MXPA06008133A - Secondary battery electrode active materials and methods for making the same - Google Patents

Abstract

The invention provides an electrochemical cell which includes a first electrode and a second electrode which is a counter electrode to said first electrode, and an electrolyte material interposed there between. The first electrode comprises an electrode active material represented by the general nominal formula Aa[Mm,Mln,MIIo](XY4)dZe, wherein at least one of M, MI and MII is a redox active element, 0(ES) La invención proporciona una celda electroquímica que incluye un primer electrodo y un segundo electrodo que es un contra-electrodo para el primer electrodo, y un material de electrólito interpuesto entre ellos. El primer electrodo comprende un material activo del electrodo novedoso representado por la fórmula nominal general Aa[Mm,Mn,MIIo](XY4)bZe, en donde al menos uno de M, MI y MII es un elemento activo redox, o

Description

ACTIVE MATERIALS FOR SECONDARY ACCUMULATOR ELECTRODE AND METHODS FOR MANUFACTURING THEMSELVES Field of the Invention This invention relates to improved materials that can be used as active materials for electrode, to methods for manufacturing such improved materials, and to electrochemical cells employing such improved materials . BACKGROUND OF THE INVENTION An "accumulator" consists of one or more electrochemical cells, wherein each cell typically includes a positive electrode, a negative electrode or an electrolyte or other material to facilitate movement of the ion charge carriers between the negative electrode and the electrode. positive electrode When the cell is charged the cations migrate from the positive electrode to the electrolyte, and, consecutively, from the electrolyte to the negative electrode During the discharge, the cations migrate from the negative electrode to the electrolyte, and, consecutively, from the electrolyte to the positive electrode Such accumulators generally include an electrochemically active material having a crystalline grid structure or framework from which the ions can be extracted and consecutively re-inserted, and / or the ions are allowed to be inserted or intercalated and subsequently extracted. Ref .174279 Recient the three-dimensional structured compounds comprising polyanions (for example, (S04) n ~, (P04) n ~, (As04ln_ and the like), have been contemplated as viable alternatives for oxide-based electrode materials such as LiMxOy. Examples of such polyanion-based materials include the ordered olivine compounds Li P04, where = Mn, Fe, Co or the like. Other examples of such polyanion-based materials include NASICON compounds Li3M2 (P0) 3, wherein M = Mn, Fe, Co or the like. Although three classes of polyanion-based compounds, lithiated, have exhibited some promise as electrode components, many such polyanion-based materials are not economical in their production, produce insufficient voltage, have insufficient voltage capacity, exhibit low ionic and / or electrical conductivity, or lose their ability to be recharged during multiple cycles. Therefore, there is a real need for an active material of the electrode that exhibits a high load capacity, that is economical in its production, that produces a sufficient voltage, that exhibits a greater electrical and ionic conductivity, and that retains the capacity during multiple cycles. Brief Description of the Invention The present invention is directed to a novel active material for an electrode containing alkali metal. The novel active material of the present invention is represented by the nominal general formula Aa [Mm, MIn, MII0] (XY4) dZe, wherein: (i) A is selected from the group consisting of the elements of group I of the table periodically, and mixtures thereof, and 0 < a < 9; (ii) at least one of M, MI and Mil is an active element -redox, 0 < m, n, or < 4, and Já [V (MI) + V (MII)] = V (M), where V (M) is the valence state of M, V (MI) is the valence state of MI, and V ( MII) is the valence state of Mil; (iii) XY4 is selected from the group consisting of X '[04-xY'x], X' [04-y, Y'2y], X "S4, [Xz" ', X'? - z] 04, and mixtures thereof, wherein: (a) X 'and X' '' are each independently selected from the group consisting of P, As, Sb, Si, Ge, V, S, and mixtures thereof; (b) X "is selected from the group consisting of P, As, Sb, Si, Ge, V, and mixtures thereof; (c) Y 'is selected from the group consisting of a halogen, S, N, and mixtures thereof; and (d) 0 < x 3, 0 £ and 2, 0 < z _ < 1, and 1 £ d £ 3, and (iv) Z is selected from the group consisting of a hydroxyl (OH), a halogen, and mixtures thereof, and 0 £ e where A, M, MI, Thousand X , Y, Z, a, m, n, o, d, and e are selected to maintain the electroneutrality of the material. This invention also provides electrodes that utilize an active material of the electrode of this invention.

