微量碲基成核位点用于稳定水系锌离子电池负极的研究

目前，由于锂资源的稀缺与锂离子电池使用的有机系电解液高度易燃的特性，更安全的电化学储能体系亟需得到开发。水系锌离子电池以锌金属负极较高的体积比容量、Zn²⁺较低的氧化还原电势与水系电解质绿色安全的特性引起了研究人员的高度关注。然而，锌金属负极在循环过程中存 在枝晶生长、锌金属负极腐蚀、电化学析氢反应和阻碍 Zn²⁺传导的副产物形成等问题，严重降低锌金属负极的循环寿命，更是水系锌离子电池实用化进程中的巨大挑战。 构建亲锌性的成核位点是抑制锌枝晶生长的重要方法。本论文通过微量 TeO₂ 电解液添加剂和较为简便的水溶液置换法设计碲基成核位点，其中前者对应微量的纳米级 Te 成核位点，后者对应含量更多、尺寸更大的 Te 颗粒成核位点。研究发现使用含 1 mM TeO₂ 添加剂的 1 M ZnSO₄ 电解液在锌金属负极表面构建微量 Te 纳米颗粒的方法更有利于稳定锌金属负极。本论文证明了通过 1 mM TeO₂ 添加剂在锌金属负极表面构建的 Te 纳米颗粒（< 100 nm）能够显著降低锌沉积的成核过电势，改善锌的沉积-剥离动力学特征，明显抑制枝晶生长，使锌金属负极循环后形貌均匀性显著提高，从而在 10 mA cm^-2 电流密度与 2 mAh cm^-2 的容量条件下达到 400 h 的良好循环寿命。TeO2 添加剂的使用同时提高了锌金属负极的抗腐蚀性能，减少阻碍 Zn²⁺传导的副产物生成，且使用含 1 mM TeO₂ 添加剂的电解液的 Zn|MnO₂ 全电池在 1 A g^-1 的电流下进行 300 次循环后可达到 79.84%的容量保持率。另外，本论文通过密度泛函理论（DFT）计算和锌沉积动力学的表征研究了 Te 成核位点稳定锌金属负极的机理。本论文从微量无机添加剂的角度，为提升锌金属负极循环稳定性的研究提供了一种可行的方法。 

[1] BROCKWAY P E, OWEN A, BRAND-CORREA L I, et al. Estimation of global final-stage energy-return-on-investment for fossil fuels with comparison to renewable energy sources[J]. Nature Energy, 2019, 4 (7): 612-621.
[2] SCHUBERT C. Renewable energy: making fuels for the future[J]. Nature, 2011, 474 (7352): 531-533.
[3] LI X, YANG Z, FU Y, et al. Germanium anode with excellent lithium storage performance in a germanium/lithium-cobalt oxide lithium-ion battery[J]. ACS Nano, 2015, 9 (2): 1858-1867.
[4] DENHOLM P, MARGOLIS R M. Evaluating the limits of solar photovoltaics (PV) in electric power systems utilizing energy storage and other enabling technologies[J]. Energy Policy, 2007, 35 (9): 4424-4433.
[5] 何姣.我国电池储能电站发展的现状、问题及建议[J]. 新能源科技, 2021, No.12 (06): 30-33.
[6] LEE S H, KIM Y H, DESHPANDE R, et al. Reversible lithium‐ion insertion in molybdenum oxide nanoparticles[J]. Advanced Materials, 2008, 20 (19): 3627-3632.
[7] LI M, LU J, CHEN Z, et al. 30 Years of Lithium-Ion Batteries[J]. Advanced Materials, 2018: 1800561.
[8] LARCHER D, TARASCON J M. Towards greener and more sustainable batteries for electrical energy storage[J]. Nature Chemistry, 2015, 7 (1): 19-29.
[9] QIU F, REN S, ZHANG X, et al. A high efficiency electrolyte enables robust inorganic–organic solid electrolyte interfaces for fast Li metal anode[J]. Science Bulletin, 2021, 66 (9): 897-903.
[10] KWON B, LEE J, KIM H, et al. Janus behaviour of LiFSI-and LiPF6-based electrolytes for Li metal batteries: chemical corrosion versus galvanic corrosion[J]. Journal of Materials Chemistry A, 2021, 9 (44): 24993-25003.
