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  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/40—Alloys based on alkali metals
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  • 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
  • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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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  • Y02E60/10—Energy storage using batteries

Definitions

• solid inorganic electrolytes are promising candidates for solid state batteries, as they provide higher lithium ion conductivity which is comparable to liquid electrolytes.
• the unique ion conduction property of inorganic electrolytes enables lower concentration polarization at the interface of metallic lithium and enables high speed battery charging and discharging.
• complete cells using solid ceramic electrolytes suffer from poor electrochemical performance due to significant interface resistance at the cell boundaries.
• grains of the ceramic particles and between the particles of the composite electrodes made up of a mixture of particles of active material, carbon additive and solid electrolyte.
• the conduction of Li + ions must be carried out in particle-to-particle mode, the electrochemical performance is limited by the poor distribution of the solid electrolyte particles as well as by the existence of a vacuum between the particles.
• Electrochemical instability problems can also be encountered with these composite electrolytes, in particular at the interface between the electrolyte layer and one of the electrodes, for example a metallic lithium electrode.
• these composite electrolytes in particular at the interface between the electrolyte layer and one of the electrodes, for example a metallic lithium electrode.
• they still face different challenges in terms of ionic conductivity, electrochemical stability and interfacial interactions.
• the present technology relates to a composite material comprising inorganic particles, a fluorinated compound, and optionally a polymer, the fluorinated compound being of Formula I: Formula I in which:
• X 1 is selected from O and NH or X 1 is absent;
• R 1 is a group substituted by one or more fluorine atoms, for example, R 1 can be a perfluorinated group.
• R 1 is a linear or branched C1-ealkyl group, or a linear or branched C1-4alkyl group, or a C1-2alkyl group.
• the fluorinated compound is chosen from the compounds /V-methyltrifluoroacetamide (NMTFAm), /V-methylpentaproprionamide (NMPPPAm), /V-cylcopentyltrifluoroacetamide (NCPTFAm), N-trifluoromethylsulfonyl trifluoroacetamide (NTFMSTFAm), /V-trimethylsilyl trifluoroacetamide (NTMSTFAm), and bistrifluoroacetamide (BTFAm).
• NMTFAm /V-methyltrifluoroacetamide
• NMPPPAm /V-methylpentaproprionamide
• NCPTFAm /V-cylcopentyltrifluoroacetamide
• NFMSTFAm N-trifluoromethylsulfonyl trifluoroacetamide
• NTMSTFAm /V-trimethylsilyl trifluoroacetamide
• BTFAm bistrifluoroace
• Ra is (CH 2 -CH 2 -0)y; and Rb is a C1-C10alkyl group.
• the composite material comprises the polymer and in addition a plasticizer.
• the plasticizer can be chosen from liquids of glycol diether types (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, ionic liquids, and the like.
• the plasticizer may be present in the composite material at a concentration in the range of 0.1% to 50% by weight, or 10% to 50% by weight, or 20% at 40% by weight.
• the positive electrode comprises a positive electrode material optionally on a current collector, wherein the positive electrode material comprises an electrochemically active positive electrode material.
• the positive electrode electrochemically active material is chosen from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides.
• M'PC
• the positive electrode material further comprises a binder, for example, the binder is a polymer as defined above, or a binder chosen from rubber-type binders (such as SBR (styrene rubber - butadiene), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber)), or fluorinated polymer type binders (such as PVDF (polyvinylidene fluoride ), PTFE (polytetrafluoroethylene), and their combinations), optionally comprising an additive such as CMC (carboxymethylcellulose).
• the positive electrode material further comprises a salt, inorganic particles of the ceramic or glass type, or even other compatible active materials (for example, sulfur), and/or the material positive electrode further comprises the composite material defined here.
• the alloy comprising at least 75% by weight of lithium, or between 85% and 99, 9% by mass of lithium.
• the electrochemically active negative electrode material is in the form of optionally coated particles (eg, polymer, ceramic, carbon, or a combination of two or more thereof).
• the negative electrode material further comprises a salt, inorganic particles of ceramic or glass type, or other compatible active materials, and/or the composite material as defined here.
• the present technology relates to an electrochemical accumulator comprising at least one electrochemical cell as defined here.
• the electrochemical accumulator is a lithium battery or a lithium-ion battery.
