticles anodes for Li-ion batteries prepared by galvanic replacement reaction.J Solid State Electrochem,2014,18:1137-1145
2 Armand M,Tarascon JM.Building better batteries.Nature,2008,451:652-657
3 Dunn B,Kamath H,Tarascon JM.Electrical energy storage for the grid:A battery of choices.Science,2011,334:928-935
4 Assat G,Tarascon JM.Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries.Nat Energy,2018,3:373-386
5 Kaskhedikar NA,Maier J.Lithium storage in carbon nanostructures.Adv Mater,2009,21:2664-2680
6 Kim HK,Bak SM,Kim KB.Li4Ti5O12/reduced graphite oxide nano-hybrid material for high rate lithium-ion batteries.Electrochem Commun,2010,12:1768-1771
7 Park H,Wu HB,Song T,et al.Porosity-controlled TiNb2O7microspheres with partial nitridation as a practical negative electrode for high-power lithium-ion batteries.Adv Energy Mater,2015,5:1401945
8 Agyeman DA,Song K,Lee GH,et al.Carbon-coated Si nanoparticles anchored between reduced graphene oxides as an extremely reversible anode material for high energy-density Li-ion battery.Adv Energy Mater,2016,6:1600904
9 Zhu Y,Cao T,Li Z,et al.Two-dimensional SnO2/graphene heterostructures for highly reversible electrochemical lithium storage.Sci China Mater,2018,61:1527-1535
10 Geng Z,Li B,Liu H,et al.Oxygen-doped carbon host with enhanced bonding and electron attraction abilities for efficient and stable SnO2/carbon composite battery anode.Sci China Mater,2018,61:1067-1077
11 Zhou L,Yi Z,Lyu F,et al.Facile one-pot fabrication ofα-Fe2O3nano-coffee beans by etching along[001]direction for high lithium storage.Sci China Mater,2017,60:1187-1195
12 An C,Liu X,Gao Z,et al.Filling and unfilling carbon capsules with transition metal oxide nanoparticles for Li-ion hybrid supercapacitors:Towards hundred grade energy density.Sci China Mater,2017,60:217-227
13 Li H,Liu X,Zhai T,et al.Li3VO4:A promising insertion anode material for lithium-ion batteries.Adv Energy Mater,2013,3:428-432
14 Choi NS,Chen Z,Freunberger SA,et al.Challenges facing lithium batteries and electrical double-layer capacitors.Angew Chem Int Ed,2012,51:9994-10024
15 Zhu GN,Liu HJ,Zhuang JH,et al.Carbon-coated nano-sized Li4Ti5O12nanoporous micro-sphere as anode material for high-rate lithium-ion batteries.Energy Environ Sci,2011,4:4016-4022
16 Sha Y,Zhao B,Ran R,et al.Synthesis of well-crystallized Li4Ti5O12nanoplates for lithium-ion batteries with outstanding rate capability and cycling stability.J Mater Chem A,2013,1:13233-13243
17 Zhang C,Song H,Liu C,et al.Fast and reversible Li ion insertion in carbon-encapsulated Li3VO4as anode for lithium-ion battery.Adv Funct Mater,2015,25:3497-3504
18 Ni S,Lv X,Zhang J,et al.The electrochemical performance of lithium vanadate/natural graphite composite material as anode for lithium ion batteries.Electrochim Acta,2014,145:327-334
19 Shen L,Chen S,Maier J,et al.Carbon-coated Li3VO4spheres as constituents of an advanced anode material for high-rate long-life lithium-ion batteries.Adv Mater,2017,29:1701571
20 Yang G,Zhang B,Feng J,et al.Morphology controlled lithium storage in Li3VO4anodes.J Mater Chem A,2018,6:456-463
21 Ni S,Zhang J,Ma J,et al.Superior electrochemical performance of Li3VO4/N-doped C as an anode for Li-ion batteries.J Mater Chem A,2015,3:17951-17955
