立体构造石墨烯材料对铅酸蓄电池负极性能影响的研究

doi:10.13208/j.electrochem.200306

摘要/Abstract

摘要：

以具有高比表面积、优良的导电性和高稳定性的立体构造石墨烯材料（stereotaxically-constructed graphene, SCG）作为添加剂,加入到铅酸蓄电池负极活性材料中,通过XRD、SEM和电化学测试手段系统地分析其对电池性能的影响. 结果表明,SCG材料可以抑制硫酸铅晶体的生长,促进硫酸铅向海绵状铅的转变,延缓不可逆硫酸铅在负极的积累,在0.1 C放电速率下,添加有SCG材料的铅酸蓄电池的负极活性材料的初始放电容量为173.8 mAh·g ^-1,比未添加碳材料的(151.6 mAh·g ^-1)高14%. 在高速率部分荷电状态(HRPSoC)条件下, 添加SCG材料的电池循环寿命达到10,889圈,是未在负极活性材料中添加碳材料的电池的循环寿命的303%. 这些结果验证了立体构造石墨烯材料对铅酸蓄电池的积极影响,展现了其在铅酸蓄电池中的良好的应用前景.

关键词: 立体构造石墨烯, 铅酸蓄电池, 负极活性材料, 不可逆硫酸盐化, 循环寿命

Abstract:

With the advantages of high ratio surface area, excellent conductivity and high stability, the stereotaxically-constructed graphene (SCG) material was added to the negative active material (NAM) of lead-acid battery for improving battery performance. XRD, SEM and cyclic voltammetry tests were carried out to analyze the influence of SCG on negative active material. It is found that the conversion efficiency of lead sulfate to lead in the negative active material added with SCG material was higher than that of control group, and the particle size of the lead sulfate obtained after the discharge reaction was smaller, which are favorable factors for inhibiting the irreversible sulfation of the negative active material. At the discharge rate of 0.1 C, the initial discharge capacity of the NAM with SCG added was 173.8 mAh·g ^-1, being 14% higher than that of the NAM without carbon adding (151.6 mAh·g ^-1). The cycle life under the high-rate partial-state-of charge (HRPSoC) state reached 10,889 cycles, which was 303% longer than the control one. Finally, for explaining the benefits of SCG materials in lead-acid batteries, possible mechanism is proposed as below: SCG material has a porous structure and excellent conductivity, which allows it to build a conductive network in the NAM and provides an ion channel for the electrolyte, thereby, reducing the ohmic resistance of the negative plate, improving the efficiency of material exchange in chemical reaction as well as the charge acceptance ability of the battery. Furthermore, LSV and EIS tests confirmed that the addition of SCG material would not cause serious hydrogen evolution reaction to the NAM, which can reduce the loss of electrolyte and maintain the stability of the battery. These results verify the positive effect of SCG on lead-acid battery, and show potential application prospect in lead-acid battery.

Key words: stereotaxically-constructed graphene, lead-acid battery, negative active material, irreversible sulfation, cycle life

中图分类号:

O646

陈品松, 胡一涛, 张信义, 沈培康. 立体构造石墨烯材料对铅酸蓄电池负极性能影响的研究[J]. 电化学（中英文）, 2020, 26(6): 834-843.

Pin-song Chen, Yi-tao Hu, Xin-yi Zhang, Pei-kang Shen. Effect of Stereotaxically-Constructed Graphene on the Negative Electrode Performance of Lead-Acid Batteries[J]. Journal of Electrochemistry, 2020, 26(6): 834-843.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.200306