Accumulators having a first electrode including the active material of the electrode of this invention are also provided; a second counter-electrode having a compatible active material; and an electrolyte interposed between them. In a preferred embodiment, the active material of the novel electrode of this invention is used as an active positive electrode material (cathode), reversely recycling the alkali metal ions with an active material of the compatible negative electrode (anode). Detailed Description of the Invention It has been found that the electrode materials, the electrodes, and the novel accumulators of this invention produce benefits over such materials and devices from those known in the art. Such benefits include one or more of increased capacity, improved recyclability, improved reversibility, improved ionic conductivity, improved electrical conductivity, and reduced costs. The benefits and specific embodiments of the present invention are apparent from the detailed description described hereinafter, It should be understood, however, that the detailed description and specific examples, while indicating modalities among those preferred, are proposed for purposes only of illustration and are not intended to limit the scope of the invention The present invention provides active electrode materials for use in an electrochemical cell producing electricity Each electrochemical cell includes a positive electrode, a negative electrode, and an electrolyte in a communication ion transfer with the electrode both positive and negative, to transfer the carriers of the ion charge between them An "accumulator" refers to a device that has one or more electrochemical cells that produce electricity Two or more electrochemical cells can be combined, or "apil adas ", to create an accumulator of multiple cells. The active materials of the electrode of this invention can be used in the negative electrode, in the positive electrode, or both. Preferably, the active materials of this invention are used in the positive electrode. When used herein, the terms "negative electrode" and "positive electrode" refer to electrodes in which oxidation and reduction occur, respectively, during the discharge of the accumulator; During the loading of the accumulator, the oxidation and reduction sites are inverted. Materials - Electrode Active: The present invention is directed to an active material of the electrode containing a novel alkali metal. The novel active material of the present invention is represented by the general formula (I): Aa [Mm, MIn, MII0] (XY4) dZa. (1) The term "Nominal general formula" refers to the fact that the relative proportion of atomic species may vary slightly, in the order of 2 percent to 5 percent, or more typically, 1 percent to 3 percent. The composition of A, M, MI, Mil, XY4 and Z of the general formulas. (I) to (V) here, as well as the stoichiometric values of the elements of the active material, are selected to maintain the electroneutrality of the active material of the electrode. The stoichiometric values of one or more elements of the composition may take values that are not integers. For all embodiments herein, portion A is selected from the group consisting of the elements of Group I of the Periodic Table, and mixtures thereof. When referenced here, "Group" refers to the numbers of the Groups (ie, the columns) of the Periodic Table as defined in the Periodic Table of the current IUPAC. See, for example, the U.S. patent. 6,136,472, Barker et al, issued October 24, 2000, incorporated herein by reference. In one embodiment, A is selected from the group consisting of Li (lithium) Na (sodium), K (potassium), and mixtures thereof. A can be a mixture of Li with Na, a mixture of Li with K, or a mixture of Li, Na and K. In another embodiment, A is Na, or a mixture of Na with K. In a preferred embodiment, A is Li. When used herein, the description of a gender of the elements, materials or other components, of which an individual component or a mixture of components may be selected, is proposed to include all possible generic combinations of the listed components, and mixtures thereof. thereof. In addition, the words "preferred" and "preferably" refer to the embodiments of the invention that produce certain benefits, under certain circumstances. However, other