Method for manufacturing a protected negative electrode and the resulting negative electrode

Abstract

The invention discloses a negative electrode material comprising an electrochemically active material and a coating layer on the surface thereof. The coating layer comprises a coating material based on a lithiophilic calcined organometallic structure comprising at least one lithiophilic metal and at least one at least partially calcined organic ligand. The invention further discloses the methods for manufacturing the electrode material, the electrodes comprising the material, and the use of the electrodes in electrochemical cells and batteries.

Description

[0001] METHOD FOR PRODUCING PROTECTED NEGATIVE ELECTRODE AND NEGATIVE ELECTRODE PRODUCED THEREBY

[0002] RELATED REQUEST

[0003] This application claims priority under applicable law from Canadian Provisional Patent Application No. 3,147,039 filed on January 28, 2022, the contents of which are incorporated herein by reference in their entirety and for all purposes.

[0004] TECHNICAL FIELD

[0005] The present technology relates to the field of negative electrode materials comprising a coating layer on one of its surfaces, to electrodes comprising them, to methods of preparing these materials and to their uses in electrochemical cells.

[0006] STATE OF THE ART

[0007] Liquid electrolytes used in lithium-ion batteries are flammable and slowly degrade to form a passivation layer on the surface of the lithium film called the solid electrolyte interface (SEI) that irreversibly consumes lithium, decreasing the battery's Coulombic efficiency. In addition, lithium anodes undergo significant morphological changes during battery cycling, and lithium dendrites are formed. Since these typically migrate through the electrolyte, they can eventually cause short circuits.

[0008] Safety concerns and the requirement for higher energy density have stimulated research for the development of an all-solid-state rechargeable lithium battery with a polymer or ceramic electrolyte, both of which are more stable towards metallic lithium and reduce the growth of lithium dendrites. However, some disadvantages result from the use of such solid electrolytes, e.g., loss of ionic reactivity or conductivity, poor contact between solid interfaces, etc.

[0009] Therefore, there is a need for the development of new methods for protecting the surface of metal electrodes. SUMMARY

[0010] In one aspect, the present technology relates to a method for preparing a negative electrode material comprising an electrochemically active material and a coating layer comprising a lithiophilic calcined metal-organic framework-based coating material resting on a surface of said electrochemically active material, the method comprising the following steps:

[0011] (i) contacting at least one organic ligand with at least one lithiophilic metal precursor in order to obtain a lithiophilic organometallic structure;

[0012] (ii) calcining the lithiophilic organometallic framework obtained in (i) to obtain the calcined lithiophilic organometallic framework of the coating material; and

[0013] (iii) deposition of the coating material on the surface of the electrochemically active material.

[0014] In one embodiment, the lithiophilic metal is selected from Ag, Zn, Sn, Sb, Mg, Al, Ni, Cu, Co and a combination of at least two of these.

[0015] In another embodiment, the organic ligand is an organic ligand comprising a nitrogen function, an organic ligand comprising a carboxylate, or a mixed organic ligand comprising a nitrogen function and / or a carboxylate. In one example, the organic ligand is 1,2,4,5-benzenetetracarboxylic acid or 1H-benzimidazole-6-carboxylic acid.

[0016] In another embodiment, the lithiophilic organometallic structure obtained in (i) is of Formula 1:

[0017] Formula 1. In another embodiment, the lithiophilic organometallic structure obtained in (i) is of Formula 2: In another embodiment, the lithiophilic organometallic structure obtained in (i) is of Formula 3:

[0018] In another embodiment, the lithiophilic organometallic structure obtained in (i) is of Formula 4:

[0019] In another embodiment, the lithiophilic organometallic structure obtained in (i) is of Formula 5:

[0020]

[0021] In another embodiment, the lithiophilic organometallic structure obtained in (i) is of Formula 6: wherein, ni and ri2 denote the ratio of each unit and are numbers independently selected from the range of 0.1 to 0.9. In another embodiment, the lithiophilic organometallic structure obtained in (i) is of Formula 7:

[0022] Formula 7 in which, ni and n2 denote the ratio of each unit and are independently chosen numbers in the range 0.1 to 0.9.

[0023] In another embodiment, the lithiophilic organometallic structure obtained in (i) is of Formula 8:

[0024] Formula 8 in which, ni and n2 denote the ratio of each unit and are independently chosen numbers in the range 0.1 to 0.9.

[0025] In another embodiment, the lithiophilic organometallic structure obtained in (i) is of Formula 9:

[0026] Formula 9.

[0027] In another embodiment, the calcining step is carried out at a temperature of about 500°C to about 1050°C. In one example, the calcining step is carried out at a temperature of about 550°C to about 1000°C.

[0028] In another embodiment, the calcining step is performed under an inert atmosphere. In one example, the inert atmosphere comprises a gas selected from argon, oxygen, nitrogen, helium, a fluorinated gas, and a mixture comprising at least two of these. In one example of interest, the inert atmosphere comprises argon. In another embodiment, the deposition step is performed by at least one of doctor blade coating, comma coating, reverse-comma coating, gravure coating, slot-die coating, or spray deposition.In one example, the deposition step is performed by a spray deposition method.

[0029] In another embodiment, said method further comprises a step of depositing a second coating layer.

[0030] According to one example, the step of depositing the second coating layer is performed by at least one of a doctor blade coating method, a comma coating method, a reverse-comma coating method, a printing method such as gravure coating, a slot-die coating method, or a spray deposition method. According to one example of interest, the step of depositing the second coating layer is performed by a spray deposition method.

[0031] According to another aspect, the present technology relates to a negative electrode material obtained according to the method as defined herein.

[0032] According to another aspect, the present technology relates to a negative electrode material comprising an electrochemically active material and a coating layer comprising a coating material based on a lithiophilic calcined organometallic framework comprising at least one lithiophilic metal and at least one at least partially calcined organic ligand, said coating layer resting on a surface of said electrochemically active material.

[0033] In one embodiment, the electrochemically active material comprises an alkali metal, an alkaline earth metal, a non-alkali and non-alkaline earth metal, or an alloy comprising at least one of these. In one example, the electrochemically active material comprises an alkali metal, an alkaline earth metal, or an alloy comprising at least one alkali or alkaline earth metal. For example, the electrochemically active material comprises metallic lithium or an alloy including or based on metallic lithium. In another example, the electrochemically active material comprises nickel.

[0034] In another embodiment, the electrochemically active material is in the form of a film having a thickness in the range of about 5 pm to about 75 pm, or about 15 pm to about 70 pm, or about 25 pm to about 65 pm, or about 30 pm to about 60 pm, or about 45 pm to about 55 pm, upper and lower limits inclusive.

[0035] In another embodiment, the lithiophilic metal is selected from Ag, Zn, Sn, Sb, Mg, Al, Ni, Cu, Co and a combination of at least two of these.

[0036] In another embodiment, the organic ligand is an organic ligand comprising a nitrogen function, an organic ligand comprising a carboxylate, or a mixed organic ligand comprising a nitrogen function and / or a carboxylate. In one example, the organic ligand is 1,2,4,5-benzenetetracarboxylic acid or 1H-benzimidazole-6-carboxylic acid.

[0037] In another embodiment, the lithiophilic organometallic structure before calcination is of Formula 1:

[0038] In another embodiment, the lithiophilic organometallic structure before calcination is of Formula 2:

[0039]

[0040] In another embodiment, the lithiophilic organometallic structure before calcination is of Formula 3:

[0041] In another embodiment, the lithiophilic organometallic structure before calcination is of Formula 4:

[0042] In another embodiment, the lithiophilic organometallic structure before calcination is of Formula 5:

[0043]

[0044] In another embodiment, the lithiophilic organometallic structure before calcination is of Formula 6: in which, ni and n2 denote the ratio of each unit and are independently chosen numbers in the range 0.1 to 0.9.

[0045] In another embodiment, the lithiophilic organometallic structure before calcination is of Formula 7:

[0046] Formula 7 in which, ni and n2 denote the ratio of each unit and are independently chosen numbers in the range 0.1 to 0.9.

[0047] In another embodiment, the lithiophilic organometallic structure before calcination is of Formula 8:

[0048] Formula 8 in which, ni and n2 denote the ratio of each unit and are independently chosen numbers in the range 0.1 to 0.9.

[0049] In another embodiment, the lithiophilic organometallic structure before calcination is of Formula 9:

[0050] Formula 9.

[0051] In another embodiment, the lithiophilic calcined metal-organic framework further comprises a silver source. In one embodiment, the silver source is a silver salt. In one example, the silver salt is AgCl or AgNCh. In another example, the salt is present in a lithiophilic metal:silver ratio in the range of about 4:3 to about 4:1, inclusive.

[0052] In another embodiment, the coating material further comprises a solid polymer electrolyte comprising a salt in a solvating polymer. In one example, the solid polymer electrolyte is a copolymer of ethylene oxide and at least one substituted oxirane comprising a crosslinkable function. In one example, the copolymer comprises ethylene oxide-based units and -O-CH2- CHR units, wherein R is a substituent comprising a radically crosslinkable functional group and is independently selected from one unit to another. For example, R' is a substituent being free of radically crosslinkable functional groups and is independently selected from one unit to another.

[0053] According to another example, the copolymer has a polymolecularity index (I = M p / M n ) less than or equal to 2.2 in which M nis the number average molecular mass of the copolymer and is greater than or equal to 20,000 and M p is the weight average molecular mass.

[0054] In another example, the copolymer is crosslinked.

[0055] In another example, the salt is a lithium salt. For example, the lithium salt is selected from the group consisting of lithium hexafluorophosphate (LiPFe), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (UBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (UNO3), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiCl>4), lithium hexafluoroarsenate (LiAsFe), lithium trifluoromethanesulfonate lithium (USO3CF3) (LiTf), lithium fluoroalkylphosphate Li[PF3(CF2CF3)3] (LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF3)4] (LiTFAB), bis(1,2-benzenediolato(2-)-O,Lithium borate Li[B(CeO2)2] (LiBBB) and a combination of at least two of these. In a variant of interest, the lithium salt is LiTFSI.,

[0056] In another embodiment, the coating layer has a thickness in the range of about 1 μm to about 20 μm, or about 1 μm to about 19 μm, or about 1 μm to about 18 μm, or about 1 μm to about 17 μm, or about 1 μm to about 16 μm, or about 1 μm to about 15 μm, or about 1 μm to about 14 μm, or about 1 μm to about 13 μm, or about 2 μm to about 12 μm, inclusive. In one example, the thickness of the coating layer is in the range of about 2 μm to about 12 μm, inclusive.

[0057] In another embodiment, the electrochemically active material is lubricated.

[0058] In another embodiment, the coating layer is a first coating layer and the electrode material comprises a second layer of coating material.

[0059] According to one example, the second coating layer has a thickness in the range of about 1 pm to about 20 pm, or from about 1 pm to about 19 pm, or from about 1 pm to about 18 pm, or from about 1 pm to about 17 pm, or from about 1 pm to about 16 pm, or from about 1 pm to about 15 pm, or from about 1 pm to about 14 pm, or from about 2 pm to about 14 pm, upper and lower limits inclusive. According to a variant of interest, the thickness of the second coating layer is in the range of about 2 pm to about 14 pm, upper and lower limits inclusive.

[0060] In another example, the second coating layer comprises a non-crosslinked polymer.

[0061] According to another aspect, the present technology relates to a method of preparing an electrode material as defined herein, the method comprising a step of depositing the lithiophilic calcined organometallic framework-based coating layer on the surface of the electrochemically active material.

[0062] In one embodiment, the method further comprises a step of depositing the second coating layer.

[0063] In another embodiment, the deposition step is performed by at least one of a doctor blade coating method, a comma coating method, a reverse-comma coating method, a printing method such as gravure coating, a slot-die coating method, or a spray deposition method. In one example, the deposition step is performed by a spray deposition method.

[0064] In one embodiment, the method further comprises preparing the lithiophilic calcined metal-organic framework coating layer.

[0065] According to one example, the preparation of the coating layer based on a lithiophilic calcined organometallic framework further comprises a step of preparing the lithiophilic calcined organometallic framework. For example, the step of preparing the lithiophilic calcined organometallic framework comprises (i) a step of contacting at least one organic ligand with at least one lithiophilic metal precursor in order to obtain a lithiophilic organometallic framework, and (ii) a step of calcining the lithiophilic organometallic framework obtained in (i) to obtain the calcined lithiophilic organometallic framework.

[0066] In another aspect, the present technology relates to a negative electrode comprising the electrode material as defined herein or an electrode material obtained according to the method as defined herein on a current collector.

[0067] In another aspect, the present technology relates to a self-supporting negative electrode comprising the electrode material as defined herein or an electrode material obtained according to the method as defined herein.

[0068] In another aspect, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein the negative electrode is as defined herein or comprises an electrode material as defined herein.

