發(fā)布時(shí)間：2018-01-26 03:53

  本文關(guān)鍵詞： 能源存儲(chǔ)器件 三維復(fù)合電極 柔性 可穿著性線狀 納米材料 鋰離子電池 超級(jí)電容器 鎂離子電池　出處：《華中科技大學(xué)》2014年博士論文　論文類型：學(xué)位論文

【摘要】：未來電子器件的主要發(fā)展趨勢(shì)是柔性化、便攜化、微型化,這就需要新型的高性能能源存儲(chǔ)器件作為電源來驅(qū)動(dòng)它們。但是,現(xiàn)有的電池存在著諸多缺陷,例如：笨重、不可彎折、價(jià)格昂貴、功率/能量密度偏低、微型化和集成化較差等,阻礙了新一代電子器件的發(fā)展。針對(duì)以上問題,本論文的主要內(nèi)容是基于三維復(fù)合電極的新型能源存儲(chǔ)器件的創(chuàng)新性研究,主要涵蓋的工作有： (1)基于ZnCo2O4納米線陣列/碳布三維復(fù)合電極的柔性鋰離子電池：采用水熱法構(gòu)建出新穎的ZnCo2O4納米線陣列/碳布三維復(fù)合電極,并且對(duì)樣品的晶體結(jié)構(gòu)和形貌等進(jìn)行表征。進(jìn)一步將這種材料分別封裝于扣式和柔性鋰離子電池之中進(jìn)行各項(xiàng)電池器件測(cè)試。測(cè)試結(jié)果顯示：在長(zhǎng)達(dá)160次充放電循環(huán)中,該復(fù)合電極保持了較高的可逆比容量(1200～1340mAh-1),而且顯示出良好的倍率性能。這說明ZnCo2O4納米線材料的比容量遠(yuǎn)遠(yuǎn)高于現(xiàn)有的碳負(fù)極(372mAh g-1)。在反復(fù)彎折(120次)柔性電池的過程中,其比電容量未受到任何影響。為了驗(yàn)證柔性電池的實(shí)用性,我們已成功利用其驅(qū)動(dòng)了LED燈、手機(jī)顯示屏和掌上游戲機(jī),即使在柔性電池彎曲或折疊情況下,這些器件也能夠被其驅(qū)動(dòng)。 (2)基于ZnCo2O4海膽狀納米結(jié)構(gòu)/碳纖維三維復(fù)合電極的柔性鋰離子電池：基于工作(1),調(diào)節(jié)實(shí)驗(yàn)參數(shù),利用水熱條件合成ZnCo2O4海膽狀納米材料/碳纖維三維復(fù)合電極。封裝電池后進(jìn)行測(cè)試,結(jié)果顯示：在100次充放電循環(huán)之后,該電極的比容量依然能夠達(dá)到1180mAhg-1,反映出ZnCo2O4本身具有高比容量特性和優(yōu)良的循環(huán)穩(wěn)定性。在高達(dá)18Ag-1的電流密度下,經(jīng)過100次循環(huán),測(cè)得該電極的可逆比容量為750mAh g-1(為ZnCo2O4材料理論比容量的83.3%),優(yōu)于己報(bào)道的其他ZnCo2O4材料電極。實(shí)驗(yàn)結(jié)果表明,具有新穎三維結(jié)構(gòu)的ZnCo2O4/碳纖維復(fù)合電極呈現(xiàn)出明顯的電化學(xué)優(yōu)勢(shì),對(duì)于提高電池性能具有重要作用。而且,基于ZnCo2O4材料負(fù)極的柔性電池也保證了良好的電化學(xué)性能和不同彎曲狀態(tài)下的高穩(wěn)定性。此外,這些柔性電池可以隨意集成在衣物和旅行背包上,滿足未來電子器件便攜性和可穿著性的需求。 (3)基于Si納米線/碳布三維復(fù)合電極的柔性鋰離子電池：通過化學(xué)氣相沉積法制備出高純度的Si納米線,之后用簡(jiǎn)易的噴涂法將Si納米線溶液噴涂在高柔性的碳布上,制備成Si納米線/碳布三維復(fù)合電極。對(duì)這些樣品進(jìn)行晶體和形貌表征,分別將其封裝入扣式和柔性電池中進(jìn)行電池測(cè)試。該三維復(fù)合電極具有高的可逆比容量(2950mAhg-1),穩(wěn)定的循環(huán)性(長(zhǎng)達(dá)200次)和增強(qiáng)的倍率性。而且,基于Si納米線/／碳布三維復(fù)合電極的高柔性鋰離子電池在外界不同溫度、濕度和彎曲狀態(tài)下均保持其電壓和電容量的穩(wěn)定性。通過此三維復(fù)合電極構(gòu)建的柔性鋰離子電池的各項(xiàng)電池性能良好,這為采用高性能的Si材料替代當(dāng)前低容量的石墨負(fù)極材料提供了可行性。 (4)基于Mn2O3立方體陣列/碳線和ZnCo2O4納米線陣列/碳線三維復(fù)合電極的線狀超級(jí)電容器：采用水熱法合成出Mn2O3立方體陣列/碳線三維復(fù)合電極,并且對(duì)樣品進(jìn)行了晶體和形貌表征以及電容器性能測(cè)試。這些三維線狀復(fù)合電極首次被排列成直線型、曲線型和環(huán)型這三種線狀超級(jí)電容器模型,經(jīng)過5000次充放電,它們的電容量剩余率分別高達(dá)91%、93%和94%。實(shí)驗(yàn)數(shù)據(jù)顯示,環(huán)型線狀超級(jí)電容器電容量分別超出直線型線狀超級(jí)電容器和曲線型線狀超級(jí)電容器電容量的100%和83%。環(huán)型線狀超級(jí)電容器的性能最優(yōu)歸因于環(huán)形電極間產(chǎn)生的協(xié)同增強(qiáng)的電容性效應(yīng)。此外,該項(xiàng)工作闡明了不同電極長(zhǎng)度和間距對(duì)三種線狀超級(jí)電容器性能影響的研究。并我們首次引入了對(duì)這些線狀能源存儲(chǔ)器件的模擬計(jì)算,模擬結(jié)果與實(shí)驗(yàn)結(jié)論相一致。該項(xiàng)工作揭示出可以通過改變微型器件電極的集成方式來實(shí)現(xiàn)性能的最優(yōu)化以及器件尺寸小型化和功能最大化的目標(biāo)。此外,采用水熱法成功制備出ZnCo2O4納米線陣列/碳線三維復(fù)合電極,并將這些電極以平面集成的方式構(gòu)建出柔性線狀超級(jí)電容器。 (5)基于WSe2納米線/鎢箔三維復(fù)合電極的新型鎂離子電池：采用化學(xué)氣相沉積法制備出WSe2納米線/鎢箔三維復(fù)合電極,并且對(duì)樣品進(jìn)行晶體和形貌表征以及鎂離子電池性能測(cè)試。實(shí)驗(yàn)結(jié)果發(fā)現(xiàn)新型WSe2/鎢箔三維復(fù)合正極的比容量高達(dá)203mAhg-1,可以媲美鋰離子電池正極材料。在160次充放電循環(huán)中,鎂離子電池保持了非常好的穩(wěn)定性。在相對(duì)較高的電流密度(800mAg-1)下,電極的比容量依然可以達(dá)到142mAh g-1,電容量剩余率高達(dá)83.5%,顯示該三維復(fù)合電極具有高效的Mg2+嵌入脫出活性、良好的循環(huán)穩(wěn)定性、增強(qiáng)的電容量值和優(yōu)越的倍率性能。我們通過實(shí)驗(yàn)結(jié)果和計(jì)算模擬相結(jié)合的方式可以評(píng)估出WSe2的類石墨烯層狀結(jié)構(gòu)和三維復(fù)合電極的優(yōu)勢(shì)。本項(xiàng)工作證明了新穎的WSe2納米線/鎢箔三維復(fù)合物作為高性能鎂離子電池理想正極的可行性,這將會(huì)推動(dòng)替代性電池技術(shù)的進(jìn)一步發(fā)展。
