Se encapsulated into honeycomb 3D porous carbon with Se-C bonds as superb performance cathodes for Li-Se Batteries

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College of Metrology and Measurement Engineering, China Jiliang University (CJLU), Hangzhou 310018, P.R. China
2.
College of Materials and Chemisty, China Jiliang University (CJLU), Hangzhou 310018, China

Funds: The authors are very grateful for the financial support from the project of the Fundamental Research Funds for the Provincial Universities of Zhejiang (No. 2021YW51)

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Corresponding author: E-mail: jingjingzhang@cjlu.edu.cn; fanmeiqiang@126.com

摘要

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Abstract: Li-Se Batteries has been considered as promising lithium-ion batteries due to their super volumetric energy density and high electrical conductivity of Se. However, the development of Li-Se batteries application is impeded by the boring volume expansion and polyselenide dissolution of electrodes during cycling, as well as the low selenium loading. A feasible and effective approach to settle these three issues is to keep selenium into a carbon host with sufficient pore volume and simultaneously enhance the interfacial interaction between selenium and carbon. A novel cathode material of Se encapsulated into honeycomb 3D porous carbon (HPC@Se) with Se-C bonds for Li-Se Batteries is synthesized by impregnating Se into the tartrate salt derived honeycomb 3D porous carbon. The pore volume of the obtained honeycomb 3D porous carbon is up to 1.794 cm³ g⁻¹, which allows 65%wt selenium to be uniformly encapsulated. Moreover, the strong chemical bonds between selenium and carbon are beneficial for stabilizing selenium, thus further relieving its huge volume expansion and polyselenide dissolution as well as promote the charge transfer during cycling. As expected, HPC@Se cathode presents fantastic cyclability and rate performance. After 200 cycles, its specific capacity remained at 561 mA h g⁻¹ (83% of the theoretical specific capacity) at 0.2 C. And the capacity recession is just 0.058 percentage each cycle. Besides, HPC@Se cathode can also demonstrate a considerable capacity of 472.8 mA h g⁻¹ under the higher current density of 5 C.
- Li-Se Batteries /
- cathodes /
- honeycomb 3D porous carbon /
- high loading /
- Se-C bonds

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Figure 1. SEM images of HPC (a, b), HPC@Se (c, d) and Elemental mapping of Se (e) and carbon (f) in HPC@Se composite. Insert in (a) is the digital photograph of honeycomb.

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Figure 2. (a, b) TEM images of HPC and (c, d) HPC@Se, (e) N₂ adsorption-desorption isotherms and (f) pore size distributions of HPC and HPC@Se.

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Figure 3. (a) Typical XRD spectra, (b) FTIR patterns, (c) Raman patterns of pristine Se, HPC@Se and HPC, (d) TGA of HPC@Se, XPS spectra of Se3d signal (e) and C1s signal (f).

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Figure 4. (a) CV curves between 1.0 and 3.0 V (ver. Li/Li⁺) at a scan rate of 0.1 mV s^-1, (b) Galvanostatic charge/discharge profiles for the first 3 cycles at 0.2 C, (c) Cycle capacity at 0.2 C, (d) The rate performance for HPC@Se and (e) Nyquist plots of the HPC@Se and pristine Se.

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S1. (a) The first discharge-charge profiles for HPC@Se (5 mg) at 0.2 C in 1.0–3.0 V, (b) Cycle performance at 0.2 C in 1.0–3.0 V for the HPC@Se (2 mg) and the HPC@Se (5 mg).

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Figure 5. (a and b) Digital photos of pristine Se and HPC@Se electrodes after 200 cycles at 0.2 C in electrolyte. (c) SEM image of HPC@Se after 200 cycles and its elemental mapping of (d) carbon and Se (e).

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Figure 6. (a) XRD spectra of pristine Se, Ex-situ XRD spectra of HPC@Se discharged to 1.0 V and charged to 3.0 V, (b) FTIR spectra of HPC@Se discharged to 1.0 V and charged to 3.0 V at 0.2 C.

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Figure 7. (a) CV profiles of HPC@Se with gradually increasing scan rates from 0.1 to 5 mV s⁻¹, (b) b-value for the oxidation peak and reduction peak, (c) Contribution ratio of capacitance and diffusion behavior at 0.1, 0.5, 1 and 5 mV s⁻¹ scan rates, (d) Summary of the ratio of capacitive-controlled and diffusion-controlled contribution with gradually increasing scan rates for HPC@Se electrode.

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Table 1. comparison between HPC@Se (this work) and the published Se/C electrodes.

