DE102015201077A1 - Electrolyte for lithium-based energy storage - Google Patents

Abstract

The invention relates to an electrolyte for a lithium ion battery comprising lithium hexafluorophosphate and an additive selected from the group consisting of dimethyl fluorophosphonate and diethyl fluorophosphonate. Furthermore, the invention relates to a lithium-ion battery comprising the electrolyte and a motor vehicle comprising the lithium-ion battery. In particular, the life of the lithium-ion battery can be increased with the electrolyte according to the invention.

Description

The invention relates to an electrolyte for lithium-based energy storage.

Electrolytes, d. H. Conductive salts dissolved in solvents or in a polymer matrix are ubiquitous and indispensable in all electrochemical devices, and their basic function is independent of the chemistry and the widely diversified applications of these devices. The roles of electrolytes in electrolysis cells, capacitors, fuel cells or batteries are the same: they serve as a medium for the transfer of charges in the form of ions between a pair of electrodes.

Conceptually, there should be no net chemical changes in the electrolyte during battery operation, and all Faraday processes should be performed within the electrodes. Therefore, to a great extent, the electrolyte can be considered as an inert component in the battery, and thus must exhibit stability to both cathode and anode surfaces. This electrochemical stability of the electrolyte, which is typically realized in actual devices in a kinetic (passivation) rather than a thermodynamic manner, is of particular importance for rechargeable battery systems, although these are difficult to meet because of the strong oxidizing and reducing nature of the cathode and anode is.

A prerequisite for the components used in the electrolyte for lithium-ion batteries, especially solvents, is that they are anhydrous or more precisely aprotic, d. H. that the solvent contains no active protons that can react with lithium. In addition, the solvent should be in a liquid state in the service temperature range.

A disadvantage of the conventional lithium hexafluorophosphate in carbonates based electrolytes for lithium-ion batteries is in particular in the low oxidative stability of 4.5 V against Li / Li ⁺ . Only up to this voltage, the electrolyte is stable, while outside of this range, the oxidative decomposition of the electrolyte and thus associated with the dissolution of the cathode material. Also in lithium ion batteries with high energy density or high power density, the preferred active material for the positive electrode lithium-nickel-manganese-cobalt mixed oxides, also referred to as "NMC", or lithium-nickel-manganese oxide (LNMO ), charging voltages greater than 4.4 V and 4.7 V, respectively, against Li / Li ^{+ result} in decomposition of the electrolyte and dissolution of the cathode material. The result is a low cycle stability and thus battery life.

US 2012/0225359 A1 discloses various phosphorus-containing additives for use in nonaqueous electrolytes.

The object of the present invention was to provide an electrolyte for lithium-ion batteries with improved stability.

This object is achieved in a first aspect by an electrolyte according to claim 1, in a second aspect by a lithium-ion battery according to claim 7, in a third aspect by a motor vehicle comprising the lithium-ion battery according to claim 10. Preferred embodiments are presented in the dependent claims.

For all aspects of the invention, where applicable, the following definitions apply.

Lithium Ion Battery

According to the invention, the terms "lithium ion battery", "lithium ion battery", "lithium ion battery", "rechargeable lithium ion battery" and "lithium ion secondary battery" are used interchangeably. The terms also include the terms "lithium battery", "lithium-ion battery" and "lithium-ion cell" as well as all lithium or alloy batteries, in particular also Li-sulfur or alloy systems. Thus, the term "lithium ion battery" is used as a generic term for the conventional terms used in the prior art. It means both rechargeable batteries (secondary batteries) as well as non-rechargeable batteries (primary batteries). In particular, a "battery" in the context of the present invention also includes a single or single "electrochemical cell". Preferably, in a "battery" two or more such electrochemical cells are connected together, either in series (ie one behind the other) or in parallel.

electrodes

The electrochemical cell according to the invention has at least two electrodes, d. H. a positive (cathode) and a negative electrode (anode).