[11] WANG Q, PING P, ZHAO X, et al. Thermal runaway caused fire and explosion of lithium ion battery[J]. Journal of Power Sources, 2012, 208: 210-224.
[12] MURMANN P, MÖNNIGHOFF X, ASPERN N V et al. Influence of the Fluorination Degree of Organophosphates on Flammability and Electrochemical Performance in Lithium Ion Batteries: Studies on Fluorinated Compounds Deriving from Triethyl Phosphate[J]. Journal of the Electrochemical Society, 2016, 163(5): A751-A757.
[13] WINTER M, BRODD R J. What are batteries, fuel cells, and supercapacitors?[J]. Chemical Reviews, 2004, 104 (10): 4245-4270.
[14] SELVAKUMARAN D, PAN A, LIANG S, et al. A review on recent developments and challenges of cathode materials for rechargeable aqueous Zn-ion batteries[J]. Journal of Materials Chemistry A, 2019, 7 (31): 18209-18236.
[15]
[15] SHI Y, CHEN Y, SHI L, et al. An Overview and Future Perspectives of Rechargeable Zinc Batteries[J]. Small, 2020, 16 (23): 2000730.
[16] SONG M, TAN H, CHAO D, et al. Recent Advances in Zn-Ion Batteries[J].Advanced Functional Materials, 2018, 28 (41): 1802564.
[17] ELIA G A, KRAVCHYK K V, KOVALENKO M V, et al. An overview and prospective on Al and Al-ion battery technologies[J]. Journal of Power Sources, 2021, 481: 228870.
[18] SHTERENBERG I, SALAMA M, GOFER Y, et al. The challenge of developing rechargeable magnesium batteries[J]. Mrs Bulletin, 2014, 39 (5): 453-460.
[19] YOO H D, SHTERENBERG I, GOFER Y, et al. Mg rechargeable batteries: an on-going challenge[J]. Energy & Environmental Science, 2013, 6 (8): 2265-2279.
[20] WIPPERMANN K, SCHULTZE J, KESSEL R, et al. The inhibition of zinc corrosion by bisaminotriazole and other triazole derivatives[J]. Corrosion Science, 1991, 32 (2): 205-230.
[21] LI H F, MA L T, HAN C P, et al. Advanced rechargeable zinc-based batteries: Recent progress and future perspectives[J]. Nano Energy, 2019, 62: 550-587.
[22] YAMAMOTO T, SHOJI T. Rechargeable Zn|ZnSO4|MnO2-type cells[J]. Inorganica Chimica Acta, 1986, 117 (2): L27-L28.
[23] ZHAO Q, HUANG W, LUO Z, et al. High-capacity aqueous zinc batteries using sustainable quinone electrodes[J]. Science Advances, 2018, 4 (3): eaao1761.
[24] GRGUR B N, GVOZDENOVIĆ M M, STEVANOVIĆ J, et al. Polypyrrole as possible electrode materials for the aqueous-based rechargeable zinc batteries[J]. Electrochimica Acta, 2008, 53 (14): 4627-4632.
[25] TIE Z, LIU L, DENG S, et al. Proton Insertion Chemistry of a Zinc-Organic Battery[J]. Angewandte Chemie, 2020, 132 (12): 4950-4954.
[26] SUN W, WANG F, HOU S, et al. Zn|MnO2 Battery Chemistry With H+ and Zn2+ Coinsertion[J]. Journal of the American Chemical Society, 2017, 139 (29): 9775-9778.
[27] MCKUBRE M, MACDONALD D. The dissolution and passivation of zinc in concentrated aqueous hydroxide[J]. Journal of the Electrochemical Society, 1981, 128 (3): 524.
[28] EIN-ELI Y, AUINAT M, STAROSVETSKY D. Electrochemical and surface studies of zinc in alkaline solutions containing organic corrosion inhibitors[J]. Journal of Power Sources, 2003, 114 (2): 330-337.
[29] YANG Q, LIANG G, GUO Y, et al. Do zinc dendrites exist in neutral zinc batteries: a developed electrohealing strategy to in situ rescue in‐service batteries[J]. Advanced Materials, 2019, 31 (43): 1903778.
