储氢合金作为直接硼氢化物燃料电池阳极催化剂的研究进展
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摘要
直接硼氢化物燃料电池(DBFC)是一种可以直接将化学能转化成电能的新型燃料电池,该类电池因具有理论电压高、能量密度大、环境污染小等优点而备受关注。然而,在DBFC工作的过程中,BH_4~-容易发生水解而释放出氢气,导致实际转移的电子数目减少,燃料利用率降低,同时生成的氢气还会给电池带来隐患。研究表明,DBFC的性能很大程度取决于硼氢化物分子在DBFC阳极上发生的电化学反应,而阳极上的电化学反应又直接受阳极催化剂的控制。因此,阳极催化剂是影响DBFC电化学性能的关键因素。以往研究者们多采用贵金属单质(例如Au、Pt、Ag、Pd等)或贵金属合金作为DBFC阳极催化剂,也有的采用过渡金属(例如Ni)。贵金属催化剂具有优异的催化性能,但高昂的成本限制了它们的广泛应用。过渡金属成本较低,但其催化性能却不够突出。因此,阳极催化剂的选择是DBFC能否广泛应用的关键。近年来,具有可逆吸、放氢性能的储氢合金由于其特殊的储氢特性引起了DBFC研究者们的极大关注,他们将储氢合金用作DBFC阳极催化剂。研究表明,储氢合金除了具有与贵金属催化剂相类似的催化能力外,还能将DBFC工作过程中发生的水解副反应释放出来的氢吸附(或存储),并在一定条件下再将氢以电能的形式释放出来,从而提高了燃料的利用率。此外,储氢合金作为DBFC阳极催化剂,不仅降低了原材料成本,还抑制了水解副反应,从而提高了燃料的利用率,同时该合金在稳定性方面也有一定的优势。为进一步发挥储氢合金的催化性能,研究者们对储氢合金进行表面修饰、晶体结构改变、成分优化等多角度研究。理论和实验研究证明,储氢合金是一种具有应用潜力的DBFC非贵金属催化剂。本文在简要说明DBFC工作原理、介绍储氢合金吸放氢机理以及储氢合金作为DBFC阳极催化剂反应机制的基础上,综述了近年来储氢合金作为DBFC阳极催化剂的研究进展,特别对比了近年来研究比较多的AB_5型和AB_2型储氢合金作为DBFC阳极催化剂的性能。最后指出了储氢合金作为DBFC阳极催化剂存在的问题和未来发展趋势。
Direct borohydride fuel cell(DBFC) is a new kind of fuel cell that can convert chemical energy directly into power.This battery has been paid much attention because of its high theoretical voltage,high energy density,less pollution to environment and so on. However,in the process of working in DBFC,since BH-4 is prone to hydrolysis and releases hydrogen,the number of actually transferred electrons is reduced,the fuel utilization rate is lowered,and the generated hydrogen gas also brings hidden danger to the battery. Studies have shown that the performance of DBFC largely depends on the electrochemical reaction of borohydride molecules at the anode,while the electrochemical reaction on the anode is directly controlled by the anode catalyst. So that,the anode catalyst is the key factor affecting DBFC electrochemical performance. In the past,people usually used precious metals(such as Au,Pt,Ag,Pd,etc.) or precious metal alloys as the anode catalyst of DBFC,and some have used transition metals(such as Ni). Although the precious metal catalyst has good catalytic properties,it cannot be widely used because of its cost problem. In spite of the transition metal has low cost,its catalytic performance is not outstanding enough. Therefore,the choice of anode catalyst is the key to the wide application of DBFC.In recent years,hydrogen storage alloys with reversible hydrogen absorption and release properties have attracted great attention from DBFC researchers due to their special hydrogen storage characteristics,so thatresearchers have took hydrogen storage alloys as anode catalysts of DBFC. Studies have shown that in addition to the direct catalytic ability similar to noble metal catalysts,hydrogen storage alloys can also adsorb(or storage) hydrogen released from the hydrolysis side reactions that occur during DBFC operation,and then released in the form of electrical energy under certain conditions,thus improving fuel utilization. In addition,as anode catalyst of DBFC,hydrogen storage alloys not only reduce the cost of raw materials,inhibit the side reaction and improve the fuel efficiency,but also have some advantages in stability. In order to make full use of the catalytic properties of hydrogen storage alloys,people have tried to modify the surface of the hydrogen storage alloy,change the crystal structure,optimize the composition and other multiple methods. Theory and experiment studied show that hydrogen storage alloy is a DBFC non-precious metal catalyst with potential application.In this paper,the working principle of DBFC,the mechanism of hydrogen absorption and desorption of hydrogen storage alloy and the reaction mechanism of hydrogen storage alloy as anode catalyst of DBFC are briefly introduced. The research progress of hydrogen storage alloy as anode catalyst of DBFC in recent years is reviewed. The performance of AB_5 and AB_2 hydrogen storage alloys as anode catalysts of DBFC is studied,especially in recent years. Finally,the problems and future development trends of hydrogen storage alloys as anode catalysts of DBFC are pointed out.
