无机材料学报 ›› 2020, Vol. 35 ›› Issue (2): 145-157.DOI: 10.15541/jim20190108
所属专题： 2020年能源材料论文精选(二)：超级电容器； 【虚拟专辑】超级电容器(2020~2021)； 【虚拟专辑】柔性材料(2020~2021)
• 综述 • 下一篇
马丽娜1,石川2,赵宁2,毕志杰2,郭向欣2(
),黄玉东3
收稿日期:2019-03-12
修回日期:2019-05-17
出版日期:2020-02-20
网络出版日期:2019-06-17
作者简介:马丽娜(1988-), 女, 副教授. E-mail: malina@qdu.edu.cn
基金资助:
MA Li-Na1,SHI Chuan2,ZHAO Ning2,BI Zhi-Jie2,GUO Xiang-Xin2(),HUANG Yu-Dong3
Received:2019-03-12
Revised:2019-05-17
Published:2020-02-20
Online:2019-06-17
Supported by:摘要：
细菌纤维素(Bacterial Cellulose, BC)是由微生物发酵获得的具有纳米尺寸的聚合物生物材料, 具有比表面积大、机械强度高、持水能力强、化学稳定性好及环境友好等特质, 可用于制备三维纳米碳材料的前驱体或支撑其他功能材料的柔性骨架。本文介绍了基于BC制备的各种碳纳米纤维(Carbon Nanofiber, CNF)及其复合材料, 包括掺杂CNF、CNF/金属氧化物、CNF/导电聚合物等材料。描述了这些材料在超级电容器中的应用, 关注BC用于可弯曲电极的设计和制备; 进一步阐述了当前BC应用于能源存储领域所面临的挑战和机遇, 并对其未来发展包括在高性能二次电池方面的应用等进行了展望。
中图分类号:
马丽娜,石川,赵宁,毕志杰,郭向欣,黄玉东. 细菌纤维素基纳米生物材料在储能领域的应用[J]. 无机材料学报, 2020, 35(2): 145-157.
MA Li-Na,SHI Chuan,ZHAO Ning,BI Zhi-Jie,GUO Xiang-Xin,HUANG Yu-Dong. Bacterial Cellulose Based Nano-biomaterials for Energy Storage Applications[J]. Journal of Inorganic Materials, 2020, 35(2): 145-157.
图1 (a) BC生产线照片[3]; (b)植物纤维素(左)和BC(右)模型的比较[5]; (c) BC膜的实物、(d) SEM及(e)TEM照片[4]
Fig. 1 (a) Photograph of the production line for BC[3]; (b) Schematic model of the plant cellulose fibrils (left) and the BC microfibers (right)[5]; (c) Photograph of BC slice; (d) SEM and (e)TEM images of BC[4]
| Material | Function of BC | Potential window/V | Capacitance/ (F∙g-1) | Rate capability | Stability (cycle number) | Highest energy density/ (Wh∙kg-1) | Highest power density/ (kW∙kg-1) | Ref. |
|---|---|---|---|---|---|---|---|---|
| CO2 activated CNF | Active material | -0.2-0.2 (vs. Ag/AgCl) | 42 (1 mV∙s-1) (659 mF∙cm-2) | 70% (10 mV∙s-1) | — | — | — | [14] |
| CNF | Active material | -1-0 (vs. Ag/AgCl) | 108 (2 A∙g-1) | — | — | — | — | [15] |
| PCN/CNF | Active material | -1-0 (vs. Hg/HgO) | 261 (2 mV∙s-1) | 76.6 (500 mV∙s-1) | 97.6% (10000) | — | — | [18] |
| PCN/CNF// PCN/CNF | Active material | 0-1.8 | — | — | 94.8% (10000) | 20.4 | 17.8 | [18] |
| N,P-CNF// N,P-CNF | Active material | 0-1 | 204.9 (1 A∙g-1) | — | 100% (4000) | 7.76 | 26.1 | [2] |
| N-S-CNF-700 | Active material | 0-1 (vs. Ag/AgCl) | 171.2 (0.5 A∙g-1) | 105.2 (10 A∙g-1) | >90% (1000) | — | — | [20] |
| KOH activated N-CNF | Active material | 0.9-0.1 (vs. SHE) | 296 (2 mV∙s-1) | 75% (500 mV∙s-1) | 99% (10000) | — | — | [12] |
| N-CNF | Active material | -1-0 (vs. Ag/AgCl) | 120 (1 A∙g-1) | — | 98.2% (5000) | — | — | [13] |
| N,P-CNWs | Active material | -1-0 (vs. Hg/HgO) | 258 (1 A∙g-1) | 208 (10 A∙g-1) | 98% (30000) | — | — | [26] |
| N,P-CNWs// N,P-CNWs | Active material | 0-1 | 74 (0.5 A∙g-1) | — | 87% (6000) | 5.4 | 0.2 | [26] |
| CNF aerogels | Active material | -1-0 (vs. Ag/AgCl) | 194.7 (0.5 A∙g-1) | 108.7(10 A∙g-1) | 94% (5000) | — | — | [19] |