[30] SHIN J, LEE J, PARK Y, et al. Aqueous zinc ion batteries: focus on zinc metal anodes[J]. Chemical Science, 2020, 11 (8): 2028-2044.
[31] ZENG X, HAO J, WANG Z, et al. Recent progress and perspectives on aqueous Zn-based rechargeable batteries with mild aqueous electrolytes[J]. Energy Storage Materials, 2019, 20: 410-437.
[32] YANG H S, PARK J H, RA H W, et al. Critical rate of electrolyte circulation for preventing zinc dendrite formation in a zinc–bromine redox flow battery[J]. Journal of Power Sources, 2016, 325: 446-452.
[33] ZHOU M, GUO S, LI J, et al. Surface-preferred crystal plane for a stable and reversible zinc anode[J]. Advanced Materials, 2021, 33 (21): 2100187.
[34] CHOPARD B, HERRMANN H, VICSEK T. Structure and growth mechanism of mineral dendrites[J]. Nature, 1991, 353 (6343): 409-412.
[35] ZHAO K, WANG C, YU Y, et al. Ultrathin surface coating enables stabilized zinc metal anode[J]. Advanced Materials Interfaces, 2018, 5 (16): 1800848.
[36] PARKER J F, KO J S, ROLISON D R, et al. Translating materials-level performance into device-relevant metrics for zinc-based batteries[J]. Joule, 2018, 2 (12): 2519-2527.
[37] LIANG P, YI J, LIU X, et al. Highly reversible Zn anode enabled by controllable formation of nucleation sites for Zn-based batteries[J]. Advanced Functional Materials, 2020, 30 (13): 1908528.
[38] JIA H, WANG Z, TAWIAH B, et al. Recent advances in zinc anodes for high-performance aqueous Zn-ion batteries[J]. Nano Energy, 2020, 70: 104523.
[39] KANG L, CUI M, JIANG F, et al. Nanoporous CaCO3 coatings enabled uniform Zn stripping/plating for long-life zinc rechargeable aqueous batteries[J]. Advanced Energy Materials, 2018, 8 (25): 1801090.
[40] HAO J, LI B, LI X, et al. An In-Depth Study of Zn Metal Surface Chemistry for Advanced Aqueous Zn-Ion Batteries[J]. Advanced Materials, 2020, 32 (34): e2003021.
[41] GUO W, CONG Z, GUO Z, et al. Dendrite-free Zn anode with dual channel 3D porous frameworks for rechargeable Zn batteries[J]. Energy Storage Materials, 2020, 30: 104-112.HUANG Y, CHANG Z, LIU W, et al. Layer-by-layer zinc metal anodes to achieve long-life zinc-ion batteries[J]. Chemical Engineering Journal, 2022, 431: 133902.
[43] HUANG H, YUN J, FENG H, et al. Towards high-performance zinc anode for zinc ion hybrid capacitor: Concurrently tailoring hydrodynamic stability, zinc deposition and solvation structure via electrolyte additive[J]. Energy Storage Materials, 2023, 55: 857-866.
[44] LIU Z, REN J, WANG F, et al. Tuning Surface Energy of Zn Anodes via Sn Heteroatom Doping Enabled by a Codeposition for Ultralong Life Span Dendrite-Free Aqueous Zn-Ion Batteries[J]. ACS Applied Materials & Interfaces, 2021, 13(23): 27085-27095.
[45] ZHANG C, HOLOUBEK J, WU X, et al. A ZnCl2 water-in-salt electrolyte for a reversible Zn metal anode[J]. Chemical Communications, 2018, 54(100): 14097-14099.
[46] HE H, TONG H, SONG X, et al. Highly stable Zn metal anodes enabled by atomic layer deposited Al2O3 coating for aqueous zinc-ion batteries[J]. Journal of Materials Chemistry A, 2020, 8 (16): 7836-7846.
[47] SO S, AHN Y N, KO J, et al. Uniform and oriented zinc deposition induced by artificial Nb2O5 Layer for highly reversible Zn anode in aqueous zinc ion batteries[J]. Energy Storage Materials, 2022, 52: 40-51.