In this case, both electrodes each have at least one active material. This is able to absorb or donate lithium ions and at the same time to take in or donate electrons.

The term "positive electrode" means the electrode that is capable of accepting electrons when the battery is connected to a consumer, such as an electric motor. It represents the cathode in this nomenclature.

The term "negative electrode" means the electrode that is capable of delivering electrons when in use. It represents the anode in this nomenclature.

The electrodes include inorganic material or inorganic compounds or substances that can be used for or in or on an electrode or as an electrode. These compounds or substances can, under the working conditions of the lithium-ion battery, due to their chemical nature, take up (insert) and also release lithium ions or metallic lithium. In the present specification, such material is referred to as "active cathode material" or "active anode material" or generally "active material". This active material is preferably applied to a carrier for use in an electrochemical cell or battery, preferably a metallic carrier, preferably aluminum for the cathode or copper for the anode. This carrier is also referred to as "arrester" or as a "collector" or collector foil.

Cathode (positive electrode)

As the active material for the positive electrode or active cathode material, all known from the related art materials may be used. These include z. B. LiCoO ₂ , NCM, NCA, high-energy NCM or HE-NCM (High-Energy NCM), lithium iron phosphate, Li-manganese spinel (LiMn ₂ O ₄ ), Li-manganese-nickel Oxide (LMNO) or lithium-rich transition metal oxides of the type (Li ₂ MnO ₃ ) _x (LiMO ₂ ) _1-x . Thus, there is no limitation with regard to the positive electrode in the sense of the present invention.

In a preferred embodiment, as the active cathode material, a material selected from a group consisting of a lithium transition metal oxide (hereinafter also referred to as "lithium metal oxide"), layered oxides, spinels, olivine compounds, silicate compounds, and mixtures thereof. Such cathode active materials are described, for example, in US Pat Bo Xu et al. "Recent progress in cathode materials research for advanced lithium ion batteries", Materials Science and Engineering R 73 (2012) 51-65 described. Another preferred cathode material is HE-NCM. Layered oxides and HE-NCM are also disclosed in the patents US 6,677,082 B2 . US 6,680,143 B2 and US Pat. No. 7,205,072 B2 of the Argonne National Laboratory.

Examples of olivine compounds are lithium phosphates of the empirical formula LiXPO ₄ with X = Mn, Fe, Co or Ni, or combinations thereof.

Examples of lithium metal oxide, spinel compounds and layered oxides are lithium manganate, preferably LiMn ₂ O ₄ , lithium cobaltate, preferably LiCoO ₂ , lithium nickelate, preferably LiNiO ₂ , or mixtures of two or more of these oxides, or their mixed oxides.

The active material may also contain mixtures of two or more of the substances mentioned.

To increase the electrical conductivity, further compounds may be present in the active material, preferably carbon-containing compounds, or carbon, preferably in the form of carbon black or graphite.

The carbon can also be introduced in the form of carbon nanotubes. Such additives are preferably applied in an amount of 0.1 to 10 wt .-%, preferably 1 to 8 wt .-% based on the applied to the carrier mass of the positive electrode.

Anode (negative electrode)

As active material for the negative electrode or active anode material, all known from the related art materials can be used. There is therefore no restriction with regard to the negative electrode in the context of the present invention. In particular, it is also possible to use mixtures of different active anode materials.

The active anode material may be selected from the group consisting of lithium metal oxides such as lithium titanium oxide, metal oxides (e.g., Fe ₂ O ₃ , ZnO, ZnFe ₂ O ₄ ), carbonaceous materials such as graphite, graphite, mesocarbon, doped carbon, hardcarbon, softcarbon, fullerenes, mixtures of silicon and carbon, silicon, lithium alloys, metallic lithium, and mixtures thereof. As the electrode material for the negative electrode, niobium pentoxide, tin alloys, titanium dioxide, tin dioxide, silicon can also be used.

