本文選題：液流電池 + 泡沫炭復合涂層��； 參考：《西安理工大學》2017年碩士論文

【摘要】：分布式電站是新能源實現(xiàn)就地消納和長足發(fā)展的重要電力設施,其核心是開發(fā)大容量、高性能和低成本的儲能系統(tǒng)。依據(jù)溶液中Pb2+以固態(tài)PbO2和Pb形式儲電并可逆轉(zhuǎn)換的永久性,單液流無隔膜的廉價性,功率和容量分別通過電極對數(shù)和Pb2+濃度可調(diào)控的靈活性,H2O2可回收殘余儲電層并達到無污染的環(huán)保性,鉛酸液流電池引起分布式儲能電站領(lǐng)域的高度關(guān)注。但目前因使用的傳統(tǒng)石墨板和泡沫炭電極導電性較差、比表面積小和析氫過電位小等因素影響,電池表現(xiàn)出負極枝晶嚴重,儲能容量較小,充放電效率較低等不足�；诖�,本文以泡沫炭為基體進行化學鍍銅和電沉積鉛,系統(tǒng)研究泡沫炭復合涂層的制備工藝、機理和涂層相關(guān)性能;探索泡沫炭復合涂層電極較石墨板和泡沫炭所具有的優(yōu)良理化和結(jié)構(gòu)特性在鉛酸液流電池應用中對儲電沉積層和效率的影響及其提升電池容量的機理。研究表明:對泡沫炭基體前處理,化學鍍銅后電沉積鉛制備泡沫炭復合涂層。合理粗化基體增強與鍍銅層間的機械結(jié)合,施鍍中間銅層增強與鍍鉛層間的電化學結(jié)合�？刂苹瘜W鍍銅厚度3 ～4 μm和電沉積鉛電流密度20 mA/cm2及其他工藝參數(shù)可得到表表面平整和顆粒均勻的鍍層�；瘜W鍍銅機理遵循電化學混合電位理論,生長過程通過Cu胞的融合進行;電沉積鉛遵循電結(jié)晶理論,從電化學角度分析可分為欠電位沉積和過電位沉積。泡沫炭復合涂層理化特性方面:經(jīng)冷熱循環(huán)法定性檢測鍍層結(jié)合力良好,XRD分析鍍層無雜質(zhì)元素摻入。化學鍍銅層厚度3～4 μm時電極電導率高達1315.79 s/cm且電極載流量滿足30～40 mA/cm2的要求;復合高韌性銅/鉛涂層有效阻止預裂紋于薄弱骨架上集結(jié),其整體壓縮強度提高至0.5 MPa;經(jīng)循環(huán)伏安測試泡沫炭復合涂層電極具有較好的電極反應可逆性,并隨掃描速度和循環(huán)次數(shù)增加,電極反應可逆程度增強。結(jié)構(gòu)特性方面:孔隙率高達93.71%,表觀密度0.663 g/cm3體現(xiàn)其優(yōu)良的輕質(zhì)多孔特性;電極真實表面積為石墨板3～4倍。泡沫炭復合涂層負極上儲電Pb層的顆粒較石墨板和泡沫炭電極均勻細膩,且其表面多孔結(jié)構(gòu)有效分散電荷而不易枝狀結(jié)晶。所對正極上儲電Pb02層的顆粒結(jié)合緊湊或因電場均勻密集而影響正極羥基自由基OHads的分布。泡沫炭復合涂層負極因其表面理化特性和結(jié)構(gòu)特性而具有較小的電極反應極化過電位和歐姆分壓,使得電池充放電庫倫效率高達93%～95%,電壓效率89%～90%,能量效率83%～85%電極表面容量提高至50 nmAh/cm2時庫倫效率仍穩(wěn)定在96±0.5%,并且表現(xiàn)出極佳的快速充放電性能。
[Abstract]:Distributed power station is an important power facility for local absorption and rapid development of new energy. Its core is to develop large capacity, high performance and low cost energy storage system. According to the permanent storage and reversible conversion of Pb2 in solution in the form of solid PbO2 and Pb, the single flow without diaphragm is cheap. The power and capacity can be recovered from the residual storage layer by the logarithm of electrode and the flexibility of Pb2 concentration. Lead acid flow battery has attracted great attention in the field of distributed energy storage power plant. However, due to the poor conductivity, small specific surface area and low hydrogen evolution overpotential of traditional graphite plate and foamed carbon electrode, the battery shows negative dendrite, low energy storage capacity and low charge / discharge efficiency. Based on this, electroless copper plating and electrodeposition of lead were carried out on the base of foamed carbon, and the preparation process, mechanism and related properties of the coating were systematically studied. To explore the effect of the excellent physicochemical and structural properties of the composite coated electrode on the storage layer and efficiency of lead-acid liquid battery compared with graphite plate and foamed carbon and the mechanism of improving the battery capacity. The results showed that the carbon foam composite coating was prepared by electroless copper plating. The mechanical bonding between coarsening matrix and copper plating layer is reasonable, and the electrochemical bonding between copper plating layer and lead coating layer is also discussed. By controlling electroless copper plating thickness of 3 ~ 4 渭 m and electrodeposition current density of 20 mA/cm2 and other process parameters, a flat and uniform surface coating can be obtained. The electroless copper plating mechanism follows the electrochemical mixing potential theory, and the growth process is carried out by the fusion of Cu cells, and the electrodeposition of lead follows the electrocrystallization theory, which can be divided into underpotential deposition and overpotential deposition from the electrochemical point of view. The physicochemical properties of carbon foam composite coating were determined qualitatively by hot and cold cycle method. XRD analysis showed that there was no impurity element in the coating. When the thickness of electroless copper coating is 3 ~ 4 渭 m, the conductivity of the electrode is up to 1315.79 s/cm and the electrode current meets the requirement of 30 ~ 40 mA/cm2, and the composite high toughness copper / lead coating can effectively prevent the pre-crack from accumulating on the weak skeleton. The overall compressive strength of the electrode was increased to 0.5 MPA, and the electrode reaction reversibility was tested by cyclic voltammetry, and the reversible degree of electrode reaction increased with the increase of scanning speed and cycle times. The porosity is 93.71, the apparent density is 0.663 g/cm3, and the real surface area of the electrode is 3 ~ 4 times that of graphite plate. The particles of Pb layer on the negative electrode of carbon foam composite coating are more uniform and fine than those of graphite plate and foamed carbon electrode, and the porous structure of the surface is effective in dispersing charge but not in dendritic crystallization. The particle binding of the Pb02 layer on the positive electrode is compact or the distribution of the hydroxyl radical OHads is affected by the uniform and dense electric field. Because of the physical and chemical properties and structural characteristics of carbon foam composite coating, the electrode reaction polarization overpotential and ohmic partial pressure are smaller. The charge / discharge Coulomb efficiency of the battery is as high as 933 / 95, the voltage efficiency is 8990 / 90, and the energy efficiency of 830.85% electrode surface is increased to 50 nmAh/cm2, the Coulomb efficiency is still stable at 96 鹵0.5, and it shows excellent rapid charge and discharge performance.
【學位授予單位】：西安理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TM912

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