22 Yang Y,Li J,He X,et al.A facile spray drying route for mesoporous Li3VO4/C hollow spheres as an anode for long life lithium ion batteries.J Mater Chem A,2016,4:7165-7168
23 Mu C,Lei K,Li H,et al.Enhanced conductivity and structure stability of Ti4+doped Li3VO4as anodes for lithium-ion batteries.JPhys Chem C,2017,121:26196-26201
24 Zhang C,Liu C,Nan X,et al.Hollow-cuboid Li3VO4/C as highperformance anodes for lithium-ion batteries.ACS Appl Mater Interfaces,2016,8:680-688
25 Shen L,Lv H,Chen S,et al.Peapod-like Li3VO4/N-doped carbon nanowires with pseudocapacitive properties as advanced materials for high-energy lithium-ion capacitors.Adv Mater,2017,29:1700142
26 Zheng YZ,Ding H,Uchaker E,et al.Nickel-mediated polyol synthesis of hierarchical V2O5hollow microspheres with enhanced lithium storage properties.J Mater Chem A,2015,3:1979-1985
27 Ragupathy P,Shivakumara S,Vasan HN,et al.Preparation of nanostrip V2O5by the polyol method and its electrochemical characterization as cathode material for rechargeable lithium batteries.J Phys Chem C,2008,112:16700-16707
28 Zeng L,Pan A,Liang S,et al.Novel synthesis of V2O5hollow microspheres for lithium ion batteries.Sci China Mater,2016,59:567-573
29 Wang H,Ma D,Huang Y,et al.Electrospun V2O5nanostructures with controllable morphology as high-performance cathode materials for lithium-ion batteries.Chem Eur J,2012,18:8987-8993
30 Yue Y,Liang H.Micro-and nano-structured vanadium pentoxide(V2O5)for electrodes of lithium-ion batteries.Adv Energy Mater,2017,7:1602545
31 Deng Z,Tang F,Chen D,et al.A simple solution route to singlecrystalline Sb2O3nanowires with rectangular cross sections.J Phys Chem B,2006,110:18225-18230
32 Deng Z,Chen D,Tang F,et al.Orientated attachment assisted selfassembly of Sb2O3nanorods and nanowires:end-to-end versus side-by-side.J Phys Chem C,2007,111:5325-5330
33 Uchaker E,Zhou N,Li Y,et al.Polyol-mediated solvothermal synthesis and electrochemical performance of nanostructured V2O5hollow microspheres.J Phys Chem C,2013,117:1621-1626
34 Liu Y,Uchaker E,Zhou N,et al.Facile synthesis of nanostructured vanadium oxide as cathode materials for efficient Li-ion batteries.JMater Chem,2012,22:24439-24445
35 Liu J,Lu PJ,Liang S,et al.Ultrathin Li3VO4nanoribbon/graphene sandwich-like nanostructures with ultrahigh lithium ion storage properties.Nano Energy,2015,12:709-724
36 Li Q,Wei Q,Sheng J,et al.Mesoporous Li3VO4/C submicronellipsoids supported on reduced graphene oxide as practical anode for high-power lithium-ion batteries.Adv Sci,2015,2:1500284
37 Li S,Wang T,Zhu W,et al.Controllable synthesis of uniform mesoporous H-Nb2O5/rGO nanocomposites for advanced lithium ion hybrid supercapacitors.J Mater Chem A,2019,7:693-703
38 Di Noto V,Negro E,Polizzi S,et al.Synthesis,studies and fuel cell performance of“core-shell”electrocatalysts for oxygen reduction reaction based on a PtNixcarbon nitride“shell”and a pyrolyzed polyketone nanoball“core”.Int J Hydrogen Energy,2014,39:2812-2827
39 Sathiya M,Prakash AS,Ramesha K,et al.V2O5-anchored carbon nanotubes for enhanced electrochemical energy storage.J Am Chem Soc,2011,133:16291-16299
40 Cai Z,Xu L,Yan M,et al.Manganese oxide/carbon yolk-shell nanorod anodes for high capacity lithium batteries.Nano Lett,2015,15:738-744
