Supporting Information High Performance Lithium-Ion Hybrid Capacitors Employing Fe 3 O 4 -Graphene Composite Anode and Activated Carbon Cathode Shijia Zhang a,b,1, Chen Li a,b,1, Xiong Zhang a,b*, Xianzhong Sun a, Kai Wang a, Yanwei Ma a,b* a Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190, PR China b University of Chinese Academy of Sciences, Beijing 100049, PR China 1 These authors contributed equally to this work. E-mail address: zhangxiong@mail.iee.ac.cn; ywma@mail.iee.ac.cn
Figure S-1. Schematic structure of soft packaging LIC. Figure S-2. N 2 adsorption desorption isotherm and BJH model pore size distribution of RGO.
Figure S-3. (a) Nitrogen adsorption-desorption isotherm and density function theory (DFT) pore size distribution of AC. (b) Galvanostatic charge-discharge curves of AC at different current densities. (c) Rate performance of AC at different current densities in the voltage range of 2-4.2 V. (d-f) Prelithiation processes of full cells; (d) first galvanostatic charge-discharge curve of cathode in the voltage range of 2-4.2 V at current density of 50 ma g -1 ; (e) first galvanostatic charge-discharge curves of anode
in the voltage range of 0.03-3.0 V at current density of 50 ma g -1. (f) intercalation capacity of lithium ion curves. Figure S-4. Charge-discharge curves of electrodes and LIC at 0.1 and 0.2 A g -1.
Figure S-5. Cycling life, coulombic efficiency and charge discharge curves of Fe 3 O 4 -G//AC soft packaging hybrid capacitors with a mass ratio of 1:2.
Table S-1. Electrochemical performances of recently published Li-ion hybrid capacitors in organic system. Hybrid System (anode//cathode) Energy density (Wh kg 1 ) Power density (kw kg 1 ) Capacity retention //Cycing number Ref. TiC//PHPNC 112 67.5 83% 1 at 450 W kg 1 at 35.6 Wh kg -1 //5000 cycles Graphene/Li 4 Ti 5 O 12 //Graphene 95 at 45 W kg 1 3 at 32 Wh kg -1 87% //500 cycles 2 CNT/V 2 O 5 //AC 25.5 6.3 80% 3 TiO 2 belt //Graphene Graphene/Li 4 Ti 5 O 12 //AC Li 4 Ti 5 O 12 //carbo n cuboids Fe 3 O 4 /G //graphene at 40 W kg 1 82 at 570 W kg 1 at 6.9 Wh kg -1 19 50 Wh kg 1 2.5 65 Wh kg 1 10 147 at 150 W kg 1 at 21 Wh kg -1 at 15 Wh kg -1 at 9 Wh kg -1 2.587 at 86 Wh kg -1 //10000 cycles 73%, 600 cycles 75% 82% //10000 cycles 70% LiTi 2 (PO 4 ) 3 //AC 14 Wh kg 1 0.18 kw kg -1 68% 4 5 6 7 8 H 2 Ti 6 O 13 //CMK- 3 Nb 2 O 5 @Carbon //250 cycles 90 Wh kg 1 11 kw kg -1 80% 63 16.5 100% 9 10 //MSP-20 at 70 W kg 1 at 5 Wh kg -1 m-nb 2 O 5 -C //MSP-20 74 Wh kg -1 18.5 at 15 Wh kg -1 90% 11
T Nb 2 O 5 /Graph ene paper//ac 47 at 393 W kg 1 18 at 15 Wh kg -1 93% //2000 cycles 12 Graphene-VN 162 10 86% 13 //carbon at 200 W kg 1 nanorods B-Si/SiO 2 /C//AC 128 at 64 Wh kg -1 9.7 70% 14 at 1200 W kg 1 at 89 Wh kg -1 //6000 cycles H 2 Ti 12-x Nb x O 25 // AC 24.3 at 1800 W kg 1 5.8 at 11.3 Wh kg -1 84% //10000 cycles 15 N-GMCS//PLM G 80 at 152 W kg 1 88 at 32.2 Wh kg -1 93% //4000 cycles 16 Graphite//URGO 106 4.2 100% 17 at 84 W kg 1 at 85 Wh kg -1 //1000 3D-MnO//CNS 184 15 76% 18 at 83 W kg 1 at 90 Wh kg -1 //5000 NbN//NG 122.7 2 81.7% 19 at 100 W kg 1 at 98.4 Wh kg -1 //1000 MnO@GNS//H NC 127 at 125 W kg 1 15 at 83.25 Wh kg -1 76% //3000 20 G-MoO 2 // G-MoO 2 142.6 at 150 W kg 1 3 at 33.2 Wh kg -1 91.2% //500 21 Graphene//graph ene 148.3 at 141 W kg 1 7.8 at 71.5 Wh kg -1 68% //2000 22 CPIMS900//AC 28.5 6.9 97.1% 23 at 348 W kg 1 at 13.1 Wh kg -1 //5000 MCMB//AC 92.3 5.5 97% 24 at 114 W kg 1 at 23.3 Wh kg -1 //1000
