IMPROVED RECHARGEABLE BATTERIES AND PRODUCTION THEREOF

Abstract

An electrochemical cell is disclosed comprising a carbonate:nitrile type solvent mixture based electrolyte. The electrolyte may comprise an alkali salt and/or at least one polymer additive. The alkali salt cation may be a lithium cation and/or the alkali salt anion may comprise an oxalato-borate group. The electrolyte may further comprise one or more electrolyte additives, which may be an SEI improving additive. The anode may comprise carbon. The anode may be an alkali metal anode. The operating voltage and energy density performance of the disclosed invention is at the same level as the performance of presently market—leading battery cells, thereby these disclosed improvements do not come at the expense of battery performance. The utility of the herein disclosed battery electrolyte allows stable cycling of advanced Li-ion battery electrodes, an extended operating temperature range and improves battery safety by making the electrolyte less reactive and volatile than conventional LiPF6 electrolyte salt in carbonate solvents.

Claims

1.-18. (canceled)

19. An electrolyte for an electrochemical battery cell comprising: i. a carbonate:nitrile type solvent mixture based electrolyte, wherein the electrolyte comprises at least one polymer additive; or ii. a dimethylcarbonate (DMC): malononitrile (MLN) solvent mixture based electrolyte or a dimethylcarbonate (DMC): (succinonitrile (SCN):malononitrile (MLN)) solvent mixture based electrolyte, wherein the electrolyte further comprises an alkali salt and the electrolyte is liquid during electrochemical operation.

20. The electrolyte of claim 19, wherein the nitrile type solvent comprises succinonitrile (SCN) and/or malononitrile (MLN).

21. The electrolyte of claim 19, wherein the carbonate type solvent is dimethylcarbonate (DMC).

22. The electrolyte of claim 19, wherein the alkali salt cation is lithium cation.

23. The electrolyte cell of claim 19, wherein the alkali salt anion comprises an oxalato-borate group.

24. The electrolyte of claim 19, wherein the alkali salt is lithium-difluoro(oxalato)borate (LiDFOB).

25. The electrolyte of claim 19, wherein the electrolyte comprises one or more electrolyte additives.

26. The electrolyte of claim 25, wherein the electrolyte additive is a fluorinated carbonate additive.

27. The electrolyte of claim 19, wherein the electrolyte additive is fluoro-ethylenecarbonate (FEC).

28. The electrolyte of claim 19, wherein the polymer additive is poly(methyl vinyl ether-alt-maleic anhydride).

29. An electrochemical cell comprising the electrolyte of claim 1 and an anode and a cathode.

30. The electrochemical cell of claim 29, wherein the cathode comprises LiMn.sub.xFe.sub.1-xPO.sub.4 (LMFP or LFMP), lithium iron phosphate (LFP), lithium cobalt oxide (LCO), lithium manganese oxide (LMO), and/or lithium nickel manganese cobalt oxide (NMC).

31. The electrochemical cell of claim 29, wherein the anode comprises carbon, lithium titanate (LTO), tin/cobalt alloy and/or silicon/carbon.

32. The electrochemical cell of claim 31, wherein the carbon is graphite and/or hard carbon.

33. The electrochemical cell of claim 29, wherein the anode comprises a metallic alkali metal.

34. The electrochemical cell of claim 33, wherein the metallic alkali metal is lithium.

35. The use of the electrolyte of claim 19 in a device.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0008] FIG. 1: The discharge capacity evolution of LMFP cathodes with respect to the charge-discharge cycle number, wherein the electrolyte solvent comprises 1:1 volumetric ratio of DMC:SCN, 2 weight % FEC electrolyte additive, 1 molar LiDFOB salt, and it is indicated in the figure whether or not 12 weight % poly(methyl vinyl ether-alt-maleic anhydride) polymer has been added into the electrolyte. The vertical axis is normalized to the capacity of the first cycle.

[0009] FIG. 2: The discharge capacity evolution of LMFP cathodes with respect to the charge-discharge cycle number, wherein the electrolyte solvent comprises 1:1 volumetric ratio of DMC:SCN, weight % poly(methyl vinyl ether-alt-maleic anhydride) polymer additive, 1 molar LiDFOB salt, and the employed electrolyte additive is indicated in the figure. The vertical axis is normalized to the capacity of the first cycle.