• this document relates to the use of an electrochemical accumulator as defined here, in portable devices, for example mobile telephones, cameras, tablets or portable computers, in electric vehicles or hybrids, or in the storage of renewable energy.
• Figure 2 shows the solid state NMR results: (a) 1 H NMTFAm and NMTFAm/LATP mixture; (b) 6Li of LATP; (c) 6Li of the NMTFAm/LATP mixture.
• Figure 5 presents the potential as a function of time for Cell 4 cycled at current densities ranging from C/3 to 5C.
• the fluorinated amide is a compound of Formula I:
• X 2 is selected from C(O), S(0)2, and Si(R 3 R 4 ), where R 3 and R 4 are independently at each occurrence an optionally substituted linear or branched Ci-salkyl group, or X 2 is absent; wherein at least one of R 1 , R 2 , R 3 and R 4 is a group substituted by one or more fluorine atoms.
• R 1 is a group substituted by one or more fluorine atoms, for example, a perfluorinated group.
• This group can be a linear or branched C1-salkyl group, or a linear or branched C1-4alkyl group, or else a C1-2alkyl group.
• the R 2 group can be a group substituted by one or more fluorine atoms, for example a perfluorinated group.
• This group can be a Ci-salkyl group linear or branched, or a linear or branched C1-4alkyl group, or a C1-2alkyl group.
• R 2 can be an optionally substituted C3-8cycloalkyl group, or an optionally substituted C3-6cycloalkyl group, or an optionally substituted C5-6cycloalkyl group.
• Non-limiting examples of fluorinated compounds include N-methyltrifluoroacetamide (NMTFAm), /V-methylpentaproprionamide (NMPPPAm), /V-cylcopentyltrifluoroacetamide (NCPTFAm), /V-trifluoromethylsulfonyl trifluoroacetamide (NTFMSTFAm), /V-trimethylsilyl trifluoroacetamide (NTMSTFAm) , and bistrifluoroacetamide (BTFAm).
• NMTFAm N-methyltrifluoroacetamide
• NMPPPAm /V-methylpentaproprionamide
• NCPTFAm /V-cylcopentyltrifluoroacetamide
• NFMSTFAm /V-trifluoromethylsulfonyl trifluoroacetamide
• NTMSTFAm /V-trimethylsilyl trifluoroacetamide
• BTFAm bistrifluor
• the concentration of the compound in the composite material may be, for example, in the range of 1% to 90% by weight, or 1% to 70% by weight, or 1% to 50% by weight, or 1% to 40% by weight, or 5% to 30% by weight, or 10% to 25% by weight, or 15% to 20% by weight.
• the polymer when it is present in the composite material, may comprise at least one polymer segment chosen from ionic conductor segments of the polyether, polythioether, polyester, polythioester, polycarbonate, polythiocarbonate, polyimide, polysulfonimide, polyamide, polysulfonamide, polyphosphazene, or from polyacrylate, polymethacrylate, polystyrene, polysiloxane, polyurethane, polyethylene, polypropylene ionically non-conductive segments.
• the polymer can also be a copolymer comprising the units of two or more of these segments or a combination of two or more of these.
• the copolymer can be a random, random, alternating, block, etc. copolymer.
• the polymer is preferably a cross-linked aprotic polymer and/or a branched polymer, preferably of the multi-branched type (star, comb configuration, etc.).
• the polymer includes at least one polymer segment comprising a block copolymer with at least two different repeating units to reduce the crystallinity of the crosslinked polymer.
• the polymer segment can comprise, before crosslinking, a block copolymer comprising at least one an alkali or alkaline earth metal ion solvating segment and a crosslinkable segment comprising crosslinkable units.
• An example of an alkali or alkaline earth metal ion solvating segment is selected from homo- and copolymers comprising repeating units of Formula II:
• R is selected from F1, C1-C10alkyl, and -(CFte-O-RaRb);
• Ra is (CH2-CH 2 -0) y ;
• Rb is a Ci-Cioalkyl group.
• Non-limiting examples of crosslinkable units include functional groups chosen from acrylates, methacrylates, allyls, vinyls, hydroxides, epoxides, aldehydes, carboxylic acids, halophenyls, halobenzyls, alkynes, azides, amines, thiols and one of their combinations.
• the composite material comprises the crosslinked polymer, where the crosslinkable group has been converted into its crosslinked version.
