Electrochemical reduction of graphite in LiClO4-propylene carbonate electrolyte: Influence of the nature of the surface protective layer

Naji, A.; Ghanbaja, Jaâfar; Willmann, P.; Billaud, D.

doi:10.1016/s0008-6223(97)00041-9

Cited by 33 publications

(18 citation statements)

References 13 publications

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“…To explain the evolution of the capacity values vs. temperature, one may suggest the changes occurring in the surface morphology and chemistry which could strongly modify the interaction between the carbon surface and the electrolyte. [30][31][32] Indeed, a good correlation can be established between the electrochemical performances of these carbon materials and the presence of hydrogen and alkaline cations on their surface. As mentioned in Table II, the highest r 1 , r 2 , and r 3 ratios are observed for sample 2.…”

Section: Resultsmentioning

confidence: 99%

Lithium Insertion into Carbonaceous Anode Materials Prepared by Electrolysis of Molten Li-K-Na Carbonates

Groult

Kaplan

Komaba

et al. 2002

J. Electrochem. Soc.

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Carbon powders were prepared by electroreduction of molten lithium-sodium-potassium carbonates at 450°C. The influence of the potential and the heat-treatment after washing in HCl solution on their electrochemical performances when they are used as anode in Li-ions battery were studied. Correlation between the presence of surface disordering ͑Raman spectroscopy͒ and the presence H, Li, K, and Na on the outermost layer on the powder surface ͑secondary ion mass spectroscopy͒, and their electrochemical performances was pointed out: samples having both the higher surface disordering and the lower H, Li, K, and Na content on their surface exhibit the lowest electrochemical performances. The best results were obtained for carbon deposited at Ϫ2.4 V vs. CO 2 -O 2 and heat-treated at 400°C: the reversible capacity obtained in 1 M LiPF 6 -ethylene carbonate:diethyl carbonate:dimethyl carbonate is 1080 mAh g Ϫ1 ͑composition of Li 2.9 C 6 ). This value is 2.9 times higher than the theoretical one observed with graphite (372 mAh g Ϫ1 , composition of LiC 6 ). The potential profile obtained in galvanostatic mode is intermediate between that usually observed for graphite and amorphous carbon, because in the potential range 1.5-0.3 V vs. Li/Li ϩ , the potential profile shows rather continuous charge-discharge curves sloping, and between 0.3 and 0.02 V vs. Li/Li ϩ , phase transformations between different stages occur successively as in the case of pure graphite.Rechargeable lithium-ion batteries are widely used as power sources in electrical equipment. These batteries are commercially available and are composed of LiCoO 2 , LiNiO 2 , or LiMn 2 O 4 as positive electrode, 1-8 and lithiated graphite instead of metallic lithium as negative electrode. 9-17 The use of lithiated graphite avoids growth of metallic Li dendrite usually observed upon chargedischarge cycles with a metallic lithium anode. It exists in numerous carbonaceous materials which exhibit different electrochemical performances when they are used as a reservoir of lithium in lithiumion batteries. Among these carbon materials, graphite or graphitized carbon materials have high reversible capacity, low irreversible capacity, low potential and flat potential profiles, high coulombic efficiency, long life cycle, and high safety level compared to other compounds such as metal oxides, lithium alloys, or lithium metal. Hexagonal graphite has a layered lattice structure with a perfect stacking order of graphene layers ͑sequence of ABAB type͒. Owing to this lamellar structure, Li cations can be easily inserted and deinserted between two carbon sheets. A maximum lithium ion content of one lithium guest atom per six carbon host atoms can be achieved, giving rise to a composition of LiC 6 and to a theoretical specific capacity of 372 mAh g Ϫ1 . The charge-discharge voltage profile in galvanostatic mode exhibits three distinct plateaus appearing approximately at around 0.21, 0.11, and 0.06-0.08 V vs. Li/Li ϩ due to a staging mechanism which involves one or more graphene layers: 1...