Material	Selenium content	Reversible capacity (mA h g⁻¹)	Percentage of theoretical capacity (678 mA h g⁻¹)	current density (C, 1C = 678 mA h g⁻¹)	Ref.
HPC@Se	65% wt	561/200 cycles	82.7%	0.2 C	this work
Mic/Se	44.2% wt	400/500 cycles	59.0%	0.5 C	[13]
Se@LHPC	52% wt	450/500 cycles	66.4%	0.5 C	[14]
Se-HPCF	50% wt	533/50 cycles	78.6%	0.2 C	[15]
C/Se	54% wt	430/250 cycles	63.4%	100 mA g⁻¹	[16]
Se@3D MIL-68 (Al)@MWCNTs	56% wt	453/200 cycles	66.8%	0.2 C	[25]
Se@HPCNBs	60% wt	560/100 cycles	82.6%	0.2 C	[26]

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参考文献(32)

[1]	Xie J, Li J, Mai W, et al. A decade of advanced rechargeable batteries development guided by in situ transmission electron microscopy[J]. Nano Energy,2021,83:105780. doi: 10.1016/j.nanoen.2021.105780
[2]	Liang Y, Zhao C Z, Yuan H, et al. A review of rechargeable batteries for portable electronic devices[J]. InfoMat,2019,1(1):6-32. doi: 10.1002/inf2.12000
[3]	Zhang X, Ju Z, Zhu Y, et al. Multiscale understanding and architecture design of high energy/power lithium-ion battery electrodes[J]. Advanced Energy Materials,2021,11(2):2000808. doi: 10.1002/aenm.202000808
[4]	Wu Y, Wang W, Ming J, et al. An exploration of new energy storage system: high energy density, high safety, and fast charging lithium ion battery[J]. Advanced Functional Materials,2019,29(1):1805978. doi: 10.1002/adfm.201805978
[5]	Li Q, Fung K Y, Xu L, et al. Process synthesis: selective recovery of lithium from lithium-ion battery cathode materials[J]. Industrial & Engineering Chemistry Research,2019,58(8):3118-3130.
[6]	Manthiram A. A reflection on lithium-ion battery cathode chemistry[J]. Nature communications,2020,11(1):1-9. doi: 10.1038/s41467-019-13993-7
[7]	Huang S, Wang Z, Von Lim Y, et al. Recent advances in heterostructure engineering forlithium–sulfur batteries[J]. Advanced Energy Materials,2021,11(10):2003689. doi: 10.1002/aenm.202003689
[8]	Wei P, Fan M, Chen H, et al. High-capacity graphene/sulfur/polyaniline ternary composite cathodes with stable cycling performance[J]. Electrochimica Acta,2015,174:963-969. doi: 10.1016/j.electacta.2015.06.052
[9]	Wang B, Zhang J, Xia Z, et al. Polyaniline-coated selenium/carbon composites encapsulated in graphene as efficient cathodes for Li-Se batteries[J]. Nano Research,2018,11(5):2460-2469. doi: 10.1007/s12274-017-1870-2
[10]	Sun J, Du Z, Liu Y, et al. State-of-the-art and future challenges in high energy lithium–selenium batteries[J]. Advanced Materials,2021,33(10):2003845. doi: 10.1002/adma.202003845
[11]	Gu X, Tang T, Liu X, et al. Rechargeable metal batteries based on selenium cathodes: progress, challenges and perspectives[J]. Journal of Materials Chemistry A,2019,7(19):11566-11583. doi: 10.1039/C8TA12537F
[12]	Zhang J, Fan L, Zhu Y, et al. Selenium/interconnected porous hollow carbon bubbles composites as the cathodes of Li–Se batteries with high performance[J]. Nanoscale,2014,6(21):12952-12957. doi: 10.1039/C4NR03705G
[13]	Wang X, Tan Y, Liu Z, et al. New insight into the confinement effect of microporous carbon in Li/Se battery chemistry: a cathode with enhanced conductivity[J]. Small,2020,16(17):2000266. doi: 10.1002/smll.202000266
[14]	Lu P, Liu F, Zhou F, et al. Lignin derived hierarchical porous carbon with extremely suppressed polyselenide shuttling for high-capacity and long-cycle-life lithium–selenium batteries[J]. Journal of Energy Chemistry,2021,55:476-483. doi: 10.1016/j.jechem.2020.07.022
[15]	Chen X, Xu L, Zeng L, et al. Synthesis of the Se-HPCF composite via a liquid-solution route and its stable cycling performance in Li–Se batteries[J]. Dalton Transactions,2020,49(41):14536-14542. doi: 10.1039/D0DT03035J
[16]	Luo C, Wang J, Suo L, et al. In situ formed carbon bonded and encapsulated selenium composites for Li–Se and Na–Se batteries[J]. Journal of Materials Chemistry A,2015,3(2):555-561. doi: 10.1039/C4TA04611K
