多孔炭负载氢氧化镍复合电极研究
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摘要
锌镍单液流电池是一种适合规模储能的化学电源体系，该电池以氢氧化镍电极为正极，沉积/溶解型锌电极为负极，流动的碱性锌酸盐溶液为电解液。电池容量及寿命受制于镍正极，因此研究新型的高容量的镍电极具有重要的意义。本文提出了多孔炭负载氢氧化镍复合电极，通过对多孔炭制备、氢氧化镍与多孔炭的复合、氢氧化镍及多孔炭的改性等实验研究，得到创新性的结果。
本文首先研究了多孔炭(MPC)的制备方法。以酚醛树脂作为碳源及粘结剂、聚乙烯醇缩丁醛等作为造孔剂、活性炭作为导电剂及支撑骨架，制备得到具有亚微米-微米结构的一体化多孔炭材料。通过单因素分析法及正交分析法，考察了活性炭及聚乙烯醇缩丁醛的添加量、树脂固化温度、碳化温度等因素对制备的多孔炭材料孔结构、机械强度及电导率的影响，探讨了多孔炭的成孔机理，优化了制备条件。以酚醛树脂、聚乙烯醇缩丁醛和活性炭的质量比为4:2:1，且固化温度为185℃，碳化温度为1000℃的条件下制备的多孔炭材料最适合作为电极的导电基体。该条件下制备的多孔炭材料不仅具有较高的机械强度，而且具有较高的孔容(0.766mL g~(-1))、合适的孔径分布(0.1-5μm)及高的电导率(11.24S cm~(-1))。
通过电化学浸渍的方法在多孔炭孔内载入氢氧化镍制备得到多孔炭-氢氧化镍(MPC-Ni(OH)_2)复合电极，探索了氢氧化镍在多孔炭基内沉积机理，优化了浸渍反应条件。研究表明，在反应温度为80℃，硝酸镍溶液浓度为2mol L~(-1)，溶液初始pH=3.5，以80mA cm~(-2)的电流密度，在搅拌条件下恒流沉积3h，制备的MPC-Ni(OH)_2复合电极具有最优的电化学性能。在该条件下制备的电极活性物质的比容量(SCAM)、电极质量比容量(SCEW)和面积比容量(SCEA)分别为259mAh g~(-1)，136mAh g~(-1)和24mAh cm~(-2)。
采用电化学浸渍的方法在多孔炭片中共沉积Ni、Co及Zn制备得到Ni_(1-x-y)Co_xZn_y(OH)_2固溶体用于Ni(OH)_2材料的改性，提高了沉积于炭孔中的Ni(OH)_2的利用率。共沉积Co/Zn的MPC-Ni(OH)_2电极的SCAM、 SCEW和SCEA分别为271mAh g~(-1)，145mAh g~(-1)和26mAh cm~(-2)。
探索了MPC-Ni(OH)_2复合电极放电过程中电位双平台现象产生的原因，研究了多孔炭片在碱性条件下的析氧特性，通过对Ni(OH)_2表层镀镍和对多孔炭片表层镀镍改性两种方法来抑制电极双平台现象的发生，提高电极的循环寿命。Ni(OH)_2表层镀镍提高了活性物质与多孔炭片的结合强度。多孔炭片表层镀镍提高了多孔炭片的析氧电位，抑制了在充电过程中的析氧反应。研究表明，两种方法均可在很大程度上提高电极的循环寿命，30次循环后电极活性物质比容量分别具有83%和90%的保持率。
Single flow zinc nickel battery is suitable for large scale energystorage applications. In this battery, nickel hydroxide electrode as positiveelectrode, conductive inert material as negative electrode and flowingzincates in alkali solutions as electrolyte were used, respectively. Owingto the capacity and cycle life of this battery is restricted by the nickelhydroxide electrode, it is important to study a new-type nickel oxideelectrode with high capacity. In the dissertation, monolithic porouscarbon (MPC) as substrates for nickel hydroxide electrodes is proposedby our team. A novel MPC-Ni(OH)_2electrode has been obtained throughthe experimental study of preparation of MPC, electrochemicalimpregnation of Ni(OH)_2, modification of nickel hydroxide and MPC.
The preparation method and the principle of MPC were studied. In thepaper, adopting phenolic resin (PF) as carbon precursors and binders,polyvinyl butyral (PVB) as pore former, and active carbon (AC) asconducting additives and underprop for bating contractility to makepolymer blend, sub-micron/micron monolithic porous carbon (MPC)were prepared by blend carbonization. The single factor and orthogonal methods were used to study the effects of solidified temperature,carbonization temperature, and content of AC and PVB on the porestructure, mechanical strength and conductivity of MPC. When the ratioof PF, PVB and AC is4:2:1, stabilized temperature is185℃, andcarbonization temperature is1000℃, a optimized MPC is prepared. Theoptimized MPC has a good mechanical strength, a high pore volume(0.766mL g~(-1)), a suitable pore diameter distribution (0.1-5μm) and a goodconductivity (11.24S cm~(-1)).
