鋰離子混合超級電容器的材料制備及其研究
發(fā)布時間：2018-08-19 13:27
【摘要】：由于現(xiàn)代社會的便攜式電子設備發(fā)展的驅動,可再生能源的產品,以及對電氣或混合電動車輛的需求不斷增加,對具有高性能、低成本的環(huán)境友好的能量儲存設備的研究已經顯著地增加。超級電容器和鋰離子電池是目前公認的兩個最具有發(fā)展前景的能量儲存系統(tǒng)。因而在當今社會,對電能存儲裝置的設計制造時,將具有高功率密度的超級電容器(SC)和具有高能量密度的鋰離子電池(LIB)作為新型環(huán)保、低制造成本和高性能的兩種優(yōu)秀的能量存儲裝置的備選,以滿足現(xiàn)階段能量存儲高需求。LIB通�？梢源鎯Ω哌_150～200 Wh·kg~(-1)的能量,但是它們的低功率密度(低于100 W·kg~(-1))和較差的循環(huán)壽命常小于1000次循環(huán))限制了它的發(fā)展及應用,相反,超級電容器則可以提供高得多的功率密度(10kW.kg~(-1)),更長的循環(huán)壽命(超過1000個循環(huán))和快速充電-放電過程(大電流,約在幾秒鐘以內),但是其較低的能量密度一直是影響它實際應用的一個大問題。在追求更高的能量密度而不犧牲功率密度的情況下,超級電容器-電池混合能量存儲裝置,即鋰離子混合超級電容器,組合了電化學雙電層電容(EDLC)型正極電極與鋰離子電池型負極電極的混合型電容器便應運而生了。然而,在對鋰離子混合超級電容器的研究過程中依然存在很多的問題等待解決,各項性能也有待提高。本文旨在構建一個以石墨烯紙為正極材料的layer-by-layer形式的鋰離子混合超級電容器,即在扣式電池雙電極體系下構成的鋰離子混合超級電容器。第一個工作就是設計并制備石墨烯paper作為鋰離子混合電容器的正極材料。將石墨烯的三維多孔碳紙(Graphenepaper)作為正極材料,充分利用其高表面積(～800 m2·g~(-1))的特性。除此之外,將石墨烯paper作為正極材料,不同于傳統(tǒng)電極材料制備過程中需要加入super-p、PVDF等導電劑、粘結劑,這樣做的優(yōu)勢就在于在減少電極質量的同時也降低了制備電極材料的成本。第二個工作,我們通過二次水熱法和一種較為簡單的化學方法制備了比容量很高的MnCO_3@FGS和FeS_2@FGS來作為鋰離子混合電容器的負極材料。MnCO_3@FGS在100 mA.g~(-1)的電流密度下,能達到1360 mAh·g~(-1)的容量,并且從第二周開始衰減很少,在100個循環(huán)后還能保留912 mAh·g~(-1)的容量。在組裝成鋰離子混合超級電容器后,在能量密度達到36.2Wh·kg~(-1)時,功率密度能夠達到250W·kg~(-1)。我們還通過一種相對簡單的方法制備了不同碳含量的Fe_2O_3@FGS以及FeS_2@FGS,能夠控制氧化物或者硫化物的顆粒大小以及在石墨烯基上的分布,增大了整體材料的比表面積,增大了電極材料與電解液的接觸面積,提高了材料的利用效率,提高了材料的導電性和能量密度。FeS_2@FGS在電流密度為0.2 A·g~(-1)第一周能得到882 mAh·g~(-1)的比容量,并且在100次循環(huán)之后還能保留665 mAh·g~(-1)的容量。通過構建量子點與石墨烯的復合結構,大大增強了材料的電化學性能,應用于石墨烯paper組裝成鋰離子混合超級電容器,在能量密度達到34.6Wh·kg~(-1),功率密度達到250W·kg~(-1)。這些都顯示了MnCO_3@FGS和FeS_2@FGS作為鋰離子混合超級電容器負極的優(yōu)異性能。
[Abstract]:Driven by the development of portable electronic devices in modern society, renewable energy products and the increasing demand for electric or hybrid electric vehicles, research on environmentally friendly energy storage devices with high performance and low cost has increased significantly. Therefore, in today's society, supercapacitors (SC) with high power density and lithium-ion batteries (LIB) with high energy density are used as alternatives to two excellent energy storage devices with environmental protection, low manufacturing cost and high performance in order to meet the needs of today's society. LIBs can usually store up to 150-200 Wh.kg-1 of energy, but their low power density (less than 100 W.kg-1) and poor cycle life (often less than 1,000 cycles) limit their development and application. On the contrary, supercapacitors can provide much higher power density (10 kW.kg-1) and longer power density. Cycle life (more than 1,000 cycles) and rapid charge-discharge (high current, less than a few seconds), but its low energy density has always been a major problem affecting its practical application. Hybrid capacitors with sub-hybrid supercapacitors, which combines electrochemical double-layer capacitor (EDLC) cathode electrode with lithium-ion battery cathode electrode, have emerged as the times require. However, there are still many problems to be solved in the research of lithium-ion hybrid supercapacitors and their performances need to be improved. A layer-by-layer lithium-ion hybrid supercapacitor with graphene paper as cathode material, i.e. a lithium-ion hybrid supercapacitor with button-type battery double-electrode system, was developed. The first task was to design and prepare graphene paper as cathode material for lithium-ion hybrid capacitors. Graphenepaper is used as cathode material to make full use of its high surface area (~800m2 (-1)). In addition, graphene paper is used as cathode material, which is different from the traditional electrode material in the preparation process of super-p, PVDF and other conductive agents, binder, the advantage of this way is to reduce the quality of the electrode and also reduce the production. Second, we prepared MnCO_3@FGS and FeS_2@FGS with high specific capacity as anode materials for lithium-ion hybrid capacitors by secondary hydrothermal method and a simpler chemical method. MnCO_3@FGS can reach the capacity of 1360 mAh.g~(-1) at the current density of 100 mA.g~(-1) and from the second one. After assembling the lithium-ion hybrid supercapacitor, the power density can reach 250W.kg-1 at the energy density of 36.2Wh.kg-1. We also prepared Fe_2O_3@FGS and FeS_2@FGS with different carbon content by a relatively simple method. It can control the particle size of oxide or sulfide and its distribution on graphene, increase the specific surface area of the whole material, increase the contact area between electrode material and electrolyte, improve the material utilization efficiency, improve the conductivity and energy density of the material. The specific capacity of 882 mAh g (- 1) was obtained and 665 mAh G All these show the excellent performance of MnCO_3@FGS and FeS_2@FGS as anodes for lithium-ion hybrid supercapacitors.
