锂硫电池发展前景广阔,但锂硫电池在反应过程中涉及复杂且漫长的16电子氧化还原反应过程。大量研究表明,硫转化势垒最高的阶段为硫化锂(Li2S)的生成阶段,该阶段释放的理论容量占锂硫电池整体容量的3/4,但是由于Li2S本身固有绝缘性和在反应过程中不可控沉积导致电极界面钝化,影响了活性物质硫的利用率,进而影响电池的容量释放。综述了影响正极Li2S沉积形貌的因素,如温度、溶剂、电流密度,介绍了调控正极Li2S沉积形貌的方法。
Although lithium-sulfur batteries have a promising future,lithium-sulfur batteries involve a complex and lengthy 16-electron redox reaction process during the reaction.A large number of studies indicate that the highest sulfur conversion barrier stage is the generation stage of lithium sulfide (Li2S),and the theoretical capacity release of this process accounts for 3/4 of the total capacity of Li-S batteries.However,due to the inherent insulating properties of Li2S itself and the uncontrollable deposition during the reaction process leading to passivation of the electrode interface,the utilization of sulfur of the active substance is affected,which in turn affects the capacity release of the battery.The factors affecting the deposition morphology of anode Li2S,such as temperature,solvent,and current density,were summarized,and the methods of regulating the deposition morphology of anode Li2S was introduced.
[1] Bruce P G,Freunberger S A,Hardwick L J,et al.Li-O2 and Li-S batteries with high energy storage[J].Nat Mater,2012,11:19-29.
[2] Ji X L,Lee K T,Nazar L F,et al.A highly ordered nanostructured carbon-sulphur cathode for lithium-sulfur batteries[J].Nat Mater,2009,8:500-506.
[3] Manthiram A,Chung S H,Zu C X,et al.Lithium-sulfur batteries:progress and prospects[J].Adv Mater,2015,27:1980-2006.
[4] Shan J W,Wang W,Zhang B,et al.Unraveling the atomic-le-vel manipulation mechanism of Li2S redox kinetics via electron-donor doping for designing high-volumetric-energy-density,lean-electrolyte lithium-sulfur batteries[J].Adv Sci,2022,9(33):2204192.
[5] Jin Z,Lin T,Jia H,et al.Expediting the conversion of Li2S2 to Li2S enables high-performance Li-S batteries[J].ACS Nano,2021,15:7318-7327.
[6] Kang W,Deng N,Ju J,et al.A review of recent developments in rechargeable lithium-sulfur batteries[J].Nanoscale,2016,8(37):16541-16588.
[7] Liu J B,Song Y F,Lin C J,et al.Regulating Li+ migration and Li2S deposition by metal-organic frameworkderived Co4S3-embedded carbon nanoarrays for durable lithium-sulfur batteries[J].Sci China Material,2022,65(4):947-957.
[8] Xu R,Lu J,Amine K,et al.Progress in mechanistic understanding and characterization techniques of Li-S batteries[J].Adv Energy Mater,2015,5(16):1500408.
[9] Yang Y,Zheng G Y,Misra S,et al.High-capacity micrometer-sized Li2S particles as cathode materials for advanced rechargeable lithium-ion batteries[J].J Am Chem Soc,2012,134:15387-15394.
[10] Peng H J,Zhang G,Chen X,et al.Enhanced electrochemical kinetics on conductive polar mediators for lithium-sulfur batteries[J].Angew Chem Int Ed,2016,55(42):1-6.
[11] Lang S Y,Xiao R J,Gu L,et al.Interfacial mechanism in lithium-sulfur batteries:how salts mediate the structure evolution and dynamics[J].J Am Chem Soc,2018,140(26):8147-8155.
[12] Kim H,Lee J T,Yushin G,et al.High temperature stabilization of lithium-sulfur cells with carbon nanotube current collector[J].J Power Sources,2013,226:256-265.
[13] Wang Z F,Tang Y F,Zhang L Q,et al.In situ TEM observations of discharging/charging of solid-state lithium-sulfur batteries at high temperatures[J].Small,2020,16:2001899.
[14] Wang S A,Huang F Y,Li X P,et al.Regulating Li2S deposition by ostwald ripening in lithium-sulfur batteries[J].ACS Appl Mater Interfaces,2022,14(3):4204-4210.
