Electrode materials comprising an fe-doped tunnel-type oxide of sodium, lithium, manganese and metal, electrodes comprising same and use thereof in electrochemistry

Abstract

The present technology relates to electrochemically active materials comprising an Fe-doped tunnel-type oxide of sodium, manganese and at least one metallic element, substituted with lithium and of formula NaaLibFecMndMeO2, wherein a is a number such that 0 < a < 0.22; b is a number such that 0.18 < b < 0.40 and is such that a + b is 0.38 < a + b < 0.62; c is a number such that 0 < c ≤ 0.40; d is a number such that 0.44 < d < 1; e is a number such that c + d + e = 1; and M is chosen from manganese (Mn), titanium (Ti), vanadium (V), nickel (Ni), cobalt (Co), chromium (Cr), molybdenum (Mo), zirconium (Zr), tin (Sn), ruthenium (Ru), other similar metals, and a combination of at least two thereof. Also described are electrode materials, electrodes, electrochemical cells and batteries comprising said electrochemically active materials.

Description

[0001] ELECTRODE MATERIALS COMPRISING AN FE-DOPED TUNNEL-TYPE SODIUM, LITHIUM, MANGANESE AND METAL OXIDE, ELECTRODES COMPRISING THEM AND THEIR USE IN ELECTROCHEMISTRY

[0002] RELATED REQUEST

[0003] This application claims priority under applicable law from U.S. Provisional Patent Application No. 63 / 362,616 filed on April 7, 2022, the contents of which are incorporated herein by reference in their entirety and for all purposes.

[0004] TECHNICAL FIELD

[0005] The present application relates generally to the field of electrochemically active materials and their uses in electrochemical applications. More particularly, the present application relates to electrode materials comprising an oxide of sodium, magnesium and at least one tunnel-type metal partially substituted with lithium as the electrochemically active material, electrodes comprising them, methods of manufacturing them and their use in electrochemical cells.

[0006] STATE OF THE ART

[0007] One of the main drawbacks of the positive electrode materials currently used commercially in lithium-ion batteries (LIBs) and so-called all-solid-state batteries, such as LiCoO2, I© LiNi o,33 Mn o,33 Co o,33 02(NMC 111), I© LiNio,6Mn o,2 Co o,202(NMC 622), and LiNio,sMno,iCoo,i02 (NMC 811) is their high production cost. The raw materials used in the manufacturing of positive electrode materials are becoming increasingly important in the total battery cost, which could be problematic for the growth of the market share of LIBs and so-called all-solid-state batteries. For example, the weighted average price of cobalt could limit the future applications of LIBs and so-called all-solid-state batteries. Positive electrode materials containing reduced amounts of cobalt and cobalt-free positive electrode materials are therefore attracting a lot of attention, especially in large-scale and high-energy density energy storage systems. For example, lithium iron phosphate (LiFePCO4 or LFP) has attracted great interest due to its cost-effective materials.However, the energy density of LFP batteries has not improved sufficiently to meet the demands of the electric vehicle market. Therefore, there is still a need for the development of new electrode materials that exclude one or more of the disadvantages of conventional commercial positive electrode materials. For example, there is a need for the development of new low-cost, high-capacity, and high-voltage positive electrode materials for LFPs and so-called all-solid-state batteries.

[0008] SUMMARY

[0009] In one aspect, the present technology relates to an electrochemically active material comprising an oxide of sodium, manganese and at least one iron-doped and lithium-substituted tunnel-type metallic element of formula NaaLi b Fe c Mn d M eO2, wherein a is a number such that 0 < a < 0.22; b is a number such that 0.18 < b < 0.40 and is such that a + b is 0.38 < a + b < 0.62; c is a number such that 0 < c < 0.40; d is a number such that 0.44 < d < 1; e is a number such that c + d + e = 1; and M is selected from manganese (Mn), titanium (Ti), vanadium (V), nickel (Ni), cobalt (Co), chromium (Cr), molybdenum (Mo), zirconium (Zr), tin (Sn), ruthenium (Ru), other similar metals and a combination of two or more thereof.

[0010] In one example, M is selected from manganese (Mn), titanium (Ti), vanadium (V), nickel (Ni), cobalt (Co), chromium (Cr), molybdenum (Mo), zirconium (Zr), ruthenium (Ru), other similar metals, and a combination of at least two of these. In one example of interest, M is titanium (Ti).

[0011] In another example, a is a number such that 0.01 < a < 0.22, or 0.02 < a < 0.22, or 0.03 < a < 0.22, or 0.04 < a < 0.22, or 0.05 < a < 0.22, or 0.06 < a < 0.22, or 0.07 < a < 0.22, or 0.08

[0012] < a < 0.21. According to an example of interest, a is a number such that 0.08 < a < 0.21.

[0013] As another example, b is a number such that 0.19 < b < 0.40, or 0.20 < b < 0.40, or 0.20 < b

[0014] < 0.39, or 0.20 < b < 0.38. According to an example of interest, b is a number such that 0.20 < b < 0.38.

[0015] In another example, c is a number such that 0.05 < c < 0.40, or 0.10 < c < 0.40, or 0.15 < c

[0016] < 0.40, or 0.20 < c < 0.40, or 0.25 < c < 0.40, or 0.30 < c < 0.40. According to an example of interest, c is a number such that 0.30 < c < 0.40.

[0017] According to another example, d is a number such that 0.44 < d < 1, or 0.44 < d < 0.95, or 0.44 < d < 0.90, or 0.44 < d < 0.85, or 0.44 < d < 0.80, or 0.44 < d < 0.75, or 0.44 < d < 0.70, or 0.44 < d < 0.65, or 0.44 < d < 0.60, or 0.44 < d < 0.55. According to an example of interest, d is a number such that 0.44 < d < 0.55.

[0018] In another example, the oxide of sodium, manganese and at least one iron-doped and lithium-substituted tunnel-type metallic element is selected from the group consisting of Na0, 10 Li o,33 Fe o,34 Mn o,44 You o,22 02, from Na 0,08 Li 0,38 Fe 0,30 Mn 0,55 You 0,15 O2, Na 0,20 Li 0,24 Fe 0,34 Mn 0,55 You 0, 11 O2, Na 0,21 Li 0,20 Fe 0,40 Mn 0,50 You 0, 10 02, from Na 0,10 Li 0,40 Fe 0,08 Mn 0,81 Ti0,nO2 and Na 0,10 Li 0,40 Fe0.11Mn 0,78 You 0,11 02.

[0019] In another aspect, the present technology relates to an electrode material comprising the electrochemically active material as defined herein.