The active anode material may also be a lithium alloyable material. This may be a lithium alloy or a non-lithiated or partially lithiated precursor thereto, resulting in the formation of a lithium alloy. Preferred lithium-alloyable materials are lithium alloys selected from the group consisting of silicon-based, tin-based, and antimony-based alloys. Such alloys are described, for example, in the review article W.-J. Zhang, Journal of Power Sources 196 (2011) 13-24 described.

Electrode binder

The materials used for the positive or the negative electrode, such as the active materials, are held together by one or more binders, which or these materials hold these materials on the electrode or on the arrester.

The binder (s) may be selected from the group consisting of polyvinylidene fluoride (PVdF), polyvinylidene fluoride-hexa-fluoro-propylene-co-polymer (PVdF-HFP), polyethylene oxide (PEO), polytetrafluoroethylene, polyacrylate, styrene-butadiene Rubber, and carboxymethylcellulose (CMC) and blends and copolymers thereof. Styrene-butadiene rubber and optionally carboxymethyl cellulose and / or the further binders such as PVdF are preferably present in an amount of 0.5-8 wt .-% before based on the total amount of the active material used in the positive or negative electrode.

separator

The electrochemical cell according to the invention comprises a material which separates the positive electrode and the negative electrode from each other. This material is permeable to lithium ions, so it conducts lithium ions, but is a non-conductor for electrons. Such materials used in lithium ion batteries are also referred to as separators.

In a preferred embodiment according to the present invention, polymers are used as separators. In one embodiment, the polymers are selected from the group consisting of: polyester, preferably polyethylene terephthalate; Polyolefin, preferably polyethylene, polypropylene; polyacrylonitrile; polyvinylidene fluoride; Polyvinylidene-hexafluoropropylene; polyetherimide; Polyimide, polyether; Polyether ketone or mixtures thereof. The separator has porosity so that it is permeable to lithium ions. In a preferred embodiment according to the present invention, the separator is at least one polymer.

electrolyte

The term "electrolyte" preferably means a liquid in which a lithium-conducting salt is dissolved. Preferably, the liquid is a solvent for the conducting salt. Preferably, the Li-conducting salt is then present as an electrolyte solution.

In the following, the various aspects of the present invention are illustrated in greater detail.

In a first aspect of the invention, the invention is an electrolyte comprising lithium hexafluorophosphate and electrolyte for a lithium-ion battery comprising lithium hexafluorophosphate and an additive selected from the group consisting of dimethyl fluorophosphonate and diethyl fluorophosphonate.

The additive selected from the group consisting of dimethylfluorophosphonate and diethylfluorophosphonate is accessible via the following synthesis:
Diethylfluorophosphonat is the following synthesis based on Acharya, J., et al. Synthetic Communications 38 (2008) 3760-3765 accessible under inert gas and reflux in dry acetonitrile in 20 hours:

The yield is 55% with a purity of more than 99%, as measured by ¹ H-NMR and gas chromatography mass spectroscopy (GC-MS). The water content of the product is below 20 ppm. Dimethylfluorophosphonate can be prepared analogously.

Surprisingly, it has been found that cells in which electrolytes containing lithium hexafluorophosphate as the conducting salt and an additive selected from the group consisting of dimethyl fluorophosphonate and diethyl fluorophosphonate were used, compared to the sole use of lithium hexafluorophosphate as the conducting salt Additive show higher cycle stability and service life. In addition, the resolution of the cathode material is suppressed. Finally, a lower self-discharge occurs.

Without wishing to be bound by theory, it is believed that the addition of an additive selected from the group consisting of dimethylfluorophosphonate and diethylfluorophosphonate to an electrolyte containing LiPF ₆ causes in-situ formation of a cathodic passivation layer, especially at end-of-charge potentials of more as 4.5 V against Li / Li ⁺ kinetically inhibits the dissolution of metals from the active cathode material and the oxidative decomposition of the electrolyte.