[15] An D C,Wang J J,Zhang J,et al.Retarding ostwald ripening through gibbs adsorption and interfacial complexions leads to high-performance SnTe thermoelectrics[J].Energy Environ Sci,2021,14:5469-5479.
[16] Pan H L,Chen J Z,Cao R G,et al.Non-encapsulation approach for high-performance Li-S batteries through controlled nucleation and growth[J].Nat Energy,2017,2:813-820.
[17] Fan F Y,Chiang Y M.Electrodeposition kinetics in Li-S batteries:effects of low electrolyte/sulfur ratios and deposition surface composition[J].J Electrochem Soc,2017,164:917-922.
[18] Liang X,Wen Z Y,Liu M F,et al.Improved cycling perfor-mances of lithium sulfur batteries with LiNO3-modified electrolyte[J].J Power Sources,2011,196:9839-9843.
[19] Lin Z,Liu Z C,Fu W J,et al.Phosphorous pentasulfide as a novel additive for high-performance lithium sulfur batteries[J].Adv Funct Mater,2013,23:1064-1069.
[20] Zhou Y C,Li Z J,Lu Y C,et al.A stable lithium-selenium interface via solid/liquid hybrid electrolytes:blocking polyselenides and suppressing lithium dendrite[J].Nano Energy,2017,39:554-561.
[21] Longo R C,Camacho-Forero L E,Balbuena,et al.Li2S growth on graphene:impact on the electrochemical performance of Li-S batteries[J].J Chem Phys,2020,152:14701.
[22] Kong L,Chen X,Li B Q,et al.A bifunctional perovskite promoter for polysulfide regulation toward stable lithium-sulfur batteries[J].Adv Mater,2018,30:1705219.
[23] Zhang Z W,Peng H J,Zhao M,et al.Heterogeneous/homogeneous mediators for high-energy-density lithium-sulfur batteries:progress and prospects[J].Adv Funct Mater,2018,28:1707536.
[24] Kong L,Chen J X,Peng H J,et al.Current-density dependence of Li2S/Li2S2 growth in lithium-sulfur batteries[J].Energy Environ Sci,2019,12:2976-2982.
[25] Lang S Y,Shi Y,Guo Y G,et al.Insight into the interfacial process and mechanism in lithium-sulfur batteries:an in situ AFM study[J].Angew Chem Int Ed,2016,55:15835-15839.
[26] Zeng F L,Li N,Shen Y Q,et al.Improve the electrodeposition of sulfur and lithium sulfide in lithium-sulfur batteries with a comb-like ion-conductive organo polysulfide polymer binder[J].Energy Storage Mater,2019,18:190-198.
[27] Schmeisser M,Peter I,Ralph,et al.Gutmann donor and acceptor numbers for ionic liquids[J].Chem Eur J,2012,18:10969-10982.
[28] Burke C M,Pande V,Khetan,et al.Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li-O2 battery capacity[J].Proc Natl Acad Sci,2015,112:9293-9298.
[29] Chu H,Noh H,Kim,et al.Achieving three-dimensional lithium sulfide growth in lithium-sulfur batteries using high-donor number anions[J].Nat Commun,2019,10:188.
[30] Peng H J,Huang J Q,Liu X Y,et al.Healing high-loading sulfur electrodes with unprecedented long cycling life:spatial hetero geneity control[J].J Am Chem Soc,2017,139:8458-8466.
[31] Zhao M,Peng H J,Wei J Y,et al.Dictating high-capacity lithium-sulfur batteries through redox-mediated lithium sulfide growth[J].Small Methods,2020,4:1900344.
[32] Gerber L C H,Frischmann P D,Fan F Y,et al.Three-dimensional growth of Li2S in lithium-sulfur batteries promoted by a redox mediator[J].Nano Letters,2016,16:549-554.
[33] Yang B,Jiang H R,Zhou Y C.Critical role of anion donicity in Li2S deposition and sulfur utilization in Li-S batteries[J].ACS Appl Mater Interfaces,2019,11:25940-25948.
[34] Tian S H,Liu G,Xu S X.Deposition mode design of Li2S:transmitted orbital overlap strategy in highly stable lithium-sulfur battery[J].Adv Funct Mater,2024,34:2309437.
基金资助
国家自然科学基金青年科学基金项目(22309136);浙江省自然科学基金青年基金项目(LQ22B030003)
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