An overlooked issue for high-voltage Li-ion batteries: Suppressing the intercalation of anions into conductive carbon
نویسندگان
چکیده
•The anion intercalation into carbon is an overlooked issue for high-voltage systems•A concentrated sulfolane-based electrolyte helps to prevent the intercalation•An extremely stable 5.2 V-class Li2CoPO4F/graphite full cell was achieved The energy stored in batteries defined as product of capacity and voltage. Because reaching theoretical limit Li-ion battery concept, increasing voltage from current 3.8 5 V major target achieve high-energy densities. Various approaches have been taken address issues batteries, including oxidative decomposition at high voltages. However, their charge-discharge operation has not achieved, suggesting presence unknown yet essential that must be solved. Here, we unveil counter cathode conductive critical issue. On this basis, design a specific blocks demonstrate unprecedented cycling batteries. This finding offers fundamental basis developing advanced with High-voltage extensively studied increase density stability remained poor, despite various strategies being proposed overcome high-potential cathodes, such oxidation transition metal dissolution. Herein, report We propose sulfolane (SL)-based prevents via two mechanisms: (1) by offering activation barrier its strong anion-Li+ interaction (2) forming sulfur-containing, anion-blocking SL-derived interphase. electrolyte, used graphitized acetylene black, which oxidatively but usually susceptible intercalation, enables (cut-off = V), 93% retention after 1,000 cycles average Coulombic efficiency ?99.9%. pivotal strategy enhance reversibility >5 on commercial level. Next-generation densities are crucial development electrical devices, mobile phones electric vehicles.1Armand M. Tarascon J.M. 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For instance, salt-concentrated developed, only showed also suppressed dissolution.11Yamada Wang Ko Watanabe E. Yamada Advances electrolytes.Nat. Energy. 2019; 4: 269-280Crossref (11) Furthermore, functional separators, binders, additives, coating agents developed.5Hu Scholar,12Li Enhancing performances carbon-coating: present future.Chem. 48: 1201-1217Crossref Scholar,13Pieczonka N.P.W. Borgel V. Ziv Leifer N. Dargel Kim J.H. Liu Huang Krachkovskiy S.A. al.Lithium polyacrylate (LiPAA) binder passivating agent Li-Ion 2015; 5: 1501008Crossref (138) These technologies contribute ways: preventing direct contact between passivation layer (cathode-electrolyte interphase, CEI) scavenging HF acid accelerates dissolution.5Hu Nevertheless, few groups cells operate V.14Chen Fan Chen Hou Deng T. Li Su C. Achieving through output voltage: highly reversible 5.3 battery.Chem. 896-912Abstract Full Text PDF (95) Scholar,15Ko 4.8 Li2CoPO4F/Graphite enabled optimized design.Batter Supercaps. 2020; 3: 910-916Crossref (9) Moreover, performance still far practical requirement commercialization. Hence, there solved electronic conductivity (e.g., black) introduced additive or surface agent. area tens thousands times greater than material; therefore, it acts reaction site oxidation.16Younesi Christiansen A.S. Scipioni Ngo D.-T. Simonsen S.B. Edström Hjelm Norby P. Analysis interphase black formed Electrochem. 162: A1289-A1296Crossref (59) 17Saneifar Delaporte Zaghib Bélanger Functionalization cathode.J. 7: 1585-1597Crossref 18Metzger Marino Sicklinger Haering Gasteiger H.A. Anodic ethylene carbonate quantified on-line electrochemical mass spectrometry.J. A1123-A1134Crossref (119) 19Ko Lander Stability additives batteries.Carbon. 158: 766-771Crossref (10) 20Nilssen B.E. Tezel A.O. Svensson A.M. carbon-electrolyte interface cathodic voltages.ECS Trans. 69: 1-12Crossref (4) 21Li Nguyen C.C. Nie Lucht B.L. inactive components laminates potential.J. 161: A576-A582Crossref (20) 22Streipert Stolz Homann G. Janßen Cekic-Laskovic I. Winter Kasnatscheew Conventional batteries: determining cumulative impact voltage.ChemSusChem. 13: 5301-5307Crossref (16) More importantly, salt anions can intercalate interlayer spaces potentials ?4.5 versus Li/Li+.19Ko Scholar,23Seel J.A. Dahn J.R. Electrochemical PF6 graphite.J. 2000; 147: 892-898Crossref (318) 24Huesker Placke Dilatometric study bis(trifluoromethanesulfonyl) imide hexafluorophosphate carbon-based electrodes.ECS 9-21Crossref (26) 25Heckmann Fromm O. Rodehorst U. Münster New insights carbonaceous dual-ion graphitization degree.Carbon. 2018; 131: 201-212Crossref (48) 26Qi Blizanac DuPasquier Meister Oljaca Investigation PF6- TFSI- blacks influence batteries.Phys. 16: 25306-25313Crossref 27Read In-situ graphite selective cointercalation solvent.J. 119: 8438-8446Crossref repeated intercalation/deintercalation (sometimes together solvent molecules) during damages layered structure irreversibly.19Ko generates significant number defects act new sites, leads loss electrode, leading (Figure 1A).19Ko Scholar,24Huesker Unfortunately, occurs more readily higher degree graphitization.19Ko Scholar,25Heckmann Scholar,26Qi Scholar,28Ishihara Koga Matsumoto Yoshio carbons dual-carbon battery.Electrochem. Solid-State Lett. 2007; 10: A74-A76Crossref (142) limits utilization carbon, improve well-aligned sp2-hybridized crystal minimize parasitic reactions (degradation both carbon) fewer oxygen groups, adsorbed water molecules, 1B).29Campion C.L. 