[0020] According to one embodiment, said electrode material further comprises an electronically conductive material. According to one example, the electronically conductive material is selected from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes and a combination of at least two thereof. According to an example of interest, the electronically conductive material comprises carbon black. For example, the carbon black is Super P carbon MC or Ketjen carbon MC . According to another example of interest, the electronically conductive material comprises carbon fibers. For example, the carbon fibers are gas-formed carbon fibers (VGCFs).

[0021] According to another embodiment, said electrode material further comprises a binder. According to one example, the binder is selected from the group consisting of a polyether polymer binder, a fluoropolymer and a water-soluble binder. According to an example of interest, the binder is a fluoropolymer. For example, the fluoropolymer is polyvinylidene fluoride (PVDF).

[0022] According to another embodiment, said electrode material further comprises an additive. According to one example, the additive is selected from the group consisting of ionic conductors, inorganic particles, glass particles, ceramic particles, salts, and other similar additives.

[0023] In another aspect, the present technology relates to an electrode comprising the electrode material as defined herein on a current collector.

[0024] In one embodiment, the electrode is a positive electrode. In another aspect, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein the positive electrode is as defined herein.

[0025] In one embodiment, the negative electrode comprises an alkali metal, an alloy comprising an alkali metal, or a prelithiated electrochemically active material. In one example, the negative electrode comprises metallic lithium or an alloy comprising metallic lithium. In one example of interest, the negative electrode comprises metallic lithium.

[0026] According to another embodiment, the electrolyte is a glass or ceramic electrolyte.

[0027] According to another embodiment, the electrolyte is a liquid electrolyte comprising a salt in a solvent.

[0028] According to another embodiment, the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer.

[0029] According to another embodiment, the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer.

[0030] 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 (LiBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (UNO3), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiCIO4), lithium hexafluoroarsenate (LiAsFe), lithium trifluoromethanesulfonate (LiSO3CF3) (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 an example of interest, the lithium salt is lithium hexafluorophosphate (LiPF6).,

[0031] According to another aspect, the present technology relates to a battery comprising at least one electrochemical cell as defined herein. According to 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 example, said battery is a lithium battery or a lithium-ion battery.

[0032] BRIEF DESCRIPTION OF THE FIGURES

[0033] Figure 1 is an X-ray diffraction pattern for a tunnel-type sodium lithium manganese oxide powder of formula Na 0,08 Li0,36 Mn02, as described in Example 1(d).

[0034] Figure 2 is an X-ray diffraction pattern for a tunnel-type sodium, lithium, iron, manganese, and titanium oxide powder of formula

[0035] N / A 0, 10 Li 0,33 Fe 0,34 Mn 0,44 You 0,22 O2, as described in Example 1(d).

[0036] Figure 3 is an X-ray diffraction pattern for a tunnel-type sodium, lithium, iron, manganese, and titanium oxide powder of formula

[0037] N / A 0,08 Li 0,38 Fe 0,30 Mno,55Ti 0,15 O2, as described in Example 1(d).

[0038] Figure 4 is an X-ray diffraction pattern for a tunnel-type sodium, lithium, iron, manganese, and titanium oxide powder of formula

[0039] N / A 0,20 Li 0,24 Fe 0,34 Mn 0,55 You 0,11O2, as described in Example 1(d).

[0040] Figure 5 is an X-ray diffraction pattern for a tunnel-type sodium, lithium, iron, manganese, and titanium oxide powder of formula

[0041] N / A 0,21 Li 0,20 Fe 0,40 Mn 0,50 You 0, 10 02, as described in Example 1(d).

[0042] Figure 6 shows charge and discharge profiles obtained for Cell 1 and recorded in (1) at a cycling rate of 0.1 C between 2.0 V and 4.8 V vs Li + / Li, and in (2) between 2.0 V and 4.6 V vs Li + / Li, as described in Example 2(b). Results are shown for the second discharge and charge cycle.

[0043] Figure 7 shows a charge and discharge profile obtained for Cell 2 and recorded at a cycling rate of 0.1 C between 2.0 V and 4.6 V vs Li + / Li, as described in Example 2(b). Results are shown for the second discharge and charge cycle. Figure 8 shows a charge and discharge profile obtained for Cell 3 and recorded at a cycling rate of 0.1 C between 2.0 V and 4.6 V vs Li + / Li, as described in Example 2(b). Results are shown for the second discharge and charge cycle.

[0044] Figure 9 shows charge and discharge profiles obtained for Cell 4 and recorded at a cycling rate of 0.1 C between 2.0 V and 4.8 V vs Li + / Li, as described in Example 2(b). The results are presented for the second (1) and fifth (2) charge and discharge cycles.

[0045] Figure 10 shows charge and discharge profiles obtained for Cell 5 and recorded at a cycling rate of 0.1 C between 2.5 V and 4.8 V vs Li + / Li, as described in Example 2(b). Results are shown for the second charge and discharge cycle.

[0046] Figure 11 shows in (a) charge and discharge profiles recorded at a cycling rate of 0.1 C between 2.0 V and 4.8 V vs Li7Li; and in (b) a graph representing the capacity as a function of the number of cycles obtained for Cell 6, as described in Example 2(b).

[0047] Figure 12 shows in (a) charge and discharge profiles recorded at a cycling rate of 0.1 C between 2.0 V and 4.8 V vs Li7Li; and in (b) a graph representing the capacity as a function of the number of cycles obtained for Cell 7, as described in Example 2(b).

[0048] DETAILED DESCRIPTION

[0049] 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.

[0050] 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 the nominal value. This term may also take into account, for example, the experimental error of a measuring device or rounding.

[0051] Where 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. Where a range of values ​​is referred to in this application, then all intermediate ranges and sub-ranges, as well as individual values ​​included in ranges of values, are also included in the definition.

[0052] When the article "a" is used to introduce an element in the present 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 all embodiments.

[0053] The present technology generally relates to electrochemically active materials, their manufacturing processes and their use in electrochemical cells. More particularly, the present technology relates to an electrochemically active material comprising an oxide of sodium, manganese and at least one tunnel-type metallic element doped with iron and substituted with lithium.

[0054] In one example, the metallic element of the lithium-substituted iron-doped sodium oxide, manganese oxide, and at least one tunnel-type metallic element may be a transition metal, a post-transition metal, a metalloid, an alkali metal other than lithium or sodium, an alkaline earth metal, or a combination thereof, where compatible. For example, the metal may be a transition metal or a post-transition metal selected from the group consisting of manganese (Mn), titanium (Ti), vanadium (V), nickel (Ni), cobalt (Co), chromium (Cr), molybdenum (Mo), zirconium (Zr), tin (Sn), ruthenium (Ru), and other similar metallic elements, or a combination thereof, where compatible.