It is further advantageous that the additive selected from the group consisting of dimethyl fluorophosphonate and diethyl fluorophosphonate has good lithium ion conductivity and sufficient cathodic stability. Further, the additive selected from the group consisting of dimethyl fluorophosphonate and diethyl fluorophosphonate is usable in a wide temperature range.

The additive selected from the group consisting of dimethylfluorophosphonate and diethylfluorophosphonate is therefore advantageously suitable as an additive for LiPF _6- containing electrolytes for commercial lithium-ion batteries.

Preferably, the electrolyte of the invention comprises the additive selected from the group consisting of dimethyl fluorophosphonate and diethyl fluorophosphonate dissolved in an organic solvent. For example, the electrolyte can be prepared by introducing and dissolving lithium hexafluorophosphate and the additive selected from the group consisting of dimethylfluorophosphonate and diethylfluorophosphonate into a solvent or solvent mixture.

In preferred embodiments, with respect to the amount of electrolyte used comprising lithium hexafluorophosphate in a solvent or solvent mixture, 0.01 to 10% by weight, preferably 0.5 to 5% by weight of the additive selected from the group is consisting of dimethylfluorophosphonate and diethylfluorophosphonate present.

In preferred embodiments, the concentration of lithium hexafluorophosphate in the electrolyte is in the range of> 0.1 M to <2 M, preferably in the range of> 0.5 M to <1.5 M, particularly preferably in the range of> 0.7 M to <1.2 M. In a particularly preferred embodiment, the concentration of lithium hexafluorophosphate in the electrolyte is 1 M.

In preferred embodiments, the electrolyte comprises an organic solvent, an ionic liquid and / or a polymer matrix. Preferably, an electrolyte comprises lithium hexafluorophosphate, the additive selected from the group consisting of dimethyl fluorophosphonate and diethyl fluorophosphonate consists, and an organic solvent. It has been found that the additive selected from the group consisting of dimethyl fluorophosphonate and diethyl fluorophosphonate has good solubility in organic solvents, especially in cyclic and / or linear carbonates. This advantageously allows the use of the additive selected from the group consisting of dimethyl fluorophosphonate and diethyl fluorophosphonate in LiPF ₆ -containing liquid electrolytes.

In preferred embodiments, the organic solvent is selected from the group comprising ethylene carbonate (EC), propylene carbonate, diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate (EMC), acetonitrile, glutaronitrile, adiponitrile, pimelonitrile, gamma-butyrolactone, gamma-valerolactone, dimethoxyethane, 1,3- Dioxalane, methyl acetate, ethyl methanesulfonate, dimethyl methyl phosphonate and / or mixture thereof. Suitable organic solvents are in particular selected from the group comprising cyclic carbonates such as ethylene carbonate and propylene carbonate and / or linear carbonates such as diethyl carbonate, dimethyl carbonate and ethyl methyl carbonate.

Preferably, the organic solvent is selected from the group comprising ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate and / or mixtures thereof. A preferred solvent is ethylene carbonate. Ethylene carbonate is also referred to as 1,3-dioxolan-2-one according to the IUPAC nomenclature. Ethylene carbonate is commercially available. Ethylene carbonate has a high boiling point and a high flash point. It is also advantageous that ethylene carbonate allows a high conductivity by a good Salzdissoziation.

In a preferred embodiment, the organic solvent comprises a mixture of ethylene carbonate and at least one further organic solvent, preferably gamma-butyrolactone. Binary mixtures of carbonates, in particular of ethylene carbonate with a further carbonate, for example diethyl carbonate, dimethyl carbonate and / or ethyl methyl carbonate, in particular ethyl methyl carbonate, are also preferred.

The ratio of ethylene carbonate and the at least one further organic solvent, preferably ethyl methyl carbonate, is preferably in the range of> 1:99 to <99: 1, preferably in the range of> 1: 9 to <9: 1, preferably in the range of ≥3 : 7 to ≤ 1: 1. Unless indicated otherwise, the ratio given refers to the parts by weight of the solvents. In a solvent mixture of ethylene carbonate and ethyl methyl carbonate in the ratio 1: 1, a high conductivity in a temperature range of -25 ° C to + 60 ° C could be achieved in an advantageous manner.

