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3D printed carbon-based microbatteries: progress on technologies, materials and applications

HE Su-jiao ZHANG Kai-qiang ZOU Ya-jun TIAN Zhi-hong

贺素姣, 张凯强, 邹雅珺, 田志红. 3D打印碳基微电池的技术、材料与应用进展. 新型炭材料. doi: 10.1016/S1872-5805(22)60634-6
引用本文: 贺素姣, 张凯强, 邹雅珺, 田志红. 3D打印碳基微电池的技术、材料与应用进展. 新型炭材料. doi: 10.1016/S1872-5805(22)60634-6
HE Su-jiao, ZHANG Kai-qiang, ZOU Ya-jun, TIAN Zhi-hong. 3D printed carbon-based microbatteries: progress on technologies, materials and applications. New Carbon Mater.. doi: 10.1016/S1872-5805(22)60634-6
Citation: HE Su-jiao, ZHANG Kai-qiang, ZOU Ya-jun, TIAN Zhi-hong. 3D printed carbon-based microbatteries: progress on technologies, materials and applications. New Carbon Mater.. doi: 10.1016/S1872-5805(22)60634-6

3D打印碳基微电池的技术、材料与应用进展

doi: 10.1016/S1872-5805(22)60634-6
基金项目: 国家自然科学基金项目(52003251);河南省杰出外籍科学家工作室(GZS2022014)
详细信息
    通讯作者:

    邹雅珺,工程师. E-mail:yajun-zou@geidco.org

    田志红,教授. E-mail:zhihong.tian@henu.edu.cn

3D printed carbon-based microbatteries: progress on technologies, materials and applications

Funds: This work was partly supported by the National Natural Science Foundation of China (No. 52003251) and Henan Center for Outstanding Overseas Scientists (GZS2022014)
More Information
  • 摘要: 可充电微型电池可以为下一代可穿戴便携设备提供储能装置。增材制造也称为三维(3D)打印技术,具有构建复杂3D构型的能力,为制备尺寸可调、形状一致性好、兼具高能量密度和高功率密度的微电池提供了新的机遇。与其他多孔金属电极材料相比,轻质碳材料具有比表面积大、导电性好、化学稳定性高等优点。近年来,基于碳基墨水的3D打印技术已被用于制备多种类型的可充电微电池。为了对碳基微电池的电化学性能进行优化,并充分发挥其潜力,亟需对3D打印技术、材料设计以及应用方向进行梳理,从而深入理解3D打印电池方法的设计优化策略。本文首先介绍了四种主要3D打印技术的最新进展,阐述了导电碳材料在解决3D打印微电池挑战中的研究方法,总结了其在一系列储能设备和可穿戴电子设备集成中的应用。最后,进一步讨论了3D打印技术制造碳基微电池面临的关键科学问题和未来的发展方向。
  • Figure  1.  Schematic diagram of the major techniques, printable carbon materials and applications of 3D printing in rechargeable microbatteries[6, 9, 19, 23-32]. Reprinted with permission.

    Figure  2.  (a) Conventional battery geometries. (b) 3D designed microbatteries with interdigitated anode and cathode plates configuration[35]. Reprinted with permission.

    Figure  3.  Schematic diagram of direct writing (DIW) technique (a), fused deposition modeling (FDM) technique (b), selective laser sintering (SLS) technique (c), stereolithography (SLA) technique (d) and material jetting technique (e)[40]. Reprinted with permission.

    Figure  4.  (a) Digital image displaying the procedure of printing the 3D architectures line-by-line (upper), and isometric view of the holey graphene oxide (hGO) mesh with a 0.8 mm line spacing (bottom)[54]. (b) Schematic illustration of the 3D printing process for Sulfur/carbon black thick cathodes (10 mm grid diameter)[31]. (c) Schematic of synthesis of 3D graphene foams (GFs)[61]. (d) Designed structure of C-MEMS 3D microbattery[62]. Reprinted with permission.

    Figure  5.  (a) Schematic illustration of the 3D printed negative electrode disc (graphite/PLA) elaboration process[50]. (b) Digital photo of the 3D printing process of graphene/PLA filament. (c) Schematic of the coin cell fabrication with graphene/PLA anode. (d) Coulombic efficiency of the 3D printed graphene/PLA anode. (e) Rate capability of the 3D printed graphene/PLA anode[47]. Reprinted with permission.

