EP3861579A1

EP3861579A1 - Electrode materials comprising a lamellar oxide of sodium and of metal, electrodes comprising same and use of same in electrochemistry

Info

Publication number: EP3861579A1
Application number: EP19868747.7A
Authority: EP
Inventors: Yuesheng Wang; Abdelbast Guerfi; Karim Zaghib; Gilles Lajoie; Marie-Josée VIGEANT
Original assignee: Hydro Quebec
Current assignee: Hydro Quebec
Priority date: 2018-10-02
Filing date: 2019-10-02
Publication date: 2021-08-11
Also published as: EP3861579A4; CN112913052A; KR20210062701A; US20220052330A1; CA3112163A1; JP2022503995A; WO2020069618A1

Abstract

The present technology relates to electrode materials comprising an electrochemically active material, wherein the electrochemically active material comprises a lamellar oxide of sodium and of metal of P2 type or of O3 type. The electrochemically active material has the formula Na_xMO₂, where 0.5 ≤ x ≤ 1.0 and M is chosen from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Sb and combinations thereof. Electrodes, electrochemical cells and batteries comprising the electrode materials are also described.

Description

ELECTRODE MATERIALS COMPRISING A LAMELLAR OXIDE OF SODIUM AND METAL, ELECTRODES COMPRISING THEM AND THEIR

USE IN ELECTROCHEMISTRY

RELATED APPLICATION This application claims priority, under applicable law, from U.S. Provisional Patent Application No. 62 / 740,185 filed October 2, 2018, the content of which is incorporated herein by reference in its entirety and for all purposes.

TECHNICAL AREA

The present application relates to the field of electrochemically active materials and their uses in electrochemical applications. More particularly, the present application generally relates to electrode materials comprising a lamellar oxide of sodium and of metal as an electrochemically active material, the electrodes comprising them, their methods of manufacture and their use in electrochemical cells. STATE OF THE ART

The lamellar oxides of lithium and metal of formula L1MO2 (M = transition metal), such as the oxides of lamellar structure such as cobalt and lithium dioxide (LiCoO2) and nickel and lithium dioxide (LiNi02) positive electrode materials used commercially in lithium-ion batteries (BLIs). Lamellar L1MO2 can be classified according to their stacking geometry. The different types of stacks differ in the sequence of the oxygen layers, modifying the arrangement of the sheets (MO2) as well as the geometry of the sites occupied by the lithium ions. The oxygen environment of the lithium ion can be, for example, octahedral (O), prismatic (P) or tetrahedral (T). Lamellar L1MO2 can also be characterized by the number of MO2 sheets found inside a unit cell. The structure of lamellar L1MO2 significantly influences the electrochemical properties of the material such as its capacity, its cyclability, and its charge rate and discharge. Lamellar structures of type P2 and 03 are, for example, of interest for use in electrochemical cells.

One of the main drawbacks of the electrode materials currently used and comprising lamellar oxides as electrochemically active materials is their high production cost. For example, an increase in lithium prices could pose a problem to the growth of the market share occupied by BLIs. Indeed, lithium is used in several components of conventional BLIs, such as in positive and negative electrodes and in electrolytes. Supply problems and the cost of lithium are therefore central to the main factors affecting their expansion in certain commercial applications in the renewable energy field.

Therefore, there is therefore a need for the development of new electrode materials. For example, an electrode material comprising a lamellar oxide of type P2 and / or 03 as an electrochemically active material and excluding one or more of the drawbacks of conventional lamellar oxide materials.

SUMMARY

According to one aspect, the present technology relates to an electrode material comprising an electrochemically active material, the electrochemically active material comprising a lamellar oxide of sodium and metal of formula Na _x M02, in which 0.5 <x <1.0, and M is chosen from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Sb and their combinations.

In one embodiment, the electrochemically active material comprises a lamellar oxide of sodium and of metal chosen from:

a P2 type metal and sodium lamellar oxide of formula Na _x M02, in which x is a number such that 0.5 <x <0.8 and M is chosen from Co, Mn, Fe, Ni, Ti, Cr, V, Cu and combinations thereof; and a lamellar sodium and metal oxide of type 03 of the formula Na _x M02, in which x is a number such that 0.8 <x <1.0, 0 and M is chosen from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Sb and their combinations.

In another embodiment, the electrochemically active material comprises a lamellar oxide of sodium and metal of formula NaxM'i _-y M _y 02, in which x and M are as defined here, y is a number such as 0 <y <1, 0 and M 'is different from M and is chosen from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Sb and their combinations.

