The present invention is directed towards an electrochemical cell for lithium battery, comprising a specific electrolyte, with which it is possible in particular to obtain very good electrochemical performances and more particularly strong cyclic charge retention, together with high first-cycle coulombic efficiency.
The general field of the invention can therefore be defined as concerning lithium batteries, and more specifically batteries of lithium-ion type.
Batteries of lithium-ion type are increasingly used as independent power sources notably in portable electronic equipment (such as mobile telephones, laptop computers, tooling) in which they are gradually replacing nickel-cadmium (NiCd) and nickel-metal hydride (NiMH) rechargeable batteries. They are also much used to power new micro-applications, such as smart cards, sensors or other electromechanical systems.
Lithium-ion batteries operate via an insertion-desinsertion process (or lithiation-delithiation) along the following principle.
When the battery discharges, the lithium extracted from the negative electrode in Li+ ionic form migrates through the ion-conducting electrolyte and comes to intercalate itself within the crystalline lattice of the active material of the positive electrode. The passing of each Li+ ion in the internal circuit of the battery is exactly offset by the passing of an electron in the external circuit, thereby generating an electric current. The specific energy density by mass released by these reactions is proportional both to the difference in potential between the two electrodes and to the amount of lithium that has intercalated in the active material of the positive electrode.
When the battery is charging, the reactions occurring within the battery are reverse reactions to discharge, namely:
With this operating principle, batteries of lithium-ion type therefore require the presence of a material at the electrodes that is able to insert or extract lithium, but also requires an electrolyte allowing the conducting of lithium ions that is stable and allows very good electrochemical performance and more particularly strong cyclic charge retention together with high first-cycle coulombic efficiency.
The authors of the present invention have therefore set themselves this objective, in particular for batteries having a composite silicon-graphite material as active material.
The invention therefore relates to an electrochemical cell for lithium battery comprising a positive electrode and a negative electrode, separated from each other by an electrolyte comprising at least one lithium salt and at least one compound selected from among the compounds of the cyclic ether family having at least one ring comprising an oxygen atom and at least one unsaturation. Advantageously, the electrolyte is composed solely of at least one compound from the cyclic ether family having at least one ring comprising an oxygen atom and at least one unsaturation, and at least one lithium salt.
The reasoned choice of the constituent ingredients of the above-mentioned electrolyte contributes towards obtaining very good electrochemical performances, and more particularly strong cycle charge retention together with high first-cycle coulombic efficiency.
As mentioned above, the electrolyte inter alia comprises at least one lithium salt.
The lithium salt can be selected from the group formed by LiPF6, LiClO4, LiBF4, LiAsF6, LiCF3SO3, lithium 4,5-dicyano-2-(trifluoromethyl)imidazolate (known under the abbreviation LiTDI), or from the sulfonylimide family such as lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) LiN[SO2CF3]2, lithium bis(fluorosulfonyl)imide (known under the abbreviation LiFSI) LiN[SO2F]2, lithium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonylimide LiN[SO2(CF2)3SO2] and mixtures thereof, preference being given to the LiTFSI salt.
The lithium salt may be contained in the electrolyte in a concentration ranging from 0.1 M to 5 M, e.g. 1 M.
As mentioned above, the electrolyte comprises at least one compound selected from among the compounds of the cyclic ether family having at least one ring comprising an oxygen atom and at least one unsaturation, for example one unsaturation or two unsaturations, said compound conventionally meeting the function of organic solvent(s).
More specifically, according to a first embodiment, it may be a compound having a ring which, in addition to an oxygen atom, comprises 4 to 7 carbon atoms and has two unsaturations, and more specifically a compound having a ring comprising 4 carbon atoms and two unsaturations i.e. in other words a compound belonging to the family of furan compounds, for example meeting following formula (I):
where R1 to R4 are each independently a hydrogen atom or alkyl group.
In particular, specific compounds coming within those of formula (I) can be:
this compound being commonly designated as a furan;
this compound being called 2-methylfuran.
In a second embodiment, the compound can be a compound having a ring which, in addition to an oxygen atom, comprises 3 to 7 carbon atoms and has one unsaturation, and more specifically a compound having a ring comprising 4 carbon atoms and one unsaturation.
More specifically, it may be a compound having a ring comprising 4 carbon atoms and one unsaturation meeting following formula (IV):
where R5 and R6 are each independently a hydrogen atom or alkyl group, and in particular where one of the groups R5 and R6 is an alkyl group whilst the other group is a hydrogen atom, one particular compound coming within this definition being the compound of following formula (V):
this compound being called 2,3-dihydro-5-methylfuran.
The electrolyte is advantageously composed solely of at least one cyclic ether compound having at least one ring comprising an oxygen atom, at least one unsaturation and at least one lithium salt allowing very good electrochemical performances to be obtained, and more specifically strong cyclic charge retention and high first-cycle coulombic efficiency.
Examples of specific electrolytes able to be included in the composition of the electrochemical cells of the invention are:
As mentioned in the foregoing, the electrochemical cells of the invention comprise a positive electrode and a negative electrode.
By positive electrode, in the foregoing and in the remainder hereof, it is conventionally meant the electrode acting as cathode when the generator is delivering current (i.e. when it is discharging) and acting as anode when the generator is charging.