    Figure  6.  (a) Model of the 3D-printed graphene-based electrodes. The external walls are the current collector (Cu), and the internal walls are graphene (b) Digital image of the chemically modified graphene (CMG)/Cu one-leg component after freeze-drying. (c) SEM images of the interface of reduced chemically modified graphene (rCMG)/Cu. (d) SEM images inside the rCMG filaments[36]. (e) Digital image of a miniaturized version of the 3D-printed LFP/rGO and LTO/rGO electrodes. (f) Digital photo of the 3D-printed LFP/rGO and LTO/rGO electrodes arrays. (g) Charge and discharge curves of the LFP/rGO half-cell at current density of 10 mA g−1. Inset is a schematic of the planar battery. (h) Charging and discharging curves of the full cell[19]. Reprinted with permission.

    Figure  7.  (a) Schematic diagram of the IJP setup. (b-c) Schematic diagram of the 3D printed ATM/GO composite droplets. (d) Formation of ice crystal during 3D printing. (e) ATM/GO composite aerogel after freeze drying. (f) Image of the ATM/GO aerogel after freeze drying. (g) Image of the ATM/GO aerogel after annealing[9]. (h) SEM image of the yarn composed of three LFP fibers. (i) Schematic diagram of the all-fiber Li-ion battery device[69]. (k) Schematic diagram of the 3D-printed full cell[39]. Reprinted with permission.

    Figure  8.  (a) Schematic illustration of 3DP-Air-electrode. (b) Schematic illustration of the reaction region of the Zn-O2 battery. The double green balls represent oxygen molecules[26]. (c) Schematic illustration of the Ni/r-GO framework. (d) Low-magnification FESEM images of the Ni/r-GO electrode. (e) Discharge and charge curves of the Ni/r-GO cathode at a current density of 100 mA g−1. (f) Discharge and charge curves of the Ni/r-GO cathode at various current densities with a capacity limit of 1000 mA h g−1[24]. Reprinted with permission.

    Figure  9.  (a) Independent components of the 3D printed coin cell. (b) Assembled coin cell. (c) 3D printed glasses with a LCD lens and 3D printed batteries integrated. (d) Digital photos showing the sunglasses transmitting and blocking the image of the Duke Chapel with LCD off and on, respectively. (e) Separated components of a 3D printed bangle battery integrated with LED. (f) LED powered by the 3D printed bangle battery[74]. (g) Prototype photo of the printed battery before being integrated into the textile and (h) after being integrated into the biomonitoring belt to provide 22 h autonomy[91]. Reprinted with permission.

    Table  1.   Comparison of different 3D-printing techniques.

    3D printing techniquesInksMacroporosityFraction of active materialsResolu-tion (μm)StrengthsWeaknesses
    Direct ink writing (DIW) Metal, ceramic, or polymer gels with high viscosity, suitable rheological and viscoelastic properties 5–10 μm[41]~
    200 μm[23,30] 300–
    400 μm[42]
    0.06–0.43 (v/v)[41]
    70 wt.%[19]
    1–100 Versatile Easy operation Required post-processing Low resolution
    Fused deposition modeling (FDM) Thermoplastic filaments with active materials ~500 μm[34] 8 wt.%[47] 50–200 Low cost Single material
    Selective laser sintering (SLS) Metal, polymer or ceramic powders 0.0012–0.0071 mm3[43] 5–40 wt.%[45] 80–250 Simple material processing High cost
    Stereolitho-graphy (SLA) Photosensitive liquid resin consisting of active materials, photoinitiators, and prepolymers with good flowability and suitable refractive index ~300 μm[46] 0.08–0.20 (v/v) [41] >10 High resolution and efficiency Good surface quality Limited to photocurable materials Required solvents (resins)
    Inkjet printing (IJP) Low viscosity Newtonian
    liquid (40–100 cP)
    65–70%[51] 70 wt.%[9] 5–200 High flexibility of multi-material capability Lack of self-standing ability, low printing speed
    下载: 导出CSV

    Table  2.   Electrochemical performance over a series of 3D printed carbon-based microbatteries.

