The present invention relates to rechargeable electrochemical battery cells. In particular, the invention concerns battery chemistry improvements for electrochemical cells in terms of costs, safety, and operating temperature range.
High performance and low cost batteries are advantageous for many applications, e.g. energy storage for electric vehicles or electric grids. The presently market-leading battery technology is the lithium-ion battery technology. State-of-the-art batteries employ graphite-based anodes, metal-oxide cathodes, and organic electrolytes. The commercially preferred cathode formulation is based on a nickel-cobalt-manganese oxide (NCM) formulation. However, the future prospects of this cathode formulation are hindered by the limited supply of cobalt, which is a known bottleneck for a future increase in battery production volumes. The commercially preferred electrolyte formulation is based on a mixture of carbonate solvents with LiPF6 electrolyte salt. However, the high flammability of these solvents present a safety risk, and causes numerous battery fire accidents annually. Moreover, the low chemical stability of the LiPF6 electrolyte salt restricts the battery operating temperature range and necessitates complex and costly thermal management of battery packs. In order to improve the operating temperature range of batteries, the low chemical stability LiPF6 electrolyte salt should be replaced by a more stable salt, which gives at least similar electrolyte conductivity.
The present invention aims to solve the above mentioned problems with state-of-the-art battery cells. 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 is derived from three aspects: i) it allows stable cycling of advanced Li-ion battery electrodes; ii) it allows an extended operating temperature range of Li-ion batteries; and iii) it improves battery safety by making the electrolyte less reactive and volatile than conventional LiPF6 electrolyte salt in carbonate solvents. Consequently, the described invention is beneficial to industry and commerce.
An improved electrolyte formulation for electrochemical cells is disclosed. The electrolyte may comprise a carbonate:nitrile type solvent mixture based electrolyte. The electrolyte may comprise an alkali salt. The electrolyte may comprise one or more polymer additives. The alkali salt cation may be a lithium cation. The alkali salt anion may comprise an oxalato-borate group. The alkali salt may be lithium-difluoro(oxalato)borate (LiDFOB). The electrolyte may comprise one or more electrolyte additives. The electrolyte additive may be an SEI improving additive. The nitrile type solvent may comprise malononitrile (MLN). The nitrile type solvent may comprise succinonitrile (SCN). The nitrile type solvent may be succinonitrile (SCN). The nitrile type solvent may comprise a mixture of MLN and SCN. The carbonate type solvent may be dimethylcarbonate (DMC). The electrolyte additive may be fluoro-ethylenecarbonate (FEC). The polymer additive may be poly(methyl vinyl ether-alt-maleic anhydride).
The electrolyte may be used in an electrochemical cell. The electrochemical cell may comprise additionally a cathode and an anode. The cathode may comprise LiMnxFe1-xPO4 (LMFP or LFMP), lithium iron phosphate (LFP), lithium cobalt oxide (LCO), lithium manganese oxide (LMO), and/or lithium nickel manganese cobalt oxide (NMC). The anode may comprise carbon, lithium titanate (LTO), tin/cobalt alloy and/or silicon/carbon. The carbon may be graphite and/or hard carbon. The anode may comprise a metallic alkali metal. The metallic alkali metal may be metallic lithium. The electrochemical cell may be used in a device.
Table 1 summarizes the benefits of the herein disclosed electrolyte formulations. It is highly advantageous for battery production that these benefits may be simultaneously achieved, and it is highly challenging to discover such electrolyte formulations. In comparison to currently feasible Li-ion cells' energy density, improved cell level energy density becomes feasible through the disclosed electrolyte formulations' ability to simultaneously support the stable cycling of advanced cathode materials, such as LMFP, as well as metallic alkali metal based anodes, such as metallic lithium based anodes.
Detailed embodiments of the present invention are disclosed herein with the reference to accompanying drawings.
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.
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.
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 LiPF6, 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.
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(CH2)2CN or SCN). One preferred example of a nitrile type solvent according to the invention is malononitrile (CN(CH2)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(CH2)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].
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.
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 (C3H6O) and maleic-anhydride (C3H6O) polymer constituents in the poly(methyl vinyl ether-alt-maleic anhydride). Preferably, the mass ratio between the methyl-vinyl-ether (C3H6O) and maleic-anhydride (C3H6O) 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.
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
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.
It has been surprisingly discovered that the polymer additive and the SEI improving electrolyte additive may have a synergistically beneficial effect. As shown in
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.
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 %.
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.
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.
A cobalt-free battery cathode which has gained recent attention is LiMnxFe1-xPO4 (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.
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.
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.
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.
Number | Date | Country | Kind |
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20185836 | Oct 2018 | FI | national |
This application is a National Stage Application of PCT/FI2019/050714, filed 4 Oct. 2019, which claims benefit of Serial No. 20185836, filed 4 Oct. 2018 in Finland, and which applications are incorporated herein by reference. To the extent appropriate, a claim of priority is made to each of the above disclosed applications.
Filing Document | Filing Date | Country | Kind |
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PCT/FI2019/050714 | 10/4/2019 | WO |