[0069] In one embodiment, the positive electrode comprises an electrochemically active material selected from a metal oxide, a metal sulfide, a metal oxysulfide, a metal phosphate, a metal fluorophosphate, a metal oxyfluorophosphate, a metal sulfate, a metal halide, a metal fluoride, sulfur, selenium, and a combination of at least two thereof.

[0070] In one example, the metal of the electrochemically active material is selected from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb) and a combination of at least two of these.

[0071] According to another example, the metal of the electrochemically active material further comprises an alkali or alkaline earth metal selected from lithium (Li), sodium (Na), potassium (K) and magnesium (Mg).

[0072] In another example, the electrochemically active material is a lithium metal phosphate. For example, lithium metal phosphate is LiFePCL.

[0073] In another embodiment, the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer. In one alternative, the electrolyte is a liquid electrolyte comprising a salt in a solvent. In another alternative, the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer. In one example, the salt is a lithium salt. For example, the lithium salt is selected from the group consisting of lithium hexafluorophosphate (LiPFe), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (UBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (UNO3), lithium chloride (LiCl), lithium bromide (LiBr),lithium fluoride (LiF), lithium perchlorate (l_iCIC>4), lithium hexafluoroarsenate (LiAsFe), lithium trifluoromethanesulfonate (USO3CF3) (LiTf), lithium fluoroalkylphosphate Li[PF3(CF2CF3)3] (LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF3)4] (LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O')borate Li[B(CeO2)2] (LiBBB) and a combination of at least two of these. In a variant of interest, the lithium salt is LiTFSI.,

[0074] According to another aspect, the present technology relates to a battery comprising at least one electrochemical cell as defined herein.

[0075] In one embodiment, said battery is selected from the group consisting of a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a potassium battery, a potassium-ion battery, a magnesium battery, and a magnesium-ion battery. According to one variant of interest, said battery is a lithium battery. According to another variant of interest, said battery is a lithium-ion battery.

[0076] BRIEF DESCRIPTION OF THE FIGURES

[0077] Figure 1 shows thermogravimetric analysis results in (A) for MOF 1, in (B) for MOF 2, in (C) for MOF 3 (solid line) and MOF 4 (dashed line), and in (D) for MOF 5, as described in Example 1(b).

[0078] Figure 2 shows images of MOF 1 particles obtained by scanning electron microscopy (SEM) at different magnifications, as described in Example 1 (c).

[0079] Figure 3 shows images of MOF 2 particles obtained by SEM at different magnifications, as described in Example 1(c).

[0080] Figure 4 shows images of MOF 3 particles obtained by SEM at different magnifications, as described in Example 1(c).

[0081] Figure 5 shows images of MOF 4 particles obtained by SEM at different magnifications, as described in Example 1(c).

[0082] Figure 6 shows images of MOF 5 particles obtained by SEM at different magnifications, as described in Example 1(c).

[0083] Figure 7 shows in (A) an image obtained by SEM of MOF 1 particles and in (B) to (D) mapping images obtained by energy dispersive X-ray spectroscopy (EDS) of the elements C, O and Ou respectively, as described in Example 1 (d).

[0084] Figure 8 shows in (A) an SEM image of MOF 2 particles and in (B) to (D) EDS mapping images of the elements Ni, C and O respectively, as described in Example 1(d).

[0085] Figure 9 shows in (A) an image obtained by SEM of MOF 3 particles and in (B) to (D) mapping images obtained by EDS of the elements O, C and Zn respectively, as described in Example 1(d). Figure 10 shows in (A) an image obtained by SEM of MOF 4 particles and in (B) to (D) mapping images obtained by EDS of the elements C, O and Zn respectively, as described in Example 1(d).

[0086] Figure 11 shows thermogravimetric analysis results in (A) for MOF 6, in (B) for MOF 7, and in (C) for MOFs 8 to 10, as described in Example 2(b).

[0087] Figure 12 shows Raman spectra obtained for MOFs 6, 7 and 10, as described in Example 2(c).

[0088] Figure 13 shows Raman spectra obtained for MOFs 8 and 9, as described in Example 2(c).

[0089] Figure 14 shows in (A) a graph of the volume of nitrogen adsorbed per gram of sample as a function of the relative nitrogen pressure (P / Po), in (B) a graph of the distribution of pore volumes as a function of pore width, in (C) a graph of the specific surface area as a function of pore width, and in (D) a graph of the total pore volume as a function of pore width obtained for MOF 6, as described in Example 2(d).

[0090] Figure 15 shows in (A) a graph of the volume of nitrogen adsorbed per gram of sample as a function of the relative nitrogen pressure (P / Po), in (B) a graph of the distribution of pore volumes as a function of pore width, in (C) a graph of the specific surface area as a function of pore width, and in (D) a graph of the total pore volume as a function of pore width obtained for MOF 7, as described in Example 2(d).

[0091] Figure 16 shows in (A) a plot of the volume of nitrogen adsorbed per gram of sample versus relative nitrogen pressure (P / Po), in (B) a plot of the pore volume distribution versus pore width, in (C) a plot of the specific surface area versus pore width, and in (D) a plot of the total pore volume versus pore width obtained for MOF 8 (♦), MOF 9 (★) and MOF 10 (■), as described in Example 2(d).

[0092] Figure 17 shows transmission electron microscopy (TEM) images for MOF 6, as described in Example 2(e). Figure 18 shows in (A) to (C) TEM images of MOF 6, in (D) an EDS mapping image of Cu and in (E) a graph showing the EDS analysis results obtained for the area delineated in (D), as described in Example 2(e).

[0093] Figure 19 shows TEM images for MOF 6, as described in Example 2(e).

[0094] Figure 20 shows in (A) to (C) TEM images of MOF 6, in (D) an EDS mapping image of Cu, in (E) an EDS mapping image of C (red) and Cu (green), and in (F) a graph showing the EDS analysis results obtained for the area delimited in (D) and (E), as described in Example 2(e).

[0095] Figure 21 shows TEM images for MOF 6, as described in Example 2(e).

[0096] Figure 22 shows TEM images for MOF 6, as described in Example 2(e).

[0097] Figure 23 shows in (A) to (C) TEM images of MOF 7, in (D) an EDS mapping image of Ni, and in (E) and (F) graphs presenting the EDS analysis results obtained for the area delineated in (D), as described in Example 2(e).

[0098] Figure 24 shows TEM images for MOF 7, as described in Example 2(e).

[0099] Figure 25 shows TEM images for MOF 7, as described in Example 2(e).

[0100] Figure 26 shows in (A) and (B) images obtained by TEM for MOF 10, and in (C) the results of the corresponding EDS analysis, as described in Example 2(e).

[0101] Figure 27 shows in (A) and (B) TEM images for MOF 10, and in (C) an EDS mapping image of Zn, as described in Example 2(e).

[0102] Figure 28 shows in (A) a TEM image for MOF 10, in (B) an EDS mapping image of Zn, and in (C) a graph showing the EDS analysis results obtained for the area delimited in (B), as described in Example 2(e). Figure 29 shows in (A) a TEM image for MOF 9, in (B) to (E) EDS mapping images of Zn, C, O and Si respectively, and in (F) the corresponding EDS analysis results obtained for the two areas delimited in (A) to (E), as described in [Example 2(e).

[0103] Figure 30 shows in (A) to (C) images obtained by TEM for MOF 9, in (D) to (G) EDS mapping images of Zn, O, C and Si respectively, and in (H) the results of the corresponding EDS analysis obtained for the two areas delimited in (C) to (G), as described in [Example 2(e).

[0104] Figure 31 shows in (A) and (B) images obtained by TEM for MOF 9, in (C) to (F) the results of the corresponding EDS analysis obtained for the two areas indicated by arrows in (B), as described in [Example 2(e).

[0105] Figure 32 shows TEM images for MOF 9, as described in [Example 2(e).

[0106] Figure 33 shows TEM images for MOF 8, as described in [Example 2(e).

[0107] Figure 34 shows in (A) an image obtained by TEM for MOF 8, in (B) to (D) EDS mapping images of Zn, C and O respectively, and in (E) the results of the corresponding EDS analysis obtained for the area delimited in (A) to (D), as described in [Example 2(e).

[0108] Figure 35 shows in (A) and (C) images obtained by TEM for MOF 8, in (D) to (F) EDS mapping images of Zn, C and O respectively, and in (G) the results of the corresponding EDS analysis obtained for the area delimited in (C) to (F), as described in [Example 2(e).

[0109] Figure 36 shows in (A) and (C) images obtained by TEM for MOF 8, and in (D) the results of the EDS analysis obtained for the two areas indicated by arrows in the corresponding TEM image also shown in (D), as described in [Example 2(e).

[0110] Figure 37 shows in (A) an image obtained by TEM for MOF 8, in (B) to (D) EDS mapping images of Zn, C and O respectively, and in (E) and (F) the results of the corresponding EDS analysis obtained respectively for zones 1 and 2 delimited in (A) to (D), as described in Example 2(e).

[0111] Figure 38 shows TEM images for MOF 8, as described in Example 2(e).

[0112] Figure 39 shows SEM images obtained for MOF 8 in (A) before milling, in (B) after about 5 minutes of milling, and in (C) after two times about 5 minutes of milling, as described in Example 2(f).

[0113] Figure 40 shows in (A) a TEM image for MOF 8 after two times about 5 minutes of milling, and in (B) and (C) EDS mapping images of C and Zn respectively, as described in Example 2(f).

[0114] Figure 41 shows thermogravimetric analysis results in (A) for MOF 11, in (B) for MOF 12, in (C) for MOF 13, in (D) for MOF 14, and (E) for MOF 15, as described in Example 3(b).

[0115] Figure 42 shows SEM images obtained for MOF 11, as described in Example 3(c).

[0116] Figure 43 shows SEM images for MOF 12, as described in Example 3(c).

[0117] Figure 44 shows SEM images for MOF 13, as described in Example 3(c).

[0118] Figure 45 shows SEM images for MOF 14, as described in Example 3(c).

[0119] Figure 46 shows SEM images obtained for MOF 15, as described in Example 3(c).

[0120] Figure 47 shows in (A) an image obtained by SEM for MOF 11, and in (B) to (E) EDS mapping images of C, Zn, Ou and O respectively, as described in Example 3(d). Figure 48 shows in (A) an image obtained by SEM for MOF 11, and in (B) to (E) EDS mapping images of Zn, C, O and Cu respectively, as described in Example 3(d).

[0121] Figure 49 shows in (A) an image obtained by SEM for MOF 13, and in (B) to (E) EDS mapping images of Zn, C, O and Cu respectively, as described in Example 3(d).

[0122] Figure 50 shows in (A) an image obtained by SEM for MOF 14, and in (B) to (E) EDS mapping images of C, O, Cu and Zn respectively, as described in Example 3(d).

[0123] Figure 51 shows in (A) an image obtained by SEM for MOF 15, and in (B) to (E) EDS mapping images of Zn, C, O and Cu respectively, as described in Example 3(d).

[0124] Figure 52 shows thermogravimetric analysis results in (A) for MOF 11, in (B) for MOF 12, and in (C) for MOF 13, as described in Example 3(e).

[0125] Figure 53 shows in (A) and (B) SEM images for a MOF that has been calcined at a temperature of about 1000 °C and ground, and in (C) the results of the corresponding EDS analysis, as described in Example 3(f).

[0126] Figure 54 shows thermogravimetric analysis results in (A) for MOF 16, in (B) for MOF 17, in (C) for MOF 18, and in (D) for MOF 19, as described in Example 4(b).

[0127] Figure 55 shows in (A) a nitrogen adsorption / desorption isotherm, in (B) a plot of the pore volume distribution versus pore width, in (C) a plot of the specific surface area versus pore width, and in (D) a plot of the total pore volume versus pore width obtained for MOFs 16 (■), 17 (A), 18 (•) and 19 (★), as described in Example 4(c).

[0128] Figure 56 shows SEM images for MOF 16, as described in Example 4(d). Figure 57 shows SEM images for MOF 17, as described in Example 4(d).

[0129] Figure 58 shows SEM images for MOF 18, as described in Example 4(d).

[0130] Figure 59 shows SEM images for MOF 19, as described in Example 4(d).

[0131] Figure 60 shows in (A) an SEM image obtained for MOF 16, and in (B) graphs presenting the results of the EDS analysis obtained for the areas delineated in (A), as described in Example 4(e).

[0132] Figure 61 shows in (A) an image obtained by SEM for MOF 17, and in (B) to (E) EDS mapping images of C, Ag, O and Zn respectively, as described in Example 4(e).

[0133] Figure 62 shows in (A) an image obtained by SEM for MOF 18, and in (B) to (E) EDS mapping images of C, O, Ag and Zn respectively, as described in Example 4(e).

[0134] Figure 63 shows thermogravimetric analysis results in (A) for MOF 20, and in (B) for MOF 21, as described in Example 5(b).

[0135] Figure 64 shows SEM images for MOF 20, as described in Example 5(c).

[0136] Figure 65 shows SEM images for MOF 21 before and after calcination at a temperature of about 750°C, as described in Example 5(c).

