PDF(2733 KB)
原子界面催化合成SnP/CoP异质纳米晶嵌入碳杂化物用于高功率型锂离子电池
Chen Hu, Yanjie Hu, Aiping Chen, Xuezhi Duan, Hao Jiang, Chunzhong Li
工程（英文） ›› 2022, Vol. 18 ›› Issue (11) : 154-160.
PDF(2733 KB)
PDF(2733 KB)
原子界面催化合成SnP/CoP异质纳米晶嵌入碳杂化物用于高功率型锂离子电池
Atomic Interface Catalytically Synthesizing SnP/CoP Hetero-Nanocrystals within Dual-Carbon Hybrids for Ultrafast Lithium-Ion Batteries
磷化锡（SnP）具有极佳的锂离子扩散能力和高理论比容量，是高功率锂离子电池的理想负极材料。然而，SnP的合成难度高，大尺寸晶粒导致的电化学不可逆也阻碍了其应用。根据密度泛函理论（DFT）计算，使用原位催化磷化方法可以显著降低SnP的相对生成能。因此，在还原氧化石墨烯（rGO）包裹的碳骨架内合成了SnP/CoP异质纳米晶。所得复合材料具有超快充放电能力（50 A·g−1时容量为260 mA·h·g−1），且循环1500次不会出现容量衰减（2 A·g−1时容量为645 mA·h·g−1）。充放电机理分析表明尺寸为4.0 nm的SnP/CoP纳米晶具有高反应可逆性，且CoP在较高电位生成的金属Co加速了低电位SnP反应的动力学，从而赋予材料超快充放电能力。相对电流密度的有限元模拟进一步验证了这一现象。
Tin phosphides are attractive anode materials for ultrafast lithium-ion batteries (LIBs) because of their ultrahigh Li-ion diffusion capability and large theoretical-specific capacity. However, difficulties in synthesis and large size enabling electrochemical irreversibility impede their applications. Herein, an in situ catalytic phosphorization strategy is developed to synthesize SnP/CoP hetero-nanocrystals within reduced graphene oxide (rGO)-coated carbon frameworks, in which the SnP relative formation energy is significantly decreased according to density functional theory (DFT) calculations. The optimized hybrids exhibit ultrafast charge/discharge capability (260 mA·h·g−1 at 50 A·g−1) without capacity fading (645 mA·h·g−1 at 2 A·g−1) through 1500 cycles. The lithiation/delithiation mechanism is disclosed, showing that the 4.0 nm sized SnP/CoP nanocrystals possess a very high reversibility and that the previously formed metallic Co of CoP at a relatively high potential accelerates the subsequent reaction kinetics of SnP, hence endowing them with ultrafast charge/discharge capability, which is further verified by the relative dynamic current density distributions according to the finite element analysis.Graphical abstractDownload : Download high-res image (191KB)Download : Download full-size image
催化磷化 / 磷化锡 / 异质纳米晶 / 快速充电 / 锂离子电池
Catalytic phosphorization / SnP / Hetero-nanocrystals / Fast charging / Li-ion batteries
| [1] |
Liu Y, Zhu Y, Cui Y. Challenges and opportunities towards fast-charging battery materials. Nat Energy 2019;4(7):540–50.
|
| [2] |
Zhao W. A forum on batteries: from lithium-ion to the next generation. Natl Sci Rev 2020;7(7):1263–8.
|
| [3] |
Babu B, Simon P, Balducci A. Fast charging materials for high power applications. Adv Energy Mater 2020;10(29):2001128.
|
| [4] |
Choi S, Kwon TW, Coskun A, Choi JW. Highly elastic binders integrating polyrotaxanes for silicon microparticle anodes in lithium ion batteries. Science 2017;357(6348):279–83.
|
| [5] |
Liu T, Chu Q, Yan C, Zhang S, Lin Z, Lu J. Interweaving 3D network binder for high-areal-capacity Si anode through combined hard and soft polymers. Adv Energy Mater 2019;9(3):1802645.
|
| [6] |
Jin H, Wang H, Qi Z, Bin DS, Zhang T, Wan Y, et al. A black phosphorus-graphite composite anode for Li-/Na-/K-ion batteries. Angew Chem Int Ed Engl 2020;59 (6):2318–22.
|
| [7] |
Wu Y, Wang W, Ming J, Li M, Xie L, He X, et al. An exploration of new energy storage system: high energy density, high safety, and fast charging lithium ion battery. Adv Funct Mater 2019;29(1):1805978.
