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    Journals >Journal of Semiconductors >Volume 41 >Issue 9 >Page 091704 > Article
    • Journal of Semiconductors
    • Vol. 41, Issue 9, 091704 (2020)
    Recent progress in organic electrodes for zinc-ion batteries
    Shuaifei Xu, Mingxuan Sun, Qian Wang, and Chengliang Wang
    Author Affiliations
  • School of Optical and Electronic Information, Wuhan National Laboratory for Optoelectronics (WNLO), Huazhong University of Science and Technology, Wuhan 430074, China
    • show less
    DOI: 10.1088/1674-4926/41/9/091704 Cite this Article
    Shuaifei Xu, Mingxuan Sun, Qian Wang, Chengliang Wang. Recent progress in organic electrodes for zinc-ion batteries[J]. Journal of Semiconductors, 2020, 41(9): 091704 Copy Citation Text show less
    The molecular structures of reported quinones as cathodes for ZIBs.
    Fig. 1. The molecular structures of reported quinones as cathodes for ZIBs.
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    (Color online) (a) The voltages and capacities of 1,2-NQ, 9,10-PQ, 1,4-AQ, 9,10-AQ and C4Q in ZIBs. (b) The charge-discharge profiles of C4Q at 0.02 A/g and (c) cycling performance at 0.5 A/g in ZIBs with a Nafion separator. (d) The ESP mapping of C4Q. (e) The optimized structure of the C4Q and Zn3C4Q. Reproduced with permission from Ref. [34]. Copyright © 2018 American Association for the Advancement of Science.
    Fig. 2. (Color online) (a) The voltages and capacities of 1,2-NQ, 9,10-PQ, 1,4-AQ, 9,10-AQ and C4Q in ZIBs. (b) The charge-discharge profiles of C4Q at 0.02 A/g and (c) cycling performance at 0.5 A/g in ZIBs with a Nafion separator. (d) The ESP mapping of C4Q. (e) The optimized structure of the C4Q and Zn3C4Q. Reproduced with permission from Ref. [34]. Copyright © 2018 American Association for the Advancement of Science.
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    (Color online) (a) The charge-discharge profiles of flexible Zn//PTO battery at flat state and 180° bending state at 1 A/g. (b) the cycling performance of flexible Zn//PTO battery at different bending state at 1 A/g. (c) the photos of LEDs and fan powered by the flexible Zn//PTO battery. Repoduced with permission from Ref. [35]. Copyright © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Fig. 3. (Color online) (a) The charge-discharge profiles of flexible Zn//PTO battery at flat state and 180° bending state at 1 A/g. (b) the cycling performance of flexible Zn//PTO battery at different bending state at 1 A/g. (c) the photos of LEDs and fan powered by the flexible Zn//PTO battery. Repoduced with permission from Ref. [35]. Copyright © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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    (Color online) (a) The schematic diagram of the synthesis (top), photo (bottom left), and Zn-storage mechanism (bottom right) of PDA/CNTs. (b) The schematic diagram of the synthesis of PC/graphene. (c) Cycling performance of PDA/CNTs at 0.2 A/g in ZIBs. (d) Rate capability of PC/graphene. (a), (c) Reproduced with permission from Ref. [37]. Copyright © 2019 Royal Society of Chemistry. (b), (d) Reproduced with permission from Ref. [38]. Copyright © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Fig. 4. (Color online) (a) The schematic diagram of the synthesis (top), photo (bottom left), and Zn-storage mechanism (bottom right) of PDA/CNTs. (b) The schematic diagram of the synthesis of PC/graphene. (c) Cycling performance of PDA/CNTs at 0.2 A/g in ZIBs. (d) Rate capability of PC/graphene. (a), (c) Reproduced with permission from Ref. [37]. Copyright © 2019 Royal Society of Chemistry. (b), (d) Reproduced with permission from Ref. [38]. Copyright © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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    (Color online) (a) The charge-discharge curves of p-chloranil at 0.2 C at different cycles. (b) The cycling performance of p-chloranil/CMK-3 at 1 C. (c) The calculated crystal structure of p-chloranil and Zn2+-inserted p-chloranil; (d) SEM images of p-chloranil electrode and (e) p-chloranil/CMK-3 composite electrode at pristine (left), discharged (middle), and charged (right) state. Reproduced with permission from Ref. [51]. Copyright © 2018 American Chemical Society.