Also preferred are ternary mixtures comprising at least one carbonate as solvent. Particular preference is given to mixtures of ethylene carbonate with a further solvent, for example ethyl methyl carbonate, and a compound which is suitable for forming a so-called solid electrolyte interphase (SEI), a solid-electrolyte interface. The electrolyte may therefore further comprise additives, in particular film-forming electrolyte additives. In preferred embodiments, the electrolyte comprises a compound selected from the group consisting of chloroethylene carbonate, fluoroethylene carbonate, vinylene carbonate, vinyl ethylene carbonate, ethylene sulfite, ethylene sulfate, propanesulfonates, sulfites, preferably dimethylsulfite and propylene sulfite, sulfates, optionally F, Cl or Br substituted butyrolactones, phenylethylene carbonate, vinyl acetate and or trifluoropropylene carbonate. Of the carbonate-based compounds, chloro or fluoro-substituted carbonates are preferred, especially fluoroethylene carbonate (FEC). The connections can improve battery performance, such as capacity or cycle life. In particular, fluoroethylene carbonate can lead to improved long-term stability of a cell.

Preferably, the electrolyte contains at least one further additive, in particular a compound selected from the group consisting of chloroethylene carbonate, fluoroethylene carbonate, vinylene carbonate, vinyl ethylene carbonate, ethylene sulfite, ethylene sulfate, propanesulfonates, sulfites, preferably dimethyl sulfite and propylene sulfite, sulfates, optionally F, Cl or Br substituted butyrolactones, Phenylethylene carbonate, vinyl acetate, trifluoropropylene carbonate or a mixture thereof, preferably fluoroethylene carbonate, in the range from> 0.1% by weight to <10% by weight, preferably in the range from> 1% by weight to <5% by weight, preferably in the range of> 2 wt .-% to <3 wt .-%, based on the total weight of the electrolyte.

The organic solvent preferably comprises a mixture of ethylene carbonate and at least one further organic solvent, preferably selected from the group comprising linear carbonates, in particular ethylmethyl carbonate, and fluoroethylene carbonate.

Thus, fluoroethylene carbonate can form a protective layer on a graphite anode and reduce overpotentials of the electrode. Further promising ionic liquids have proven to be promising solvents since they combine high thermal and electrochemical stability with high ionic conductivity. In particular, this is advantageous for use with lithium 2-methoxy-1,1,2,2-tetrafluoroethanesulfonate. Preferred ionic liquids include a cation selected from the group consisting of 1-ethyl-3-methylimidazolium (EMI ⁺ ), 1,2-dimethyl-3-propylimidazolium (DMPI ⁺ ), 1,2-diethyl-3,5-dimethylimidazolium (DEDMI ⁺ ), Trimethyl-n-hexylammonium (TMHA ⁺ ), N-alkyl-N-methylpyrrolidinium (PYR _IR ⁺ ), N-alkyl-N-methylpiperidinium (PIP _IR ⁺ ) and / or N-alkyl-N-methylmorpholinium (MORP _IR ⁺ ) and an anion selected from the group comprising bis (trifluoromethanesulfonyl) imide (TFSI ^- ), bis (pentafluoroethanesulfonyl) imide (BETI ^- ), bis (fluorosulfonyl) imide (FSI ^- ), 2,2,2-trifluoro-N - (trifluoromethanesulfonyl) acetamide (TSAC ^- ), tetrafluoroborate (BF ₄ ^- ), pentafluoroethane trifluoroborates (C ₂ F ₅ BF ₃ ^- ), hexafluorophosphate (PF ₆ ^- ) and / or tris (pentafluoroethane) trifluorophosphate ((C ₂ F ₅ ) ₃ PF ₃ ^- ). Preferred N-alkyl-N-methylpyrrolidinium (PYR _IR ⁺ ) cations are selected from the group comprising N-butyl-N-methylpyrrolidinium (PYR ₁₄ ⁺ ) and / or N-methyl-N-propylpyrrolidinium (PYR ₁₃ ⁺ ).

