發(fā)布時間：2018-06-20 06:49

  本文選題：無機(jī)復(fù)合材料 + 微孔分子篩��； 參考：《上海交通大學(xué)》2014年博士論文

【摘要】：無機(jī)復(fù)合材料是一類重要的功能材料，是由不同組分在微納尺度或者分子水平上復(fù)合或者組裝所形成的一類新材料。通過復(fù)合，各組分在性能互補(bǔ)的基礎(chǔ)上，可以產(chǎn)生協(xié)同效應(yīng)，從而賦予無機(jī)復(fù)合材料獨(dú)特的性質(zhì)。多孔和二維無機(jī)復(fù)合材料因其獨(dú)特的結(jié)構(gòu)特點(diǎn)，已廣泛的應(yīng)用于人類生活的各個領(lǐng)域，如石油加工、汽車和航空等工業(yè)領(lǐng)域。然而，隨著能源和環(huán)境問題日益突出，人們迫切需要開發(fā)具有更高性能的新型多孔和二維無機(jī)復(fù)合材料，比如在催化領(lǐng)域，開發(fā)新型汽車尾氣凈化催化劑，有效提高催化活性，降低貴金屬的消耗；在電化學(xué)儲鋰領(lǐng)域，開發(fā)出容量高、循環(huán)穩(wěn)定性好和倍率性能優(yōu)異的新型鋰離子電池材料，滿足電動汽車對高能量密度和高功率密度鋰離子電池的需求。因此，開發(fā)新型多孔和二維無機(jī)復(fù)合材料，探索其復(fù)合結(jié)構(gòu)以及協(xié)同作用對其應(yīng)用性能的影響，具有重要的理論和實(shí)際意義。本論文以功能為導(dǎo)向，設(shè)計合成了一系列具有獨(dú)特結(jié)構(gòu)和優(yōu)異性能的新型多孔和二維無機(jī)復(fù)合材料，探究了其復(fù)合結(jié)構(gòu)制備中的關(guān)鍵問題，考查了其電化學(xué)儲鋰和催化等性能，研究了復(fù)合結(jié)構(gòu)與性能之間關(guān)系。具體內(nèi)容包括： (1)貴金屬/微孔分子篩復(fù)合材料的制備及其催化性能研究 通過改進(jìn)浸漬法制備了貴金屬鉑與SAPO-44型磷酸硅鋁分子篩復(fù)合的無機(jī)材料(Pt/SAPO-44)，利用X射線吸收光譜、透射電鏡和程序升溫還原技術(shù)考察了分子篩負(fù)載貴金屬鉑的價態(tài)及尺寸，發(fā)現(xiàn)貴金屬鉑在空氣中以納米鉑簇的形式負(fù)載到SAPO-44分子篩上，鉑簇的粒徑在2-4nm之間。考察了Pt/SAPO-44復(fù)合材料在汽車尾氣凈化中的應(yīng)用，研究發(fā)現(xiàn)SAPO-44分子篩骨架表面Br nsted酸與鉑納米粒子之間存在強(qiáng)烈的協(xié)同催化作用，有效提高了催化劑的尾氣凈化性能，大大減少了貴金屬鉑的用量。 (2)新型graphene/MoS2異質(zhì)復(fù)合薄膜材料的制備及其電化學(xué)性能研究以氯化鉬與油酸鈉反應(yīng)生成的油酸鉬為碳源和鉬源，通過熱處理在硫酸鈉晶體表面合成了graphene/MoS2異質(zhì)復(fù)合薄膜材料，結(jié)構(gòu)表征發(fā)現(xiàn)，復(fù)合薄膜由硫化鉬層和石墨烯層復(fù)合而成，且表面平整、結(jié)構(gòu)均一、具有較大的表面積（160μm）。在合成過程中，硫酸鈉不僅提供硫源，，其晶體表面作為復(fù)合薄膜生長的基體。通過改變原料中氯化鉬與油酸鈉摩爾配比，可以調(diào)控復(fù)合薄膜中硫化鉬的層數(shù)。Graphene/MoS2復(fù)合薄膜材料表現(xiàn)出非常優(yōu)異的電化學(xué)儲鋰性能，在高電流密度充放電情況下，依然具有非常高的電池容量和非常突出的循環(huán)穩(wěn)定性。 (3)二氧化錫納米晶/碳復(fù)合薄膜材料的的制備及其電化學(xué)性能研究以硫酸鈉晶體為基體，油酸錫和氯化錫為碳源和錫源，通過一步熱處理合成了二氧化錫納米晶/碳復(fù)合薄膜材料。結(jié)構(gòu)表征發(fā)現(xiàn)，二氧化錫納米晶尺寸均一，平均晶粒直徑為2-3nm，均勻分散在石墨化的碳薄膜中。二氧化錫納米晶/碳復(fù)合薄膜材料表現(xiàn)出非常優(yōu)異的電化學(xué)儲鋰性能，在恒定電流密度0.5、1.0和10.0A g-1下循環(huán)50圈后，其可逆容量分別高達(dá)826、728和400mAhg-1。二氧化錫納米晶/碳復(fù)合薄膜材料的優(yōu)異電化學(xué)性能得益于其獨(dú)特的復(fù)合結(jié)構(gòu)。氧化錫納米晶，可以有效的縮短鋰離子的擴(kuò)散距離；石墨化的碳薄膜，不僅可以改善材料的導(dǎo)電性，還可以極大緩沖充放電過程中納米晶體積變化對復(fù)合薄膜材料結(jié)構(gòu)穩(wěn)定性的影響；此外，石墨化碳薄膜的有效包覆，可以避免電解液與氧化錫納米晶的直接接觸，防止電解液在高活性納米晶表面的分解等不利反應(yīng)，從而改善材料的循環(huán)穩(wěn)定性。
[Abstract]:Inorganic composite is a kind of important functional material, which is a kind of new material formed by the composite or assembly of different components at the microscale or molecular level. By composite, the synergistic effect can be produced on the basis of the performance complementation, which gives the unique properties of the inorganic compound material. Porous and two-dimensional inorganic compound. Because of its unique structural characteristics, materials have been widely used in various fields of human life, such as petroleum processing, automobile and aviation industries. However, with the increasingly prominent energy and environment problems, people urgently need to develop new porous and two-dimensional inorganic composite materials with higher performance, such as the development of new type of steam in the field of catalysis. The catalyst of vehicle exhaust purification can effectively improve the catalytic activity and reduce the consumption of precious metals. In the field of electrochemical lithium storage, a new type of lithium ion battery material with high capacity, good circulation stability and excellent multiplying performance is developed to meet the demand for high energy density and high power density lithium ion batteries for electric vehicles. In this paper, a series of new porous and two-dimensional inorganic complex materials with unique structures and excellent properties are designed and synthesized in this paper, and the key to the preparation of composite structures is explored. The electrochemical lithium storage and catalytic properties were investigated, and the relationship between the composite structure and properties was studied.
