β-Co（OH）_2的室温固相制备和电化学性能研究
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摘要
Co(OH)_2作为二次电池的重要添加剂,其制备方法和电化学性能受到广泛的关注。然而,传统的制备方法存在生产环节多、过滤困难、易氧化等缺点,因此,采用室温固相反应法制备了β–Co(OH)_2,利用X射线衍射(XRD),场发射扫描电镜(FE–SEM),热重(TG)分析等方法分析了β–Co(OH)_2的相结构、表面形貌和热失重情况。研究了β–Co(OH)_2电极的电化学性能,以及物理掺杂对Co(OH)_2电极电化学性能的影响,并讨论了其作为电极材料的可能性。
XRD和TG分析表明所制备的样品为β–Co(OH)_2,属于六方晶系,纯净无杂质。FE–SEM表明样品粒度小于500 nm。电化学测试表明,β–Co(OH)_2电极经过2周循环即可活化,最大放电容量可达到466 mAh/g。同时,β–Co(OH)_2电极具有良好的高倍率充电性能,1500 mA/g下的高倍率充电性能为83.5%。电极对环境温度变化敏感,在293～333 K之间,电极的放电容量随着温度的升高而增大,放电平台则随着温度的升高而降低。目前存在的主要问题是其放电电压平台较低,在充放电循环时,放电容量有波动。
添加剂提高了β–Co(OH)_2电极的高倍率放电性能,提高程度的顺序为石墨>活性炭>La_2O_3>铜粉。添加石墨和La2O3后,电极放电中值电压分别为1156 mV和1150 mV,均明显高于未掺杂电极的放电中值电压(1138 mV)。并且添加剂改善了电极的循环稳定性。
Co(OH)_2 as additive of secondary batteries has been attached great importance. Several investigations were focused on the synthesis and the electrochemical properties of Co(OH)_2. However, the traditional preparation methods needs several steps, consuming lots of energy, and even the products is difficult to filtrate and easy to be oxidized. Therefore,β–Co(OH)_2 was synthesized by solid-state reaction and electrochemical properties were tested in this paper. X-ray diffraction (XRD), Field-emission scanning electron microscope (FE-SEM) and thermal gravity (TG) were employed to determine the microstructure, morphology and weight losing, respectively. Moreover, the effect of additives on electrochemical properties ofβ–Co(OH)_2 electrode was investigated. The possibility of theβ–Co(OH)_2 as the candidate materials for negative electrodes of batteries was discussed.
The XRD showed that the as-synthesized sample wasβ–Co(OH)_2 with hexagonal structure. FE-SEM indicated that the size of theβ–Co(OH)_2 powder was less than 500 nm. Theβ–Co(OH)_2 electrode can be activated within 2 cycles and reached the maximum discharge capacity of 466 mAh/g. Theβ–Co(OH)_2 exhibited high rate chargeability. The ratio of HRC1500 vs. HRC60 was 83.5%. Theβ–Co(OH)_2 electrode was sensitived to temperature. From 293 to 333 K, the discharge capacity increases, while the discharge platform descends. The drawbacks ofβ–Co(OH)_2 used as electrode materials were lower discharge platform and undulation of the discharge capacity during charge-discharge cycling.
The additives improved the high rate dischargeability ofβ–Co(OH)_2 electrode. The improvement order is graphite>activated charcoal>La2O3>copper powder. The discharge platform is 1156 mV (with graphite) and 1150 mV (with La2O3), respectively, while that of the blank electrode is 1138 mV. The cycle stability ofβ–Co(OH)_2 with an additive has also been improved.
