高容量C/Si-O-C负极材料的制备及其嵌脱锂离子机理的研究
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摘要
锂离子电池是兼具高能量密度、高功率密度和高工作电压等优点的绿色能源，已经成为手机、数码相机和笔记本电脑等便携式电子设备的主流电源，未来还可能应用于电动汽车等动力电源领域，为缓解人类对化石能源的依赖具有重要意义。在高性能锂离子电池中，提高负极材料的比容量对提高整个锂离子电池的容量具有重要意义。目前锂离子电池商用负极材料均为石墨材料，其理论容量为372mAh/g，为了提高锂离子电池的容量，需要将负极材料的比容量提高至800mAh/g以上。Si-O-C材料据报道具有较高的可逆容量和较好的循环性能，是一种有潜力的锂离子电池负极材料。
本文选择高容量Si-O-C复合负极材料作为研究对象，采用先驱体转化法制备了具有不同组成和结构的Si-O-C负极材料，研究了制备工艺、元素组成对其电化学性能的影响，同时采用一系列的分析测试对Si-O-C负极材料在嵌脱锂离子过程中的结构变化进行了研究，并且制备了利用Si-O-C材料包覆纳米硅的新型Si/Si-O-C负极材料，为进一步改善Si-O-C材料的电化学性能奠定了良好的基础。
首先以聚硅氧烷为先驱体，通过裂解气氛、裂解温度、增加碳源等工艺条件的改变制备了碳含量为4.1wt%~42.1wt%、硅含量为30wt%~47.9wt%的C/Si-O-C负极材料，系统研究了工艺条件对材料组成结构及电化学性能的影响；在此基础上，系统研究了C/Si-O-C负极材料的可逆及不可逆容量与元素组成的关系。
以聚硅氧烷为先驱体，在还原性和惰性气氛中，800~1000℃温度下分别制备了碳含量为22.1wt%~23.2wt%和14.1wt%~15.1wt%的C/Si-O-C负极材料。还原性气氛中制备的C/Si-O-C负极材料具有更高的可逆容量和库伦效率。可逆容量受到裂解温度的影响，但是二者不存在线性关系。
以聚硅氧烷为硅源，以二乙烯基苯为碳源，在氢气气氛中，800~1000℃温度下制备了碳含量为26.3wt%~42.1wt%、硅含量为29.4wt%~40.3wt%的C/Si-O-C负极材料。该材料的可逆容量随着碳含量的增加显示出缓慢增长的趋势。
通过对C/Si-O-C材料原子比容量与元素组成关系的统计分析发现，当O/Si摩尔比为1~2，C/Si摩尔比为0.5~3.5时，C/Si-O-C材料的可逆容量与O/Si摩尔比没有线性关系；而随着C/Si摩尔比例的增加而显示出逐渐增加的趋势。
通过对仅含有Si、C或O等元素的负极材料的容量微分曲线的比较，分析了C/Si-O-C负极材料可逆容量的主要来源；采用硅核磁等技术分析了Si-O-C相中不同硅结构单元在嵌脱锂离子过程中结构的演变，研究了硅结构单元对锂离子的可逆性，统计了各种硅结构单元对可逆容量的贡献，为设计新型高容量Si-O-C材料奠定基础。
通过将C/Si-O-C负极材料同文献报道的无定形炭、无定形硅、无定形二氧化硅和无定形一氧化硅材料充放电过程中的容量微分曲线作分别比较，逆向推出C/Si-O-C负极材料的主要嵌锂平台对应的是Si-O-C玻璃相同锂离子的相互作用；Si-O-C玻璃相与无定形硅、无定形二氧化硅、无定形一氧化硅材料嵌锂机理不同。
利用29Si MAS NMR和XPS等手段，分析C/Si-O-C负极材料中的硅结构在嵌脱锂离子过程化学位移的可逆移动，证实了在Si-O-C玻璃相中所存在的五种硅化学结构单元中，对于锂离子的嵌脱过程可逆的化学结构单元为[SiO4]、[SiO3C]、Si2O2，而[SiOC3]单元是不可逆的，[SiC4]单元是惰性的；
利用溶胶凝胶法制备了一系列[SiO4]、[SiO3C]、[SiO2C2]结构单元占主体的C/Si-O-C负极材料。其中，[SiO4]单元占总重88wt%的C/Si-O-C负极材料循环20次以后的稳定容量为653mAh/g；[SiO4]和[SiO3C]单元占总重78wt%的C/Si-O-C负极材料的稳定容量898mAh/g；[SiO4]、[SiO3C]和[SiO2C2]单元占总重87wt%的C/Si-O-C负极材料的稳定容量为724mAh/g。证明[SiO4]、[SiO3C]、[SiO2C2]结构单元具有较高的储锂容量。
利用硅结构单元同锂离子反应的独立性建立了C/Si-O-C负极材料可逆容量与硅结构单元的统计模型。根据模型，按比容量大小排序，[SiO4]>[SiO3C]>[SiO2C2]>[SiOC3]。其中，[SiO4]和[SiO3C]单元的比容量是石墨的3倍以上。
为进一步提高Si-O-C负极的电化学性能，采用裂解聚甲基硅烷和溶胶凝胶法等两种方法制备出Si-O-C基体包覆纳米硅的Si/Si-O-C复合负极材料，系统考察了工艺条件对该材料循环性能及倍率性能的影响。
以聚甲基硅烷为先驱体，在还原性气氛中高温裂解制备了单质硅含量<5.7wt%的Si/Si-O-C负极材料。其在900~1000℃之间制备的Si/Si-O-C材料循环20次以后的稳定容量最高，分别为470、400mAh/g。