Preferred ionic liquids are selected from the group comprising N-butyl-N-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide (PYR ₁₄ TFSI) and / or N-methyl-N-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide (PYR ₁₃ TFSI).

Other suitable electrolyte materials are polymer electrolytes wherein the polymer electrolyte may be present as a gel polymer electrolyte or a solid polymer electrolyte. Solid polymer electrolytes show good properties with respect to the requirements of future battery generations. They enable a solvent-free structure that is easy to produce and versatile in shape. In addition, the energy density can be increased because it eliminates the three-layer structure of electrolyte-separator-electrolyte, so that only a thin polymer film between the electrodes is needed. As a rule, solid electrolytes are chemically and electrochemically stable to electrode materials and furthermore do not leave the cell. Gel polymer electrolytes usually comprise an aprotic solvent and a polymer matrix.

Preferred polymers for solid polymer electrolytes and gel polymer electrolytes are selected from the group comprising homopolymers or copolymers of polyethylene oxide (PEO), polypropylene oxide (PPO), polyvinylidene fluoride (PVdF), polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), polyacrylonitrile (PAN), polymethylmethacrylate (PMMA ), Polyethyl methacrylate (PEMA), polyvinyl acetate (PVAc), polyvinyl chloride (PVC), Polyphophazene, polysiloxanes, polyvinyl alcohol (PVA) and / or homo and (block) copolymers comprising functional side chains selected from the group consisting of ethylene oxide, propylene oxide, acrylonitrile and / or siloxanes.

In a second aspect of the invention, the invention is directed to a lithium-ion battery with anode, cathode, separator and the electrolyte according to the invention.

In preferred embodiments, the cathode comprises a cathode active material selected from the group consisting of lithium metal oxide, layered oxides, spinels, olivine compounds, silicate compounds, HE-NCM and NMC, respectively, and mixtures thereof. Because of their high-voltage stability, active cathode materials are selected from the group comprising lithium nickel manganese cobalt mixed oxide (NMC), lithium nickel manganese oxide (LNMO) and / or lithium-rich transition metal oxides of the type (Li ₂ MnO ₃ ) _x (LiMO ₂ ) _1-x preferred. In addition, in all three preferred cathode active materials, the addition of lithium 2-pentafluoroethoxy-1,1,2,2-tetrafluoroethanesulfonate to the LiPF _6- containing electrolyte can kinetically disproportionate and disassociate manganese, as well as other transition metals, from the cathode active material be inhibited.

In preferred embodiments, the anode comprises an active anode material selected from the group consisting of carbon, graphite, mixtures of silicon and carbon / graphite, silicon, lithium, lithium metal oxide, lithium alloyable materials, and mixtures thereof. Particularly preferred is graphite.

In a third aspect of the invention, the present invention is directed to a motor vehicle comprising the lithium-ion battery of the invention. The lithium-ion battery according to the invention is particularly suitable for this purpose due to its high-voltage stability.

Examples and figures which serve to illustrate the present invention are given below.

Here are the figures:

1 shows the influence of Diethylfluorophosphonat (DEFP) as an additive in LiPF _6- containing electrolytes in lithium half-cells with NCM (4.6 V vs. Li / Li ⁺ ) on the discharge capacity.

2 shows the influence of diethylfluorophosphonate (DEFP) as an additive in LiPF _6- containing electrolytes on the self-discharge in LMNO half-cells (4.95 V vs. Li / Li ⁺ ).

example 1

Preparation of the electrolyte solutions

The electrolyte mixtures were prepared in a glove box with H ₂ O and O ₂ contents below 0.5 ppm. All stated mixing ratios are based on the mass ratio (wt .-%).