By negative electrode, in the foregoing and in the remainder hereof, it is conventionally meant the electrode acting as anode when the generator is delivering current (i.e. when it is discharging) and acting as cathode when the generator is charging.
It is specified that each of the electrodes comprises an active material i.e. a material that is directly involved in lithium insertion and desinsertion reactions.
In addition to the presence of an active material, the electrode may comprise a polymeric binder such as polyvinylidene fluoride (known under the abbreviation PVDF), a mixture of carboxymethylcellulose (known under the abbreviation CMC) with a latex of styrene-butadiene type (known under the abbreviation SBR) or with polyacrylic acid (known under the abbreviation PAA) and one or more electricity-conducting additives which may be carbon materials such as carbon black.
Therefore, from a structural viewpoint, the electrode can be in the form of a composite material comprising a matrix of polymeric binder(s) in which fillers are dispersed composed of the active material and optionally the electricity-conducting additive(s).
This may particularly be the case when one of the electrodes, as active material, comprises a composite silicon-graphite material, this composite material possibly being contained in a proportion ranging from 50 to 95 weight % relative to the total weight of the electrode.
By silicon-graphite composite material, in the foregoing and in the remainder hereof, it is meant as is conventional a material comprising an aggregate of graphite particles and silicon particles, and in one particular embodiment aggregate silicon particles on graphite particles, the assembly being dispersed within a carbon matrix e.g. a disordered carbon matrix.
The electrode comprising a silicon-graphite composite material as active material can particularly be the positive electrode.
The negative electrode on the other hand, as active material, may comprise lithium metal, in which case the negative electrode can be in the form of lithium metal foil.
Finally, the invention relates to a lithium battery comprising one or more electrochemical cells such as defined above.
Other characteristics and advantages of the invention will become apparent from the following additional description referring to particular embodiments.
Evidently, this additional description is only given for illustration and does not in any manner limit the invention.
The present example illustrates an electrochemical cell conforming to the invention, in the form of a button cell comprising:
The negative electrode was obtained by cutting a disc 16 mm in diameter from lithium metal foil.
The positive electrode was obtained by coating a copper foil with an ink composed of 90 weight % silicon-graphite composite, 5 weight % electronic conductor (more specifically a mixture of Super P® grade carbon black and VGCF carbon fibres with 5 weight % of polymeric binder (more specifically a mixture of carboxymethylcellulose [250 000 g/mol] and polyacrylic acid [250 000 g/mol]). This electrode was calendered and cut into the form of a disc 14 mm in diameter.
The button cell was produced from these electrodes by stacking:
The electrolyte comprised furan of formula (II) such as defined above, in which LiTFSI was dissolved at a concentration of 1 mol/L.
This cell was subjected to a galvanostatic cycling test whereby a first charge/discharge cycle between 1 V and 0.01 V was applied at a C/20 regime with a plateau at 0.01 V held until a current was reached corresponding to a C/100 regime, followed by a C/5 regime for the consecutive cycles with a plateau at 0.01 V held until a current was reached corresponding to a C/100 regime for each cycle.
The results are given in
It can clearly be seen that the cell conforming to the invention has excellent cycling retention after 10 cycles.
In parallel, the efficiencies were also calculated i.e. the ratios of discharge capacities to charge capacities (expressed for the active material of the positive electrode) expressed in % as a function of number of cycles, the results being given in
It can clearly be seen in the curve that the cell conforming to the invention has excellent first-cycle efficiency (higher than 80%) and at the following cycles (close to 100%).
This example illustrates electrochemical cells conforming to the invention, in the form of a button cell, comprising:
The negative electrode was obtained by cutting a disc 16 mm in diameter from lithium metal foil.
The positive electrode was obtained by coating copper foil with an ink composed of 90 weight % of silicon-graphite composite, 5 weight % of electronic conductor (more specifically a mixture of Super P® grade carbon black and VGCF carbon fibres, with 5 weight % of polymeric binder (more specifically a mixture of carboxymethylcellulose (250 000 g/mol) and polyacrylic acid (250 000 g/mol). This electrode was calendered and cut into the form of a disc 14 mm in diameter.
The button cells were produced from these electrodes by stacking:
The cells conforming to the invention were the following:
These different cells were subjected to a galvanostatic cycling test whereby a first charge/discharge cycle was applied between 3.7 V and 2 V, at a regime of C/20 with a plateau at 3.7 V held for 2 hours, followed by a C/10 regime with a plateau at 3.7 V held until a current corresponding to a C/50 regime was reached for the second cycle, and finally a C/5 regime for the consecutive cycles with a plateau at 3.7 V held until a current was reached corresponding to a C/50 regime for each cycle.
The results are given in
It clearly follows from these curves that the cells conforming to the invention have excellent cycling retention (in the region of 100%) after more than about ten cycles.
In parallel the efficiencies were also determined i.e. the ratios of discharge capacities to charge capacities expressed in %, as a function of number of cycles, the results being given in
It clearly follows from these curves that the cells conforming to the invention have excellent first-cycle efficiency (higher than 80%) and at the following cycles (close to 100%).
Number | Date | Country | Kind |
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15 62013 | Dec 2015 | FR | national |
Filing Document | Filing Date | Country | Kind |
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PCT/EP2016/079897 | 12/6/2016 | WO | 00 |