[48] YANG X, LI C, SUN Z, et al. Interfacial Manipulation via In Situ Grown ZnSe Cultivator toward Highly Reversible Zn Metal Anodes[J]. Advanced Materials, 2021, 33 (52): 2105951.
[49] HUANG C, ZHAO X, HAO Y, et al. Self-Healing SeO2 Additives Enable Zinc Metal Reversibility in Aqueous ZnSO4 Electrolytes[J]. Advanced Functional Materials, 2022, 32 (18): 2112091.
[50] BIE Z, YANG Q, CAI X, et al. One‐Step Construction of a Polyporous and Zincophilic Interface for Stable Zinc Metal Anodes[J]. Advanced Energy Materials, 2022, 12 (44): 2202683.
[51] HAN W, XIONG L, WANG M, et al. Interface engineering via in-situ electrochemical induced ZnSe for a stabilized zinc metal anode[J]. Chemical Engineering Journal, 2022, 442: 136247.
[52] WANG R, XIN S, CHAO D, et al. Fast and Regulated Zinc Deposition in a Semiconductor Substrate toward High-Performance Aqueous Rechargeable Batteries[J]. Advanced Functional Materials, 2022, 32 (51): 2207751.
[53] HIEU L T, SO S, KIM I T, et al. Zn anode with flexible β-PVDF coating for aqueous Zn-ion batteries with long cycle life[J]. Chemical Engineering Journal, 2021, 411: 128584.
[54] ZHAO Z, ZHAO J, HU Z, et al. Long-life and deeply rechargeable aqueous Zn anodes enabled by a multifunctional brightener-inspired interphase[J]. Energy & Environmental Science, 2019, 12 (6): 1938-1949.
[55] CAI Z, OU Y, WANG J, et al. Chemically resistant Cu-Zn|Zn composite anode for long cycling aqueous batteries[J]. Energy Storage Materials, 2020, 27: 205-211.
[56] WANG S-B, RAN Q, YAO R-Q, et al. Lamella-nanostructured eutectic zinc-aluminum alloys as reversible and dendrite-free anodes for aqueous rechargeable batteries[J]. Nature Communications, 2020, 11 (1): 1634.
[57] ZHAO Q, LIU W, CHEN Y, et al. Ultra-stable Zn metal batteries with dendrite-free Cu-Sn alloy induced high-quality composite Zn mesh[J]. Chemical Engineering Journal, 2022, 450: 137979.
[58] OUYANG K, MA D, ZHAO N, et al. A New Insight into Ultrastable Zn Metal Batteries Enabled by In Situ Built Multifunctional Metallic Interphase[J]. Advanced Functional Materials, 2021, 32 (7): 2109749.
[59] WAN F, ZHANG L, DAI X, et al. Aqueous rechargeable zinc/sodium vanadate batteries with enhanced performance from simultaneous insertion of dual carriers[J]. Nature Communications, 2018, 9 (1): 1656.
[60] LUAN J, YUAN H, WANG H, et al. Nanofluid Electrolyte with Fumed Al2O3 Additive Strengthening Zincophilic and Stable Surface of Zinc Anode toward Flexible Zinc–Nickel Batteries[J]. Advanced Functional Materials, 2022, 33 (7): 2210807.
[61] ZHANG W, DAI Y, CHEN R, et al. Highly Reversible Zinc Metal Anode in a Dilute Aqueous Electrolyte Enabled by a pH Buffer Additive[J]. Angewandte Chemie International Edition, 2023, 62 (5): e202212695.
[62] FENG X, LI P, YIN J, et al. Enabling Highly Reversible Zn Anode by Multifunctional Synergistic Effects of Hybrid Solute Additives[J]. ACS Energy Letters, 2023, 8 (2): 1192-1200.
[63] DING F, XU W, GRAFF G L, et al. Dendrite-free lithium deposition via self-healing electrostatic shield mechanism[J]. Journal of the American Chemical Society, 2013, 135 (11): 4450-4456.
[64] XU W, ZHAO K, HUO W, et al. Diethyl ether as self-healing electrolyte additive enabled long-life rechargeable aqueous zinc ion batteries[J]. Nano Energy, 2019, 62: 275-281.