[0137] Figure 66 shows SEM images for MOF 22 before and after calcination at a temperature of about 1000°C, as described in Example 5(c).

[0138] Figure 67 shows in (A) an image obtained by SEM for MOF 21 before calcination, and in (B) to (E) EDS mapping images of O, Mg, C and Zn respectively, as described in Example 5(d). Figure 68 shows in (A) an image obtained by SEM for MOF 21 after calcination at a temperature of about 750 °C, in (B) to (E) EDS mapping images of Zn, Mg, C and O respectively, and in (F) the results of the corresponding EDS analysis, as described in [Example 5(d).

[0139] Figure 69 shows in (A) an image obtained by SEM for MOF 22 before calcination, and in (B) to (F) EDS mapping images of C, O, Ir, Zn and Mg respectively, as described in [Example 5(d).

[0140] Figure 70 shows in (A) an image obtained by SEM for MOF 22 after calcination at a temperature of about 1000 °C, in (B) to (E) EDS mapping images of C, O, Mg and Zn respectively, and in (F) the results of the corresponding EDS analysis, as described in [Example 5(d).

[0141] Figure 71 shows SEM images for MOF 23, as described in [Example 6(b).

[0142] Figure 72 shows SEM images for MOF 24, as described in [Example 6(b).

[0143] Figure 73 shows in (A) a TEM image for MOF 23, in (B) to (D) EDS mapping images of C, O and Mg respectively, and in (E) the results of the corresponding EDS analysis, as described in [Example 6(c).

[0144] Figure 74 shows in (A) a TEM image for MOF 24, in (B) to (D) EDS mapping images of C, O and Mg respectively, and in (E) the results of the corresponding EDS analysis, as described in [Example 6(c).

[0145] Figure 75 shows SEM images for MOF 25, as described in [Example 7(b).

[0146] Figure 76 shows SEM images for MOF 26, as described in [Example 7(b).

[0147] Figure 77 shows SEM images for MOF 27, as described in [Example 7(b). Figure 78 shows SEM images for MOF 28, as described in Example 7(b).

[0148] Figure 79 shows SEM images for MOF 29, as described in Example 7(b).

[0149] Figure 80 shows SEM images for MOF 30, as described in Example 7(b).

[0150] Figure 81 shows in (A) an image obtained by SEM for MOF 25, and in (B) to (D) EDS mapping images of C, O and Sb respectively, as described in Example 7(c).

[0151] Figure 82 shows in (A) an image obtained by SEM for MOF 26, and in (B) to (E) EDS mapping images of C, O, Zn and Sb respectively, as described in Example 7(c).

[0152] Figure 83 shows in (A) an image obtained by SEM for MOF 27, and in (B) to (E) EDS mapping images of C, O, Zn and Sb respectively, as described in Example 7(c).

[0153] Figure 84 shows in (A) an image obtained by SEM for MOF 28, and in (B) to (E) EDS mapping images of C, O, Zn and Sb respectively, as described in Example 7(c).

[0154] Figure 85 shows in (A) an image obtained by SEM for MOF 29, and in (B) to (E) EDS mapping images of C, O, Sb and Zn respectively, as described in Example 7(c).

[0155] Figure 86 shows in (A) an image obtained by SEM for MOF 30, and in (B) to (E) EDS mapping images of C, O, Sb and Zn respectively, as described in Example 7(c).

[0156] Figure 87 shows SEM images for MOF 31, as described in Example 8(b).

[0157] Figure 88 shows SEM images for MOF 32 before calcination, as described in Example 8(b). Figure 89 shows an SEM image for MOF 32 after calcination at a temperature of about 1000°C, as described in Example 8(b).

[0158] Figure 90 shows in (A) an image obtained by SEM for MOF 31, and in (B) to (E) EDS mapping images of Ag, Zn, N and O respectively, as described in Example 8(c).

[0159] Figure 91 shows in (A) an image obtained by SEM for MOF 32 before calcination, and in (B) to (E) EDS mapping images of Zn, Ag, N and O respectively, as described in Example 8(c).

[0160] Figure 92 shows in (A) an SEM image obtained for MOF 32 after calcination at a temperature of about 1000 °C as well as an EDS mapping of C (red) and Ag (green), and in (B) and (C) EDS mapping images of Ag and C respectively obtained for the areas delimited in (A), as described in Example 8(c).

[0161] Figure 93 shows the results of the EDS analysis for MOF 32 after calcination at a temperature of about 1000 °C obtained in (A) for the sum of the spectra, in (B) for Spectrum 14, and in (C) for Spectrum 15), as described in Example 8(c).

[0162] Figure 94 shows a graph of capacity versus number of cycles obtained at charge and discharge currents of C / 6, C / 4, C / 3, C / 2 and 1 C for Cells 8 (A ) and 9 (▼) and References 3 (■) and 4 (•), as described in Example 9(c).

[0163] Figure 95 shows SEM images for Layer 1, as described in Example 10(b).

[0164] Figure 96 shows an image obtained by SEM for Layer 2, as described in Example 10(b).

[0165] Figure 97 shows in (A) an SEM image obtained for Layer 1 as well as an EDS mapping of Zn (blue), Cu (green) and Al (red), and in (B) and (C) EDS mapping images of Cu and Zn respectively obtained for the area delimited in (A), as described in Example 10(c).

[0166] Figure 98 shows in (A) an SEM image obtained for Layer 2, in (B) an SEM image as well as an EDS map of Cu (pink), Al (blue), O (green) and C (red) obtained for Layer 2, and in (C) and (D) respectively EDS map images of Cu and C obtained for the area delimited in (A) and (B), as described in Example 10(c).

[0167] Figure 99 shows in (A) an SEM image obtained for Layer 2 as well as an EDS mapping of O (green) and C (red), and in (B) and (C) EDS mapping images of C and O respectively obtained for the area delimited in (A), as described in Example 10(c).

[0168] Figure 100 shows a graph of capacity versus number of cycles obtained at charge and discharge currents of C / 6, C / 4, C / 3, C / 2 and 1 C for Cells 10 (■), 11 (•), 12 (A) and 13 (▼) and References 5 (★) and 6 (•), as described in Example 10(d).

[0169] Figure 101 shows a graph of Coulombic efficiency versus cycle number obtained for Cells 10 (■), 11 (•), 12 (A ) and 13 (▼) and References 5 (★) and 6 (•), as described in Example 10(d).

[0170] DETAILED DESCRIPTION

[0171] All technical and scientific terms and expressions used herein have the same definitions as those generally understood by those skilled in the art of the present technology. Definitions of certain terms and expressions used are nevertheless provided below.

[0172] When the term "about" is used here, it means approximately, in the region of, or around. For example, when the term "about" is used in connection with a numerical value, it modifies it above and below by a variation of 10% from its nominal value. This term may also take into account, for example, the experimental error of a measuring device or rounding.

[0173] When a range of values ​​is referred to in this application, the lower and upper bounds of the range are, unless otherwise indicated, always included in the definition. When a range of values ​​is referred to in this application, then all intermediate ranges and subranges, as well as individual values ​​included in the ranges of values, are included in the definition. When the article "a" is used to introduce an element in this application, it does not have the meaning of "a single one," but rather of "one or more." Of course, where the description states that a particular step, component, element, or feature "may" or "could" be included, that particular step, component, element, or feature is not required to be included in every embodiment.

[0174] The term "self-supporting electrode" as used herein refers to an electrode without a metallic current collector.

[0175] The chemical structures described here are drawn according to the conventions of the field. Also, when an atom, such as a carbon atom, as drawn appears to include an incomplete valence, then the valence is assumed to be satisfied by one or more hydrogen atoms even if they are not explicitly drawn.

[0176] The term "aromatic" refers to an aromatic moiety having 4n+2 conjugated Tr(pi) electrons in which n is a number from 1 to 3, in a monocyclic group, or a fused bicyclic or tricyclic system having a total of 6 to 15 ring members, in which at least one of the rings in a system is aromatic.

[0177] The present technology relates to the formation of a layer of coating material on an electrode material comprising an electrochemically active material. This coating material comprises a metal organic framework (MOF) forming a network of at least one lithiophilic metal and at least one organic ligand. The metal organic framework of the coating is calcined, preferably before its application to the electrode film. The electrode is preferably a negative electrode.

[0178] The present technology therefore relates to an electrode material comprising an electrochemically active material and a coating layer comprising a coating material based on a lithiophilic calcined metal-organic framework comprising at least one lithiophilic metal and at least one at least partly calcined organic ligand, said coating layer resting on a surface of said electrochemically active material. The electrochemically active material may comprise an alkali metal, an alkaline earth metal, a non-alkaline and non-alkaline earth metal or an alloy comprising at least one of these, for example, in the form of a metal film. Preferably, the electrochemically active material comprises an alkali metal, an alkaline earth metal, or an alloy comprising at least one alkali or alkaline earth metal. For example, the electrochemically active material comprises metallic lithium or an alloy including or based on metallic lithium.The electrochemically active material may also include nickel. In one example, the electrochemically active material is a lubricated metal film.

[0179] When the electrochemically active material is in film form, it may have a thickness in the range of about 5 pm to about 75 pm, or about 15 pm to about 70 pm, or about 25 pm to about 65 pm, or about 30 pm to about 60 pm, or about 45 pm to about 55 pm, upper and lower limits inclusive.

[0180] The metal-organic framework comprises a lithiophilic metal. Any known compatible lithiophilic metal is contemplated. Non-limiting examples of lithiophilic metals include Ag, Zn, Sn, Sb, Mg, Al, Ni, Cu, Co, and a combination of two or more thereof. After calcination, the lithiophilic metal may be present in the calcined lithiophilic metal-organic framework, for example, in elemental, metal oxide, metal nitride, and / or metal fluoride form. For example, the form in which the lithiophilic metal is present in the calcined lithiophilic metal-organic framework may vary depending on the gas or gas mixture present in the atmosphere used during calcination of the lithiophilic metal-organic framework.

[0181] The organic ligand before calcination is generally an organic compound comprising at least two functions capable of forming a bond (e.g., ionic, covalent, etc.) with the lithiophilic metal. Each of these functions generally comprises at least one heteroatom (e.g., N, O, S, P, etc.). For example, the organic ligand is an organic ligand comprising a nitrogen function, an organic ligand comprising a carboxylate, or a mixed organic ligand comprising a nitrogen and / or carboxylate function. For example, the ligand comprises at least two, or at least three, or at least four carboxylate groups, preferably linked by an aromatic or polyaromatic group (such as 1,2,4,5-benzenetetracarboxylic acid). Alternatively, the ligand comprises at least one carboxylate group and one nitrogen function linked by or forming part of an aromatic group (such as 1H-benzimidazole-6-carboxylic acid).Any type of compatible organic ligand forming a repeating structure with a lithiophilic metal is contemplated. Non-limiting examples of lithiophilic metal-organic structures (before calcination) include Formulas 1 to 9 or one of their positional isomers:. in which ni and n2, when present, denote the ratio of each unit and are independently chosen numbers in the range 0.1 to 0.9.

[0182] Some of the lithiophilic calcined metal-organic frameworks may also further comprise a metal source, for example, a silver source. In one example, the silver source is a silver salt such as silver chloride (AgCl) or silver nitrate (AgNCh). When a silver salt is included, it may be present in a lithiophilic metal:silver ratio in the range of from about 1:1 to about 5:1, or from about 4:3 to about 4:1, both upper and lower bounds inclusive.

[0183] The coating material may also comprise other elements, such as a preferably crosslinked solid electrolyte polymer. This may also be composed of a salt in a solvating polymer. The solid polymer electrolyte included in the coating material may then be a copolymer of ethylene oxide and at least one substituted oxirane comprising a crosslinkable function.

[0184] According to one example, the copolymer comprises units based on ethylene oxide and -O-CH2-CHR- units, in which R is a substituent comprising a functional group that can be crosslinked, for example by radical means, and is independently selected from one unit to another. The copolymer may also further comprise -O-CH2-CHR- units, in which R' is a substituent being free of functional groups that can be crosslinked by radical means and is independently selected from one unit to another.

[0185] In some examples, the copolymer has a polymolecularity index (I = M p / M n ) less than or equal to 2.2 in which M n is the number average molecular mass of the copolymer and is greater than or equal to 20,000 and M pis the weight-average molecular mass. For example, the polydispersity index can be determined by size exclusion chromatography (SEC).

[0186] The salt included in the solid polymer electrolyte of the coating material is preferably a lithium salt.Non-limiting examples of lithium salts include lithium hexafluorophosphate (LiPFe), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (UBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (UNO3), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (UCIO4), lithium hexafluoroarsenate (LiAsFe), lithium trifluoromethanesulfonate (USO3CF3) (LiTf), lithium fluoroalkylphosphate Li[PF3(CF2CF3)3] (LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF3)4] (LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O')borate Li[B(CeO2)2] (LiBBB) or a combination of two or more of these.Preferably, the lithium salt comprises LiTFSI.

