以纳米TiN为研磨剂,采用机械球磨技术制备了NaF-M(M = Fe, Cu)纳米复合物,探索了这类复合物作为钠离子电池转换正极材料的可能性. 电化学测试表明,NaF-Fe和NaF-Cu纳米复合物电极在钠离子电解液中能实现与Na+的逆向转换反应,其可逆放电容量达150 mAh.g-1以上,并具有较好的循环寿命. 只要创造了适合相转变反应进行的微区结构,钠离子的转换反应也可以通过可逆的电化学转换反应实现,并从起始的富钠放电态直接充电至贫钠的荷电态. 本工作为开发高容量钠离子电池正极材料提供了新途径.
李婷
,
陈重学
,
曹余良
,
杨汉西
. NaF-M(M=Fe, Cu)钠离子电池转换正极材料的研究[J]. 电化学, 2012
, 18(4)
: 291
-294
.
DOI: 10.61558/2993-074X.2918
The NaF-M (M = Fe, Cu) nanocomposites were prepared by high-energy ball milling using TiN grinding nanoparticles and investigated as cathode materials for sodium ion batteries. The experimental results demonstrated that NaF-Fe and NaF-Cu nanocomposites can go through electrochemical conversion reaction with Na+ uptake or removal, delivering a reversible capacity of ~ 150 mAh.g-1, even through a reversed conversion from initial discharged state to a charged state. These results reveal the possibility to realize a conversion reaction as long as NaF and elemental metal particles are intimately contacted to form active nanocomposites at nanodomain, which suggests a potential feasibility to use these nanocomposites as sodium-rich cathode materials for sodium ion batteries.
[1] Palac?′n M R. Recent advances in rechargeable battery materials: A chemist’s perspective[J]. Chemical Society Reviews, 2009, 38(9): 2565-2575.
[2] Gao X P, Yang H X. Multi-electron reaction materials for high energy density batteries[J]. Energy Environmental Science, 2010, 3(2): 174-189.
[3] Bruce P G, Scrosati B, Tarascon J M. Nanomaterials for rechargeable lithium batteries[J]. Angewandte Chemie-International Edition, 2008, 47(16): 2930-2946.
[4] Cabana J, Monconduit L, Larcher D, et al. Beyond intercalation-based Li-ion batteries: The state of the art and challenges of electrode materials reacting through conversion reactions[J]. Advanced Materials, 2010, 22(35): E170-E192.
[5] Li H, Balaya P, Maier J. Li-storage via heterogeneous reaction in selected binary metal fluorides and oxides[J]. Journal of the Electrochemical. Society, 2004, 151(11): A1878-A1885.
[6] Amatucci G G. Pereira N. Fluoride based electrode materials for advanced energy storage devices[J]. Journal of Fluorine Chemistry, 2007, 128(4): 243-262.
[7] Hamani D, Ati M, Tarascon J M, et al. NaxVO2 as possible electrode for Na-ion batteries[J]. Electrochemistry Communication, 2011, 13(9): 938-941.
[8] Zhuo H T, Wang X Y, Tang A P, et al. The preparation of NaV1-xCrxPO4F cathode materials for sodium-ion battery[J]. Journal of Power Sources, 2006, 160(1): 698-703.
[9] Barker J, Saidi M Y, Swoyer J L. A sodium-ion cell based on the fluorophosphate compound NaVPO4F[J]. Electrochemical and Solid State Letters, 2003, 6(1): A1-A4.
[10] Trad K, Carlier D, Croguennec L, et al. NaMnFe2(PO4)3 alluaudite phase: Synthesis, structure, and electrochemical properties as positive electrode in lithium and sodium batteries[J]. Chemistry of Materials, 2010, 22(19): 5554-5562.
[11] Berthelot R, Carlier D, Delmas C. Electrochemical investigation of the P2-NaxCoO2 phase diagram[J]. Nature Materials, 2011, 10(1): 74-80.
[12] Yu X Q, Sun J P, Tang K, et al. Reversible lithium storage in LiF/Ti nanocomposites[J]. Physical Chemistry Chemical Physics, 2009, 11(41): 9497-9503.
[13] Liao P, MacDonald B L, Dunlap R A, et al. Combinatorially prepared[LiF]1-xFex nanocomposites for positive electrode materials in Li-ion batteries[J]. Chemistry of Materials, 2008, 20(2): 454-461.
[14] Prakash R, Wall C, Mishra A K, et al. Modified synthesis of[Fe/LiF/C] nanocomposite, and its application as conversion cathode material in lithium batteries[J]. Journal of Power Sources, 2011, 196(14): 5936-5944.
[15] Li T, Ai X P, Yang H X. Reversible electrochemical conversion reaction of Li2O/CuO nanocomposites and their application as high-capacity cathode materials for Li-ion batteries[J]. Journal of Physical Chemistry C, 2011, 115(13): 6167-6174.
[16] Li T, Li L, Cao Y L, et al. Reversible three-electron redox behaviors of FeF3 nanocrystals as high-capacity cathode-active materials for Li-ion batteries[J]. Journal of Physical Chemistry C, 2010, 114(7): 3190-3195.