[0055] In another example, the electrochemically active material comprises an oxide of sodium, manganese and at least one iron-doped and lithium-substituted tunnel-type metallic element of formula Naa LibFe c MndM e O2, wherein a is a number such that 0 < a < 0.22; b is a number such that 0.18 < b < 0.40 and such that a + b is 0.38 < a + b < 0.62; c is a number such that 0 < c < 0.40; d is a number such that 0.44 < d < 1; e is a number such that c + d + e = 1; and M is selected from the group consisting of manganese (Mn), titanium (Ti), vanadium (V), nickel (Ni), cobalt (Co), chromium (Cr), molybdenum (Mo), zirconium (Zr), tin (Sn), ruthenium (Ru), and other similar metallic elements, or a combination thereof, when compatible. It is understood that when the metallic element (M) is manganese (Mn), the oxide of sodium, manganese and at least one tunnel-type metallic element doped with iron and substituted with lithium includes manganese with at least two different oxidation states.

[0056] In some examples, the metallic element (M) is a transition metal selected from the group consisting of manganese (Mn), titanium (Ti), vanadium (V), nickel (Ni), cobalt (Co), chromium (Cr), molybdenum (Mo), zirconium (Zr), ruthenium (Ru) and other similar transition metals, or a combination thereof, when compatible. In some examples of interest, the metallic element is titanium (Ti).

[0057] In some examples, a is a number such that 0.01 < a < 0.22, or 0.02 < a < 0.22, or 0.03 < a < 0.22, or 0.04 < a < 0.22, or 0.05 < a < 0.22, or 0.06 < a < 0.22, or 0.07 < a < 0.22, or 0.08

[0058] < a < 0.21. According to some examples of interest, a is a number such that 0.08 < a < 0.21.

[0059] In some examples, b is a number such that a + b is 0.38 < a + b < 0.61, or 0.38 < a + b

[0060] < 0.60, or 0.38 < a + b < 0.59, or 0.38 < a + b < 0.58, or 0.38 < a + b < 0.57, or 0.38 < a + b < 0.56, or 0.38 < a + b < 0.55, or 0.38 < a + b < 0.54, or 0.38 < a + b < 0.53, or 0.38 < a + b < 0.52, or 0.38 < a + b < 0.51, or 0.38 < a + b < 0.50, or 0.38 < a + b < 0.49, or 0.38 < a + b < 0.48, or 0.38 < a + b < 0.47, or 0.39 <a+b< 0.47, or 0.40 < a + b < 0.47. According to some examples of interest, b is a number such that a + b is 0.40 < a + b < 0.47. For example, b can be a number such that 0.19 < b < 0.40, or 0.20 < b < 0.40, or 0.20 < b < 0.39, or 0.20 < b < 0.38. According to some examples of interest, b is a number such that 0.20 < b < 0.38.

[0061] According to some examples, c is a number such that 0.05 < c < 0.40, or 0.10 < c < 0.40, or 0.15 < c < 0.40, or 0.20 < c < 0.40, or 0.25 < c < 0.40, or 0.30 < c < 0.40. According to some examples of interest, c is a number such that 0.30 < c < 0.40.

[0062] In some examples, d is a number such that 0.44 < d < 1, or 0.44 < d < 0.95, or 0.44 < d < 0.90, or 0.44 < d < 0.85, or 0.44 < d < 0.80, or 0.44 < d < 0.75, or 0.44 < d < 0.70, or 0.44 < d

[0063] < 0.65, or 0.44 < d < 0.60, or 0.44 < d < 0.55. In some examples of interest, d is a number such that 0.44 < d < 0.55.

[0064] Non-limiting examples of iron-doped and lithium-substituted oxides of sodium, manganese, and at least one tunnel-type metal element include

[0065] N / A 0, 10 Li 0,33 Fe 0,34 Mn 0,44 You 0,22 O2, Na 0,08 Li 0,38 Fe 0,30 Mn 0,55 You 0,15 O2, Na 0,20 Li 0,24 Fe 0,34 Mn 0,55 You 0, 11 O2,

[0066] Na0, 21 Li 0,20 Fe 0,40 Mn0, 50 You 0,10 O2, Na 0,10 Li 0,40 Fe 0,08 Mn 0,81 You 0, 11 02 and Na 0,10 Li0,40 Fe 0, 11 Mn 0,78 You 0, 11 O2. According to another example, the electrochemically active material may further include at least one doping element that may be included in smaller amounts, for example, to modulate or optimize its electrochemical properties. For example, the electrochemically active material may be doped by partially substituting the metallic element with at least one other element. For example, the electrochemically active material may be lightly doped with at least one doping element selected from a transition metal (e.g., iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), titanium (Ti), chromium (Cr), copper (Cu), vanadium (V), zinc (Zn), and / or yttrium (Y)), a post-transition metal (e.g., Al), an alkaline earth metal (e.g., Mg), and / or a metalloid (e.g., Sb).

[0067] In another example, the electrochemically active material may be in the form of particles (e.g., microparticles or nanoparticles) that may be freshly formed and may further include a coating material. The coating material may be an electronically conductive material, e.g., a carbon coating.

[0068] For example, partial substitution of sodium ions with lithium ions can significantly improve the electrochemical performance of an electrochemical cell comprising the present electrochemically active material.

[0069] In some examples, partial substitution of sodium ions with lithium ions in lithium-substituted sodium, manganese, and at least one iron-doped tunnel-type metal element can substantially improve the electrochemical properties of the electrochemically active material. Without being bound by theory, partial substitution of sodium ions with lithium ions can stabilize the structure of the electrochemically active material based on sodium, manganese, and at least one iron-doped tunnel-type metal element and, consequently, substantially improve its electrochemical performance. For example, the electrochemical properties of the electrochemically active material can be modulated by varying the degree of lithium substitution.

[0070] In some examples, doping sodium oxide, manganese oxide, and at least one tunnel-type metallic element substituted with lithium with iron ions can also substantially improve the electrochemical properties of the electrochemically active material. For example, partial substitution of manganese with iron ions can significantly increase the average operating voltage of the electrochemically active material. For example, the electrochemical properties of the electrochemically active material can be modulated by varying the degree of iron substitution.

[0071] In some examples, cationic doping of sodium oxide, manganese oxide, and at least one iron-doped tunnel-like metal element substituted with lithium by a transition metal or a post-transition metal such as those described above can also substantially improve the electrochemical properties of the electrochemically active material. For example, partial substitution of manganese by titanium can substantially improve the electrochemical properties of the electrochemically active material. For example, the electrochemical properties of the electrochemically active material can be modulated by varying the composition of said transition metal or said post-transition metal in sodium oxide, manganese oxide, and at least one iron-doped tunnel-like metal element substituted with lithium.