• the inorganic particles preferably comprise an inorganic compound of the amorphous, ceramic or glass-ceramic type, for example, oxide, sulphide or oxysulphide, preferably an oxide.
• the inorganic compound may or may not be ionically conductive, preferably ionically conductive.
• the inorganic particles comprise a compound chosen from compounds of formula Lii+ z Al z M2-z(P0 4 )3, where M is Ti, Ge or a combination thereof, and 0 ⁇ z ⁇ 1, for example, z can be in the range of 0.1 to 0.9, or 0.3 to 0.7, or 0.4 to 0.6, or 0.2 to 0.5, or from 0.2 to 0.4.
• the inorganic particles comprise a compound chosen from the compounds of formulas LÎ7-xLa3Zr2M x x Oi2 and Li3yLa(2/3)-yTii- y M y y 03 in which M x is chosen from Al, Ga, Ta, Fe, and Nb; M y is selected from Ba, B, Al, Si and Ta; x is such that 0 ⁇ x ⁇ 1; y is such that 0 ⁇ y ⁇ 0.67; and y' is such that 0
• x is in the range of 0 to 0.5, or x is zero and M x is absent, preferably y' is in the range of 0 to 0.5, or y' is 0 and M y is absent.
• the content of inorganic particles in the composite material can range from 1% to 95% by weight, or from 5% to 90% by weight, or from 5% to 80% by weight, or from 5% to 70% by weight, or from 5% to 60% by weight, or from 5% to
• This composite material is prepared according to a process comprising at least one step of mixing the inorganic particles, the fluorinated compound, and optionally the polymer and other optional elements as described here.
• the mixing step of the process can therefore include the polymer and optionally a crosslinking agent.
• the mixing step of such a process can then be followed by a crosslinking step.
• the composite material can enter into the composition of a layer of solid electrolyte or of an electrode material.
• the electrolyte comprises the composite material as defined here in a solid layer.
• This layer can be formed by mixing, in any order, inorganic particles, electrolyte polymer or precursor thereof, fluorinated amide, and optionally solvent, plasticizer and/or salt, and spreading the mixture on a stand.
• Support may be temporary (such as stainless steel, polypropylene, etc.) and removed prior to assembly with the rest of the electrochemical cell.
• the support can also be the surface of an electrode material, which will have been prepared beforehand.
• the spread layer is treated in order to polymerize or crosslink the polymer, for example, by heat treatment, by irradiation (such as by UV, microwaves, gamma rays, X-rays, beam of 'electrons), or a combination of the two, optionally in the presence of an initiator.
• irradiation such as by UV, microwaves, gamma rays, X-rays, beam of 'electrons
• the material is preferably dried, for example, before crosslinking or assembling with the other components of the electrochemical cell.
• the present composite material is present in an electrochemical cell in at least one of the electrolyte, the positive electrode or the negative electrode, preferably in the electrolyte layer.
• the electrode material can be prepared in the same way as the electrolyte layer, except that the support for spreading can be the surface of a solid electrolyte layer or a current collector.
• the positive electrode material does not include the composite material
• the latter may include the electrochemically active material as defined here, a binder and optionally an electronic conductive material and/or a salt as defined here.
• Non-limiting examples of electrode material binders include the polymers described above in connection with the composite material, but also rubber type binders (such as SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber ), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber)), or fluoropolymer type binders (such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and combinations thereof). Certain binders, such as those of the rubber type, may also include an additive such as CMC (carboxymethylcellulose).
• CMC carboxymethylcellulose
• additives may also be present in the positive electrode material, such as inorganic particles of the ceramic or glass type, or even other compatible active materials (for example, sulfur).
• the negative electrode comprises a negative electrode electrochemically active material which may be formed from a metal film, for example, comprising an alkali or alkaline earth metal.
• the metallic film consists of lithium comprising less than 1000 ppm (or less than 0.1% by mass) of impurities.
• the alloy may comprise at least 75% by weight lithium, or between 85% and 99.9% by weight lithium.
• negative electrode electrochemically active material examples include an intermetallic compound (e.g., SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2, and CoSn2), metal oxide, metal nitride, metal phosphide, metal phosphate (eg, LiT2(PO4)3), metal halide (eg, metal fluoride), metal sulfide, metal oxysulfide, carbon (eg, graphite, graphene , reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite and amorphous carbon), silicon (Si), silicon-carbon composite (Si-C), silicon oxide (SiOx), a silicon oxide-carbon composite (SiOx-C), tin (Sn), a tin-carbon composite (Sn-C), a tin oxide (SnOx), an oxide composite tin-carbon (SnOx-C), and combinations thereof, when compatible.