表1 BC基碳材料超级电容器电极的电化学性能
Table 1 BC-based carbon material electrodes for supercapacitor
| Material | Function of BC | Potential window/V | Capacitance/ (F∙g-1) | Rate capability | Stability (cycle number) | Highest energy density/ (Wh∙kg-1) | Highest power density/ (kW∙kg-1) | Ref. |
|---|---|---|---|---|---|---|---|---|
| CO2 activated CNF | Active material | -0.2-0.2 (vs. Ag/AgCl) | 42 (1 mV∙s-1) (659 mF∙cm-2) | 70% (10 mV∙s-1) | — | — | — | [14] |
| CNF | Active material | -1-0 (vs. Ag/AgCl) | 108 (2 A∙g-1) | — | — | — | — | [15] |
| PCN/CNF | Active material | -1-0 (vs. Hg/HgO) | 261 (2 mV∙s-1) | 76.6 (500 mV∙s-1) | 97.6% (10000) | — | — | [18] |
| PCN/CNF// PCN/CNF | Active material | 0-1.8 | — | — | 94.8% (10000) | 20.4 | 17.8 | [18] |
| N,P-CNF// N,P-CNF | Active material | 0-1 | 204.9 (1 A∙g-1) | — | 100% (4000) | 7.76 | 26.1 | [2] |
| N-S-CNF-700 | Active material | 0-1 (vs. Ag/AgCl) | 171.2 (0.5 A∙g-1) | 105.2 (10 A∙g-1) | >90% (1000) | — | — | [20] |
| KOH activated N-CNF | Active material | 0.9-0.1 (vs. SHE) | 296 (2 mV∙s-1) | 75% (500 mV∙s-1) | 99% (10000) | — | — | [12] |
| N-CNF | Active material | -1-0 (vs. Ag/AgCl) | 120 (1 A∙g-1) | — | 98.2% (5000) | — | — | [13] |
| N,P-CNWs | Active material | -1-0 (vs. Hg/HgO) | 258 (1 A∙g-1) | 208 (10 A∙g-1) | 98% (30000) | — | — | [26] |
| N,P-CNWs// N,P-CNWs | Active material | 0-1 | 74 (0.5 A∙g-1) | — | 87% (6000) | 5.4 | 0.2 | [26] |
| CNF aerogels | Active material | -1-0 (vs. Ag/AgCl) | 194.7 (0.5 A∙g-1) | 108.7(10 A∙g-1) | 94% (5000) | — | — | [19] |
图2 (a)非对称型超级电容器的原理图, (b)N-CNF/MnO2的TEM照片, (c)N-CNF/MnO2电极的GCD曲线, (d)质量比电容和(e)循环稳定性测试[12]
Fig. 2 (a) Schematic diagram for asymmetric supercapacitor device; (b) TEM images, (c) GCD curves, (d) specific capacitance and (e) cycle performance of N-CNF/MnO2[12]
图3 (a)杂原子掺杂CNF的制备流程图, (b)映射图像, (c) CV曲线, (d) GCD曲线和(e)循环稳定性测试[2]
Fig. 3 (a) Fabrication process of heteroatom-doped CNF; (b) Elemental mapping images of C, N, P, and O for N, P-CNF; (c) CV curves, (d) GCD curves and (e) cycling stability test of N,P-CNF supercapacitor[2]
图4 (a)PPY/BC/GO复合物的制备流程图, (b~f)不同物质的SEM照片[38]
Fig. 4 (a) Synthesis scheme of PPY/BC/GO composites; SEM images of (b) pristine GO, (c) cross-linked BC/GO, (d) a single layer and (e) multilayers of PPY/BC/GO hybrid, and (f) PPY/BC core-sheath hybrid[38]
| Material | Function of BC | Potential window/V | Capacitance/ (F∙g-1) | Rate capability | Stability (cycle number) | Highest energy density/ (Wh∙kg-1) | Highest power density/ (kW∙kg-1) | Ref. |
|---|---|---|---|---|---|---|---|---|
| CNF@MnO2 | Active material | 0-1 (vs. Ag/AgCl) | 254.64 (1 A∙g-1) | 77.53% (10 A∙g-1) | — | — | — | [24] |
| CNF@MnO2// N-CNF | Active material | 0-2 | — | — | 95.4% (2000) | 32.91 | 284.63 | [24] |