modalities may also be preferred, - under the same or other circumstances. In addition, the description of one or more modalities does not imply that other modalities are not useful, and are not proposed to exclude other embodiments of the scope of the invention. The removal of an amount of the alkali metal (A) from the active material of the electrode is effected by a change in the oxidation state of at least one of the "redox active" elements in the active material, as defined hereinafter. The amount of the redox active material available from the oxidation / reduction in the active material determines the amount of the alkali metal (A) that can be removed. Such concepts are, in the general application, well known in the art, for example, as described in U.S. Pat. 4,477,541, by Fraioli, issued on October 16, 1984; and the U.S. patent 6,136,472, Barker, et al., Issued October 24, 2000, both of which are incorporated herein by reference. A sufficient amount of the alkali metal (A) must be present to allow all of the "redox active" elements of M, MI and Mil (as defined hereinafter) to undergo oxidation / reduction. In one modality, 0 < to 9. In another modality, 0 < a £ 3. In yet another mode, 0 <a < 1. Unless otherwise specified, a variable described herein algebraically as a number equal to ("="), less than or equal to ("£"), or greater than or equal to (">") it is proposed to reassume values or ranges of values approximately equal or functionally equivalent to the established number. In general, the amount (a) in the active material varies during loading / unloading. Where the active materials of the present invention are synthesized for use in the preparation of an electrochemical cell in a discharged state, such active materials are characterized by a relatively high value of "a", with a correspondingly low oxidation state of the active redox components of the active material. When the electrochemical cell is charged from its initial non-charged state, an amount (a ') of the alkali metal (A) is removed from the active material as described above. The resulting structure, which contains less alkali metal (i.e., aa ') than in the state as it was "prepared, and at least one of the redox active components having a higher oxidation state than in the state as prepared, essentially maintains the original value of c The active materials of this invention include such materials in their state of origin (ie, as manufactured prior to inclusion in an electrode) and the materials formed during the operation of the accumulator (i.e. by the insertion or removal of the alkali metal (A).) For all modalities described herein, at least one of M, MI, and Mil is an active redox element, and [V (MI) + V [MII)] = V (M), where V (M) is the valence state of M, V (MI) is the valence state of MI, and V (MII) is the valence state of Mil. When used here, the term "redox active element" includes those elements characterized as those that are capable of undergoing oxidation / reduce tion to another oxidation state when the electrochemical cell is operating under normal operating conditions. When used herein, the term "normal operating conditions" refers to the proposed voltage at which the cell is charged, which, in turn, depends on the materials used to construct the cell. In the embodiment described for the general formula (I), 0 < m, n, or £ 4. The redox active elements useful here with respect to M, MI, Thousand include, without limitation, the elements of the Groups 4 to 11 of the Periodic Table, as well as metals that are not transitional, selected, including, without limitation, Ti (titanium), V (vanadium), Cr (Chromium), Mn (Manganese) Fe (Iron), Co (Cobalt), Ni (Nickel), Cu (Copper), Nb (Niobium), Mo (Molybdenum), Ru (Ruthenium), Rh (Rhodium), Pd (Palladium), Os (Osmium), Ir (Iridium), Pt (Platinum), Au (Gold), Si (Silicon), Sn (Tin), Pb (Lead), and mixtures thereof. When reference is made here, "includes" and its variants, are proposed so that they are not limiting, so that the description of the terms in a list is not the exclusion of other similar terms that may also be useful in the materials, compositions, devices, and methods of the invention. In one modality, M, Mi, and Mil are each. An active redox element. In another modality, at least one of M, MI and Mil is an