Direct borohydride fuel cell(DBFC) is a new kind of fuel cell that can convert chemical energy directly into power.This battery has been paid much attention because of its high theoretical voltage,high energy density,less pollution to environment and so on. However,in the process of working in DBFC,since BH-4 is prone to hydrolysis and releases hydrogen,the number of actually transferred electrons is reduced,the fuel utilization rate is lowered,and the generated hydrogen gas also brings hidden danger to the battery. Studies have shown that the performance of DBFC largely depends on the electrochemical reaction of borohydride molecules at the anode,while the electrochemical reaction on the anode is directly controlled by the anode catalyst. So that,the anode catalyst is the key factor affecting DBFC electrochemical performance. In the past,people usually used precious metals(such as Au,Pt,Ag,Pd,etc.) or precious metal alloys as the anode catalyst of DBFC,and some have used transition metals(such as Ni). Although the precious metal catalyst has good catalytic properties,it cannot be widely used because of its cost problem. In spite of the transition metal has low cost,its catalytic performance is not outstanding enough. Therefore,the choice of anode catalyst is the key to the wide application of DBFC.In recent years,hydrogen storage alloys with reversible hydrogen absorption and release properties have attracted great attention from DBFC researchers due to their special hydrogen storage characteristics,so thatresearchers have took hydrogen storage alloys as anode catalysts of DBFC. Studies have shown that in addition to the direct catalytic ability similar to noble metal catalysts,hydrogen storage alloys can also adsorb(or storage) hydrogen released from the hydrolysis side reactions that occur during DBFC operation,and then released in the form of electrical energy under certain conditions,thus improving fuel utilization. In addition,as anode catalyst of DBFC,hydrogen storage alloys not only reduce the cost of raw materials,inhibit the side reaction and improve the fuel efficiency,but also have some advantages in stability. In order to make full use of the catalytic properties of hydrogen storage alloys,people have tried to modify the surface of the hydrogen storage alloy,change the crystal structure,optimize the composition and other multiple methods. Theory and experiment studied show that hydrogen storage alloy is a DBFC non-precious metal catalyst with potential application.In this paper,the working principle of DBFC,the mechanism of hydrogen absorption and desorption of hydrogen storage alloy and the reaction mechanism of hydrogen storage alloy as anode catalyst of DBFC are briefly introduced. The research progress of hydrogen storage alloy as anode catalyst of DBFC in recent years is reviewed. The performance of AB_5 and AB_2 hydrogen storage alloys as anode catalysts of DBFC is studied,especially in recent years. Finally,the problems and future development trends of hydrogen storage alloys as anode catalysts of DBFC are pointed out.
引文
1 Li X L,Wang X J,Zhao J,et al.Materials Review A:Review Papers,2018,32(4),1057 (in Chinese).李旭力,王晓静,赵君,等.材料导报:综述篇,2018,32 (4),1057.
2 Xiao Y P,Wang X F,Pinson P,et al.IEEE Transactions on Power Systems,2018,33 (4),3898.
3 Rosen M A,Koohi-Fayegh S.Energy,Ecology and Environment,2016,1(1),10.
4 Jiang X J,Wu Y,Fu K,et al.Intermetallics,2018,95,73.
5 Ma J,Choudhury N A,Sahai Y.Renewable and Sustainable Energy Reviews,2010,14(1),183.
6 Wang J Y ,Wang H L ,Fan Y I.Engineering,2018,4,352.
7 Wang S Y,Jiang S P.National Science Review,2017,4(2),163.
8 Merino-Jimenez I,De Leon C P,Shah A A,et al.Journal of Power Sources,2012,219,339.
9 Olu P Y,Job N,Chatenet M,et al.Journal of Power Sources,2016,327,235.
10 Gao X Y,Ma J F,Xue W,et al.CIESC Journal,2017,68(5),0438(in Chinese).高翔宇,马金福,薛伟,等.化工学报,2017,68(5),0438.
11 Feng R X,Cao Y L,Ai X P,et al.Acta Physico-chimica sinica,2007,23(6),932(in Chinese).冯瑞香,曹余良,艾新平,等.物理化学学报,2007,23(6),932.