• intermetallic compound
• M. is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof
• lithium titanate such as LUTisO4
• lithium molybdenum oxide such as U2MO4O13
• the negative electrode when it is not in the form of a metallic film, it instead comprises particles of an electrochemically active negative electrode material optionally coated (e.g., polymer, ceramic, carbon or a combination of two or more of these).
• the negative electrode material may also include other components such as those described for the negative electrode (such as an electronically conductive material, the present composite material, a salt, a binder, inorganic particles of the ceramic or glass type, or other compatible active materials).
• an electrochemical accumulator comprising at least one electrochemical cell as defined here.
• the electrochemical accumulator is a lithium or lithium-ion battery.
• the electrochemical accumulators of the present application are intended for use in portable devices, for example mobile telephones, cameras, tablets or portable computers, in electric or hybrid vehicles, or in the renewable energy storage.
• crosslinkable polymers used in the examples which follow are polyethers comprising crosslinkable units, as described in United States Patent No. 7,897,674 (referred to below as “polymer US'674", which is a branched polymer of the multibranched type comprising crosslinkable units) or in U.S. Patent No. 6,903,174 (referred to below as “polymer US'174", which is linear and includes pendant crosslinkable groups).
• LiTFSI lithium bis(trifluoromethanesulfonyl)imide
• US'674 polymer 0.08 g of Irgacure MC
• LiTFSI LiTFSI
• TEGDME tetraethylene glycol dimethyl ether
• DAEDAm L/,/V-diacetylethylenediamine
• HNT Halloysite nanotubes
• 0.5g of LiTFSI, 0.69g of TEGDME, 0.44g of N-methyltrifluoroacetamide (NMTFAm) and 0.26g of HNT are mixed well in a flask at room temperature. Once a homogeneous dispersion has been obtained, 0.67 g of US'674 polymer and 0.01 g of Irgacure MC are added. After 1 hour of stirring at room temperature, the dispersion is coated on a thin stainless steel sheet. The composite electrolyte membrane thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
• LiTFSI LiTFSI
• TEGDME 0.77g of TEGDME
• NMTFAm 0.26g of Li1,3Alo,3Ti1,7(PO4)3 (LATP)
• 0.67 g of US'674 polymer and 0.01 g of Irgacure MC are added. After 1 hour of stirring at room temperature, the dispersion is coated on a thin stainless steel sheet. The composite electrolyte membrane thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
• LiTFSI 0.5g LiTFSI, 0.77g TEGDME, 0.25g DAEDAm and 0.24g LATP are mixed well in a flask at room temperature. Once a homogeneous dispersion has been obtained, 0.75 g of US'674 polymer and 0.01 g of Irgacure MC are added. After 1 hour of stirring at room temperature, the dispersion is coated on a thin stainless steel sheet. The composite electrolyte membrane thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
• LiTFSI, 0.77g TEGDME, 0.44g NMTFAm and 0.26g L17La3Zr2012 (LLZO) are mixed well in a flask at room temperature.
• 0.67 g of US'674 polymer and 0.01 g of Irgacure MC are added. After 1 hour of stirring at room temperature, the dispersion is coated on a thin sheet of stainless steel. The composite electrolyte membrane thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
• 0.5g LiTFSI, 0.77g TEGDME, 0.44g N-trimethylsilyl trifluoroacetamide (NTMSTFAm) and 0.26g LATP are mixed well in a flask at room temperature. Once a homogeneous dispersion has been obtained, 0.67 g of US'674 polymer and 0.01 g of Irgacure MC are added. After 1 hour of stirring at room temperature, the dispersion is coated on a thin stainless steel sheet. The composite electrolyte membrane thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
• Figure 2(a) shows that the signals from NMTFAm are broader than those from the NMTFAm/LATP mixture, indicating an interaction between NMTFAm and LATP that significantly decreases the molecular mobility restriction in NMTFAm. Also, a shift of the peak corresponding to the NH protons of NMTFAm to a higher frequency may indicate that more NH protons in the mixture are involved in hydrogen bonds.