[Abstract]:The main development trend of future electronic devices is flexible, portable and miniaturization, which requires high performance energy storage model as the power to drive them. However, the existing battery has many defects, such as heavy, can not be bent, expensive, power / energy density is low, miniaturization and the integration of the poor, hindered the development of a new generation of electronic devices. In view of the above problems, the main content of this paper is to study the innovation of new energy storage device based on 3D composite electrode, mainly covers the work:
(1) flexible lithium ion battery ZnCo2O4 nanowires / carbon composite electrode based on 3D cloth: construct the ZnCo2O4 nanowire array / novel three-dimensional carbon cloth composite electrodes by hydrothermal method, and the samples of the crystal structure and morphology were characterized. The materials were further encapsulated in the buckle type lithium ion and flexible the battery the battery device test. The test results show that after 160 charge discharge cycles, the composite electrode to maintain a high reversible capacity (1200 ~ 1340mAh-1), and showed good rate capability. This indicates that ZnCo2O4 nanowire material than the capacity is far higher than that of carbon anode current (372mAh g-1) in the repeated bending. (120) the process of flexible batteries, the specific capacitance is not affected in any way. In order to verify the practicability of flexible batteries, we have succeeded in using the drive LED lights, mobile phone screen And handheld games, even when flexible batteries are bent or folded, these devices can also be driven by them.
(2) flexible lithium ion battery ZnCo2O4 urchinlike nanostructures / three-dimensional carbon fiber composite electrode based on: (1) based on the work, adjusting the experimental parameters, the use of water and heat conditions of the synthesis of ZnCo2O4 urchinlike nano materials / three-dimensional carbon fiber composite electrodes. The package of the battery after the test, the results showed: after 100 charge discharge in this cycle, the specific capacity of the electrode can still reach 1180mAhg-1, reflecting the ZnCo2O4 itself has high specific capacity and excellent cycle stability. The current density of up to 18Ag-1, after 100 cycles, the reversible measured the specific capacity of the electrode is 750mAh g-1 (for the ZnCo2O4 material theoretical capacity of 83.3%), other ZnCo2O4 electrode materials is better than reported. The experimental results show that ZnCo2O4/ has a carbon fiber composite electrode exhibits a novel 3D structure of electrochemical advantages, plays an important role in improving the performance and battery. The flexible battery based on ZnCo2O4 negative electrode also ensures good electrochemical performance and high stability under different bending conditions. Besides, these flexible batteries can be integrated on clothing and travel backpacks freely to meet the needs of portability and wearability of future electronic devices.
(3) Si nano flexible lithium ion battery wire / carbon cloth 3D composite electrode based on Preparation of high purity Si nanowires by chemical vapor deposition, followed by simple spraying Si nanowires solution sprayed on the high flexible carbon cloth, preparation of Si nanowires / three-dimensional carbon cloth composite electrode. The crystal and morphology of these samples, respectively. The package into the buckle and a flexible battery battery test. The three-dimensional composite electrode has a high reversible capacity (2950mAhg-1), cyclic stability (up to 200) and enhanced rate. Moreover, based on the Si nanowires / carbon cloth / 3D composite electrode high flexible lithium ion battery under various temperature, keep the stability of the voltage and capacitance humidity and bending condition. The performance of the flexible battery lithium ion battery is constructed by the three-dimensional composite electrode is good, this is the high The available Si materials provide the possibility of replacing the current low capacity graphite negative electrode materials.