12 Sanli A E,Yilmaz E S,Ozden S K,et al.International Journal of Hydrogen Energy,2018,43(2),992.
13 Atwan M H,Macdonald C L B,Northwood D O,et al.Journal of Power Sources,2006,158(1),36.
14 Cheng H,Scott K.Electrochimica Acta,2006,51(17),3429.
15 Liu B H,Li Z P,Suda S.Electrochimica Acta,2004,49(19),3097.
16 Liu B H,Li Z P.Journal of Power Sources,2009,187(2),527.
17 Lee H M,Park S Y,Park K T,et al.Research on Chemical Interme-diates,2008,3(8-9),787.
18 Lam V W S,Kannangara D C W,Alfantazi A,et al.Journal of Power Sources,2012,212,57.
19 Coowar F A,Vitins G,Mepsted G O,et al.Journal of Power Sources,2008,175(1),317.
20 Karadag C I,Behmenyar G,Boyaci San F G,et al.Fuel Cells,2015,15(2),262.
21 Merino-Jimenez I,Janik M J,Leon C P,et al.Journal of Power Sources,2014,269,498.
22 Yi L H,Wei W,Zhao C X,et al.Electrochimica Acta,2015,158,209.
23 Yu D M,Shen Y,Ye Z,et al.Chinese Science Bulletin,2013,58(20),2435.
24 He P Y,Wang X Y,Fu P,et al.International Journal of Hydrogen Energy,2011,36,8857.
25 Yi L H,Wei W,Zhao C X,et al.Journal of Power Sources,2015,285,325.
26 Duan D H,You X,Liang J W,et al.Electrochimica Acta,2015,176,1126.
27 Celikkan H,Sahin M,Aksu M L,et al.International Journal of Hydrogen Energy,2007,32(5),588.
28 Liu B H,Li Z P,Arai K,et al.Electrochimica Acta,2005,50(18),3719.
29 Züttel A.Materials Today,2003,6(9),24.
30 Wang L B,Ma C A,Mao X B,et al.Electrochemistry Communications,2005,7,1477.
31 Wang L B,Ma C A,Sun Y M,et al.Journal of Alloy and Compounds,2005,391,318.
32 Wang G L,Wang X Y,Miao R R,et al.International Journal of Hydrogen Energy,2010,35,1227.
33 Yang Z Z,Wang L B,Gao Y F,et al.Journal of Power Sources,2008,184,260.
34 Wang L B,Ma C A,Mao X B,et al.Journal of Materials Science and Technology,2005,31(6),831.
35 Liu B H,Suda S.Journal of Alloys and Compounds,2008,454,280.
36 Lota G,Sierczynska A,Acznik I,et al.International Journal of Electrochemical Science,2014,9(2),659.
37 Zhang D M,Wang G L,Cheng K,et al.Journal of Power Sources,2014,245,482.
38 Li S,Yang X D,Zhu H Y,et al.Journal of Materials Science and Technology,2011,27(12),1089.
39 Choudhury N A,Sahai Y,Buchheit R G.Electrochemistry Communications,2011,13(1),1.
40 Wang L B,Ma C A,Mao X B.Journal of Alloys and Compounds,2005,397(1-2),313.
41 Gras M,Sierczynska A,Lota K,et al.Ionics,2016,22,2539.
42 Zhan X Y.Studies on the anode catalyst for direct borohydride fuel cells.Master's Thesis,Zhejiang University of Technology,China,2011(in Chinese).詹星月.直接硼氢化物燃料电池阳极催化剂研究.硕士学位论文,浙江工业大学,2011.
