EP2399263A1 - High safety lithium-ion battery - Google Patents

High safety lithium-ion battery

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Publication number
EP2399263A1
EP2399263A1 EP10708596A EP10708596A EP2399263A1 EP 2399263 A1 EP2399263 A1 EP 2399263A1 EP 10708596 A EP10708596 A EP 10708596A EP 10708596 A EP10708596 A EP 10708596A EP 2399263 A1 EP2399263 A1 EP 2399263A1
Authority
EP
European Patent Office
Prior art keywords
lithium
group
battery
ethyl
ionic liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10708596A
Other languages
German (de)
French (fr)
Inventor
Bruno Scrosati
Priscilla Reale
Alessandra Fernicola
Werner Tillmetz
Margret Wohlfahrt-Mehrens
Pierre Kubiak
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zentrum fuer Sonnenenergie und Wasserstoff Forschung Baden Wuerttemberg
Universita degli Studi di Roma La Sapienza
Original Assignee
Zentrum fuer Sonnenenergie und Wasserstoff Forschung Baden Wuerttemberg
Universita degli Studi di Roma La Sapienza
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Publication of EP2399263A1 publication Critical patent/EP2399263A1/en
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention refers to the technical field of Lithium-Ion batteries and more in particular to safety and to ameliorate efficiency of this type of batteries. Thanks to their high energy content, Lithium-Ion batteries prevail in the consumer electronics area and promote spreading of cellular phones, lap-top computers, digital audio players and so on. However, Lithium-Ion batteries need improved efficiency to be applied in the expanding markets of power stations fed by discontinuous sources or power systems for electric or hybrid vehicles.
  • Safety is one of the unsolved problems affecting said batteries, due to the instability of the battery's components. More in particular, the use of electrolyte solutions of lithium salts in volatile organic solvents is dangerous. Vaporization of solvents, which is triggered by local overheating and/or by electrochemical decomposition of the same solvents, may produce gaseous side products which increase the internal pressure. This event may cause not only cell breaking, but also to violent side-reactions or fires and explosions. These risks are related to battery abuse, such as high working temperatures or mechanical shock.
  • Patent US 6,413,678 suggests solving safety problems of said type of batteries by using a gas evolving system.
  • a carbonyl compound subject to temperature increasing, decomposes and produces gaseous products, which are insoluble, or poorly soluble in the electrolyte.
  • a suitable breaking valve stably and safely increases the pressure within the battery.
  • ionic liquids namely salts in the liquid state at room or sub-room or at least at the battery's working temperature.
  • the ionic liquids are composed by several combinations of different anions and cations.
  • Patent application US 2007/026318 discloses some of said ionic liquids and their drawbacks due to their reactivity with the electrodes (see for example patent applications JP 4-349365, JP 11 -86905). Said document disclose the technical solution of inserting allyl phosphate in the ionic liquid.
  • the compounds bearing the quaternary ammonium cation pyrrolidinium derivatives are mentioned, all characterised by a methyl on the quaternary nitrogen residue, which are useful to counteract side reactions on the electrodes.
  • imidazole derivatives are preferred since they lower the viscosity of the ionic liquid and enhance battery performances, as suggested in patent application US 2008/0076030.
  • Allyl phosphate is preferred as essential component to enhance safety and avoid explosions by acting as a flame retardant.
  • Examples of Lithium-Ion batteries using non-aqueous electrolytes, like ionic liquids, are disclosed in EP 1 906 841 , US 2007/023801 , WO 2005/104288.
  • the ionic liquid was disclosed for uses different from those being object of the present patent and precisely for a Lithium-metal battery.
  • the organic electrolyte becomes unstable for cyclation and reacts giving a solid product, which, in a small extent, protects the electrode (passivation), then the solid deposition proceeds and a non-uniform layer forms stacked structures (dendrites) which can cause short-circuits.
  • safety problem is mainly linked to accidental overheating of the battery above a threshold temperature.
  • the solution proposed by the present invention consists of ionic liquids as electrolytic components being non-volatile, non-flammable and stable compared with the material for electrodes proposed in the cells combinations herein disclosed.
  • a Lithium-Ion battery with a particular configuration of electrodes and the ionic liquid of the invention shows particularly advantageous features.
  • one object of the present invention is a Lithium-Ion battery characterised in that the ionic liquid comprises a) an ionic liquid consisting of a cationic portion of quaternary ammonium of formula
  • R1 is a linear or branched alkyl with from 2 to 5 carbon atoms, optionally substituted with an alkoxyethyl group with from 1 to 3 carbon atoms;
  • R2, R3 e R4, being the same or different, are a linear or branched alkyl with from 2 to 5 carbon atoms, or R3 and R4, together with the nitrrogen atom to which they are bound form a pyrrolidinium or piperidinium group; b) an anionic part, wherein the anion is selected form the group consisting of: N, N- bis(trifluoromethanesulphonyl)imide tetrafluoborate, and N,N-bis(trifluoromethanesulphonyl)imide esafluophosphate;
  • a lithium salt selected form the group consisting of lithium N, N-
  • the Lithium-Ion battery according to the present invention has the advantage of maintaining satisfactory performance, despite the absence of a solvent and of maintaining the increase of viscosity due to the ionic liquid and in particular of ensuring compatibility with electrodes.