|
| [8] |
Genser O, Hafner J. Structure and bonding in crystalline and molten Li–Sn alloys: a first-principles density-functional study. Phys Rev B 2001;63 (14):144204.
|
| [9] |
Wen CJ, Huggins RA. Chemical diffusion in intermediate phases in the lithium– tin system. J Solid State Chem 1980;35(3):376–84.
|
| [10] |
Shi J, Wang Z, Fu YQ. Density functional theory study of diffusion of lithium in Li–Sn alloys. J Mater Sci 2016;51(6):3271–6.
|
| [11] |
Fedorov AS, Kuzubov AA, Eliseeva NS, Popov ZI, Visotin MA, Galkin NG. Theoretical study of the lithium diffusion in the crystalline and amorphous silicon as well as on its surface. Solid State Phenom 2014;213:29–34.
|
| [12] |
Levi MD, Aurbach D. Diffusion coefficients of lithium ions during intercalation into graphite derived from the simultaneous measurements and modeling of electrochemical impedance and potentiostatic intermittent titration characteristics of thin graphite electrodes. J Phys Chem B 1997;101(23): 4641–7.
|
| [13] |
Chou CY, Kim H, Hwang GS. A comparative first-principles study of the structure, energetics, and properties of Li–M (M = Si, Ge, Sn) alloys. J Phys Chem C 2011;115(40):20018–26.
|
| [14] |
Kim Y, Hwang H, Yoon CS, Kim MG, Cho J. Reversible lithium intercalation in teardrop-shaped ultrafine SnP0.94 particles: an anode material for lithium-ion batteries. Adv Mater 2007;19(1):92–6.
|
| [15] |
Nazri G. Preparation, structure and ionic conductivity of lithium phosphide. Solid State Ion 1989;34(1–2):97–102.
|
| [16] |
Park MG, Lee DH, Jung H, Choi JH, Park CM. Sn-based nanocomposite for Li-ion battery anode with high energy density, rate capability, and reversibility. ACS Nano 2018;12(3):2955–67.
|
| [17] |
Liang SZ, Cheng YJ, Zhu J, Xia YG, Müller-Buschbaum P. A chronicle review of nonsilicon (Sn, Sb, Ge)-based lithium/sodium-ion battery alloying anodes. Small Methods 2020;4(8):2000218.
|
| [18] |
Hu R, Chen D, Waller G, Ouyang Y, Chen Yu, Zhao B, et al. Dramatically enhanced reversibility of Li2O in SnO2-based electrodes: the effect of nanostructure on high initial reversible capacity. Energy Environ Sci 2016;9 (2):595–603.
|
| [19] |
Xia Y, Han S, Zhu Y, Liang Y, Gu M. Stable cycling of mesoporous Sn4P3/SnO2@C nanosphere anode with high initial coulombic efficiency for Li-ion batteries. Energy Storage Mater 2019;18:125–32.
|
| [20] |
Wang J, Huang W, Kim YS, Jeong YK, Kim SC, Heo J, et al. Scalable synthesis of nanoporous silicon microparticles for highly cyclable lithium-ion batteries. Nano Res 2020;13(6):1558–63.
|
| [21] |
Ying H, Han WQ. Metallic Sn-based anode materials: application in highperformance lithium-ion and sodium-ion batteries. Adv Sci 2017;4(11): 1700298.
|
| [22] |
Gullman J. The crystal structure of SnP. J Solid State Chem 1990;87(1):202–7.
|
| [23] |
Ritscher A, Schmetterer C, Ipser H. Pressure dependence of the tin–phosphorus phase diagram. Monatsh Chem 2012;143(12):1593–602.
|
| [24] |
Katz G, Kohn JA, Broder JD. Crystallographic data for tin monophosphide. Acta Crystallogr 1957;10(9):607.
|
| [25] |
Aso K, Kitaura H, Hayashi A, Tatsumisago M. SnP0.94 active material synthesized in high-boiling solvents for all-solid-state lithium batteries. J Ceram Soc Jpn 2010;118(1379):620–62.
|
| [26] |
Liu J, Kopold P, Wu C, van Aken PA, Maier J, Yu Y. Uniform yolk-shell Sn4P3@C nanospheres as high-capacity and cycle-stable anode materials for sodium-ion batteries. Energy Environ Sci 2015;8(12):3531–8.