active element that is not redox. When referenced herein, "active elements that are not redox" include elements that are capable of forming stable active materials, and that do not suffer from oxidation / reduction when the active material of the electrode is operating under normal operating conditions. Among the active elements that are not redox, useful herein include, without limitation, those selected from group 1 elements, particularly Li, K, Na, Ru (Rubidium), Cs (Cesium); Group 2 elements, particularly -Be (Beryllium), Mg (Magnesium), Ca (Calcium), Sr (Strontium), Ba (Barium), elements of group 3, particularly Sc (Scandium), Y (Itrium), and lanthanides, particularly La (Lantano), Ce (Cerium), Pr (Praseodinio), Nd (Neodymium), Sm (Samarium); Group 12 elements, particularly Zn (Zinc) and Cd (Cadmium); Group 13 elements, particularly - "" B (Boron), Al (Aluminum), Ga (Gallium), In (Indian), Ti (Thallium); elements of group 14, particularly C (Carbon), Ge (Germanium); Group 15 elements, particularly As (Arsenic), Sb (Antimony) and Bi (Bismuth); elements of Group 16, particularly Te (Telurio); and mixtures thereof. In one embodiment, each of M, MI, and Mil is a redox active element, MI is selected from the group consisting of the redox active elements with an oxidation state 1+, the oxidation state 2+, the oxidation state 3+ and mixtures thereof, and M [V (MI) + V (MII)] = V (M), where V (M) is the valence state of M, V (MI) is the valence state of MI, and V (MII) is the valence state of Mil. AND? an alternative mode, M and / or Mil is an active element that is not redox. In one embodiment, each of M, MI and Mil is an active redox element, MI is selected from the group consisting of Cu1 +, Ag1 + and mixtures thereof, M and Mil are each redox active elements, and% [V ( MI) + V (MII)] = V (M). In an alternative mode, M and / or Mil is an active element that is not redox. In another modality, each of M, Mi and Mil is a redox active element, A thousand is selected from the group consisting of Ti2 +, V2 +, Cr2 +, Mn2 +, Fe2 +, Co2 +, Ni2 +, Cu2 +, Mo2 +, Si2 +, Sn2 +, Pb2 +, and mixtures thereof, M and Mil are each redox active elements, and M [V (MI) + V (MII)] = V (M). In an alternative mode, M and / or Mil is an active element that is not redox. In another embodiment, each of M, MI and Mil is a redox active element, MI is selected from the group consisting of Ti3 +, V3 +, Cr3 +, Mn3 +, Fe3 +, Co3 +, Ni3 +, Mo3 +, Nb3 +, and mixtures thereof, M and Mil are each redox active elements, and ^ [V (MI) + V (MIII)] = V (M). In an alternative mode, M and / or Mil is an active element that is not redox. In one embodiment, M and Mil are redox active elements, MI is selected from the group consisting of active elements that are not redox with the oxidation state 1+, the oxidation state 2+, the oxidation state 3+ and mixtures of the same, and% [V (MI) + V (MII)] = V (M). In an alternative mode, M and / or Mil is an active element that is not redox. In another modality, MI is selected from the group that ~ consists of Li1 +, K1 +, Na1 +, Ru1 +, Cs1"" 1", and mixtures thereof, M and Mil are each active elements that are not redox, and [V (MI) + V (MII)] = V (M). In a particular embodiment, MI is selected from the group consisting of K1 +, Na1 + -, and mixtures thereof In an alternative embodiment, M or Mil is an active element that is not redox. ~ In another embodiment, MI is selected of the group "consisting of Be2 +, Mg2 +, Ca2 +, Sr2 +, Ba2 +, Zn2 +, Cd2 +, C2 +, Ge2 +, and mixtures thereof, M and Mil are each an active redox element, and [V (MI) + V ( MII)] = V (M). In a particular embodiment, MI is selected from the group consisting of Be2 +, Mg2 +, Ca2 +, Sr2 +, Ba2 +, and mixtures thereof. In another embodiment, MI is selected from the group consisting of Zn2 +, Cd2 +, and mixtures thereof. In yet another particular embodiment, MI is selected from the group consisting of C2 +, Ge2 +, and mixtures thereof. In an alternative mode, M or Mil is an active element that is not redox. In yet another embodiment, MI is selected from the group consisting of Sc3 +, Y3 +, B3 +, Al3 +, Ga3 +, In3 + and mixtures thereof, M and Mil are each redox active elements, and [V (MI) + V (MII )] = V (M). In an alternative mode, M or Mil is an active element that is not redox. In each of the