| Ni3S2/CNF | Active material | 0-0.6 (vs. Ag/AgCl) | 957 (1 A∙g-1) | 703 (8 A∙g-1) | 16.5% (1000) | — | — | [15] |
| Ni3S2/CNF//CNF | Active material | 0-1.7 | 56.6 (1 A∙g-1) | 35.4 (10 A∙g-1) | 97% (2500) | 25.8 | 0.425 | [15] |
| CNF/MnO2 | Active material | 0.15-1.15 (vs. SCE) | 273 (2 mV∙s-1) | 75% (100 mV∙s-1) | — | — | — | [12] |
| CNF//CNF/MnO2 | Active material | 0-2 | 113 (20 mV∙s-1) | 53% (10~200 mV∙s-1) | 92% (5000) | 63 | 8 | [12] |
| N-CNF@LDH | Active material | 0-0.5 (Ag/AgCl) | 1949.5 (1 A∙g-1) | 54.7 (10 A∙g-1) | 74.4% (5000) | — | — | [23] |
| N-CNF@LDH// N-CNF | Active material | 0-1.6 | 101.9 (1 A∙g-1) | 63.8 (10 A∙g-1) | 89.3% (2500) | 36.3 | 8 | [23] |
表2 BC基复合材料超级电容器电极的电化学性能
Table 2 BC-based composites electrodes for supercapacitor
| Material | Function of BC | Potential window/V | Capacitance/ (F∙g-1) | Rate capability | Stability (cycle number) | Highest energy density/ (Wh∙kg-1) | Highest power density/ (kW∙kg-1) | Ref. |
|---|---|---|---|---|---|---|---|---|
| CNF@MnO2 | Active material | 0-1 (vs. Ag/AgCl) | 254.64 (1 A∙g-1) | 77.53% (10 A∙g-1) | — | — | — | [24] |
| CNF@MnO2// N-CNF | Active material | 0-2 | — | — | 95.4% (2000) | 32.91 | 284.63 | [24] |
| Ni3S2/CNF | Active material | 0-0.6 (vs. Ag/AgCl) | 957 (1 A∙g-1) | 703 (8 A∙g-1) | 16.5% (1000) | — | — | [15] |
| Ni3S2/CNF//CNF | Active material | 0-1.7 | 56.6 (1 A∙g-1) | 35.4 (10 A∙g-1) | 97% (2500) | 25.8 | 0.425 | [15] |
| CNF/MnO2 | Active material | 0.15-1.15 (vs. SCE) | 273 (2 mV∙s-1) | 75% (100 mV∙s-1) | — | — | — | [12] |
| CNF//CNF/MnO2 | Active material | 0-2 | 113 (20 mV∙s-1) | 53% (10~200 mV∙s-1) | 92% (5000) | 63 | 8 | [12] |
| N-CNF@LDH | Active material | 0-0.5 (Ag/AgCl) | 1949.5 (1 A∙g-1) | 54.7 (10 A∙g-1) | 74.4% (5000) | — | — | [23] |
| N-CNF@LDH// N-CNF | Active material | 0-1.6 | 101.9 (1 A∙g-1) | 63.8 (10 A∙g-1) | 89.3% (2500) | 36.3 | 8 | [23] |
图5 (a)BC纸和(b)CNT/BC纸的照片; (c)CNT/BC纸的SEM截面照片; 柔性超级电容器的 (d)GCD曲线和(e)CV曲线; (f)柔性超级电容器照片[41]
Fig. 5 Photographs of (a) BC paper and (b) flexible CNT/BC paper; (c) Cross-sectional image of CNT/BC paper; (d) GCD curve and (e) CV curves for CNT/BC/ion gel flexible supercapacitors; (f) Photograph of a LED turned on by the flexible supercapacitors[41]
| Material | Function of BC | Potential window/V | Capacitance/ (mF∙cm-2) | Capacitance/ (F∙g-1) | Rate capability | Stability (cycle number) | Highest energy density | Highest power density | Ref. |
|---|---|---|---|---|---|---|---|---|---|
| N-CNF/RGO/BC | Active material & substrate | -0.8-0.2 (vs. Hg/HgO) | 2106 (1 mV∙s-1) | 263 | 76% (50 mV∙s-1) | 100% (2×104) | — | — | [45] |
| N-CNF/RGO/BC//N-CNF/RGO/BC | Active material & substrate | 0-1 | 810 (2 mV∙s-1) | — | 755 (50 mV∙s-1) | 99.6% (104) | 0.11 mWh∙cm-2 | 27 mW∙cm-2 | [46] |