|
| [27] |
Wang W, Zhang J, Yu DYW, Li Q. Improving the cycling stability of Sn4P3 anode for sodium-ion battery. J Power Sources 2017;364:420–45.
|
| [28] |
Xu Y, Peng B, Mulder FM. A high-rate and ultrastable sodium ion anode based on a novel Sn4P3–P@Graphene nanocomposite. Adv Energy Mater 2018;8 (3):1701847.
|
| [29] |
Choi J, Kim WS, Kim KH, Hong SH. Sn4P3–C nanospheres as high capacitive and ultra-stable anodes for sodium ion and lithium ion batteries. J Mater Chem A 2018;6(36):17437–43.
|
| [30] |
Ding Y, Li ZF, Timofeeva EV, Segre CU. In situ EXAFS-derived mechanism of highly reversible tin phosphide/graphite composite anode for Li-ion batteries. Adv Energy Mater 2018;8(9):1702134.
|
| [31] |
Fan X, Gao T, Luo C, Wang F, Hu J, Wang C. Superior reversible tin phosphidecarbon spheres for sodium ion battery anode. Nano Energy 2017;38:350–7.
|
| [32] |
Wang A, Qin M, Guan J, Wang L, Guo H, Li X, et al. The synthesis of metal phosphides: reduction of oxide precursors in a hydrogen plasma. Angew Chem Int Ed Engl 2008;47(32):6052–4.
|
| [33] |
Yang Y, Zhao X, Wang H, Li M, Hao C, Ji M, et al. Phosphorized SnO2/graphene heterostructures for highly reversible lithium-ion storage with enhanced pseudocapacitance. J Mater Chem A 2018;6(8):3479–87.
|
| [34] |
Lou XW, Wang Y, Yuan C, Lee JY, Archer LA. Template-free synthesis of SnO2 hollow nanostructures with high lithium storage capacity. Adv Mater 2006;18 (17):2325–9.
|
| [35] |
Li H, Zhu Y, Zhao K, Fu Q, Wang K, Wang Y, et al. Surface modification of coordination polymers to enable the construction of CoP/N, P-codoped carbon nanowires towards high-performance lithium storage. J Colloid Interface Sci 2020;565:503–12.
|
| [36] |
Jiang Y, Li Y, Zhou P, Lan Z, Lu Y, Wu C, et al. Ultrafast, highly reversible, and cycle-stable lithium storage boosted by pseudocapacitance in Sn-based alloying anodes. Adv Mater 2017;29(48):1606499.
|
| [37] |
Mo R, Tan X, Li F, Tao R, Xu J, Kong D, et al. Tin–graphene tubes as anodes for lithium-ion batteries with high volumetric and gravimetric energy densities. Nat Commun 2020;11(1):1374.
|
| [38] |
Zhou X, Dai Z, Liu S, Bao J, Guo YG. Ultra-uniform SnOx/carbon nanohybrids toward advanced lithium-ion battery anodes. Adv Mater 2014;26(23): 3943–9.
|
| [39] |
Wu C, Maier J, Yu Y. Sn-based nanoparticles encapsulated in a porous 3D graphene network: advanced anodes for high-rate and long life Li-ion batteries. Adv Funct Mater 2015;25(23):3488–96.
|
| [40] |
Ferrara G, Arbizzani C, Damen L, Guidotti M, Lazzari M, Vergottini FG, et al. High-performing Sn–Co nanowire electrodes as anodes for lithium-ion batteries. J Power Sources 2012;211:103–7.
|
| [41] |
Ke FS, Huang L, Jamison L, Xue LJ, Wei GZ, Li JT, et al. Nanoscale tin-based intermetallic electrodes encapsulated in microporous copper substrate as the negative electrode with a high rate capacity and a long cycle ability for lithium-ion batteries. Nano Energy 2013;2(5):595–603.
|
| [42] |
Yang Y, Qu X, Zhang X, Liu Y, Hu J, Chen J, et al. Higher than 90% initial coulombic efficiency with staghorn-coral-like 3D porous LiFeO2x as anode materials for Li-ion batteries. Adv Mater 2020;32(22):1908285.
|
| [43] |
Xu Y, Zhu Y, Liu Y, Wang C. Electrochemical performance of porous carbon/tin composite anodes for sodium-ion and lithium-ion batteries. Adv Energy Mater 2013;3(1):128–33.
|
/
| 〈 |
|
〉 |