• Figure 2(c) shows that an additional signal at 1.2 ppm appeared in the 6 Li NMR spectrum of the mixture after 1 day of storage compared to Figure 2(b), indicating that new Li + ions have were generated by the interaction between NMTFAm and LATP.
• Example 1(d) The ionic diffusion coefficient of the various elements of the membrane prepared in Example 1(d) was evaluated by pulsed-field gradient solid-state NMR spectroscopy of the 1 H, 7 Li, and 19 F nuclei.
• the NMR experiments were carried out on a 500 MHz NMR spectrometer equipped with a Diff50 MC probe and 7 Li -19 F and 1 H -19 F double resonance RF insertions.
• the diffusion coefficients of Li in LATP at 25 and 50°C correspond to the values obtained with other samples containing LATP. This observation confirms that the diffusion of lithium in LATP is not dependent on the LATP particles surrounded by polymer, in particular considering that the mean square displacement of the species during the NMR experiment is approximately 0.5 to 1 pm (much smaller than the particle size of LATP which is about 10 pm).
• Cell 1 Electrode/Example 1 (a)/Electrode
• Cell 2 Electrode/Example 1 (b)/Electrode
• Electrode Metallic Lithium or Stainless Steel (b) Ion Conductivity Electrochemical impedance spectroscopy was performed with a Bio- logic® VMP-300 system at an amplitude of 100 mV and the frequency range of 1 MHz to 200 mHz.
• Figures 4(a) and 4(b) show the ionic conductivity results for Cells 1 through 15. Conductivity results at 50°C and 25°C are also shown in Table 2 below.
• the ionic conductivity in the electrolyte LATP/fluorinated amide (NMTFAm, 3.62 x 10 4 S/cm) at 20° C. is much higher than that of non-fluorinated LATP/amide (DAEDAm , 9.29 x 10 5 S/cm) and Halloysite nanotubes/NMTFAm (2.64 ⁇ 10 5 S/cm).
• the ionic conductivity at 20°C is also generally higher for all electrolytes comprising a fluorinated amide compared to the electrolyte without fluorinated amide.
• Electrolyte composition (% by weight) and results of Cells 1 to 15 has. US'674 polymer except Cell 9, where US'174 polymer was used. b. NM: not measured c.
• the electrolyte also comprises 15% by weight of bis(trifluoromethanesulfonyl)imide of 1,1'-hexamethylene bis(l-methylpyrrolidinium).
• Example 1(a) or Example 1(d) was coated on the carbonaceous membrane.
• the electrolyte layer is hardened by UV irradiation under nitrogen for 3 minutes. The complete membrane for the measurement of electrochemical stability is thus obtained.
• N-methyltrifluoroacetamide (NMTFAm) in a composite electrolyte based on US'674 polymer and LATP (a phosphate type oxide ceramic) can greatly improve the ionic conductivity and the stability to the Li/electrolyte interface (see Figure 1) at 25°C, oxidation stability up to 4.5V.
• NMTFAm N-methyltrifluoroacetamide
• LATP a phosphate type oxide ceramic
• a cathode was prepared as described in patent application PCT/CA2022/050159 by including 73.2% by weight of lithium manganese cobalt nickel oxide active material (NMC811), which gives a loading rate of approximately 8 mg /cm 2 .
• the Example 1(d) electrolyte dispersion was coated directly onto the cathode and cured by UV irradiation under nitrogen for 3 minutes. The electrolyte thickness is about 40 ⁇ m.
• a metallic lithium foil with a thickness of 50 ⁇ m was used as the anode.
• a 3.8cm 2 button cell was therefore assembled to evaluate the performance.
• the battery capacity is around 4.4 mAh (1.2 mAh/cm 2 ).
• a LiFePC>4 (LFP) cathode was prepared as in Example 3(e)(i) replacing NMC811 with LFP as the active material at a concentration by weight of 70%, which gives a loading rate of about 12 mg/cm 2 .
• the Example 1(d) electrolyte dispersion was coated directly onto the cathode and cured by UV irradiation under nitrogen for 3 minutes. The electrolyte thickness is about 40 ⁇ m.
• a metallic lithium foil with a thickness of 40 ⁇ m was used as the anode.
• a 3.8 cm 2 button cell was assembled to evaluate performance.
• the battery capacity is approximately 3 mAh (0.8 mAh/cm 2 ).

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• 2021
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