[17]	Zhou J, Chen M, Wang T, et al. Covalent selenium embedded in hierarchical carbon nanofibers for ultra-high areal capacity Li-Se Batteries[J]. Iscience,2020,23(3):100919. doi: 10.1016/j.isci.2020.100919
[18]	Liu Y, Si L, Du Y, et al. Strongly bonded selenium/microporous carbon nanofibers composite as a high-performance cathode for lithium–selenium batteries[J]. The Journal of Physical Chemistry C,2015,119(49):27316-27321. doi: 10.1021/acs.jpcc.5b09553
[19]	Jia D, Yang Z, Zhang H, et al. High performance of selenium cathode by encapsulating selenium into the micropores of chitosan-derived porous carbon framework[J]. Journal of Alloys and Compounds,2018,746:27-35. doi: 10.1016/j.jallcom.2018.02.276
[20]	Bhatia P, Pandey S, Prakash R, et al. Enhanced anti-oxidant activity as a function of selenium hyperaccumulation in agaricus bisporus cultivated on Se-rich agri-residues[J]. Journal of Biologically Active Products from Nature,2014,4(5-6):354-364. doi: 10.1080/22311866.2014.961103
[21]	Luo C, Xu Y, Zhu Y, et al. Selenium@ mesoporous carbon composite with superior lithium and sodium storage capacity[J]. ACS nano,2013,7(9):8003-8010. doi: 10.1021/nn403108w
[22]	Wang B, Li Z, Zhang J, et al. N-doped 3D interconnected carbon bubbles as anode materials for lithium-ion and sodium-ion storage with excellent performance[J]. Journal of nanoscience and nanotechnology,2019,19(11):7301-7307. doi: 10.1166/jnn.2019.16655
[23]	Xiao S, Li Z, Liu J, et al. Se-C bonding promoting fast and durable Na⁺ storage in yolk–shell SnSe₂@Se-C[J]. Small,2020,16(41):2002486. doi: 10.1002/smll.202002486
[24]	Sha L, Gao P, Ren X, et al. A self-repairing cathode material for lithium–selenium batteries: Se-C chemically bonded selenium–graphene composite[J]. Chemistry–A European Journal,2018,24(9):2151-2156. doi: 10.1002/chem.201704079
[25]	Li C, Wang Y, Li H, et al. Weaving 3D highly conductive hierarchically interconnected nanoporous web by threading MOF crystals onto multi walled carbon nanotubes for high performance Li–Se battery[J]. Journal of Energy Chemistry,2021,59:396-404. doi: 10.1016/j.jechem.2020.11.023
[26]	Dong W D, Yu W B, Xia F J, et al. Melamine-based polymer networks enabled N, O, S Co-doped defect-rich hierarchically porous carbon nanobelts for stable and long-cycle Li-ion and Li-Se batteries[J]. Journal of Colloid and Interface Science,2021,582:60-69. doi: 10.1016/j.jcis.2020.06.071
[27]	Choi W, Shin H C, Kim J M, et al. Modeling and applications of electrochemical impedance spectroscopy (EIS) for lithium-ion batteries[J]. Journal of Electrochemical Science and Technology,2020,11(1):1-13. doi: 10.33961/jecst.2019.00528
[28]	Cui Y, Abouimrane A, Sun C J, et al. Li–Se battery: absence of lithium polyselenides in carbonate based electrolyte[J]. Chemical Communications,2014,50(42):5576-5579. doi: 10.1039/C4CC00934G
[29]	Wu F, Lee J T, Xiao Y, et al. Nanostructured Li₂Se cathodes for high performance lithium-selenium batteries[J]. Nano Energy,2016,27:238-246. doi: 10.1016/j.nanoen.2016.07.012
[30]	Yao W, Wu S, Zhan L, et al. Two-dimensional porous carbon-coated sandwich-like mesoporous SnO₂/graphene/mesoporous SnO₂ nanosheets towards high-rate and long cycle life lithium-ion batteries[J]. Chemical Engineering Journal,2019,361:329-341. doi: 10.1016/j.cej.2018.08.217
[31]	Ding J, Zhou H, Zhang H, et al. Selenium impregnated monolithic carbons as free-standing cathodes for high volumetric energy lithium and sodium metal batteries[J]. Advanced Energy Materials,2018,8(8):1701918. doi: 10.1002/aenm.201701918
[32]	Tian H, Tian H, Wang S, et al. High-power lithium–selenium batteries enabled by atomic cobalt electrocatalyst in hollow carbon cathode[J]. Nature communications,2020,11(1):1-12. doi: 10.1038/s41467-019-13993-7