  • the battery is safe thanks to the high thermal stability of the ionic liquid as used in the present invention. Furthermore, opposite to the batteries known in the art which use ionic liquids-based electrolytes, the combination of said ionic liquid with the proposed electrolytes ensure the stability of each component without using additives, as flame retardant or other additives.
  • the invention is herein disclosed in detail also referring to the figures and examples.
  • Figure 1 shows TGA (Thermo Gravimetric Analysis) curves of pure ionic liquid Py 24 -TFSI and of its solutions with LiTFSI.
  • Figure 2 shows conductivity of pure ionic liquid Py 24 -TFSI and of its solutions with LiTFSI.
  • Figure 3 shows a charge-discharge cycle of the Li 4 Ti 5 O 12 / Py 24 TFSI - LiTFSI /LiFePO 4 Lithium-Ion battery.
  • Figure 4 shows charge-discharge cycles of SnC/ Py 24 TFSI-LiTFSI / LiFePO 4 battery.
  • Figure 5 shows charge-discharge cycles Of TiO 2 / Py 24 TFSI-LiTFSI / LiFePO 4 battery.
  • Figure 6 show conductivity at room temperature of a hybrid gel-like membrane assembled by the Py 24 TFSI-LiTFSI solution on the PVdF-HFP matrix, compared with a similar membrane containing LiPF 6 - PC-EC.
  • the ionic liquid is made of a cationic portion as disclosed in the above formula (I).
  • a first group of preferred compounds consists of: N-n-butyl-N-ethylpirrolidinium, N-ethyl-N-propylpirrolidinium, N-ethyl-N-pethylpirrolidinium, N-ethyl-N- propoxyethylpirrolidinium, N-ethyl-N-propylpiperidinium, N-ethyl-N-isopropylpiperidinium, N-butyl-N- ethylpiperidinium, N-isobutyl-N-ethylpiperidinium, N-secbutyl-N-ethylpiperidinium, N-methoxyethyl-N- piperidinium, N-ethyl-N-etoxyethylpiperidinium, N-butyl-N,N,N-triethylammonium, N,N,N-triethyl-N- propy
  • the anionic portion of the ionic liquid is N,N-(bis(methantrifluoridesul- phonyl)imide.
  • the ionic liquid is N-n-butyl-N-ethylpirrolidinium, N,N-(bis(methantri- fluoridesulphonyl)imide.
  • the compound N-n-butyl-N-ethylpirrolidinium, N,N-(bis(methantrifluoridesulphonyl)imide being the ionic liquid of the best embodiment for the Lithium-Ion battery, its preparation and investigation on its possible use as a ionic liquid and herein indicated as Py 24 TFSI have been disclosed in the above mentioned A. Fernicola, F. Croce, B. Scrosati, T. Watanabe, H. Ohno; Journal of Power Sources 174 (2007) 342-348,.
  • the ionic liquid of the invention is prepared as disclosed in the paper of Fernicola et al, as summarised in the following scheme:
  • Said method of preparation can be used for anyone of the compounds of the above formula (I) wherein R 3 and R 4 with the nitrogen atom to which they are bound form a pirrolidinic or piperidinic ring.
  • the heterocyclic compound with an alkyl chain on the nitrogen atom is available on the market or can be prepared following known methods.
  • the alkyl halide of the required length, according to the above definition of R 2, is also available on the market or can be prepared with the known methods.
  • the reaction between nitrogen heterocycle and the alkyl halide is well-known to the organic chemist with ordinary skills in the art, said reaction is carried out in an organic solvent under time and temperature conditions which can easily set also looking at similar reactions known in the art.
  • the isolation of the reaction product is made conventionally for example by solvent crystallization or by chromatography or by equivalent methods.
  • the intermediate product reacts with a salt of the anion which forms the final ionic liquid.
  • Helpful reference, disclosing the synthesis of ionic liquids similar to these herein disclosed are: D. R. MacFarlane, P. Meakin, J. Sun, N. Amini, M. Forsyth J. Phys. Chem. B 103 (1999) 4164-4170; e G. B. Appetecchi, S. Scaccia, C. Tizzani, F. Alessandrini, S. Passerini, J. Electrochem. Soc. 153 (2006) A1685-A1691.
  • Py 24 TFSI ionic liquid is added to a lithium salt, LiTFSI, to ensure an appropriate carriage of the lithium ion in the battery. It has been experimentally proved that, being the anion of the salt the same used in ionic liquid, the components are compatible. In a further preferred embodiment, said ionic liquid is engulfed in a membrane as herein disclosed in details.
  • the battery according to the present invention comprises an anode-cathode system.
  • Anode- cathode systems known in the art may be used.
  • the cathode in selected in the group consisting of: lithium phosphates and metals, metal oxides intercalated by lithium ions, lithium oxides and manganese.
  • said cathode is selected in the group consisting of: LiFePO 4 , LiCoPO 4 , LiMnPO 4 , LiCO-MnPO 4 ; LiCoO 2 , LiNiO 2 , LiCo-NiO 2 ; LiMn 2 O 4 , LiNio ,5 Mni ,5 04, LiCo 1Z3 Mn 1Z3 Ni 1Z3 O 2 .
  • the anode is selected in the group consisting of: graphite, titanium oxides containing lithium or MC alloys, wherein M is selected in the group consisting of silicon, antimony, aluminium or a combination thereof.
