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A review of nitrogen-doped carbon materials for lithium-ion battery anodes

Majid Shaker Ali Asghar Sadeghi Ghazvini Taieb Shahalizade Mehran Ali Gaho Asim Mumtaz Shayan Javanmardi Reza Riahifar MENG Xiao-min JIN Zhan GE Qi

Majid Shaker, Ali Asghar Sadeghi Ghazvini, Taieb Shahalizade, Mehran Ali Gaho, Asim Mumtaz, Shayan Javanmardi, Reza Riahifar, MENG Xiao-min, JIN Zhan, GE Qi. 氮掺杂炭材料在锂离子电池负极的研究进展. 新型炭材料(中英文), 2023, 38(2): 247-282. doi: 10.1016/S1872-5805(23)60724-3
引用本文: Majid Shaker, Ali Asghar Sadeghi Ghazvini, Taieb Shahalizade, Mehran Ali Gaho, Asim Mumtaz, Shayan Javanmardi, Reza Riahifar, MENG Xiao-min, JIN Zhan, GE Qi. 氮掺杂炭材料在锂离子电池负极的研究进展. 新型炭材料(中英文), 2023, 38(2): 247-282. doi: 10.1016/S1872-5805(23)60724-3
Majid Shaker, Ali Asghar Sadeghi Ghazvini, Taieb Shahalizade, Mehran Ali Gaho, Asim Mumtaz, Shayan Javanmardi, Reza Riahifar, MENG Xiao-min, JIN Zhan, GE Qi. A review of nitrogen-doped carbon materials for lithium-ion battery anodes. New Carbon Mater., 2023, 38(2): 247-282. doi: 10.1016/S1872-5805(23)60724-3
Citation: Majid Shaker, Ali Asghar Sadeghi Ghazvini, Taieb Shahalizade, Mehran Ali Gaho, Asim Mumtaz, Shayan Javanmardi, Reza Riahifar, MENG Xiao-min, JIN Zhan, GE Qi. A review of nitrogen-doped carbon materials for lithium-ion battery anodes. New Carbon Mater., 2023, 38(2): 247-282. doi: 10.1016/S1872-5805(23)60724-3

氮掺杂炭材料在锂离子电池负极的研究进展

doi: 10.1016/S1872-5805(23)60724-3
详细信息
    通讯作者:

    Majid Shaker. E-mail: majidshacker@outlook.com

  • 中图分类号: TQ127.1+1

A review of nitrogen-doped carbon materials for lithium-ion battery anodes

  • 摘要:

    硬碳、活性炭、碳纳米管(CNTs)、石墨烯、多孔炭和炭纤维等炭材料替代锂离子电池的石墨阳极是目前的研究热点。与石墨相比,这种材料已表现出更好的储锂电化学性能,但仍有待进一步发展空间。其中一种有效的方法是在炭材料结构中加入杂原子(例如氮),提高其作为锂离子负极时的电化学性能。本综述首先描述了氮掺杂如何对锂离子电池的性能产生积极影响,并举例说明了氮掺杂炭材料的优势。然后,比较了不同N掺杂炭材料中的X射线光电子能谱和扫描隧道显微镜的表征结果,通过统计分析了掺氮量对掺氮碳材料比容量的影响。

  • FIG. 2232.  FIG. 2232.

    FIG. 2232..  FIG. 2232.

    Figure  1.  Various sites of doped nitrogen atoms in carbon materials, reproduced with permission[96], Copyright 2021 John Wiley and Sons

    Figure  2.  Configurations of N defect in graphene on Ni (111). The two top rows demonstrate the experimental and simulated STM images for various defects caused by N doping with the image size of 1 nm×1 nm. (3) N graphitic top (I = 3 nA, V = −0.2 V), (b) N graphitic fcc (I = 4 nA, V = −0.2 V), (c) 2N pyridinic fcc (I = 0.6 nA, V = −0.2 V), (d) 3N pyridinic fcc (I = 0.6 nA, V = −0.2 V) and (e) 3N pyridinic top (I = 0.6 nA, V = −0.2 V). For computational details, the readers can read reference[113]. The bottom section shows both the top and side views of the ball-and-stick model of DFT relaxed structures. Ni atoms are shown in dark grey, C atoms that delimit the defect cite in red, N atoms in blue, and graphene network in black, reproduced with permission[113], Copyright 2021 Elsevier

