【作者】 侯建；

【导师】 陈智超；

【作者基本信息】 哈尔滨工业大学 ， 动力工程及工程热物理， 2023， 硕士

【摘要】 随着全球对环境保护的关注,煤气化技术作为一种清洁利用技术,得到广泛应用。煤气化细灰作为煤气化过程中产生的固体废弃物存在一定的孔隙,具有制备超级电容器活性炭的潜力。超级电容器作为一种新型储能器件,具有快速充放电、高能量/功率密度和稳定的循环性能等特点,并广泛应用于电力电子、电动汽车和计算机电源备份等领域。若实现以煤气化细灰为原料制备超级电容器活性炭,可促进煤气化细灰的大规模、高值化利用。论文以煤气化细灰为原料,通过研究不同方式对煤气化细灰脱灰效果的影响以及不同活化剂对活性炭孔隙结构和电化学性能的影响,确定煤气化细灰活化步骤。在此基础上,改变活化条件对活性炭理化结构进行调控,并研究其理化性质和电化学性能。通过活性炭的等温吸附/脱附测试,表征其孔隙结构,通过XRD测试和拉曼测试研究活性炭的石墨化程度,通过XPS测试研究活性炭的表面官能团,通过CV、GCD、EIS测试研究活性炭的电化学性能。论文的主要研究内容包括:研究HF、HCl、HF-HCl三种脱灰方式对煤气化细灰脱灰效果的影响;研究Zn Cl₂、H₃PO₄、KOH三种活化剂对活性炭孔隙结构和电化学性能的影响;研究不同活化温度、活化时间、碱碳比对活性炭孔隙结构、石墨化程度等理化性质的影响;研究活性炭和镍钴掺杂活性炭电化学性能。论文主要结论:（1）HF、HCl、HF-HCl三种脱灰方式中,HF-HCl酸洗脱灰效果最佳。在HF-HCl酸洗脱灰的条件下,改变脱灰温度,发现80℃时脱灰效果最佳。确定采用80℃HF-HCl对煤气化细灰进行脱灰。（2）Zn Cl₂、H₃PO₄、KOH三种活化剂中,采用KOH活化制备的活性炭具有最佳的比表面积（1989.47 m²/g）和电化学性能（211.89 F/g）。确定采用KOH活化的方式制备活性炭。（3）在活化温度650℃、活化时间1h、碱碳比5:1的条件下制备得活性炭平均孔径达到3.14 nm,比表面积达到2399.87 m²/g,石墨化程度I_D/I_G达到1.12,含氧官能团占比达到22%。（4）在活化温度为800℃、活化时间为60min、碱碳比为5:1的条件下制备得活性炭具有最佳的电化学性能,质量比电容达到211.84 F/g（1 A/g）,电容保持率达到84.9%（1-20 A/g）。在双电极体系下,比电容达到208.24 F/g（1 A/g）,保持率为86.4%（1-10 A/g）,功率密度为0.6 k W/kg时,能量密度达到5.21 Wh/kg,在10000圈的循环寿命达到102.51%。（5）镍钴掺杂活性炭在三电极测试体系中,其比电容最高为416 F/g（1 A/g）,电容保持率为78.8%（1-20 A/g）。在双电极体系下,质量比电容达到80.89 F/g（1A/g）,保持率达到75.94%（1-10 A/g）,功率密度为1.4 k W/kg时,能量密度达到22.02 Wh/kg,在5000圈循环寿命测试中保持率达到77.92%。更多还原

【Abstract】 With the global attention to environmental protection,coal gasification technology as a clean utilization technology has been widely used.Coal gasification fine ash,as a solid waste produced in the process of coal gasification,has certain pores and has the potential to prepare activated carbon for supercapacitors.As a new type of energy storage devices,supercapacitors have the characteristics of fast charge and discharge,high energy/power density and stable cycle performance,and are widely used in power electronics,electric vehicles and computer power backup.If the coal gasification fine ash is used as raw material to prepare activated carbon for supercapacitor,the large-scale and high-value utilization of coal gasification fine ash can be promoted.Taking fine ash of coal gasification as raw material,the paper determines the activation steps of fine ash of coal gasification by studying the influence of different methods on the deashing effect of fine ash of coal gasification and the influence of different activators on the pore structure and electrochemical performance of activated carbon.On this basis,the physicochemical structure of activated carbon was regulated by changing the activation conditions,and its physicochemical properties and electrochemical properties were studied.The pore structure of activated carbon was characterized by isothermal adsorption/desorption test,the graphitization degree of activated carbon was studied by XRD test and Raman test,the surface functional groups of activated carbon were studied by XPS test,and the electrochemical properties of activated carbon were studied by CV,GCD and EIS test.The main research contents of this paper include:the influence of HF,HCl and HF-HCl deashing methods on the deashing effect of coal gasification fine ash;The effects of Zn Cl₂,H₃PO₄ and KOH activators on the pore structure and electrochemical properties of activated carbon were investigated.The effects of different activation temperature,activation time,alkali-carbon ratio on the pore structure and graphitization degree of activated carbon were studied.The electrochemical properties of activated carbon and nickel cobalt doped activated carbon were studied.Main conclusions of the paper:（1）Among the three deashing methods of HF,HCl and HF-HCl,HF-HCl pickling has the best deashing effect.Under the condition of HF-HCl pickling and deashing,it is found that 80℃has the best deashing effect by changing the deashing temperature.It is determined that 80℃HF-HCl is used to deash fine ash from coal gasification.（2）Among the three activators Zn Cl₂,H₃PO₄ and KOH,activated carbon prepared by KOH activation had the best specific surface area（1989.47 m²/g）and electrochemical performance（211.89 F/g）.The preparation of activated carbon by KOH activation was determined.（3）Under the conditions of activation temperature 650℃,activation time 1h,alkali to carbon ratio 5:1,the average pore size of activated carbon reached 3.14 nm,specific surface area reached 2399.87 m²/g,graphitization degree I_D/I_G reached 1.12,and oxygen tube energy group ratio reached 22%.（4）Under the conditions of activation temperature of 800℃,activation time of60min and alkali-carbon ratio of 5:1,activated carbon has the best electrochemical performance,mass specific capacitance of 211.84F/g（1 A/g）,capacitor retention rate of84.9%（1-20 A/g）.Under the dual electrode system,the specific capacitance reaches208.24F/g（1 A/g）,the retention rate is 86.4%（1-10 A/g）,the power density is 0.6k W/kg,the energy density is 5.21Wh/kg,and the cycle life at 10000 cycles is 102.51%.（5）In the three-electrode test system,the maximum specific capacitance of Ni-Co doped activated carbon is 416 F/g（1 A/g）,and the capacitor retention rate is 78.8%（1-20 A/g）.In the dual-electrode system,the mass specific capacitance reaches 80.89F/g（1 A/g）,the retention rate reaches 75.94%（1-10 A/g）,the power density reaches22.0Wh/kg when the power density is 1.4 k W/kg,and the retention rate reaches 77.92%during the 5000 cycles life test.更多还原