以聚硅氧烷为先驱体，通过在先驱体中引入3wt%~10wt%的纳米硅，利用溶胶凝胶的方法制备了富硅的Si/Si-O-C负极材料。先驱体中纳米硅含量为8wt%，裂解温度为1100℃，制备的Si/Si-O-C负极材料拥有最佳的电化学性能：首次脱锂容量为1371.6mAh/g，首次库伦效率为78%，循环30次以后依然保持了990mAh/g，容量保持率为72%。同时它还具有优异的倍率性能，以3C倍率放电时在循环30次以后的可逆容量为715.9mAh/g，库伦效率超过96%。
The lithium-ion battery, as a new type of green secondary power supply withadvantages such as high energy density, high power density and high operating voltage,has being developed rapidly. Nowadays, it has already become the main power of theportable electronic devices such as mobile phones, digital cameras and notebook PC.Great expectation is placed on it as the power source of electronic vehicles in future, topartially alleviate the dependence on fossil fuel. For fabricating the high-performancelithium-ion battery, it is crucial to increase the specific capacity of the anode materials.More specifically, the anode materials with a capacity more than800mAh/g arerequired to replace the commercial anode material, graphite (theoretical capacity of372mAh/g). Therefore much attention is paid to search for high-capacity anodematerials.
Si-O-C materials are one of the promising anode materials because they exhibithigh capacities and good cyclic performances. The thesis employed polysiloxane as theprecursor to prepare Si-O-C materials with different elemental distribution by apyrolytic polymer-to-ceramic conversion. The effect of preparation method andelemental distribution on their electrochemical performances was studied. Then mucheffort was devoted to the mechanism study of lithium storage in Si-O-C materials inorder to guide the design of high-capacity Si-O-C anode materials.
The thesis prepared Si-O-C materials with silicon content of30-47.9wt%andcarbon content of4.1-42.1wt%using polysiloxane by changing the pyrolysistemperature and atmosphere, with addition of divinylbenzene as the carbon source. Andthen, the effect of the preparation method on elemental distribution and electrochemicalperformances of the materials was studied. Finally, the relationship between thecapacity and elemental distribution was investigated.