[0187] The coating layer may have a thickness in the range of about 1 pm to about 20 pm, or about 1 pm to about 19 pm, or about 1 pm to about 18 pm, or about 1 pm to about 17 pm, or about 1 pm to about 16 pm, or about 1 pm to about 15 pm, or about 1 pm to about 14 pm, or about 1 pm to about 13 pm, or about 2 pm to about 12 pm, upper and lower limits inclusive, preferably in the range of about 2 pm to about 12 pm, upper and lower limits inclusive.

[0188] In another example, the coating layer is a first coating layer and the electrode material comprises a second layer of coating material, for example, the second coating layer may have a thickness in the range of about 1 pm to about 20 pm, or about 1 pm to about 19 pm, or about 1 pm to about 18 pm, or about 1 pm to about 17 pm, or about 1 pm to about 16 pm, or about 1 pm to about 15 pm, or about 1 pm to about 14 pm, or about 2 pm to about 14 pm, upper and lower limits inclusive, preferably in the range of about 2 pm to about 14 pm, upper and lower limits inclusive. Preferably, the second coating layer comprises a polymer, such as a solid, non-crosslinked electrolyte polymer.

[0189] The electrode material as defined herein is generally prepared by a method comprising a step of depositing the coating layer based on lithiophilic calcined organometallic frameworks on the surface of the electrochemically active material. According to certain examples, the method further comprises a step of depositing the second coating layer. The deposition step (or steps) may be carried out by at least one of a doctor blade coating method, a comma coating method, a reverse comma coating method, a printing method such as gravure coating, a slot-die coating method, or a spray deposition method.Preferably, the deposition step(s) is(are) carried out by a spray deposition method.

[0190] The method may also further comprise preparing the coating material based on lithiophilic calcined metal-organic frameworks, for example, comprising preparing the lithiophilic calcined metal-organic frameworks. For example, preparing the lithiophilic calcined metal-organic frameworks comprises a step of contacting at least one organic ligand with at least one lithiophilic metal precursor to obtain a lithiophilic metal-organic framework, and a step of calcining the lithiophilic metal-organic framework to obtain the calcined lithiophilic metal-organic framework. For example, the calcining step is carried out at a temperature in the range of about 500°C to about 1050°C, upper and lower limits inclusive, preferably in the range of about 550°C to about 1000°C, upper and lower limits inclusive.The calcination step may be carried out under an inert atmosphere comprising, for example, a gas selected from argon, nitrogen, helium, a fluorinated gas and a mixture comprising at least one of these. Preferably, the gas of the inert atmosphere comprises argon.

[0191] The present electrode material is used in the manufacture of electrodes, for example, negative electrode. For example, a negative electrode as contemplated herein comprises the electrode material as defined herein or the electrode material obtained according to the method defined above, with or without a current collector (self-supporting).

[0192] An electrochemical cell comprising the present electrode material or the above negative electrode is also contemplated. This electrochemical cell comprises, for example, a negative electrode, a positive electrode and an electrolyte, wherein the negative electrode is as defined above or comprises an electrode material as defined herein.

[0193] The positive electrode comprises an electrochemically active material. Examples of electrochemically active materials of the positive electrode include a metal oxide, a metal sulfide, a metal oxysulfide, a metal phosphate, a metal fluorophosphate, a metal oxyfluorophosphate, a metal sulfate, a metal halide, a metal fluoride, sulfur, selenium, and a combination of at least two thereof when compatible. For example, the metal of the electrochemically active material is selected from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb), and a combination of at least two thereof. The metal may further comprise an alkali or alkaline earth metal selected from lithium (Li), sodium (Na), potassium (K) and magnesium (Mg).In one example, the electrochemically active material of the positive electrode is a lithium metal phosphate, such as LiFePCL.

[0194] The electrolyte of the electrochemical cell is preferably a solid electrolyte, for example, a solid polymer electrolyte comprising a salt in a solvating polymer which may be as defined for the coating material.

[0195] This document also relates to electrochemical accumulators or batteries comprising at least one electrochemical cell as defined herein. For example, the battery is selected from the group consisting of a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a potassium battery, a potassium-ion battery, a magnesium battery, and a magnesium-ion battery, preferably a lithium or lithium-ion battery.

[0196] The present technology also includes the use of the present electrochemical accumulators or batteries, among others, in portable devices (such as mobile phones, cameras, tablets or laptops), in electric or hybrid vehicles, or in the storage of renewable energy.

[0197] EXAMPLES

[0198] The following examples are for illustrative purposes and should not be construed as further limiting the scope of the invention as contemplated. These examples will be better understood by reference to the accompanying Figures.

[0199] Example 1 - Preparation and characterization of lithiophilic MOFs based on metal cations bound to aromatic polycarboxylate ligands a) Preparation of lithiophilic MOFs

[0200] Lithiophile MOFs based on metal cations (M = Cu 2+ , Neither 2+ , Zn 2+ or Co 2+) were prepared from 1,2,4,5-benzenetetracarboxylic acid (FLbtec) and at least one metal salt or metal compound (e.g., copper(ll) acetate (Cu(OAc)2), nickel(ll) carbonate (NiCOs), zinc oxide (ZnO), or cobalt(ll) carbonate (CoCOs)). The MOFs prepared in this example are shown in Table 1.

[0201] Table 1. Formulas of the MOFs prepared in this example b) Characterization of lithiophilic MOFs by thermogravimetric analysis (TGA)

[0202] The MOFs prepared in Example 1(a) were characterized by thermogravimetric analysis to evaluate their thermal stability and conversion process. The thermogravimetric analyses were carried out under a constant air flow rate of 100 mL / min in a temperature range from about 30 °C to about 1000 °C and at a temperature ramp rate of 5 °C / min. The results of the thermogravimetric analyses obtained for MOFs 1 to 5 are shown in Figure 1 and summarized in Table 2.

[0203] Table 2. Summary of thermogravimetric analyses (MOFs 1 to 5) Figure 1 (A) shows a first mass loss at a temperature below 100 °C that can be attributed to the elimination of water, a second mass loss from a temperature of about 150 °C that can be attributed to the decomposition of coordinated water molecules, and a third mass loss that can be attributed to the decomposition of the organic ligand starting at a temperature of about 250 °C.

[0204] Figure 1 (B) shows a first mass loss at a temperature below 150 °C which can be attributed to the elimination of water and a second mass loss which can be attributed to the decomposition of the organic ligand starting at a temperature of about 360 °C.

[0205] Figure 1(C) shows a first mass loss at a temperature below 100 °C which can be attributed to the elimination of water and a second mass loss which can be attributed to the decomposition of the organic ligand starting at a temperature of about 450 °C.

[0206] Figure 1(D) shows a first mass loss at a temperature below 250 °C which can be attributed to the elimination of water and a second mass loss which can be attributed to the decomposition of the organic ligand starting at a temperature of about 350 °C. c) Characterization of lithiophilic MOFs by SEM

[0207] The MOFs prepared in Example 1(a) were imaged using a scanning electron microscope (SEM) equipped with a secondary electron (SE) detector to highlight the topography and morphology and a backscattered electron (BSE) detector for chemical contrast study or only a BSE detector when indicated. All SEM images were obtained at an accelerating voltage of 10.0 kV. The images obtained for MOFs 1 to 5 are shown in Figures 2 to 6 and summarized in Table 3.

[0208] Table 3. Summary of SEM images obtained for MOFs 1 to 5

[0209] It can be observed in Figures 2 and 3 that the particles of MOFs 1 and 2 have a substantially elongated rod-shaped morphology having a diameter ranging from about 2 pm to about 30 pm.

[0210] Figures 4 and 5 show that the particles of MOFs 3 and 4 have a variable morphology and have a diameter in the range from about 20 pm to about 200 pm, upper and lower limits inclusive.

[0211] Figure 6 shows SEM images obtained in (A) with an SE detector and a BSE detector, and in (B) with a BSE detector. It can be observed that the MOF 5 particles have a variable morphology with a diameter ranging from about 20 pm to about 100 pm. d) Characterization of lithiophilic MOFs by EDS

[0212] Elemental analysis or chemical characterization of the MOFs prepared in Example 1(a) was performed using an SEM equipped with an X-ray detector for EDS analysis. Figures 7 to 10 show in (A) SEM images of the elements for MOFs 1 to 4 respectively, and in (B) to (D) the corresponding EDS mapping images. The obtained EDS mapping images are summarized in Table 4

[0213] Table 4. Summary of EDS images obtained for MOFs 1 to 4 The EDS mapping images in Figures 7 to 10 allow us to observe that the composition of the particles of MOFs 1 to 4 is substantially homogeneous at the element level.

[0214] Example 2 - Preparation and characterization of calcined lithiophilic MOFs based on metal cations bound to aromatic polycarboxylate ligands a) Preparation of calcined lithiophilic MOFs

[0215] Calcined MOFs based on metal cations bound to aromatic polycarboxylate ligands were prepared from metal cations (M = Cu 2+ , Neither 2+ , Zn 2+ or Co 2+ ) and 1,2,4,5-benzenetetracarboxylic acid (FLbtec). The MOFs were calcined under an inert argon atmosphere following the following protocol:

[0216] 1. temperature rise from room temperature to 200°C at a temperature rise rate of 1°C / min;

[0217] 2. 1 hour plateau at 200°C;

[0218] 3. temperature rise from 200°C to the calcination temperature at a temperature rise rate of 3°C / min; and

[0219] 4. 2-hour plateau at calcination temperature.

[0220] The calcined MOFs prepared in this example, the calcination temperatures, the theoretical yields after calcination determined by TGA, as well as the yields after calcination are presented in Table 5.

[0221] Table 5. Calcination temperatures, theoretical yields after calcination determined by TGA and yields after calcination for MOFs 6 to 10 b) Characterization of calcined lithiophilic MOFs by ATG

[0222] The calcined MOFs prepared in Example 2(a) were characterized by TGA to evaluate their respective metal content. Thermogravimetric analyses were performed under a constant air flow rate of 100 mL / min and a temperature rise rate of 5 °C / min. The results of the thermogravimetric analyses obtained for MOFs 6 to 10 are shown in Figure 11 and summarized in Table 6.

[0223] Table 6. Summary of thermogravimetric analyses obtained for MOFs 6 to 10

[0224] Figure 11 (A) shows the thermogravimetric curve obtained for MOF 6. The thermogravimetric analysis was carried out in a temperature range from about 30 °C to about 700 °C. It can be observed that the oxidation mechanism of the metal in air does not allow an adequate quantification of it.

[0225] Figure 11 (B) shows the thermogravimetric curve obtained for MOF 7. The thermogravimetric analysis was carried out in a temperature range from about 30 °C to about 900 °C. It can be observed that the oxidation mechanism of the metal in air does not allow an adequate quantification of it.

[0226] Figure 11(C) shows the thermogravimetric curves obtained for MOFs 8 to 10. The thermogravimetric analyses were carried out in a temperature range from about 50 °C to about 800 °C. The mass of metal present in MOFs 8 to 10 was estimated to be about 70 wt%. It can be observed in Figure 11(C) that the carbon of the MOFs calcined at a higher temperature appears graphitic and requires a higher temperature to degrade in air. It is also possible to observe in Figure 11(C) the absence of a mass gain which can be attributed either, for example, by the presence of ZnO particles or by the presence of a ZnO layer on the surface of Zn particles. c) Characterization of the calcined lithiophilic MOFs by Raman microspectroscopy

[0227] The analysis of the molecular composition of the calcined MOFs prepared in Example 2(a) was carried out by Raman microspectroscopy.

[0228] Figure 12 shows Raman spectra obtained for MOFs that were calcined at a temperature of 750 °C (MOFs 6, 7 and 10). It is possible to observe a substantially graphitic carbon for the calcined Ni-based MOF 2+ (MOF 7). Calcined Cu-based MOFs 2+ and Zn 2+ (MOFs 6 and 10) appear to produce a carbon of a similar nature and substantially disordered.

[0229] Figure 13 shows Raman spectra obtained for Zn-based MOFs 2+calcined at a temperature of 550 °C and 650 °C (MOFs 8 and 9). Figure 13 shows in (A) an intensity ratio of the D band to the G band (ID / IG) for MOF 8 of 0.95 and for MOF 9 of 0.87. The carbon produced by the calcination of these two MOFS would therefore be substantially amorphous. A comparison between the Raman spectrum presented in Figure 13 (B) with those of other Raman spectroscopy work carried out on ZnO (Song, Yin, et al. "Raman spectra and microstructure of zinc oxide irradiated with swift heavy ion." Crystals 9.8 (2019): 395) highlights the presence of ZnO in the analyzed samples. d) Characterization of the surface of calcined lithiophilic MOFs by the Brunauer, Emmett and Teller (BET) method

[0230] The pore size, specific surface area and pore volume of the calcined MOFs prepared in Example 2(a) were characterized.