https://electrochem.xmu.edu.cn/CN/Y2020/V26/I6/834

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参考文献 36

[1]	Hamelink M, Opdenakker R . How business model innovation affects firm performance in the energy storage market[J]. Renewabel Energy, 2019,113:120-127.
[2]	Blanco H, Faaij A . A review at the role of storage in energy systems with a focus on Power to Gas and long-term storage[J]. Renewable and Sustainable Energy Reviews, 2018,81:1049-1086.
[3]	Laslett D, Carter C, Creagh C , et al. A large-scale renewable electricity supply system by 2030: Solar, wind, energy efficiency, storage and inertia for the South West Interconnected System (SWIS) in Western Australia[J]. Renewable Energy, 2017,113:713-731.
[4]	Li Y, Li Y B, Ji P F , et al. Development of energy storage industry in China: A technical and economic point of review[J]. Renewable & Sustainable Energy Reviews, 2015,49:805-812.
[5]	Braff W A, Mueller J M, Trancik J E . Value of storage technologies for wind and solar energy[J]. Nature Climate Change, 2016,6:964-969.
[6]	Palizban O, Kauhaniemi K . Energy storage systems in modern grids-matrix of technologies and applications[J]. Journal of Energy Storage, 2016,6:248-259.
[7]	Lach J, Wróbe K, Wróbel J , et al. Applications of carbon in lead-acid batteries: a review[J]. Journal of Solid State Electrochemistry, 2019,23(3):693-705.
[8]	McAllister S D, Patankar S N, Cheng I F , et al. Lead dioxide coated hollow glass microspheres as conductive additives for lead acid batteries[J]. Scripta Materialia, 2009,61(4):375-378.
[9]	Newell J D, Patankar S N, Edwards D B . Porous microspheres as additives in lead-acid batteries[J]. Journal of Power Sources, 2009,188(1):292-295.
[10]	Wang L Y( 王乐莹), Zhang H( 张浩), Hu C( 胡晨 ), et al. Review of carbon materials energy storage mechanism in lead-carbon battery[J]. Journal of Electrochemistry( 电化学), 2014,20(5):476-481.
[11]	Kumar S M, Kiran U V, Raju A K , et al. Effect of boron-carbon-nitride as a negative additive for lead acid batteries operating under high-rate partial-state-of-charge conditions[J]. RSC Advances, 2016, 6(79): 75122-75125.
[12]	Lam L T, Haigh N P, Phyland C G, , et al. Failure mode of valve-regulated lead-acid batteries under high-rate partial-state-of-charge operation[J]. Journal of Power Sources, 2004,133(1):126-134.
[13]	Ebner E, Burow D, Börger A , et al. Carbon blacks for the extension of the cycle life in flooded lead acid batteries for micro-hybrid applications[J]. Journal of Power Sources, 2013,239:483-489.
[14]	Wang L Y, Zhang H, Cao G P , et al. Effect of activated carbon surface functional groups on nano-lead electrodeposition and hydrogen evolution and its applications in lead-carbon batteries[J]. Electrochimica Acta, 2015,186:654-663.
[15]	Zhang S K, Zhang H, Cheng J , et al. Novel polymer-graphite composite grid as a negative current collector for leadacid batteries[J]. Journal of Power Sources, 2016,334:31-38.
[16]	Banerjee A, Ziv B, Shilina Y , et al. Single-wall carbon nanotube doping in lead-acid batteries: A new horizon[J]. ACS Applied Materials & Interfaces, 2017,9(4):3634-3643.
[17]	Shiomi M, Funato T, Nakamura K , et al. Effects of carbon in negative plates on cycle-life performance of valveregulated lead-acid batteries[J]. Journal of Power Sources, 1997,94:147-152.
[18]	Nakarnura K, Shiomi M, Takahashi K , et al. Failure modes of valve-regulated lead/acid batteries[J]. Journal of Power Sources, 1996,59:153-157.
[19]	Tong P Y, Zhao R R, Zhang R B , et al. Characterization of lead (II) - containing activated carbon and its excellent performance of extending lead-acid battery cycle life for high-rate partial-state-of-charge operation[J]. Journal of Power Sources, 2015,286:91-102.
