Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M6/00—Primary cells; Manufacture thereof
  • H01M6/14—Cells with non-aqueous electrolyte
  • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
• • 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
  • H01M10/0567—Liquid materials characterised by the additives
• • 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
  • H01M10/06—Lead-acid accumulators
  • H01M10/08—Selection of materials as electrolytes
• • 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
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
• • 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
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
  • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• • 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
  • H01M4/581—Chalcogenides or intercalation compounds thereof
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
  • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M6/00—Primary cells; Manufacture thereof
  • H01M6/14—Cells with non-aqueous electrolyte
  • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
  • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
  • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
• • 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 invention relates to a lithium battery comprising at least one positive electrode, one negative electrode and a non-aqueous electrolyte disposed between the positive and negative electrodes and comprising at least one lithium salt dissolved in an aprotic organic solvent to which is added a polymerizable additive intended to block the operation of the battery as soon as the voltage across the battery reaches a value causing polymerization of the additive.
• the invention also relates to the use of a polymerizable additive chosen from carbazole and its derivatives and intended to block the operation of a lithium battery during inappropriate use, the battery comprising at least:
• nonaqueous electrolyte placed between the positive and negative electrodes and comprising at least one lithium salt dissolved in an aprotic organic solvent, the polymerizable additive being added to the solvent of the nonaqueous electrolyte.
• Lithium batteries and more particularly batteries belonging to the Lithium-Ion sector, tend to replace rechargeable batteries with nickel-cadmium (Ni-Cd) or nickel-hydride (Ni-MH) base as an autonomous energy source, in particular in portable elements.
• Lithium batteries have, in fact, performances, and in particular a mass energy density, greater than those of Ni-Cd and Ni-MH accumulators.
• lithium is a very reactive element
• safety problems can nevertheless occur in lithium batteries, in particular in the case of improper use, for example during use with an overload.
• the use of an overcharged battery can lead to increases in temperature and pressure inside the battery, which can lead to an explosion or a risk of fire.
• a battery comprising a separating element constituted by a microporous polyethylene film impregnated with an electrolyte according to patent US5506068 and a positive electrode at low voltage, other than MnO 2 , was tested. It includes a negative electrode in Li 4 Ti 5 0 12 , a positive electrode in LiFePO 4 and an electrolyte constituted by a lithium salt LiAsF 6 dissolved, at one mole per liter, in a solvent 1, 3-dioxolane, stabilized by 100 ppm of tributylamine.
• the positive LiFeP0 4 electrode has a lithium insertion and deinsertion potential equal to 3.5V relative to the electrochemical potential of the LiVLi pair, denoted V Li + / Li .
• FIG. 1 represents the evolution of the voltage at the terminals of the battery as a function of time (curve A1) and the evolution of the intensity traversing the battery as a function of time (curve B1), thus illustrating, the charge cycles and discharging the battery tested, in a voltage range between 1.5V and 2V.
• the maximum voltage under load is chosen at 2Volts, which means that the potential of the positive electrode does not exceed the value of 3.55V compared to the potential of the Li + / Li couple.
• the polymerization potential of 1,3-dioxolane, of the order of 4V, is thus never reached.
• FIG. 1 illustrates the performance of the battery in normal operation. Charges and discharges are carried out under C / 10 galvanostatic conditions. At the end of charging, when the battery voltage reaches the value of 2 Volts, the battery is maintained at this voltage if one of the following two conditions is not met: a duration of the charging step greater than or equal at 5 o'clock or a current less than or equal to 10 ⁇ A. The next step is then the galvanostatic discharge in C / 10 regime.
• C / 10 regime it is meant that, theoretically, the charging and discharging of the battery must be done respectively in 10 hours and a complete cycle including charging and discharging should last approximately 20 hours. However, as observed in FIG.
• the first charge and discharge cycle of the battery takes place in 14 hours instead of the expected 20 hours and the following cycles are shorter and shorter.
• the shortening of the cycles proves a progressive deterioration of the battery following a deterioration of the electrolyte, the 1, 3-dioxolane having probably deteriorated prematurely.
• a monomer additive was added to the aprotic organic solvent of the nonaqueous electrolyte of a battery, the positive electrode of which is said to be at high voltage.
• the monomer additive is capable of forming an electronically conductive polymer, when the voltage across the battery reaches a predetermined value, from which the monomer can polymerize.
• the polymer thus formed then creates a conductive bridge between the two electrodes and therefore an internal short circuit limiting the overcharge then leading to the automatic discharge of the battery.
• the monomer additive can be an aromatic additive, optionally heterocyclic.
• pyrrole, N-methylpyrrole and thiophene are, for example, used for batteries with maximum charge voltages less than 4 Volts, furan, indole or 3-chlorothiophene are used for charge voltages higher and biphenyl is used for batteries operating at a voltage of the order of 4 Volts.
• the polymerization potential of these compounds is thus suitable for batteries whose positive electrode is said to be at high voltage, and more particularly for batteries containing positive electrodes of the LiNiO 2 , LiCo0 2 or LiMn 2 O 4 type , which insert and deinsert lithium at a potential of around 3.8V to 4V compared to V Li + / Li .