    Figure  3.  Initial CV curves of (a) rGO and (b) NrGO anodes at 0.1 mV s−1; galvanostatic curves of (c) rGO and (d) NrGO anodes measured at 0.1 A g−1; life cycle of (e) rGO and (f) NrGO electrodes measured at the current densities of 0.1, 2 and 10 Ag−1 over 100 cycles between 0.01 and 3.0 V; reproduced with permission[165] Copyright 2021 Elsevier

    Figure  4.  (a) Raman spectra of GNSPs and N-GNSPs; (b) XPS spectrum and (c) high-resolution N 1s XPS spectrum of N-GNSPs, adapted and reproduced with permission[156], Copyright 2020 Royal Society of Chemistry

    Figure  5.  N1s XPS peak profiles in the course of LIB operation, adapted and reproduced with permission[156], Copyright 2020 Royal Society of Chemistry

    Figure  6.  (a) SEM and (b) TEM images of NCNFs, adapted and reproduced with permission[184], Copyright 2019 John Wiley & Sons

    Figure  7.  Schematic illustration of some biomass-derived electrode materials and their intrinsic advantages, reproduced with permission[193], Copyright 2022 MDPI

    Figure  8.  Typical methods for the production of activated carbon materials from biomass, reproduced with permission[205], Copyright 2020 Taylor & Francis Group

    Figure  9.  SEM images of (a, b) oyster shell and (c, d) a sheet-like carbon sample, (e) its TEM image, and (f) SEM image of C-900; reproduced with permission[218], Copyright 2018 Elsevier

    Figure  10.  (a, b) FESEM images at two different magnifications (c) SEM and (d) TEM images of BNCMs; Reproduced with permission[227], Copyright 2019 Elsevier

    Figure  11.  Suggested formation mechanism for the CDots and N-PCFs; reproduced with permission[228]. Copyright 2019 American Chemical Society

    Figure  12.  Carbon plates in hard carbon, soft carbon , and graphite , adapted with permission[241], Copyright 2018, John Wiley and Sons

    Figure  13.  Initial (a) CV at 0.1 mV s−1 (The inset is for CLM.) and (b) CDC profiles of CLM-Ni at 0.1 A g−1; (c) galvanic CDC profiles of the fifth cycle of the samples at 0.1 A g−1; (d) Rate capability of the probing samples at multiple current densities; (e) Nyquist plots obtained after 5 cycles at 0.1 A g−1; (f) Long cycle performance of the samples at 0.1 A g−1, reproduced with permission[247], Copyright 2018 Elsevier

    Figure  14.  Lithium specific storage capacity vs nitrogen content of (a) all carbonaceous materials surveyed in this study, (d) graphene; histogram distribution curves of lithium specific storage capacity of (b) all carbonaceous materials surveyed in this study and (e) graphene; histogram distribution curves of N content of (c) all carbonaceous materials surveyed in this study and (f) graphene. The points shown in these plots are taken from the references depicted in the Tables of this review paper

    Figure  15.  Lithium storage specific capacity vs the atomic percentage of (a) pyridinic, (b) pyrrolic, and (c) graphitic doped N; Histograms of (d) pyridinic, (e) pyrrolic and (f) graphitic doped N

    Table  1.   Precursors, constituting elements, electrolyte and lithium storage capacity of N-doped graphenes

