Pouch-type gel Li-ion batteries were fabricated by in-situ polymerization and constructed from a LiCoO2 cathode, a graphite anode, a ceramics-coated polyethylene separator, and a gel electrolyte that was dispersed in between. Electrochemical tests showed that the battery using the gel electrolyte exhibited comparable capacity and cycling stability compared with that using the liquid electrolyte. The differential scanning calorimeter tests indicated that the gel electrolyte exhibited an improved thermal stability toward LiCoO2 and graphite than the liquid electrolyte. The hot-plate and accelerating rate calorimetry tests suggested that the safety property of the battery can be enhanced using gel electrolytes instead of liquid electrolytes. An ultrathin pouch battery was also fabricated by in-situ polymerization, and it showed good flexibility and can still operate after folding and cutting.
TU Jian. Fabrication of gel-type Li-ion batteries and their electrochemical and safety properties[J]. Energy Storage Science and Technology, 2021, 10(3): 1025-1031
Fig. 1
(a) schematic illustration of electrolyte before and after polymerization; (b) DSC curve of mixture of liquid electrolyte, monomer and initiator; (c) FTIR of monomer and its polymer; digital and optical microscopy images of (d) cathode and (e) anode from dismantled gel battery
Fig. 2
Voltage profiles of (a) liquid battery and (b) gel battery; (c) EIS of liquid battery and gel battery; (d) cycling stability of liquid battery and gel battery at room temperature (charge and discharge at 0.5 C); (e) cycling stability of liquid battery and gel battery at 60 ℃ (charge at 0.3 C and discharge at 0.5 C)
Fig. 4
(a) hot-plate test of liquid and gel batteries; (b) appearance of batteries after hot-plate test; (c) surface temperature and OCV of batteries during hot-plate test
YANG H C, LI J, SUN Z H, et al. Reliable liquid electrolyte for lithium metal batteries[J]. Energy Storage Materials, 2020, 30: 113-129.
NOLAN A M, ZHU Y Z, HE X F, et al. Computation-accelerated design of materials and interfaces for all-solid-state lithium-ion batteries[J]. Joule, 2018, 2(10): 2016-2046.
HUANG W L, ZHAO N, BI Z J, et al. Can we find solution to eliminate Li penetration through solid garnet electrolytes?[J]. Materials Today Nano, 2020, 10: doi: 10.1016/j.mtnano.2020.100075.
HUANG X, WU L B, HUANG Z, et al. Characterization and testing of key electrical and electrochemical properties of lithium-ion solid electrolytes[J]. Energy Storage Science and Technology, 2020, 9(2): 479-500.
DANG H Y, GUO X M, HUANG Y P, et al. Structure and properties of NASICON synthesized by two different zirconium salts[J]. International Journal of Minerals, Metallurgy, and Materials, 2012, 19(8): 768-773.
JIANG P F, SHI Y S, LI K W, et al. Recent progress on the Li7La3Zr2O12(LLZO)solid electrolyte[J]. Energy Storage Science and Technology, 2020, 9(2): 523-537.
QUARTARONE E, MUSTARELLI P. Electrolytes for solid-state lithium rechargeable batteries: Recent advances and perspectives[J]. Chemical Society Reviews, 2011, 40(5): 2525-2540.
TSAO C H, LIN Y T, HSU S Y, et al. Crosslinked solidified gel electrolytes via in-situ polymerization featuring high ionic conductivity and stable lithium deposition for long-term durability lithium battery[J]. Electrochimica Acta, 2020, 361: doi: 10.1016/j.electacta.2020.137076.
WANG Q J, SONG W L, FAN L Z, et al. Facile fabrication of polyacrylonitrile/alumina composite membranes based on triethylene glycol diacetate-2-propenoic acid butyl ester gel polymer electrolytes for high-voltage lithium-ion batteries[J]. Journal of Membrane Science, 2015, 486: 21-28.
GAO H, HUANG Y, ZHANG Z, et al. Li6.7La3Zr1.7Ta0.15Nb0.15O12 enhanced UV-cured poly(ethylene oxide)-based composite gel polymer electrolytes for lithium metal batteries[J]. Electrochimica Acta, 2020, 360: doi: 10.1016/j.electacta.2020.137014.
LI X T, HAN X Q, ZHANG H R, et al. Frontier orbital energy-customized ionomer-based polymer electrolyte for high-voltage lithium metal batteries[J]. ACS Applied Materials & Interfaces, 2020, 12(46): 51374-51386.
ZHANG H R, ZHANG J J, MA J, et al. Polymer electrolytes for high energy density ternary cathode material-based lithium batteries[J]. Electrochemical Energy Reviews, 2019, 2(1): 128-148.