MPC-Ni(OH)_2electrode is fabricated by electrochemicalimpregnation Ni(OH)_2from metal nitrate solutions on to the monolithicporous carbon (MPC), which is used for the substrates of nickel electrode.The impregnation principle was studied and the impregnation reactionfactors were optimized. When the reaction temperature is80℃, theconcentration of nickel nitrate is2M, the initial pH of solution is3.5, thecurrent density is80mA cm~(-2), the impregnation time is3h and thesolution is string, the prepared MPC-Ni(OH)_2electrode has the bestelectrochemical performance. In this condition, the MPC-Ni(OH)_2electrode reach a specific capacity of active material (SCAM) of259mAh g~(-1), a specific capacity of electrode weight (SCEW) of136mAh g~(-1)and a specific capacity of electrode Area (SCEA) of24mAh cm~(-2).
MPC-Ni(OH)_2electrode with Co and Zn additives is fabricated by electrodepositing from metal nitrate solutions on to MPC. It is found thatthe prepared Co and Zn additives are substituted for nickel in the solidstate of Ni_(1-x-y)Co_xZn_y(OH)_2. Compared to pure MPC-Ni(OH)_2electrodes,the electrochemical performance and cycle life of MPC-Ni(OH)_2electrodes with Co and Zn additives improve. SCAM, SCEW and SCEAof MPC-Ni(OH)_2electrode with Co and Zn additives is271mAh g~(-1),145mAh g~(-1)and26mAh cm~(-2), respectively.
The appearance of two potential plateaus during the discharge ofMPC-Ni(OH)_2electrode and the oxygen evolution characteristic on MPCin alkali solutions was studied. To restrain the oxygen evolution reactionand improve the cycle life of MPC-Ni(OH)_2electrode, two ways wereused. One was plating nickel on the surface of the Ni(OH)_2, the other wasplating nickel on the surface of the MPC. The former improved thecontact intensity between Ni(OH)_2and MPC. The latter improved theoverpotential of the oxygen evolution reaction on MPC and restrained theoxygen evolution reaction during the charge process. It is evident that thetwo ways all could enhance the cycle life of MPC-Ni(OH)_2electrodes.After30cycles, the two modified electrodes still keep83%and90%ofthe highest discharge capacity, respectively.
本文首先研究了多孔炭(MPC)的制备方法。以酚醛树脂作为碳源及粘结剂、聚乙烯醇缩丁醛等作为造孔剂、活性炭作为导电剂及支撑骨架，制备得到具有亚微米-微米结构的一体化多孔炭材料。通过单因素分析法及正交分析法，考察了活性炭及聚乙烯醇缩丁醛的添加量、树脂固化温度、碳化温度等因素对制备的多孔炭材料孔结构、机械强度及电导率的影响，探讨了多孔炭的成孔机理，优化了制备条件。以酚醛树脂、聚乙烯醇缩丁醛和活性炭的质量比为4:2:1，且固化温度为185℃，碳化温度为1000℃的条件下制备的多孔炭材料最适合作为电极的导电基体。该条件下制备的多孔炭材料不仅具有较高的机械强度，而且具有较高的孔容(0.766mL g~(-1))、合适的孔径分布(0.1-5μm)及高的电导率(11.24S cm~(-1))。
通过电化学浸渍的方法在多孔炭孔内载入氢氧化镍制备得到多孔炭-氢氧化镍(MPC-Ni(OH)_2)复合电极，探索了氢氧化镍在多孔炭基内沉积机理，优化了浸渍反应条件。研究表明，在反应温度为80℃，硝酸镍溶液浓度为2mol L~(-1)，溶液初始pH=3.5，以80mA cm~(-2)的电流密度，在搅拌条件下恒流沉积3h，制备的MPC-Ni(OH)_2复合电极具有最优的电化学性能。在该条件下制备的电极活性物质的比容量(SCAM)、电极质量比容量(SCEW)和面积比容量(SCEA)分别为259mAh g~(-1)，136mAh g~(-1)和24mAh cm~(-2)。
采用电化学浸渍的方法在多孔炭片中共沉积Ni、Co及Zn制备得到Ni_(1-x-y)Co_xZn_y(OH)_2固溶体用于Ni(OH)_2材料的改性，提高了沉积于炭孔中的Ni(OH)_2的利用率。共沉积Co/Zn的MPC-Ni(OH)_2电极的SCAM、 SCEW和SCEA分别为271mAh g~(-1)，145mAh g~(-1)和26mAh cm~(-2)。
探索了MPC-Ni(OH)_2复合电极放电过程中电位双平台现象产生的原因，研究了多孔炭片在碱性条件下的析氧特性，通过对Ni(OH)_2表层镀镍和对多孔炭片表层镀镍改性两种方法来抑制电极双平台现象的发生，提高电极的循环寿命。Ni(OH)_2表层镀镍提高了活性物质与多孔炭片的结合强度。多孔炭片表层镀镍提高了多孔炭片的析氧电位，抑制了在充电过程中的析氧反应。研究表明，两种方法均可在很大程度上提高电极的循环寿命，30次循环后电极活性物质比容量分别具有83%和90%的保持率。