    Fig. 5. (Color online) (a) The charge-discharge curves of p-chloranil at 0.2 C at different cycles. (b) The cycling performance of p-chloranil/CMK-3 at 1 C. (c) The calculated crystal structure of p-chloranil and Zn2+-inserted p-chloranil; (d) SEM images of p-chloranil electrode and (e) p-chloranil/CMK-3 composite electrode at pristine (left), discharged (middle), and charged (right) state. Reproduced with permission from Ref. [51]. Copyright © 2018 American Chemical Society.
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    (Color online) (a) The FTIR spectra and (b) XPS spectra of PQ-Δ at pristine, discharged and charged states. (c) The energy storage mechanism of PQ-Δ in 2 M ZnSO4. Reproduced with permission from Ref. [53]. Copyright © 2020 American Chemical Society. (d) CV curves of DTT. Reproduced with permission from Ref. [33]. Copyright © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Fig. 6. (Color online) (a) The FTIR spectra and (b) XPS spectra of PQ-Δ at pristine, discharged and charged states. (c) The energy storage mechanism of PQ-Δ in 2 M ZnSO4. Reproduced with permission from Ref. [53]. Copyright © 2020 American Chemical Society. (d) CV curves of DTT. Reproduced with permission from Ref. [33]. Copyright © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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    The schematic diagram of the redox mechanism of PANI.
    Fig. 7. The schematic diagram of the redox mechanism of PANI.
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    Reported monomers for co-polymerization with aniline to form self-doped PANI.
    Fig. 8. Reported monomers for co-polymerization with aniline to form self-doped PANI.
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    (Color online) (a) The dQ/dV curve of PANI-co-m-ABS (also called as PANI-S) at 30th cycle. (b) The cycling performance of PANI-co-m-ABS and PANI at 1 A/g. (c) The redox pathways of PANI-co-m-ABS in 1 M ZnSO4. Reproduced with permission from Ref. [65]. Copyright © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Fig. 9. (Color online) (a) The dQ/dV curve of PANI-co-m-ABS (also called as PANI-S) at 30th cycle. (b) The cycling performance of PANI-co-m-ABS and PANI at 1 A/g. (c) The redox pathways of PANI-co-m-ABS in 1 M ZnSO4. Reproduced with permission from Ref. [65]. Copyright © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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    (Color online) (a) The schematic diagram of the synthesis process, (b) long-term cycling performance at 10 A/g, and (c) proposed reduction mechanism of PANI-PEDOT:PSS-CNTs composite cathode in 2 M ZnSO4. Reproduced with permission from Ref. [72]. Copyright © 2019 American Chemical Society.
    Fig. 10. (Color online) (a) The schematic diagram of the synthesis process, (b) long-term cycling performance at 10 A/g, and (c) proposed reduction mechanism of PANI-PEDOT:PSS-CNTs composite cathode in 2 M ZnSO4. Reproduced with permission from Ref. [72]. Copyright © 2019 American Chemical Society.