(1) preparation and catalytic properties of noble metal / microporous molecular sieve composites
Inorganic materials (Pt/SAPO-44) of noble metal platinum and SAPO-44 type Si Al molecular sieve were prepared by improved impregnation method. The valence state and size of noble metal platinum supported by molecular sieves were investigated by X ray absorption spectrum, transmission electron microscope and temperature programmed reduction technology. It was found that precious metal platinum was loaded to SAPO-4 in the form of nano platinum cluster in the air. On the 4 molecular sieve, the particle size of the platinum cluster is between 2-4nm. The application of Pt/SAPO-44 composite in the purification of automobile exhaust is investigated. It is found that there is a strong synergistic catalysis between Br nsted Acid and platinum nanoparticles on the skeleton surface of the SAPO-44 molecular sieve, which can effectively improve the purification performance of the catalyst, and greatly reduce the use of precious metal platinum. Quantity.
(2) the preparation and electrochemical properties of a new graphene/MoS2 heterostructure composite film material. Molybdenum oleate was produced by molybdenum chloride and sodium oleate as carbon source and molybdenum source. Graphene/MoS2 heterostructure composite film was synthesized by heat treatment on the surface of sodium sulfate crystal. The structure characterization found that the composite film was reproduced by molybdenum sulfide layer and graphene layer. In the process of synthesis, sodium sulfate not only provides sulfur source, but its crystal surface is the substrate for the growth of the composite film. By changing the molar ratio of molybdenum chloride to sodium oleate in the raw material, the layer number of molybdenum sulfide in the composite film can be controlled in the synthesis process, and the number of layers of.Graphene/MoS2 composite films in the compound film can be regulated in the synthesis process. The material exhibits excellent electrochemical lithium storage performance. Under the condition of high current density charge and discharge, it still has very high battery capacity and very prominent circulation stability.
(3) the preparation and electrochemical properties of two tin oxide nanocrystalline / carbon composite film materials, with sodium oleate as the matrix, tin oleate and tin chloride as carbon source and tin source, two Sn nanocrystalline / carbon composite films were synthesized by one step heat treatment. The structure characterization found that the size of two tin oxide nanocrystals was uniform, and the average grain diameter was found. 2-3nm, uniformly dispersed in graphitized carbon films, two tin oxide nanocrystalline / carbon composite films exhibit excellent electrochemical lithium storage properties. The reversible capacity is up to 826728 and 400mAhg-1. two tin nanocrystalline / carbon composite films, respectively, after a constant current density of 0.5,1.0 and 10.0A g-1. The chemical properties benefit from its unique composite structure. The tin oxide nanocrystals can effectively shorten the diffusion distance of the lithium ion. The graphitized carbon film can not only improve the conductivity of the material, but also greatly buffer the influence of the change of the volume of nanocrystalline on the structural stability of the composite film during the charge discharge process; in addition, graphite carbon The effective coating of the film can avoid the direct contact between the electrolyte and the nanocrystalline oxide, prevent the disadvantageous reaction of the electrolyte on the surface of the highly active nanocrystalline, and thus improve the cyclic stability of the material.
【學(xué)位授予單位】：上海交通大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2014
【分類號】：TB33;TM912

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本文編號：2043370