  • the anode is selected in the group consisting of Li 4 Ti 5 O 12 , SnC, TiO 2 .
  • the material of the anode SnC is prepared starting form a tin-based organometallic, which is engulfed in a resorcinol-formaldehyde gel.
  • the product is calcinated in argon flux to reduce the tin content in the tin metallic precursor and carbonization of the gel. Said procedure allows obtaining a final material with a nominal composition Sn / C 1 :1.
  • the synthesis has been disclosed in G. Derrien, J. Hassoun, S. Panero, B. Scrosati, Adv. Mater. 19 (2007) 2336.
  • TiO 2 is an electrod ic material in P . Ku biak, J . Gesereick, N. H ⁇ sing, M. Wohlfahrt-Mehrens Electrochemical performance of mesoporous TiO2 anatase Journal of Power Sources, 175 (1 ) pp. 510- 516 (2008).
  • Li 4 Ti 5 O 12 is a material known in the field of Lithium-Ion batteries.
  • anode negative electrode
  • cathode positive electrode
  • LiFePO 4 LiFePO 4
  • electrolyte Li 4 Ti 5 O 12
  • Figure 1 shows the thermal stability in a thermogravimetric analysis of the ionic liquid and of the two solutions with LiTFSI, the results are shown in figure 1. It has to be underlined that the high thermal stability of the pure ionic liquid rises up to 368 0 C, similar values can be obtained with its solution with the lithium salt. Said feature is responsible for the better safety grade of the battery using said system.
  • Figure 2 shows the conductivity of the tested systems. The conductivity of the solution decreases when the salt concentration increases (for the corresponding increase of the viscosity) the values are in the range of mS/cm, thus high enough to allow their use in the Lithium-Ion batteries and in the Lithium batteries, being comparable with those of the electrolytic solutions currently used in said devices.
  • Said membranes are stable up to 325 0 C, and maintain the high thermal stability of the solution making the ionic liquid.
  • the conductivity is a 6,4 x 10 '4 Scnrf 1 , said value is similar in the electrolytic solutions used in the Lithium-Ion batteries available on the market.
  • the Py 24 TFSI-LiTFSI, PVdF-HFP membranes can be thus applied in new designed lithium batteries having high thermal stability, safety, reliability and modular development geometry. Like the Py 24 TFSI-LiTFSI solution of which they are made, said membranes can be used as electrolytic walls in batteries using the electrolytic materials of the present invention.
  • Polymeric matrix based on several polymers including polyvinylydene fluoride (PVdF), a co-polymeric polyvinylidene fluoride exafluoropropylene (PVdF-HFP), polyacrylonitrile (PAN), Poly(methyl methacrylate) (PMMA), Polyvinyl alcohol (PVA) and combinations thereof can be used in the preparation of the ionic liquid engulfed in a membrane.
  • PVdF polyvinylydene fluoride
  • PVdF-HFP co-polymeric polyvinylidene fluoride exafluoropropylene
  • PAN polyacrylonitrile
  • PMMA Poly(methyl methacrylate)
  • PVA Polyvinyl alcohol
  • said membranes can include several liquid solutions comprising a lithium salt which can be selected in the families of lithium tetrafluoroborate, lithium esafluorophosphate and lithium bis(trifluoromethansulphonyl)imide dissolved in mixtures of aprotic organic solvents which be selected in the families of carbonates, as ethylene carbonate, EC, propylene carbonate, PC, dimethylcarbonate, DMC e diethylcarbonate, DEC.
  • a lithium salt which can be selected in the families of lithium tetrafluoroborate, lithium esafluorophosphate and lithium bis(trifluoromethansulphonyl)imide dissolved in mixtures of aprotic organic solvents which be selected in the families of carbonates, as ethylene carbonate, EC, propylene carbonate, PC, dimethylcarbonate, DMC e diethylcarbonate, DEC.
  • the battery according to the present invention can be manufactured according to the common general knowledge in the field and any specific description is required. As an example, see Gold Peak Industries Ltd. Lithium Ion Technical Handbook and the references cited thereof.
  • the battery according to the present invention can have different manufacturing configurations as, for example, disclosed in US 2008/0076030, US 2007/0026318, US 2003/0054254.
  • a battery with the following configuration has been prepared: anode (negative electrode): Li 4 Ti 5 Oi 2 cathode (positive electrode): LiFePO 4 electrolyte: Py 24 TFSI-LiTFSI
  • the operative process is the lithium ion exchange from one electrode to the other, where the electrolyte acts as a lithium ions transporter.
  • Figure 3 shows a charge cycle:
  • Figure 3 shows a charge-discharge cycle of the above disclosed battery.
  • a battery with the following configuration has been prepared: anode (negative electrode): SnC cathode (positive electrode): LiFePO 4 electrolyte: Py 24 TFSI-LiTFSI
  • the operative process is the reversible lithium ion exchange from the cathode to the anode.
  • Figure 4 shows charge-discharge cycles of SnC/ Py 24 TFSI-LiTFSI / LiFePO 4 battery.
  • a battery with the following configuration has been prepared: anode (negative electrode): TiO 2 cathode (positive electrode): LiFePO 4 electrolyte: Py 24 TFSI-LiTFSI
  • the cell reaction is the following: LiFePO 4 + TiO 2 ⁇ Li- ⁇ x FePO 4 + Li x TiO 2 .
