Classifications

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  • H01M50/10—Primary casings; Jackets or wrappings
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• • 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
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  • 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 relates to a lithium-air lithium electrochemical accumulator comprising, within a cell, an original association between a positive electrode material and a negative electrode material, this combination having the consequence of result in a safer battery and whose reactions to the electrodes are easily reversible.
• the field of the invention can thus be defined as that of energy storage devices, in particular that of electrochemical accumulators of the lithium-air type.
• the energy storage devices are conventionally electrochemical accumulators operating on the principle of electrochemical cells capable of delivering an electric current thanks to the presence in each of them of a pair of electrodes (respectively, a positive electrode and a negative electrode) separated by an electrolyte, the electrodes comprising specific materials capable of reacting in an oxidation-reduction reaction, whereby there is production of electrons at the origin of the electric current and productions of ions that will circulate from one electrode to another through an electrolyte.
• Devices of this type may be lithium-air accumulators, which conventionally comprises, at the level of each basic electrochemical cell, a negative electrode formed of a lithium-based material, which may be either lithium metal or a lithium-based alloy, as specified in FR 2,941,091, and a positive electrode of the air electrode type separated by a lithium ion conductive electrolyte.
• the operation of an electrochemical cell of a lithium-air accumulator is based, more precisely, on a reduction of the oxygen at the positive electrode by the Li + ions present in the electrolyte and coming from the negative electrode and on an oxidation of lithium metal to the negative electrode, during the discharge process, the reactions occurring at the electrodes can be symbolized by the following electrochemical equations:
• the main locks of lithium-air technology are as follows: -the safety of the accumulator;
• the discharge products such as Li 2 0 2 or Li 2 0, insoluble are caused to settle in the porosity of the air electrode, compromising the reversibility of the reactions. and, consequently, the cycling behavior of the accumulator.
• the inventors of the present invention set themselves the goal of proposing a new architecture of lithium-air accumulators comprising an original association between a specific positive electrode and a specific negative electrode, which have a security aspect and for which the reactions to the electrodes are easily reversible.
• the invention relates to a lithium-air accumulator comprising at least one electrochemical cell comprising:
• a negative electrode which is an air electrode
• a positive electrode which comprises a lithium insertion material
• positive electrode is meant, conventionally, in the foregoing and the following, the electrode which acts as a cathode, when the accumulator delivers current (that is to say when it is in the process of discharge ) and which acts as anode when the accumulator is in charging process.
• negative electrode is meant, conventionally, in what precedes and what follows, the electrode which acts as anode, when the accumulator discharges the current (that is to say when it is in the process of discharge) and which acts cathode, when the accumulator is in process of charge.
• the negative electrode of the accumulator of the invention is an air electrode, which is conventionally used in the accumulators of the prior art as positive electrode and not as negative electrode as is the case of the invention.
• the oxygen is reduced during the charging of the cell according to the following electrochemical equations:
• the air electrode is intended to be in direct contact with the air, in order to allow the reduction of oxygen and must therefore conventionally have catalytic sites and allow the exchange of electrons, which results in by the following properties:
• an air electrode adapted to enter the constitution of an accumulator according to the invention may comprise:
• At least one binder to ensure cohesion between said material and said catalyst.
• the electronically conductive material may preferably be a carbonaceous material, namely a material comprising carbon in the elemental state.
• carbon black such as acetylene black, tunnel black, furnace black, lamp black, anthracene black, charcoal black, gas black, thermal black
• the electronically conductive material may also be an electrically conductive ceramic belonging to the family of transition element nitrides, such as TiN, transition element carbides and / or metalloid element (s). s), such as TiC, SiC, carbonitrides of transition element (s), such as TiCN, simple oxides of transition element (s), such as TiO and ZnO.
• transition element nitrides such as TiN, transition element carbides and / or metalloid element (s).
• s such as TiC, SiC, carbonitrides of transition element (s), such as TiCN, simple oxides of transition element (s), such as TiO and ZnO.
• the electronically conductive material may contain both a carbonaceous material as mentioned above and an electronic conductive ceramic, as mentioned above.