[0010] FIG. 3: The discharge capacity evolution of a graphite anode with respect to the charge-discharge cycle number wherein the electrolyte solvent comprises 1:1 volumetric ratio of DMC:SCN, 12 weight % poly(methyl vinyl ether-alt-maleic anhydride) polymer additive, 2 weight % FEC electrolyte additive, and 1 molar LiDFOB salt. The vertical axis is normalized to the capacity of the first cycle.

[0011] FIG. 4: The discharged energy evolution with respect to the charge-discharge cycle number of a cell comprising metallic Li anode and LMFP cathode. The electrolyte solvent comprises 1:1 volumetric ratio of DMC:SCN, 12 weight % poly(methyl vinyl ether-alt-maleic anhydride) polymer additive, 1 molar LiDFOB salt, and 2 weight % FEC electrolyte additive. The vertical axis is normalized to the discharged energy of the first cycle.

[0012] FIG. 5: The charging time evolution with respect to the charge-discharge cycle number of a cell comprising metallic Li anode and LMFP cathode. The electrolyte solvent comprises 1:1 volumetric ratio of DMC:SCN, 12 weight % poly(methyl vinyl ether-alt-maleic anhydride) polymer additive, 1 molar LiDFOB salt, and 2 weight % FEC electrolyte additive. The vertical axis is normalized to the charging time of the first cycle.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0013] Detailed embodiments of the present invention are disclosed herein with the reference to accompanying drawings.

[0014] We herein disclose electrolyte formulations encompassed by the invention. The electrolyte may be used in an electrochemical cell. An electrochemical cell may comprise, at least, an anode, a cathode and the electrolyte at least partially between the anode and cathode. An electrochemical cell may further comprise a separator between the anode and cathode. An electrochemical cell may further comprise one or more charge carriers (current collectors). An anode and/or a cathode may also be a charge carrier. An electrochemical cell may further comprise a housing.

[0015] The electrolyte salt of the electrolyte may comprise an alkali metal salt. The alkali metal cation of the of the alkali metal salt may comprise lithium cation. The anion of the alkali metal salt may comprise an oxalato-borate group. The anion of the alkali metal salt may further comprise one or more halogen groups.

[0016] One preferred example of an electrolyte salt according to the invention is lithium-difluoro(oxalato)borate (LiDFOB), which comprises an oxalato-borate group, and wherein the alkali metal is Li, and wherein the halogen is F. LiDFOB is found to remain stable at elevated temperature, to be less water sensitive than LiPF.sub.6, and to be suitable for battery charging at 4.2 V or higher voltage. Preferably, the molar concentration of alkali metal salts in the electrolyte is between 0.01 and 5 molar and more preferably between 0.1 and 2 molar and more preferably between 0.5 and 1.5 molar and most preferably between 0.67 and 1.2 molar and more preferably between 0.9 and 1.1 molar and most preferably approximately 1 molar. Other alkali metal salts and molar concentrations are possible according to the invention. Here, alkali metals include, but are not limited to, Li, Na, K, Rb, Cs, and Fr. Here halogens include, but are not limited to, F, Cl, Br, I, and At.

[0017] The herein disclosed electrolyte may further comprise a carbonate:nitrile type solvent mixture. One preferred example of a carbonate type solvent according to the invention is dimethylcarbonate (DMC). Other carbonate type solvents are possible according to the invention. One preferred example of a nitrile type solvent according to the invention is succinonitrile (CN(CH.sub.2).sub.2CN or SCN). One preferred example of a nitrile type solvent according to the invention is malononitrile (CN(CH.sub.2)CN or MLN). A nitrile type solvent according to the invention may comprise a single nitrile solvent, a mixture of nitrile solvents or a mixture of nitrile and other solvents. Other nitrile type solvents are possible according to the invention. The carbonate:nitrile type solvent volume mixture ratio is preferably between 0.001:1 and 1:0.001 and more preferably between 0.01:1 and 1:0.01 and more preferably between 0.1:1 and more preferably between 0.5:1 and 1:0.5 and more preferably between 0.9:1 and 1:0.9 and most preferably approximately 1:1. It is known that LiDFOB salt based electrolytes have approximately 3 mS/cm conductivity when the nitrile solvent component is adiponitrile (CN(CH.sub.2).sub.4CN) [1]. It has been surprisingly discovered that, even though SCN is solid at room temperature, its 1:1 volume ratio mixture with DMC co-solvent is liquid. According to the invention, a preferred electrolyte solvent is a mixture of a DMC and SCN, most preferably in the 1:1 volumetric ratio. It has been found that this mixture gives higher ionic conductivity of the LiDFOB salt than the dimethylcarbonate:adiponitrile solvent mixture based electrolyte of reference [1].