Employing polysiloxane as the precursor, Si-O-C materials with carbon content of22.1-23.2wt%or14.1-15.1wt%were prepared under hydrogen or inert atmosphere,respectively. The C/Si-O-C materials prepared under hydrogen atmosphere exhibitlarger capacities and higher coulombic efficiency than those under Ar atmosphere. Thepyrolysis temperature affects the reversible capacity of C/Si-O-C materials, though thereversible capacity does not linearly increase with the increment of the pysolysistemperature.
Employing polysiloxane as the silicon source and divinylbenzene as the carbonsource, C/Si-O-C materials with Si content of29.4-40.3wt%and C content of26.3-42.1wt%were prepared at800-1000℃under hydrogen atmosphere. The reversible capacity gradually rises with the increment of carbon content. Among all theseC/Si-O-C materials, the sample with Si:30.4wt%and C:42.1wt%exhibit the largestcapacity of751mAh/g with coulombic efficiency larger than97.4%.
Based on all the C/Si-O-C samples prepared with different preparation methods,the relationship between the reversible capacity and elemental content was studied. It isfound that, when O/Si mol ratio is among1-2and C/Si ratio is between0.5and3.5, thereversible capacity gradually increases with the increase of C/Si ratio, which does notlinearly increase with the increment of O/Si ratio.
The main electrochemically active site of C/Si-O-C materials was suggested, bycomparing the derivative curves of anode materials composed of Si, O, or C. Thestructure transformation and the lithium reversibility of silicon species in Si-O-C phasewere studied by29Si MAS NMR and XPS. Finally, the contribution of each siliconspecies to the reversible capacity of the whole materials was evaluated.
Si-O-C glass phase was proved to be the main source of lithium storage inC/Si-O-C materials, by comparing the derivative curves of anode materials composed ofSi, O, or C reported in the literature. The mechanism of lithium insertion in Si-O-Cphase is totally different from that of silicon, silicon dioxide and silicon monoxidematerials.
Of all the bonded silicon species of Si, C, and O in Si-O-C glass phase,[SiO4],[SiO3C],[SiO2C2] are confirmed to be reversible with lithium, with [SiOC3] irreversibleand [SiC4] inactive, by following the structure changes of silicon species during lithiuminsertion/distraction by29Si MAS NMR and XPS.
C/Si-O-C materials with [SiO4],[SiO3C], or [SiO2C2] units as the majorcomponent were prepared by a sol-gel method. The C/Si-O-C materials with88wt%of[SiO4] units can deliver a capacity of653mAh/g after20discharge/charge cycles. Thematerials with78wt%of [SiO4] and [SiO3C] units can offer a capacity of898mAh/g;and those with87wt%of [SiO4],[SiO3C] and [SiO2C2] units exhibit a capacity of725mAh/g. Herein, the large reversibility of [SiO4],[SiO3C], or [SiO2C2] is verified.
Based on the independence of the reactions between silicon species and lithium, astatistical model was established to express the relationship between the reversiblecapacity and silicon species distribution. According to the model, the order of reversiblecapacity is as follows:[SiO4]>[SiO3C]>[SiO2C2]>[SiOC3]. Furthermore, the capacityof [SiO4] and [SiO3C] units are3times larger than that of graphite.
In order to further increase the capacity, Si/Si-O-C materials with excess ofelemental silicon were prepared by simply pyrolyzing poly (methylsilane) or byutilizing a sol-gel method. The electrochemical performances of these Si/Si-O-C materials were studied.
Si/Si-O-C materials with excess silicon of <5.7wt%were prepared by pyrolyzingpoly(methylsilane) under hydrogen atmosphere. The materials formed at900℃,1000℃have a capacity of470mAh/g, and400mAh/g, respectively.