In another embodiment, the electrochemically active material comprises a lamellar oxide of sodium and metal of formula Na _x M'i _-y Mn _y 02, in which x is as defined herein and in which y is such that 0 <y <1, 0 and M 'is chosen from Co, Fe, Ni, Ti, Cr, V, Cu, Sb and their combinations.

In another embodiment, the electrode material also comprises an electronic conductive material chosen from carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, nanotubes carbon, and combinations thereof.

In another embodiment, the electrode material further comprises a binder selected from the group consisting of a polymer binder of the polyether type, a fluoropolymer and a water-soluble binder.

According to another aspect, the present technology relates to an electrode comprising the electrode material as defined here on a current collector. In one embodiment, the electrode is a positive electrode.

According to another aspect, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, in which the positive electrode is as defined here. In one embodiment, the negative electrode comprises metallic lithium. Alternatively, the negative electrode includes metallic sodium. In another embodiment, the electrolyte is a liquid electrolyte comprising a salt in a solvent. Alternatively, the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer. According to another alternative, the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer. In one embodiment, the salt is a lithium salt. Alternatively, the salt is a sodium salt.

According to another aspect, the present technology relates to a battery comprising at least one electrochemical cell as defined here. In one embodiment, the battery is chosen from a lithium-ion battery and a sodium-ion battery. BRIEF DESCRIPTION OF THE FIGURES

Figure 1 is an X-ray diffraction diagram for a type P2 lamellar sodium and cobalt oxide powder and of formula Nao, sCo02 obtained using the solid state process.

Figure 2 is an X-ray diffraction diagram for a mixed lamellar oxide powder of sodium and transition metals type 03 and of formula

NaNio, 4Coo, 2Mno, 402 obtained using the solid state process.

Figure 3 shows the charge and discharge profiles of Cell 1, the charge and discharge being performed at 0.1 C, and recorded vs Li / Li ⁺ at a temperature of 25 ° C.

Figure 4 shows the charge and discharge profiles of Cell 1 at different cycling speeds, the charge and discharge being carried out at 0, 1 C, 0.2C, 0.5C, 1 C, 2C and 4C and recorded vs Li / Li ⁺ at a temperature of 25 ° C.

Figure 5 shows a graph representing the capacity (mAh / g) as a function of the number of cycles, that is to say an aging curve for Cell 1. The experiment of long cycling or cycling in stability was carried out at a constant charge / discharge current of 1 C and the results were recorded vs Li / Li ⁺ at a temperature of 25 ° C. Figure 6 shows the charge and discharge profiles of Cell 2. The charge and discharge were carried out at 0.3C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 50 ° C.

Figure 7 shows the charge and discharge profiles of Cell 2. The charge and discharge were carried out at 0.3C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 80 ° C.

Figure 8 shows the charge and discharge profiles of Cell 3. The charge and discharge were carried out at 0.1 C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 25 ° C . Figure 9 presents the charge and discharge profiles of Cell 3 at different cycling speeds, the charges and discharges being carried out at 0, 1 C, 0.2C, 0.5C, 1 C, 2C and 4C and recorded vs Li / Li ⁺ at a temperature of 25 ° C.

Figure 10 shows a graph representing the capacity (mAh / g) as a function of the number of cycles for Cell 3. The long cycling experiment was carried out at a constant charge / discharge current of 2C and the results were recorded. vs Li / Li ⁺ at a temperature of 25 ° C.

Figure 11 shows the initial charge and discharge curves for Cell 4. The charge and discharge were carried out at 0.1 C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 25 ° vs. Figure 12 shows two charge and discharge profiles for Cell 5, i.e. the first cycle and the fifth cycle. Charging and discharging were carried out at 0.3C between 2.0 and 4.0 V vs Li / Li ⁺ at a temperature of 80 ° C.

Figure 13 shows the charge and discharge profiles of Cell 6, the charge and discharge being carried out at 0.1 C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 25 ° C. Figure 14 shows the charge and discharge profiles of Cell 7, the charge and discharge being carried out at 0.1 C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 25 ° C.

Figure 15 shows the charge and discharge profiles of Cell 8, the charge and discharge being carried out at 0.1 C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 25 ° C.

Figure 16 shows the charge and discharge profiles of Cell 9, the charge and discharge being carried out at 0.1 C between 2.0 and 4.5 V vs Li / Li ⁺ at a temperature of 25 ° C. Figure 17 shows the charge and discharge profiles of Cell 10, the charge and discharge being carried out at 0.1 C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 25 ° C.

