Mesoporous Graphene Hosts for Dendrite-Free Lithium Metal Anode in Working Rechargeable Batteries

Abstract

Lithium (Li) metal anode has received extensive attentions due to its ultrahigh theoretical capacity and the most negative electrode potential. However, dendrite growth severely impedes the practical applications of the Li metal anode in rechargeable batteries. In this contribution, a mesoporous graphene with a high specific surface area was synthesized to host the Li metal anode. The mesoporous graphene host (MGH) has a high specific surface area (2090 m²/g), which affords free space and an interconnected conductive pathway for Li plating and stripping, thus alleviating the volume variation and reducing the generation of dead Li during repeated cycles. More importantly, the high specific surface area of MGH efficiently reduces the local current density of the electrode, which favors a uniform Li nucleation and plating behavior, rendering a dendrite-free deposition morphology at a low overpotential. These factors synergistically boost the Li utilization (90.1% vs. 70.1% for Cu foil) and life span (150 cycles vs. 100 cycles for Cu foil) with a low polarization of MGH electrode at an ultrahigh current of 15.0 mA/cm². The as-prepared MGH can provide fresh insights into the electrode design of the Li metal anode operating at high rates.

Keywords

Lithium metal anode / Mesoporous graphene hosts / Dendrite-free plating behavior / Working rechargeable batteries / Composite electrode

References

[1] Huang Q, Turcheniuk K, Ren XL, et al. Cycle stability of conversion-type iron fluoride lithium battery cathode at elevated temperatures in polymer electrolyte composites. Nat Mater, 2019, 18(12): 1343-1349.

[2] Jiang LL, Cheng XB, Peng HJ, et al. Carbon materials for traffic power battery. eTransportation, 2019, 2: 100033.

[3] Liang YR, Zhao CZ, Yuan H, et al. A review of rechargeable batteries for portable electronic devices. InfoMat, 2019, 1(1): 6-32.

[4] Cheng XB, Zhang R, Zhao CZ, et al. Toward safe lithium metal anode in rechargeable batteries: a review. Chem Rev, 2017, 117(15): 10403-10473.

[5] Shen X, Liu H, Cheng XB, et al. Beyond lithium ion batteries: Higher energy density battery systems based on lithium metal anodes. Energy Storage Mater, 2018, 12: 161-175.

[6] Yang Y, Davies DM, Yin YJ, et al. High-efficiency lithium-metal anode enabled by liquefied gas electrolytes. Joule, 2019, 3(8): 1986-2000.

[7] Song YH, Wu KJ, Zhang TW, et al. A nacre-inspired separator coating for impact-tolerant lithium batteries. Adv Mater, 2019, 31(51): 1905711.

[8] Xu HH, Wang SF, Manthiram A. Hybrid lithium-sulfur batteries with an advanced gel cathode and stabilized lithium-metal anode. Adv Energy Mater, 2018, 8(23): 1800813.

[9] Wang P, Qu WJ, Song WL, et al. Electro–chemo–mechanical issues at the interfaces in solid-state lithium metal batteries. Adv Funct Mater, 2019, 29(27): 1900950.

[10] Zhang R, Shen X, Cheng XB, et al. The dendrite growth in 3D structured lithium metal anodes: electron or ion transfer limitation?. Energy Storage Mater, 2019, 23: 556-565.

[11] Cheng XB, Zhao CZ, Yao YX, et al. Recent advances in energy chemistry between solid-state electrolyte and safe lithium-metal anodes. Chem, 2019, 5(1): 74-96.

[12] Liu T, Feng XL, Jin X, et al. Protecting the lithium metal anode for a safe flexible lithium-air battery in ambient air. Angew Chem Int Ed, 2019, 131(50): 18408-18413.

[13] Wang SH, Yue JP, Dong W, et al. Tuning wettability of molten lithium via a chemical strategy for lithium metal anodes. Nat Commun, 2019, 10: 4930.

[14] Wang CZ, Wang AX, Ren LX, et al. Controlling Li ion flux through materials innovation for dendrite-free lithium metal anodes. Adv Funct Mater, 2019, 29(49): 1905940.

[15] Liu H, Cheng XB, Jin ZH, et al. Recent advances in understanding dendrite growth on alkali metal anodes. Energy Chem, 2019, 1(1): 100003.

[16] Zhang Y, Wang CW, Pastel G, et al. 3D wettable framework for dendrite-free alkali metal anodes. Adv Energy Mater, 2018, 8(18): 1800635.

[17] Zhao CZ, Duan H, Huang JQ, et al. Designing solid-state interfaces on lithium-metal anodes: a review. Sci China Chem, 2019, 62(10): 1286-1299.

[18] Xu R, Cheng XB, Yan C, et al. Artificial interphases for highly stable lithium metal anode. Matter, 2019, 1(2): 317-344.

[19] Yan C, Li HR, Chen X, et al. Regulating the inner Helmholtz plane for stable solid electrolyte interphase on lithium metal anodes. J Am Chem Soc, 2019, 141(23): 9422-9429.

[20] Xu R, Xiao Y, Zhang R, et al. Dual-phase single-ion pathway interfaces for robust lithium metal in working batteries. Adv Mater, 2019, 31(19): 1970135.

[21] Cao X, Xu YB, Zhang LC, et al. Nonflammable electrolytes for lithium ion batteries enabled by ultraconformal passivation interphases. ACS Energy Lett, 2019, 4(10): 2529-2534.

[22] Shangguan XH, Xu GJ, Cui ZL, et al. Additive-assisted novel dual-salt electrolyte addresses wide temperature operation of lithium–metal batteries. Small, 2019, 15(16): 1970082.