    SampleMaterialC sourceN sourceN (at.%)Capacity
    ( mAh g−1)
    ElectrolyteCDC rateRef.
    NGS1 N-doped graphene Glucose Melamine 12.68 780 1 mol L−1 LiPF6
    EC/DMC/ EMC (1/1/1 V)
    100 mA g−1 [132]
    NGS2 S Glucose Urea 17.25 687 S S [132]
    NGS3 S Glucose Dicyandiamide 19.59 662 S S [132]
    NGS4 S Methyl cellulose Melamine 16.34 600 S S [132]
    NGS5 S Sucrose Melamine 11.58 660 S S [132]
    N-rGO N-doped graphene Expanded graphite Ammonium hydroxide 7.98 530 1 mol L−1 LiPF6
    EC/DMC (1/1 V)
    S [133]
    NPGM N-doped
    porous graphene
    GO Melamine- formaldehyde 5.80 672 S S [134]
    PGM Porous graphene S S 0 450 S S [134]
    N-GS N-doped graphene GO Poly(aniline) PANi 7.17 384 1 mol L−1 LiPF6
    EC/DEC (1/1 V)
    S [135]
    GN N-doped graphene Black graphene (TCNQ) Acetonitrile 3.90 977 1 mol L−1 LiPF6
    EC/DEC (1/1 V)
    C/5 [106]
    G Graphene Black graphene - - 878 S C/5 [106]
    NGSs N-doped graphene sheets Monohydrate glucose Dicyandiamide 19.46 727 1 mol L−1 LiPF6 in
    (EC, DMC, DEC)
    S [136]
    MLG Multilayer graphene S S 6.20 435 S S [136]
    GNSs Graphene nanosheets Exfoliated graphite oxides - 2.04 478 S S [136]
    NDG N-doped graphene Monohydrate glucose Dicyandiamide 13.10 1 mol L−1 LiPF6 in
    EC/DMC/DEC
    (1∶1∶1 V)
    S [137]
    NG2 N-doped graphene Natural flake graphite powder NH3 3.06 896 S 50 mA g−1 [138]
    NG1 S S S 2.04 467 S 500 mA g−1 [138]
    NG2 S S S 3.06 470 S 500 mA g−1 [138]
    NG3 S S S 3.18 509 S 500 mA g−1 [138]
    N-FLGS N-doped few-layer graphene sheets Pyrolytic graphite Aqueous ammonia 6.05 318 S 100 mA g−1 [139]
    NGHS N-doped graphene Hollow microspheres GO Melamine 9.37 1400 S 0.5 C [140]
    NHGHS N-doped holey graphene hollow microspheres Holey GO Melamine 9.63 1580 S S [140]
    GP Graphene paper Graphite oxide - 0 161 S S [141]
    N-GP N-doped GP Graphite oxide Concentrated ammonia 6.81 316 S S [141]
    N-C-700 N-doped graphene ZIF-8 ZIF-8 22.80 1030 1 mol L−1 LiPF6
    EC/DEC (1/1 V)
    100 mA g−1 [142]
    N-C-800 S S S 16.98 2163 1746@40 cycles S S [142]
    N-C-900 S S S 10.10 882 S S [142]
    N-rGO N-doped reduced graphene oxide GO Melamine 5.00 519 1 mol L−1 LiPF6
    EC/DMC (1/1 V)
    S [143]
    N-rGO GO Hydrazine hydrate 7.05 1401 1 mol L−1 LiPF6
    EC/DMC (1/1 V)
    100 mA g−1 [144]
    MC-650 Nitrogen self-doped graphene nanosheets Melamine Melamine - 859 1 mol L−1 LiPF6 in
    EC, DMC, and EMC
    (1/1/1 V)
    0.1 C [145]
    MC-750 S S S - 1248 S S [145]
    MC-850 S S S - 1554 S S [145]
    N-3D GFs N-doped 3D graphene frameworks GO NH3 2.02 1006 1 mol L−1 LiPF6
    EC/DEC (1/1 V)
    100 mA g−1 [146]
    3D GFs 3D graphene frameworks S - 0 865 S S [146]
