本文選題：金屬有機(jī)框架 + 多孔碳骨架�。� 參考：《西南大學(xué)》2017年碩士論文

【摘要】：鋰硒電池是繼鋰硫電池之后的一種新型高能量密度電池體系,極具發(fā)展前景。與鋰硫電池一樣,容量衰減迅速、庫(kù)倫效率低也是阻礙鋰硒電池實(shí)現(xiàn)產(chǎn)業(yè)化的關(guān)鍵問(wèn)題,因此對(duì)鋰硒電池的研究重點(diǎn)和熱點(diǎn)主要集中在探索具有高導(dǎo)電性、高比表面積、適宜孔結(jié)構(gòu)及孔尺寸的多孔碳骨架,與硒復(fù)合后得到比能量高、循環(huán)性能優(yōu)異的硒基正極材料,以此提高硒正極的電化學(xué)活性和循環(huán)穩(wěn)定性,使硒負(fù)載量和硒利用率協(xié)同作用并達(dá)到最大值,這對(duì)于高能量密度鋰硒電池的發(fā)展具有重要的理論意義及實(shí)用價(jià)值。本文以金屬有機(jī)框架材料為研究對(duì)象,將其作為多孔碳骨架的前驅(qū)體,成功制備了三種比表面積理想、孔徑適宜的多孔金屬有機(jī)框架,分別為Ni2O(BDC)2、Ni3(BTC)2和Zn2ONi2O(BDC)2(BDC=對(duì)苯二甲酸,BTC=均苯三甲酸),通過(guò)高溫碳化進(jìn)一步改性得到三種電化學(xué)性能優(yōu)異的多孔碳骨架,進(jìn)而通過(guò)熔融-擴(kuò)散過(guò)程實(shí)現(xiàn)多孔碳骨架與活性物質(zhì)硒的高效復(fù)合,分別合成了硒/介孔碳復(fù)合正極材料(meso-C@Se),硒/空心分級(jí)多孔碳微球復(fù)合正極材料(MHPCS/Se)以及硒/分級(jí)多孔碳立方體復(fù)合電極材料(Se/CMCs),研究其物理化學(xué)和電化學(xué)性能,獲得結(jié)果如下:1.硒/介孔碳復(fù)合正極材料:以MOF-Ni為前驅(qū)體,利用一步碳化法得到具有介孔碳特性的基體,經(jīng)過(guò)熔融浸漬封裝硒后作為鋰硒電池的正極材料。熱重分析結(jié)果顯示硒高度均勻地分布在復(fù)合材料中,其質(zhì)量百分含量高達(dá)48%。電化學(xué)性能測(cè)試發(fā)現(xiàn),在3 C的高電流密度下,meso-C@Se初始放電比容量為599.7 mAh g-1,100次循環(huán)后仍保持有417 mAh g-1,庫(kù)侖效率一度高達(dá)99.9%,其優(yōu)異的電化學(xué)性能歸因于MOFs衍生碳骨架導(dǎo)電性能的提升和多孔通道結(jié)構(gòu)。2.硒/空心分級(jí)多孔碳微球復(fù)合正極材料(MHPCS/Se):采用溶劑熱法和高溫碳化過(guò)程成功制備了一種空心分級(jí)多孔碳微球(MHPCS),研究顯示MHPCS既具有介孔結(jié)構(gòu)又存在大量微孔結(jié)構(gòu),微米碳球由彼此緊密堆積的半徑約20 nm、厚度約5 nm的納米碳空心氣泡組成。MHPCS/Se復(fù)合材料作為L(zhǎng)i-Se電池正極,在0.5 C的電流密度下提供高達(dá)588.2 mAh g-1的初始比容量,在500次循環(huán)過(guò)程中表現(xiàn)出突出的循環(huán)穩(wěn)定性,其衰減速率低至0.08%,即使在1C電流密度下循環(huán)1000次后依然能夠保持大于200 mAh g-1的比容量。改善的電化學(xué)性能應(yīng)該歸功于MHPCS的分級(jí)多孔結(jié)構(gòu),介孔有利于硒的大量浸入及離子傳輸,而微孔有利于固定硒,使其不會(huì)在充放電過(guò)程中由于體積膨脹而溶解流失。3.硒/分級(jí)多孔碳立方體復(fù)合電極材料(Se/CMCs):選取雙金屬離子(Ni2+,Zn2+)作為中心,溶劑熱反應(yīng)得到Zn/Ni-MOF-2立方塊,氬氣中高溫煅燒后CMCs高度保持了前驅(qū)體的立方體形貌特征。CMCs具有分級(jí)多孔結(jié)構(gòu),比表面積高達(dá)1013.6 m2 g-1,這使得Se負(fù)載量高達(dá)50 wt%。在碳酸鹽基電解質(zhì)中,Se/CMCs復(fù)合材料表現(xiàn)出超高的初始放電比容量及循環(huán)可逆容量。值得一提的是,CMCs多孔結(jié)構(gòu)有效地緩解了體積膨脹效應(yīng),同時(shí)因其具有優(yōu)異的導(dǎo)電性,能有效降低電荷轉(zhuǎn)移電阻并抑制碳酸鹽基電解液中多硒化物的溶解,從而使硒基正極的電化學(xué)性能得到顯著改善。綜上所述,我們以金屬有機(jī)框架材料為前驅(qū)體構(gòu)建了多種分級(jí)多孔碳骨架,對(duì)活性物質(zhì)硒具有較好的負(fù)載和固定作用,可以用于改善鋰硒電池存在的“穿梭效應(yīng)”和體積膨脹問(wèn)題,為鋰硒電池高容量正極復(fù)合材料的制備提供了新的思路。
[Abstract]:Lithium selenium battery is a new type of high energy density battery system after lithium sulfur battery. It has a great development prospect. As the lithium and sulfur battery, the capacity attenuation is rapid and the low efficiency of Kulun is the key problem that hinders the industrialization of lithium selenium battery. Therefore, the focus and focus of research on lithium selenium battery is to explore high conductivity and high performance. The specific surface area, porous carbon skeleton suitable for pore structure and pore size, and selenium based positive material with high specific energy and excellent cycling performance are obtained after combined with selenium, in order to improve the electrochemical activity and cyclic stability of the selenium positive pole, make the selenium load and selenium utilization synergistic and reach the maximum value, which is the development of the high energy density lithium selenium battery. It has important theoretical significance and practical value. In this paper, three kinds of porous metal organic frameworks with ideal specific surface area and suitable aperture are prepared by using metal organic frame materials as precursors of porous carbon skeleton, which are Ni2O (BDC) 2, Ni3 (BTC) 2 and Zn2ONi2O (BDC) 2 (BDC= terephthalic acid, BTC= mean three formic acid), respectively. Three porous carbon frameworks with excellent electrochemical properties were further modified by high temperature carbonization, and then the efficient recombination of the porous carbon skeleton and the active substance selenium was achieved through the melt diffusion process. The