Si/Si-O-C materials were also synthesized by utilizing a sol-gel method, with3-10wt%of nano silicon in the precursor. The Si/Si-O-C materials prepared with8wt%ofnano silicon in the precursor at1100℃have the best electrochemical performances.They own a first delithiation capacity of1371.6mAh/g, with a first coulombic efficiencyof78%. After30repeated cycles, the materials still keep a capacity of990mAh/g, witha capacity retaining ratio of72%. Furthermore, the materials still bear good C-rateperformances. They can deliver a capacity of715.9mAh/g after30cycles at a3C rate.
本文选择高容量Si-O-C复合负极材料作为研究对象，采用先驱体转化法制备了具有不同组成和结构的Si-O-C负极材料，研究了制备工艺、元素组成对其电化学性能的影响，同时采用一系列的分析测试对Si-O-C负极材料在嵌脱锂离子过程中的结构变化进行了研究，并且制备了利用Si-O-C材料包覆纳米硅的新型Si/Si-O-C负极材料，为进一步改善Si-O-C材料的电化学性能奠定了良好的基础。
首先以聚硅氧烷为先驱体，通过裂解气氛、裂解温度、增加碳源等工艺条件的改变制备了碳含量为4.1wt%~42.1wt%、硅含量为30wt%~47.9wt%的C/Si-O-C负极材料，系统研究了工艺条件对材料组成结构及电化学性能的影响；在此基础上，系统研究了C/Si-O-C负极材料的可逆及不可逆容量与元素组成的关系。
以聚硅氧烷为先驱体，在还原性和惰性气氛中，800~1000℃温度下分别制备了碳含量为22.1wt%~23.2wt%和14.1wt%~15.1wt%的C/Si-O-C负极材料。还原性气氛中制备的C/Si-O-C负极材料具有更高的可逆容量和库伦效率。可逆容量受到裂解温度的影响，但是二者不存在线性关系。
以聚硅氧烷为硅源，以二乙烯基苯为碳源，在氢气气氛中，800~1000℃温度下制备了碳含量为26.3wt%~42.1wt%、硅含量为29.4wt%~40.3wt%的C/Si-O-C负极材料。该材料的可逆容量随着碳含量的增加显示出缓慢增长的趋势。
通过对C/Si-O-C材料原子比容量与元素组成关系的统计分析发现，当O/Si摩尔比为1~2，C/Si摩尔比为0.5~3.5时，C/Si-O-C材料的可逆容量与O/Si摩尔比没有线性关系；而随着C/Si摩尔比例的增加而显示出逐渐增加的趋势。
通过对仅含有Si、C或O等元素的负极材料的容量微分曲线的比较，分析了C/Si-O-C负极材料可逆容量的主要来源；采用硅核磁等技术分析了Si-O-C相中不同硅结构单元在嵌脱锂离子过程中结构的演变，研究了硅结构单元对锂离子的可逆性，统计了各种硅结构单元对可逆容量的贡献，为设计新型高容量Si-O-C材料奠定基础。
通过将C/Si-O-C负极材料同文献报道的无定形炭、无定形硅、无定形二氧化硅和无定形一氧化硅材料充放电过程中的容量微分曲线作分别比较，逆向推出C/Si-O-C负极材料的主要嵌锂平台对应的是Si-O-C玻璃相同锂离子的相互作用；Si-O-C玻璃相与无定形硅、无定形二氧化硅、无定形一氧化硅材料嵌锂机理不同。
利用29Si MAS NMR和XPS等手段，分析C/Si-O-C负极材料中的硅结构在嵌脱锂离子过程化学位移的可逆移动，证实了在Si-O-C玻璃相中所存在的五种硅化学结构单元中，对于锂离子的嵌脱过程可逆的化学结构单元为[SiO4]、[SiO3C]、Si2O2，而[SiOC3]单元是不可逆的，[SiC4]单元是惰性的；
利用溶胶凝胶法制备了一系列[SiO4]、[SiO3C]、[SiO2C2]结构单元占主体的C/Si-O-C负极材料。其中，[SiO4]单元占总重88wt%的C/Si-O-C负极材料循环20次以后的稳定容量为653mAh/g；[SiO4]和[SiO3C]单元占总重78wt%的C/Si-O-C负极材料的稳定容量898mAh/g；[SiO4]、[SiO3C]和[SiO2C2]单元占总重87wt%的C/Si-O-C负极材料的稳定容量为724mAh/g。证明[SiO4]、[SiO3C]、[SiO2C2]结构单元具有较高的储锂容量。
利用硅结构单元同锂离子反应的独立性建立了C/Si-O-C负极材料可逆容量与硅结构单元的统计模型。根据模型，按比容量大小排序，[SiO4]>[SiO3C]>[SiO2C2]>[SiOC3]。其中，[SiO4]和[SiO3C]单元的比容量是石墨的3倍以上。
为进一步提高Si-O-C负极的电化学性能，采用裂解聚甲基硅烷和溶胶凝胶法等两种方法制备出Si-O-C基体包覆纳米硅的Si/Si-O-C复合负极材料，系统考察了工艺条件对该材料循环性能及倍率性能的影响。
以聚甲基硅烷为先驱体，在还原性气氛中高温裂解制备了单质硅含量<5.7wt%的Si/Si-O-C负极材料。其在900~1000℃之间制备的Si/Si-O-C材料循环20次以后的稳定容量最高，分别为470、400mAh/g。
