本文關(guān)鍵詞： 鋅空氣燃料電池 衰減機(jī)理 空氣電極孔隙再生 鋅粒再生　出處：《清華大學(xué)》2015年博士論文　論文類型：學(xué)位論文

【摘要】：鋅空氣燃料電池(ZAFC)具有燃料存儲攜帶方便、成本低及安全無污染等優(yōu)點(diǎn),將其用作離網(wǎng)電源及汽車電源具有廣闊前景。開展ZAFC性能影響因素及性能衰減機(jī)理研究,是提升其功率密度和使用壽命的必要工作,可為科學(xué)設(shè)計(jì)及合理使用ZAFC提供重要依據(jù)。本文提出了一種ZAFC方案,以鋅顆粒為燃料,以Mn O2為催化劑。采用開放式陽極室以利于電池堆各節(jié)電池內(nèi)燃料和電解液的均勻分配,采用電解液循環(huán)將反應(yīng)產(chǎn)物從電池中攜帶出來,通過陽極室結(jié)構(gòu)優(yōu)化保障了反應(yīng)區(qū)有效面積,通過電極采電方案的優(yōu)化降低了電池內(nèi)阻。實(shí)驗(yàn)結(jié)果表明,燃料電池功率密度可達(dá)到435 mW/cm2,相當(dāng)于一般ZAFC性能的2倍以上;進(jìn)一步研究了電解液溫度、流量及氧氣分壓對電池性能的影響規(guī)律,優(yōu)化后ZAFC在供氣為空氣和純氧時(shí)功率密度分別達(dá)544 mW/cm2和899 mW/cm2,而且動(dòng)態(tài)響應(yīng)時(shí)間為毫秒級,無電壓超調(diào)現(xiàn)象。進(jìn)行了ZAFC性能衰減機(jī)理研究。建立ZAFC等效電路模型,進(jìn)行交流阻抗分析,得知ZAFC使用過程中的性能衰減在于空氣電極傳荷阻抗及傳質(zhì)阻抗的增大;通過SEM形貌及氣體滲透率分析,揭示出性能衰減機(jī)理為空氣電極的催化劑流失和疏水透氣層孔隙堵塞;通過停放實(shí)驗(yàn),發(fā)現(xiàn)干式停放時(shí)存在鋅粒結(jié)塊及陽極膨脹現(xiàn)象,濕式停放時(shí)電解液的腐蝕作用使空氣電極疏水性降低及孔隙結(jié)構(gòu)變化,并發(fā)現(xiàn)空氣電極兩側(cè)分別用電解液和去離子水浸沒時(shí)有水穿越空氣電極向電解液側(cè)遷移的現(xiàn)象,可用于重新再生空氣電極中被堵塞的孔隙。開發(fā)了包含控制單元的ZAFC系統(tǒng),通過多次啟停實(shí)驗(yàn)驗(yàn)證了該方案的可行性,并研究了鋅粒電解直接制備技術(shù),成功電解出致密的鋅顆粒。本文的創(chuàng)新性研究成果極大的提升了ZAFC的功率密度,揭示了ZAFC的性能影響因素及性能衰減機(jī)理,實(shí)現(xiàn)了空氣電極孔隙再生和鋅粒再生技術(shù),為ZAFC的科學(xué)設(shè)計(jì)提供了理論指導(dǎo),并為其商業(yè)化應(yīng)用提供了技術(shù)基礎(chǔ)。
[Abstract]:Zinc air fuel cell (ZAFC) with fuel storage and portability, low cost and no pollution, which is used as power supply and auto power off network has broad prospects. To carry out the study on the mechanism of attenuation performance and factors influence on the performance of ZAFC, is necessary to enhance its power density and service life, and can provide an important basis for the scientific design and reasonable use of ZAFC. This paper proposes a ZAFC scheme with zinc particles as fuel, with Mn O2 as catalyst. The open type anode chamber to each battery in the fuel cell stack and the uniform distribution of the electrolyte, electrolyte circulation will carry out the reaction product from the battery, by optimizing the structure of anode chamber ensure the effective area of the reaction zone, reduce the internal resistance of the battery by optimizing the electrode electric scheme. Experimental results show that the fuel cell power density can reach 435 mW/cm2, equivalent to the general performance of ZAFC More than 2 times; further study of the electrolyte temperature, flow rate and oxygen partial pressure influences the performance of the battery, the optimized ZAFC in gas supply for air and oxygen when the power density reached 544 mW/cm2 and 899 mW/cm2, and the dynamic response time in millisecond, no voltage overshoot phenomenon. The ZAFC performance degradation mechanism Study on the establishment of ZAFC equivalent circuit model of AC impedance analysis, that the performance of ZAFC used in the process of decay is increased and the air electrode charge transfer impedance and mass transfer impedance; through the SEM morphology and gas permeability analysis, reveals the performance degradation mechanism for the loss of catalyst of air electrode and hydrophobic breathable layer pore clogging; through the parking experiment found dry parking zinc agglomerate and the anodic corrosion of wet expansion phenomenon, parking the electrolyte hydrophobic air electrode decreased and the change of pore structure, and found it empty Gas electrodes on both sides respectively with electrolyte and deionized water immersion when water through the air electrode migration to the electrolyte side phenomenon, can be used to regenerate the blocked air electrode porosity. The development contains the ZAFC system control unit, through repeated on-off experiment verify the feasibility of the scheme, and study the direct preparation of electrolytic zinc particle the preparation technology, the success of electrolytic zinc particles dense. This innovative research results greatly enhance the power density of ZAFC, reveals the impact of the performance of ZAFC factors and attenuation mechanism of the air electrode pore regeneration and zinc particle regeneration technology, provides a theoretical guidance for the scientific design of ZAFC, and provides technology the foundation for its commercial application.

【學(xué)位授予單位】：清華大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TM911.41

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