Sn-Co合金复合负极材料的制备与电化学性能研究
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摘要
金属锡具有理论容量高(992mAh/g)、密度大等优点，成为高容量锂离子电池负极材料研究的热点，但金属锡在充放电过程中体积膨胀显著，容易导致结构破坏，循环性能变差，不能满足实际应用的需求。因此，提高Sn基材料的循环性能成亟待解决的关键技术问题。
本文采用适合产业化生产的固相烧结法和球磨法制备了Sn-Co合金复合负极材料，对Sn-Co纳米晶合金粉、石墨的粉碎提纯以及Sn-Co/C和Sn-Co/G两大体系复合材料的制备、结构和电化学性能等方面进行了较为系统的探讨。
在Sn-Co二元合金方面，合金的相结构对电化学性影响显著，四方晶系的CoSn_2相具有很高的放电容量和充放电效率，而正交晶系的Co_3Sn_2相具有很高的循环性能，六方晶系的CoSn相具有适当的容量和循环性能。将Sn-Co合金继续球磨使颗粒晶粒细化，可以提升合金的容量和循环性能。
在Sn-Co/C(C为炭黑的简写)体系方面，添加第4组元Zn制备的新型Sn-Co-Zn/C复合材料具有优异的电化学性能，C的复合和使颗粒晶粒细化，Zn的固溶强化以及CoSn与CoSn_2、Co_3Sn_2、Zn、Sn的多相合金复合等多种作用共同提高了Sn-Co合金的结构稳定性和电化学性能，首次放电容量和充放电效率分别为440mAh/g和76.2%，经过25次循环后的容量保持率达88.6%，该复合材料适用于高容量锂离子电池。
在Sn-Co/G(G为石墨的简写)体系方面，首先将人造石墨颗粒进行粉碎和提纯除杂，再采用球磨法将Sn-Co合金嵌入石墨制备了Sn-Co/G复合材料，研究了表面活性剂、球磨时间、球磨转速和物料配比对Sn-Co/G复合材料结构和电化学性能的影响规律；并对复合材料进行热处理提高了Sn-Co合金与石墨的结合强度，经过500℃热处理后的Sn-Co/G复合材料的首次放电容量和充放电效率分别为362mAh/g和83.6%，经过25次循环后的容量保持率高达92.8%，找到了一条适合制备长循环寿命的锂离子电池电极材料的技术途径。
在Sn-Co/B(B为硼的简写)体系方面，将与Sn-Co合金复合的非金属元素选择范围拓宽至B，研究了B对Sn-Co合金结构和电化学性能的影响规律和机理。B的复合作用和颗粒晶粒细化作用提高了复合材料的电化学性能，首次放电容量和充放电效率分别为216mAh/g和51.1%，经过25次循环后的容量保持率为82.9%，但过量的B导致CoSn相基础上形成更多的CoSn2相，使循环性能降低。
Because of its high theoretical capacity (992mAh/g) and high density, tin has become ahighlighted topic in high capacity anode material for lithium ion battery. However, its structureis suffered from pulverization which is resulted from the large volume expansion during thecharge-discharge, leading to the deterioration of the cycle performance and thus losing itspractical value. Therefore, improving the cycle performance of Sn-based has become key scienceproblem.
In this paper, the Sn-Co alloy composite was prepared by solid-state sintering method andball milling method, which is appropriate for industrial production. The structures andelectrochemical properities of nano Sn-Co alloy powder, graphite, Sn-Co/C and Sn-Co/Gcomposite were investigated systematically.
In the Sn-Co alloy, the phase structure has significantly influence on the electrochemicalproperities. The CoSn2phase alloy with tetragonal crystal has high discharge capacity andcharge-discharge efficiency, the Co3Sn2phase alloy with orthorhombic crystal has high cycleperformance and the CoSn phase alloy with hexagonal crystal has appropriate discharge capacityand cycle performance. Besides, the refinement of particle size and grain size of Sn-Co alloyresults in the improvement of capacity and cycle performance.
In the Sn-Co/C system, the novel Sn-Co-Zn/C composite prepared by adding the forthelement Zn into Sn-Co/C composite exhibis excellent electrochemical properities. The compositeeffect and the refinement of paticle size and grain size by adding C, the solid solution strengtheneffect and the multiphase compound effect of CoSn, CoSn2, Co3Sn2, Zn and Sn by adding Znimprove together the structure stabilities and electrochemical properities. The discharge capacityand charge-discharge efficiency of Sn-Co-Zn/C composite is440mAh/g and76.2%espectivelyand the capacity retention is88.6%after25cycles. So, the Sn-Co-Zn/C composite is appropriatefor application in lithium ion battery with high capacity.
In the Sn-Co/G system, the artificial graphite is crushed and pickled firstly, and then makeSn-Co alloy into graphite by ball milling. The influence of surfactant, balling time and speed,alloy content on the structures and electrochemical properities of Sn-Co/G composite isinvestigated. Then, the integrate degree of Sn-Co alloy and graphite is improved by heattreatment. The discharge capacity and charge-discharge efficiency of Sn-Co/G composite after500℃heat treatment is362mAh/g and83.6%espectively and the capacity retention is92.8% after25cycles. Therefore, a technology approach to prepare the anode material for lithiumbattery with long cycle life has been found.
In the Sn-Co/B system, the scope of nonmetal element which is compound with Sn-Co alloyextends to B element, the influence of B element on the structures and electrochemicalproperities of Sn-Co/B composite is investigated. The composite effect and the refinement ofpaticle size and grain size by adding B improve together the electrochemical properities ofcomposite. The discharge capacity and charge-discharge efficiency of Sn-Co/B composite is216mAh/g and51.1%espectively and the capacity retention is82.9%after25cycles. Howerer,more CoSn2phase forms by adding excessive B, which leads to the decreasing of cycleperformance.