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    (Color online) (a) Ex situ XPS spectra of PANI/CFs for ZIB at different state. (b) The schematic diagram of the ion storage mechanism of PANI/CFs. (c) The proposed redox mechanism of PANI/CFs in 1 M Zn(CF3SO3)2. Reproduced with permission from Ref. [80]. Copyright © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Fig. 11. (Color online) (a) Ex situ XPS spectra of PANI/CFs for ZIB at different state. (b) The schematic diagram of the ion storage mechanism of PANI/CFs. (c) The proposed redox mechanism of PANI/CFs in 1 M Zn(CF3SO3)2. Reproduced with permission from Ref. [80]. Copyright © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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    (Color online) (a) The schematic diagram of the self-healing process of the all-in-one ZIB. (b) The CV curves of the original ZIB and the ZIB after self-healing. (c) The cycling performance of the ZIB after several self-healing. (d) The practical presentation of the self-healing ZIB. Repoduced with permission from Ref. [85]. Copyright © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Fig. 12. (Color online) (a) The schematic diagram of the self-healing process of the all-in-one ZIB. (b) The CV curves of the original ZIB and the ZIB after self-healing. (c) The cycling performance of the ZIB after several self-healing. (d) The practical presentation of the self-healing ZIB. Repoduced with permission from Ref. [85]. Copyright © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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    The molecular structures of reported CPs as cathodes for ZIBs apart from PANI.
    Fig. 13. The molecular structures of reported CPs as cathodes for ZIBs apart from PANI.
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    (Color online) (a) The schematic diagram of the fabricating process of flexible Zn and PPy electrode on PET. (b) The color change of flexible Zn//PPy battery at different voltages. (c) The cycling performance of flexible Zn//PPy battery. Repoduced with permission from Ref. [88]. Copyright © 2018 Royal Society of Chemistry.
    Fig. 14. (Color online) (a) The schematic diagram of the fabricating process of flexible Zn and PPy electrode on PET. (b) The color change of flexible Zn//PPy battery at different voltages. (c) The cycling performance of flexible Zn//PPy battery. Repoduced with permission from Ref. [88]. Copyright © 2018 Royal Society of Chemistry.