  • Figure 5 shows charge-discharge cycles of said battery.
  • Said membranes have been prepared by casting the liquid solutions commonly used in the Lithium-Ion batteries (as control example a exafluorophosphate solution has been LiPF 6 used) in a mixture of aprotic organic solvents (for example a solution of ethylene carbonate and EC-PC) in a polymeric matrix (for example the same PVdF-HFP matrix above disclosed).
  • aprotic organic solvents for example a solution of ethylene carbonate and EC-PC
  • a polymeric matrix for example the same PVdF-HFP matrix above disclosed.
  • Figure 6 shows conductivity at room temperature of a hybrid gel-like membrane prepared by assembling the LiPF 6 -PC-EC (• - upper line) and the LiTFSI-Py 24 TFSI (• - lower line) solution in the PVdF-HFP matrix.
  • Figure 6 shows that conductivity at room temperature of the hybrid gel-like membrane prepared by assembling the LiPF 6 -PC-EC solution in the PVdF-HFP matrix is ,7 x 10 3 Scnrf 1 , at room temperature, similar to the conductivity of the liquid solution of which it is made.
  • the conductivity of the membrane stays in a range of interesting values for the use in batteries in a wide range of temperature, which is around 10 '4 Scm '1 at 0 0 C to around 10 '3 Scm '1 at 60 0 C.
  • the advantage of said membrane is that they maintain the same operational features of the liquid solution even in a polymeric configuration.
  • the hybrid membranes can be applied in Lithium-Ion batteries with a new polymeric configuration and with high safety, reliability and modular development geometry. Similarly with the configurations previously disclosed, said membranes can be used as electrolytic walls in batteries using the electrodic materials disclosed in the present invention. Industrial applicability of the present invention is clear. As an example mobile electronic, last generation mobile phones, sustainable transportation and Renewable energy.

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Abstract

A Lithium-Ion battery characterised in that it comprises: a. an ionic liquid consisting of a cationic portion of quaternary ammonium of formula R1N+R2 R3 R4 where: R1 is a linear or branched alkyl with from 2 to 5 carbon atoms, optionally substituted with an ethyl alkoxy group with from 1 to 3 carbon atoms; R2, R3 e R4, being the same or different, are a linear or branched alkyl with from 2 to 5 carbon atoms, or R3 and R4, together with the nitrous atom to which they are bound form a pyrrolidinium or piperidinium; b. an anionic part, wherein the anion is selected form the group consisting of: bis(methantrifluoridesulphonyl)imide, tetrafluorideborate, esafluoridephosphate; c. a lithium salt selected form the group consisting of lithium N,N- (bis(methantrifluoridesulphonyl)imide, lithium tetrafluorideborate, lithium esafluoridephosphate and lithium bisoxalateborate; is disclosed. The battery is safe thanks to the high thermal stability of the ionic liquid as used in the present invention, without additives, as flame retardant or other additives, being suitable for the use in the field of mobile electronic, sustainable transportation and Renewable energy.

Description

High safety Lithium-Ion Battery
Description
The present invention refers to the technical field of Lithium-Ion batteries and more in particular to safety and to ameliorate efficiency of this type of batteries. Thanks to their high energy content, Lithium-Ion batteries prevail in the consumer electronics area and promote spreading of cellular phones, lap-top computers, digital audio players and so on. However, Lithium-Ion batteries need improved efficiency to be applied in the expanding markets of power stations fed by discontinuous sources or power systems for electric or hybrid vehicles.
Safety is one of the unsolved problems affecting said batteries, due to the instability of the battery's components. More in particular, the use of electrolyte solutions of lithium salts in volatile organic solvents is dangerous. Vaporization of solvents, which is triggered by local overheating and/or by electrochemical decomposition of the same solvents, may produce gaseous side products which increase the internal pressure. This event may cause not only cell breaking, but also to violent side-reactions or fires and explosions. These risks are related to battery abuse, such as high working temperatures or mechanical shock. Regarding the problems related to the use of non-aqueous electrolytes, also from the point of view of battery safety and of battery efficiency, especially in case of anodes of carbonaceous materials see patents US 5,340,670 e US 5,612,155 which suggest to improve battery's features by using innovative carbonaceous materials.
Patent US 6,413,678 suggests solving safety problems of said type of batteries by using a gas evolving system. In the battery, a carbonyl compound, subject to temperature increasing, decomposes and produces gaseous products, which are insoluble, or poorly soluble in the electrolyte. A suitable breaking valve stably and safely increases the pressure within the battery.
Consequently, one important goal in this field is to design and develop battery configurations performing better than present systems in terms of safety, energy, power and costs. One way to solve safety problems of Lithium-Ion batteries with organic solvents, as non-aqueous electrolytes, is the use of ionic liquids, namely salts in the liquid state at room or sub-room or at least at the battery's working temperature.
This choice is justified by the features of the above materials which induce high ionic conductivity (thus a low internal battery resistance), low volatility (preventing pressure variation in the battery) and high thermal stability (ensuring reliable operability in a wide range of temperature) and non-flammability (ensuring operational safety).
The ionic liquids are composed by several combinations of different anions and cations.