Figure 18 shows the charge and discharge profiles of Cell 11, the charge and discharge being carried out at 0.1 C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 25 ° C.

Figure 19 shows a graph representing the capacity (mAh / g) as a function of the number of cycles for Cell 11. The long cycling experiment was carried out at a constant charge / discharge current of 0.1 C and the results were recorded vs Li / Li ⁺ at a temperature of 25 ° C. DETAILED DESCRIPTION

The following detailed description and examples are presented for illustrative purposes only and should not be construed as further limiting the scope of the invention.

All technical and scientific terms and expressions used here have the same definitions as those generally understood by the person skilled in the art of this technology. The definition of certain terms and expressions used is nevertheless provided below.

When the term "approximately" or its equivalent term "approximately" is used here, it means in the region of, or around. For example, when the terms "approximately" or "approximately" are used in connection with a numerical value, they modify it above and below by a variation of 10% compared to the nominal value. This term can also take into account, for example, the experimental error of a measuring device or rounding.

When a range of values is mentioned in this application, the lower and upper limits of the range are, unless otherwise indicated, always included in the definition.

The present technology relates to the use of lamellar oxides of sodium and at least one metallic element as electrochemically active materials. Lamellar oxide of sodium and at least one metallic element has a stack of type P2 or type 03.

According to one example, the metallic element is a metal, for example, a transition metal, a post-transition metal, a metalloid, an alkali metal, an alkaline earth metal or combinations thereof. For example, the metal is selected from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Sb and a combination of at least two of these. According to an example, the electrochemically active material comprises a lamellar oxide of sodium and metal of formula Na _x M02, in which x is a number such that 0.5 <x <1.0, 0 and M is chosen from Co, Mn, Fe , Ni, Ti, Cr, V, Cu, Sb and their combinations.

According to another example, the electrochemically active material comprises a lamellar sodium and metal oxide of type P2 of formula Na _x M02, in which x is a number such that 0.5 <x <0.8 and M is chosen from Co , Mn, Fe, Ni, Ti, Cr, V, Cu and their combinations. According to another example, the electrochemically active material comprises a lamellar sodium and metal oxide of type 03 of the formula Na _x M02, in which x is a number such that 0.8 <x <1, 0 and M is chosen from Co , Mn, Fe, Ni, Ti, Cr, V, Cu, Sb and their combinations. According to another example, the electrochemically active material is a lamellar oxide of sodium and of cobalt of formula Na _x CoO2, in which x is as defined here. For example, the lamellar oxide of sodium and cobalt has a P2-type stack. An example of lamellar oxide of sodium and cobalt corresponds to the formula Nao.sCoC.

According to another example, the electrochemically active material is a lamellar oxide of sodium and manganese of formula Na _x MnO2, in which x is as defined here.

An additional example of an electrochemically active material comprises a mixed lamellar oxide of formula Na _x M'i _-y MyO2, in which x and M are as defined here, y is a number such that 0 <y <1, 0 and M 'and is chosen from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Sb and their combinations, where M and M' are different. For example, the electrochemically active material comprises a mixed lamellar oxide of sodium, manganese and metal of formula Na _x M'i _-y MnyO2, in which x and y are as defined here and M 'is chosen from Co, Fe, Ni, Ti, Cr, V, Cu, Sb and their combinations. For example, the electrochemically active material is chosen from mixed lamellar oxides of formulas Na _x (NiCo) i _-y Mn _y 02, Na _x Coi _-y Mn _y 02, Na _x Nii- _y Mn _y 02 and Na _x (CoTi ) i _-y Mni _-y 02, in which x and y are as defined here. Non-limiting examples of electrochemically active materials include Nao, 5Co02, Nao, 67Co02, Nao, 67Coo, 67Mno, 3302, Nao, 67Nio, 33Mno, 6702, Nao, 67Coo, 6Mno, 402, Nao, 67Coo, 55Mno, 4502, Nao , 67Coo, 5Mno, 502, Nao, 67Coo, 5oMno, 33Tio, i702, Nao, 6Mn02,

NaNio, 4Coo, 2Mno, 402 and NaNio, 33Feo, 33Mno, 3302. The electrochemically active material can optionally be doped with other elements or impurities included in smaller quantities, for example to modulate or optimize its electrochemical properties. In certain cases, the electrochemically active material can be doped by the partial substitution of the metal (M) by other ions. For example, the electrochemically active material can be doped with a transition metal (for example Fe, Co, Ni, Mn, Ti, Cr, Cu, V) and / or a metal other than a transition metal (for example, Mg, Al, Sb).