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    Active materialElectrode composition (active material/ conductive additive/binder); conductive additive; binder ElectrolytesVoltage range; discharge voltage (V) vs. Zn/Zn2+Capacity (mAh/g), current density (A/g)Capacity retention (cycle number, current density (A/g))Ref.
    Quinone-based cathodes with insertion of Zn2+ ions
    AQ5.6 : 3.4 : 1; SP; PTFE2 M ZnSO4/221.8, 0.844.9% (500, 0.8)[113]
    AQ4.9 : 3.6 : 1.5; SP; PTFE1 M ZnSO4+0.05 M MnSO40.1–1.2; 0.45204.5, 0.284.3% (200, 0.2)[114]
    AQ6 : 3.5 : 0.5; SP; PVDF3 M Zn(CF3SO3)20.25–1.75; 0.51194, 0.02/[34]
    1,2-NQ6 : 3.5 : 0.5; SP; PVDF3 M Zn(CF3SO3)20.25–1.7569, 0.02/[34]
    1,4-NQ6 : 3.5 : 0.5; SP; PVDF3 M Zn(CF3SO3)20.25–1.75150, 0.02/[34]
    9,10-PQ6 : 3.5 : 0.5; SP; PVDF3 M Zn(CF3SO3)20.25–1.75112, 0.02/[34]
    C4Q6 : 3.5 : 0.5; SP; PVDF3 M Zn(CF3SO3)20.25–1.75; 1.0335, 0.05; 172, 187% (1000, 0.5)[34]
    PTO6 : 3 : 1; KB; PTFE2 M ZnSO40.36–1.46; 0.63, 1.0336, 0.04; 162, 570% (100, 3)[35]
    PBQS6 : 3 : 1; conductive carbon; PVDF3 M Zn(CF3SO3)20.2–1.8; 0.95203, 0.1C (0.02 A/g); 126, 5 C86% (50, 0.2 C)[36]
    HqTp-COF/3 M ZnSO40.2–1.6; 1.0276, 0.125; 85, 3.7595% (1000, 0.15)[46]
    PDA/CNTs (38/62)/3.3 M ZnSO40.3–1.4; 0.91126.2, 0.02; 43.2, 596% (500, 0.2)[37]
    PC7 : 2 : 1; AB; PVDF3 M ZnSO40.2–1.9; 0.86204, 0.1 C (0.05 A/g); 51, 10 C62.2% (2000, 2 C)[38]
    PC/graphene (1/2)7 : 2 : 1; AB; PVDF3 M ZnSO40.2–1.9355, 0.1 C; 171, 10 C74.4% (3000, 2 C)[38]
    p-chloranil6 : 3.5 : 0.5; SP; CMC and SBR1 M Zn(CF3SO3)20.8–1.4; 1.1205, 0.2 C34.15% (30, 0.2 C)[51]
    p-chloranil6 : 3.5 : 0.5; CMK-3; CMC and SBR1 M Zn(CF3SO3)20.8–1.4170, 0.2 C; 118, 1 C70.34% (200, 1 C)[51]
    Quinone-based cathodes with insertion of more than Zn2+ ions
    PQ-Δ6 : 3 : 1; AB; PVDF3 M Zn(CF3SO3)20.25–1.6; 0.84225, 0.03; 210, 0.1599.9% (500, 0.15)[53]
    PQ-Δ6 : 3 : 1; KB; PTFE0.5 M Zn(CF3SO3)2-DMF 0.1–1.7; 0.66145, 0.05; 60, 50negligible fading (20000, 1)[54]
    DTT6 : 3 : 1; KB; PTFE2 M ZnSO40.3–1.4210.9, 0.05; 97, 283.8% (23000, 2)[33]
    Conducting polymers : PANI
    PANI/1 M ZnCl2+0.5 M NH4Cl 0.8–1.7; 1.22235.6, 0.31 mA/cm267.5% (100, 0.31 mA/cm2) [58]
    PANI/1 M ZnCl2, pH~4 0.65–1.40; 1.05151.5, 0.75 mA/cm2; 64.625, 12 mA/cm295.5% (30, 0.75 mA/cm2) [59]
    PANI7 : 2 : 1; SWCNT; PVDFPVA-2 M Zn(CF3SO3)20.5–1.5; 0.75, 1.05123, 0.1; 94, 397.1% (1000, 1)[85]
    PANI/PVA-Zn(CF3SO3)20.5–1.5; 0.73, 1.1627.88 μAh/cm2, 0.33 A/cm3; 5.84 μAh/cm2, 4 A/cm356.7% (500, 0.66 A/cm3) [86]
    PANI8 : 1.5 : 0.5; CNT; PVDF0.3 M Zn(TFSI)2- propylene carbonate 0.3–1.6148, 0.5 C; 70, 12 C85% (2000, 1 C)[115]