[0231] Nitrogen adsorption / desorption isotherms (graph of the volume of nitrogen adsorbed (cm 3 / g) as a function of the relative nitrogen pressure P / P o ) were obtained for each of the MOFs prepared in Example 2(a). The pore size (nm), pore volume distribution (dV / dw) (cm 3 / g.nm), the specific surface area (m 2 / g) and the total pore volume (cm 3 / g) were extracted from these isotherms. Pore size determination was performed by the Broekhoff and de Boer (BdB) method. Pore volume distribution was determined by the Barett, Joyner and Halenda (BJH) method. Specific surface area and pore volume were calculated using the BET method. Figures 14 and 15 show (A) a nitrogen adsorption / desorption isotherm, (B) a plot of pore volume distribution versus pore width, (C) a plot of specific surface area versus pore width, and (D) a plot of total pore volume versus pore width obtained for MOFs 6 and 7, respectively.

[0232] Figure 16 shows in (A) a nitrogen adsorption / desorption isotherm, in (B) a plot of the pore volume distribution versus pore width, in (C) a plot of the specific surface area versus pore width, and in (D) a plot of the total pore volume versus pore width obtained for MOF 8 (♦), MOF 9 (★) and MOF 10 (■).

[0233] It is possible to observe the presence of a hysteresis loop characteristic of mesoporous materials on the nitrogen adsorption / desorption isotherm of each of the calcined MOFs (MOFs 6 to 10).

[0234] Furthermore, it is also possible to conclude that a substantial part of the specific surface area and porosity of each of the calcined MOFs (MOFs 6 to 10) originates from mesopores and not from micropores. e) Characterization of the surface area of ​​calcined lithiophilic MOFs by TEM and EDS

[0235] The calcined MOFs prepared in Example 2(a) were characterized by TEM and EDS.

[0236] Figures 17 to 38 present TEM images, EDS mapping images and the EDS analysis results obtained for MOFs 6 to 10. The experimental conditions used during the TEM and MET-EDS analyses performed for MOFs 6 to 10 are presented in Table 7.

[0237] Table 7. Experimental conditions used during MET and MET-EDS analyses performed for MOFs 6 to 10

[0238]

[0239]

[0240] Analysis of MET and MET-EDS images obtained for MOF 6

[0241] Figure 17 shows nanoscale metal particles substantially dispersed inside and on the surface of the carbon. The arrows in Figures 17(B) and 17(C) each point to a copper particle. Figure 18(E) shows the EDS analysis results obtained for the area outlined in the EDS mapping image shown in Figure 18(D). Figure 18(E) shows the presence of copper and its approximate relative abundance in MOF 6.

[0242] Figure 20(F) shows the EDS analysis results obtained for the area outlined in the EDS mapping images presented in Figures 18(D) and (E). Figures 21 and 22 show that the carbon is substantially amorphous and substantially disordered. This is consistent with the Raman microspectroscopy analysis presented in Example 2(c). Analysis of the TEM and TEM-EDS images obtained for MOF 7

[0243] Figures 23(E) and (F) respectively present a plot of intensity (counts / second) versus energy in (keV) and a plot of electron count versus energy in (eV) obtained for the area outlined in the EDS mapping image shown in Figure 23(D). Figures 23(E) and (F) show the presence of copper and nickel and their approximate relative abundance.

[0244] Figure 24 shows TEM images of MOF 7 in which nanoscale metal particles can be observed substantially dispersed in the carbon matrix. The lines in Figure 24 each indicate a nickel particle.

[0245] Figure 25 shows two TEM images of MOF 7 in which a substantially more graphitic carbon can be observed. This is consistent with the Raman microspectroscopy analysis presented in Example 2(c). Carbon planes can also be observed in this figure.

[0246] Analysis of MET and MET-EDS images obtained for MOF 10

[0247] Figure 26 shows in (A) and (B) TEM images of MOF 10, and in (C) the results of the corresponding EDS analysis. The two arrows in Figure 26(B) each point to a zinc particle. Figure 26 shows that MOF 10 is substantially heterogeneous, comprising, in some places, only a few nanometric metal particles.

[0248] Figure 28(C) is a graph showing the EDS analysis results obtained for the area delineated on the EDS mapping image shown in Figure 28(B).

[0249] Figures 27 and 28 show the presence of agglomerates comprising zinc on the surface and in the carbon matrix. These agglomerates form at a substantially high temperature. Part of the porosity could therefore be attributed to a loss of zinc. Indeed, a specific surface area of ​​560 m 2 / g for MOF 10 was obtained by BET.

[0250] Analysis of MET and MET-EDS images obtained for MOF 9

[0251] Figure 29(F) shows the EDS analysis results obtained for the two areas delineated in the images presented in Figures 29(A) to (E). The images in Figure 29 show the presence of irregularly shaped elongated particles. It is also possible to observe the presence of silicon in the carbon-rich areas.

[0252] Figure 30 shows in (H) the results of the EDS analysis obtained for the two areas delimited on the images presented in Figures 30(C) to (G).

[0253] Figure 31 shows in (A) and (B) TEM images of MOF 9, in (C) to (F) the corresponding EDS analysis results obtained for the two areas indicated by arrows in (B). Figures 31(C) and (D) respectively present an intensity versus energy plot and an electron count versus energy plot obtained for the Sp75 area indicated in (B). Figures 31(E) and (F) respectively present an intensity versus energy plot and an electron count versus energy plot obtained for the Sp72 area indicated in (B). It can be observed that the elongated rod-shaped particle is rich in Zn while the irregularly shaped particles are Zn-free.

[0254] Figure 32 shows in (A) to (F) TEM images of MOF 9. Figure 32

[0255] (A) shows more precisely an image of an irregularly shaped particle and Figures 32(B) to (F) show images of the elongated rod-shaped particle framed in

[0256] (B). It can be observed that the irregularly shaped particle has amorphous carbon while the elongated rod-shaped particles rich in Zn have crystalline planes.

[0257] Analysis of MET and MET-EDS images obtained for MOF 8

[0258] Figure 33 shows elongated rod-shaped particles having a width in the range of about 100 nm to about 200 nm and a length of about 1 pm.

[0259] Figure 34 shows in (E) the results of the EDS analysis obtained for the area delineated in the images presented in Figures 34(A) to (D).

[0260] Figure 35 shows in (G) the EDS analysis results obtained for the area delineated in the images presented in Figures 35(C) to (F). Figure 35 the substantial presence of Zn in the composition of the elongated rod-shaped particles. Figure 36 shows irregularly shaped particles comprising a substantial number of nanoscale Zn particles. Figure 36 shows in (D) the EDS analysis results obtained for the two areas indicated by arrows in the corresponding TEM image.

[0261] Figure 37 shows in (E) and (F) the EDS analysis results obtained for zones 1 (elongated rod-shaped particle) and 2 (irregularly shaped particle) delineated in the images shown in Figures 37(A) to (D), respectively. Figure 37(E) confirms that the elongated rod-shaped particles are substantially rich in Zn and Figure 37(F) confirms that the irregularly shaped particles are substantially amorphous and less rich in Zn.

[0262] Figure 38 shows the presence of Zn nanoparticles with a length ranging from about 2 nm to about 5 nm in the carbon matrix. f) Effect of milling on calcined lithiophilic MOFs

[0263] The effect of grinding was also characterized using an SEM equipped with an SE detector as well as by EDS.

[0264] Figure 39 shows SEM images obtained for MOF 8 in (A) before milling, in (B) after approximately 5 minutes of milling (SPEX ball mill MC ), and in (C) after two times about 5 minutes of grinding. Scale bars represent 10 pm.

[0265] Figure 40 shows in (A) an SEM image of MOF 8 particles after two times of about 5 min of milling, and the mapping images of C and Zn elements are shown in (B) and (C), respectively. Scale bars represent 5 pm.

[0266] Example 3 - Preparation and characterization of calcined bimetallic lithiophilic MOFs based on Zn and Ou a) Preparation of calcined bimetallic lithiophilic MOFs based on Zn and Ou

[0267] Calcined bimetallic lithiophilic MOFs were prepared with different proportions of copper and zinc (Ou:Zn ratio) according to Equation 1:

[0268] Equation 1

[0269] The prepared MOFs were then purified by filtration and dried under vacuum for approximately 18 hours at room temperature. The MOFs were calcined under an inert argon atmosphere using the following protocol:

[0270] 1. temperature rise from room temperature to 200°C at a temperature rise rate of 1°C / min;

[0271] 2. 1 hour plateau at 200°C; 3. temperature rise from 200°C to 750°C at a temperature rise rate of 3°C / min; and

[0272] 4. 2-hour plateau at 750°C.

[0273] The structure, Cu:Zn ratio and theoretical yield after calcination determined by TGA of the calcined MOFs prepared in the present example are presented in Table 8. Table 8. Structure, Cu:Zn ratio and theoretical yield after calcination determined by TGA of MOFs 11 to 15

[0274]

[0275] The MOFs prepared in Example 3(a) were characterized by TGA to evaluate their thermal stability and conversion process. Thermogravimetric analyses were performed under a constant air flow rate of 100 mL / min in a temperature range from about 30 °C to about 1000 °C and at a temperature ramp rate of 5 °C / min. The results of the thermogravimetric analyses obtained for MOFs 11 to 15 are shown in Figure 41 and summarized in Table 9.

[0276] Table 9. Summary of thermogravimetric analyses obtained for MOFs 11 to 15 Figure 41 shows two mass losses that can be attributed to the copper-ligand moiety and the zinc-ligand moiety, respectively. It can be observed that the percentage of mass loss seems substantially consistent with the Cu:Zn ratios. c) Characterization of bimetallic calcined lithiophilic MOFs by SEM The MOFs prepared in Example 3(a) were imaged using an SEM equipped with an SE detector. The images obtained for MOFs 11 to 15 are presented in Figures 42 to 46 and summarized in Table 10.

[0277] Table 10. Summary of SEM images obtained for MOFs 11 to 15 d) Characterization of bimetallic calcined lithiophilic MOFs by EDS The elemental analysis or chemical characterization of the MOFs prepared in Example 3(a) was carried out using an SEM equipped with an X-ray detector for EDS analysis. Figures 47 to 51 show in (A) SEM images obtained for MOFs 11 and 13 to 15, and in (B) to (E) the corresponding EDS mapping images. The experimental conditions used during the EDS analyses carried out for MOFs 11 and 13 to 15 are presented in Table 11. Table 11. Experimental conditions used during the EDS analyses carried out for

[0278] MOFs 11 and 13 to 15

[0279] Figures 46 and 51 show that MOF sample 15 comprises substantially large Zn-rich particles and substantially smaller elongated needle-like Cu-rich particles. e) Characterization of calcined bimetallic lithiophilic MOFs by TGA (in air)

[0280] The calcined MOFs prepared in Example 3(a) were characterized by TGA to evaluate their respective metal content. Thermogravimetric analyses were performed under a constant air flow rate of 100 mL / min and a temperature rise rate of 5 °C / min. The results of the thermogravimetric analyses obtained for MOFs 11 to 13 are shown in Figure 52 and summarized in Table 12.

[0281] Table 12. Summary of thermogravimetric analyses obtained for MOFs 11 to

[0282] 13 | Figure 52(C) (dashed line) | | 750 |

[0283] Figure 52 (B) shows that the mass loss for MOF 12 calcined at a temperature of about 910 °C is slightly higher than for MOF 12 calcined at a temperature of about 750 °C. This could be explained by the presence of more carbon, and therefore, a small amount of Zn could probably have been lost. Figure 52 (B) also shows a substantially large mass loss for MOF 12 calcined at a temperature of about 1000 °C as well as a copper oxidation phenomenon at a temperature of about 200 °C to about 400 °C, which shows that there is no more zinc or very little zinc. f) Characterization of calcined and milled bimetallic lithophile MOFs by SEM and EDS

[0284] Figure 53 shows in (A) and (B) SEM images of a MOF similar to MOF 12, but having been calcined at a temperature of about 1000 °C instead of at a temperature of about 750 °C and having been milled three times for about 5 minutes with a SPEX ball mill MC . Scale bars in (A) and (B) represent 50.0 pm and 5.00 pm, respectively. Figure 53 shows spherical nanoscale particles substantially well dispersed in the carbon matrix.

[0285] Figure 53 (C) shows the results of EDS analysis confirming the absence of Zn in the matrix and the presence of carbon and copper.

[0286] Example 4 - Preparation and characterization of calcined bimetallic lithiophilic MOFs based on Zn and Ag a) Preparation of calcined bimetallic lithiophilic MOFs based on Zn and Ag

[0287] Calcined bimetallic lithiophilic MOFs were prepared with different proportions of zinc and silver (Zn:Ag ratio). To this end, Zn-based MOFs were prepared according to Equation 2:

[0288] Equation 2

[0289] The MOFs thus prepared were then purified by filtration and dried under vacuum for approximately 20 hours at a temperature of approximately 160 °C.