Single flow zinc nickel battery is suitable for large scale energystorage applications. In this battery, nickel hydroxide electrode as positiveelectrode, conductive inert material as negative electrode and flowingzincates in alkali solutions as electrolyte were used, respectively. Owingto the capacity and cycle life of this battery is restricted by the nickelhydroxide electrode, it is important to study a new-type nickel oxideelectrode with high capacity. In the dissertation, monolithic porouscarbon (MPC) as substrates for nickel hydroxide electrodes is proposedby our team. A novel MPC-Ni(OH)_2electrode has been obtained throughthe experimental study of preparation of MPC, electrochemicalimpregnation of Ni(OH)_2, modification of nickel hydroxide and MPC.
The preparation method and the principle of MPC were studied. In thepaper, adopting phenolic resin (PF) as carbon precursors and binders,polyvinyl butyral (PVB) as pore former, and active carbon (AC) asconducting additives and underprop for bating contractility to makepolymer blend, sub-micron/micron monolithic porous carbon (MPC)were prepared by blend carbonization. The single factor and orthogonal methods were used to study the effects of solidified temperature,carbonization temperature, and content of AC and PVB on the porestructure, mechanical strength and conductivity of MPC. When the ratioof PF, PVB and AC is4:2:1, stabilized temperature is185℃, andcarbonization temperature is1000℃, a optimized MPC is prepared. Theoptimized MPC has a good mechanical strength, a high pore volume(0.766mL g~(-1)), a suitable pore diameter distribution (0.1-5μm) and a goodconductivity (11.24S cm~(-1)).
MPC-Ni(OH)_2electrode is fabricated by electrochemicalimpregnation Ni(OH)_2from metal nitrate solutions on to the monolithicporous carbon (MPC), which is used for the substrates of nickel electrode.The impregnation principle was studied and the impregnation reactionfactors were optimized. When the reaction temperature is80℃, theconcentration of nickel nitrate is2M, the initial pH of solution is3.5, thecurrent density is80mA cm~(-2), the impregnation time is3h and thesolution is string, the prepared MPC-Ni(OH)_2electrode has the bestelectrochemical performance. In this condition, the MPC-Ni(OH)_2electrode reach a specific capacity of active material (SCAM) of259mAh g~(-1), a specific capacity of electrode weight (SCEW) of136mAh g~(-1)and a specific capacity of electrode Area (SCEA) of24mAh cm~(-2).
MPC-Ni(OH)_2electrode with Co and Zn additives is fabricated by electrodepositing from metal nitrate solutions on to MPC. It is found thatthe prepared Co and Zn additives are substituted for nickel in the solidstate of Ni_(1-x-y)Co_xZn_y(OH)_2. Compared to pure MPC-Ni(OH)_2electrodes,the electrochemical performance and cycle life of MPC-Ni(OH)_2electrodes with Co and Zn additives improve. SCAM, SCEW and SCEAof MPC-Ni(OH)_2electrode with Co and Zn additives is271mAh g~(-1),145mAh g~(-1)and26mAh cm~(-2), respectively.
The appearance of two potential plateaus during the discharge ofMPC-Ni(OH)_2electrode and the oxygen evolution characteristic on MPCin alkali solutions was studied. To restrain the oxygen evolution reactionand improve the cycle life of MPC-Ni(OH)_2electrode, two ways wereused. One was plating nickel on the surface of the Ni(OH)_2, the other wasplating nickel on the surface of the MPC. The former improved thecontact intensity between Ni(OH)_2and MPC. The latter improved theoverpotential of the oxygen evolution reaction on MPC and restrained theoxygen evolution reaction during the charge process. It is evident that thetwo ways all could enhance the cycle life of MPC-Ni(OH)_2electrodes.After30cycles, the two modified electrodes still keep83%and90%ofthe highest discharge capacity, respectively.
引文
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