    N-GA 3D N-doped graphene aerogel Graphite Ammonia 4.45 690 - S [147]
    GA 3D graphene aerogel S - 0 480 - S [147]
    NGNS N-doped graphene nanosheets - - 4.17 wt.% 437 1 mol L−1 LiPF6
    EC/DEC (1/1 V)
    S [148]
    GNS Graphene nanosheets - - 0 wt.% 303 S S [148]
    NGHSs N-doped graphene hollow microspheres GO Ammonia 9.37 1386 1 mol L−1 LiPF6
    EC/DMC (1/1 V)
    0.5 C [149]
    GHSs Graphene hollow microspheres S - 0 948 S S [149]
    N-GNS N-doped graphene nanosheets Graphite oxide NH3 2.00% 717 S 0.1 C [150]
    GNS Graphene nanosheets S - 0 366 S S [150]
    N-RGN N-doped reduced graphite oxide Reduced graphite oxide Melamine 8.52 1095.2 1 mol L−1 LiPF6
    EC/DEC (1/1 V)
    100 mA g−1 [151]
    N-GT N-doped graphite oxide Graphite oxide S 11.36 809 S S [151]
    N-GN N-doped graphene oxide Graphene oxide S 12.06 707 S S [151]
    N-rGO N-doped reduced graphene oxide films GO Melamine 7.11 993 1 mol L−1 LiPF6
    EC/DEC/EMC (1/1/1 V)
    100 mA g−1 [152]
    N-doped graphene N-doped graphene Hexamethylenet etramine Hexamethylenet etramine 1.68 655 1 mol L−1 LiPF6
    EC/DMC (1/1 V)
    100 mA g−1 [153]
    N-graphene Nitrogen- self-doped graphene Poly (acrylonitril edivinylbenzene- triallyl isocyanurate) Poly (acrylonitril edivinylbenzene- triallyl isocyanurate) 2.10 776.0 S 100 mA g−1 [154]
    NGr N-doped graphene GO Ammonium hydroxide 2.80% XPS 798 1 mol L−1 LiPF6
    EC/DEC (1/1 V)
    0.5 A g−1 [155]
    N-GNSPs N-doped graphene nanostripes Methane 3-chloropyridine 7.50% XPS 415 1 mol L−1 LiPF6
    EC/DMC (1/1 V)
    0.1 A g−1 [156]
    GNSPs Graphene nanostripes S 1,2-dichlorobenzene - 365 S S [156]
    N-RGO N-doped reduced graphene oxide Natural flake graphite NH3 2.10 wt.% 895 1 mol L−1 LiPF6
    EC/DMC (1/1 V)
    0.1 C [157]
    N-doped graphene N-doped graphene Dimethylforma mide Dimethylforma mide 12.25 wt.% 577 1 mol L−1 LiPF6
    EC/DEC (1/1 V)
    0.2 A g−1 [158]
    Graphene Pristine graphene Methanol Methanol 0.09 wt.% 479 S S [158]
    PGSs Pristine graphene sheets Graphite powder - 0 741 S 0.05 A g−1 [80]
    N-GSs N-doped graphene sheets S Melamine 7.04 1136 S S [80]
    N-RGO N-doped reduced graphene oxide Natural flake graphite Melamine 2.0 wt.% 650 1 mol L−1 LiPF6
    EC/DMC (1/1 Wt.)
    0.1 C [159]
    GP Graphite powder Graphite powder - - 251 S 0.1 A g−1 [160]
    GS Graphene sheets Graphite powder +methyl methacrylate binder - - 291 S S [160]
    NGS-5 N-doped graphene sheets S Melamine 1.96 370 S S [160]
    NGS-9 S S S 4.63 420 S S [160]
    Note: S-Same with the above cell; -No data was found or existed; V-Volume EC-ethylene carbonate; DMC-dimethylcarbonate EMC-ethyl methyl carbonate; DEC-diethyl carbonate; PC-propylene carbonate; Wt-weight
    下载: 导出CSV