XRD和TG分析表明所制备的样品为β–Co(OH)_2,属于六方晶系,纯净无杂质。FE–SEM表明样品粒度小于500 nm。电化学测试表明,β–Co(OH)_2电极经过2周循环即可活化,最大放电容量可达到466 mAh/g。同时,β–Co(OH)_2电极具有良好的高倍率充电性能,1500 mA/g下的高倍率充电性能为83.5%。电极对环境温度变化敏感,在293～333 K之间,电极的放电容量随着温度的升高而增大,放电平台则随着温度的升高而降低。目前存在的主要问题是其放电电压平台较低,在充放电循环时,放电容量有波动。
添加剂提高了β–Co(OH)_2电极的高倍率放电性能,提高程度的顺序为石墨>活性炭>La_2O_3>铜粉。添加石墨和La2O3后,电极放电中值电压分别为1156 mV和1150 mV,均明显高于未掺杂电极的放电中值电压(1138 mV)。并且添加剂改善了电极的循环稳定性。
Co(OH)_2 as additive of secondary batteries has been attached great importance. Several investigations were focused on the synthesis and the electrochemical properties of Co(OH)_2. However, the traditional preparation methods needs several steps, consuming lots of energy, and even the products is difficult to filtrate and easy to be oxidized. Therefore,β–Co(OH)_2 was synthesized by solid-state reaction and electrochemical properties were tested in this paper. X-ray diffraction (XRD), Field-emission scanning electron microscope (FE-SEM) and thermal gravity (TG) were employed to determine the microstructure, morphology and weight losing, respectively. Moreover, the effect of additives on electrochemical properties ofβ–Co(OH)_2 electrode was investigated. The possibility of theβ–Co(OH)_2 as the candidate materials for negative electrodes of batteries was discussed.
The XRD showed that the as-synthesized sample wasβ–Co(OH)_2 with hexagonal structure. FE-SEM indicated that the size of theβ–Co(OH)_2 powder was less than 500 nm. Theβ–Co(OH)_2 electrode can be activated within 2 cycles and reached the maximum discharge capacity of 466 mAh/g. Theβ–Co(OH)_2 exhibited high rate chargeability. The ratio of HRC1500 vs. HRC60 was 83.5%. Theβ–Co(OH)_2 electrode was sensitived to temperature. From 293 to 333 K, the discharge capacity increases, while the discharge platform descends. The drawbacks ofβ–Co(OH)_2 used as electrode materials were lower discharge platform and undulation of the discharge capacity during charge-discharge cycling.
The additives improved the high rate dischargeability ofβ–Co(OH)_2 electrode. The improvement order is graphite>activated charcoal>La2O3>copper powder. The discharge platform is 1156 mV (with graphite) and 1150 mV (with La2O3), respectively, while that of the blank electrode is 1138 mV. The cycle stability ofβ–Co(OH)_2 with an additive has also been improved.
引文
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2 H.Ye, Y.X. Huang, J.X. Chen, et al. MmNi3.55Co0.75Mn0.4Al0.3B0.3 Hydrogen Storage Alloys for High-power Nickel/Metal Hydride Batteries. Journal of Power Sources, 2002, 103(2): 293-299
3 Q.Arnaud, P.Barbic, P.Bernard, et al. Effect of AB2 Alloy Addition on the Phase Structures and Electrochemical Characteristics of LaNi5 Hydride Electrode. Alloys and Compounds, 2002, 330-332: 262-267
4 C.Khaldi, H. Mathlouthi. Effect of Partial Substitution of Co with Fe on the Properties of LaNi3.55Mn0.4Al0.3Co0.75-xFex (x=0, 0.15, 0.55) Alloys. International Hydrogen Energy, 2004, 29: 307-311
5唐有根,李文良著.镍氢电池.北京:化学工业出版社, 2007: 188–189
6杨云霞,章健康,张蕾等.纳米Co(OH)2的制备与电化学性能的研究.功能材料, 2001, 32(1): 57-58
7 R.D. Armstrong, E.A. Charles. Some Effects of Cobalt Hydroxide upon the Electro- chemical Behavior of Nickel Hydroxide Electrodes. Journal of Power Sources, 1989, (25): 89-97
8袁安保,张鉴清,曹楚南.镍电极研究进展.电源技术, 2001, 25(1): 53-59
9丁万春,袁安保,张鉴清等. Co(OH)2包覆的Ni(OH)2电化学性能研究.电源技术, 2000, 24(4): 204-206