Figure S-6. Ragone plots comparison between Fe 3 O 4 -G//AC LICs (the mass ratio of anode/cathode is 1:3 and 1:2, respectively) and commercial energy storage devices, calculated by ratio of 35%. References 1. Wang, H.; Zhang, Y.; Ang, H.; Zhang, Y.; Tan, H. T.; Zhang, Y.; Guo, Y.; Franklin, J. B.; Wu, X. L.; Srinivasan, M.; Fan, H. J.; Yan, Q. A High-Energy Lithium-Ion Capacitor by Integration of a 3D Interconnected Titanium Carbide Nanoparticle Chain Anode with a Pyridine-Derived Porous Nitrogen-Doped Carbon Cathode. Adv. Funct. Mater. 2016, 26, 3082-3093. 2. Leng, K.; Zhang, F.; Zhang, L.; Zhang, T.; Wu, Y.; Lu, Y.; Huang, Y.; Chen, Y. Graphene-Based Li-Ion Hybrid Supercapacitors with Ultrahigh Performance. Nano Res. 2013, 6, 581-592. 3. Chen, Z.; Augustyn, V.; Wen, J.; Zhang, Y.; Shen, M.; Dunn, B.; Lu, Y. High-Performance Supercapacitors Based on Intertwined CNT/V 2 O 5 Nanowire Nanocomposites. Adv. Mater. 2011, 23, 791-795.
4. Wang, H.; Guan, C.; Wang, X.; Fan, H. J. A High Energy and Power Li-Ion Capacitor Based on a TiO 2 Nanobelt Array Anode and a Graphene Hydrogel Cathode. Small 2015, 11, 1470-1477. 5. Kim, H.; Park, K.-Y.; Cho, M.-Y.; Kim, M.-H.; Hong, J.; Jung, S.-K.; Roh, K. C.; Kang, K. High-Performance Hybrid Supercapacitor Based on Graphene-Wrapped Li 4 Ti 5 O 12 and Activated Carbon. ChemElectroChem 2014, 1, 125-130. 6. Banerjee, A.; Upadhyay, K. K.; Puthusseri, D.; Aravindan, V.; Madhavi, S.; Ogale, S. Mof-Derived Crumpled-Sheet-Assembled Perforated Carbon Cuboids as Highly Effective Cathode Active Materials for Ultra-High Energy Density Li-Ion Hybrid Electrochemical Capacitors (Li-HECs). Nanoscale 2014, 6, 4387-4394. 7. Zhang, F.; Zhang, T.; Yang, X.; Zhang, L.; Leng, K.; Huang, Y.; Chen, Y. A High-Performance Supercapacitor-Battery Hybrid Energy Storage Device Based on Graphene-Enhanced Electrode Materials with Ultrahigh Energy Density. Energy Environ. Sci. 2013, 6, 1623-1632. 8. Aravindan, V.; Chuiling, W.; Reddy, M. V.; Rao, G. V.; Chowdari, B. V.; Madhavi, S. Carbon Coated Nano-LiTi 2 (PO 4 ) 3 Electrodes for Non-Aqueous Hybrid Supercapacitors. Phys. Chem. Chem. Phys. 2012, 14, 5808-5814. 9. Wang, Y.; Hong, Z.; Wei, M.; Xia, Y. Layered H 2 Ti 6 O 13 -Nanowires: A New Promising Pseudocapacitive Material in Non-Aqueous Electrolyte. Adv. Funct. Mater. 2012, 22, 5185-5193. 10. Lim, E.; Jo, C.; Kim, H.; Kim, M. H.; Mun, Y.; Chun, J.; Ye, Y.; Hwang, J.; Ha, K. S.; Roh, K. C.; Kang, K.; Yoon, S.; Lee, J. Facile Synthesis of Nb 2 O 5 @Carbon Core-Shell Nanocrystals with Controlled Crystalline Structure for High-Power Anodes in Hybrid Supercapacitors. ACS Nano 2015, 9, 7497-7505. 11. Lim, E.; Kim, H.; Jo, C.; Chun, J.; Ku, K.; Kim, S.; Lee, H. I.; Nam, I. S.; Yoon, S.; Kang, K. Advanced Hybrid Supercapacitor Based on a Mesoporous Niobium Pentoxide/Carbon as High-Performance Anode. ACS Nano 2014, 8, 8968-8978. 12. Kong, L.; Zhang, C.; Wang, J.; Qiao, W.; Ling, L.; Long, D. Free-Standing T-Nb 2 O 5 /Graphene Composite Papers with Ultrahigh Gravimetric/Volumetric Capacitance for Li-Ion Intercalation Pseudocapacitor. ACS Nano 2015, 9, 11200-11208. 13. Wang, R.; Lang, J.; Zhang, P.; Lin, Z.; Yan, X. Fast and Large Lithium Storage in 3D Porous VN Nanowires-Graphene Composite as a Superior Anode toward High-Performance Hybrid Supercapacitors. Adv. Funct. Mater. 2015, 25, 2270-2278.