[0018] It has been surprisingly discovered that certain polymers can be beneficial additives to the disclosed electrolyte (here termed polymer additives). The polymer additive according to the invention may be an oxygen-rich polymer additive. The polymer additive according to the invention may be highly soluble in the disclosed electrolyte. Oxygen-rich polymer here means a polymer having a atomic mole fraction of oxygen in the polymer preferably greater than 7% and more preferably greater than 10% and more preferably greater than 15% and most preferably greater than 20% or having preferably greater than 15% and more preferably greater than 25% and more preferably greater than 35% and most preferably greater than 40% mass fraction of oxygen in the polymer. The preferred polymer additives according to the invention are highly soluble in the electrolyte. Highly soluble polymer additives here means a polymer additive being preferably greater than 5% mass fraction and more preferably greater than 8% and more preferably greater than 11% and most preferably greater than 12% soluble.

[0019] A preferred polymer additive according to the invention is poly(methyl vinyl ether-alt-maleic anhydride). Poly(methyl vinyl ether-alt-maleic anhydride) is an oxygen-rich polymer additive. Other polymer additives, including, but not limited to, other oxygen-rich polymer additives, are possible according to the invention. With regard to poly(methyl vinyl ether-alt-maleic anhydride) polymer additive, this invention allows any ratio between the methyl-vinyl-ether (C.sub.3H.sub.6O) and maleic-anhydride (C.sub.3H.sub.6O) polymer constituents in the poly(methyl vinyl ether-alt-maleic anhydride). Preferably, the mass ratio between the methyl-vinyl-ether (C.sub.3H.sub.6O) and maleic-anhydride (C.sub.3H.sub.6O) polymer constituents is between 0.001:1 and 1:0.001 and more preferably between 0.01:1 and 1:0.01 and more preferably between 0.1:1 and 1:0.1 and most preferably 1:1.

[0020] Although the electrolyte's viscosity becomes significantly higher after the addition of one or more of the above said polymer additives, its ionic conductivity is found to not dramatically decrease. For example, the addition of 12 w % poly(methyl vinyl ether-alt-maleic anhydride) additive was found to reduce the electrolyte conductivity by only approximately 32%. As shown in FIG. 1, similar battery cell capacity evolution can be achieved either with or without the polymer additive, however, the obtained capacity results are slightly better without the polymer additive. It has been surprisingly found that one or more of the above said polymer additives are highly advantageous when a metallic alkali anode is used. The anode according to the invention is preferably a metallic lithium based anode, but other metallic alkali metals are possible according to the invention. Without the polymer additive in carbonate:nitrile solvent based electrolytes, alkali metals in general, and lithium in particular, tend to grow dendrites during charging. Such dendrites may reduce the Coulombic efficiency and create internal short-circuit risk. In contrast, when one or more of the above said polymer additives has been used in the electrolyte, preferably in more than 5 w % and more preferably in more than 10 w % mass ratio, the electrochemical cycling of alkali metals in general, and lithium in particular, was surprisingly found to be dendrite-free and long-term stable. FIGS. 4-5 show the long-term cycling data of a cell comprising metallic lithium anode and LMFP cathode. The cycling program employed constant current discharge cycles, and constant current charging until a 4.2 V threshold, followed by constant voltage charging at 4.2 V. The cell gave a stable capacity for the observed duration. During the discharge cycles, an increase of the anodic electrode-electrolyte interface resistance would have been observed as a decrease of discharged energy. As seen in FIG. 4, the discharged energy remained very stable during the cycling process. During the charging cycles, an increase of the anodic electrode-electrolyte interface resistance would have been observed as a lengthening of charging time, since part of the cell charging was in constant voltage mode. As seen in FIG. 5, the charging time also remained stable during the cycling process. Altogether, these data indicate a very stable anodic electrode-electrolyte interface, which allows long-term stable and dendrite-free cycling of the lithium anode, or other alkali metal based anodes.