    Printed carbon-based component3D-printing
    technique
    Anode/CathodeBattery typeElectrochemical performance
    Si/C-graphite[93]DIW[Si/C-graphite]/LiLi-ion battery484 mA·h g−1 (C/4)
    graphite/PLA[50]FDM[graphite/PLA]/LiLi-ion battery200 mAh·g−1 (cathode) at 18.6 mA·g−1 (C/20)
    graphite/PLA and LFP/carbon black[33]FDM[graphite/PLA]/[LFP/carbon black]Li-ion battery165 mAh·g−1 (anode) at 10 mA·g−1
    rGO-AgNWs-LTO[94]DIWLi/rGO-AgNWs-LTOLi-ion battery121 mAh·g−1 (10 C)
    4.74 mAh·cm−2
    LFP/GO, LTO/GO[19]DIW[LTO/GO]/[LFP/GO]Li-ion battery~160 mAh·g −1 (cathode)
    and ~170 mAh·g −1 (anode) at 10 mA·g−1
    graphene/PLA[48]FDM[graphite/PLA]/LiLi-ion battery500 mAh·g-1 at 40 mA·g-1 (anode)
    PoPD/nanocarbon/LMO[29]FDMPt/[PoPD/nanocarbon/LMO]Li-ion battery69.1 mAh·g−1 at 0.036 mA·cm−2 (cathode)
    LFP/CNTs[34]FDMLi/[LFP/CNTs]Li-ion battery7.5 mAh·cm−2 (cathode)
    69.41 J·cm−2 at
    2.99 mW·cm−2
    LTO/CNTs, LFP/CNTs[39]DIW[LTO/CNTs]/[LFP/CNTs]Li-ion battery~110 mAh·g−1 at 50 mA·g−1
    LiNi0.8Co0.15Al0.05O2/CF, CF[32]DIWCF/[LiNi0.8Co0.15Al0.05O2/CF]Li-ion battery191 mAh·g−1 (0.1 C)
    LTO/Graphene, LMO/MWCNT[74]FDM[LTO/Graphene]/[LMO/MWCNT]Li-ion battery3.91 mAh·cm–3, coulombic
    Sulfur/DIB/GO[42]DIW&FDMSulfur/[Sulfur/DIB/GO]Li-S battery812.8 mAh·g−1 at 50 mA·g−1
    aMWCNT[64]IJPLi/aMWCNTLi-S battery~7 mAh·cm−2 at 11.5 mA·cm−2
    S@SWCNTs[65]IJPLi/[S@SWCNTs]Li-S battery850 mAh·g–1 (C/2), between 700 and
    800 mAh·g–1 for 100 cycles (C/2)
    S/C composite[95]DIWLi/[S/C composite]Li-S battery530 mAh·g−1 at 10 mA·cm−2
    LaB6/C@S[96]DIWLi/[LaB6/C@S]Li-S battery693 mAh·g−1
    S/C[31]DIWLi/[S/C]Li-S battery1009 mAh·g−1
    Li/CNTs, Se[27]DIW[Li/CNTs]/SeLi-Se battery12.99 mAh·cm−2 at 3 mA·cm−2
    Li-plated 3DP-NC[30]DIW[Li-plated 3DP-NC]/LiFePO4Li-metal battery30 mAh·cm–2 at 10 mA·cm–2
    hGO meshes[54]DIWLi/hGOLi-O2 battery13.3 mAh·cm−2 at 0.1 mA·cm−2 (cathode)
    (~4.8 mA·h or ~3879 mAh·g−1 in total capacity)
    Co/N-doped carbon[23]DIWLi/[Co/N-doped carbon flakes]Li-O2 batteryEnergy density of 798 Wh·kg–1 cell
    Ni-rGO[24]DIWLi/[Ni-rGO]Li-CO2 battery14.6 mAh·cm–2 at 0.1 mA·cm–2
    (8991.0 mAh·g–1)
    rGO/Na3V2(PO4)3[12]DIWrGO/Na3V2(PO4)3Na-ion battery1.26 mAh·cm–2 (0.2C) (cathode)
    0.39 mAh·cm–2 (1C) (full cell)
    MoS2/rGO[9]IJP[MoS2/rGO]/NaNa-ion battery429 mAh·g−1 at 100 mA·g−1 (~ C/3.3)
    rGO[28]DIWCP-protected Na/rGONa-O2 battery13484.6 mAh·g−1 at 0.2 A g−1
    Zn/CB/CF, MnO2/GO/CNTs[26]DIW[Zn/CB/CF]/[MnO2/GO/CNTs]Zn-O2 battery670 mAh·g–1 at 5mA·cm–2
    Ag2O-SIS, Ga-CB-SIS[91]DIWGa-CB-SIS/Ag2O-SISAg-Ga battery~19.4 mAh·cm−2
    下载: 导出CSV
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  • 收稿日期:  2022-01-01
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