微撞击流反应器制备镍钴复合氢氧化物超级电容器材料及其性能研究

doi:10.11949/0438-1157.20220593

摘要/Abstract

摘要：

镍基复合超级电容器电极材料如镍钴复合氢氧化物，由于其比电容大、循环性能好等优点受到了电化学界的广泛关注。相比于纯Ni(OH)₂，镍钴复合氢氧化物材料由于过渡金属元素之间的协同作用，其电化学性能一般会更佳。但是镍钴复合氢氧化物材料的性能与其颗粒内部的组分分布均匀性有很大关联，而组分分布又依赖于沉淀反应时反应器内的微观混合均匀程度。将微观混合性能优良的微撞击流反应器（MISR）应用于镍钴复合氢氧化物材料的共沉淀制备，结果表明MISR能够显著改善镍钴复合氢氧化物材料的颗粒粒径、尺寸分布、团聚程度以及电化学性能：三电极体系测试下，所制备材料的初始比电容为1548.0 F/g，1000圈充放电循环后电容保持率为106.0%；二电极体系测试下，器件的初始比电容为30.6 F/g，1000圈循环后电容保持率为75.6%。

关键词: 微反应器, 沉淀, 复合材料, 超级电容器, 粒度分布

Abstract:

Nickel-cobalt composite supercapacitor electrode materials such as nickel-cobalt hydroxide composites have attracted extensive attention in the field of electrochemistry due to their advantages of large specific capacitance and excellent cycle performance. The electrochemical properties of nickel-cobalt composites are generally better than those of single transition metal compounds due to the synergic interaction between the transition metal elements. However, the performance of metal composites is closely related to the component element distribution within the particles, which depends strongly on the micromixing efficiency of the precipitation reaction environment. In this work, a micro-impinging stream reactor (MISR) with excellent micromixing performance was applied to the preparation of nickel-cobalt hydroxide composites. The results showed that MISR could significantly reduce the particle scale and improve the size distribution, agglomeration degree as well as the electrochemical performance of the prepared nickel-cobalt hydroxide composites. In the three-electrode testing system, the initial specific capacitance of the MISR-prepared material was 1548.0 F/g, and the capacitance retention was 106.0% after 1000 charge-discharge cycles. In the two-electrode system, the initial specific capacitance of the device was 30.6 F/g, and the capacitance retention was 75.6% after 1000 cycles.

Key words: microreactor, precipitation, composites, supercapacitor, size distribution

中图分类号:

顾仁杰, 张加威, 靳雪阳, 文利雄. 微撞击流反应器制备镍钴复合氢氧化物超级电容器材料及其性能研究[J]. 化工学报, 2022, 73(8): 3749-3757.

Renjie GU, Jiawei ZHANG, Xueyang JIN, Lixiong WEN. Synthesis of nickel-cobalt hydroxide composites as supercapacitor materials by micro-impinging stream reactors and their performance study[J]. CIESC Journal, 2022, 73(8): 3749-3757.

图/表 13

图1 实验装置

Fig.1 Experimental device

图2 二电极测试体系

Fig.2 Two-electrode test system

图3 镍钴复合氢氧化物的XRD谱图

Fig.3 XRD patterns of nickel-cobalt hydroxide composites

图4 镍钴复合氢氧化物的SEM图

Fig.4 SEM images of nickel-cobalt hydroxide composites

图5 MISR中制备的材料的XPS谱图

Fig.5 XPS spectra of materials prepared in MISR

图6 MISR中制备的镍钴复合氢氧化物的整体元素分布

Fig.6 Global element distribution of materials prepared in MISR

图7 MISR中制备的镍钴复合氢氧化物的局部元素分布

Fig.7 Local element distribution of materials prepared in MISR

表1 MISR中制备的镍钴复合氢氧化物材料元素分布

Table 1 Element distributions of materials prepared in MISR

元素	原子百分比/%
元素	整体	Line 1	Line 2	Line 3	Line 4	Line 5
Ni	25.96	24.70	31.88	33.10	24.06	24.22
Co	8.87	8.32	10.26	10.76	7.71	7.99
O	65.17	66.98	57.86	56.14	68.22	67.79

图8 MISR制备的镍钴复合氢氧化物的TEM及EDS图

Fig.8 TEM and EDS images of materials prepared in MISR

图9 MISR中制备的镍钴复合氢氧化物的N2吸附/脱附等温线（插图为孔径分布）

Fig.9 N2 absorption/desorption isotherms of materials prepared in MISR(insert is pore size distributions)