[0021] According to the invention, the electrolyte may include a further one or more electrolyte additives, here termed electrolyte additives. The electrolyte additive according to the invention may be an SEI (solid electrolyte interface) improving additive. The electrolyte additive according to the invention may be a fluorinated carbonate additive. The fluorinated carbonate according to the invention may be a fluoro-ethylenecarbonate (4-fluoro-1,3-dioxolan-2-one, referred to as FEC). Other electrolyte additives or combinations of electrolyte additives are possible according to the invention.

[0022] It has been surprisingly discovered that the polymer additive and the SEI improving electrolyte additive may have a synergistically beneficial effect. As shown in FIGS. 2 and 3, the cycling stabilities of an exemplary anode and cathode according to the invention are particularly high when both poly(methyl vinyl ether-alt-maleic anhydride) and FEC additives are present in the electrolyte.

[0023] Suitable anode and cathode electrodes, which may be stably cycled in the herein disclosed electrolyte are disclosed. In general, any anode and/or cathode which may be compatible with the disclosed electrolyte and/or derivatives thereof (i.e., in which the electrolyte comprises components in addition to the disclosed electrolyte) is possible according to the invention. Examples of anodes according to the invention include, but are not limited to, various forms and/or allotropes of carbon, lithium titanate (LTO), tin/cobalt alloy and/or silicon/carbon. The anode may be a metallic alkali anode, such as metallic sodium or lithium anode. Other anode materials are possible according to the invention. The carbon according to the invention may be, e.g., hard carbon and/or graphite. Examples of cathodes include, but are not limited to, lithium manganese iron phosphate (LMFP or LFMP), lithium iron phosphate (LFP), lithium cobalt oxide (LCO), lithium manganese oxide (LMO) and/or lithium nickel manganese cobalt oxide (NMC). Other cathode materials are possible according to the invention.

[0024] According to one embodiment of the invention, the concentration of FEC additive may have a volume fraction between 0.5 vol % and 20 vol % and more preferably between 1 vol % and 16 vol % and more preferably between 2 vol % and 13 vol % and most preferably between 4 vol % and 11 vol %. In one embodiment of the invention, the concentration of FEC additive may have a volume fraction of approximately 10 vol %.

[0025] According to one embodiment of the invention, succinonitrile (SCN) and/or malononitrile (MLN) (alone or in combination) may be employed in high concentration and so may be considered to be a solvent in the context of the invention as opposed to being an additive. According to one embodiment of the invention, succinonitrile (SCN) and/or malononitrile (MLN) (alone or in combination) may be employed in a volume fraction between 30 vol % and 60 vol %. The SCN and/or MLN (alone or in combination) concentration should be high to act as a solvent. However, to achieve the desired effect and be liquid in a useful operational temperature range (e.g. around room temperature) the concentration of SCN and/or MLN (alone or in combination) in the mixture cannot be too high.

[0026] According to one embodiment of the invention, the electrolyte may be liquid during electrochemical cell operation. According to one embodiment of the invention, the electrolyte is not a gel during electrochemical cell operation.

EXAMPLES

[0027] A cobalt-free battery cathode which has gained recent attention is LiMn.sub.xFe.sub.1-xPO.sub.4 (abbreviated as LMFP, also known as LFMP). We tested the cycling stability of LMFP cathodes at a 4.2 V charging voltage limit, and investigated the effect of electrolyte additives. FIG. 2 shows the resulting cathode stability of the LMFP electrodes in different electrolyte variants and, in particular, shows the discharge capacity evolution of LMFP cathodes with respect to the charge-discharge cycle number. The scale is normalized to the initial discharge capacity of each electrode. In all cases, the initial gravimetric discharge capacity is approximately 150 mAh/g with respect to the LMFP weight. The electrolyte solvent comprises 1:1 volumetric ratio of DMC:SCN, and further comprises 12 weight % poly(methyl vinyl ether-alt-maleic anhydride) additive, and further comprises 1 molar LiDFOB salt. The employed further electrolyte additive is indicated in the figure. It is found that the electrode stability in one embodiment of the disclosed electrolyte (LiDFOB salt in DMC and SCN solvent (1:1 volumetric ratio) with 12 weight % poly(methyl vinyl ether-alt-maleic anhydride) additive) is relatively stable even without further additive, and it is highly stable in the electrolyte further comprising 2 weight % fluoro-ethylenecarbonate (FEC) electrolyte additive. This result is particularly surprising, since LMFP cathodes show definite fading in similar but polymer-free electrolytes, even with the use of FEC additive [1]. Without intending to be bound by theory, we ascribe this improvement to the complementary beneficial effects of the employed polymer additive, which is preferably poly(methyl vinyl ether-alt-maleic anhydride), and the employed electrolyte additive, which is preferably FEC. Other anodes, cathodes, electrolyte compositions, polymer additives and electrolyte additives are possible according to the invention.