43 Ni X M,Wang Y,Cao Y L,et al.Electrochemistry Communications,2010,12,710.
44 Ma J F,Wang J,Liu Y N.Journal of Power Sources,2007,172,220.
45 Ma J F,Liu Y N,Zhang P,et al.Electrochemistry Communication,2008,10,100.
46 Ni X M,Wang Y D,Guo F,et al.Journal of Rare Earths,2012,30(5),437.
47 Liu Y,Liu Y N,Ma J F,et al.Journal of Power Sources,2010,195,1854.
48 Liu Y,Ma J F,Lai J H,et al.Journal of Alloy and Compounds,2009,488,204.
49 Duan D H,Sun Y P.Progress in Chemistry,2010,22(9),1720.
50 Raman R K,Prashant S K,Shukla A K.Journal of Power Sources,2006,162,1073.
51 Raman R K,Shukla A K.Fuel Cells,2007,7(3),225.
52 Raman R K,Shukla A K.Journal of Applied Electrochemistry,2005,35,1157.
53 Wang Y G,Xia Y Y.Electrochemistry Communications,2006,8(11),1775.
54 Selvarani G,Prashant S K,Sahu A K,et al.Journal of Power Sources,2008,178,86.
55 Ma J F,Liu Y,Liu Y,et al.Fuel Cells,2008,8(6),394.
56 Kim C,Kim K J,Ha M Y.Journal of Power Source,2008,180,154.
57 Lee S M,Kim J K,Lee H H,et al.Journal of the Electrochemical Society,2002,149(5),A603.
58 Li Z P,Liu B H,Arai K,et al.Journal of the Electrochemical Society,2003,150(7),A868.
59 Liu B H,Li Z P.Journal of Power Sources,2009,187(2),291.
60 Li Z P,Liu B H,Arai K,et al.Journal of Power Sources,2004,126,28.
61 Choudhury N A,Raman R K,Sampath S,et al.Journal of Power Sources,2005,143,1.
62 Liu B H,Li Z P,Kitani R,et al.Journal of Alloys and Compounds,2002,(330-332),825.
63 Liu B H,Li Z P,Higuchi E,et al.Journal of Alloys and Compounds,1999,(293-295),702.
64 Wang L B,Zhan X Y,Yang Z Z,et al.Chinese Journal of Chemical Engineering,2011,19(4),693.
2 Xiao Y P,Wang X F,Pinson P,et al.IEEE Transactions on Power Systems,2018,33 (4),3898.
3 Rosen M A,Koohi-Fayegh S.Energy,Ecology and Environment,2016,1(1),10.
4 Jiang X J,Wu Y,Fu K,et al.Intermetallics,2018,95,73.
5 Ma J,Choudhury N A,Sahai Y.Renewable and Sustainable Energy Reviews,2010,14(1),183.
6 Wang J Y ,Wang H L ,Fan Y I.Engineering,2018,4,352.
7 Wang S Y,Jiang S P.National Science Review,2017,4(2),163.
8 Merino-Jimenez I,De Leon C P,Shah A A,et al.Journal of Power Sources,2012,219,339.
9 Olu P Y,Job N,Chatenet M,et al.Journal of Power Sources,2016,327,235.
10 Gao X Y,Ma J F,Xue W,et al.CIESC Journal,2017,68(5),0438(in Chinese).高翔宇,马金福,薛伟,等.化工学报,2017,68(5),0438.
11 Feng R X,Cao Y L,Ai X P,et al.Acta Physico-chimica sinica,2007,23(6),932(in Chinese).冯瑞香,曹余良,艾新平,等.物理化学学报,2007,23(6),932.