An electrolyte containing 1 M LiPF ₆ in EC: EMC (1: 1) was prepared by initially charging 50% by weight of ethylene carbonate (EC) and 50% by weight of ethylmethyl carbonate (EMC) and in this solvent mixture the required amount of LiPF ₆ was dissolved to give a concentration of 1 M LiPF ₆ . This electrolyte served as a comparative electrolyte.

Diethylfluorophosphonate (DEFP) was added to this electrolyte mixture to prepare the additized electrolytes of the invention. The percentage by weight of the additive (A) in% by weight refers to the electrolyte (E) without additive, not to the entire electrolyte mixture including additive, d. H. w (A) = m (A) / m (E). The water content of the electrolytes was less than 20 ppm according to Karl Fischer.

Electrochemical investigations:

The experiments were conducted in a 3-electrode assembly ^® in modified Swagelok T-pieces (pipe connector, stainless steel body) with a nickel-manganese-cobalt oxide (NMC) electrode (12 mm diameter) or lithium-nickel-manganese oxide (LNMO ) (12 mm diameter) as a working electrode and lithium foil (12 mm or 5 mm) diameter as a counter and reference electrode performed. The inner cell components were isolated from the stainless steel housing by a polyester film. The electrodes were separated with a glass fiber filter, which was impregnated with the appropriate electrolyte (200 μL). Due to the hydrolysis and air sensitivity of the cell components, the cells were assembled in a glovebox.

Measurements at constant current:

Constant current measurements were performed on a Series 4000 (Maccor) battery tester at 20 ° C ± 2 ° C. The cyclization of the NMC half-cells was carried out in the potential range of 3.0 V to 4.6 V versus Li / Li ⁺ . For the LMNO half cells, a potential range of 3.0 V to 4.95 V versus Li / Li ^{+ was} chosen.

The following test plan was used:

After three cycles of formation with a charge and discharge rate (C and D rate) of C / 5 (where 150 mAh g ^-1 corresponds to a C rate of 1C for NMC and 140 mAh g ^{-1 to} a C rate of 1C for LMNO), the cyclization behavior was checked for 50 cycles at a charge and discharge rate of 1C.

Example 2

Determination of the cyclization behavior of diethylfluorophosphonate (DEFP) as an additive in LiPF _6- containing electrolytes in lithium half-cells with NCM (4.6 V vs. Li / Li ⁺ )

The preparation of an electrolyte containing 1 M lithium hexafluorophosphate (LiPF ₆ ) in a solvent mixture of ethylene carbonate and ethyl methyl carbonate (EC: EMC 1: 1) with the addition of 1 wt .-% DEFP, and a comparative electrolyte without the addition of DEFP was carried out as described in Example 1 , The determination of the cyclization behavior was carried out using a NMC half cell at constant current as described above.

In 1 the discharge capacity is plotted against the number of cycles of 1 M LiPF ₆ in a solvent mixture of ethylene carbonate and ethyl methyl carbonate (EC: EMC 1: 1) with and without the addition of DEFP in a NMC half-cell. As the 1 shows, the decrease of the discharge capacity was reduced with the addition of DEFP with increasing number of cycles (capacity fading).

Example 3

Measurement of the self-discharge of diethylfluorophosphonate (DEFP) as an additive in LiPF _6- containing electrolytes in lithium half-cells with LMNO (4.95 V vs. Li / Li ⁺ ).

In the 2 shows the self-discharge of a lithium-ion half cell with 1 M lithium hexafluorophosphate (LiPF ₆ ) in a solvent mixture of ethylene carbonate and ethyl methyl carbonate (EC: EMC 1: 1) with and without the addition of 1 wt .-% DEFP. As a working electrode, the cathode material lithium-nickel-manganese oxide (LNMO) was used. The electrolyte preparation and the cell assembly were carried out according to Example 1. After three cycles of formation with C / 5 in the potential range of 3.0 V to 4.95 V against Li / Li ⁺ was again up to a final charge potential of 4.95 V against Li / Li ⁺ and then tracking the open circuit voltage between the LMNO electrode and the lithium reference electrode over time. It was reduced by the addition of DEFP self-discharge. The profile of the self-discharge follows the course of the discharge curve of the cathode material.

