本文選題：釩氧化物 + 微納米結(jié)構(gòu)��； 參考：《大連理工大學(xué)》2016年博士論文

【摘要】：微納米釩氧化物因其多變的價(jià)態(tài)、可調(diào)的微觀結(jié)構(gòu)及特殊的電學(xué)性質(zhì)在電極材料、氣敏及開(kāi)關(guān)材料等方面展現(xiàn)出潛在應(yīng)用價(jià)值,已成為國(guó)內(nèi)外研究熱點(diǎn)。本文針對(duì)當(dāng)前廣泛關(guān)注的釩氧化物微納米結(jié)構(gòu)調(diào)控方法學(xué)及結(jié)構(gòu)與性能關(guān)系開(kāi)展研究,旨在獲得可批量化定向制備不同微納米結(jié)構(gòu)釩氧化物的新方法,研究解決其結(jié)構(gòu)對(duì)鋰電等性能控制關(guān)系問(wèn)題,為將微納米釩氧化物推向應(yīng)用提供技術(shù)和理論支撐�；谶@一指導(dǎo)思想,本文跳出前人水熱法等調(diào)控釩氧化物微納米結(jié)構(gòu)的傳統(tǒng)方式,提出一種基于直接沉淀和前驅(qū)體結(jié)構(gòu)調(diào)控獲得相應(yīng)微納米結(jié)構(gòu)釩氧化物的新思路：首先用簡(jiǎn)單的直接沉淀法獲得結(jié)構(gòu)可控的釩氧化物前驅(qū)體-釩酸銨,再利用在不同條件下熱處理時(shí)材料微結(jié)構(gòu)的演化得到與前驅(qū)體骨架結(jié)構(gòu)相同的釩氧化物,并詳細(xì)研究所獲得產(chǎn)物作為鋰電池材料的正極性能,同時(shí)探討了微納米結(jié)構(gòu)與性能之間相互關(guān)系規(guī)律。具體研究?jī)?nèi)容如下：(1)直接沉淀法控制合成不同微納米結(jié)構(gòu)釩酸銨前驅(qū)體。論文研究了V205與熔融尿素固液反應(yīng),并以此反應(yīng)產(chǎn)物為原料,基于釩酸鹽結(jié)構(gòu)多變的特點(diǎn),選擇醇水混合溶劑體系,以氨水作為沉淀劑控制合成了微球與花狀結(jié)構(gòu)釩酸銨前驅(qū)體。研究醇水比例和陳化時(shí)間等因素對(duì)釩酸銨前驅(qū)體形貌及結(jié)構(gòu)的影響。結(jié)果表明：隨著醇水比的增加會(huì)導(dǎo)致制得釩酸銨微球的粒徑逐漸減��；醇水比提高能阻止組成花狀(NH4)2V3O8的納米片進(jìn)-步長(zhǎng)厚；因而在高醇水比時(shí),陳化時(shí)間的增加會(huì)促使形成花瓣密集堆積的花狀結(jié)構(gòu),而醇水比低時(shí),則會(huì)隨著晶體生長(zhǎng)形成較厚的塊狀結(jié)構(gòu)。(2)釩酸銨鹽前驅(qū)體對(duì)其相應(yīng)釩氧化物微納米結(jié)構(gòu)的影響與控制關(guān)系。以直接沉淀法制得的不同微納米結(jié)構(gòu)釩酸銨前驅(qū)體為研究對(duì)象,基于氧化還原及熱分解反應(yīng)的熱力學(xué)定律,研究了熱處理氣氛和溫度等因素對(duì)前驅(qū)物形成釩氧化物的價(jià)態(tài)和微納米結(jié)構(gòu)的影響：結(jié)果發(fā)現(xiàn),在氨氣氣氛下熱處理釩酸銨微球以及花狀結(jié)構(gòu)(NH4)2V3O8能分別制得V203空心微球和花狀多級(jí)結(jié)構(gòu)的V203；氮?dú)鈿夥障聼崽幚礅C酸銨微球和花狀(NH4) 2V3O8則能分別得到V02多孔微球以及花狀的V02；空氣氣氛下煅燒這些低價(jià)態(tài)釩氧化物可以獲得相應(yīng)微納米結(jié)構(gòu)V205。(3)微納米結(jié)構(gòu)V02及W摻雜V02對(duì)相變性質(zhì)以及鋰電池性能影響關(guān)系研究。研究了多孔微球和花狀VO2與摻雜VO2的相變性質(zhì)以及作為鋰電池正極材料的性能。結(jié)果表明其中多孔微球V02(B)具有較高的充放電比容量(140mAh·g-1),且同時(shí)具有最穩(wěn)定循環(huán)性能,充放電循環(huán)100次后的容量保持率為87%；而W摻雜或Na、W共摻雜V02雖能降低相變溫和內(nèi)阻,一定程度上改善了VO2(M/R)鋰離子可逆插入能力,但是相比于V02(B)和V205的性能還有一定差距。實(shí)驗(yàn)探討分析了相關(guān)機(jī)理,認(rèn)為V02(B)轉(zhuǎn)變?yōu)榻鸺t石相(R)和單斜相(M),導(dǎo)致可逆儲(chǔ)存鋰離子能力大幅降低。研究不同熱處理溫度對(duì)于摻雜VO2相變性質(zhì)的影響,結(jié)果表明經(jīng)過(guò)適當(dāng)高溫?zé)崽幚砗?可以提高摻雜VO2在室溫或更低溫度時(shí)相變的溫敏性,使其在熱敏電阻開(kāi)關(guān)方面展現(xiàn)潛在應(yīng)用。(4)不同微納米結(jié)構(gòu)V2O5鋰電池性能研究。研究了上述獲得的不同微納米結(jié)構(gòu)V2O5(包括納米棒、空心微球、多孔微球、花狀以及花狀多級(jí)結(jié)構(gòu)等)作為鋰電池正極材料時(shí)的鋰電池性能。結(jié)果表明,這些微納米結(jié)構(gòu)的V2O5均表現(xiàn)出了比上述VO2或商業(yè)V2O5更高的充放電比容量等鋰電池性能；其中花狀多級(jí)結(jié)構(gòu)V2O5展現(xiàn)出了最高的充放電比容量286 mAh·g-1(接近理論值294 mAh·g-1),而空心微球則具有最穩(wěn)定循環(huán)性能,充放電循環(huán)100次后的可逆放電比容量仍可達(dá)210 mAh·g-1,容量保持率為78%。
[Abstract]:Micro nano vanadium oxide has been a research hotspot at home and abroad because of its changeable valence state, adjustable microstructure and special electrical properties in electrode materials, gas sensing and switching materials. This paper has been concerned with the relationship between structure and properties of vanadium oxide micro nanostructures. The aim of this study is to obtain a new method for batch oriented preparation of vanadium oxides with different micro nanostructures, to study the relationship between the structure and control of lithium, so as to provide technical and theoretical support for the application of micro nano vanadium oxide to the application. Based on this guiding ideology, this paper leapt out of the previous hydrothermal method and other regulation of vanadium oxide micro nanorips. A new way of obtaining the corresponding micro nanostructure vanadium oxide based on the direct precipitation and precursor structure regulation is proposed in the traditional way. First, a simple direct precipitation method is used to obtain the structure controlled vanadium oxide precursor, ammonium vanadate, and then the microstructure evolution of the material is obtained with the precursor bone during the heat treatment under different conditions. The vanadium oxide with the same structure was studied, and the positive properties of the products were studied in detail. The relationship between the microstructure and properties of the micro nanostructures was discussed. The specific contents were as follows: (1) the direct precipitation method was used to control the synthesis of the precursor of ammonium vanadate with different