以聚硅氧烷为先驱体，通过在先驱体中引入3wt%~10wt%的纳米硅，利用溶胶凝胶的方法制备了富硅的Si/Si-O-C负极材料。先驱体中纳米硅含量为8wt%，裂解温度为1100℃，制备的Si/Si-O-C负极材料拥有最佳的电化学性能：首次脱锂容量为1371.6mAh/g，首次库伦效率为78%，循环30次以后依然保持了990mAh/g，容量保持率为72%。同时它还具有优异的倍率性能，以3C倍率放电时在循环30次以后的可逆容量为715.9mAh/g，库伦效率超过96%。
The lithium-ion battery, as a new type of green secondary power supply withadvantages such as high energy density, high power density and high operating voltage,has being developed rapidly. Nowadays, it has already become the main power of theportable electronic devices such as mobile phones, digital cameras and notebook PC.Great expectation is placed on it as the power source of electronic vehicles in future, topartially alleviate the dependence on fossil fuel. For fabricating the high-performancelithium-ion battery, it is crucial to increase the specific capacity of the anode materials.More specifically, the anode materials with a capacity more than800mAh/g arerequired to replace the commercial anode material, graphite (theoretical capacity of372mAh/g). Therefore much attention is paid to search for high-capacity anodematerials.
Si-O-C materials are one of the promising anode materials because they exhibithigh capacities and good cyclic performances. The thesis employed polysiloxane as theprecursor to prepare Si-O-C materials with different elemental distribution by apyrolytic polymer-to-ceramic conversion. The effect of preparation method andelemental distribution on their electrochemical performances was studied. Then mucheffort was devoted to the mechanism study of lithium storage in Si-O-C materials inorder to guide the design of high-capacity Si-O-C anode materials.
The thesis prepared Si-O-C materials with silicon content of30-47.9wt%andcarbon content of4.1-42.1wt%using polysiloxane by changing the pyrolysistemperature and atmosphere, with addition of divinylbenzene as the carbon source. Andthen, the effect of the preparation method on elemental distribution and electrochemicalperformances of the materials was studied. Finally, the relationship between thecapacity and elemental distribution was investigated.
Employing polysiloxane as the precursor, Si-O-C materials with carbon content of22.1-23.2wt%or14.1-15.1wt%were prepared under hydrogen or inert atmosphere,respectively. The C/Si-O-C materials prepared under hydrogen atmosphere exhibitlarger capacities and higher coulombic efficiency than those under Ar atmosphere. Thepyrolysis temperature affects the reversible capacity of C/Si-O-C materials, though thereversible capacity does not linearly increase with the increment of the pysolysistemperature.