[0072] The present technology also relates to a method of manufacturing the electrochemically active material as defined herein, the method including the following steps:

[0073] (i) preparation of an oxide of sodium, manganese and at least one iron-doped tunnel-type metallic element; and

[0074] (ii) partial substitution of sodium ions of sodium oxide, manganese oxide and at least one iron-doped tunnel-type metallic element by lithium ions to obtain the electrochemically active material.

[0075] In one example, the oxide of sodium, manganese and at least one iron-doped tunnel-type metal element prepared in step (i) has the formula NaaFe c MndM eO2, wherein a is a number such that 0.38 < a < 0.62; c is a number such that 0 < c < 0.40; d is a number such that 0.44 < d < 1; e is a number such that c + d + e = 1; and M is selected from the group consisting of manganese (Mn), titanium (Ti), vanadium (V), nickel (Ni), cobalt (Co), chromium (Cr), molybdenum (Mo), zirconium (Zr), tin (Sn), ruthenium (Ru) and other similar metals, or a combination thereof, when compatible.

[0076] In some examples, the metallic element (M) is a transition metal selected from the group consisting of manganese (Mn), titanium (Ti), vanadium (V), nickel (Ni), cobalt (Co), chromium (Cr), molybdenum (Mo), zirconium (Zr), ruthenium (Ru) and other similar transition metals, or a combination thereof, when compatible. In some examples of interest, the metallic element is titanium (Ti). According to some examples, a is a number such that 0.38 < a < 0.62, or 0.38 < a < 0.60, or 0.38 < a < 0.58, or 0.38 < a < 0.56, or 0.38 < a < 0.54, or 0.38 < a < 0.52, or 0.38 < a < 0.50, or 0.38 < a < 0.48, or 0.38 < a < 0.46, or 0.40 < a < 0.46, or 0.41 < a < 0.46. According to some examples of interest, a is a number such that 0.41 < a < 0.46.

[0077] Non-limiting examples of iron-doped oxides of sodium, manganese, and at least one tunnel-type metal element include NaO, 44FeO, 34Mno, 44Tio, 2202, Na 0,43 Fe 0.34Mn 0, 44 You 0,22 O2, Na 0,44 Fe 0,30 Mn 0,55 Ti0.1502, Nao,46Feo.3oMno,55Tio.i502,

[0078] Na0.44Feo.34M no, 5sTio,n02, Nao.44Feo.40Mn o.50 Tio.10O2, Nao,4i Feo,4oMno.5oTio,io02,

[0079] Nao,5oFeo,o8Mno,8iTio,ii02, and Nao,5oFeo,nMno,78Tio,n02.

[0080] In one example, the iron-doped tunnel-type metal element sodium oxide, manganese oxide, and at least one iron-doped tunnel-type metal element may be prepared by a solid-state synthesis technique or a liquid-state synthesis technique. For example, the liquid-state synthesis technique may be a sol-gel process.

[0081] In some examples, the iron-doped sodium, manganese, and at least one tunneling metal element oxide may be prepared via a solid-state synthesis process. The solid-state synthesis process may involve mixing and grinding the appropriate precursors (metal oxides or metal carbonates) in selected amounts to obtain an iron-doped sodium, manganese, and at least one tunneling metal element oxide having a desired stoichiometry. The mixing and grinding steps may be performed sequentially, simultaneously, or with partial overlap in time. In some examples, the mixing and grinding steps are performed simultaneously. Any compatible mixing and grinding methods are contemplated. For example, the solid precursors may be mixed and ground manually or by any compatible mechanical method, such as mechanical grinding.The solid-state synthesis process may also involve heating the mixed and ground precursors to obtain the desired sodium, manganese, and at least one iron-doped tunnel metal element oxide. The heating step may be carried out at a temperature and for a time sufficient to obtain the powder of sodium, manganese, and at least one iron-doped tunnel metal element. The heating step may be carried out, for example, in a furnace at a temperature of from about 800°C to about 1000°C, inclusive. The heating step may be carried out, for example, for a period of from about 3 hours to about 24 hours, inclusive. The heating step may be carried out under any suitable conditions to obtain the desired powder of sodium, manganese, and at least one iron-doped tunnel metal element.For example, the heating step can be carried out under an air or oxygen atmosphere, but any other compatible atmosphere is considered.

[0082] In some examples, the iron-doped tunnel-like sodium, manganese, and at least one metallic element oxide may be prepared via a liquid chemical synthesis process, such as a sol-gel process. The sol-gel process may be carried out in an aqueous medium using inorganic salt precursors and a chelating agent. For example, the inorganic salt precursors may be metal carbonate, acetate, oxalate, or alkoxide precursors, and the chelating agent may be an organic acid, such as citric acid. The sol-gel process may include dissolving an appropriate amount of inorganic salt precursors in water and a (Na + Mn): chelating agent in a molar ratio of about 10. For example, the dissolving step may be carried out with stirring. The resulting solution may then be heated with stirring to a temperature and for a time sufficient to form the sol-gel precursors.For example, the solution may then be heated to a temperature of about 80°C until the sol-gel precursors are formed. The resulting sol-gel precursors may then be calcined at a temperature and for a time sufficient to decompose the organic and inorganic contents. For example, the sol-gel precursors may then be calcined in a furnace at a temperature of about 400°C for about 6 hours. The resulting powders may then be ground and calcined at a temperature and for a time sufficient to obtain the desired powder of sodium oxide, manganese oxide, and at least one iron-doped tunnel-type metal element. For example, the calcination step may be carried out in a furnace at a temperature of about 900°C for about 9 hours.The calcination step may be carried out under any suitable conditions to obtain the desired powder of sodium oxide, manganese oxide and at least one iron-doped tunnel-type metal element. For example, the calcination step may be carried out under an air or oxygen atmosphere, but any other compatible atmosphere is contemplated.

[0083] In some examples, the partial substitution of sodium ions with lithium ions may be carried out via a one- or two-step ion exchange process. The ion exchange reaction may be carried out by mixing the powder of sodium oxide, manganese oxide, and at least one iron-doped tunnel-type metal element prepared in step (i) with an excess amount of a lithium salt or lithium salt composition. The lithium salt composition may be a mixture of lithium nitrate (UNO3) and lithium chloride (LiCl) or lithium hydroxide (LiOH), for example, in a molar ratio of UNO3:LiCl or LiOH of about 2:1. For example, the powder prepared in step (i) may be mixed with up to a 20-fold molar excess of a lithium salt or lithium salt composition.The mixture may then be heated to a temperature and for a time sufficient to obtain the electrochemically active material, namely an oxide of sodium, manganese, and at least one iron-doped, lithium-substituted tunnel-type metal element having a desired stoichiometry. For example, the mixture may be heated to a temperature between about 240°C and about 400°C, either once for about 4 hours to about 15 hours, or twice for about 2 hours to about 10 hours.