The electrochemically active material as described herein is preferably substantially free from lithium. For example, the electrochemically active material comprises less than 2% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.1% by weight, less than 0.05% by weight or less 0.01% by weight of lithium. The electrochemically active material can therefore potentially reduce production costs compared to the corresponding type P2 or type 03 lithium oxide and metal structures. The electrochemically active material can also maintain the same structure as the corresponding P2 or type 03 lithium oxide and metal structures and have similar electrochemical performance.

The present technology also relates to electrode materials comprising the electrochemically active material as defined here. According to one example, the electrode material as described here can also comprise an electronic conductive material. Nonlimiting examples of electronic conductive material include a carbon source such as carbon black, Ketjen ^MC carbon, Super P ^MC carbon, acetylene black, Shawinigan carbon, Denka ^MC carbon black, graphite , graphene, carbon fibers (eg, carbon fibers formed in the gas phase (VGCFs)), carbon nanofibers, carbon nanotubes, or a combination of at least two of these. According to one example, the electronic conductive material is Ketjen ^MC carbon. According to an alternative, the electronic conductive material is carbon Super P ^MC . According to another alternative, the electronic conductive material is VGCFs.

The electrode material as described herein may also further include a binder. For example, the binder is chosen for its compatibility with the various elements of an electrochemical cell. Any known compatible binder is envisaged. For example, the binder is chosen from a polymer binder of the polyether type, a fluoropolymer and a binder soluble in water (water soluble). According to one example, the binder is a fluoropolymer such as polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE). According to another example, the binder is a water-soluble binder such as styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), hydrogenated NBR (FINBR), epichlorohydrin rubber (CFIR) , or acrylate rubber (ACM), and optionally comprising a thickening agent such as carboxymethylcellulose (CMC), or a polymer such as poly (acrylic acid) (PAA), poly (methyl methacrylate) (PMMA) or a combination of these. According to one example, the binder is a polymeric binder of the polyether type. For example, the polyether polymer binder is linear, branched and / or crosslinked and is based on poly (ethylene oxide) (PEO), poly (propylene oxide) (PPO) or on a combination of the two ( such as an EO / PO copolymer), and optionally comprises crosslinkable units. According to a variant of interest, the binder is PVdF or a polymer of polyether type as defined here.

The electrode material as described here may optionally further comprise additional components or additives such as inorganic particles, glass or ceramic particles, ionic conductors, salts (for example, lithium salts) and other similar additives.

The present technology also relates to an electrode comprising the electrode material as defined here on a current collector (for example, aluminum, copper) alternatively the electrode can be self-supporting. According to a variant of interest, the electrode is a positive electrode.

The present technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, in which the positive electrode is as defined here. According to one example, the electrochemically active material of the negative electrode or counter-electrode can be chosen from all known compatible materials. For example, the electrochemically active material of the negative electrode can be selected for its electrochemical compatibility with the electrochemically material active as defined here. For example, the electrochemically active material of the negative electrode may comprise an alkali metal film, for example, a metallic lithium film, a metallic sodium film or a film of an alloy comprising at least one of these. this. The electrolyte is also chosen for its compatibility with the various elements of the electrochemical cell. Any type of compatible electrolyte is envisaged. According to one example, the electrolyte is a liquid electrolyte comprising a salt in a solvent. According to an alternative, the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer. According to another alternative, the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer.

The salt is preferably an ionic salt such as a lithium salt or a sodium salt. Nonlimiting examples of lithium salts include lithium hexafluorophosphate (LIPF6), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), bis (fluorosulfonyl) lithium imide (LiFSI), 2-trifluoromethyl-4,5 - lithium dicyano-imidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis (pentafluoroethylsulfonyl) imide (LiBETI), lithium tetrafluoroborate (L1BF4), lithium bis (oxalato) borate (LiBOB), lithium nitrate (L1NO3), lithium chloride (LiCI), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (L1CIO4 ), lithium hexafluoroarsenate (LiAsFe), lithium trifluoromethanesulfonate (L1SO3CF3) (LiTf), lithium fluoroalkylphosphate Li [PF3 (CF2CF3) 3] (LiFAP), tetrakis (trifluoroacetoxy) lithium borate Li [B ( OCOCF3) 4] (LiTFAB), bis (1, 2-benzenediolato (2 -) - 0,0 ') lithium borate Li [B (C602) 2] (LBBB) and combinations thereof. According to a first variant of interest, the lithium salt is LiPF6. According to a second variant of interest, the lithium salt is LiFSI. According to a third variant of interest, the lithium salt is LiTFSI. Nonlimiting examples of sodium salts include the salts described above where the lithium ion is replaced by a sodium ion.