• they are not suitable for batteries whose positive electrode is said to be low voltage, and in particular to batteries comprising a positive electrode with a lower lithium insertion and deinsertion potential. Indeed, the voltage from which the battery deteriorates, with a possible explosion, may be reached before the additive polymerizes.
• the purpose of the additive is to generate a gas in a lithium battery, the positive electrode of which is said to be at high voltage, that is to say a battery having a maximum charge voltage greater than 4 volts, so as to activate an electrical disconnection device. It also describes the possibility of using a polymerized additive to create an increase in the internal resistance of the battery so as to reduce the charging current during overcharging. These compounds are, however, not suitable for low voltage batteries.
• organometallic compounds known as metallocenes
• metallocenes are used to protect the batteries from possible overcharging.
• the compound reversibly oxidizes at a potential slightly higher than that of the charge and discharge plate of the positive electrode and, once oxidized, the compound can be reduced under secondary reaction on the surface of the electrode. negative.
• the round trips of the organometallic compound between oxidized and reduced states make it possible to preserve the battery from possible overcharging while leaving it operational.
• this type of compound can only be used for batteries whose positive electrode has a lithium insertion and deinsertion potential of less than 3 Volts compared to V Li + / Li . This reduces considerably the field of application of these additives because few positive electrodes make it possible to obtain such a potential.
• the object of the invention is to obtain a lithium battery, the positive electrode of which is said to be low voltage and protected in the case of inappropriate use, and more particularly in the case of use in overload, while retaining good performance under normal operating conditions.
• the positive electrode comprising a material having a lithium insertion and disinsertion potential less than or equal to 3.5 volts relative to the electrochemical potential of the LiVLi couple
• the polymerizable additive is chosen from carbazole and its derivatives.
• the electrolyte comprises between 2% and 10% by mass of polymerizable additive relative to the total mass of the electrolyte.
• the positive electrode comprises a compound chosen from LiFeP0 4 , V 2 O 5 , LiV 3 O 8 , MnO 2 , V 6 0 13 and TiS 2 .
• the negative electrode comprises at least one lithium insertion compound.
• the lithium insertion compound is chosen from a carbonaceous composite material or a titanium and lithium oxide.
• the object of the invention is also an efficient and appropriate use of a polymerizable additive chosen from carbazole and its derivatives to block the operation of a lithium battery during inappropriate use.
• the positive electrode comprising a material having a lithium insertion and deinsertion potential less than or equal to 3.5 Volts relative to the electrochemical potential of the LiVLi couple
• l polymerizable additive blocks the operation of the battery as soon as the voltage across the battery reaches a value causing polymerization of the additive.
• FIG. 1 represents a galvanostatic cycle in C / 10 regime carried out on the field [1, 5V-2V] of a lithium battery whose positive electrode is said to be at low voltage and comprising a non-aqueous electrolyte according to the prior art .
• FIG. 2 represents a galvanostatic cycle in C / 10 regime carried out on the field [1, 5V-3.5V] of a lithium battery according to the invention and whose positive electrode is said to be at low voltage, said battery having previously undergone charge and discharge cycles in normal operation. Description of particular embodiments
• a lithium battery preferably from the Lithium-Ion system, comprises at least one positive electrode, one negative electrode and one non-aqueous electrolyte disposed between the positive and negative electrodes.
• battery belonging to the Lithium-Ion sector is meant lithium batteries for which the negative electrode comprises at least one lithium intercalation or insertion material, unlike batteries of the Lithium-Metal sector for which l 'negative electrode consists of a source of Li + cations, for example metallic lithium.
• the positive electrode comprises a material having a lithium insertion and de-insertion potential of 3.5 Volts or less relative to the electrochemical potential of the LrVLi couple (V L
• the positive electrode may comprise a compound chosen from
• the negative electrode preferably includes at least one lithium insertion compound chosen, for example, from a carbonaceous composite material or a titanium and lithium oxide such as Li 4 Ti 5 0 12 .
• the non-aqueous electrolyte comprises at least one lithium salt dissolved in an aprotic organic solvent.
• the lithium salt is preferably chosen from LiPF 6 , LiBF 4 , LiCIO 4 , LiAsF 6 , LiPF 4 , LiR F SO 3 , LiCH 3 S0 3 , LiN (R F SO 2 ) 2 , LiN (R F S0 2 ) 3 , R F being chosen from a fluorine atom and a perfluoroalkyl group comprising between 1 and 8 carbon atoms.
• the aprotic organic solvent advantageously consists of a mixture chosen from a mixture of ethylene carbonate and dimethyl carbonate and a mixture of ethylene carbonate, dimethyl carbon and carbonate of Diethyl.
• a separator element disposed between the positive and negative electrodes is impregnated with the non-aqueous electrolyte so as to support the electrolyte.
• a separating element is, for example, constituted by a microporous polyethylene film.
• a polymerizable additive chosen from carbazole and its derivatives is added to the aprotic organic solvent of the nonaqueous electrolyte.
• the crude formula of carbazole also called 9-azafluorene, dibenzopyrrole or diphenylenimine, is C 12 H 9 N and, by carbazole derivative, is meant a carbazole substituted by any type of known groups.