[0084] The present technology also relates to electrode materials comprising the electrochemically active material as defined herein or an electrochemically active material prepared by the method as defined herein.

[0085] In one example, the electrode material as defined herein may further include an electronically conductive material. Non-limiting examples of electronically conductive materials include a carbon source such as carbon black (e.g., Ketjen carbon MC and Super P carbon MC ), acetylene black (e.g., Shawinigan carbon and Denka carbon black MC ), graphite, graphene, carbon fibers (e.g., gas-formed carbon fibers (VGCFs)), carbon nanofibers, carbon nanotubes (CNTs), and a combination of at least two of these. In a variant of interest, the electronically conductive material is selected from Ketjen carbon MC , Super P carbon MC , VGCFs and a combination of at least two of these. In an example of interest, the electronically conductive material is a mixture of VGCFs and carbon black.

[0086] In another example, the electrode material as defined herein may further include a binder. For example, the binder may be selected for its compatibility with the various elements of an electrochemical cell. Any known compatible binder is contemplated. For example, the binder may be a polyether-type polymer binder, a fluoropolymer, or a water-soluble binder. In one example, the binder is a fluoropolymer such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE). In another example, the binder is a water-soluble binder such as styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), hydrogenated NBR (HNBR), epichlorohydrin rubber (CHR), or acrylate rubber (ACM), optionally including a thickening agent such as carboxymethylcellulose (CMC) or an acidic polymer such as poly(acrylic acid) (PAA), poly(methyl methacrylate) (PMMA), or a combination thereof.In another example, the binder is an optionally crosslinked polyether polymer binder. For example, the polyether polymer binder is linear, branched and / or branched and is based on poly(ethylene oxide) (PEO), poly(propylene oxide) (POP) or a combination of both (or as an EO / POP copolymer), and optionally includes crosslinkable units. In a variant of interest, the binder is polyvinylidene fluoride (PVDF).

[0087] According to another example, the electrode material as defined herein may further optionally include at least one additional additive such as ionic conductors, inorganic particles, glass or ceramic particles, nanoceramics (e.g., aluminum oxide (AI2O3), titanium dioxide (TiO2), silicon dioxide (SiO2) and other similar compounds), salts (e.g., lithium salts) and other similar additives. For example, the additional additive may be an ionic conductor selected from the group consisting of NASICON, LISICON, thio-LiSICON, garnets, sulfides, sulfur halides, phosphates, thio-phosphates, in crystalline and / or amorphous form, and a combination of at least two thereof.

[0088] In another aspect, the present technology relates to an electrode comprising the electrode material as defined herein on a current collector (e.g., aluminum or copper foil). The electrode may also be a self-supporting electrode. In one example of interest, the electrode is a positive electrode.

[0089] In another aspect, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein the positive electrode is as defined herein.

[0090] According to one example, the negative electrode (counter electrode) includes an electrochemically active material selected from among all known compatible electrochemically active materials. For example, the electrochemically active material of the negative electrode may be chosen for its electrochemical compatibility with the various elements of the electrochemical cell as defined herein. Non-limiting examples of electrochemically active materials of negative electrodes include alkali metals, alkali metal alloys and prelithiated electrochemically active materials. According to an example of interest, the electrochemically active material of the negative electrode may be a metallic lithium film or an alloy including metallic lithium.

[0091] In another example, the electrolyte may be chosen for its compatibility with the various elements of the electrochemical cell. Any type of compatible electrolyte is considered. For example, the electrolyte may be a liquid electrolyte comprising a salt in a solvent. The electrolyte may also be a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer. The electrolyte may also be a solid polymer electrolyte comprising a salt in a solvating polymer. The electrolyte may also be a glass or ceramic electrolyte.

[0092] The salt, if present in the electrolyte, may be an ionic salt, such as 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) and a combination of two or more of these.In an example of interest, the lithium salt is lithium hexafluorophosphate (LiPFe).

[0093] The solvent, if present in the electrolyte, is preferably a non-aqueous solvent. Non-limiting examples of non-aqueous solvents include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC); acyclic carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dipropyl carbonate (DPC); lactones such as γ-butyrolactone (γ-BL) and γ-valerolactone (γ-VL); acyclic ethers such as 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), ethoxy methoxy ethane (EME), trimethoxymethane, tetraethylene glycol dimethyl ether or tetraglyme (TEGDME) 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 mixtures thereof. In some examples of interest, the non-aqueous solvent is a mixture of at least two carbonates, e.g., a mixture of ethylene carbonate and ethyl methyl carbonate (EC / EMC). In one example of interest, the electrolyte is a liquid electrolyte and comprises LiPFe in an EC / EMC mixture ([3:7] by volume) with 5% fluoroethylene carbonate (FEC).;

[0094] In some examples, the electrolyte is a liquid electrolyte, and the electrode material comprises an electrochemically active material as defined herein or an electrochemically active material prepared by the method as defined herein, PVDF as a binder, and an electronically conductive material selected from the group consisting of Ketjen carbon MC , Super P carbon MC and VGCFs.

[0095] In some examples, the electrolyte is a gel electrolyte or a gel polymer electrolyte. The gel polymer electrolyte may comprise, for example, a polymer precursor, a salt (e.g., a salt as defined above), a solvent (e.g., a solvent as defined above), and a polymerization and / or crosslinking initiator, if desired. Examples of gel electrolytes include, but are not limited to, gel electrolytes such as those described in PCT patent applications published under numbers WO2009 / 111860 (Zaghib et al.) and WO2004 / 068610 (Zaghib et al.).

[0096] In some examples, a liquid electrolyte or a gel electrolyte as defined above may also impregnate a separator. Examples of separators include, but are not limited to, separators, such as Whatman filters MC made of GF type glass fibers.

[0097] In some examples, the electrolyte is a solid polymer electrolyte including a salt in a polymer solvent. For example, the solid polymer electrolyte may be selected from any known solid polymer electrolyte and may be selected for its compatibility with the various elements of the electrochemical cell. For example, the solid polymer electrolyte is selected for its compatibility with lithium. Solid polymer electrolytes may generally include one or more solid polar polymer(s), optionally crosslinked, and a salt (e.g., a salt as defined previously). Polyether-type polymers may be used, such as those based on PEO, but several other compatible polymers are also known for the preparation of solid polymer electrolytes and are also contemplated. The polymer may be crosslinked.Examples of such polymers include branched polymers, e.g., star polymers or comb polymers such as those described in U.S. Patent No. 7,897,674 B2 (Zaghib et al.) (IIS'674).