• the aforementioned catalyst is, from a functional point of view, a catalyst capable of accelerating the electrochemical reactions occurring at the level of the air electrode (whether in the process of discharging or charging) and also suitable to increase the operational voltage at which these electrochemical reactions take place.
• a catalyst responding to these specificities can be:
• a catalyst consisting of a noble metal with a degree of oxidation 0, such as platinum or palladium or a noble metal alloy and another metallic element, such as a Pt-Fe alloy;
• a catalyst comprising a single oxide of ruthenium, such as RuO 2 , a single oxide of manganese, such as M n0 2 , Mn 2 0 3 , a single oxide of iron, such as Fe 3 O 4 , Fe 2 O 3 , a single oxide of cobalt, such as Co 3 0 4 or a single oxide of copper, such as CuO; or
• a catalyst comprising a mixed cobalt oxide, such as CoFe 2 O 4 , a mixed manganese oxide, such as LaMnO 3 , a mixed nickel oxide, such as LaNiO 3 ; and
• the catalyst used in accordance with the invention is a mixed or single manganese oxide, a mixed or single iron oxide, a mixed or single iron oxide or mixtures thereof.
• the negative electrode may comprise one or more binders, in particular, one or more polymeric binders.
• the fluorinated (co) polymers optionally conducting protons such as:
• fluorinated polymers such as polytetrafluoroethylene (known by the abbreviation PTFE), polyvinylidene fluoride (known by the abbreviation PVDF);
• fluorinated copolymers such as poly (vinylidene fluoride-co-hexafluoropropene) (known by the abbreviation PVDF-HFP);
• elastomeric polymers such as a styrene-butadiene copolymer (known by the abbreviation SBR), an ethylene-propylene-diene monomer copolymer (known by the abbreviation EPDM);
• SBR styrene-butadiene copolymer
• EPDM ethylene-propylene-diene monomer copolymer
• cellulosic polymers such as sodium carboxymethylcellulose
• the binder used is a binder based on a fluorinated polymer, such as polytetrafluoroethylene, polyvinylidene fluoride and mixtures thereof, this type of binder making it possible to obtain a good percolating network.
• a fluorinated polymer such as polytetrafluoroethylene, polyvinylidene fluoride and mixtures thereof
• the electronically conductive material as defined above may be present in a proportion ranging from 40 to 97% by weight relative to the total mass of the mixture comprising said material and the binding agent (s) (which means in return, that the binder or binders may be present in a proportion ranging from 3 to 60% by weight relative to the total mass of the aforementioned mixture).
• the negative electrode may also comprise a support intended, as its name indicates, to support the ingredients above mentioned, this support may further contribute to ensure good mechanical strength of the electrode and good electronic conduction and allow the diffusion of gases, in particular, oxygen. It is thus possible to qualify this supported electrode electrode.
• This support may be in the form of a foam, a grid or a fibrous support and may be a material comprising a metal or a metal alloy or a carbon material.
• It may be, in particular, a carbon support, a titanium support, a palladium support, a copper support, a gold support, an aluminum support , a nickel support or a stainless steel support.
• the negative electrode comprises a nickel grid or foam serving as a support for a composition comprising carbon black (acting as an electronically conductive material), PVDF (acting as a binder). and manganese oxide (acting as a catalyst), the manganese oxide being in the form of nanowires.
• the positive electrode comprises a lithium insertion material whose discharge voltage is greater than 4.5 V expressed relative to the Li + / Li pair.
• a material that responds to this specificity can be a material of the lithiated material type with a spinel structure, this material being known under the name of "spinel 5V".
• it may be a material having the following characteristics:
• LiM 1 PO 4 a material of formula LiM 1 PO 4 , in which M 1 is a transition element, materials of this type which may be L 1 COPO 4 or LiNiPO 4 ;
• LiM 2 SO 4 X 1 a material of formula LiM 2 SO 4 X 1 , in which M 2 is a transition element and X 1 is a halogen element, materials of this type which may be LiCoSO 4 F, LiNiSO 4 F;
• the positive electrode may comprise:
• At least one binder for ensuring cohesion between said lithium insertion material and said electronically conductive material
• the electronically conductive material may preferably be a carbonaceous material, namely a material comprising carbon in the elemental state.
