Four kinds of fluorinated carbon cathodes were fabricated with the industrial carbon materials (activated carbon, spherical graphite, expanded graphite and industrial graphene) to realize the universal applications of lithium/fluorinated carbon primary battery. The morphology, crystalline structure, chemical structure and electrochemical performance were systematically studied by scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), Raman spectra (Raman), fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectro scopy(XPS), N2 adsorption-desorption isotherms and electrochemical test, etc. It was found that the fluorinated industrial graphene shows the highest specific capacity (945.4 mAh·g-1) at the discharge current density of 20 mA·g-1, which may benefit from the monofluorocarbon structure, high specific area and stable carbon structure. The fluorinated active carbon has the highest initial discharge voltage due to the abundant semi-covalent C—F bond, but its discharge voltage declines rapidly caused by the unstable structure. Although the fluorinated spherical graphite and fluorinated expanded graphite have the similar structure with the fluorinated industrial graphene, their specific capacities are lower, due to the presence of the highly fluorinated carbon atoms (CF2 and CF3). However, at high discharge current density, the fluorinated spherical graphite and fluorinated expanded graphite possess the similar value with the fluorinated industrial graphene. Considering the cost, they may be more suitable for the high power applications.
LINDEN D , REDDY T B . Handbook of batteries[M]. New York: McGraw-Hill, 2004: 72.
2
JAYASINGHE R , THAPA A K , DHARMASENA R R , et al. Optimization of multi-walled carbon nanotube based CFx electrodes for improved primary and secondary battery performances[J]. J Power Sources, 2014, 253, 404- 411.
doi: 10.1016/j.jpowsour.2013.12.076
3
LI Y , WU X , LIU C , et al. Fluorinated multi-walled carbon nanotubes as cathode materials of lithium and sodium primary batteries: effect of graphitization of carbon nanotubes[J]. Journal of Materials Chemistry A, 2019, 7 (12): 7128- 7137.
doi: 10.1039/C8TA12074A
4
LI Y , FENG Y , FENG W . Deeply fluorinated multi-wall carbon nanotubes for high energy and power densities lithium/carbon fluorides battery[J]. Electrochim Acta, 2013, 107, 343- 349.
doi: 10.1016/j.electacta.2013.06.086
5
YUE H , ZHANG W , LIU H , et al. Synthesis and characterization of fluorinated carbon nanotubes for lithium primary batteries with high power density[J]. Nanotechnology, 2013, 24 (42): 424003.
doi: 10.1088/0957-4484/24/42/424003
6
FENG W , LONG P , FENG Y , et al. Two-dimensional fluorinated graphene: synthesis, structures, properties and applications[J]. Advanced Science, 2016, 3 (7): 1500413.
doi: 10.1002/advs.201500413
7
BI X , LI Y , QIU Z , et al. Fluorinated graphene prepared by direct fluorination of N, O-doped graphene aerogel at different temperatures for lithium primary batteries[J]. Materials, 2018, 11 (7): 1072.
doi: 10.3390/ma11071072
8
DAMIEN D , SUDEEP P M , NARAYANAN T N , et al. Fluorinated graphene based electrodes for high performance primary lithium batteries[J]. RSC Adv, 2013, 3 (48): 25702- 25706.
doi: 10.1039/c3ra45377d
9
YAZAMI R , HAMWI A , GUÉRIN K , et al. Fluorinated carbon nanofibres for high energy and high power densities primary lithium batteries[J]. Electrochem Commun, 2007, 9 (7): 1850- 1855.
doi: 10.1016/j.elecom.2007.04.013
10
SHAO Y , YUE H , QIAO R , et al. Synthesis and reaction mechanism of novel fluorinated carbon fiber as a high-voltage cathode material for rechargeable Na batteries[J]. Chem Mater, 2016, 28 (4): 1026- 1033.
doi: 10.1021/acs.chemmater.5b03762
11
DUBOIS M , GUÉRIN K , ZHANG W , et al. Tuning the discharge potential of fluorinated carbon used as electrode in primary lithium battery[J]. Electrochim Acta, 2012, 59, 485- 491.
doi: 10.1016/j.electacta.2011.11.015
12
ZHANG W , DUBOIS M , GUÉRIN K , et al. Effect of curvature on C—F bonding in fluorinated carbons: from fullerene and derivatives to graphite[J]. Phys Chem Chem Phys, 2010, 12 (6): 1388- 1398.
doi: 10.1039/B914853A
13
FULVIO P F , BROWN S S , ADCOCK J , et al. Low-temperature fluorination of soft-templated mesoporous carbons for a high-power lithium/carbon fluoride battery[J]. Chem Mater, 2011, 23 (20): 4420- 4427.
14
FULVIO P F , VEITH G M , ADCOCK J L , et al. Fluorination of "brick and mortar" soft-templated graphitic ordered mesoporous carbons for high power lithium-ion battery[J]. Journal of Materials Chemistry A, 2013, 1 (33): 9414- 9417.
doi: 10.1039/c3ta10710h
15
LI X , ZHANG H , LIU C , et al. A MOF-derived multifunctional nano-porous fluorinated carbon for high performance lithium/fluorinated carbon primary batteries[J]. Microporous Mesoporous Mater, 2021, 310, 110650.
doi: 10.1016/j.micromeso.2020.110650
16
ROOT M J , DUMAS R , YAZAMI R , et al. The effect of carbon starting material on carbon fluoride synthesized at room temperature: characterization and electrochemistry[J]. J Electrochem Soc, 2001, 148 (4): A339- A345.
doi: 10.1149/1.1354612
17
CHAMSSEDINE F , DUBOIS M , GUÉRIN K , et al. Reactivity of carbon nanofibers with fluorine gas[J]. Chem Mater, 2007, 19 (2): 161- 172.
doi: 10.1021/cm061731m
18
WANG L , LI Y , WANG S , et al. Fluorinated nanographite as a cathode material for lithium primary batteries[J]. ChemElectroChem, 2019, 6 (8): 2201- 2207.
doi: 10.1002/celc.201900194
19
PENG C , LI Y , YAO F , et al. Ultrahigh-energy-density fluorinated calcinated macadamia nut shell cathode for lithium/fluorinated carbon batteries[J]. Carbon, 2019, 153, 783- 791.
20
MEDURI P , CHEN H , XIAO J , et al. Tunable electrochemical properties of fluorinated graphene[J]. Journal of Materials Chemistry A, 2013, 1 (27): 7866- 7869.