【摘要】：將具有間歇性和不穩(wěn)定性特點(diǎn)的風(fēng)、光可再生能源與儲能系統(tǒng)配套使用是優(yōu)化能源結(jié)構(gòu)、緩解并網(wǎng)壓力,改善電力質(zhì)量的核心手段。甲基磺酸鉛液流電池以其結(jié)構(gòu)簡單、成本低廉、耐候性強(qiáng)及易再生循環(huán)等優(yōu)點(diǎn),而被認(rèn)為是有望成為萬次循環(huán)的長壽命周期和兆瓦級容量的電站式儲能系統(tǒng)。但甲基磺酸鉛液流電池充電過程中,因可溶性Pb2+優(yōu)先以枝晶形態(tài)于負(fù)極沉積,容易引發(fā)電池正負(fù)極短路,從而嚴(yán)重影響電池的儲電效率和使用壽命�；诖�,本文以1.0mol/LH+和0.7mol/LPb2+為電解液,通過向電解液中添加金屬離子添加劑(Sn2+)、有機(jī)添加劑十烷基三甲基氫氧化銨(HDTAH)來抑制電池負(fù)極枝晶生長和改善電池循環(huán)性能,利用LAND動力電池測試系統(tǒng)、循環(huán)伏安法(CV)、計時電流法(CA)、線性掃描(LSV)等電化學(xué)方法并結(jié)合掃描電子顯微鏡(SEM)、X射線衍射(XRD)、X射線光電子能譜(XPS )等表面檢測方法系統(tǒng)地探究添加劑對電池負(fù)極枝晶的抑制機(jī)理及其對儲電效率和循環(huán)壽命影響的規(guī)律,得到以下的研究結(jié)果:一、電解液添加劑為金屬離子Sn2+,添加濃度為0.8mmol/L～1.Ommol/L時,鉛在電池負(fù)極沉積較為平整,且鉛顆粒團(tuán)聚體之間緊湊致密,電池的平均放電容量提高。電解液中使用Sn2+添加劑抑制負(fù)極枝晶形態(tài)的作用機(jī)制:1)促進(jìn)鉛的電沉積,提高Pb/Pb2+電對的可逆性及Pb2+在電極表面的擴(kuò)散系數(shù);2)改變鉛的電結(jié)晶方式,由“三維瞬時成核”轉(zhuǎn)變?yōu)椤叭S連續(xù)成核”,使鉛的成核密度提高;3)使鉛和錫共沉積生成PbSn固溶體先于鉛在(111)面上的生長,從而抑制了負(fù)極鉛的枝晶形態(tài)。電解液中Sn2+的加入使電池的平均庫侖效率提高至約90%、平均能量效率提高至86.4%,電池的使用壽命提高216%。Sn2+的最佳添加量為 0.8mmol/L。二、電解液添加劑HDTAH,濃度為1.5mmol/L～2.5mmol/L時,改變電池負(fù)極的枝晶形態(tài),使鉛在負(fù)極沉積更加平整、致密,從而提高放電容量。電解液中添加HDTAH作用:1)吸附在電極表面,提高電池的陰極極化,可達(dá)到細(xì)化負(fù)極鉛晶粒的作用;2)可抑制鉛在負(fù)極表面的電沉積,但Pb/Pb2+電對可逆性有所提高;3) HDTAH吸附在鉛晶粒生長點(diǎn)上,改變鉛的生長方向;4)使鉛在負(fù)極上的以“三維瞬時成核”方式沉積,從而提高鉛的成核密度,但降低Pb2+在電極表面的擴(kuò)散系數(shù);(5)使電池的充放電效率提高至89%、平均能量效率約80%、循環(huán)壽命較未使用添加劑提高190%。HDTAH添加劑的最佳添加量為2.5mmol/L。
[Abstract]:It is the core means to optimize the energy structure, relieve the grid pressure and improve the power quality by combining the wind with the energy storage system with intermittent and unstable wind. Lead methanesulfonate flow battery is considered to be a power plant energy storage system with long life cycle and megawatt capacity due to its simple structure, low cost, strong weathering resistance and easy regeneration cycle. However, in the charging process of lead methanesulfonate battery, soluble Pb2 is preferentially deposited in the negative electrode in dendritic form, which can lead to the short circuit of the positive and negative electrode of the battery, which seriously affects the storage efficiency and service life of the battery. In this paper, 1.0mol/LH and 0.7mol/LPb2 were used as electrolyte, and metal ion additive (Sn2) was added to the electrolyte. The organic additive decyl trimethyl ammonium hydroxide (HDTAH) was used to inhibit the growth of negative dendrite and improve the cycle performance of the battery. The cyclic voltammetry (CV),) chronoamperometric method (CA),) was used to test the battery with LAND power battery test system. Linear scanning (LSV) and other electrochemical methods combined with scanning electron microscope (SEM), X ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and other surface detection methods are used to study the inhibition mechanism of additives on negative dendrite and its influence on storage efficiency and cycle life. The results are as follows: 1. The electrolyte additive is metal ion Sn2, and when the concentration of 0.8mmol/L~1.Ommol/L is added, the lead deposition in the negative electrode of the battery is relatively smooth, and the lead particles are compact and compact, and the average discharge capacity of the battery is increased. The mechanism of inhibition of negative dendritic morphology by Sn2 additive in electrolyte: 1) promoting the electrodeposition of lead, improving the reversibility of Pb/Pb2 pair and the diffusion coefficient of Pb2 on the electrode surface; 2) changing the electrocrystallization mode of lead from "three dimensional instantaneous nucleation" to "three dimensional continuous nucleation", so as to increase the nucleation density of lead; 3) PbSn solid solution was formed by co-deposition of lead and tin, which inhibited the dendritic morphology of negative lead. The addition of Sn2 in electrolyte increases the average Coulomb efficiency of the battery to about 90 and the average energy efficiency to 86.4. The optimum addition amount of 216%.Sn2 for increasing the life of the battery is 0.8 mmol / L. Secondly, when the concentration of electrolyte additive HDTAH, is 1.5mmol/L~2.5mmol/L, the dendrite morphology of the negative electrode of the battery is changed, which makes the deposition of lead in the negative electrode more smooth and dense, thus increasing the discharge capacity. The effect of adding HDTAH into electrolyte is as follows: 1) adsorbing on the electrode surface to improve cathode polarization of the battery, and 2) inhibiting the electrodeposition of lead on the surface of negative electrode, but improving the reversibility of Pb/Pb2; (3) HDTAH adsorbed on lead grain growth point to change the growth direction of lead, 4) lead was deposited on negative electrode in "three dimensional instantaneous nucleation" mode, thus increasing the nucleation density of lead, but decreasing the diffusion coefficient of Pb2 on the electrode surface; (5) the charge and discharge efficiency of the battery is increased to 89, and the average energy efficiency is about 80. The optimum addition amount of 190%.HDTAH additive is 2.5 mmol / L.
【學(xué)位授予單位】：西安理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TM912

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