[65] BAYAGUUD A, LUO X, FU Y, et al. Cationic Surfactant-Type Electrolyte Additive Enables Three-Dimensional Dendrite-Free Zinc Anode for Stable Zinc-Ion Batteries[J]. ACS Energy Letters, 2020, 5 (9): 3012-3020.
[66] SHEN Z, MAO J, YU G, et al. Electrocrystallization Regulation Enabled Stacked Hexagonal Platelet Growth toward Highly Reversible Zinc Anodes[J]. Angewandte Chemie, 2023, 62: e2022184.
[67] HOU Z, TAN H, GAO Y, et al. Tailoring desolvation kinetics enables stable zinc metal anodes[J]. Journal of Materials Chemistry A, 2020, 8 (37): 19367-19374.
[68] LIU M, YAO L, JI Y, et al. Nanoscale Ultrafine Zinc Metal Anodes for High Stability Aqueous Zinc Ion Batteries[J]. Nano Letters, 2023, 23 (2): 541-549.
[69] WANG F, BORODIN O, GAO T, et al. Highly reversible zinc metal anode for aqueous batteries[J]. Nature Materials, 2018, 17 (6): 543-549.
[70] CHEN S, LAN R, HUMPHREYS J, et al. Salt-concentrated acetate electrolytes for a high voltage aqueous Zn|MnO2 battery[J]. Energy Storage Materials, 2020, 28: 205-215.
[71] CHANG G, LIU S, FU Y, et al. Inhibition Role of Trace Metal Ion Additives on Zinc Dendrites during Plating and Striping Processes[J]. Advanced Materials Interfaces, 2019, 6(23): 1901358.
[72] SUN K E K, HOANG T K A, DOAN T N L, et al. Highly Sustainable Zinc Anodes for a Rechargeable Hybrid Aqueous Battery[J]. Chemistry-A European Journal, 2018, 24(7): 1667-1673.
[73] LIU Q, DENG W, SUN C-F. A potassium-tellurium battery[J]. Energy Storage Materials, 2020, 28: 10-16.
[74] ZHANG J, YIN Y X, YOU Y, et al. A High-Capacity Tellurium@Carbon Anode Material for Lithium-Ion Batteries[J]. Energy Technology, 2014, 2(9‐10): 757-762.
[75] ZHANG Y, MANAIG D, FRESCHI D J, et al. Materials design and fundamental understanding of tellurium-based electrochemistry for rechargeable batteries[J]. Energy Storage Materials, 2021, 40: 166-188.
[76] ZHANG J, YIN Y-X, GUO Y-G. High-capacity Te anode confined in microporous carbon for long-life Na-ion batteries[J]. ACS Applied Materials & Interfaces, 2015, 7 (50): 27838-27844.
[77] CHEN Z, LI C, YANG Q, et al. Conversion-Type Nonmetal Elemental Tellurium Anode with High Utilization for Mild/Alkaline Zinc Batteries[J]. Advanced Materials, 2021, 33 (51): 2105426.
[78] CHEN Z, YANG Q, MO F, et al. Aqueous zinc–tellurium batteries with ultraflat discharge plateau and high volumetric capacity[J]. Advanced Materials, 2020, 32 (42): 2001469.
[79] WANG J, DU J, ZHAO J, et al. Unraveling H+/Zn2+ sequential conversion reactions in tellurium cathodes for rechargeable aqueous zinc batteries[J]. The Journal of Physical Chemistry Letters, 2021, 12 (41): 10163-10168.
[80] DUFFY N, PETER L, WANG R, et al. Electrodeposition and characterisation of CdTe films for solar cell applications[J]. Electrochimica Acta, 2000, 45 (20): 3355-3365.
[81] RUDNIK E, BISKUP P. Electrochemical studies of lead telluride behavior in acidic nitrate solutions[J]. Archives of Metallurgy and Materials, 2015, 60 (1): 95-100.
[82] MURASE K, SUZUKI T, UMENAKA Y, et al. Thermodynamics of Cathodic ZnTe Electrodeposition Using Basic Ammoniacal Electrolytes: Why CdTe Can Deposit While ZnTe Cannot[J]. High Temperature Materials and Processes, 2011, 30 (4-5): 451-458.