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By utilizing LiBF4-SL-based combination suitable traditional susceptibility (93% cycles) successfully upper cut-off slow C-rate. operated previous publications (Table S1). behavior dependent concentration salts solvents electrolyte,34Wang Tang features 8: 1703320Crossref (219) well carbon.19Ko model allowed us easily analyze 1B).28Ishihara As shown Figures 2A S1, performed linear sweep voltammetry (LSV) electrodes SL-based different concentration, whose basic physicochemical Table S2; Figure S2, 1.0 M LiPF6/ethylene (EC):dimethyl (DMC) (1:1 v/v) electrolyte. onset potential slightly upshifted LiBF4/SL (4.78 Li/Li+, S1) further nearly saturated 5.8 (4.90 2A) (4.59 2A). supported situ Raman spectra recorded galvanostatic (inset shed light effect cyclic (CV) three-electrode S3A). Generally, quasi-reference composition Li+ activities solvation energies.35Gagne R.R. Koval C.A. Lisensky G.C. Ferrocene internal standard measurements.Inorg. 1980; 19: 2854-2855Crossref (1026) Scholar,36Mozhzhukhina Calvo E.J. Perspective—the correct assessment reference solution.J. 164: A2295-A2297Crossref (25) Thus, calibrated ferrocene (Fc/Fc+) produce true solvent-independent redox S4). 35Gagne S3B, difference LiPF6/EC:DMC (1.34 Fc/Fc+) (1.40 insignificant. In contrast, dramatically (1.72 Fc/Fc+). upshift contradicts expectation decrease based increased activity Nernst equation, kinetic factor. impedance spectroscopy (EIS) analysis demonstrated interfacial resistance significantly concentrations (Figures 2B S5A–S5C). particular, transfer 59 kJ mol?1 LiBF4/SL, four (15 mol?1) 2C S5D). results indicate retards (the SL discussed next section). addition, LSV floating tests powders (acetylene degrees 3 S6). LiPF6/EC:DMC, anodic leakage much 3) amorphous actively degree.19Ko opposite trend current, indicating suppressed. proven S7) irreversible charges (parasitic capacities) occurred lowest LiBF4/SL. Importantly, reflected Li2CoPO4F/Li half-cell S8 S9). Li2CoPO4F, (and current). Overall, suppressing strongly influences enhances cathodes. clarify mechanism behind retarded analyzed spectroscopy. 4A, band gradually 767 777 cm?1 extensive ion-pairing solvent-separated pairs (SSIPs; directly Li+) (CIPs; one ion) aggregate clusters (AGGs; ions)37Seo D.M. Boyle P.D. Allen J.L. Han S.-D. Jónsson Johansson Henderson W.A. Solvate structures computational/spectroscopic characterization LiBF4 electrolytes.J. 118: 18377-18386Crossref (29) Scholar; words, BF4?–Li+ coordination intensified concentrations. means required ions material, agrees 2B, 2C, S5. unique AGG-predominant provides excellent suppression intercalation. recent revealed diffuse slowly electrolytes,38Alvarado Schroeder M.A. Borodin Gobrogge Olguin Ding M.S. Gobet Greenbaum Meng Y.S. Xu carbonate-free, sulfone-based batteries.Mater. Today. 21: 341-353Crossref (178) Scholar,39Dokko Ugata Thomas M.L. Tsuzuki Shinoda Hashimoto Ueno Umebayashi Direct evidence hopping conduction liquid 122: 10736-10745Crossref (83) may known sulfurous compound-based CEI, while enabling cation exchange.40Xing Tu Vatamanu Zeng battery.Electrochim. 133: 117-122Crossref (23) 41Cai Jing Shen Improving additive.J. A714-A720Crossref 42Han Du Cui An reinforcement achieving long 9: 1804022Crossref (53) Indeed, compounds (S-S, 161 163–164 eV; RSO2, 166–167 RSO3, 168–170 eV) detected cycled 4B).40Xing indicates stabilizes delaying diffusion surface. Notably, minimized (fluoroethylene carbonate, FEC)-based S7, S10, S11), even though exhibit stabilities Pt S12). contrast common belief ensuring electrolyte,5Hu Scholar,6Tan essential. Also, importance agents, binders.13Pieczonka Scholar,17Saneifar Scholar,42Han ensure anode, FEC, supports efficient formation solid (SEI) layer, co-solvent developed 6.6 LiBF4/SL:FEC (9:1 n/n) improved anodes S13) maintaining merits S14–S17), exhibited S18), half S19 S20). long-term 5. up material. retained initial discharge (only 0.007% per cycle) ?99.9%, those obtained state-of-the-art (?60% 350 <97%) S21). S14–S17 S22–S23), enhanced reduction dissolution Li2CoPO4F S24). attributes electrolytes. hindered realization commercial-level use LiBF4/SL-based electrolytes, offer benefits: BF4?-Li+ interactions, electrolytes; layer. stable, without activating result, V, novel protecting will step toward commercialization
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ژورنال
عنوان ژورنال: Joule
سال: 2021
ISSN: ['2542-4351', '2542-4785']
DOI: https://doi.org/10.1016/j.joule.2021.02.016