    Table  2.   Precursors, constituting elements, electrolyte and lithium storage capacity of N-doped CNTs and fibers

    SampleMaterialC sourceN sourceN (at.%)Capacity
    (mAh g−1)
    ElectrolyteCDC rateRef
    CNTCNTS-0121Commercial LB3030.2 C[180]
    N-CNTN-doped CNTCNTAcetonitrile6.00 wt.%516SS[180]
    N-Gr/CNTN-doped Graphene/
    Carbon nanotube
    GO+CNTUric acid11.2111501 mol L−1 LiPF6 EC/DEC (1/1 V)100 mA g−1[181]
    N-SCNTsN-doped carbon nanotubesFormaldehyde3-aminophenol,
    L-C16PheCOOH template
    9.503781 mol L−1 LiPF6 in a
    1∶1 (w/w) EC/DEC
    S[182]
    N-HCNTs-1SS3-aminophenol,
    L-C16PhgCOOH template
    9.60466SS[182]
    N-HCNTs-2SSS2.00114SS[182]
    CNFWsN-doped Porous carbon
    nanofiber webs
    Polypyrrole nanofiber websPolypyrrole nanofiber webs10.25 wt.%13211 mol L−1 LiPF6 EC/DMC (1/1 V)100 mA g−1[183]
    NCNFNsN-doped carbon fiberCarbon fiberPolyacrylonitrile1.70224commercial LBC3008A50 mA g−1[184]
    NCNFNs-rGO-5N-doped carbon fiber-
    reduced graphene oxide
    Carbon fiber + GOS2.60243SS[184]
    NCNFNs-rGO-10SCarbon fiber + GOS2.90271SS[184]
    N-CNFsCoral-like N-doped
    carbon nanofibers
    AcetyleneImidazole2.838501 mol L−1 LiPF6 EC/DEC (1/1 V)200 mA g−1[185]
    CNFsCoral-like N-doped
    carbon nanofibers
    S-0750SS[185]
    Note: V-Volume, wt-weight percentage.
    下载: 导出CSV

    Table  3.   Precursors, constituting elements, electrolyte, and lithium storage capacity of N-doped porous carbons

    SampleMaterialC sourceN sourceN (at.%)Capacity
    mAh g−1
    ElectrolyteCDC rateRef.
    NPC-1N-doped porous carbonsFoam polystyreneUrea5.747501 mol L−1 LiPF6 EC/
    DMC/EMC (1/1/1 V)
    0.1 A g−1[223]
    NPC-3SSS5.77450SS[223]
    NPC-5SSS7.751101SS[223]
    PC-600N-doped aqueous alkyd
    resin-based carbons
    Soybean oil-based aqueous
    alkyd resin emulsion
    Ammonia1.382850.2 A g−1[224]
    PC-800SSS1.77527S[224]
    N-MCHSs-800N-doped mesoporous carbon
    hollow spheres
    DopamineDopamine4.484861 mol L−1 LiPF6 EC/DEC (1/1 V)0.5 A g−1[225]
    3D NPGS3D N-doped graphene-like
    microspheres
    Polyethylene glycolUrea1.99 wt. %8401 mol L−1 LiPF6 EC/DMC (1/1 V)0.1 A g−1[226]
    BNCMBiogenic N-doped carbon
    microspheres
    Resorcinol, formaldehydeAmmonia8.00%6021 mol L−1 LiPF6 EC/DMC (1/1 V)0.05 A g−1[227]
    N-PCFN-doped carbon dotsCitric acidUrea19.0014371 mol L−1 LiPF6 EC/DMC (1/1 V)0.1 A g−1[228]
    NPC-1N-doped porous carbonTP- pphenylenediamine
    covalent-organic
    Frameworks
    (TPPA-COFs)
    TP- pphenylenediamine
    covalent-organic
    Frameworks
    (TPPA-COFs)
    11.504201 mol L−1 LiPF6 EC/PC (1/1 weight)0.1 A g−1[229]
    NPC-2SSS9.75500SS[229]
    NPC-3SSS8.38480SS[229]
    NPGFMonolithic 3D N-doped
    graphene nanoarchitecture
    PolyimidePolyimide2.6 wt. %6401 mol L−1 LiPF6 EC/DEC (1/1 V)0.5 A g−1[230]
    NFCs-550N-doped 3D flower-like
    carbon
    PolyimidePolyimide15.124001 mol L−1 LiPF6 EC/DMC (1/1 V)0.1 A g−1[231]
    NPC(20Zn-80Co)-600 °CZnCo-ZIF-based N-doped
    porous carbon
    ZIF-8 polyhedraZIF-8 polyhedra9.496001 mol L−1 LiPF6 EC/DEC (1/1 V)1 A g−1[232]
    Zn-Co/NPC-500Zn-Co N-doped porous carbon
    (Zn-Co/NPC)
    Zn-Co-ZIFZn-Co-ZIF-4031 mol L−1 LiPF6 EC/DEC/DMC (1/1/1 V)0.1 A g−1[233]
    Zn-Co/NPC-600SSS-849SS[233]
    Zn-Co/NPC-700SSS-598SS[233]
    PNC@GPorous N-doped
    carbon@ graphene
    ZIF-8, GrapheneZIF-814.806501 mol L−1 LiPF6 EC/DEC (1/1 V)0.1 A g−1[234]
    MPNC@G-1(ZIF)-derived N-doped
    carbon- anchored graphene
    ZIF-8, GrapheneZIF-8, melamine11.90730SS[234]
    MPNC@G-2SSS12.20500SS[234]
    N-C-700N-doped graphene particleZIF-8ZIF-824.45 wt.%1030S0.1 A g−1[142]
    N-C-800SSS17.72 wt.%2132SS[142]
    N-C-900SSS10.73 wt.%882SS[142]
    SNCMs-800N-doped porous carbonDuckweedsDuckweeds4.311091S100 mA g−1[194]
    SNCMs-700SSS4.61-SS[194]
    SNCMs-900SSS2.58-SS[194]
    SPC-700Soybean derived porous carbonSoybeansSoybeans1.668641 mol L−1 LiPF6 EC/DMC (1/1 V)0.1 C[235]
    Note: V-Volume, wt-weight percentage.
    下载: 导出CSV