Patent application US 2007/026318 discloses some of said ionic liquids and their drawbacks due to their reactivity with the electrodes (see for example patent applications JP 4-349365, JP 11 -86905). Said document disclose the technical solution of inserting allyl phosphate in the ionic liquid. Among the compounds bearing the quaternary ammonium cation pyrrolidinium derivatives are mentioned, all characterised by a methyl on the quaternary nitrogen residue, which are useful to counteract side reactions on the electrodes. However, imidazole derivatives are preferred since they lower the viscosity of the ionic liquid and enhance battery performances, as suggested in patent application US 2008/0076030. Allyl phosphate is preferred as essential component to enhance safety and avoid explosions by acting as a flame retardant. Examples of Lithium-Ion batteries using non-aqueous electrolytes, like ionic liquids, are disclosed in EP 1 906 841 , US 2007/023801 , WO 2005/104288.
It is well known in the art that, although the ionic liquid ensures safety of the battery, performance is due to the solvent capable of maintaining satisfactory viscosity levels in the system in term of battery's efficiency.
The stability of the electrodes in consideration of the electrolyte used cannot be presumed and requires investigation of the system.
The technical problem of safety of Lithium-Ion batteries, including those using organic solvents, is not yet solved in the state of the art, in particular relating to the stability of the ionic liquid and the performance required by the devices using said the batteries and considering their use in more challenging fields such as the storage in stations powered by discontinuous sources or power systems for electric or hybrid vehicles.
The compound N-n-butyl-N-ethylpyrrolidinium N,N-bis(methyltrifluoridesulphonyl)imide, herein indicated as Py24TFSI, its preparation, and its possible use as a ionic liquid has been disclosed in A. Fernicola, F. Croce, B. Scrosati, T. Watanabe, H. Ohno; Journal of Power Sources 174 (2007) 342-348.
In this paper the ionic liquid was disclosed for uses different from those being object of the present patent and precisely for a Lithium-metal battery. In the case of a Lithium-metal battery the organic electrolyte becomes unstable for cyclation and reacts giving a solid product, which, in a small extent, protects the electrode (passivation), then the solid deposition proceeds and a non-uniform layer forms stacked structures (dendrites) which can cause short-circuits. On the other hand, in the Lithium-Ion batteries safety problem is mainly linked to accidental overheating of the battery above a threshold temperature. If the device is unable to efficiently dissipate heat in excess, overheating causes side reactions of the organic solvent in the electrolyte and produces inflammable gases which increase internal pressure and heighten the risk of fire and explosions. The solution proposed by the present invention consists of ionic liquids as electrolytic components being non-volatile, non-flammable and stable compared with the material for electrodes proposed in the cells combinations herein disclosed.
Summary of the invention
It has now been found that the use of a particular salt as an ionic liquid solves the above problems. In particular, a Lithium-Ion battery with a particular configuration of electrodes and the ionic liquid of the invention shows particularly advantageous features.
Therefore, one object of the present invention is a Lithium-Ion battery characterised in that the ionic liquid comprises a) an ionic liquid consisting of a cationic portion of quaternary ammonium of formula
R1 N+R2 R3 R4 where:
R1 is a linear or branched alkyl with from 2 to 5 carbon atoms, optionally substituted with an alkoxyethyl group with from 1 to 3 carbon atoms;
R2, R3 e R4, being the same or different, are a linear or branched alkyl with from 2 to 5 carbon atoms, or R3 and R4, together with the nitrrogen atom to which they are bound form a pyrrolidinium or piperidinium group; b) an anionic part, wherein the anion is selected form the group consisting of: N, N- bis(trifluoromethanesulphonyl)imide tetrafluoborate, and N,N-bis(trifluoromethanesulphonyl)imide esafluophosphate;
c) a lithium salt selected form the group consisting of lithium N, N-
(bis(methantrifluoridesulphonyl)imide, lithium tetrafluorideborate, lithium esafluoridephosphate and lithium bisoxalateborate.
The Lithium-Ion battery according to the present invention has the advantage of maintaining satisfactory performance, despite the absence of a solvent and of maintaining the increase of viscosity due to the ionic liquid and in particular of ensuring compatibility with electrodes.
The battery is safe thanks to the high thermal stability of the ionic liquid as used in the present invention. Furthermore, opposite to the batteries known in the art which use ionic liquids-based electrolytes, the combination of said ionic liquid with the proposed electrolytes ensure the stability of each component without using additives, as flame retardant or other additives. The invention is herein disclosed in detail also referring to the figures and examples.
Figure 1 shows TGA (Thermo Gravimetric Analysis) curves of pure ionic liquid Py24-TFSI and of its solutions with LiTFSI.
Figure 2 shows conductivity of pure ionic liquid Py24-TFSI and of its solutions with LiTFSI.
Figure 3 shows a charge-discharge cycle of the Li4Ti5O12/ Py24TFSI - LiTFSI /LiFePO4 Lithium-Ion battery.
Figure 4 shows charge-discharge cycles of SnC/ Py24TFSI-LiTFSI / LiFePO4 battery. Figure 5 shows charge-discharge cycles Of TiO2 / Py24TFSI-LiTFSI / LiFePO4 battery.
Figure 6 show conductivity at room temperature of a hybrid gel-like membrane assembled by the Py24TFSI-LiTFSI solution on the PVdF-HFP matrix, compared with a similar membrane containing LiPF6- PC-EC.
Detailed description of the invention
According to the present invention, the ionic liquid is made of a cationic portion as disclosed in the above formula (I).