(4) Mn2O3 cube array / carbon line and ZnCo2O4 nanowire arrays / carbon composite electrode line 3D linear super capacitor based on synthesized Mn2O3 cube array / carbon line 3D composite electrode by hydrothermal method, and the samples were crystal and morphology characterization and performance of capacitor test. These three dimensional linear composite electrode for the first time are arranged in a linear curve, and ring the three line super capacitor model, after 5000 charge discharge capacity, their residual rates were as high as 91%, 93% and 94%., the experimental data show that the linear ring of super capacitor electric capacity exceeds the optimal performance of linear linear linear and curve type super capacitor the super capacitor capacitance of 100% 83%. and linear ring of super capacitor is attributed to the ring electrode generated synergistically enhanced capacitive effect. In addition, this work illustrates the different electrode length Study on the degree and distance on the three line super capacitor performance. And we introduce a simulation calculation for the linear energy storage device, the simulation results are consistent with the experimental results. This work reveals that can be integrated through changing the micro electrode device to achieve optimal performance and device size and the function of maximization. In addition, successfully prepared ZnCo2O4 nanowires / carbon 3D composite electrode by hydrothermal method, and the electrode to construct the integrated planar flexible linear capacitors.
(5) the new magnesium ion battery WSe2 nanowires / tungsten foil 3D composite electrode was prepared based on WSe2 nanowires / tungsten foil 3D composite electrode by chemical vapor deposition, and crystal morphology and characterization and properties of magnesium ion battery testing of samples. Experimental results show that the new WSe2/ 3D composite cathode than tungsten foil capacity up to 203mAhg-1, comparable with that of cathode materials for lithium ion batteries. In 160 cycles, magnesium ion battery maintains good stability. In a relatively high current density (800mAg-1), the specific capacity of the electrode can still reach 142mAh g-1, capacitance residual rate as high as 83.5%, showing the three-dimensional composite electrode with efficient Mg2+ insertion and extraction activity, good cycle stability, enhanced capacitance value and superior rate performance. Through experimental results and numerical simulation method can evaluate The advantages of WSe2 like graphene layered structure and three-dimensional composite electrode are proved. The work proves that the novel WSe2 nanowire / tungsten foil 3D composite is feasible for high-performance cathode of magnesium ion battery, which will further promote the further development of alternative battery technology.

【學(xué)位授予單位】：華中科技大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類號(hào)】：TM912

【共引文獻(xiàn)】

相關(guān)期刊論文 前10條

1 劉芯言;彭媒，

本文編號(hào)：1464596