The solvent if present in the electrolyte can be a polar and aprotic non-aqueous solvent. Nonlimiting examples of solvents include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), carbonate of butylene (BC) and vinylene carbonate (VC); acyclic carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) and dipropyl carbonate (DPC); lactones such as γ-butyrolactone (g-BL) and g-valerolactone (g-VL); non-cyclic ethers such as 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), ethoxy methoxy ethane (EME), trimethoxymethane, and ethylmonoglyme; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane and dioxolane derivatives; and other solvents such as dimethyl sulfoxide, formamide, acetamide, dimethylformamide, acetonitrile, propylnitrile, nitromethane, phosphoric acid triesters, sulfolane, methylsulfolane, propylene carbonate derivatives, and their mixtures.

An example of an electrolyte includes lithium hexafluorophosphate (LiPFe) dissolved in a mixture of non-aqueous solvents such as a mixture of ethylene carbonate and diethyl carbonate (EC / DEC) ([3: 7] by volume) or a mixture of ethylene carbonate and dimethyl carbonate (EC / DMC) ([4: 6] by volume).

When the electrolyte is a gel electrolyte or a gel polymer electrolyte. The gel polymer electrolyte can comprise, for example, a polymer precursor and a salt (for example, a salt as defined above), a solvent and a polymerization and / or crosslinking initiator, if necessary. Nonlimiting examples of gel electrolyte include, without limitation, the gel electrolytes described in the PCT patent applications published under the numbers WO2009 / 111860 (Zaghib et al.) And WO2004 / 068610 (Zaghib et al.).

The electrolyte can also be a solid polymer electrolyte (SPE) comprising a salt in a solvating polymer. Any type of known compatible SPE is envisaged. For example, the SPE is chosen for its compatibility with the various elements of the electrochemical cell. For example, SPE is selected for its compatibility with lithium and / or sodium. The SPEs can generally comprise a salt as well as one or more solid polar polymer (s), optionally crosslinked. Polyether polymers, such as those based on poly (ethylene oxide) (PEO), can be used, but several other compatible polymers are also known for the preparation of SPE and are also envisaged. According to one example, the polymer can also be crosslinked. Examples of such polymers include branched polymers, for example, star polymers or comb polymers such as those described in the PCT patent application published under the number WO2003 / 063287 (Zaghib et al.).

A gel electrolyte or a liquid electrolyte as defined above can also impregnate a separator such as a polymer separator. Nonlimiting examples of separators include polyethylene (PE), polypropylene (PP), cellulose, polytetrafluoroethylene (PTFE), poly (vinylidene fluoride) (PVdF) and polypropylene-polyethylene-polypropylene (PP / PE) membranes. / PP). For example, the separator is a commercial polymer separator of the Celgard ^MC type.

The electrolyte can also optionally include additional components or additives such as ionic conductors, inorganic particles, glass or ceramic particles; for example, nanoceramics (such as AI2O3, T1O2, S1O2 and other similar compounds) and other similar additives.

The present technology also generally relates to a battery comprising at least one electrochemical cell as defined herein. For example, the battery is chosen from a lithium battery, a lithium-ion battery, a sodium battery and a sodium-ion battery. According to a variant of interest, the battery is a lithium battery or a lithium-ion battery.

EXAMPLES

The examples which follow are by way of illustration and should not be interpreted as further limiting the scope of the invention as envisaged. These examples will be better understood with reference to the appended Figures. Example 1: Synthesis of electrochemically active materials

Lamellar oxides of formulas Nao, sCo02, Nao, 67Co02, Nao, 67Coo, 67Mno, 3302, Nao, 67Nio, 33Mno, 6702, Nao, 67Coo, 6Mno, 402, Nao, 67Coo, 55Mno, 4502, Nao, 67Coo, 5Mno , 502,

Nao, 67Coo, 5oMno, 33Tio, i 7O2, Nao, 6Mn02, NaNio, 4Coo, 2Mno, 402 and NaNio, 3Feo, 33Mno, 3302 were prepared using solid state reaction techniques. The respective precursors (Na2C03 and metal oxides such as Mh2q3, C02O3, NiO, Fe2O3 and T1O2) were weighed in order to obtain the desired stoichiometries. The samples were prepared by grinding and mixing the precursor powders. The ground and mixed powders of precursors were then placed in an oven and heated between 700 ° C and 1000 ° C under an atmosphere of air or oxygen for 5 to 24 hours.