[0290] AgNOs was incorporated into Zn-based MOFs by an impregnation method according to Equation 3:

[0291] Equation 3

[0292] An aqueous solution of AgNCh was added to the Zn-based MOF powders. The resulting solutions were stirred for about 2 hours at room temperature. The water was then evaporated, and the Zn- and Ag-based MOFs were dried under vacuum for about 18 hours at room temperature.

[0293] The MOFs were calcined under an inert argon atmosphere following the following protocol:

[0294] 1. temperature rise from room temperature to 200°C at a temperature rise rate of 1°C / min;

[0295] 2. 1 hour plateau at 200°C;

[0296] 3. temperature rise from 200°C to 750°C at a temperature rise rate of 3°C / min; and

[0297] 4. 2-hour plateau at 750°C.

[0298] The structure and Zn:Ag ratio of the calcined bimetallic MOFs prepared in this example are shown in Table 13. b) Characterization of calcined bimetallic lithiophilic MOFs by TGA

[0299] The MOFs prepared in Example 4(a) were characterized by TGA to evaluate their thermal stability and conversion process. Thermogravimetric analyses were performed under a constant air flow rate of 100 mL / min in a temperature range from about 30 °C to about 1000 °C and at a temperature ramp rate of 5 °C / min. The results of the thermogravimetric analyses obtained for MOFs 16 to 19 are shown in Figure 54 and summarized in Table 14.

[0300] Table 14. Summary of thermogravimetric analyses (MOFs 16 to 19)

[0301] Figure 54 shows a mass loss at a temperature below 300 °C that can be attributed to silver. c) Surface characterization of calcined bimetallic lithiophilic MOFs by the BET method

[0302] The pore size, specific surface area and pore volume of the calcined MOFs prepared in Example 4(a) were characterized.

[0303] Nitrogen adsorption / desorption isotherms (graph of adsorbed nitrogen volume versus relative nitrogen pressure P / P o ) were obtained for each of the MOFs prepared in Example 4(a). The pore size, pore volume distribution, specific surface area, and total pore volume were extracted from these isotherms. Pore size determination was performed by the BdB method. The pore volume distribution was determined by the BJH method. The specific surface area and pore volume were calculated using the BET method.

[0304] Figure 55 shows in (A) a nitrogen adsorption / desorption isotherm, in (B) a plot of the pore volume distribution versus pore width, in (C) a plot of the specific surface area versus pore width, and in (D) a plot of the total pore volume versus pore width obtained for MOFs 16 (■), 17 (A), 18 (•) and 19 (★). It can be observed that the more silver salt is incorporated, the more the BET surface area decreases and pores with a width between about 3.5 nm and about 6 nm are filled. A substantial part of the specific surface area comes from mesopores with a width between about 2 nm and about 8 nm. The method of incorporating the silver salt into the mesoporosity therefore seems effective. d) Characterization of calcined bimetallic lithiophilic MOFs by SEM

[0305] The MOFs prepared in Example 4(a) were imaged using an SEM equipped with an SE detector. The images obtained for MOFs 16 to 19 are shown in Figures 56 to 59 and summarized in Table 15. Table 15. Summary of SEM images obtained for MOFs 16 to 19

[0306] Figures 56 to 59 show heterogeneous mixtures comprising particles of various sizes and shapes. e) Characterization of calcined bimetallic lithiophilic MOFs by EDS

[0307] Elemental analysis or chemical characterization of the MOFs prepared in Example 4(a) was performed using an SEM equipped with an X-ray detector for EDS analysis.

[0308] Figure 60 shows in (A) an SEM image obtained for MOF 16, and in (B) graphs presenting the results of the EDS analysis obtained for the areas delimited in (A). The scale bar represents 10 pm.

[0309] Figures 61 and 62 show in (A) SEM images obtained for MOFs 16 to 18, and (B) to (E) the corresponding EDS mapping images. The experimental conditions used during the EDS analyses performed for MOFs 17 and 18 are presented in Table 16. Table 16. Experimental conditions used during the EDS analyses performed for

[0310] MOFs 17 and 18

[0311] Example 5 - Preparation and characterization of Mg-based lithiophilic MOFs and Mg- and Zn-based bimetallic lithiophilic MOFs a) Preparation of Mg-based lithiophilic MOFs and Mg- and Zn-based bimetallic lithiophilic MOFs

[0312] Lithiophile Mg-based MOFs were prepared from magnesium carbonate hydroxide pentahydrate ((MgCOs)4 Mg(OH)2 5H2O) and FLbtec. Two bimetallic Mg-Zn MOFs were prepared from (MgCOs)4 Mg(OH)2 ôFLO, ZnO and FLbtec. The prepared MOFs were then purified by filtration and dried under vacuum for approximately 18 hours at room temperature.

[0313] The MOFs prepared in this example are shown in Table 17.

[0314] Table 17. Structure and Mg:Zn ratio of MOFs 20 to 22

[0315] b) Characterization of Mg-based lithiophilic MO Fs by TGA

[0316] The MOFs prepared in Example 5(a) were characterized by TGA to evaluate their thermal stability and conversion process. Thermogravimetric analyses were carried out under a constant air flow rate of 100 ml / min in a temperature range from about 30 °C to about 1000 °C and at a temperature ramp rate of 5 °C / min. The results of the thermogravimetric analyses obtained for MOFs 20 and 21 are shown in Figure 63 and summarized in Table 18.

[0317] Table 18. Summary of thermogravimetric analyses obtained (MOFs 20 and 21) c) Characterization of Mg-based lithiophilic MOFs by SEM The MOFs prepared in Example 5(a) were imaged using an SEM equipped with an SE detector. The images obtained for MOFs 20 to 22 are shown in Figures 64 to 66 and summarized in Table 19.

[0318] Table 19. Summary of SEM images obtained for MOFs 20 to 22 | (after calcination at 1000 °C) | Figure 66(E) | 200 |

[0319] Figures 65(D) and (E) show SEM images of MOF 21 obtained after calcination at a temperature of about 750 °C. It is possible to observe the appearance of substantially small spheres on the carbon surface after calcination.

[0320] Figures 66(D) and (E) show SEM images of MOF 22 obtained after calcination at a temperature of about 1000 °C. It is possible to observe the appearance of substantially small spheres in the carbon matrix after calcination. d) Characterization of Mg-based lithiophilic MOFs by EDS

[0321] The elemental analysis or chemical characterization of MOFs 21 and 22 prepared in Example 5(a) was carried out using an SEM equipped with an X-ray detector for EDS analysis. Figure 67 shows in (A) an SEM image obtained for MOF 21 before calcination, and in (B) to (E) the corresponding EDS mapping images. Figure 68 shows in (A) an SEM image obtained for MOF 21 after calcination at a temperature of about 750 °C, in (B) to (E) the corresponding EDS mapping images, and in (F) the results of the corresponding EDS analysis. Figure 69 shows in (A) an SEM image obtained for MOF 22 before calcination, and in (B) to (F) the corresponding EDS mapping images. Figure 70 shows in (A) an SEM image obtained for MOF 22 after calcination at a temperature of about 1000 °C, in (B) to (E) the corresponding EDS mapping images, and in (F) the results of the corresponding EDS analysis.The experimental conditions used during the EDS analyses performed for MOFs 21 and 22 are presented in Table 20.

[0322] Table 20. Experimental conditions used during EDS analyses performed for the

[0323] MOFs 21 and 22

[0324] The EDS analysis results obtained for MOF 21 after calcination at a temperature of about 750 °C are shown in Table 21. A significant amount of oxygen (about 17.85 atomic %) can be observed, which is substantially close to the sum of zinc and magnesium (about 16 atomic %). This indicates that metal oxides such as magnesium oxide (MgO) and ZnO are possibly formed. It is also possible to observe from the EDS spectra that the zinc-rich areas are also oxygen-rich.

[0325] Table 21. EDS analysis results obtained for MOF 21 after calcination

[0326] The EDS analysis results obtained for MOF 22 before calcination at a temperature of about 1000 °C are shown in Table 22. The results shown in Table 22 were obtained in the boxed areas on the SEM image in Figure 69(A). It can be observed that the composition varies depending on the particle shape.

[0327] Table 22. EDS analysis results obtained for MOF 22 before calcination

[0328] The EDS analysis results obtained for MOF 22 after calcination at a temperature of about 1000 °C are shown in Table 23. It can be observed that the spheres present in the carbon matrix are rich in oxygen and metals such as zinc and magnesium. Again, this suggests that metal oxides such as MgO and ZnO can be formed.

[0329] Table 23. EDS analysis results obtained for MOF 22 after calcination

[0330] Example 6 - Preparation and characterization of lithiophilic Mg-based MOFs a) Preparation of lithiophilic Mg-based MOFs

[0331] Lithiophile Mg-based MOFs were prepared from magnesium carbonate (MgCOs) or magnesium acetate (Mg(OAc)2) and FLbtec according to Equation 4:

[0332] Equation 4

[0333] The MOFs thus prepared were then purified by filtration and dried under vacuum for approximately 18 hours at room temperature. The MOFs prepared in this example are shown in Table 24.

[0334] Table 24. Structure of MOFs 23 and 24

[0335] It was observed that Mg(OAc)2 appears to be a suitable precursor for the synthesis of Mg-based MOFs. b) Characterization of lithiophilic Mg-based MOFs by SEM The MOFs prepared in Example 6(a) were imaged using an SEM equipped with an SE detector. The images obtained for MOFs 23 and 24 are shown in Figures 71 and 72 and summarized in Table 25. Table 25. Summary of SEM images obtained for MOFs 23 and 24 c) Characterization of Mg-based lithiophilic MOFs by EDS

[0336] The elemental analysis or chemical characterization of the MOFs prepared in Example 6(a) was carried out using an SEM equipped with an X-ray detector for EDS analysis. Figures 73 and 74 show in (A) SEM images obtained for MOFs 23 and 24, respectively, in (B) to (D) the EDS mapping images, and in (E) the results of the corresponding EDS analysis. The experimental conditions used during the EDS analyses carried out for MOFs 23 and 24 are presented in Table 26.

[0337] Table 26. Experimental conditions used during EDS analyses performed for MOFs 23 and 24

[0338] Example 7 - Preparation and characterization of bimetallic lithiophilic MOFs based on Sb and Zn a) Preparation of bimetallic lithiophilic MOFs based on Sb and Zn

[0339] Bimetallic lithiophilic MOFs based on Sb and Zn were prepared from antimony(III) acetate (Sb(OAc)3), ZnO and FLbtec according to Equation 5:

[0340] Equation 5 The MOFs thus prepared were then purified by filtration and dried under vacuum for approximately 18 hours at room temperature.

[0341] The structure and Sb:Zn ratio of the bimetallic MOFs prepared in this example are shown in Table 27. Table 27. Structure and Sb:Zn ratio of MOFs 25 to 30

[0342]

[0343] The MOFs prepared in Example 7(a) were imaged using an SEM equipped with an SE detector. The images obtained for MOFs 25 to 30 are shown in Figures 75 to 80 and summarized in Table 28. Table 28. Summary of SEM images obtained for MOFs 25 to 30 c) Characterization of bimetallic lithiophilic MOFs by EDS

[0344] Elemental analysis or chemical characterization of the MOFs prepared in Example 7(a) was performed using an SEM equipped with an X-ray detector for EDS analysis. Figures 81 to 86 show in (A) SEM images obtained respectively for MOFs 25 to 30, in (B) to (D) or (E) the EDS mapping images. The experimental conditions used during the EDS analyses performed for MOFs 25 to 30 are presented in Table 29.

[0345] Table 29. Experimental conditions used during EDS analyses performed for the

[0346] MOFs 25 to 30 Example 8 - Preparation and characterization of bimetallic lithiophilic MOFs based on Zn and Ag with bifunctional ligands a) Preparation of bimetallic lithiophilic MOFs based on Zn and Ag with bifunctional ligands

[0347] Zn and Ag-based bimetallic lithiophilic MOFs with bifunctional ligands were prepared from a commercial bifunctional ligand according to Equation 7:

[0348] Equation 7

[0349] Zn and Ag-based bimetallic lithiophilic MOFs with bifunctional ligands were also prepared from a synthetic bifunctional ligand according to Equations 8 and 9:

[0350] Equation 9 The structure and Zn:Ag ratio of the bimetallic MOFs prepared in this example are shown in Table 30.

[0351] Table 30. Structure and Zn:Ag ratio of MOFs 31 and 32 b) Characterization of bimetallic lithiophilic MOFs by SEM

[0352] The MOFs prepared in Example 8(a) were imaged using an SEM equipped with an SE detector. The images obtained for MOFs 31 and 32 are shown in Figures 87 to 89 and summarized in Table 31. Table 31. Summary of SEM images obtained for MOFs 31 and 32 c) Characterization of bimetallic lithiophilic MOFs by EDS

[0353] Elemental analysis or chemical characterization of the MOFs prepared in Example 8(a) was performed using an SEM equipped with an X-ray detector for EDS analysis. Figures 90 to 92 show in (A) SEM images obtained for MOFs 31 and 32, respectively, in (B) to (E) the EDS mapping images. The experimental conditions used during the EDS analyses performed for MOFs 31 and 32 are presented in Table 32.