[0098] In some examples, the solid polymer electrolyte may include a block copolymer composed of at least one lithium ion solvation segment and optionally at least one crosslinkable segment. Preferably, the lithium ion solvation segment is selected from homo- or copolymers having repeating units of Formula I:

[0099] -(CH2-CH-O) X -

[0100] R

[0101] Formula (I) in which,

[0102] R is selected from a hydrogen atom, and a C1-C2 alkyl group or -(CH2-OR a R b );

[0103] R a is (CH2-CH2-O) y ;

[0104] R bis selected from a hydrogen atom and a C 1 -C alkyl group; x is an integer selected from the range of 10 to 200,000; and y is an integer selected from the range of 0 to 10.

[0105] According to another example, the crosslinkable segment may be a polymer segment comprising at least one functional group crosslinkable multidimensionally by irradiation or heat treatment.

[0106] In some examples, the electrolyte is a solid polymer electrolyte including LiPF6 and a POE-based solvating polymer. In some examples, the electrolyte is a solid polymer electrolyte as defined above and the electrode material comprises an electrochemically active material as defined herein or an electrochemically active material prepared by the method as defined herein and an electronically conductive material selected from the group consisting of Ketjen carbon MC , Super P carbon MCand VGCFs.

[0107] In examples where the electrolyte is a solid polymer electrolyte, the electrode material may, for example, include from about 80 wt% to about 90 wt% of the electrochemically active material, from about 1 wt% to about 5 wt% of the electronically conductive material, and from about 5 wt% to about 19 wt% of the solid polymer electrolyte. In some examples, the electrolyte is a glass or ceramic electrolyte. For example, the glass or ceramic electrolyte may include an ion-conducting crystalline ceramic, an ion-conducting amorphous ceramic, an ion-conducting amorphous glass, or an ion-conducting glass-ceramic.Non-limiting examples of glass or ceramic electrolytes include site-deficient perovskite electrolytes, garnet electrolytes, NASICON glass-ceramic electrolytes, LISICON electrolytes, sodium ion-conducting aluminum oxides (AI2O3) + ) lithium stabilized, and other similar glass or ceramic electrolytes.

[0108] In some examples, the electrolyte may also optionally include at least one additional additive, such as ionically conductive materials, inorganic particles, glass or ceramic particles, e.g., nanoceramics (e.g., aluminum oxide (AI2O3), titanium dioxide (TiCh), silicon dioxide (SiCh) and other similar compounds), and other additives of the same type. For example, the additional additive may be selected from NASICON, LISICON, thio-LISICON, garnets, sulfides, sulfur halides, phosphates, thio-phosphates, in crystalline and / or amorphous form, and combinations thereof. In one example, the additional additive may be substantially dispersed in the electrolyte. The additional additive may also be in a separate layer.

[0109] The present technology also relates to a battery comprising at least one electrochemical cell as defined herein. For example, the battery may be a lithium battery or a lithium-ion battery, a sodium battery or a sodium-ion battery, a magnesium battery or a magnesium-ion battery, or a potassium battery or a potassium-ion battery. According to one variant of interest, the battery is a lithium battery or a lithium-ion battery. According to another variant of interest, the battery is a sodium battery or a sodium-ion battery.

[0110] EXAMPLES

[0111] 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.

[0112] Unless otherwise indicated, all numbers expressing component amounts, preparation conditions, concentrations, properties, etc. used herein are to be understood as being modified in all cases by the term "about." At a minimum, each numerical parameter should be interpreted in light of the number of significant figures reported and by applying common rounding techniques. Therefore, unless otherwise indicated, the numerical parameters set forth herein are approximations that may vary depending on the desired properties. Notwithstanding that the ranges of numerical values ​​and the parameters defining the scope of the embodiments are approximations, the numerical values ​​presented in the following examples are reported as accurately as possible.However, any numerical value inherently contains some errors resulting from variations in experiments, test measurements, statistical analyses, etc.

[0113] Example 1: Synthesis of electrochemically active materials a) Solid-state synthesis of iron-doped oxides of sodium, manganese and at least one tunnel-type metallic element

[0114] Iron-doped oxides of sodium, manganese, and at least one tunnel-type metallic element of formulae Na 0,44 Mn 0,55 You 0,10 O2, Na 0,43 Fe 0,34 Mn 0,44 You 0,22 O2, Na 0,46 Fe 0,30 Mn 0,55 You 0,15 O2, Na 0,44 Fe 0,34 Mn 0,55 You 0, 11 O2, Na 0,41 Fe 0,40 Mn 0,50 You 0,10 O2, Na 0,50 Fe 0,08 Mn 0,81 You 0, 11 O2 and Na 0,50 Fe 0, 11 Mn 0,78 You 0,11O2were synthesized by a simple solid-state reaction. The respective precursors, sodium carbonate (Na2CO3), manganese(III) oxide (Mn2O3), iron(III) oxide (Fe2O3), and titanium dioxide (TiO2), were weighed to obtain the desired stoichiometries. Samples were prepared by grinding and mixing the precursor powders. The ground and mixed precursor powders were then placed in a furnace and heated at a temperature between about 700 °C and about 1000 °C under an air or oxygen atmosphere for 2 to 24 hours. b) Liquid chemical synthesis of iron-doped oxides of sodium, manganese, and at least one tunnel-type metallic element

[0115] Alternatively, the oxides of sodium, manganese and at least one iron-doped tunnel-type metallic element of formulae Na0.44Mn0.55Ti0.10O2, Nao,43Feo,34Mno,44Tio,2202, Na 0,46 Fe 0,30 Mn 0,55 You 0,15 O2, Na0,44 Fe 0,34 Mn 0,55 You 0, 11 O2, Na 0,41 Fe 0,40 Mn 0,50 You 0,10 O2,

[0116] N / A 0,50 Fe 0,08 Mn 0,81 You 0, 11 O2 and Na 0,50 Fe 0, 11 Mn 0,78 You 0, 11 O2 have also been prepared by a sol-gel process. Sol-gel powders are synthesized using citric acid (C6H8O7) as a chelating agent. The respective precursors, sodium carbonate (Na2COs), manganese(II) acetate ((CH3CO2)2Mn), iron(II) oxalate and titanium tetrabutoxide (C 16 H 36 O4Ti) (all from Sigma-Aldrich, > 99.99%), were weighed to obtain the desired stoichiometry and dissolved in distilled water under magnetic stirring with CeHsO? in a molar ratio (Na + Mn) / CeHsO? = 10. The resulting solutions were then heated to a temperature of approximately 80 °C, under stirring, until transparent sol-gel precursors were obtained.