[83] MAHALINGAM T, JOHN V, RAJENDRAN S, et al. Electrochemical deposition of ZnTe thin films[J]. Semiconductor Science and Technology, 2002, 17 (5): 465.
[84] BOUROUSHIAN M, KOSANOVIC T, KAROUSSOS D, et al.Electrodeposition of polycrystalline ZnTe from simple and citrate-complexed acidic aqueous solutions[J]. Electrochimica Acta, 2009, 54 (9): 2522-2528.
[85] MAHALINGAM T, DHANASEKARAN V, SUNDARAM K, et al. Characterization of electroplated ZnTe coatings[J]. Ionics, 2011, 18 (3): 299-306.
[86] RUSSO V, BAILINI A, ZAMBONI M, et al. Raman spectroscopy of Bi-Te thin films[J]. Journal of Raman Spectroscopy, 2008, 39 (2): 205-210.
[87] JAVIER M F, SAMUEL G-P, PLACIDA R-H, et al. Anomalous Raman modes in tellurides[J]. Journal of Material Chemistry C, 2021, 9 (19): 6277-6289.
[88] WU H, YAN W, XING Y, et al. Tailoring the Interfacial Electric Field Using Silicon Nanoparticles for Stable Zinc-ion Batteries[J]. Advanced Functional Materials, 2023: 2213882.
[89] QIN R, WANG Y, ZHANG M, et al. Tuning Zn2+ coordination environment to suppress dendrite formation for high-performance Zn-ion batteries[J]. Nano Energy, 2021, 80: 105478.
[90] AN Y, TIAN Y, ZHANG K, et al. Stable Aqueous Anode-Free Zinc Batteries Enabled by Interfacial Engineering[J]. Advanced Functional Materials, 2021, 31 (26): 2101886.
[91] DENG C, XIE X, HAN J, et al. A Sieve-Functional and Uniform-Porous Kaolin Layer toward Stable Zinc Metal Anode[J]. Advanced Functional Materials, 2020, 30 (21): 2000599.
[92] XIE X, LIANG S, GAO J, et al. Manipulating the ion-transfer kinetics and interface stability for high-performance zinc metal anodes[J]. Energy & Environmental Science, 2020, 13 (2): 503-510.
[93] WANG X, MENG J, LIN X, et al. Stable Zinc Metal Anodes with Textured Crystal Faces and Functional Zinc Compound Coatings[J]. Advanced Functional Materials, 2021, 31 (48).
[94] XIE F, LI H, WANG X, et al. Mechanism for zincophilic sites on zinc-metal anode hosts in aqueous batteries[J]. Advanced Energy Materials, 2021, 11 (9): 2003419.
[95] ZENG Y, SUN P X, PEI Z, et al. Nitrogen-doped carbon fibers embedded with zincophilic Cu nanoboxes for stable Zn metal anodes[J]. Advanced Materials, 2022, 34 (18): 2200342.
[96] SCHARIFKER B, HILLS G. Theoretical and experimental studies of multiple nucleation[J]. Electrochimica acta, 1983, 28 (7): 879-889.
[97] BEWICK A, FLEISCHMANN M, THIRSK H. Kinetics of the electrocrystallization of thin films of calomel[J]. Transactions of the Faraday Society, 1962, 58: 2200-2216.
[98] LI Z, ZHOU Y, WANG Y, et al. Solvent-mediated Li2S electrodeposition: a critical manipulator in lithium–sulfur batteries[J]. Advanced Energy Materials, 2019, 9 (1): 1802207.
[99] ZHANG F, WANG C G, PAN J, et al. Polypyrrole-controlled plating/stripping for advanced zinc metal anodes[J].Materials Today Energy, 2020, 17.
[100] DI S L, NIE X Y, MA G Q, et al. Zinc anode stabilized by an organic-inorganic hybrid solid electrolyte interphase[J]. Energy Storage Materials, 2021, 43: 375-382.
[101] YUAN Y F, TU J P, WU H M, et al. Effects of stannous ions on the electrochemical performance of the alkaline zinc electrode[J]. Journal of Applied Electrochemistry, 2006, 37 (2): 249-253.