WANG S Q, WEI C, DING W W, et al. High-voltage sulfolane plasticized UV-curable gel polymer electrolyte[J]. Polymers, 2019, 11(8): doi: 10.3390/polym11081306.
ZHOU J Q, JI H Q, LIU J, et al. A new high ionic conductive gel polymer electrolyte enables highly stable quasi-solid-state lithium sulfur battery[J]. Energy Storage Materials, 2019, 22: 256-264.
HU R X, QIU H Y, ZHANG H R, et al. A polymer-reinforced SEI layer induced by a cyclic carbonate-based polymer electrolyte boosting 4.45 V LiCoO2/Li metal batteries[J]. Small, 2020, 16(13): doi: 10.1002/smll201907163.
LIU F Q, WANG W P, YIN Y X, et al. Upgrading traditional liquid electrolyte via in situ gelation for future lithium metal batteries[J]. Science Advances, 2018, 4(10): doi: 10.1126/sciadv.aat5383.
XU D, SU J M, JIN J, et al. In situ generated fireproof gel polymer electrolyte with Li6.4Ga0.2La3Zr2O12 as initiator and ion-conductive filler[J]. Advanced Energy Materials, 2019, 9(25): doi: 10.1002/aenm.201900611.
HUANG S Q, CUI Z L, QIAO L X, et al. An in-situ polymerized solid polymer electrolyte enables excellent interfacial compatibility in lithium batteries[J]. Electrochimica Acta, 2019, 299: 820-827.
CHEN L Y, FU J F, LU Q, et al. Cross-linked polymeric ionic liquids ion gel electrolytes by in situ radical polymerization[J]. Chemical Engineering Journal, 2019, 378: doi: 10.1016/j.cej.2019.122245.
JIANJUN Z, JINFENG Y, HAN W, et al. Research progress of in situ generated polymer electrolyte for rechargeable batteries[J]. Acta Polymerica Sinica, 2019, 50(9): 890-914.
AHN J H, YOU T S, LEE S M, et al. Hybrid separator containing reactive, nanostructured alumina promoting in-situ gel electrolyte formation for lithium-ion batteries with good cycling stability and enhanced safety[J]. Journal of Power Sources, 2020, 472: doi: 10.1016/j.jpowsour.2020.228519.
MA Y, MA J, CHAI J C, et al. Two players make a formidable combination: In situ generated poly(acrylic anhydride-2-methyl-acrylic acid-2-oxirane-ethyl ester-methyl methacrylate) cross-linking gel polymer electrolyte toward 5 V high-voltage batteries[J]. ACS Applied Materials & Interfaces, 2017, 9(47): 41462-41472.
LI X L, QIAN K, HE Y B, et al. A dual-functional gel-polymer electrolyte for lithium ion batteries with superior rate and safety performances[J]. Journal of Materials Chemistry A, 2017, 5(35): 18888-18895.
ZUO T T, SHI Y, WU X W, et al. Constructing a stable lithium metal-gel electrolyte interface for quasi-solid-state lithium batteries[J]. ACS Applied Materials & Interfaces, 2018, 10(36): 30065-30070.
LIU M, ZHOU D, HE Y B, et al. Novel gel polymer electrolyte for high-performance lithium-sulfur batteries[J]. Nano Energy, 2016, 22: 278-289.
LIU M, JIANG H R, REN Y X, et al. In-situ fabrication of a freestanding acrylate-based hierarchical electrolyte for lithium-sulfur batteries[J]. Electrochimica Acta, 2016, 213: 871-878.
SUN Q S, ZHU C J, XIE J, et al. Preparation and electrochemical performance of ceramic/polymer-based quasi-solid composite electrolyte[J]. Chinese Journal of Inorganic Chemistry, 2019, 35(5): 865-870.
DING W W, WEI C, WANG S Q, et al. Preparation and properties of a high-performance EOEOEA-based gel-polymer-electrolyte lithium battery[J]. Polymers, 2019, 11(8): doi: 10.3390/polym11081296.
NIU C Q, ZHANG M K, CHEN G P, et al. An effectively inhibiting lithium dendrite growth in-situ-polymerized gel polymer electrolyte[J]. Electrochimica Acta, 2018, 283: 349-356.
TSUKASAKI H, FUKUDA W, MORIMOTO H, et al. Thermal behavior and microstructures of cathodes for liquid electrolyte-based lithium batteries[J]. Scientific Reports, 2018, 8: doi: 10.1038/s41598-018-34017-2.
MALEKI H, DENG G P, ANANI A, et al. Thermal stability studies of Li-ion cells and components[J]. Journal of the Electrochemical Society, 1999, 146(9): 3224-3229.