Example 2: Characterization of electrochemically active materials a) X-ray diffraction (DRX) on powders

The atomic and molecular structure of the electrochemically active materials was studied by X-ray diffraction carried out both on structures of lamellar oxides of sodium and of metal of type P2 and of type 03, prepared in Example 1. Figure 1 shows the X-ray diffraction diagram for a Nao powder, 5CoO2 lamellar type P2 and Figure 2 shows the X-ray diffraction diagram for a NaNio powder, 4Coo, 2Mno, 402 lamellar type 03.

Example 3: Electrochemical properties All the cells were assembled in cases for button cell type 2032 with the components indicated in Table 1 and negative electrodes including a metallic lithium film on aluminum current collectors. The cells comprising liquid electrolytes were assembled with Celgard ^MC separators impregnated with a 1 M solution of LiPF6 in an EC / DEC mixture ([3: 7] by volume) or an EC / DMC mixture ([4: 6] in volume). The cells comprising solid polymer electrolytes were assembled with an SPE comprising LIFSI or LITFSI. Table 1. Cell configurations

a) Electrochemical behavior of Na _0, 67CoC> 2 type P2

This example illustrates the electrochemical behavior of a Nao, 67CoO2 lamellar type P2 material as prepared in Example 1.

Figure 3 shows the charge and discharge profiles of Cell 1. The charge and discharge were performed at 0.1 C, and recorded vs Li / Li ⁺ at a temperature of 25 ° C. Cell 1 provided a capacity of approximately 104 mAh / g.

Figure 4 shows the charge and discharge profiles for Cell 1 at different cycling speeds. Charging and discharging were carried out at 0.1 C, 0.2 C, 0.5 C, 1 C, 2 C and 4 C and recorded vs Li / Li ⁺ at a temperature of 25 ° C. At cycling speed of 4C, Cell 1 provided a capacity of approximately 92 mAh / g, effectively showing a capacity retention of 87% with cycling speeds increasing from 0.5C to 4C.

Figure 5 shows a graph representing the capacity (mAh / g) as a function of the number of cycles of Cell 1. The long cycling experiment was carried out at a constant charge / discharge current of 1 C. The results were recorded vs Li / Li ⁺ at a temperature of 25 ° C. Figure 5 shows a capacity retention of approximately 97% after 200 cycles.

The influence of the choice of binder and of the cycling temperature is demonstrated in Figures 6 and 7. Figure 6 shows the charge and discharge profiles of Cell 2. The charge and discharge were carried out at 0.3C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 50 ° C. Cell 2 provided a capacity of approximately 107 mAh / g.

Figure 7 shows the charge and discharge profiles of Cell 2. The charge and discharge were carried out at 0.3C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 80 ° C. Cell 2 provided a capacity of approximately 107 mAh / g. b) Electrochemical behavior of Nao, 67Coo, 67Mno, 33C> 2 of type P2

This example illustrates the electrochemical behavior of a Nao, 67Coo, 67Mno, 3302 lamellar type P2 material as prepared in Example 1.

Figure 8 shows the charge and discharge profiles of Cell 3. The charge and discharge were carried out at 0.1 C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 25 ° C . Cell 3 provided a capacity of approximately 150 mAh / g.

Figure 9 shows the charging and discharging profiles of Cell 3 at different cycling speeds. The charges and discharges were carried out at 0.1 ° C., 0.2 ° C., 0.5 ° C., 1 ° C., 2 ° C. and 4 ° C. and recorded vs Li / Li ⁺ at a temperature of 25 ° C. At a cycling speed of 4C, Cell 3 provided a capacity of approximately 121 mAh / g, effectively showing 80% capacity retention with cycling speeds increasing from 0.1 C to 4C. Figure 10 shows a graph representing the capacity (mAh / g) as a function of the number of cycles for Cell 3. The long cycling experiment was carried out at a constant charge / discharge current of 2C. The results were recorded vs Li / Li ⁺ at a temperature of 25 ° C. Figure 10 shows a capacity retention of approximately 93.4% after 100 cycles. c) Electrochemical behavior of Nao, 67Nio, 33Mno, 67C> 2 of type P2

This example illustrates the electrochemical behavior of a Nao, 67Nio, 33Mno, 6702 lamellar type P2 material as prepared in Example 1.

Figure 11 shows the initial charge and discharge curves for Cell 4. The charge and discharge were carried out at 0.1 C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 25 ° vs. Cell 4 provided a capacity of approximately 182 mAh / g.