41 Qin R,Shao G,Hou J,et al.One-pot synthesis of Li3VO4@C nanofibers by electrospinning with enhanced electrochemical performance for lithium-ion batteries.Sci Bull,2017,62:1081-1088
42 Glushenkov AM,Stukachev VI,Hassan MF,et al.A novel approach for real mass transformation from V2O5particles to nanorods.Cryst Growth Des,2008,8:3661-3665
43 Zhang LL,Li Y,Peng G,et al.High-performance Li3V2(PO4)3/Ccathode materials prepared via a sol-gel route with double carbon sources.J Alloys Compd,2012,513:414-419
44 Tartaj P,Amarilla JM,Vazquez-Santos MB.Aerosol-assisted synthesis of colloidal aggregates with different morphology:Toward the electrochemical optimization of Li3VO4battery anodes using scalable routes.Chem Mater,2016,28:986-993
45 Hu S,Song Y,Yuan S,et al.A hierarchical structure of carboncoated Li3VO4nanoparticles embedded in expanded graphite for high performance lithium ion battery.J Power Sources,2016,303:333-339
46 Liu H,Hu P,Yu Q,et al.Boosting the deep discharging/charging lithium storage performances of Li3VO4through double-carbon decoration.ACS Appl Mater Interfaces,2018,10:23938-23944
47 Xia L,Wang S,Liu G,et al.Flexible SnO2/N-doped carbon nanofiber films as integrated electrodes for lithium-ion batteries with superior rate capacity and long cycle life.Small,2016,12:853-859
48 Wang G,Xie J,Wu C,et al.Submicron lithium nickel manganese oxide spinel with long cycling stability and high rate performance prepared by a facile route.J Power Sources,2014,265:118-124
49 Cheng F,Wang H,Zhu Z,et al.Porous LiMn2O4nanorods with durable high-rate capability for rechargeable Li-ion batteries.Energy Environ Sci,2011,4:3668-3675
50 Lou XW,Li CM,Archer LA.Designed synthesis of coaxial SnO2@carbon hollow nanospheres for highly reversible lithium storage.Adv Mater,2009,21:2536-2539
51 Ko JS,Doan-Nguyen VVT,Kim HS,et al.High-rate capability of Na2FePO4F nanoparticles by enhancing surface carbon functionality for Na-ion batteries.J Mater Chem A,2017,5:18707-18715
52 Yang C,Tang Y,Tian Y,et al.Achieving of flexible,free-standing,ultracompact delaminated titanium carbide films for high volumetric performance and heat-resistant symmetric supercapacitors.Adv Funct Mater,2018,28:1705487
53 Brezesinski T,Wang J,Tolbert SH,et al.Ordered mesoporousα-MoO3with iso-oriented nanocrystalline walls for thin-film pseudocapacitors.Nat Mater,2010,9:146-151
54 Lou S,Cheng X,Wang L,et al.High-rate capability of threedimensionally ordered macroporous t-Nb2O5through Li+intercalation pseudocapacitance.J Power Sources,2017,361:80-86
55 Lou S,Cheng X,Gao J,et al.Pseudocapacitive Li+intercalation in porous Ti2Nb10O29nanospheres enables ultra-fast lithium storage.Energy Storage Mater,2018,11:57-66
56 Lou S,Cheng X,Zhao Y,et al.Superior performance of ordered macroporous TiNb2O7anodes for lithium ion batteries:Understanding from the structural and pseudocapacitive insights on achieving high rate capability.Nano Energy,2017,34:15-25
57 Zhao C,Yu C,Zhang M,et al.Ultrafine MoO2-carbon microstructures enable ultralong-life power-type sodium ion storage by enhanced pseudocapacitance.Adv Energy Mater,2017,7:1602880
58 Fan X,Tang X,Ma D,et al.Novel hollow Sn-Cu composite nanoparticles anodes for Li-ion batteries prepared by galvanic replacement reaction.J Solid State Electrochem,2014,18:1137-1145