• Carbonaceous material may include carbon black.
• the binder may preferably be a polymeric binder.
• the fluorinated (co) polymers optionally conducting protons, such as:
• fluorinated polymers such as polytetrafluoroethylene (known by the abbreviation PTFE), polyvinylidene fluoride (known by the abbreviation PVDF);
• fluorinated copolymers such as poly (vinylidene fluoride-co-hexafluoropropene) (known by the abbreviation PVDF-HFP);
• elastomeric polymers such as a styrene-butadiene copolymer (known by the abbreviation SBR), an ethylene-propylene-diene monomer copolymer (known by the abbreviation EPDM);
• SBR styrene-butadiene copolymer
• EPDM ethylene-propylene-diene monomer copolymer
• the electronic conductive fibers when present, can participate, in addition, in the good mechanical strength of the positive electrode and are chosen, for this purpose, so as to have a very important Young's modulus.
• Fibers adapted to this specificity may be carbon fibers, such as carbon fibers of the Tenax ® or VGCF-H ® type .
• Tenax ® carbon fibers help improve mechanical properties and have good electrical conductivity.
• the VGCF-H ® carbon fibers are vapor synthesized fibers and help improve thermal and electrical properties, dispersion and homogeneity.
• the positive electrode may also comprise a support intended, as its As the name suggests, to support the aforementioned ingredients, this support can, in addition, ensure good mechanical strength of the electrode and good electronic conduction. It is thus possible to qualify the supported electrode electrode.
• This support may be in the form of a foam, a grid or a fibrous support and may be a material comprising a metal or a metal alloy or a carbon material.
• It may be, in particular, a carbon support, a titanium support, a palladium support, a copper support, a gold support, an aluminum support , a nickel support or a stainless steel support.
• the positive electrode comprises an aluminum grid acting as a support, on which is deposited a composition comprising a material of formula LiM ni ⁇ 5 NiO, 504 (acting as insertion material lithium), carbon black (as an electronically conductive material), PVDF (as a binder) and carbon fibers (as electronically conductive fibers).
• the electrolyte intended to enter the constitution of the accumulators of the invention is an organic electrolyte conductive lithium ions disposed between said negative electrode and said positive electrode, said electrolyte does not degrade, when subjected to a voltage ranging from 3 V to 5.5 V expressed with respect to the Li + / Li pair, which means that it retains its intact properties after being subjected to such a voltage.
• An electrolyte responding to this specificity may be an electrolyte comprising:
• a lithium salt at least one organic solvent belonging to the family of carbonate solvents, sulphone solvents or lactone solvents; and
• a stabilizing additive belonging to the family of phosphate or anhydride compounds optionally a stabilizing additive belonging to the family of phosphate or anhydride compounds.
• the lithium salt may be chosen from the group consisting of LiPF 6 , LiClO 4 , LiBF 4 , LiAsF 6 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 3 , LiN (C 2 F 5 S0 2 ), lithium bis (trifluoromethylsulfonyl) imide (known by the abbreviation LiTFSI) LiN [S0 2 CF 3 ] 2, lithium bis (oxalato) borate (known by the abbreviation LI BOB), bis ( lithium fluorosulfonyl) imide (known by the abbreviation LiFSI), LiPF 3 (CF 2 CF 3 ) 3 (known by the abbreviation LiFAP), lithium trifluoromethanesulfonate (known by the abbreviation LiTf), bis-trifluoromethanesulfonylimide of lithium (known by the abbreviation Lilm) and mixtures thereof.
• LiTFSI lithium bis (trifluoromethyl
• the lithium salt can be included in the electrolyte at
• organic solvent belonging to the family of carbonate solvents mention may be made of ethylene carbonate (known under the abbreviation EC), propylene carbonate (known by the abbreviation PC), dimethyl carbonate (known under the name of abbreviation DMC), diethyl carbonate (known abbreviated as EMC) and mixtures thereof.