A first group of preferred compounds consists of: N-n-butyl-N-ethylpirrolidinium, N-ethyl-N-propylpirrolidinium, N-ethyl-N-pethylpirrolidinium, N-ethyl-N- propoxyethylpirrolidinium, N-ethyl-N-propylpiperidinium, N-ethyl-N-isopropylpiperidinium, N-butyl-N- ethylpiperidinium, N-isobutyl-N-ethylpiperidinium, N-secbutyl-N-ethylpiperidinium, N-methoxyethyl-N- piperidinium, N-ethyl-N-etoxyethylpiperidinium, N-butyl-N,N,N-triethylammonium, N,N,N-triethyl-N- propylammonium, N-butyl-N,N-diethyl-N-methylammonium and N-butyl-N,N-diethyl-N-propylammonium. In a second preferred embodiment, the compound of formula (I) is N-n-butyl-N-ethylpirrolidinium.
In a third preferred embodiment, the anionic portion of the ionic liquid is N,N-(bis(methantrifluoridesul- phonyl)imide.
In a more preferred embodiment, the ionic liquid is N-n-butyl-N-ethylpirrolidinium, N,N-(bis(methantri- fluoridesulphonyl)imide. The compound N-n-butyl-N-ethylpirrolidinium, N,N-(bis(methantrifluoridesulphonyl)imide being the ionic liquid of the best embodiment for the Lithium-Ion battery, its preparation and investigation on its possible use as a ionic liquid and herein indicated as Py24TFSI have been disclosed in the above mentioned A. Fernicola, F. Croce, B. Scrosati, T. Watanabe, H. Ohno; Journal of Power Sources 174 (2007) 342-348,.
The ionic liquid of the invention is prepared as disclosed in the paper of Fernicola et al, as summarised in the following scheme:
Said method of preparation can be used for anyone of the compounds of the above formula (I) wherein R3 and R4 with the nitrogen atom to which they are bound form a pirrolidinic or piperidinic ring. The heterocyclic compound with an alkyl chain on the nitrogen atom is available on the market or can be prepared following known methods. The alkyl halide of the required length, according to the above definition of R2, is also available on the market or can be prepared with the known methods. The reaction between nitrogen heterocycle and the alkyl halide is well-known to the organic chemist with ordinary skills in the art, said reaction is carried out in an organic solvent under time and temperature conditions which can easily set also looking at similar reactions known in the art. Equally, the isolation of the reaction product is made conventionally for example by solvent crystallization or by chromatography or by equivalent methods. Then, the intermediate product reacts with a salt of the anion which forms the final ionic liquid. Helpful reference, disclosing the synthesis of ionic liquids similar to these herein disclosed are: D. R. MacFarlane, P. Meakin, J. Sun, N. Amini, M. Forsyth J. Phys. Chem. B 103 (1999) 4164-4170; e G. B. Appetecchi, S. Scaccia, C. Tizzani, F. Alessandrini, S. Passerini, J. Electrochem. Soc. 153 (2006) A1685-A1691.
Py24TFSI ionic liquid is added to a lithium salt, LiTFSI, to ensure an appropriate carriage of the lithium ion in the battery. It has been experimentally proved that, being the anion of the salt the same used in ionic liquid, the components are compatible. In a further preferred embodiment, said ionic liquid is engulfed in a membrane as herein disclosed in details.
Obviously, the battery according to the present invention comprises an anode-cathode system. Anode- cathode systems known in the art may be used.
In a preferred reaction the cathode in selected in the group consisting of: lithium phosphates and metals, metal oxides intercalated by lithium ions, lithium oxides and manganese.
In a further preferred embodiment, said cathode is selected in the group consisting of: LiFePO4, LiCoPO4, LiMnPO4, LiCO-MnPO4; LiCoO2, LiNiO2, LiCo-NiO2; LiMn2O4, LiNio,5Mni,504, LiCo1Z3Mn1Z3Ni1Z3O2.
In a further preferred embodiment, the anode is selected in the group consisting of: graphite, titanium oxides containing lithium or MC alloys, wherein M is selected in the group consisting of silicon, antimony, aluminium or a combination thereof.
In particular, the anode is selected in the group consisting of Li4Ti5O12, SnC, TiO2.
The material of the anode SnC is prepared starting form a tin-based organometallic, which is engulfed in a resorcinol-formaldehyde gel. The product is calcinated in argon flux to reduce the tin content in the tin metallic precursor and carbonization of the gel. Said procedure allows obtaining a final material with a nominal composition Sn / C 1 :1. The synthesis has been disclosed in G. Derrien, J. Hassoun, S. Panero, B. Scrosati, Adv. Mater. 19 (2007) 2336.
TiO2 is an electrod ic material in P . Ku biak, J . Gesereick, N. Hϋsing, M. Wohlfahrt-Mehrens Electrochemical performance of mesoporous TiO2 anatase Journal of Power Sources, 175 (1 ) pp. 510- 516 (2008). Li4Ti5O12 is a material known in the field of Lithium-Ion batteries.
However, the specific combination of Li4Ti5O12 with the cathode and the electrolyte on which the ionic liquid is based in the cell disclosed in example 1 have the unexpected advantage of not requiring any additional stabilizing agent, since said combination is enough stable.