Figure 12 shows two charge and discharge profiles for Cell 5, i.e. the first cycle and the fifth cycle. Charging and discharging were carried out at 0.3C between 2.0 and 4.0 V vs Li / Li ⁺ at a temperature of 80 ° C. Cell 5 provided a capacity of approximately 120 mAh / g. d) Electrochemical behavior of Nao, 67Coo, eMno, 402 of type P2

This example illustrates the electrochemical behavior of a Nao, 67Coo, 6Mno, 402 lamellar type P2 material as prepared in Example 1.

Figure 13 shows the charge and discharge profiles of Cell 6. The charge and discharge were carried out at 0.1 C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 25 ° C . Cell 6 provided a capacity of approximately 142 mAh / g. e) Electrochemical behavior of Nao, 67Coo, 5sMno, 4502 of type P2

This example illustrates the electrochemical behavior of a Nao, 67Coo, 55Mno, 4s02 lamellar type P2 material as prepared in Example 1. Figure 14 shows the charge and discharge profiles of Cell 7. The charge and discharge were carried out at 0.1 C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 25 ° C . Cell 7 provided a capacity of approximately 110 mAh / g. f) Electrochemical behavior of Nao, 67Coo, 5Mno, s02 of type P2 This example illustrates the electrochemical behavior of a Nao material, 67Coo, 5Mno, s02 lamellar of type P2 as prepared in Example 1.

Figure 15 shows the charge and discharge profiles of Cell 8. The charge and discharge were carried out at 0.1 C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 25 ° C . Cell 8 provided a capacity of approximately 114 mAh / g. g) Electrochemical behavior of Nao, 67Coo, 5oMno, 33Tio, i702 of type P2

This example illustrates the electrochemical behavior of a Nao, 67Coo, 5oMno, 33Tio, i702 lamellar type P2 material as prepared in Example 1.

Figure 16 shows the charge and discharge profiles of Cell 9. The charge and discharge were carried out at 0.1 C between 2.0 and 4.5 V vs Li / Li ⁺ at a temperature of 25 ° C . Cell 9 provided a capacity of approximately 137 mAh / g. h) Electrochemical behavior of Nao _, eoMn0 ₂ of type P2

This example illustrates the electrochemical behavior of a Nao, 6oMn02 lamellar type P2 material as prepared in Example 1.

Figure 17 shows the charge and discharge profiles of Cell 10. The charge and discharge were carried out at 0.1 C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 25 ° C . Cell 10 provided a capacity of approximately 73 mAh / g. i) Electrochemical behavior of NaNio, 4Coo, 2Mno, 402 type 03

This example illustrates the electrochemical behavior of a NaNio, 4Coo, 2Mno, 402 lamellar material of type 03 as prepared in Example 1. Figure 18 shows the charge and discharge profiles of Cell 11. The charge and discharge were carried out at 0.1 C between 2.0 and 4.4 V vs Li / Li ⁺ at a temperature of 25 ° C . Cell 11 provided a capacity of approximately 118 mAh / g.

Figure 19 shows a graph representing the capacity (mAh / g) as a function of the number of cycles for Cell 11. The long cycling experiment was carried out at a constant charge / discharge current of 0.1 C. The results were recorded vs Li / Li ⁺ at a temperature of 25 ° C. Figure 19 shows good capacity retention after 50 cycles.

Several modifications could be made to one or other of the embodiments described above without departing from the scope of the present invention as envisaged. References, patents or scientific literature documents referred to in this application are incorporated herein by reference in their entirety and for all purposes.

Claims

1. An electrode material comprising an electrochemically active material, said electrochemically active material comprising a lamellar oxide of sodium and metal of formula Na _x M02, in which x is a number such that 0.5 <x <1.0, and M is chosen from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Sb and their combinations.

2. An electrode material according to claim 1, in which the electrochemically active material comprises a lamellar oxide of sodium and of metal chosen from:

a P2 type sodium and metal lamellar oxide of formula Na _x M02, in which x is a number such that 0.5 <x <0.8 and M is chosen from Co, Mn, Fe,

Ni, Ti, Cr, V, Cu and their combinations; and

a lamellar sodium and metal oxide of type 03 of the formula Na _x M02, in which x is a number such that 0.8 <x <1.0, 0 and M is chosen from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Sb and their combinations.

3. An electrode material according to claim 1 or 2, in which the electrochemically active material comprises a lamellar oxide of sodium and metal of the formula Na _x M'i _-y MyO2, in which x and M are as defined in claim 1 or 2, y is a number such that 0 <y <1, 0 and M 'is different from M and chosen from Co, Mn, Fe, Ni, Ti, Cr, V, Cu, Sb and their combinations.

