本文選題：銅集流體 + 鍺��； 參考：《哈爾濱工業(yè)大學(xué)》2015年碩士論文

【摘要】：Ge因?yàn)槠錁O高的比容量,被認(rèn)為是下一代極具前景的鋰離子電池負(fù)極材料。然而,由于Ge作為鋰離子電池負(fù)極材料時(shí)嚴(yán)重的體積膨脹(370%)容易造成Ge活性物質(zhì)的損失,使得Ge的比容量急劇下降,不利于電池容量的穩(wěn)定性保持,故設(shè)計(jì)出合理的Ge電極以減少Ge在充放電過(guò)程中的損失,成為國(guó)內(nèi)外科學(xué)家研究的重點(diǎn),也面臨著很大的挑戰(zhàn)。具有3D結(jié)構(gòu)的集流體可以為Ge活性物質(zhì)在充放電過(guò)程中的體積膨脹提供緩沖空間,防止Ge出現(xiàn)粉化脫落等優(yōu)點(diǎn)。因此本論文通過(guò)制備特殊形貌銅集流體,構(gòu)筑3D結(jié)構(gòu)銅集流體,在其上制備鍺電極材料,深入研究集流體的結(jié)構(gòu)對(duì)構(gòu)筑的電極材料電化學(xué)性能的影響。首先通過(guò)用電鍍法,制備出枝晶銅集流體,在此集流體上負(fù)載鍺薄膜,制備三維納米Cu/Ge電極,對(duì)其進(jìn)行SEM、XRD等分析測(cè)試,并以此Cu/Ge電極組裝電池測(cè)試其儲(chǔ)鋰性能,與商業(yè)用集流體進(jìn)行比較。結(jié)果表明,在C/10倍率下,首次充放電比容量分別為1171.3m Ah/g和1700.6m Ah/g,首次庫(kù)倫效率為68.88%,經(jīng)過(guò)100次循環(huán)后,充放電比容量為821.1m Ah/g與856.1m Ah/g,優(yōu)于商業(yè)用銅集流體材料,同時(shí)倍率性能與商業(yè)銅集流體相比,也得到了顯著提高。采用氫氣泡沫法制備了多孔銅集流體,研究多種因素,如電鍍時(shí)間、銅鹽濃度、電極間距對(duì)銅集流體孔形貌和結(jié)構(gòu)的影響,得到最佳的工藝參數(shù)。在多孔銅集流體上負(fù)載Ge薄膜,經(jīng)過(guò)高溫退火處理后,得到三維納米多孔Ge電極,該電極由于其良好的導(dǎo)電性、高比表面積和多孔結(jié)構(gòu),表現(xiàn)出良好的儲(chǔ)鋰性能。在C/10倍率下,首次充放電比容量分別為1351.6m Ah/g和1767.5m Ah/g,首次庫(kù)倫效率達(dá)到76.47%,100次循環(huán)后,放電比容量保持為1260m Ah/g,表現(xiàn)出優(yōu)異的循環(huán)穩(wěn)定性。同時(shí)在倍率為5C時(shí),比容量達(dá)到420.1m Ah/g,具備良好的高倍率性能。以離子液體電沉積方法制備棒狀銅集流體,通過(guò)研究沉積電位對(duì)銅集流體形貌的影響,制備出不同電位下的菜花狀銅集流體,并用離子液體電沉積法在銅集流體上負(fù)載鍺薄膜,設(shè)計(jì)了耐腐蝕性、穩(wěn)定性強(qiáng)的棒狀與菜花狀Cu/Ge電極。通過(guò)研究其充放電性能,得出棒狀集流體由于沒(méi)法為Ge在充放電過(guò)程中的體積膨脹提供緩沖空間而使得其比容量下降較快,而菜花狀集流體,在沉積電壓為-1.4V時(shí)得到的集流體,在C/10下,首次放電比容量為1776.8m Ah/g,經(jīng)過(guò)100次循環(huán)后,比容量依舊為655.6m Ah/g,表現(xiàn)出較好的循環(huán)穩(wěn)定性。
[Abstract]:GE is considered to be a promising cathode material for lithium ion batteries due to its high specific capacity.However, due to the serious volume expansion of GE as anode material for lithium-ion batteries, the loss of GE active substances is easy to be caused, and the specific capacity of GE decreases sharply, which is not conducive to the stability of the battery capacity.Therefore, the design of a reasonable GE electrode to reduce the loss of GE in charge and discharge process has become the focus of scientists at home and abroad, and is also facing a great challenge.The collector with 3D structure can provide buffer space for the volumetric expansion of GE active substances during charge and discharge, and prevent GE from being powdered off.Therefore, in this thesis, 3D structure copper collector was constructed by preparing copper collector with special morphology, on which germanium electrode materials were prepared, and the effect of collector structure on electrochemical properties of the electrode materials was studied in depth.Firstly, dendritic copper collector was prepared by electroplating method, on which germanium thin film was loaded. Three-dimensional nanocrystalline Cu/Ge electrode was prepared, and its lithium storage performance was tested by Cu/Ge electrode assembly battery.Compared with commercial fluid collection.The results show that at C / 10 ratio, the first charge-discharge capacity is 1171.3 Ah/g and 1700.6 m / g, respectively, and the first Coulomb efficiency is 68.88. After 100 cycles, the charge-discharge capacity is 821.1m Ah/g and 856.1 m / g, which is superior to that of commercial copper collector.At the same time, compared with commercial copper collector, the performance of the rate is also significantly improved.Porous copper was prepared by hydrogen foam method. The effects of various factors such as electroplating time, copper salt concentration and electrode spacing on the pore morphology and structure of copper collector were studied. The optimum process parameters were obtained.After high temperature annealing, three dimensional nano-porous GE electrode was obtained on porous copper collector. The electrode exhibits good lithium storage properties due to its good conductivity, high specific surface area and porous structure.At C / 10 ratio, the first charge / discharge specific capacity is 1351.6 m Ah/g and 1767.5 m / g, respectively. After the first Coulomb efficiency reaches 76.47m / 100 cycles, the discharge specific capacity remains 1260 m / g, showing excellent cycle stability.At the same time, the specific capacity is 420.1m Ah. / g when the ratio is 5C, and it has good performance of high rate.The rod copper collector was prepared by ionic liquid electrodeposition. By studying the effect of deposition potential on the morphology of copper collector, the cauliflower copper collector was prepared under different potentials. Germanium thin films were deposited on copper collector by ionic liquid electrodeposition.The rod and cauliflower Cu/Ge electrodes with strong corrosion resistance and stability were designed.By studying its charge-discharge performance, it is concluded that the specific capacity of the rod collector decreases faster because it can not provide buffer space for the volume expansion of GE during the charging and discharging process, while the cauliflower collector is obtained at the deposition voltage of -1.4 V.At C / 10, the specific capacity of the first discharge is 1776.8 m / g. After 100 cycles, the specific capacity is still 655.6 m / g, showing good cyclic stability.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TM912

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