• EC ethylene carbonate
• PC propylene carbonate
• DMC dimethyl carbonate
• EMC diethyl carbonate
• organic solvent belonging to the family of lactone solvents there may be mentioned ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone.
• organic solvent belonging to the family of sulfone solvents mention may be made of ethylmethylsulfone (known by the abbreviation EMS), trimethylenesulphone (known by the abbreviation TriMS), 1-methyltrimethylenesulphone (known by the abbreviation MTS), ethyl-sec-butylsulfone (known by the abbreviation EiBS), ethyl- ⁇ -propylsulfone (known by the abbreviation EiPS) and also 3,3,3-trifluoropropylmethylsulfone (known by the abbreviation FPMS) .
• the solvent can be used as a single solvent or a mixture of separate solvents (which can thus form a binary solvent or a ternary solvent.
• it may be only EC, an EC / EMC binary solvent (1: 1) or a ternary solvent which may include three solvents in proportions (1: 1: 1) to (1: 8 : 1) or (8: 1: 1) or alternatively (1: 1: 8), a specific example being the ternary solvent EC / PC / DMC (1: 1: 3).
• the stabilizing additive when it is a phosphate compound, mention may be made of tris (hexafluoroisopropyl) phosphate (known by the abbreviation HFiP).
• the stabilizing additive when the latter is an anhydride compound, mention may be made of ethanoic anhydride, propanoic anhydride, benzoic anhydride, butanoic anhydride, cis-butenedioic anhydride, butane-anhydride and the like.
• 1,4-dicarboxylic acid pentane-1,5-dicarboxylic anhydride, hexane-1,6-dicarboxylic anhydride, 2,2-dimethylbutane-1,4-dicarboxylic anhydride, 2,2-anhydride dimethylpentane-1,5-dicarboxylic acid, 4-bromophthalic anhydride, 4-chloroformylphthalic anhydride, phthalic anhydride, benzoglutaric anhydride and mixtures thereof.
• This additive may be present in the electrolyte in a proportion of 0.01% to less than 30% by mass relative to the total mass of the electrolyte.
• the aforementioned liquid electrolyte can be led into the electrochemical cells of the accumulators of the invention to impregnate a separator, which is disposed between the positive electrode and the negative electrode of the electrochemical cell.
• This separator may be a porous material capable of accommodating in its porosity the liquid electrolyte.
• This separator may consist of a membrane made of a material chosen from glass fiber, a polymeric material (such as a polyethylene, a polypropylene or a mixture of both).
• the electrolyte may also be an ionic liquid.
• the electrolyte may also consist of a solid electrolyte, for example a lithium ion conductive ceramic membrane, conventionally called LISICON (corresponding to the English terminology Lithium Super lonic Conductor), this ceramic membrane possibly being of the perovskite type, such that La, Li) Ti0 3 (known by the abbreviation LLTO), of the garnet type, such as Li5La 3 Ta 2 0i 2 , Li 6 La3Zr 2 0ii ; 5, of the phosphate type, such that Lii + xAlxGe2- x (0 4 ) 3 with 0 ⁇ x ⁇ 0.8 (known by the abbreviation LAGP) and ⁇ + ⁇ ⁇ 2 - ⁇ ⁇ ( ⁇ 0 4 ) 3 with 0 , ⁇ X ⁇ 0.3 / LiI + x + y Ti 2 -xAl x Si y (PO 4 ) 3- y with 0.2 ⁇ x ⁇
• the accumulator of the invention can be included in a sealed enclosure supplied with oxygen for its operation.