micro and nanoscale structures. The solid liquid of V205 and molten urea was studied in this paper. The reaction product was used as the raw material. Based on the characteristics of the vanadate structure, the mixture of alcohol and water was selected and the ammonia water was used as the precipitator to control the synthesis of the microspheres and the flower like structure of ammonium vanadate precursor. The effects of the proportion of alcohol and water and the aging time on the shape and structure of the precursor of ammonium vanadate were studied. The results showed that with alcohol, with alcohol The increase of water ratio will lead to a gradual decrease in the size of the prepared ammonium vanadate microspheres, and the increase in the ratio of alcohol and water to the thickness of the nanoscale nanoscale (NH4) 2V3O8, and the increase of the aging time in the high alcohol water ratio will lead to the formation of a flower like structure with densely stacked petals, and the thicker blocks will be formed with the crystal growth when the ratio of alcohol and water is low. (2) the influence of ammonium vanadate precursor on its corresponding vanadium oxide micro nanostructure and its control relationship. The precursor of ammonium vanadate, a different micro nano structure obtained by direct precipitation method, was studied. Based on the thermodynamic law of redox and thermal decomposition reaction, the heat treatment atmosphere and temperature were studied to form vanadium in the precursor. The valence state of oxide and the influence of micro and nano structure: the results show that the V203 hollow microspheres and the flower like multistage structure V203 can be obtained by heat treatment of ammonium vanadate microspheres and flower like structure (NH4) in ammonia atmosphere. In nitrogen atmosphere heat treated ammonium vanadate microspheres and flower like (NH4) 2V3O8 can get V02 porous microspheres and flower shape respectively. The effect of V205. (3) micro nanostructure V02 and W doped V02 on the phase transition properties and the performance of lithium battery can be obtained by calcining these low valence vanadium oxides in air atmosphere. The phase transition properties of porous microspheres and flower like VO2 and doped VO2 are studied. The results show that the properties of the doped VO2 are as the cathode material for lithium batteries. The porous microsphere V02 (B) has a high charge discharge ratio (140mAh. G-1), and has the most stable cycle performance at the same time, and the capacity retention rate is 87% after 100 times of charge discharge cycle. While W doping or Na, W Co doped V02 can reduce the phase transition mild resistance and improve the reversible insertion ability of VO2 (M/R) lithium ion to a certain extent, but compared to V02 (B). There is still a gap between the performance of V205 and the performance of V02 (B). It is considered that the conversion of V02 (B) to rutile phase (R) and Dan Xiexiang (M) leads to a significant reduction in the ability of reversible storage of lithium ion. The temperature sensitivity of phase transition at room temperature or lower temperature makes it potential applications in the field of thermistor switch. (4) study on the performance of different micro nano structure V2O5 lithium batteries. The different micro nano structure V2O5 (including nanorods, hollow microspheres, porous microspheres, flower like, multistage structure, etc.) as cathode material for lithium battery is studied. The results show that the V2O5 of these micro and nanoscale structures show higher charge discharge ratio than the above VO2 or commercial V2O5, and the flower like multistage structure V2O5 shows the highest charge discharge ratio of 286 mAh. G-1 (close to the theoretical value of 294 mAh. G-1), and the hollow microspheres have the most stable cycle. The reversible discharge specific capacity of the charge and discharge cycle after 100 cycles can still reach 210 mAh? G-1, and the capacity retention rate is 78%.
【學(xué)位授予單位】：大連理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類(lèi)號(hào)】：TQ135.11;TM912

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