    PANI/1 M ZnSO4pH=4.6 0.75–1.35108, //[116]
    PANI/2 M ZnCl2+3 M NH4Cl 0.7–1.7203.5, 0.5; 118.7, 16Nearly unchanged (1000, 8)[117]
    Self-doped PANI
    PANI-co-m-ABA/1 M ZnCl2+0.5 M NH4Cl, pH=5 0.8–1.6146.4, 1 mA/cm2~62% (200, 1 mA/cm2) [64]
    PANI-co-m-ABS/1 M ZnSO40.5–1.6184, 0.2; 130, 1084.6% (2000, 10)[65]
    PANI-co-5-ASA/0.50 M ZnCl2 +1.5 M NH4Cl, pH =4.8 0.75–1.65; 1.13140.6, 1 mA/cm2; 124.1, 5 mA/cm2/[66]
    PANI-co-o-aminophenol/2.5 M ZnCl2+3 M NH4Cl, pH=4.7 /103, 0.5 mA/cm2; 64.7, 5 mA/cm2/[67]
    PANI-co-m-aminophenol/2 M ZnCl2+3 M NH4Cl, pH=4.7 0.75–1.45; 1.05137.5, 0.5 mA/cm2; 94.5, 5 mA/cm2/[68]
    PANMTh/2 M ZnCl2+3 M NH4Cl 0.7–1.5146.3, 1 mA/cm299.4% (150, 2 mA/cm2) [70]
    PANAB/2 M ZnCl2+3 M NH4Cl, pH=4.7 0.7–1.5; 1.08134, 0.12; 127.8, 161.4% (181, 0.2)[71]
    PANAC(PANMTh)/2 M ZnCl2+3 M NH4Cl, pH=5 0.7–1.5; 1.15306.3, 0.28; 82.6, 3.9273% (1100, 0.532)[76]
    PANAC/PVA-ZnCl2-NH4Cl 0.7–1.5241.4, 0.22; 81.2, 1.3368% (1000, 0.532)[76]
    PANFc/2.5 ZnCl2+3 M NH4Cl, pH=4.4 0.7–1.4; 1.0124, 0.035/[118]
    Mixing polyaniline with materials of proton-supply ability
    CNTs-PANI-PEDOT:PSS/2 M ZnSO40.5–1.6; 0.72, 1.14238, 0.2; 145, 1077.9% (1500, 10)[72]
    CNTs-PANI-PEDOT:PSS/PAM-ZnSO40.5–1.6; 0.72, 1.13208, 0.2; 124, 5/[72]
    PANI/GO/1.5 M Zn(ClO4)2+0.5 M NH4ClO40.7–1.55183, 0.2 C; 147.8, 1 C89.4% (100, 0.2 C)[73]
    CC-PANI-FeCN/1 M ZnSO40.5–1.6162, 1; 125, 571% (1000, 5)[75]
    Compositing PANI with conductive materials
    PANI-GO/CNT/2 M Zn(CF3SO3)2 with 5 vol% diethyl ether 0.5–1.6233, 0.1; 100, 578.7% (2500, 3)[74]
    PANI/porous carbon rod/1 M ZnCl2+0.5 M NH4Cl+3.7×10–4 M HgCl21.12/~90% (100, /)[77]
    PANI/graphite/1 M ZnCl2+0.5 M NH4Cl, pH=4 0.7–1.7142.4, 0.6 mA/cm257.4% (200, 0.6 mA/cm2) [78]
    PANI/Ni foam/1 M ZnSO4 + 0.3 M (NH4)2SO40.7–1.6183.28, 2.5 mA/cm2/[79]
    PANI/carbon felts/1 M Zn(CF3SO3)20.5–1.5; 0.65, 0.85, 1.07200, 0.05; 95, 592% (3000, 5)[80]
    PANI/carbon felts/PVA-Zn(CF3SO3)20.5–1.5109, 5/[80]
    PANI/OCF/PVA-1 M ZnCl2+0.5 M NH4Cl 0.7–1.5104.67, 0.1; 83.8, 295.4% (200, 0.1)[81]
    PANI/CNT/PAAM-1 M ZnSO40.3–1.6; 1.1144, 0.2; 90, 191.1% (150, 0.5)[82]
    PANI-SWCNT/PVA-Zn(CF3SO3)20.5–1.5212, 0.1; 68, 290.7% (1000, 1)[83]
    PANI/rGO/CNF/PVA-Zn(CF3SO3)20.5–1.5175.5, 0.1; 79.5, 294.6% (500, 1)[84]
    PANI/graphite/AB (80 : 18 : 2) /2 M Zn(ClO4)2 +1 M NH4ClO4 + 3.7×10–4 M Triton-X100 pH=3 /125.4, 0.0594.1% (100, 0.05)[119]
    Other conducting polymers
    PPy/2 M ZnAc2 in ChAc + 70% H2O 0–1.5; 0.55160, 0.543.75% (50, 0.5)[92]