[20]	Blecua M, Fatas E, Ocon P , et al. Graphitized carbon nanofibers: new additive for the negative active material of lead acid batteries[J]. Electrochimica Acta, 2017,257:109-117.
[21]	Mayorov A S, Gorbachev R V, Morozov S V , et al. Micrometer-scale ballistic transport in encapsulated graphene at room temperature[J]. Nano Letter, 2011,11(6):2396-2399.
[22]	Geim A K, Novoselov K S . The rise of graphene[J]. Nature Materials, 2007,6(3):183-191.
[23]	Novoselov K S, Geim A K, Morozov S V , et al. Electric field effect in atomically thin carbon films[J]. Science, 2004,306(5696):666-669.
[24]	Chen D, Wang W J, Liu C L . Ni-encapsulated graphene chainmail catalyst for ethanol steam Blankorming[J]. International Journal of Hydrogen Energy, 2019,44(13):6560-6572.
[25]	Stoller M, Park S, Zhu Y , et al. Graphene-based ultracapacitors[J]. Nano letters, 2008,8(10):3498-3502.
[26]	Shi W P, Zhang Y M, Key J , et al. Three-dimensional graphene sheets with NiO nanobelt outgrowths for enhanced capacity and long term high rate cycling Li-ion battery anode material[J]. Journal of Power Sources, 2018,379:362-370.
[27]	Huang S Z, Zhang L L, Wang J Y , et al. In situ carbon nanotube clusters grown from three dimensional porous graphene networks as efficient sulfur hosts for high-rate ultra-stable Li-S batteries[J]. Nano Research, 2017,11(3):1731-1743.
[28]	Li X L, Zhang Y Y, Su Z L , et al. Graphene nanosheets as backbones to build a 3D conductive network for negative active materials of lead-acid batteries[J]. Journal of Applied Electrochemistry, 2017,47(5):619-630.
[29]	Yang H, Qiu Y B, Guo X P . Effects of PPy, GO and PPy/GO composites on the negative plate and on the high-rate partial-state-of-charge performance of lead-acid batteries[J]. Electrochimica Acta, 2016,215:346-356.
[30]	Li Y Y, Li Z S, Shen P K . Simultaneous formation of ultrahigh surface area and three-dimensional hierarchical porous graphene-like networks for fast and highly stable supercapacitors[J]. Advanced Materials, 2013,25(17):2474-2480. doi: 10.1002/adma.201205332 URL pmid: 23495046
[31]	Xu W G, Mao N N, Zhang J . Graphene: a platform for surface-enhanced Raman spectroscopy[J]. Small, 2013,9(8):1206-1224. URL pmid: 23529788
[32]	Wang H, Liu Z, Liang Q Q , et al. A facile method for preparation of doped-N carbon material based on sisal and application for lead-carbon battery[J]. Journal of Cleaner Production, 2018,197:332-338.
[33]	Connolly D, Lund H, Mathiesen B V , et al. The technical and economic implications of integrating fluctuating renewable energy using energy storage[J]. Renewable Energy, 2012,43:47-60
[34]	Hong B, Jiang L G, Xue H T , et al. Characterization of nano-lead-doped active carbon and its application in lead-acid battery[J]. Journal of Power Sources, 2014,270:332-341.
[35]	Zhang S K( 张淑凯), Zhang H( 张浩), Xue W H( 薛维华 ), et al. Preparations and applications of layered carbon and layered carbon-PbSO₄ composite[J]. Journal of Electrochemistry( 电化学), 2015,21(3):268-272.
[36]	Zou X P, Kang Z X, Shu D , et al. Effects of carbon additives on the performance of negative electrode of lead-carbon battery[J]. Electrochimica Acta, 2015,151:89-98.

Type	Carbon additive	Carbon additive in NAM/wt.%	Other additive material/wt.%
Type	Carbon additive	Carbon additive in NAM/wt.%	Short fibers	Humic acids	Sodium ligniusulfonate	BaSO₄
Blank	-	-	0. 05%	0.10%	0.20%	0.50%
SCG	SCG	0.10%
Cabot	Cabot carbon	0.10%
AECT	Acetylene black	0.10%

Working electrode	R1/Ω	R2/Ω	CPE1-T	CPE1-P
Blank	0.256	72.548	0.003	0.923
SCG	0.221	53.481	0.002	0.945
Cabot	0.241	38.552	0.001	0.938
AECT	0.245	42.785	0.002	0.917