本文采用适合产业化生产的固相烧结法和球磨法制备了Sn-Co合金复合负极材料，对Sn-Co纳米晶合金粉、石墨的粉碎提纯以及Sn-Co/C和Sn-Co/G两大体系复合材料的制备、结构和电化学性能等方面进行了较为系统的探讨。
在Sn-Co二元合金方面，合金的相结构对电化学性影响显著，四方晶系的CoSn_2相具有很高的放电容量和充放电效率，而正交晶系的Co_3Sn_2相具有很高的循环性能，六方晶系的CoSn相具有适当的容量和循环性能。将Sn-Co合金继续球磨使颗粒晶粒细化，可以提升合金的容量和循环性能。
在Sn-Co/C(C为炭黑的简写)体系方面，添加第4组元Zn制备的新型Sn-Co-Zn/C复合材料具有优异的电化学性能，C的复合和使颗粒晶粒细化，Zn的固溶强化以及CoSn与CoSn_2、Co_3Sn_2、Zn、Sn的多相合金复合等多种作用共同提高了Sn-Co合金的结构稳定性和电化学性能，首次放电容量和充放电效率分别为440mAh/g和76.2%，经过25次循环后的容量保持率达88.6%，该复合材料适用于高容量锂离子电池。
在Sn-Co/G(G为石墨的简写)体系方面，首先将人造石墨颗粒进行粉碎和提纯除杂，再采用球磨法将Sn-Co合金嵌入石墨制备了Sn-Co/G复合材料，研究了表面活性剂、球磨时间、球磨转速和物料配比对Sn-Co/G复合材料结构和电化学性能的影响规律；并对复合材料进行热处理提高了Sn-Co合金与石墨的结合强度，经过500℃热处理后的Sn-Co/G复合材料的首次放电容量和充放电效率分别为362mAh/g和83.6%，经过25次循环后的容量保持率高达92.8%，找到了一条适合制备长循环寿命的锂离子电池电极材料的技术途径。
在Sn-Co/B(B为硼的简写)体系方面，将与Sn-Co合金复合的非金属元素选择范围拓宽至B，研究了B对Sn-Co合金结构和电化学性能的影响规律和机理。B的复合作用和颗粒晶粒细化作用提高了复合材料的电化学性能，首次放电容量和充放电效率分别为216mAh/g和51.1%，经过25次循环后的容量保持率为82.9%，但过量的B导致CoSn相基础上形成更多的CoSn2相，使循环性能降低。
Because of its high theoretical capacity (992mAh/g) and high density, tin has become ahighlighted topic in high capacity anode material for lithium ion battery. However, its structureis suffered from pulverization which is resulted from the large volume expansion during thecharge-discharge, leading to the deterioration of the cycle performance and thus losing itspractical value. Therefore, improving the cycle performance of Sn-based has become key scienceproblem.
In this paper, the Sn-Co alloy composite was prepared by solid-state sintering method andball milling method, which is appropriate for industrial production. The structures andelectrochemical properities of nano Sn-Co alloy powder, graphite, Sn-Co/C and Sn-Co/Gcomposite were investigated systematically.
In the Sn-Co alloy, the phase structure has significantly influence on the electrochemicalproperities. The CoSn2phase alloy with tetragonal crystal has high discharge capacity andcharge-discharge efficiency, the Co3Sn2phase alloy with orthorhombic crystal has high cycleperformance and the CoSn phase alloy with hexagonal crystal has appropriate discharge capacityand cycle performance. Besides, the refinement of particle size and grain size of Sn-Co alloyresults in the improvement of capacity and cycle performance.
In the Sn-Co/C system, the novel Sn-Co-Zn/C composite prepared by adding the forthelement Zn into Sn-Co/C composite exhibis excellent electrochemical properities. The compositeeffect and the refinement of paticle size and grain size by adding C, the solid solution strengtheneffect and the multiphase compound effect of CoSn, CoSn2, Co3Sn2, Zn and Sn by adding Znimprove together the structure stabilities and electrochemical properities. The discharge capacityand charge-discharge efficiency of Sn-Co-Zn/C composite is440mAh/g and76.2%espectivelyand the capacity retention is88.6%after25cycles. So, the Sn-Co-Zn/C composite is appropriatefor application in lithium ion battery with high capacity.
In the Sn-Co/G system, the artificial graphite is crushed and pickled firstly, and then makeSn-Co alloy into graphite by ball milling. The influence of surfactant, balling time and speed,alloy content on the structures and electrochemical properities of Sn-Co/G composite isinvestigated. Then, the integrate degree of Sn-Co alloy and graphite is improved by heattreatment. The discharge capacity and charge-discharge efficiency of Sn-Co/G composite after500℃heat treatment is362mAh/g and83.6%espectively and the capacity retention is92.8% after25cycles. Therefore, a technology approach to prepare the anode material for lithiumbattery with long cycle life has been found.
In the Sn-Co/B system, the scope of nonmetal element which is compound with Sn-Co alloyextends to B element, the influence of B element on the structures and electrochemicalproperities of Sn-Co/B composite is investigated. The composite effect and the refinement ofpaticle size and grain size by adding B improve together the electrochemical properities ofcomposite. The discharge capacity and charge-discharge efficiency of Sn-Co/B composite is216mAh/g and51.1%espectively and the capacity retention is82.9%after25cycles. Howerer,more CoSn2phase forms by adding excessive B, which leads to the decreasing of cycleperformance.
引文
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