10谢朋,翟玉春,翟秀静等.蓄电池添加剂Co、CoO、Co(OH)2的研究现状.电源技术, 1998, 22(5): 222-224
11 R.S. Jayashree, P. Vishnu Kamath. Electrochemical Synthesis ofα-cobalt Hydroxide Journal of Chemistry Materials, 1999, 9(4): 961-963
12常照荣,彭鹏,任行涛等.蓄电池添加剂β-Co(OH)2合成的新工艺.化学世界, 2002, 11(03): 563-565
13谢朋,翟玉春,翟秀静等.添加剂Co(OH)2的制备研究.电源技术, 1998, 22(4): 148-151
14李阳兴,姜长印,万春荣等.β-Co(OH)2粉末的制备及结构研究.电源技术, 1999, 23(6): 325-327
15 M. Rajamathi, P. Vishnu. Kamath, R. Seshadri. Chemical Synthesis ofα-cobalt Hydroxide .Material Research Bulletin, 2000, 35 (2): 271-278
16原常洲,张校刚,高博.多孔Co(OH)2的制备及其超电容特性.应用化学, 2006, 23(4): 456-458
17 P. Elumalai, H.N. Vasan, N. Munichandraiah. Electrochemical Studies of Cobalt Hydroxide—an Additive for Nickel Electrodes. Journal of Power Sources, 2001, 93: 201-208
18杨彧,贾殿增,葛炜炜等.低热固相反应制备无机纳米材料的方法.无机化学学报, 2004, 20(8): 882-888
19 J. Smail, M.F. Hmed, P.V. Kamath. Organic Additive–Mediated Synthesis of Novel Cobalt (Ⅱ) Hydroxides. Journal Solid State Chem, 1995, 114: 550-555
20常照荣,李苞,李云平等. Co(OH)2的电化学性能研究.化学世界, 2003, 11: 566-568
21 Z.P. Xu, H.C. Zeng. A New Approach for Design and Synthesis of Co and Co Hydroxide Materials. Inorganic Materials, 2000, (2): 187-196
22 T.N. Ramesh, M. Rajamathi, P. V. Kamath. Ammonia Induced Precipitation of Cobalt Hydroxide: Observation of Turbostratic Disorder. Solid State Sciences, 2003, (5): 751-756
23张密林,刘志祥.沉淀转化法制备的Co(OH)2的超级电容特性.无机化学学报, 2002, 18(5): 513-517
24莫丽萍,石俊,冯晓娟等.片状Co(OH)2的制备及其电化学性能研究.西北师范大学学报, 2008, 44(1): 56-58
25贾殿赠,曹亚丽,刘浪等.氢氧化钴纳米棒的室温固相化学合成及其表征.无机化学学报, 2005, 21(4): 535-537
26日本化学会编,董万堂,董绍俊译.无机固态反应,北京:科学出版社, 1985: 235-247
27 J. Benard. The reactivity of Solid Yesterday and Today. Pure and Applied Chemistry, 1984, 56: 1659-1662
28 H.W. Hou, X.R. Ye, X.Q. Xin, et al. Silid-Stage Synthesis, Crystal Structure, and Nonlinear Refractive and Absorptive Preperties of the New Cluster(n-Bu4N)2[MoOS3Cu3BrCl2]. Journal Chemical materials. 1995, 7: 427-476
29 J.J. Tscherniajew, A.W. Bobkow, D.A. Nenk. Catalytic Oxidation of Olefins via an Allyl Radical Heat Resistant Stainless Steek. 1963, 152: 882-885
30雷力旭,忻新泉.室温固相反应与固相结构.化学通报, 1997, 2: 1-7
31 F. Toda. Solid-to-Solid Organic Chemistry: Efficient Recations, Remarkable Yields, and Stereoselectivity. Accounts of Chemical Research. 1995, 28(12): 480-483
32 X.Q. Xin, A.B. Dai. Coordination by as Chromatography. Pure and Applied Chemistry, 1988, 8: 1217-1221
33 W. Dickenscheid R. Birringer. Solid State Reactions in Binary Mixtures of Nanometer-sized Particles. J. Appl. Phys,1995,(77):533-539
34 X.Q. Xin, L.M. Zheng. Production of Metal Compound by Solid-phase Reaction. Solid State Chemistry, 1993, 106: 451-453
35忻新泉,郑丽敏.固相配位化学反应.化学通报, 1992, (2): 23-26
36朱慧珍,丛蓉娟,忻新泉.固相配位研究:ⅩⅩ.Ⅵ.(NS4)2WS4与(n-Bu)4NBr固相成簇反应.无机化学学报, 1989, 5(2): 129-133
37 S.Q. Xin, J.P. Lang, K.B. Yu, et al. Solid State Reactions of Coordination Compounds. Chinese Journal of Inorganic Chemistry, 1992, (04): 472-474
38 Rao CNR and Gopalakrishnan FRS著,刘新生译.固态化学新放向–结构、合成、性质、反应性及材料设计.长春:吉林大学出版社, 1990: 432-434
39袁进华,王晓平,忻新泉.固相配位化学反应研究:XXX.室温下铁氰化钾的固相反应.无机化学学报, 1991, (03): 28-32
40 L.X. Lei, X.Q. Xin. Study on the Solid State Reactions of Coordination Compoudes: LXIX. Stepwise Reaction of CuCl2·H2O with 2,2’–bipyridyl. Solid State Chemistry, 1995, 119: 299-302
41贾殿增,俞建群,忻新泉.负温度系数热敏粉体的制备方法-室温固相反应CN Patent Appl. CN 99106687.1
42俞建群,贾殿赠,张慧等. CdS纳米粉体的合成新方法―一步室温固相化学反应法.化学通报, 1998, (02): 35-36.