Overall, these results show that an additive selected from the group consisting of dimethyl fluorophosphonate (DMFP) and diethyl fluorophosphonate (DEFP) reduces capacitance fading and self-discharge, thereby prolonging cycle life of lithium-ion battery.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 2012/0225359 A1 [0006]
• US 6677082 B2 [0017]
• US 6680143 B2 [0017]
• US 7205072 B2 [0017]

Cited non-patent literature

• Bo Xu et al. "Recent progress in cathode materials research for advanced lithium ion batteries", Materials Science and Engineering R 73 (2012) 51-65 [0017]
• W.-J. Zhang, Journal of Power Sources 196 (2011) 13-24 [0025]
• Acharya, J., et al. Synthetic Communications 38 (2008) 3760-3765 [0033]

Claims (11)

An electrolyte for a lithium-ion battery comprising lithium hexafluorophosphate and an additive selected from the group consisting of dimethylfluorophosphonate and diethylfluorophosphonate. An electrolyte according to claim 1, wherein from 0.01 to 10% by weight, preferably 0.5 to 5% by weight of the additive selected from the group consisting of the amount of the electrolyte comprising lithium hexafluorophosphate in a solvent or solvent mixture consisting of dimethylfluorophosphonate and diethylfluorophosphonate is present. An electrolyte according to claim 1 or 2, wherein the concentration of lithium hexafluorophosphate is in the range of at least 0.1 M to at most 2 M, preferably in the range of at least 0.5 M to at most 1.5 M, particularly preferably in the range of at least 0.7 M is not more than 1.2M. Electrolyte according to claim 1 or 2, characterized in that the electrolyte comprises an organic solvent, an ionic liquid and / or a polymer matrix. Electrolyte according to one of the preceding claims, characterized in that the organic solvent is selected from the group comprising ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, acetonitrile, glutaronitrile, adiponitrile, pimelonitrile, gamma-butyrolactone, gamma-valerolactone, dimethoxyethane, 1, 3-dioxalane, methyl acetate and / or a mixture thereof, preferably from the group comprising ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate and / or mixtures thereof. Electrolyte according to one of the preceding claims, characterized in that the organic solvent comprises a mixture of ethylene carbonate and at least one further organic solvent, preferably ethyl methyl carbonate, preferably in a ratio in the range of> 1:99 to <99: 1, preferably in the range of> 1: 9 to <9: 1, preferably in the range of ≥ 3: 7 to ≤ 1: 1. Electrolyte according to one of the preceding claims, characterized in that the electrolyte comprises a compound selected from the group comprising chloroethylene carbonate, fluoroethylene carbonate, vinylene carbonate, vinyl ethylene carbonate, ethylene sulfite, ethylene sulfate, propanesulfonates, sulfites, preferably dimethyl sulfite and propylene sulfite, sulfates, optionally with F, Cl or Br substituted butyrolactones, phenylethylene carbonate, vinyl acetate and / or trifluoropropylene carbonate. Lithium-ion battery with anode, cathode, separator and an electrolyte according to one of claims 1 to 7. The lithium-ion battery of claim 8, wherein the cathode comprises a cathode active material selected from the group consisting of lithium metal oxide, layered oxides, spinels, olivine compounds, silicate compounds, HE-NCM, and mixtures thereof. The lithium-ion battery of claim 8 or 9, wherein the anode comprises an active anode material selected from the group consisting of carbon, graphite, mixtures of silicon and carbon / graphite, silicon, lithium, lithium metal oxide, with lithium alloyable materials and mixtures thereof. Motor vehicle comprising a lithium-ion battery according to one of claims 8 to 10.

Images