[0354] Table 32. Experimental conditions used during EDS analyses performed for the

[0355] MOFs 31 and 32 The EDS analysis results obtained for MOF 32 after calcination at a temperature of approximately 1000 °C are shown in Figure 93. The results shown in Figure 93 were obtained in the boxed areas on the images shown in Figure 92. Figure 93 shows in (A) the sum of the EDS analysis results, in (B) the EDS analysis results obtained for Spectrum 14, and in (C) the EDS analysis results obtained for Spectrum 15. The EDS analysis results obtained are summarized in Table 33.

[0356] Table 33. EDS analysis results obtained for MOF 32 after calcination at a temperature of approximately 1000 °C The results show that a carbon-rich powder is obtained (about 73 atomic % to about 83 atomic % depending on the observed area) with silver substantially uniformly distributed in the calcined MOF. It is possible to observe the presence of traces of zinc. However, there is substantially no or very little oxygen. It is possible to conclude that the metal is formed mainly in elemental form. Example 9 - Preparation and characterization of electrochemical cells a) Preparation of coating materials based on calcined lithiophilic MOFs

[0357] Coating materials based on calcined lithiophilic MOFs as described in the previous examples were prepared. The coating materials were obtained by mixing the MOFs with a 60 wt% solution of solid polymer electrolyte including LiTFSI in a solvating polymer as described in U.S. Patent No. 6,903,174 B2 (Harvey et al.) (US'174) in a polymer:LiTFSI ratio of (20:1) and 40 wt% tetraethylene glycol dimethyl ether. The composition of the coating materials is shown in Table 34. Table 34. Composition of Coating Materials Based on Calcined Lithiphilic MOFs b) Configurations of electrochemical cells

[0358] The electrochemical properties of the coating materials prepared in Example 9(a) were investigated.

[0359] Electrochemical cells have been assembled with one or two coating layers. The first coating layer is crosslinked and the second layer is non-crosslinked and placed between the first coating layer and the electrolyte. This second coating layer allows for a substantial improvement in the adhesion between the different components of the electrochemical cell, and therefore, an improvement in electrochemical performance.

[0360] The electrochemical cells were assembled with a positive electrode of lithium iron phosphate (LiFePCL, LFP) on carbon-coated aluminum current collectors (Armor MC ). The composition of the electrochemically active positive electrode material is shown in Table 35.

[0361] Table 35. Composition of the electrochemically active material of the positive electrode

[0362] All electrochemical cells were assembled with a self-supporting solid polymer electrolyte as described in US'174 ​​patent comprising 81.8 wt% polymer, 17.8 wt% LiTFSI and 0.4 wt% 2,2-dimethoxy-2-phenylacetophenone (lrgacure MC 651). The electrochemical cells were assembled with lubricated metallic lithium negative electrodes about 50 μm thick on copper current collectors.

[0363] The electrochemical cells were assembled according to the configurations shown in Table 36.

[0364] Table 36. Electrochemical cell configurations

[0365] Cells 2-9 were assembled with a second coating layer including 60% by weight of the polymer as described in US'174 ​​patent and LiTFSI in a polymer:LiTFSI ratio of (20:1) and 40% by weight of tetraethylene glycol dimethyl ether. The polymer of the second layer was not crosslinked.

[0366] The reference electrochemical cells were assembled according to the configurations shown in Table 37.

[0367] Table 37. Configurations of reference electrochemical cells c) Electrochemical behavior

[0368] Electrochemical analyses demonstrated that the second coating layer significantly improves the adhesion between the first coating layer and the electrolyte. The presence of this second coating layer also appears to improve the coulombic efficiency and initial discharge capacity while improving the reproducibility of electrochemical results. An improvement in electrochemical performance for electrochemical cells including thinner first coating layer films was also observed.

[0369] Figure 94 shows a plot of capacity versus cycle number obtained at charge and discharge currents of C / 6, C / 4, C / 3, C / 2 and 1 C for Cells 8 (A ) and 9 (▼) and References 3 (■) and 4 (•). Better reproducibility of electrochemical performance was observed for electrochemical cells including thicker second coating layer films. Figure 94 shows electrochemical performance substantially close to that of the two references, despite a total coating layer thickness of approximately 26 μm.

[0370] Example 10 - Deposition of a layer of spray-calcined lithiophilic MOFs a) Deposition of a layer of spray-calcined lithiophilic MOFs

[0371] A layer of calcined lithiophilic MOFs was spray-deposited onto a lithium foil.

[0372] The calcined lithiophilic MOF was dispersed in tetrahydrofuran (THF) at a concentration of approximately 1.5 mg / mL. 100 mL of the resulting solution was mixed in an ultrasonic bath for approximately 15 minutes. The solution was then inserted into a manual spray coater in an anhydrous chamber. A lithium foil of approximately 8 cm x 15 cm was placed flat and upright on a hard substrate and firmly immobilized. Spraying was performed by applying a dry air pressure of approximately 60 psi from a distance of approximately 30 cm. Two spray passes were made on the surface of the lithium foil from top to bottom. The lithium foil was dried under vacuum at a temperature of approximately 50 °C for one night. The depositions were performed with MOFs 11 and 12 (Zn and Cu-based bimetallic calcined lithiophilic MOFs). b) SEM characterization of calcined lithiophilic MOF layers obtained by spraying

[0373] The calcined lithiophilic MOF layers deposited in Example 10(a) were imaged using an SEM equipped with an SE detector. The images obtained for the two MOF layers 11 and 12 are shown in Figures 95 and 96 and summarized in Table 38.

[0374] Table 38. Summary of SEM images obtained for the spray-calcined lithiophilic MOF layers

[0375] Figure 95 shows SEM images of a section of a lithium foil coated with a layer of calcined lithiophilic MOFs obtained by sputtering (MOF 11 calcined at 750 °C). It is possible to observe a layer of calcined lithiophilic MOFs having a thickness ranging from a few hundred nm to about 1 pm.

[0376] Figure 96 shows an image obtained by SEM of a section of a lithium sheet covered with a layer of calcined lithiophilic MOFs obtained by sputtering (MOF 12 calcined at 1000 °C). It is possible to observe a layer of calcined lithiophilic MOFs having a thickness in the range from about 900 nm to about 1 pm. c) EDS characterization of the layers of calcined lithiophilic MOFs obtained by sputtering

[0377] Elemental analysis or chemical characterization of the calcined lithiophilic MOF layers deposited in Example 10(a) was performed using an SEM equipped with an X-ray detector for EDS analysis.

[0378] Figure 97 shows EDS mapping images obtained for Layer 1. Figure 98 shows in (A) an SEM image obtained for Layer 2, in (B) to (D) the EDS mapping images.

[0379] Figure 99 shows EDS mapping images obtained for Layer 2.

[0380] The experimental conditions used during the EDS analyses carried out on the calcined lithiophilic MOF layers obtained by spraying are presented in Table 39.

[0381] Table 39. Experimental conditions used during EDS analyses performed for the

[0382] Layers 1 and 2

[0383] Figure 97 shows in (A) an SEM image obtained for a layer of calcined lithiophilic MOFs obtained by sputtering (MOF 11 calcined at 750 °C) as well as the EDS mapping of Zn (blue), Cu (green) and Al (red). Figures 97(B) and (C) show respectively the EDS mapping images of Cu and Zn obtained for the area delimited in (A). It is possible to observe the presence of both metals (Cu and Zn) and mainly Cu.

[0384] Figure 98 shows in A an SEM image obtained for a layer of calcined lithiophilic MOFs obtained by sputtering (MOF 12 calcined at 1000 °C), in (B) an SEM image as well as the EDS mapping of Cu (pink), Al (blue), O (green) and C (red), and in (C) and (D) respectively EDS mapping images of Cu and C obtained for the area delimited in (A) and (B). It is possible to observe that the absence of Zn is due to its evaporation at high temperature. Nanoscale Cu spheres can be observed in the layer of calcined lithiophilic MOFs obtained by sputtering and on the lithium side. The presence of these can be attributed to the cryogenic cutting which can entrain the hard metal particles. Figure 99 shows in (A) an SEM image obtained for a layer of calcined lithiophilic MOFs obtained by spraying (MOF 12 calcined at 1000 °C) as well as the EDS mapping of O (green) and C (red).Figures 99 (B) and (C) show the EDS mapping images of C and O obtained for the area delimited in (A), respectively. It is possible to observe the absence of Cu and Zn. This was evaporated in order to create porosity and prevent the formation of copper particles. d) Electrochemical behavior of the calcined lithiophilic MOF layers obtained by sputtering.

[0385] The electrochemical properties of the spray-calcined lithiophilic MOF layers prepared in Example 10(a) were investigated.

[0386] The electrochemical cells were assembled with metallic lithium negative electrodes comprising a layer of calcined lithiophilic MOFs spray-deposited on the surface of a lithium foil prepared in Example 10(a) on copper current collectors. The electrochemical cells were assembled without a coating layer.

[0387] The electrochemical cells were assembled with a positive electrode of LFP on carbon-coated aluminum current collectors (Armor 1710 ). The composition of the positive electrode electrochemically active material is shown in Table 35 in Example 9(b).

[0388] All electrochemical cells were assembled with a self-supporting solid polymer electrolyte as described in US'174 ​​patent comprising 81.8 wt% polymer, 17.8 wt% LiTFSI and 0.4 wt% 2,2-dimethoxy-2-phenylacetophenone (lrgacure MC 651).

[0389] The electrochemical cells were assembled according to the configurations shown in Table 40.

[0390] Table 40. Electrochemical cell configurations

[0391] The reference electrochemical cells were assembled according to the configurations shown in Table 41.

[0392] Table 41. Configurations of reference electrochemical cells

[0393] Figure 100 shows a graph of capacity versus number of cycles obtained at charge and discharge currents of C / 6, C / 4, C / 3, C / 2 and 1 C for Cells 10 (■), 11 (•), 12 (A) and 13 (▼) and References 5 (★) and 6 (•).

[0394] Figure 101 shows a graph of the coulombic efficiency as a function of the number of cycles obtained for Cells 10 (■), 11 (•), 12 (A ) and 13 (▼) and References 5 (★) and 6 (*). It can be observed that the electrochemical performances are very close to the reference cells, especially for Cells 10 and 11.

[0395] Several modifications could be made to any of the embodiments described above without departing from the scope of the present invention as contemplated. The references, patents or scientific literature documents referred to in this application are incorporated herein by reference in their entirety and for all purposes.

Claims

DEMANDS 1. A process for preparing a negative electrode material comprising an electrochemically active material and a coating layer comprising a coating material based on a calcined lithiophilic organometallic structure resting on a surface of said electrochemically active material, the process comprising the following steps: (i) contacting at least one organic ligand with at least one lithiophilic metal precursor in order to obtain a lithiophilic organometallic structure; (ii) calcination of the lithiophilic organometallic structure obtained in (i) to obtain the calcined lithiophilic organometallic structure of the coating material; and (iii) deposition of the coating material on the surface of the electrochemically active material.

2. A method according to claim 1, wherein the lithiphilic metal is selected from Ag, Zn, Sn, Sb, Mg, Al, Ni, Cu, Co and a combination of at least two of these.

3. A method according to claim 1 or 2, wherein the organic ligand is an organic ligand comprising a nitrogen function, an organic ligand comprising a carboxylate, or a mixed organic ligand comprising a nitrogen function and / or a carboxylate.

4. A method according to claim 3, wherein the organic ligand is 1,2,4,5-benzenetetracarboxylic acid or 1 H-benzimidazole-6-carboxylic acid.

5. A method according to any one of claims 1 to 4, wherein the lithiophilic organometallic structure obtained in (i) is of Formula 1:

6. A method according to any one of claims 1 to 4, wherein the lithiophilic organometallic structure obtained in (i) is of Formula 2:

7. A process according to any one of claims 1 to 4, wherein the lithiophilic organometallic structure obtained in (i) is of Formula 3:

8. A process according to any one of claims 1 to 4, wherein the lithiophilic organometallic structure obtained in (i) is of Formula 4:

9. A process according to any one of claims 1 to 4, wherein the lithiophilic organometallic structure obtained in (i) is of Formula 5:

10. A method according to any one of claims 1 to 4, wherein the lithiophilic organometallic structure obtained in (i) is of Formula 6: in which, ni and n2 denote the ratio of each unit and are independently chosen numbers in the range of 0.1 to 0.

9.

11. A method according to any one of claims 1 to 4, wherein the lithiophilic organometallic structure obtained in (i) is of Formula 7: Formula 7 in which, ni and ri2 denote the ratio of each unit and are independently chosen numbers in the range of 0.1 to 0.

9.

12. A method according to any one of claims 1 to 4, wherein the lithiophilic organometallic structure obtained in (i) is of Formula 8: Formula 8, wherein ni and n2 denote the ratio of each unit and are independently chosen numbers in the range of 0.1 to 0.