[0117] The obtained sol-gel precursors were then calcined in a furnace at a temperature of about 400 °C for about 6 hours to decompose the organic and inorganic contents (including anionic salts and CeHsO?).

[0118] Finally, the powders thus obtained were ground in a mortar and calcined in a furnace at a temperature of about 900 °C for about 9 hours under an air or oxygen atmosphere to obtain the sol-gel powders Nao,44Mno,5sTio,io02, Nao,43Feo,34Mno,44Tio,2202, Nao,46Feo,3oMno,55Tio,is02, Nao,44Feo,34Mno,5sTio,n02, Nao,4iFeo,4oMno,soTio,io02,

[0119] Nao,5oFeo,o8Mno,8iTio,n02 and Nao,5oFeo,nMno,?8Tio,n02 finals. c) Synthesis of iron-doped oxides of sodium, lithium, manganese and at least one tunnel-type metallic element

[0120] Iron-doped oxides of sodium, lithium, manganese, and at least one tunnel-type metallic element of the formulae Na0,ioLio,33FeO,34Mn0,44Tio,2202, Nao,o8Lio,38FeO,3oMno,55Tio,is02, Nao,2oLio,24FeO,34Mno,5sTio,n02, Nao,2iLio,2oFeO,4oMno,soTio,io02, Nao,ioLio,4oFeO,o8Mno,8iTio,n02, and Nao,ioLio,4oFeO,nMno,78Tio,ii02 were prepared using a one- or two-step ion exchange process to partially replace sodium ions with lithium ions.

[0121] The ion exchange reaction was carried out by mixing the powders prepared in Examples 1(a) and 1(b) up to a 20-fold molar excess of a eutectic lithium salt composition of lithium nitrate (UNO3) and lithium chloride (LiCl) or lithium hydroxide (LiOH) (UNO3:LiCl or LiOH = 1:1 molar ratio). The mixture was then heated to a temperature between about 120°C and about 400°C, either once for about 0.5 hours to about 10 hours or twice for about 0.25 hours to about 5 hours, to obtain the desired stoichiometry.

[0122] Finally, a tunnel-type oxide of sodium, lithium, manganese and at least one metallic element of formula Nao.osLio.seMnCh was also prepared for comparison purposes. This material was obtained by the ion exchange reaction of the present example using a tunnel-type oxide of sodium and manganese of formula Nao44Mn02 as described in PCT patent application published under number WO2021 / 195778 (Wang et al.). d) Powder X-ray diffraction (XRD)

[0123] The atomic and molecular structure of the electrochemically active materials was studied by X-ray diffraction carried out on the powders of sodium, lithium, manganese and at least one tunnel-type metallic element oxides doped with iron, as prepared in Example 1 (c). Figures 1 to 5 show the X-ray diffraction patterns respectively for the tunnel-type powders of Nao,osLio,36Mn02, Nao,ioLio,33Feo,34Mno,44Tio,2202, Nao.osLio.ssFeo.soMno.ssTio sC^, Nao,2oLio,24Feo,34Mno,5sTio,n02 and Nao,2iLio,2oFeo,4oMno,soTio,io02.

[0124] Example 2: Electrochemical properties a) Configurations of electrochemical cells

[0125] The electrochemical properties of the electrochemically active materials prepared in Example 1(c) were investigated. All cells were assembled in 2032 type button cell cases with the components shown in Table 1 and negative electrodes comprising a metallic lithium film on aluminum current collectors. All cells were assembled with Whatman filter paper separators MC GF-type glass fibers impregnated with a 1 M solution of LiPFe in a non-aqueous solvent mixture of EC / EMC ([3:7] by volume) and 5% FEC as liquid electrolyte. The electronically conductive material was a mixture of Ketjen carbon MC and Super P carbon MC ([1:1] by weight).

[0126] Table 1. Electrochemical cell configurations b) Electrochemical behavior

[0127] This example illustrates the electrochemical behavior of electrochemical cells as described in Example 2(a).

[0128] Figure 6 shows the charge and discharge profiles for two comparative cells (Cell 1). Charging and discharging were performed in (1) at a cycling rate of 0.1 C between about 2.0 V and about 4.8 V vs Li + / Li, and in (2) between about 2.0 V and about 4.6 V vs Li + / Li. Charging and discharging were carried out at a temperature of approximately 25 °C. Results are presented for a second discharge and charge cycle.

[0129] Figure 7 shows a second charge and discharge profile for Cell 2. Charging and discharging were performed at a cycling rate of 0.1 C between approximately 2.0 V and approximately 4.8 V vs Li + / Li. Charging and discharging were carried out at a temperature of approximately 25°C.

[0130] Figure 8 shows a charge and discharge profile for Cell 3. Charging and discharging were performed at a cycling rate of 0.1 C between approximately 2.0 V and approximately 4.8 V vs Li + / Li. Charging and discharging were carried out at a temperature of approximately 25 °C. Results are presented for a second charge and discharge cycle.

[0131] Figure 9 shows the charge and discharge profiles for Cell 4. Charging and discharging were performed at a cycling rate of 0.1 C between approximately 2.0 V and approximately 4.8

[0132] V vs Li + / Li. Charging and discharging were carried out at a temperature of approximately 25 °C. Results are presented for a second (1) and a fifth (2) charge and discharge cycle.

[0133] Figure 10 shows a charge and discharge profile for Cell 5. Charging and discharging were performed at a cycling rate of 0.1 C between approximately 2.0 V and approximately 4.8

[0134] V vs Li + / Li. Charging and discharging were carried out at a temperature of approximately 25 °C. Results are presented for a second charge and discharge cycle.

[0135] Figure 11(a) shows charge and discharge profiles for Cell 6. Charging and discharging were performed at a cycling rate of 0.1 C between about 2.0 V and about 4.8 V vs Li + / Li. Charging and discharging were carried out at a temperature of approximately 25 °C. Figure 11(b) is a graph of capacity versus cycle count obtained for Cell 6.

[0136] Figure 12(a) shows charge and discharge profiles for Cell 7. Charging and discharging were performed at a cycling rate of 0.1 C between about 2.0 V and about 4.8

[0137] V vs Li + / Li. Charging and discharging were carried out at a temperature of approximately 25 °C. Figure 12(b) is a graph of capacity versus cycle count obtained for Cell 7.

[0138] The capacity, voltage and specific energy delivered by Cells 1 to 5 are shown in Table 2.

[0139] Table 2. Capacity, voltage and specific energy delivered by the electrochemical cells of the

[0140] Table 1

[0141] As can be observed in Table 2, the presence of iron ions substantially increases the average working potential of the electrochemically active material. Table 2 also shows that the electrochemical properties of the electrochemically active material can be substantially improved by the partial substitution of sodium ions with lithium ions and / or by the partial substitution of manganese ions with titanium ions.