【學位授予單位】：南京理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TM53
本文編號：2191792
[Abstract]:Driven by the development of portable electronic devices in modern society, renewable energy products and the increasing demand for electric or hybrid electric vehicles, research on environmentally friendly energy storage devices with high performance and low cost has increased significantly. Therefore, in today's society, supercapacitors (SC) with high power density and lithium-ion batteries (LIB) with high energy density are used as alternatives to two excellent energy storage devices with environmental protection, low manufacturing cost and high performance in order to meet the needs of today's society. LIBs can usually store up to 150-200 Wh.kg-1 of energy, but their low power density (less than 100 W.kg-1) and poor cycle life (often less than 1,000 cycles) limit their development and application. On the contrary, supercapacitors can provide much higher power density (10 kW.kg-1) and longer power density. Cycle life (more than 1,000 cycles) and rapid charge-discharge (high current, less than a few seconds), but its low energy density has always been a major problem affecting its practical application. Hybrid capacitors with sub-hybrid supercapacitors, which combines electrochemical double-layer capacitor (EDLC) cathode electrode with lithium-ion battery cathode electrode, have emerged as the times require. However, there are still many problems to be solved in the research of lithium-ion hybrid supercapacitors and their performances need to be improved. A layer-by-layer lithium-ion hybrid supercapacitor with graphene paper as cathode material, i.e. a lithium-ion hybrid supercapacitor with button-type battery double-electrode system, was developed. The first task was to design and prepare graphene paper as cathode material for lithium-ion hybrid capacitors. Graphenepaper is used as cathode material to make full use of its high surface area (~800m2 (-1)). In addition, graphene paper is used as cathode material, which is different from the traditional electrode material in the preparation process of super-p, PVDF and other conductive agents, binder, the advantage of this way is to reduce the quality of the electrode and also reduce the production. Second, we prepared MnCO_3@FGS and FeS_2@FGS with high specific capacity as anode materials for lithium-ion hybrid capacitors by secondary hydrothermal method and a simpler chemical method. MnCO_3@FGS can reach the capacity of 1360 mAh.g~(-1) at the current density of 100 mA.g~(-1) and from the second one. After assembling the lithium-ion hybrid supercapacitor, the power density can reach 250W.kg-1 at the energy density of 36.2Wh.kg-1. We also prepared Fe_2O_3@FGS and FeS_2@FGS with different carbon content by a relatively simple method. It can control the particle size of oxide or sulfide and its distribution on graphene, increase the specific surface area of the whole material, increase the contact area between electrode material and electrolyte, improve the material utilization efficiency, improve the conductivity and energy density of the material. The specific capacity of 882 mAh g (- 1) was obtained and 665 mAh G All these show the excellent performance of MnCO_3@FGS and FeS_2@FGS as anodes for lithium-ion hybrid supercapacitors.
【學位授予單位】：南京理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TM53
【參考文獻】
相關期刊論文 前2條
1 Delu Li;Yejun Zhang;Lun Li;Feng Hu;Hongchao Yang;Changhong Wang;Qiangbin Wang;;Polydopamine directed MnO@C microstructures as electrode for lithium ion battery[J];Science China(Chemistry);2016年01期
2 Jianfei Yu;Lin Zhu;Cheng Fan;Cheng Zan;Ling Hu;Shuhui Yang;Qiang Zhang;Wancheng Zhu;Lin Shi;Fei Wei;;Highly dispersed Mn_2O_3 microspheres:Facile solvothermal synthesis and their application as Li-ion battery anodes[J];Particuology;2015年05期
，本文編號：2191792
本文鏈接：http://sikaile.net/kejilunwen/dianlidianqilunwen/2191792.html