9.

13. A method according to any one of claims 1 to 4, wherein the lithiophilic organometallic structure obtained in (i) is of Formula 9: Formula 9.

14. A method according to any one of claims 1 to 13, wherein the calcination step is carried out at a temperature of about 500 °C to about 1050 °C.

15. A process according to claim 14, wherein the calcination step is carried out at a temperature of about 550 °C to about 1000 °C.

16. A method according to any one of claims 1 to 15, wherein the calcination step is carried out under an inert atmosphere. A method according to claim 16, wherein the inert atmosphere comprises a gas selected from argon, oxygen, nitrogen, helium, a fluorinated gas, and a mixture comprising at least two of these. A method according to claim 17, wherein the inert atmosphere comprises argon. A method according to any one of claims 1 to 18, wherein the deposition step is carried out by at least one doctor blade coating method, a comma coating method, a reverse-comma coating method, an gravure coating method, a slot-die coating method, or a spray deposition method.A method according to claim 19, wherein the deposition step is carried out by a spray deposition method. A method according to any one of claims 1 to 20, further comprising a step of deposition of a second coating layer. A method according to claim 21, wherein the deposition step of the second coating layer is carried out by at least one doctor blade coating method, a comma coating method, a reverse-comma coating method, an gravure coating method, a slot-die coating method, or a spray deposition method.A method according to claim 22, wherein the step of deposition of the second coating layer is carried out by a spray deposition method.

24. A negative electrode material obtained according to the process as defined in any one of claims 1 to 23.

25. A negative electrode material comprising an electrochemically active material and a coating layer comprising a coating material based on a calcined lithiophilic organometallic structure comprising at least one lithiophilic metal and at least one organic ligand at least partly calcined, said coating layer resting on a surface of said electrochemically active material.

26. Electrode material according to claim 25, wherein the electrochemically active material comprises an alkali metal, an alkaline earth metal, a non-alkaline and non-alkaline earth metal or an alloy comprising at least one of these.

27. Electrode material according to claim 26, wherein the electrochemically active material comprises an alkali metal, an alkaline earth metal, or an alloy comprising at least one alkali or alkaline earth metal.

28. Electrode material according to claim 27, wherein the electrochemically active material comprises metallic lithium or an alloy including or based on metallic lithium.

29. Electrode material according to claim 26, wherein the electrochemically active material comprises nickel.

30. Electrode material according to any one of claims 25 to 29, wherein the electrochemically active material is in the form of a film having a thickness in the range of about 5 pm to about 75 pm, or from about 15 pm to about 70 pm, or from about 25 pm to about 65 pm, or from about 30 pm to about 60 pm, or from about 45 pm to about 55 pm, inclusive of upper and lower terminals.

31. Electrode material according to any one of claims 25 to 30, wherein the lithiophilic metal is selected from Ag, Zn, Sn, Sb, Mg, Al, Ni, Cu, Co and a combination of at least two of these.

32. Electrode material according to any one of claims 25 to 31, wherein the organic ligand is an organic ligand comprising a nitrogen function, an organic ligand comprising a carboxylate, or a mixed organic ligand comprising a nitrogen function and / or a carboxylate.

33. Electrode material according to claim 32, wherein the organic ligand is 1,2,4,5-benzenetetracarboxylic acid or 1H-benzimidazole-6-carboxylic acid.

34. Electrode material according to any one of claims 25 to 33, wherein the lithiophilic organometallic structure before calcination is of Formula 1:

35. Electrode material according to any one of claims 25 to 33, wherein the lithiophilic organometallic structure before calcination is of Formula 2: Formula 2.

36. Electrode material according to any one of claims 25 to 33, wherein the lithiophilic organometallic structure before calcination is of Formula 3: Electrode material according to any one of claims 25 to 33, wherein the lithiophilic organometallic structure before calcination is of Formula 4: Electrode material according to any one of claims 25 to 33, wherein the lithiophilic organometallic structure before calcination is of Formula 5: Electrode material according to any one of claims 25 to 33, wherein the lithiophilic organometallic structure before calcination is of Formula 6: in which ni and ri2 denote the ratio of each unit and are independently chosen numbers in the range of 0.1 to 0.

9. Electrode material according to any one of claims 25 to 33, wherein the lithiophilic organometallic structure before calcination is of Formula 7: in which ni and n2 denote the ratio of each unit and are independently chosen numbers in the range of 0.1 to 0.

9. Electrode material according to any one of claims 25 to 33, wherein the lithiophilic organometallic structure before calcination is of Formula 8: in which, ni and n2 denote the ratio of each unit and are independently chosen numbers in the range of 0.1 to 0.

9.

42. Electrode material according to any one of claims 25 to 33, wherein the lithiophilic organometallic structure before calcination is of Formula 9: Formula 9.

43. Electrode material according to any one of claims 25 to 42, wherein the calcined lithiophilic organometallic structure further comprises a silver source.

44. Electrode material according to claim 43, wherein the silver source is a silver salt.

45. Electrode material according to claim 44, wherein the silver salt is the AgCI or AgNCh.

46. ​​Electrode material according to claim 44 or 45, wherein the salt is present in a lithiophilic metal:silver ratio in the range of about 4:3 to about 4:1, upper and lower terminals inclusive.

47. Electrode material according to any one of claims 25 to 46, wherein the coating material further comprises a solid polymer electrolyte comprising a salt in a solvating polymer.

48. Electrode material according to claim 47, wherein the solid polymer electrolyte is a copolymer of ethylene oxide and at least one substituted oxirane comprising a crosslinkable function.

49. Electrode material according to claim 48, wherein the copolymer comprises ethylene oxide-based units and -O-CH2-CHR units, in which R is a substituent comprising a radically crosslinkable functional group and is independently selected from one unit to another.

50. Electrode material according to claim 49, wherein the copolymer further comprises -O-CH2-CHR' units, in which R' is a substituent being free of radically crosslinkable functional groups and is independently chosen from one unit to another.

51. Electrode material according to any one of claims 48 to 50, wherein the copolymer has a polymolecularity index (I = M p / Mn ) less than or equal to 2.2 in which M n is the number-average molecular mass of the copolymer and is greater than or equal to 20,000 and M p is the average molecular mass by weight.

52. Electrode material according to any one of claims 48 to 51, wherein the copolymer is crosslinked.

53. Electrode material according to any one of claims 47 to 52, wherein the salt is a lithium salt.

54. Electrode material according to claim 53, wherein the lithium salt is selected from the group consisting of lithium hexafluorophosphate (LiPFe), lithium bis(trifluoromethanesulfonyl)imidide (LiTFSI), lithium bis(fluorosulfonyl)imidide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imidide (LiBETI), lithium tetrafluoroborate (LiBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (LiNOs), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (UCIO4), lithium hexafluoroarsenate (LiAsFe), lithium trifluoromethanesulfonate (USO3CF3) (LiTf), lithium fluoroalkylphosphate Li[PF3(CF2CF3)3] (LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF3)4] (LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O')borate Li[B(CeO2)2] (LiBBB) and a combination of at least two of these.

55. Electrode material according to claim 54, wherein the lithium salt is LiTFSI.

56. Electrode material according to any one of claims 25 to 55, wherein the coating layer has a thickness in the range of approximately 1 µm to approximately 20 µm, or approximately 1 µm to approximately 19 µm, or approximately 1 pm to approximately 6 pm, or from approximately 1 pm to approximately 5 pm, or from approximately from 1 pm to approximately 4 pm, or from approximately 1 pm to approximately 3 pm, or from approximately 1 pm to approximately 2 pm, or from approximately 1 pm to approximately 1 pm, or from approximately 2 pm to approximately 12 pm, including upper and lower terminals.

57. Electrode material according to claim 56, wherein the thickness of the coating layer is in the range of about 2 pm to about 12 pm, including upper and lower terminals.

58. Electrode material according to any one of claims 25 to 57, the electrochemically active material is lubricated.

59. Electrode material according to any one of claims 25 to 58, wherein the coating layer is a first coating layer and the electrode material comprises a second coating material layer.

60. Electrode material according to claim 59, wherein the second coating layer has a thickness in the range of approximately 1 µm to approximately 20 µm, or approximately 1 µm to approximately 19 µm, or approximately 1 µm to approximately 18 µm, or approximately 1 µm to approximately 17 µm, or approximately 1 µm to approximately 16 µm, or approximately 1 µm to approximately 15 µm, or approximately 1 µm to approximately 14 m, or ranging from approximately 2 pm to approximately 2 pm, including upper and lower bounds.

61. Electrode material according to claim 60, wherein the thickness of the second coating layer is in the range of about 2 pm to about 14 pm, upper and lower terminals inclusive.

62. Electrode material according to any one of claims 59 to 61, wherein the second coating layer comprises a non-crosslinked polymer.

63. A method for preparing an electrode material as defined in any one of claims 25 to 62, the method comprising a step of deposition of the coating layer based on a calcined lithiophilic organometallic structure onto the surface of the electrochemically active material.

64. Method according to claim 63, further comprising a step of deposition of the second coating layer.

65. A method according to claim 63 or 64, wherein the deposition step is carried out by at least one doctor blade coating method, a comma coating method, a reverse-comma coating method, an gravure coating method, a slot-die coating method, or a spray deposition method.

66. A method according to claim 65, wherein the deposition step is carried out by a spray deposition method.

67. A method according to any one of claims 63 to 66, further comprising the preparation of the coating layer based on a calcined lithiophilic organometallic structure.

68. A method according to claim 67, wherein the preparation of the coating layer based on a calcined lithiophilic organometallic structure further comprises a step of preparing the calcined lithiophilic organometallic structure.

69. A process according to claim 68, wherein the step of preparing the calcined lithiophilic organometallic structure comprises (i) a step of contacting at least one organic ligand with at least one lithiophilic metal precursor in order to obtain a lithiophilic organometallic structure, and (ii) a step of calcining the lithiophilic organometallic structure obtained in (i) to obtain the calcined lithiophilic organometallic structure.

70. Negative electrode comprising the electrode material as defined in any one of claims 24 to 62 or an electrode material obtained according to the process as defined in any one of claims 1 to 23 or 63 to 69 on a current collector.

71. Self-supporting negative electrode comprising the electrode material as defined in any one of claims 24 to 62 or an electrode material obtained according to the process as defined in any one of claims 1 to 23 or 63 to 69.

72. Electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein the negative electrode is as defined in claim 70 or 71 or comprises an electrode material as defined in any one of claims 24 to 62.

73. Electrochemical cell according to claim 72, wherein the positive electrode comprises an electrochemically active material selected from a metal oxide, a metal sulfide, a metal oxysulfide, a metal phosphate, a metal fluorophosphate, a metal oxyfluorophosphate, a metal sulfate, a metal halide, a metal fluoride, sulfur, selenium and a combination of at least two of these.

74. Electrochemical cell according to claim 73, wherein the metal of the electrochemically active material is selected from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), the chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb) and a combination of at least two of these.

75. Electrochemical cell according to claim 73 or 74, wherein the metal of the electrochemically active material further comprises an alkali or alkaline earth metal selected from lithium (Li), sodium (Na), potassium (K) and magnesium (Mg).

76. Electrochemical cell according to any one of claims 73 to 75, wherein the electrochemically active material is a lithium metal phosphate.

77. Electrochemical cell according to claim 76, wherein the lithium metal phosphate is LiFePC 78. Electrochemical cell according to any one of claims 72 to 77, wherein the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer.

79. Electrochemical cell according to any one of claims 72 to 77, wherein the electrolyte is a liquid electrolyte comprising a salt in a solvent.

80. Electrochemical cell according to any one of claims 72 to 77, wherein the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer.

81. Electrochemical cell according to any one of claims 78 to 80, wherein the salt is a lithium salt.

82. Electrochemical cell according to claim 81, wherein the lithium salt is selected from the group consisting of lithium hexafluorophosphate (LiPFe), lithium bis(trifluoromethanesulfonyl)imidide (LiTFSI), lithium bis(fluorosulfonyl)imidide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imidide (LiBETI), lithium tetrafluoroborate (LiBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (LiNCh), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride lithium (LiF), lithium perchlorate (UCIO4), lithium hexafluoroarsenate (LiAsFe), lithium trifluoromethanesulfonate (USO3CF3) (LiTf), lithium fluoroalkylphosphate Li[PF3(CF2CF3)3] (LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF3)4] (LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O')borate Li[B(CeO2)2] (LiBBB) and a combination of at least two of these.

83. Electrochemical cell according to claim 82, wherein the lithium salt is LiTFSI.

84. A battery comprising at least one electrochemical cell as defined in any one of claims 72 to 83.

85. Battery according to claim 84, wherein said battery is selected from the group consisting of a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a potassium battery, a potassium-ion battery, a magnesium battery, and a magnesium-ion battery.

86. Battery according to claim 84 or 85, wherein said battery is a lithium battery.

87. Battery according to claim 84 or 85, wherein said battery is a lithium-ion battery.

Images