selenium / mesoporous carbon composite positive electrode (meso-C@Se), the selenium / hollow fractional porous carbon microsphere composite positive material (MHPCS/Se) and selenium / selenium were synthesized respectively. A graded porous carbon cube composite electrode material (Se/CMCs) was used to study its physicochemical and electrochemical properties. The results were as follows: 1. selenium / mesoporous carbon composite cathode material: using MOF-Ni as the precursor, the matrix with mesoporous carbon properties was obtained by one step carbonization, and after the melt impregnation and encapsulation of selenium as the cathode material for lithium selenium batteries. The results show that selenium is highly distributed in the composite. Its mass content is up to 48%. electrochemical performance test. At the high current density of 3 C, the initial discharge ratio of meso-C@Se is 417 mAh g-1 and the coulomb efficiency is as high as 99.9%, and its excellent electrochemical performance is attributed to MO. The conductivity of Fs derived carbon framework and the porous channel structure.2. selenium / hollow graded porous carbon microsphere composite positive material (MHPCS/Se): a hollow graded porous carbon microsphere (MHPCS) was successfully prepared by solvothermal method and high temperature carbonization. The study shows that MHPCS has both mesoporous structure and a large number of microporous structures, and the microsphere carbon spheres are composed of microspheres. The tightly packed radius of 20 nm, and the nano carbon hollow bubbles with a thickness of about 5 nm, made up of.MHPCS/Se composites as the positive pole of the Li-Se battery, provided the initial specific capacity of up to 588.2 mAh g-1 under the current density of 0.5 C, and showed a prominent cyclic stability during the 500 cycle process, and its attenuation rate was as low as 0.08%, even in the 1C current density. The specific capacity of more than 200 mAh g-1 can still be maintained after 1000 cycles. The improved electrochemical performance should be attributed to the hierarchical porous structure of MHPCS, which is beneficial to a large amount of immersion and ion transmission of selenium, and the micropores are beneficial to the fixation of selenium, so that it will not dissolve and lose.3. Se / graded porosity during the charge discharge process by volume expansion. Carbon cube composite electrode material (Se/CMCs): select the bimetallic ion (Ni2+, Zn2+) as the center, the solvent thermal reaction to get the Zn/Ni-MOF-2 cubic block. After the high temperature calcined in the argon, the CMCs height keeps the cube morphology of the precursor,.CMCs has a hierarchical porous structure, and the specific surface area is up to 1013.6 M2 g-1, which makes the Se load up to 50 wt%.. In the carbonate base electrolyte, the Se/CMCs composite exhibits high initial discharge specific capacity and reversible reversible capacity. It is worth mentioning that the porous structure of CMCs effectively alleviates the volume expansion effect and can effectively reduce the electric charge transfer resistance and inhibit the polyselenide in the carbonate base electrolyte because of its excellent conductivity. In conclusion, a variety of graded porous carbon frameworks have been constructed with metal organic frame materials as precursors, which have good load and fixed effect on active substance selenium, and can be used to improve the "shuttle effect" and volume expansion of lithium selenium batteries. The preparation of high capacity cathode composite materials for lithium selenide batteries provides a new way of thinking.

【學(xué)位授予單位】：西南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4;TM912

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