Particularly preferred forms of the battery according to the present invention are: a) anode (negative electrode): Li4Ti5O12, cathode (positive electrode): LiFePO4, electrolyte:
Py24TFSI-LiTFSI; b) anode (negative electrode): SnC, cathode (positive electrode): LiFePO4, electrolyte: Py24TFSI- LiTFSI; c) anode (negative electrode): TiO2, cathode (positive electrode): LiFePO4, electrolyte: Py24TFSI- LiTFSI.
Figure 1 shows the thermal stability in a thermogravimetric analysis of the ionic liquid and of the two solutions with LiTFSI, the results are shown in figure 1. It has to be underlined that the high thermal stability of the pure ionic liquid rises up to 368 0C, similar values can be obtained with its solution with the lithium salt. Said feature is responsible for the better safety grade of the battery using said system. Figure 2 shows the conductivity of the tested systems. The conductivity of the solution decreases when the salt concentration increases (for the corresponding increase of the viscosity) the values are in the range of mS/cm, thus high enough to allow their use in the Lithium-Ion batteries and in the Lithium batteries, being comparable with those of the electrolytic solutions currently used in said devices.
The above features demonstrate that the Py24TFSI-LiTFSI system according to the present invention can be optimally used as electrolyte in Lithium-Ion batteries giving the advantages of thermal stability, low volatility and, in particular, safety.
To develop the technology of Lithium-Ion batteries it is important to use polymeric patterns which ensure operational reliability (absence of liquids) and design flexibility (modular development geometry). The general concept requires flexible, self-sustaining and lithium transporting membranes to be used for the electrolytic separation in polymeric batteries. In this sense, in the present work membranes, obtained engulfing the Py24TFSI-LiTFSI solution in a co-polymeric polyvinylidene-exafluoropropylene PVdF-HFP, matrix the have been developed, they are indicated as Py24TFSI-LiTFSI, PVdF-HFP.
Said membranes are stable up to 325 0C, and maintain the high thermal stability of the solution making the ionic liquid. The conductivity is a 6,4 x 10'4 Scnrf1, said value is similar in the electrolytic solutions used in the Lithium-Ion batteries available on the market. The Py24TFSI-LiTFSI, PVdF-HFP membranes can be thus applied in new designed lithium batteries having high thermal stability, safety, reliability and modular development geometry. Like the Py24TFSI-LiTFSI solution of which they are made, said membranes can be used as electrolytic walls in batteries using the electrolytic materials of the present invention. Polymeric matrix based on several polymers including polyvinylydene fluoride (PVdF), a co-polymeric polyvinylidene fluoride exafluoropropylene (PVdF-HFP), polyacrylonitrile (PAN), Poly(methyl methacrylate) (PMMA), Polyvinyl alcohol (PVA) and combinations thereof can be used in the preparation of the ionic liquid engulfed in a membrane.
In addition to the above mentioned membranes, it is meant that said membranes can include several liquid solutions comprising a lithium salt which can be selected in the families of lithium tetrafluoroborate, lithium esafluorophosphate and lithium bis(trifluoromethansulphonyl)imide dissolved in mixtures of aprotic organic solvents which be selected in the families of carbonates, as ethylene carbonate, EC, propylene carbonate, PC, dimethylcarbonate, DMC e diethylcarbonate, DEC.
The battery according to the present invention can be manufactured according to the common general knowledge in the field and any specific description is required. As an example, see Gold Peak Industries Ltd. Lithium Ion Technical Handbook and the references cited thereof.
The battery according to the present invention can have different manufacturing configurations as, for example, disclosed in US 2008/0076030, US 2007/0026318, US 2003/0054254.
The following examples further explain the invention. Example 1
A battery with the following configuration has been prepared: anode (negative electrode): Li4Ti5Oi2 cathode (positive electrode): LiFePO4 electrolyte: Py24TFSI-LiTFSI The operative process is the lithium ion exchange from one electrode to the other, where the electrolyte acts as a lithium ions transporter. Figure 3 shows a charge cycle:
Li4Ti5O12 + LiFePO4 → Li(1.x)FePO4 + Li(4+x)Ti50i2
And a discharge cycle:
Li(1.x)FePO4 + Li(4+x)Ti5012 → Li4Ti5O12 + LiFePO4 of said battery.
Figure 3 shows a charge-discharge cycle of the above disclosed battery.
Example 2
A battery with the following configuration has been prepared: anode (negative electrode): SnC cathode (positive electrode): LiFePO4 electrolyte: Py24TFSI-LiTFSI
Also in this case, the operative process is the reversible lithium ion exchange from the cathode to the anode.
Figure 4 shows charge-discharge cycles of SnC/ Py24TFSI-LiTFSI / LiFePO4 battery. Example 3
A battery with the following configuration has been prepared: anode (negative electrode): TiO2 cathode (positive electrode): LiFePO4 electrolyte: Py24TFSI-LiTFSI The cell reaction is the following: LiFePO4 + TiO2 <→ Li-^xFePO4 + LixTiO2.
Figure 5 shows charge-discharge cycles of said battery.
Example 4 Lithium-Ion batteries with hybrid gel-like membranes
Said membranes have been prepared by casting the liquid solutions commonly used in the Lithium-Ion batteries (as control example a exafluorophosphate solution has been LiPF6 used) in a mixture of aprotic organic solvents (for example a solution of ethylene carbonate and EC-PC) in a polymeric matrix (for example the same PVdF-HFP matrix above disclosed). For the preparation of the hybrid gel-like membranes see Handbook of Batteries - Second Edition, D. Linden, McGraw-Hill Inc. New York (2005).