[0142] 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. An electrochemically active material comprising a sodium oxide, manganese oxide, and at least one iron-doped, lithium-substituted tunnel-type metallic element of formula NaaUbFe c MndM e O2, in which a is a number such that 0 < a < 0.22; b is a number such that 0.18 < b < 0.40 and is such that a + b is 0.38 < a + b < 0.62; c is a number such that 0 < c < 0.40; d is a number such that 0.44 < d < 1; e is a number such that c + d + e = 1; and M is chosen from manganese (Mn), titanium (Ti), vanadium (V), nickel (Ni), cobalt (Co), chromium (Cr), molybdenum (Mo), zirconium (Zr), tin (Sn), ruthenium (Ru), other similar metals and a combination of at least two of these.

2. Electrochemically active material according to claim 1, wherein M is selected from manganese (Mn), titanium (Ti), vanadium (V), nickel (Ni), cobalt (Co), chromium (Cr), molybdenum (Mo), zirconium (Zr), ruthenium (Ru), other similar metals and a combination of at least two of these.

3. Electrochemically active material according to claim 1 or 2, wherein M is titanium (Ti).

4. Electrochemically active material according to any one of claims 1 to 3, in which a is a number such that 0.01 < a < 0.22, or 0.02 < a < 0.22, or 0.03 < a < 0.22, or 0.04 < a < 0.22, or 0.05 < a < 0.22, or 0.06 < a < 0.22, or 0.07 < a < 0.22, or 0.08 < a < 0.

21.

5. Electrochemically active material according to claim 4, wherein a is a number such that 0.08 < a < 0.

21.

6. Electrochemically active material according to any one of claims 1 to 5, wherein b is a number such that 0.19 < b < 0.40, or 0.20 < b < 0.40, or 0.20 < b < 0.39, or 0.20 < b < 0.

38.

7. Electrochemically active material according to claim 6, wherein b is a number such that 0.20 < b < 0.

38.

8. Electrochemically active material according to any one of claims 1 to 7, wherein c is a number such that 0.05 < c < 0.40, or 0.10 < c < 0.40, or 0.15 < c < 0.40, or 0.20 < c < 0.40, or 0.25 < c < 0.40, or 0.30 < c < 0.

40.

9. Electrochemically active material according to claim 8, wherein c is a number such that 0.30 < c < 0.

40.

10. Electrochemically active material according to any one of claims 1 to 9, wherein d is a number such that 0.44 < d < 1, or 0.44 < d < 0.95, or 0.44 < d < 0.90, or 0.44 < d < 0.85, or 0.44 < d < 0.80, or 0.44 < d < 0.75, or 0.44 < d < 0.70, or 0.44 < d < 0.65, or 0.44 < d < 0.60, or 0.44 < d < 0.

55.

11. Electrochemically active material according to claim 10, wherein d is a number such that 0.44 < d < 0.

55.

12. Electrochemically active material according to any one of claims 1 to 11, wherein sodium oxide, manganese oxide, and at least one iron-doped, lithium-substituted tunnel-type metal oxide are selected from the group consisting of Na₂O₁₀L₂O₁₀Fe₂O₁₀MnO₂₄Ti₂O₂, Na₂O₁₀L₂O₁₀Fe₂O₁₀MnO₂₄Ti₂O₂, Na₂O₁₀L₂O₁₀Fe₂O₁₀MnO₂₄Ti₂O₁₀, Na₂O₁₀L₂O₁₀Fe₂O₁₀MnO₂₄Ti₂O₁₀, Na₂O₁₀L₂O₁₀Fe₂O₁₀MnO₂₀ ... Nao, Lio,4oFeo,o8Mno,8iTio,ii02 and Nao, Lio,4oFeo,i iMno,7sTio,i 1O2.

13. An electrode material comprising the electrochemically active material as defined in any one of claims 1 to 12.

14. Electrode material according to claim 13, further comprising an electronically conductive material.

15. Electrode material according to claim 14, wherein the electronically conductive material is selected from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes and a combination of at least two of these.

16. Electrode material according to claim 15, wherein the electronically conductive material comprises carbon black.

17. Electrode material according to claim 16, wherein the carbon black is Super Carbon P MC .

18. Electrode material according to claim 16, wherein the carbon black is Ketjen carbon MC.

19. Electrode material according to claim 15, wherein the electronically conductive material comprises carbon fibers.

20. Electrode material according to claim 19, wherein the carbon fibers are gas-formed carbon fibers (VGCFs).

21. Electrode material according to any one of claims 13 to 20, further comprising a binder.

22. Electrode material according to claim 21, wherein the binder is selected from the group consisting of a polyether-type polymer binder, a fluorinated polymer, and a water-soluble binder.

23. Electrode material according to claim 22, wherein the binder is a fluorinated polymer.

24. Electrode material according to claim 23, wherein the fluorinated polymer is polyvinylidene fluoride (PVDF).

25. Electrode material according to any one of claims 13 to 24, further comprising an additive.

26. Electrode material according to claim 25, wherein the additive is selected from the group consisting of ionic conductors, inorganic particles, glass particles, ceramic particles, salts, and other similar additives.

27. An electrode comprising the electrode material as defined in any one of claims 13 to 26 on a current collector.

28. Electrode according to claim 27, said electrode being a positive electrode.

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

30. Electrochemical cell according to claim 29, wherein the negative electrode comprises an alkali metal, an alloy comprising an alkali metal or a prelithiated electrochemically active material.

31. Electrochemical cell according to claim 30, wherein the negative electrode comprises metallic lithium or an alloy comprising metallic lithium.

32. Electrochemical cell according to claim 31, wherein the negative electrode comprises metallic lithium.

33. Electrochemical cell according to any one of claims 29 to 32, wherein the electrolyte is a glass or ceramic electrolyte.

34. Electrochemical cell according to any one of claims 29 to 32, wherein the electrolyte is a liquid electrolyte comprising a salt in a solvent.

35. Electrochemical cell according to any one of claims 29 to 32, wherein the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer.

36. Electrochemical cell according to any one of claims 29 to 32, wherein the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer.

37. Electrochemical cell according to any one of claims 34 to 36, wherein the salt is a lithium salt.

38. Electrochemical cell according to claim 37, 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 (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) and a combination of at least two of these.

39. An electrochemical cell according to claim 38, wherein the lithium salt is lithium hexafluorophosphate (LiPFe).

40. A battery comprising at least one electrochemical cell as defined in any one of claims 29 to 39.

41. Battery according to claim 40, said battery being 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.

42. Battery according to claim 40 or 41, wherein said battery is a lithium battery or a lithium-ion battery.

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