图10 镍钴复合氢氧化物的电化学性能

Fig.10 Electrochemical properties of nickel-cobalt hydroxide composites

图11 二电极测试结果

Fig.11 Two-electrode test results

图12 器件的Ragone图

Fig.12 Ragone plot of the device

参考文献 30

1	Zhang L L, Zhao X. Carbon-based materials as supercapacitor electrodes[J]. Chemical Society Reviews, 2009, 38(9): 2520-2531.
2	Balducci A, Dugas R, Taberna P L, et al. High temperature carbon-carbon supercapacitor using ionic liquid as electrolyte[J]. Journal of Power Sources, 2007, 165(2): 922-927.
3	Largeot C, Portet C, Chmiola J, et al. Relation between the ion size and pore size for an electric double-layer capacitor[J]. Journal of the American Chemical Society, 2008, 130(9): 2730-2731.
4	Kandalkar S, Dhawale D, Kim C K, et al. Chemical synthesis of cobalt oxide thin film electrode for supercapacitor application[J]. Synthetic Metals, 2010, 160(11/12): 1299-1302.
5	Brousse T, Bélanger D, Long J W. To be or not to be pseudocapacitive?[J]. Journal of the Electrochemical Society, 2015, 162(5): A5185-A5189.
6	Wang T, Chen H C, Yu F, et al. Boosting the cycling stability of transition metal compounds-based supercapacitors[J]. Energy Storage Materials, 2019, 16: 545-573.
7	Wang Y, Song Y, Xia Y. Electrochemical capacitors: mechanism, materials, systems, characterization and applications[J]. Chem. Soc. Rev., 2016, 45(21): 5925-5950.
8	Li B, Zheng M, Xue H, et al. High performance electrochemical capacitor materials focusing on nickel based materials[J]. Inorganic Chemistry Frontiers, 2016, 3(2): 175-202.
9	Chen X, Long C, Lin C, et al. Al and Co co-doped α-Ni(OH)₂/graphene hybrid materials with high electrochemical performances for supercapacitors[J]. Electrochimica Acta, 2014, 137: 352-358.
10	Yao C, Su Y, Li Y, et al. Preparation and electrochemical properties of NiCo₂O₄/rGO composites[J]. International Journal of Electrochemical Science, 2021, 16(1): 150917.
11	Feng Q, Liu F, Yuan J, et al. Co-doped Ni(OH)₂ ultrafine particles with high supercapacitor performance[J]. International Journal of Electrochemical Science, 2020, 15: 2863-2873.
12	Sethi M, Bhat D K. Facile solvothermal synthesis and high supercapacitor performance of NiCo₂O₄ nanorods[J]. Journal of Alloys and Compounds, 2019, 781: 1013-1020.
13	Chang J, Sun J, Xu C, et al. Template-free approach to synthesize hierarchical porous nickel cobalt oxides for supercapacitors[J]. Nanoscale, 2012, 4(21): 6786-6791.
14	Wu S, Yun J M, Kim K H. Solvothermal synthesis of nickel-aluminum layered double hydroxide nanosheet arrays on nickel foam as binder-free electrodes for supercapacitors[J]. Journal of Inorganic and Organometallic Polymers and Materials, 2017, 27(6): 1933-1940.
15	Liu M C, Kong L B, Lu C, et al. A sol-gel process for fabrication of NiO/NiCo₂O₄/Co₃O₄ composite with improved electrochemical behavior for electrochemical capacitors[J]. ACS Applied Materials and Interfaces, 2012, 4(9): 4631-4636.
16	Matteucci M E, Hotze M A, Johnston K P, et al. Drug nanoparticles by antisolvent precipitation: mixing energy versus surfactant stabilization[J]. Langmuir, 2006, 22(21): 8951-8959.
17	Yue X J, Luo Y, Chen Q Y, et al. Investigation of micromixing and precipitation process in a rotating packed bed reactor with PTFE packing[J]. Chemical Engineering and Processing-Process Intensification, 2018, 125: 227-233.
18	Bałdyga J, Bourne J R. Turbulent Mixing and Chemical Reactions[M]. Chichester, UK: Wiley, 1999.
19	Chen J, Shao L. Mass production of nanoparticles by high gravity reactive precipitation technology with low cost[J]. China Particuology, 2003, 1(2): 64-69.
20	Elperin I. Heat and mass transfer in opposing currents[J]. Journal of Engineering Physics, 1961, 6(6): 62-68.
21	Zhang Q C, Cheng K P, Wen L X, et al. A study on the precipitating and aging processes of CuO/ZnO/Al₂O₃ catalysts synthesized in micro-impinging stream reactors[J]. RSC Advances, 2016, 6(40): 33611-33621.
22	Liu Z, Guo L, Huang T, et al. Experimental and CFD studies on the intensified micromixing performance of micro-impinging stream reactors built from commercial T-junctions[J]. Chemical Engineering Science, 2014, 119: 124-133.
23	Gu R, Cheng K, Wen L. Application of the engulfment model in assessing micromixing time of a micro-impinging stream reactor based on the determination of impinging zone with CFD[J]. Chemical Engineering Journal, 2021, 409: 128248.
24	Chen H, Wang J M, Pan T, et al. The structure and electrochemical performance of spherical Al-substituted α - N i ( O H ) 2 for alkaline rechargeable batteries[J]. Journal of Power Sources, 2005, 143(1/2): 243-255.
25	Aghazadeh M, Ghaemi M, Sabour B, et al. Electrochemical preparation of α - N i ( O H ) 2 ultrafine nanoparticles for high-performance supercapacitors[J]. Journal of Solid State Electrochemistry, 2014, 18(6): 1569-1584.
26	Yan J, Sun W, Wei T, et al. Fabrication and electrochemical performances of hierarchical porous Ni(OH)₂ nanoflakes anchored on graphene sheets[J]. Journal of Materials Chemistry, 2012, 22(23): 11494-11502.
27	Yang J, Yu C, Fan X, et al. Facile fabrication of MWCNT-doped NiCoAl-layered double hydroxide nanosheets with enhanced electrochemical performances[J]. Journal of Materials Chemistry A, 2013, 1(6): 1963-1968.
28	Che W, Wei M, Sang Z, et al. Perovskite LaNiO_3- _δ oxide as an anion-intercalated pseudocapacitor electrode[J]. Journal of Alloys and Compounds, 2018, 731: 381-388.
29	Liang K, Wang N, Zhou M, et al. Mesoporous LaNiO₃/NiO nanostructured thin films for high-performance supercapacitors[J]. Journal of Materials Chemistry A, 2013, 1(34): 9730-9736.
30	Zhang Q C, Tian L L, Wu Y C, et al. Fast coprecipitation of nickel-cobalt oxide in a micro-impinging stream reactor for the construction of high-performance asymmetric supercapacitors[J]. Journal of Alloys and Compounds, 2019, 792: 314-327.