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44俞建群,贾殿赠,郑毓峰等.纳米氧化镍、氧化锌的合成新方法.无机化学学报, 1999, 15(l): 95-97
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52黄振谦,申建斌,唐有根等. Co含量对MH/Ni电池性能的影响.电源技术, 2001, (4): 283-285
53董桂霞,杜军,朱磊等. CoO添加剂对La0.7Mg0.3(Ni0.85Co0.15)3.5贮氢合金电化学性能的影响.中国稀土学报, 2006, 24(4): 465-469
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2 H.Ye, Y.X. Huang, J.X. Chen, et al. MmNi3.55Co0.75Mn0.4Al0.3B0.3 Hydrogen Storage Alloys for High-power Nickel/Metal Hydride Batteries. Journal of Power Sources, 2002, 103(2): 293-299
3 Q.Arnaud, P.Barbic, P.Bernard, et al. Effect of AB2 Alloy Addition on the Phase Structures and Electrochemical Characteristics of LaNi5 Hydride Electrode. Alloys and Compounds, 2002, 330-332: 262-267
4 C.Khaldi, H. Mathlouthi. Effect of Partial Substitution of Co with Fe on the Properties of LaNi3.55Mn0.4Al0.3Co0.75-xFex (x=0, 0.15, 0.55) Alloys. International Hydrogen Energy, 2004, 29: 307-311
5唐有根,李文良著.镍氢电池.北京:化学工业出版社, 2007: 188–189
6杨云霞,章健康,张蕾等.纳米Co(OH)2的制备与电化学性能的研究.功能材料, 2001, 32(1): 57-58
7 R.D. Armstrong, E.A. Charles. Some Effects of Cobalt Hydroxide upon the Electro- chemical Behavior of Nickel Hydroxide Electrodes. Journal of Power Sources, 1989, (25): 89-97
8袁安保,张鉴清,曹楚南.镍电极研究进展.电源技术, 2001, 25(1): 53-59
9丁万春,袁安保,张鉴清等. Co(OH)2包覆的Ni(OH)2电化学性能研究.电源技术, 2000, 24(4): 204-206
10谢朋,翟玉春,翟秀静等.蓄电池添加剂Co、CoO、Co(OH)2的研究现状.电源技术, 1998, 22(5): 222-224
11 R.S. Jayashree, P. Vishnu Kamath. Electrochemical Synthesis ofα-cobalt Hydroxide Journal of Chemistry Materials, 1999, 9(4): 961-963
12常照荣,彭鹏,任行涛等.蓄电池添加剂β-Co(OH)2合成的新工艺.化学世界, 2002, 11(03): 563-565
13谢朋,翟玉春,翟秀静等.添加剂Co(OH)2的制备研究.电源技术, 1998, 22(4): 148-151
14李阳兴,姜长印,万春荣等.β-Co(OH)2粉末的制备及结构研究.电源技术, 1999, 23(6): 325-327
15 M. Rajamathi, P. Vishnu. Kamath, R. Seshadri. Chemical Synthesis ofα-cobalt Hydroxide .Material Research Bulletin, 2000, 35 (2): 271-278
16原常洲,张校刚,高博.多孔Co(OH)2的制备及其超电容特性.应用化学, 2006, 23(4): 456-458
17 P. Elumalai, H.N. Vasan, N. Munichandraiah. Electrochemical Studies of Cobalt Hydroxide—an Additive for Nickel Electrodes. Journal of Power Sources, 2001, 93: 201-208
18杨彧,贾殿增,葛炜炜等.低热固相反应制备无机纳米材料的方法.无机化学学报, 2004, 20(8): 882-888
19 J. Smail, M.F. Hmed, P.V. Kamath. Organic Additive–Mediated Synthesis of Novel Cobalt (Ⅱ) Hydroxides. Journal Solid State Chem, 1995, 114: 550-555
20常照荣,李苞,李云平等. Co(OH)2的电化学性能研究.化学世界, 2003, 11: 566-568