• Carbazole derivatives are, for example, chosen from N-alkylcarbazoles, alkyldibenzopyrroles, 3,6-dichloro-9H-carbazole.
• the electrolyte preferably comprises between 2% and 10% by mass of polymerizable additive relative to the total mass of the electrolyte.
• the polymerizable additive is, for example, added to the non-aqueous electrolyte under an inert atmosphere and at room temperature and preferably under argon with water and oxygen contents of less than 1 ppm.
• the electrolyte is then left to stand for at least 24 hours before being used in the battery.
• the value of U p ⁇ ⁇ ymerization must be between the maximum charge voltage of the battery, denoted U max , and the voltage from which there is a risk of degradation of the battery and in particular a risk of fire and / or explosion, noted U risk and which is greater than U poIymerization
• the voltage U p0 ymérisat ⁇ i 0n must be at most about 500mV higher than the value U max.
• the maximum charging voltage U max at the battery terminals is chosen according to the materials constituting the battery, so as to guarantee the lowest possible loss of capacity, typically a loss of 20% maximum over 500 charge and discharge cycles for portable applications.
• V p of carbazole or of a derivative thereof is of the order of 3.8 Volts relative to V Li + / Li
• these polymerizable additives are therefore particularly well suited to batteries whose positive electrode is said to be at low voltage, that is to say those which are composed of a positive electrode having a potential for insertion and disinsertion of lithium less than or equal to 3.5 Volts relative to V Li + / Li .
• the polymerizable additives have a polymerization potential of between 4.4V and 5.4V relative to V Li + / Li . They are therefore particularly suitable for batteries comprising a positive electrode with an insertion and deinsertion potential of between 3.8 Volts and 4 Volts relative to V Li + / Li , for example a positive electrode made of LiCoO 2 , LiNi0 2 or in LiMn 2 O 4 .
• Carbazole and its derivatives are more particularly suitable for batteries having a positive electrode comprising the compound LiFeP0 4 , the insertion and deinsertion potential of LiFePO 4 being of the order of 3.5 Volts relative to V Li + / Li .
• a lithium battery and more particularly a Lithium-Ion battery in the format of a button cell, comprises a negative electrode made of Li 4 Ti 5 O 12 and a positive electrode made of LiFePO 4 .
• a separator element consisting of a microporous polyethylene film is placed between the two electrodes and it is impregnated with electrolyte.
• the electrolyte comprises one mole of lithium salt LiPF 6 per liter of organic solvent consisting of a 1: 1 mixture of ethylene carbonate and dimethyl carbonate.
• the solvent also comprises 2.5% by mass of carbazole relative to the total mass of electrolyte.
• Figure 2 represents the evolution of the voltage across the battery as a function of time (Curve A2) and the evolution of the intensity passing through the battery as a function of time (Curve B2), at the end of charging in C / 10 mode carried out on the range between 1, 5V and 3.5V, under condition stop at 10 a.m.
• part a corresponds to a period of normal conditions of use
• part b corresponds to a period of overload causing the polymerization of the carbazole
• part c corresponds to a period of discharge, the point of complete blocking of the battery that was not reached in the test illustrated in Figure 2.
• the battery displays performance identical to that expected for an equivalent battery not containing carbazole.
• the nominal voltage at the terminals of the battery is 1.9 Volts, the potential bearings of the positive and negative electrodes being respectively 3.45V and 1.55V relative to V Li + / Li .
• patent US2003 / 099886 describes a non-aqueous electrolyte comprising an organic solvent in which is dissolved a lithium salt and an additive compound of the following general formula:
• carbazole has been cited in the prior art among the additive compounds making it possible to improve the safety of a lithium battery, the applicants have found that carbazole can only be used with a positive electrode at low voltage, that is to say a positive electrode comprising a material having a lithium insertion and deinsertion potential less than or equal to 3.5 Volts and more particularly with LiFePO 4 .
• carbazole and its derivatives cannot be used with the lithium-ion batteries usually sold and, more particularly with lithium-ion batteries comprising a positive electrode such as those described in patent US2003 / 099886, because carbazole and its derivatives polymerize before the end of battery charging.

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• 2004
  • 2004-02-12 FR FR0401404A patent/FR2866478A1/fr not_active Withdrawn
• 2005
  • 2005-02-04 KR KR1020067016271A patent/KR20070001129A/ko active IP Right Grant
  • 2005-02-04 JP JP2006552653A patent/JP2007522628A/ja active Pending
  • 2005-02-04 US US10/585,922 patent/US20070259259A1/en not_active Abandoned
  • 2005-02-04 WO PCT/FR2005/000252 patent/WO2005083819A2/fr not_active Application Discontinuation
  • 2005-02-04 CN CN201110170488A patent/CN102299379A/zh active Pending
  • 2005-02-04 EP EP05717555A patent/EP1714340A2/fr not_active Withdrawn
  • 2005-02-04 CN CNA2005800046644A patent/CN1918733A/zh active Pending
• 2010
  • 2010-08-06 US US12/852,183 patent/US20100297480A1/en not_active Abandoned

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