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Section: Resultsmentioning

confidence: 99%

Lithium Insertion into Carbonaceous Anode Materials Prepared by Electrolysis of Molten Li-K-Na Carbonates

Groult

Kaplan

Komaba

et al. 2002

J. Electrochem. Soc.

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“…PC is notorious for its cointercalation together with Li + ion into graphite interlayers and causes the exfoliation of graphene sheets and the formation of PC decomposition products within the interlayers releasing gases, resulting in an irreversible reaction and finally a sudden performance failure. [9][10][11][12][13] Combination of graphite anode with PC-based electrolyte in the absence of any functional electrolyte additive has thus been recognized to be the worst choice. This point motivated us to find a way out of the dilemma of PCgraphite combination, and to develop a better working electrolyte and thus a better working LIBs than commercial ones, pursuing the widened range of operation temperature and voltage window and higher performance and higher energydensity of LIBs.…”

Section: Introductionmentioning

confidence: 99%

Robust Solid‐Electrolyte Interphase Enables Near‐Theoretical Capacity of Graphite Battery Anode at 0.2 C in Propylene Carbonate‐Based Electrolyte

2020

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The formation of a robust solid-electrolyte interphase (SEI) layer at the surface of a graphite anode by electrolyte control is a key technology for high-performance lithium-ion batteries. Although propylene carbonate (PC) offers a lower melting point than ethylene carbonate, its combination with the graphite anode without additive is a worse choice, owing to cointercalation of PC and Li + ion into graphite, exfoliation of graphene sheets, and death of the battery. This study reports a graphite anode with an unprecedentedly high initial coulombic efficiency of 94 %, close to theoretical capacity, and excellent capacity retention of 99 % after 100 cycles in a PC-based electrolyte system, even at an unusually high rate of 0.2 C, which is generally attainable only at a very low rate of below 0.05 C in commercial electrolyte. The SEI stabilization for a graphite anode in PC-based electrolyte provides a new avenue for high-energy and high-performance batteries in widened range of working temperatures. A strong correlation between anode-electrolyte interfacial stabilization and highly reversible cycling performance is clearly demonstrated.

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“…A frequently proposed chemistry is that the electrochemical reduction of EC begins at potentials Ͼ1 V, the potential where Li ϩ intercalation into graphite begins. 1,2 The products from the initial reduction of EC prevent solvent cointercalation. Further reduction may occur as the graphite is fully charged to close to the lithium metal potential, which may include reduction of the salt as well.…”

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confidence: 99%

Evidence for Epoxide Formation from the Electrochemical Reduction of Ethylene Carbonate

Zhang

Pugh

Ross

2001

Electrochem. Solid-State Lett.

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It is now generally agreed that the electrochemical reduction of ethylene carbonate ͑EC͒ plays an important role in the formation of an effective solid electrolyte interface layer on the carbon anode in lithium-ion cells. However, neither the composition of this layer nor the reaction pathways involved in its formation have been clearly established. We report reflectance infrared spectra from a glassy carbon electrode surface after EC/tetrahydrofuran electrolyte reduction that is unlike any other we have seen in the literature. The spectrum has its strong absorption peak at 838 cm Ϫ1 , and this feature is clearly shown not to be from the monoethylcarbonate lithium salt. Ethylene oxide is suggested as a possible, but not exclusive, reduction product. The suggested reaction pathway is an electrochemical-chemical sequence, electrochemical reduction of water to form hydroxide, and hydroxide addition to form ethylene oxide and lithium bicarbonate.

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Electrochemical reduction of graphite in LiClO4-propylene carbonate electrolyte: Influence of the nature of the surface protective layer

Cited by 33 publications

References 13 publications

Lithium Insertion into Carbonaceous Anode Materials Prepared by Electrolysis of Molten Li-K-Na Carbonates

Lithium Insertion into Carbonaceous Anode Materials Prepared by Electrolysis of Molten Li-K-Na Carbonates

Robust Solid‐Electrolyte Interphase Enables Near‐Theoretical Capacity of Graphite Battery Anode at 0.2 C in Propylene Carbonate‐Based Electrolyte

Evidence for Epoxide Formation from the Electrochemical Reduction of Ethylene Carbonate

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