| N,P-CNF/RGO/BC | Active material & substrate | -0.8-0.2 (vs. Hg/HgO) | 1900 (2 mV∙s-1) | 244.8 | 1554 (50 mV∙s-1) | 100% (2×104) | — | — | [16] |
| N,P-CNF/RGO/ BC//N,P-CNF/ RGO/BC | Active material & substrate | 0-1 | 690 (2 mV∙s-1) | — | 620 (40 mV∙s-1) | 99.6% (1×104) | 0.096 mWh∙cm-2 | 19.98 mW∙cm-2 | [16] |
| BC/GO electrode | Scaffold | -0.2-0.8 (vs. SCE) | — | 160 (0.4 A∙g-1) | 68 (2 A∙g-1) | 90.3% (2×103) | — | — | [44] |
| BC/CNT/ion gel supercapacitors | Substrate | 0-3 | 18.8 (100 mV∙s-1) | 46.9 | 42.0 (500 mV∙s-1) | 99.5% (5×104) | 15.5 Wh∙kg-1 | 1.5 kW∙kg-1 | [41] |
| a-CNF//BC gel// a-CNF supercapacitors | Active material & electrolyte & separator | 0-1 | 289 (0.1 mA∙cm-2) | — | 70% (10 mA∙cm-2) | 66.7% (100) | — | — | [60] |
表3 BC基柔性超级电容器电极的电化学性能
Table 3 BC-based electrodes for flexible EDLCs
| Material | Function of BC | Potential window/V | Capacitance/ (mF∙cm-2) | Capacitance/ (F∙g-1) | Rate capability | Stability (cycle number) | Highest energy density | Highest power density | Ref. |
|---|---|---|---|---|---|---|---|---|---|
| N-CNF/RGO/BC | Active material & substrate | -0.8-0.2 (vs. Hg/HgO) | 2106 (1 mV∙s-1) | 263 | 76% (50 mV∙s-1) | 100% (2×104) | — | — | [45] |
| N-CNF/RGO/BC//N-CNF/RGO/BC | Active material & substrate | 0-1 | 810 (2 mV∙s-1) | — | 755 (50 mV∙s-1) | 99.6% (104) | 0.11 mWh∙cm-2 | 27 mW∙cm-2 | [46] |
| N,P-CNF/RGO/BC | Active material & substrate | -0.8-0.2 (vs. Hg/HgO) | 1900 (2 mV∙s-1) | 244.8 | 1554 (50 mV∙s-1) | 100% (2×104) | — | — | [16] |
| N,P-CNF/RGO/ BC//N,P-CNF/ RGO/BC | Active material & substrate | 0-1 | 690 (2 mV∙s-1) | — | 620 (40 mV∙s-1) | 99.6% (1×104) | 0.096 mWh∙cm-2 | 19.98 mW∙cm-2 | [16] |
| BC/GO electrode | Scaffold | -0.2-0.8 (vs. SCE) | — | 160 (0.4 A∙g-1) | 68 (2 A∙g-1) | 90.3% (2×103) | — | — | [44] |
| BC/CNT/ion gel supercapacitors | Substrate | 0-3 | 18.8 (100 mV∙s-1) | 46.9 | 42.0 (500 mV∙s-1) | 99.5% (5×104) | 15.5 Wh∙kg-1 | 1.5 kW∙kg-1 | [41] |
| a-CNF//BC gel// a-CNF supercapacitors | Active material & electrolyte & separator | 0-1 | 289 (0.1 mA∙cm-2) | — | 70% (10 mA∙cm-2) | 66.7% (100) | — | — | [60] |
图6 (a) CNT/BC和PANI/CNT/BC的照片; (b) PANI/CNT/BC的SEM照片和(c) CV曲线; (d) PANI/CNT/BC柔性超级电容器的结构示意图, (e)电子照片和(f)不同弯折角度的CV曲线[1]
Fig. 6 (a) Photographs of CNT/BC paper and PANI/CNT/BC paper; (b) SEM image and (c) CV curves of PANI/CNT/BC electrode; (d) Schematic structure, (e) digital images and (f) CV curves for flexible supercapacitor[1]
图7 Ni(OH)2/RGO/BC的(a)SEM和(b) TEM照片; (c,d)Ni(OH)2/RGO/BC的SEM截面照片; Ni(OH)2/RGO/BC电极的(e)CV和(f)GCD曲线[58]
Fig. 7 (a) SEM and (b) TEM images of Ni(OH)2/RGO/BC; (c, d) Cross-sectional SEM micrographs of Ni(OH)2/RGO/BC; (e) CV and (f) GCD curves of Ni(OH)2/RGO/BC electrode[58]
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