• An accumulator specific to the invention is an accumulator comprising at least one electrochemical cell comprising:
• a negative electrode comprising a nickel grid serving as a support for a composition comprising carbon black (acting as an electronically conductive material), PVDF (acting as a binder) and manganese oxide (acting as catalyst) the manganese oxide may be in the form of nanowires;
• a positive electrode comprising an aluminum grid acting as a support, on which is deposited a composition comprising a material of formula LiM n ⁇ SiNiC (acting as a lithium insertion material), carbon black (acting as electronically conductive material), PVDF (as a binder) and carbon fibers (as electronically conductive fibers); and
• a porous separator disposed between said negative electrode and said positive electrode, said separator being impregnated with an electrolyte comprising a LiPF 6 lithium salt in a solvent mixture EC / PC / DMC in volume proportions (1: 1: 3) .
• the accumulators of the invention can be made by conventional techniques within the reach of those skilled in the art, for example, by stacks the various constituent elements of the accumulator (namely, negative electrode, positive electrode and separator), this stack being maintained in a housing.
• the positive electrode and the negative electrode may be prepared beforehand, before their incorporation into the accumulator, this preparation may consist, for each of these electrodes in the following succession of steps:
• a step of preparing the electrode composition for example, for the negative electrode, a composition comprising an electronically conductive material, an organic binder, a catalyst and, for the positive electrode, a composition comprising a material for insertion of lithium, an organic binder, an electronically conductive material;
• a step of depositing these compositions on a support for example a metal grid.
• an accumulator can comprise:
• Figure 1 is a view illustrating the mounting of an accumulator according to the invention according to Example 1 described below.
• FIG. 2 illustrates the curve of the first charge of the accumulator obtained according to example 1, this curve representing the evolution of the potential V (in V) as a function of the capacitance C (in mAh / g).
• FIG. 3 illustrates the curve illustrating two charging / discharging cycles of the accumulator obtained according to example 2, this curve representing the evolution of the potential V (in V) as a function of the capacitance C (in mAh / g).
• the following example illustrates the preparation of a lithium-air accumulator comprising an air negative electrode (anode) and a positive electrode comprising a high potential material (which is expressed relative to the Li + / Li pair) and a specific electrolyte. .
• This accumulator comprises:
• step a the manufacture of the negative electrode
• step b the manufacture of the positive electrode
• step c the manufacture of the electrolyte
• the electrolyte is prepared by mixing in a glove box 100 ml of ethylene carbonate, 100 ml of propylene carbonate and 300 ml of dimethyl carbonate, to which 151.9 g of LiPF 6 have been added. The mixture is homogenized by stirring for 72 hours. d) Stack assembly
• the accumulator was assembled in an argon filled glove box comprising a proportion of oxygen and water of less than 0.1 ppm.
• the accumulator was made as shown in FIG. 1 attached in the appendix, starting with the positive electrode and then ending with the negative electrode, the various elements of the accumulator being, in the following order:
• Viledon 9 disc which is a nonwoven polyolefin fiber (polypropylene / polyethylene) membrane and a Calgard 11 disc (which is a polypropylene membrane);
• the electrolyte impregnates the two aforementioned disks at
• the resulting accumulator is subjected to a cycling test. To do this, the accumulator was introduced into a sealed glass enclosure, in which a pure oxygen stream of a pressure of 1 atmosphere allows good exposure of the accumulator to oxygen.
• the positive and negative terminals of the battery were then connected to a battery test system (potentiostat, galvanostat).
• the battery was charged at C / 20 (0.041 mA) up to 2.15 V as shown in Figure 2 attached.
• Example 2 has the same conditions as Example 1 with a few exceptions.
• the positive electrode is in turn made under similar conditions to those in Example 1, if it is not at the respective amounts of the reactants, which are as follows: 0.531 g of LiM or ⁇ 5 Ni 0, 5O 4 0.018 g Super C65 carbon, 0.018 g carbon fiber and 0.030 g polyvinylidene fluoride.
• the capacity of the electrode is 1,1511 mAh.
• the electrolyte and the assembly of the cell are in all respects similar to Example 1 mentioned above.
• the cell underwent 4 charge / discharge cycles between 1.6 V and 0.56 V at C / 20 (0.057 mA) as illustrated in Figure 3 attached, the 4 curves illustrating these cycles being similar.

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• 2012
  • 2012-04-25 FR FR1253791A patent/FR2990064B1/fr not_active Expired - Fee Related
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