4. An electrode material according to any one of claims 1 to 3, in which the electrochemically active material comprises a lamellar sodium and metal oxide of formula Na _x M'i _-y MnyO2, in which x is as defined in claim 1 or 2, y is a number such that 0 <y <1, 0 and M 'is chosen from Co, Fe, Ni, Ti, Cr, V, Cu, Sb and their combinations.

5. An electrode material according to any one of claims 1 to 4, in which the electrochemically active material comprises a lamellar sodium oxide and of cobalt of formula Na _x CoO2, in which x is as defined in claim 1 or 2.

6. An electrode material according to any one of claims 1 to 4, in which the electrochemically active material comprises a lamellar oxide of sodium and manganese of formula Na _x MnO2, in which x is as defined in claim 1 or 2.

7. An electrode material according to any one of claims 1 to 4, in which the electrochemically active material comprises a lamellar oxide of sodium and of metal of formula Na _x (NiCo) i _-y MnyO2, in which x is such that defined in claim 1 or 2 and is as defined in claim 4.

8. An electrode material according to any one of claims 1 to 4, in which the electrochemically active material comprises a lamellar oxide of sodium and of metal of formula Na _x Coi _-y MnyO2, in which x is as defined in claim 1 or 2 and is as defined in claim 4.

9. An electrode material according to any one of claims 1 to 4, in which the electrochemically active material comprises a lamellar oxide of sodium and metal of the formula Na _x Nii _-y Mn _y 02, in which x is as defined in claim 1 or 2 and is as defined in claim 4.

10. An electrode material according to any one of claims 1 to 4, in which the electrochemically active material comprises a lamellar oxide of sodium and metal of formula Na _x (CoTi) i _-y Mni _-y 02, in which x is as defined in claim 1 or 2 and y is as defined in claim 4.

11. An electrode material according to any one of claims 1 to 10, further comprising an electronic conductive material.

12. An electrode material according to claim 11, in which the electronic conductive material is chosen from carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes and combinations thereof.

13. An electrode material according to claim 12, wherein the electronic conductive material comprises carbon fibers.

14. An electrode material according to claim 13, wherein the carbon fibers are formed in the gas phase (VGCFs).

15. An electrode material according to claim 12, wherein the electronic conductive material comprises carbon black.

16. The electrode material of claim 15, wherein the carbon black and Super P ^MC carbon.

17. An electrode material according to claim 15, wherein the carbon black and Ketjen ^MC carbon.

18. An electrode material according to any one of claims 1 to 17, further comprising a binder.

19. An electrode material according to claim 18, in which the binder is chosen from the group consisting of a polymer binder of polyether type, a fluoropolymer and a water-soluble binder.

20. An electrode material according to claim 19, wherein the binder is a fluoropolymer.

21. The electrode material of claim 20, wherein the fluoropolymer is polyvinylidene fluoride (PVdF).

22. An electrode material according to claim 20, in which the fluoropolymer is polytetrafluoroethylene (PTFE).

23. The electrode material according to claim 19, in which the binder is a polymeric binder of polyether type.

24. An electrode material according to claim 23, in which the polymeric binder of polyether type is branched and / or crosslinked.

25. An electrode material according to claim 23 or 24, wherein the polyether type polymeric binder is based on poly (ethylene oxide) (PEO).

26. An electrode comprising the electrode material as defined in any one of claims 1 to 25 on a current collector.

27. The electrode of claim 26, wherein the electrode is a positive electrode.

28. An electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, in which the positive electrode is as defined in claim 26 or 27.

29. The electrochemical cell according to claim 28, wherein the negative electrode comprises metallic lithium.

30. The electrochemical cell according to claim 28, wherein the negative electrode comprises metallic sodium.

31. An electrochemical cell according to any one of claims 28 to 30, in which the electrolyte is a liquid electrolyte comprising a salt in a solvent.

32. An electrochemical cell according to any one of claims 28 to 30, in which the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer.

33. The electrochemical cell according to any one of claims 28 to 30, in which the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer.

34. An electrochemical cell according to any one of claims 31 to 33, in which the salt is a lithium salt.

35. An electrochemical cell according to any one of claims 31 to 33, in which the salt is a sodium salt.

36. A battery comprising at least one electrochemical cell as defined in any one of claims 28 to 35.

37. Battery according to claim 36, wherein said battery is chosen from a lithium-ion battery and a sodium-ion battery.

38. The battery of claim 36 or 37, wherein said battery is a lithium-ion battery.

39. The battery of claim 36 or 37, wherein said battery is a sodium-ion battery.