    Table  4.   Classification of the data of the literature based on the lithium storage specific capacity

    Capacity range (mAh g−1)N range (at.%)Average percentage of N (at.%)Number of dataStandard deviation (at.%)Standard error (at.%)
    Without N-doping00500
    0-5001.96-11.776.2063.461.41
    500-10000.02-14.208.95143.610.96
    1000-15009.37-22.8014.4635.943.43
    Above 15009.63-16.9813.3023.681.94
    下载: 导出CSV

    Table  5.   Classification of the data of the literature based on the N atomic percentage

    N quantity (at. %)Capacity range (mAh g−1)Average Capacity (mAh g−1)Number of dataStandard deviation (mAh g−1)Standard erorr (mAh g−1)
    0161-459305.65101.2420.25
    0-5370-717497.84132.8866.44
    5-10316-1580790.711397.17119.75
    10-15472-1150709.18212.7375.21
    Above 151030-21631596.52566.50400.58
    下载: 导出CSV

    Table  6.   The ratio of N types in the structure of the investigated N-doped carbon LIB anodes

    SampleN (at.%)Pyridinic N (at.%)Pyrrolic N (at.%)Graphitic N (at.%)Capacity (mAh g−1)Ref.
    NGS112.683.272.956.45780[132]
    NGHS9.371.462.172.761400[140]
    NHGHS9.632.032.402.461580[140]
    N-PC11.674.543.423.71580[252]
    N-PGNS9.484.022.293.17741.8[252]
    GP0000161[141]
    N-GP6.811.743.721.35315.6[141]
    C-50011.773.434.812.14472[253]
    C-6009.802.334.282.50539[253]
    C-7009.162.093.292.44369[253]
    N-C-70022.8011.495.106.211030[142]
    N-C-80016.987.343.616.032163[142]
    N-C-90010.103.542.094.47882[142]
    PNC@G14.206.663.494.06570[234]
    MPNC@G-111.905.182.144.58730[234]
    MPNC@G-212.204.531.386.28509[234]
    N-Gr/CNT11.215.151.613.481150[181]
    N-CNS-6007.152.711.642.14953[254]
    N-CNS-7006.302.341.272.07858[254]
    N-CNS-8005.471.671.172.00760[254]
    N-GNS0.020.010.0070.002717[150]
    GNS0000366[150]
    OMC0000458.9[255]
    N-OMC12.840.530.900.94484[255]
    N-OMC25.821.691.761.23645.7[255]
    N-OMC38.573.082.632.22535.5[255]
    GP0000251[160]
    GS0000291[160]
    NGS-51.960.431.00.53370[160]
    NGS-94.630.692.591.34420[160]
    下载: 导出CSV
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出版历程
  • 收稿日期:  2022-11-26
  • 修回日期:  2023-02-11
  • 网络出版日期:  2023-02-17
  • 刊出日期:  2023-04-07

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