Employing polysiloxane as the silicon source and divinylbenzene as the carbonsource, C/Si-O-C materials with Si content of29.4-40.3wt%and C content of26.3-42.1wt%were prepared at800-1000℃under hydrogen atmosphere. The reversible capacity gradually rises with the increment of carbon content. Among all theseC/Si-O-C materials, the sample with Si:30.4wt%and C:42.1wt%exhibit the largestcapacity of751mAh/g with coulombic efficiency larger than97.4%.
Based on all the C/Si-O-C samples prepared with different preparation methods,the relationship between the reversible capacity and elemental content was studied. It isfound that, when O/Si mol ratio is among1-2and C/Si ratio is between0.5and3.5, thereversible capacity gradually increases with the increase of C/Si ratio, which does notlinearly increase with the increment of O/Si ratio.
The main electrochemically active site of C/Si-O-C materials was suggested, bycomparing the derivative curves of anode materials composed of Si, O, or C. Thestructure transformation and the lithium reversibility of silicon species in Si-O-C phasewere studied by29Si MAS NMR and XPS. Finally, the contribution of each siliconspecies to the reversible capacity of the whole materials was evaluated.
Si-O-C glass phase was proved to be the main source of lithium storage inC/Si-O-C materials, by comparing the derivative curves of anode materials composed ofSi, O, or C reported in the literature. The mechanism of lithium insertion in Si-O-Cphase is totally different from that of silicon, silicon dioxide and silicon monoxidematerials.
Of all the bonded silicon species of Si, C, and O in Si-O-C glass phase,[SiO4],[SiO3C],[SiO2C2] are confirmed to be reversible with lithium, with [SiOC3] irreversibleand [SiC4] inactive, by following the structure changes of silicon species during lithiuminsertion/distraction by29Si MAS NMR and XPS.
C/Si-O-C materials with [SiO4],[SiO3C], or [SiO2C2] units as the majorcomponent were prepared by a sol-gel method. The C/Si-O-C materials with88wt%of[SiO4] units can deliver a capacity of653mAh/g after20discharge/charge cycles. Thematerials with78wt%of [SiO4] and [SiO3C] units can offer a capacity of898mAh/g;and those with87wt%of [SiO4],[SiO3C] and [SiO2C2] units exhibit a capacity of725mAh/g. Herein, the large reversibility of [SiO4],[SiO3C], or [SiO2C2] is verified.
Based on the independence of the reactions between silicon species and lithium, astatistical model was established to express the relationship between the reversiblecapacity and silicon species distribution. According to the model, the order of reversiblecapacity is as follows:[SiO4]>[SiO3C]>[SiO2C2]>[SiOC3]. Furthermore, the capacityof [SiO4] and [SiO3C] units are3times larger than that of graphite.
In order to further increase the capacity, Si/Si-O-C materials with excess ofelemental silicon were prepared by simply pyrolyzing poly (methylsilane) or byutilizing a sol-gel method. The electrochemical performances of these Si/Si-O-C materials were studied.
Si/Si-O-C materials with excess silicon of <5.7wt%were prepared by pyrolyzingpoly(methylsilane) under hydrogen atmosphere. The materials formed at900℃,1000℃have a capacity of470mAh/g, and400mAh/g, respectively.
Si/Si-O-C materials were also synthesized by utilizing a sol-gel method, with3-10wt%of nano silicon in the precursor. The Si/Si-O-C materials prepared with8wt%ofnano silicon in the precursor at1100℃have the best electrochemical performances.They own a first delithiation capacity of1371.6mAh/g, with a first coulombic efficiencyof78%. After30repeated cycles, the materials still keep a capacity of990mAh/g, witha capacity retaining ratio of72%. Furthermore, the materials still bear good C-rateperformances. They can deliver a capacity of715.9mAh/g after30cycles at a3C rate.
引文
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