In the same manner, a membrane engulfed with the ionic liquid of the invention Py24TFSI-LiTFSI has been prepared.
The comparison between the two membranes is shown for a measurement interval of 20 days. Conductivity of the membrane including ionic liquid is slightly lower than the membrane including the conventional electrolytes due to the higher viscosity of the ionic liquid in comparison with the conventional liquid electrolyte. The conductivity of our system is anyhow satisfactory for the purpose of the battery. Furthermore, some experiments show that conductivity strictly depends on the amount of ionic solution in the membrane. It is therefore possible to adjust the conductivity properties of the membrane by appropriately modifying the composition thereof (LiTFSI-Py24TFSI / PVdF-HFP ratio).
Figure 6 shows conductivity at room temperature of a hybrid gel-like membrane prepared by assembling the LiPF6-PC-EC (• - upper line) and the LiTFSI-Py24TFSI (• - lower line) solution in the PVdF-HFP matrix. Figure 6 shows that conductivity at room temperature of the hybrid gel-like membrane prepared by assembling the LiPF6-PC-EC solution in the PVdF-HFP matrix is ,7 x 103 Scnrf1, at room temperature, similar to the conductivity of the liquid solution of which it is made. Furthermore, the conductivity of the membrane stays in a range of interesting values for the use in batteries in a wide range of temperature, which is around 10'4 Scm'1 at 0 0C to around 10'3 Scm'1 at 60 0C. The advantage of said membrane is that they maintain the same operational features of the liquid solution even in a polymeric configuration. The hybrid membranes can be applied in Lithium-Ion batteries with a new polymeric configuration and with high safety, reliability and modular development geometry. Similarly with the configurations previously disclosed, said membranes can be used as electrolytic walls in batteries using the electrodic materials disclosed in the present invention. Industrial applicability of the present invention is clear. As an example mobile electronic, last generation mobile phones, sustainable transportation and Renewable energy.

Claims

1. Lithium-Ion batteries characterised in that the electrolytes comprising: a) an ionic liquid consisting of a cationic portion of quaternary ammonium of formula
R1 N+R2 R3 R4 where:
R1 is a linear or branched alkyl with from 2 to 5 carbon atoms, optionally substituted with an ethyl alkoxy group with from 1 to 3 carbon atoms;
R2, R3 e R4, being the same or different, are a linear or branched alkyl with from 2 to 5 carbon atoms, or R3 and R4, together with the nitrous atom to which they are bound form a pyrrolidinium or piperidinium; b) an anionic part, wherein the anion is selected form the group consisting of: bis(methantrifluoridesulphonyl)imide, tetrafluorideborate, esafluoridephosphate; c) a lithium salt selected form the group consisting of lithium N, N- (bis(methantrifluoridesulphonyl)imide, lithium tetrafluorideborate, lithium esafluoridephosphate and lithium bisoxalateborate.
2. Battery according to claim 1 , wherein said cationic portion is selected from the group consisting of N-n-butyl-N-ethylpirrolidinium, N-ethyl-N-propylpirrolidinium, N-ethyl-N-pethylpirrolidinium, N- ethyl-N-propoxyethylpirrolidinium, N-ethyl-N-propylpiperidinium, N-ethyl-N-isopropylpiperidinium, N-butyl-N-ethylpiperidinium, N-isobutyl-N-ethylpiperidinium, N-secbutyl-N-ethylpiperidinium, N- methoxyethyl-N-piperidinium, N-ethyl-N-etoxyethylpiperidinium, N-butyl-N,N,N-triethylammonium,
N,N,N-triethyl-N-propylammonium, N-butyl-N,N-diethyl-N-methylammonium and N-butyl-N,N- diethyl-N-propylammonium.
3. Battery according to anyone of claims 1-2, wherein said ionic liquid is engulfed in a membrane.
4. Battery according to anyone of claims 1-3, wherein the cathode is selected form the group consisting of lithium phosphates and metals, metal oxides intercalated by lithium ions, lithium oxides and manganese.
5. Battery according to claim 4, wherein said cathode is selected form the group consisting of: LiFePO4, LiCoPO4, LiMnPO4, LiCO-MnPO4; LiCoO2, LiNiO2, LiCo-NiO2, LiMn2O4, LiNi0 5Mn1 5O4, LiCθi/3Mni/3Nii/3θ2.
6. Battery according to anyone of claims, wherein the anode is selected form the group consisting of: graphite, titanium oxides containing lithium or MC alloys wherein dove M is selected in the group consisting of silicon, antimony, aluminium or a combination thereof.
7. Battery according to claim 6, wherein said anode is selected form the group consisting of: Li4Ti5O12, SnC, TiO2 8. Battery with the following configuration: anode Li4Ti5O12, cathode LiFePO4, electrolyte Py24TFSI-
LiTFSI.
9. Battery with the following configuration: anode SnC, cathode LiFePO4, electrolyte Py24TFSI- LiTFSI.
0. Battery with the following configuration: anode TiO2, cathode LiFePO4, electrolyte Py24TFSI- LiTFSI.
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