12 Sanli A E,Yilmaz E S,Ozden S K,et al.International Journal of Hydrogen Energy,2018,43(2),992.
13 Atwan M H,Macdonald C L B,Northwood D O,et al.Journal of Power Sources,2006,158(1),36.
14 Cheng H,Scott K.Electrochimica Acta,2006,51(17),3429.
15 Liu B H,Li Z P,Suda S.Electrochimica Acta,2004,49(19),3097.
16 Liu B H,Li Z P.Journal of Power Sources,2009,187(2),527.
17 Lee H M,Park S Y,Park K T,et al.Research on Chemical Interme-diates,2008,3(8-9),787.
18 Lam V W S,Kannangara D C W,Alfantazi A,et al.Journal of Power Sources,2012,212,57.
19 Coowar F A,Vitins G,Mepsted G O,et al.Journal of Power Sources,2008,175(1),317.
20 Karadag C I,Behmenyar G,Boyaci San F G,et al.Fuel Cells,2015,15(2),262.
21 Merino-Jimenez I,Janik M J,Leon C P,et al.Journal of Power Sources,2014,269,498.
22 Yi L H,Wei W,Zhao C X,et al.Electrochimica Acta,2015,158,209.
23 Yu D M,Shen Y,Ye Z,et al.Chinese Science Bulletin,2013,58(20),2435.
24 He P Y,Wang X Y,Fu P,et al.International Journal of Hydrogen Energy,2011,36,8857.
25 Yi L H,Wei W,Zhao C X,et al.Journal of Power Sources,2015,285,325.
26 Duan D H,You X,Liang J W,et al.Electrochimica Acta,2015,176,1126.
27 Celikkan H,Sahin M,Aksu M L,et al.International Journal of Hydrogen Energy,2007,32(5),588.
28 Liu B H,Li Z P,Arai K,et al.Electrochimica Acta,2005,50(18),3719.
29 Züttel A.Materials Today,2003,6(9),24.
30 Wang L B,Ma C A,Mao X B,et al.Electrochemistry Communications,2005,7,1477.
31 Wang L B,Ma C A,Sun Y M,et al.Journal of Alloy and Compounds,2005,391,318.
32 Wang G L,Wang X Y,Miao R R,et al.International Journal of Hydrogen Energy,2010,35,1227.
33 Yang Z Z,Wang L B,Gao Y F,et al.Journal of Power Sources,2008,184,260.
34 Wang L B,Ma C A,Mao X B,et al.Journal of Materials Science and Technology,2005,31(6),831.
35 Liu B H,Suda S.Journal of Alloys and Compounds,2008,454,280.
36 Lota G,Sierczynska A,Acznik I,et al.International Journal of Electrochemical Science,2014,9(2),659.
37 Zhang D M,Wang G L,Cheng K,et al.Journal of Power Sources,2014,245,482.
38 Li S,Yang X D,Zhu H Y,et al.Journal of Materials Science and Technology,2011,27(12),1089.
39 Choudhury N A,Sahai Y,Buchheit R G.Electrochemistry Communications,2011,13(1),1.
40 Wang L B,Ma C A,Mao X B.Journal of Alloys and Compounds,2005,397(1-2),313.
41 Gras M,Sierczynska A,Lota K,et al.Ionics,2016,22,2539.
42 Zhan X Y.Studies on the anode catalyst for direct borohydride fuel cells.Master's Thesis,Zhejiang University of Technology,China,2011(in Chinese).詹星月.直接硼氢化物燃料电池阳极催化剂研究.硕士学位论文,浙江工业大学,2011.
43 Ni X M,Wang Y,Cao Y L,et al.Electrochemistry Communications,2010,12,710.
44 Ma J F,Wang J,Liu Y N.Journal of Power Sources,2007,172,220.
45 Ma J F,Liu Y N,Zhang P,et al.Electrochemistry Communication,2008,10,100.
46 Ni X M,Wang Y D,Guo F,et al.Journal of Rare Earths,2012,30(5),437.
47 Liu Y,Liu Y N,Ma J F,et al.Journal of Power Sources,2010,195,1854.
48 Liu Y,Ma J F,Lai J H,et al.Journal of Alloy and Compounds,2009,488,204.
49 Duan D H,Sun Y P.Progress in Chemistry,2010,22(9),1720.
50 Raman R K,Prashant S K,Shukla A K.Journal of Power Sources,2006,162,1073.
51 Raman R K,Shukla A K.Fuel Cells,2007,7(3),225.
52 Raman R K,Shukla A K.Journal of Applied Electrochemistry,2005,35,1157.
53 Wang Y G,Xia Y Y.Electrochemistry Communications,2006,8(11),1775.
54 Selvarani G,Prashant S K,Sahu A K,et al.Journal of Power Sources,2008,178,86.
55 Ma J F,Liu Y,Liu Y,et al.Fuel Cells,2008,8(6),394.
56 Kim C,Kim K J,Ha M Y.Journal of Power Source,2008,180,154.
57 Lee S M,Kim J K,Lee H H,et al.Journal of the Electrochemical Society,2002,149(5),A603.
58 Li Z P,Liu B H,Arai K,et al.Journal of the Electrochemical Society,2003,150(7),A868.
59 Liu B H,Li Z P.Journal of Power Sources,2009,187(2),291.
60 Li Z P,Liu B H,Arai K,et al.Journal of Power Sources,2004,126,28.
61 Choudhury N A,Raman R K,Sampath S,et al.Journal of Power Sources,2005,143,1.
62 Liu B H,Li Z P,Kitani R,et al.Journal of Alloys and Compounds,2002,(330-332),825.
63 Liu B H,Li Z P,Higuchi E,et al.Journal of Alloys and Compounds,1999,(293-295),702.
64 Wang L B,Zhan X Y,Yang Z Z,et al.Chinese Journal of Chemical Engineering,2011,19(4),693.