[0028] In one preferred formulation, the electrolyte solvent comprises 1:1 volumetric ratio of DMC:SCN, and further comprises 12 weight % poly(methyl vinyl ether-alt-maleic anhydride) additive and 2 weight % FEC additive, and further comprises 1 molar LiDFOB salt. Even though 65 weight % of the electrolyte constituents are solid at room temperature, the resulting electrolyte was found to remain liquid down to at least −35° C. In an other preferred formulation, the electrolyte solvent comprises 1:1 volumetric ratio of DMC:SCN, and further comprises 2 weight % FEC additive, and further comprises 1 molar LiDFOB salt. The resulting electrolyte was also found to remain liquid down to at least −35° C. Table 2 shows the room temperature (20° C.) ionic conductivity of these preferred electrolyte formulations—with and without the polymer additive. This conductivity data shows that the use of succinonitrile is advantageous over the use of larger nitrile molecules, and that the electrolyte conductivity stays sufficiently high even with 12 w % of the preferred polymer additive present in the electrolyte. Other anodes, cathodes, electrolyte compositions, polymer additives and electrolyte additives are possible according to the invention.

TABLE-US-00002 TABLE 2 Ionic conductivity of the preferred electrolyte formulations 1M LiDFOB in 1:1 mixture of DMC:SCN, further comprising 12 w % poly(methyl vinyl ether-alt-maleic 1M LiDFOB anhydride) and Electrolyte in 1:1 mixture 2 w % FEC formulation of DMC:SCN additives Electrolyte 5.5 mS/cm 3.7 mS/cm conductivity

[0029] According to the invention, the electrochemical cell may employ anodes comprising carbon. Carbon may be in any form compatible with the electrolyte. Examples include, but are not limited to graphite, hard carbon, graphene, amorphous carbon, fullerenes, carbon nanotubes, carbon nanobuds, carbon nanohorns, Y-carbon, carbon nanofoam and/or any combination thereof. Other forms of carbon are possible according to the invention. We investigated the stability of the graphite anodes in the above said preferred electrolyte formulation. FIG. 3 shows the resulting anode stability of the graphite electrodes. In particular, FIG. 3 shows the discharge capacity evolution of a graphite anode with respect to the charge-discharge cycle number. The scale is normalized to the initial discharge capacity of the electrode. The electrolyte solvent comprises 1:1 volumetric ratio of DMC:SCN, and further comprises 12 weight % poly(methyl vinyl ether-alt-maleic anhydride) additive and 2 weight % FEC additive, and further comprises 1 molar LiDFOB salt. Similar cycling stability is obtained with hard carbon anodes. Other carbon anodes are possible according to the invention. This demonstrated stable cycling performance establishes that the herein disclosed electrolyte formulation allows stable cycling of both Li-ion battery electrodes. Other anodes, cathodes, electrolyte compositions, polymer additives and electrolyte additives are possible according to the invention.

[0030] While the foregoing examples are illustrative of the principles of the present invention in one or more particular applications, it will be apparent to those of ordinary skill in the art that numerous modifications in form, usage and details of implementation can be made without the exercise of inventive faculty, and without departing from the principles and concepts of the invention. Accordingly, it is not intended that the invention be limited, except as by the claims set forth below. [0031] [1] Journal of Power Sources 397 (2018) 52-58 (https://doi.org/10.1016/j.jpowsour.2018.07.004)