14. Yi, R.; Chen, S.; Song, J.; Gordin, M. L.; Manivannan, A.; Wang, D. High-Performance Hybrid Supercapacitor Enabled by a High-Rate Si-Based Anode. Adv. Funct. Mater. 2014, 24, 7433-7439. 15. Lee, J. H.; Kim, H.-K.; Baek, E.; Pecht, M.; Lee, S.-H.; Lee, Y.-H. Improved Performance of Cylindrical Hybrid Supercapacitor Using Activated Carbon/ Niobium Doped Hydrogen Titanate. J. Power Sources 2016, 301, 348-354. 16. Yu, X.; Zhan, C.; Lv, R.; Bai, Y.; Lin, Y.; Huang, Z.-H.; Shen, W.; Qiu, X.; Kang, F. Ultrahigh-Rate and High-Density Lithium-Ion Capacitors through Hybriding Nitrogen-Enriched Hierarchical Porous Carbon Cathode with Prelithiated Microcrystalline Graphite Anode. Nano Energy 2015, 15, 43-53. 17. Lee, J. H.; Shin, W. H.; Ryou, M. H.; Jin, J. K.; Kim, J.; Choi, J. W. Functionalized Graphene for High Performance Lithium Ion Capacitors. ChemSusChem 2012, 5, 2328-2333. 18. Wang, H.; Xu, Z.; Li, Z.; Cui, K.; Ding, J.; Kohandehghan, A.; Tan, X.; Zahiri, B.; Olsen, B. C.; Holt, C. M.; Mitlin, D. Hybrid Device Employing Three-Dimensional Arrays of MnO in Carbon Nanosheets Bridges Battery-Supercapacitor Divide. Nano Lett. 2014, 14, 1987-1994. 19. Liu, M.; Zhang, L.; Han, P.; Han, X.; Du, H.; Yue, X.; Zhang, Z.; Zhang, H.; Cui, G. Controllable Formation of Niobium Nitride/Nitrogen-Doped Graphene Nanocomposites as Anode Materials for Lithium-Ion Capacitors. Part. Part. Syst. Charact. 2015, 32, 1006-1011. 20. Yang, M.; Zhong, Y.; Ren, J.; Zhou, X.; Wei, J.; Zhou, Z. Fabrication of High-Power Li-Ion Hybrid Supercapacitors by Enhancing the Exterior Surface Charge Storage. Adv. Energy Mater. 2015, 5, 2416-2420. 21. Han, P.; Ma, W.; Pang, S.; Kong, Q.; Yao, J.; Bi, C.; Cui, G. Graphene Decorated with Molybdenum Dioxide Nanoparticles for Use in High Energy Lithium Ion Capacitors with an Organic Electrolyte. J. Mater. Chem. A. 2013, 1, 5949-5954. 22. Zhang, T.; Zhang, F.; Zhang, L.; Lu, Y.; Zhang, Y.; Yang, X.; Ma, Y.; Huang, Y. High Energy Density Li-Ion Capacitor Assembled with All Graphene-Based Electrodes. Carbon 2015, 92, 106-118. 23. Han, X.; Han, P.; Yao, J.; Zhang, S.; Cao, X.; Xiong, J.; Zhang, J.; Cui, G. Nitrogen-Doped Carbonized Polyimide Microsphere as a Novel Anode Material for High Performance Lithium Ion Capacitors. Electrochim. Acta 2016, 196, 603-610.
24. Shi, Z.; Zhang, J.; Wang, J.; Shi, J.; Wang, C. Effect of the Capacity Design of Activated Carbon Cathode on the Electrochemical Performance of Lithium-Ion Capacitors. Electrochim. Acta 2015, 153, 476-483.