[23] Zhang WD, Zhang SQ, Fan L, et al. Tuning the LUMO energy of an organic interphase to stabilize lithium metal batteries. ACS Energy Lett, 2019, 4(3): 644-650.

[24] Yuan YX, Wu F, Chen GH, et al. Porous LiF layer fabricated by a facile chemical method toward dendrite-free lithium metal anode. J Energy Chem, 2019, 37: 197-203.

[25] Gao ZG, Zhang SJ, Huang ZG, et al. Protection of Li metal anode by surface-coating of PVDF thin film to enhance the cycling performance of Li batteries. Chin Chem Lett, 2019, 30(2): 525-528.

[26] Cheng XB, Yan C, Chen X, et al. Implantable solid electrolyte interphase in lithium-metal batteries. Chem, 2017, 2(2): 258-270.

[27] Kong L, Jin Q, Zhang XT, et al. Towards full demonstration of high areal loading sulfur cathode in lithium–sulfur batteries. J Energy Chem, 2019, 39: 17-22.

[28] Zhao CZ, Chen PY, Zhang R, et al. An ion redistributor for dendrite-free lithium metal anodes. Sci Adv, 2018, 4(11): eaat3446.

[29] Wu JY, Rao ZX, Cheng ZX, et al. Ultrathin, flexible polymer electrolyte for cost-effective fabrication of all-solid-state lithium metal batteries. Adv Energy Mater, 2019, 9(46): 1902767.

[30] Lou JT, Wang GG, Xia Y, et al. Achieving efficient and stable interface between metallic lithium and garnet-type solid electrolyte through a thin indium tin oxide interlayer. J Power Sources, 2020, 448: 227440.

[31] Yan M, Liang JY, Zuo TT, et al. Stabilizing polymer–lithium interface in a rechargeable solid battery. Adv Funct Mater, 2020, 30(6): 1908047.

[32] Wang G, Chen C, Chen YH, et al. Self-stabilized and strongly adhesive supramolecular polymer protective layer enables ultrahigh-rate and large-capacity lithium-metal anode. Angew Chem Int Ed, 2020, 59(5): 2055-2060.

[33] Huang SB, Zhang WF, Ming H, et al. Chemical energy release driven lithiophilic layer on 1 m² commercial brass mesh toward highly stable lithium metal batteries. Nano Lett, 2019, 19(3): 1832-1837.

[34] Zhao H, Lei DN, He YB, et al. Compact 3D copper with uniform porous structure derived by electrochemical dealloying as dendrite-free lithium metal anode current collector. Adv Energy Mater, 2018, 8(19): 1800266.

[35] Li T, Shi P, Zhang R, et al. Dendrite-free sandwiched ultrathin lithium metal anode with even lithium plating and stripping behavior. Nano Res, 2019, 12(9): 2224-2229.

[36] Shen X, Cheng XB, Shi P, et al. Lithium-matrix composite anode protected by a solid electrolyte layer for stable lithium metal batteries. J Energy Chem, 2019, 37: 29-34.

[37] Pande V, Viswanathan V. Computational screening of current collectors for enabling anode-free lithium metal batteries. ACS Energy Lett, 2019, 4(12): 2952-2959.

[38] Chen X, Chen XR, Hou TZ, et al. Lithiophilicity chemistry of heteroatom-doped carbon to guide uniform lithium nucleation in lithium metal anodes. Sci Adv, 2019, 5(2): eaau7728.

[39] Cao ZJ, Zhu Q, Wang S, et al. Perpendicular MXene arrays with periodic interspaces toward dendrite-free lithium metal anodes with high-rate capabilities. Adv Funct Mater, 2020, 30(5): 1908075.

[40] Zhang R, Cheng XB, Zhao CZ, et al. Conductive nanostructured scaffolds render low local current density to inhibit lithium dendrite growth. Adv Mater, 2016, 28(11): 2155-2162.

[41] Zhai PB, Wang TS, Yang WW, et al. Uniform lithium deposition assisted by single-atom doping toward high-performance lithium metal anodes. Adv Energy Mater, 2019, 9(18): 1804019.

[42] Zhang XQ, Zhao CZ, Huang JQ, et al. Recent advances in energy chemical engineering of next-generation lithium batteries. Engineering, 2018, 4(6): 831-847.

[43] Tang C, Wang HS, Wang HF, et al. Spatially confined hybridization of nanometer-sized NiFe hydroxides into nitrogen-doped graphene frameworks leading to superior oxygen evolution reactivity. Adv Mater, 2015, 27(30): 4516-4522.

[44] Zhang R, Chen XR, Chen X, et al. Lithiophilic sites in doped graphene guide uniform lithium nucleation for dendrite-free lithium metal anodes. Angew Chem Int Ed, 2017, 56(27): 7764-7768.

[45] Fan YC, Wang TS, Legut D, et al. Theoretical investigation of lithium ions’ nucleation performance on metal-doped Cu surfaces. J Energy Chem, 2019, 39: 160-169.

[46] Wang AX, Zhang XY, Yang YW, et al. Horizontal centripetal plating in the patterned voids of Li/graphene composites for stable lithium-metal anodes. Chem, 2018, 4(9): 2192-2200.

[47] Zhang D, Wang S, Li B, et al. Horizontal growth of lithium on parallelly aligned MXene layers towards dendrite-free metallic lithium anodes. Adv Mater, 2019, 31(33): 1901820.

[48] Shi P, Li T, Zhang R, et al. Lithiophilic LiC₆ layers on carbon hosts enabling stable Li metal anode in working batteries. Adv Mater, 2019, 31(8): 1807131.