[1]	胡兴枝, 张皓焱, 庄境坤, 范雨晴, 张开银, 向军. 嵌有超小CeO₂纳米粒子的碳纳米纤维的制备及其吸波性能[J]. 化工学报, 2023, 74(8): 3584-3596.
[2]	段重达, 姚小伟, 朱家华, 孙静, 胡南, 李广悦. 环境因素对克雷白氏杆菌诱导碳酸钙沉淀的影响[J]. 化工学报, 2023, 74(8): 3543-3553.
[3]	张澳, 罗英武. 低模量、高弹性、高剥离强度丙烯酸酯压敏胶[J]. 化工学报, 2023, 74(7): 3079-3092.
[4]	王杰, 丘晓琳, 赵烨, 刘鑫洋, 韩忠强, 许雍, 蒋文瀚. 聚电解质静电沉积改性PHBV抗氧化膜的制备与性能研究[J]. 化工学报, 2023, 74(7): 3068-3078.
[5]	蔡斌, 张效林, 罗倩, 党江涛, 左栗源, 刘欣梅. 导电薄膜材料的研究进展[J]. 化工学报, 2023, 74(6): 2308-2321.
[6]	李靖, 沈聪浩, 郭大亮, 李静, 沙力争, 童欣. 木质素基碳纤维复合材料在储能元件中的应用研究进展[J]. 化工学报, 2023, 74(6): 2322-2334.
[7]	崔张宁, 胡紫璇, 吴雷, 周军, 叶干, 刘田田, 张秋利, 宋永辉. 可降解纤维素基材料的耐水性能研究进展[J]. 化工学报, 2023, 74(6): 2296-2307.
[8]	李振, 张博, 王丽伟. PEG-EG固-固相变材料的制备和性能研究[J]. 化工学报, 2023, 74(6): 2680-2688.
[9]	代佳琳, 毕唯东, 雍玉梅, 陈文强, 莫晗旸, 孙兵, 杨超. 热物性对混合型CPCMs固液相变特性影响模拟研究[J]. 化工学报, 2023, 74(5): 1914-1927.
[10]	陈韶云, 徐东, 陈龙, 张禹, 张远方, 尤庆亮, 胡成龙, 陈建. 单层聚苯胺微球阵列结构的制备及其吸附性能[J]. 化工学报, 2023, 74(5): 2228-2238.
[11]	王瑞恒, 何品晶, 吕凡, 章骅. 垃圾焚烧飞灰水洗后三种固液分离方法参数比较及优化[J]. 化工学报, 2023, 74(4): 1712-1723.
[12]	刘瑞琪, 周栖桐, 张悦, 贺莹, 高静, 马丽. 基于金纳米颗粒修饰二氧化硅纳米花的生物传感器构建及应用[J]. 化工学报, 2023, 74(3): 1247-1259.
[13]	徐东, 田杜, 陈龙, 张禹, 尤庆亮, 胡成龙, 陈韶云, 陈建. 聚苯胺/二氧化锰/聚吡咯复合纳米球的制备及其电化学储能性[J]. 化工学报, 2023, 74(3): 1379-1389.
[14]	陈瑞哲, 程磊磊, 顾菁, 袁浩然, 陈勇. 纤维增强树脂复合材料化学回收技术研究进展[J]. 化工学报, 2023, 74(3): 981-994.
[15]	付家崴, 陈帅帅, 方凯伦, 蒋新. 微反应器共沉淀反应制备铜锰催化剂[J]. 化工学报, 2023, 74(2): 776-783.