21 Z.P. Xu, H.C. Zeng. A New Approach for Design and Synthesis of Co and Co Hydroxide Materials. Inorganic Materials, 2000, (2): 187-196
22 T.N. Ramesh, M. Rajamathi, P. V. Kamath. Ammonia Induced Precipitation of Cobalt Hydroxide: Observation of Turbostratic Disorder. Solid State Sciences, 2003, (5): 751-756
23张密林,刘志祥.沉淀转化法制备的Co(OH)2的超级电容特性.无机化学学报, 2002, 18(5): 513-517
24莫丽萍,石俊,冯晓娟等.片状Co(OH)2的制备及其电化学性能研究.西北师范大学学报, 2008, 44(1): 56-58
25贾殿赠,曹亚丽,刘浪等.氢氧化钴纳米棒的室温固相化学合成及其表征.无机化学学报, 2005, 21(4): 535-537
26日本化学会编,董万堂,董绍俊译.无机固态反应,北京:科学出版社, 1985: 235-247
27 J. Benard. The reactivity of Solid Yesterday and Today. Pure and Applied Chemistry, 1984, 56: 1659-1662
28 H.W. Hou, X.R. Ye, X.Q. Xin, et al. Silid-Stage Synthesis, Crystal Structure, and Nonlinear Refractive and Absorptive Preperties of the New Cluster(n-Bu4N)2[MoOS3Cu3BrCl2]. Journal Chemical materials. 1995, 7: 427-476
29 J.J. Tscherniajew, A.W. Bobkow, D.A. Nenk. Catalytic Oxidation of Olefins via an Allyl Radical Heat Resistant Stainless Steek. 1963, 152: 882-885
30雷力旭,忻新泉.室温固相反应与固相结构.化学通报, 1997, 2: 1-7
31 F. Toda. Solid-to-Solid Organic Chemistry: Efficient Recations, Remarkable Yields, and Stereoselectivity. Accounts of Chemical Research. 1995, 28(12): 480-483
32 X.Q. Xin, A.B. Dai. Coordination by as Chromatography. Pure and Applied Chemistry, 1988, 8: 1217-1221
33 W. Dickenscheid R. Birringer. Solid State Reactions in Binary Mixtures of Nanometer-sized Particles. J. Appl. Phys,1995,(77):533-539
34 X.Q. Xin, L.M. Zheng. Production of Metal Compound by Solid-phase Reaction. Solid State Chemistry, 1993, 106: 451-453
35忻新泉,郑丽敏.固相配位化学反应.化学通报, 1992, (2): 23-26
36朱慧珍,丛蓉娟,忻新泉.固相配位研究:ⅩⅩ.Ⅵ.(NS4)2WS4与(n-Bu)4NBr固相成簇反应.无机化学学报, 1989, 5(2): 129-133
37 S.Q. Xin, J.P. Lang, K.B. Yu, et al. Solid State Reactions of Coordination Compounds. Chinese Journal of Inorganic Chemistry, 1992, (04): 472-474
38 Rao CNR and Gopalakrishnan FRS著,刘新生译.固态化学新放向–结构、合成、性质、反应性及材料设计.长春:吉林大学出版社, 1990: 432-434
39袁进华,王晓平,忻新泉.固相配位化学反应研究:XXX.室温下铁氰化钾的固相反应.无机化学学报, 1991, (03): 28-32
40 L.X. Lei, X.Q. Xin. Study on the Solid State Reactions of Coordination Compoudes: LXIX. Stepwise Reaction of CuCl2·H2O with 2,2’–bipyridyl. Solid State Chemistry, 1995, 119: 299-302
41贾殿增,俞建群,忻新泉.负温度系数热敏粉体的制备方法-室温固相反应CN Patent Appl. CN 99106687.1
42俞建群,贾殿赠,张慧等. CdS纳米粉体的合成新方法―一步室温固相化学反应法.化学通报, 1998, (02): 35-36.
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