    PPy/PVA-KCl-ZnAc20–1.2123, 1.938% (200, 8.8)[88]
    PPy/aerogel/Cellulose-2 M ZnCl2 + 3 M NH4Cl 0.6–1.6151.1, 0.5; 87.6, 1676.7% (1000, 8)[90]
    PTh/0.1 M Zn(ClO4)2 + 1 M LiClO4- propylene carbonate 0.2–1.7; 1.2//[94]
    PEDOT8.5 : 1 : 0.5; SP; PVDF[C2mim][dca] + 3 wt% water + Zn(dca)20.5–1.628.5, 0.0075; 25.5, 0.07566.7% (100, /)[95]
    PEDOT/65% p(DADMATFSI)- 35% Zn(dca)2/[emim][dca]) + water + Al2O30.5–1.651, 0.01 mA/cm2; 31, 0.02 mA/cm2/[96]
    PPP8 : 1.2 : 0.8; amorphous carbon + graphite; PVDF0.2 M Zn(TfO)2/[EMIm]TfO-PS composite 0.3–1.848, 0.2 C90% (300, 1 C)[99]
    PIn/1 M ZnSO40.75–1.4590, 20 μA/cm2/[97]
    PIn6 : 3 : 1; CB; PTFEZnCl21.0–2.081, 200 A/m2; 60, 1000 A/m298% (200, 500 A/m2) [98]
    Poly(5-cyanoindole)/1 M ZnCl21.0–2.2107, 0.2 C; 61, 10 C96% (360, 0.2 C)[100]
    PAc-exTTF5 : 5 : /; MWCNT; /1 M Zn(BF4)20.6–1.7; 1.1100, 10 C; 47, 120 C81% (10000, 10 C)[102]
    Other redox compounds
    NTCDA/2 M ZnSO40.37, 0.58//[103]
    NTCDI/2 M ZnSO40.45240, 0.1; 140, 273.7% (2000, 1)[103]
    HATN6 : 3.5 : 0.5; SP; PVDF2 M ZnSO40.3–1.1370, 0.1; 123, 2093.3% (5000, 5)[106]
    RF6 : 3.5 : 0.5; CB; PVDF3 M Zn(CF3SO3)20.2–1.4; 0.6113.5, 0.03; 95.8, 592.7% (5000, 5)[107]
    ALX6 : 3.5 : 0.5; CB; PVDF3 M Zn(CF3SO3)20.2–1.4; 0.56230.5, 0.0562.13% (50, 0.05)[107]
    LMZ6 : 3.5 : 0.5; CB; PVDF3 M Zn(CF3SO3)20.2–1.4; 0.47252.8, 0.0554.53% (50, 0.05)[107]
    BDB6 : 3.5 : 0.5; SP; CMC/SBR (2/1)19 M LiTFSI+1 M Zn(CF3SO3)20.6–1.8; 0.89, 1.27112, 3 C82% (500, 3C)[108]
    Poly(1,5-NAPD)/AC/2 M ZnSO40.1–1.8315, 0.191; 145, 14.591% (10000, 10)[87]
    PTVE5 : 4 : 1; SP; PVDF1 M ZnSO41.30–1.95; 1.7058, 1021.9% (1000, 1 A/g)[110]
    PTVE5 : 4 : 1; SP; PVDF1 M Zn(ClO4)21.30–1.95; 1.4450, 10/[110]
    PTVE5 : 4 : 1; SP; PVDF1 M Zn(CF3SO3)21.30–1.95; 1.5352, 1077.0% (1000, 1 A/g)[110]
    PTVE/glassy carbon/0.1 M ZnCl2+0.1 M NH4Cl 1.4–2.0; 1.73131, 60 C (~8 A/g)65% (500, 60 C)[109]
    Table 1. The performance of reported organic electrode materials for ZIBs. The abbreviations: Super P (SP), polytetrafluoroethylene (PTFE), poly(vinylidene fluoride) (PVDF), acetylene black (AB), carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), Ketjen black (KB), multi-walled carbon nanotubes (MWCNTs), single-walled carbon nanotubes (SWCNTs) and carbon black (CB).
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    Shuaifei Xu, Mingxuan Sun, Qian Wang, Chengliang Wang. Recent progress in organic electrodes for zinc-ion batteries[J]. Journal of Semiconductors, 2020, 41(9): 091704
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