embodiments described herein, M can be partially replaced by an equivalent stoichiometric amount of M and Mil, whereby the active material is represented by the general formula (II): Aa [Mm-n_0, MIn, MII0 ] (XY) dZe, (II) and wherein the stoichiometric amount of one or more of the other components (for example A, XY4 and Z) in the active material must be adjusted to maintain the electroneutrality of the material. However, in each of the modalities described here, M can be partially replaced by MI and Thousand for an "oxidatively" equivalent amount of MI and Mil, for which the active material is represented by the nominal general formula (III): and where V (M) is the valence state of M, V (MI) is the valence state of MI, and V (Mil) is the valence state of MU. In all the modalities described here, XY is an anion selected from the group consisting of X '[04_x, Y'x], X' [04_y, Y'2-y], X "S4, [Xz" ', X' ? -z] 04, and mixtures thereof, wherein: (a) X 'and X' '' are each independently selected from the group consisting of P, As, Sb, Si, Ge, V, S, and mixtures thereof; (b) X '' is selected from the group consisting of P, As, Sb, Si, Ge, V, and mixtures thereof; (c) Y 'is selected from the group consisting of a halogen, S, N, and mixtures thereof; and (d)? £ X £ 3, 0 £ and £ 2-, and 0 < z 1. In a modality, XY4 is selected from the group consisting of X '[04-x, Y'x], X' [0_y, Y '2-y], and mixtures thereof, and x and y are both 0. Stated another way, XY4 is an anion selected from the group consisting of P04, Si04, Ge04, V04, As04, Sb04, S04, and mixtures thereof. Preferably, XY4 is P04 or a mixture of P04 with another anion of the group indicated above (ie, where X 'is not P, Y' is not O, or both, as defined above). In one embodiment, XY4 includes about 80% or more of phosphate and up to about 20% of one or more of the anions noted above. In another embodiment, XY4 is selected from the group consisting of X '[04-x, .Y'x], X' [0-y, Y'2-y], and mixtures thereof, wherein 0 < X £ 3 and 0 < and £ 2, and wherein a portion of the oxygen (O) in the XY portion is substituted with a halogen, S, N, or a mixture thereof.

In all embodiments described herein, the Z portion (when provided) is selected from the group consisting of Z, is selected from the group consisting of a hydroxyl (OH), a halogen, and mixtures thereof. In a modality illustrated by the general formula (I), 0 £ and £ 4. In a particular modality, e = 0. In another particular mode, 0 < e £ 1. In one embodiment, Z is selected from the group consisting of OH, F (Fluorine), Cl (Chlorine), Br (Bromine), and mixtures thereof. In another-modality, Z is OH. In another embodiment, Z is F, or a mixture of F with OH, Cl, or Br. Where the Z portion is incorporated into the active material of the present invention, the active material - may not be taken on a NASICON structure or of olivine where p = 3 od = 1, respectively. It is very normal for the symmetry to be reduced with the incorporation of, for example, halogens. The composition of the active material of the electrode, as well as the stoichiometric values of the elements of the composition, are selected to maintain the electroneutrality of the active material of the electrode. The stoichiometric values of one or more elements of the composition may take values that are not integers. Preferably, the portion XY4 is, as a unitary portion, an anion having a charge of -2, -3, or -4, depending on the selection of X ', X' ', X' '' Y ', yxe and .

When XY4 is a mixture of polyanions such as the preferred phosphate / phosphate substitutes described above, the net charge on the XY4 anion can take values that are not integers, depending on the charge and composition of the individual groups XY4 in the mixture. In a particular embodiment, the active material of the electrode has a dipiramidal orthorhombic crystal structure and belongs to the spatial group Pbnm (for example an olivine or trifillite material) and is represented by the general formula (IV): Aa [Mm, MIn, MII0] XY4Ze, (IV) wherein: (a) the portions A, M, MI, Mil, X, Y and Z are as defined above herein; (b) at least one of M, MI, and Mil is an active redox element, and% [V (MI) + V (MII)] = V (M) where V (M) is the valence state of M , V (MI) is the valence state of MI, and V (MII) is the valence state of Mil; (c) 0 < at £ 2, 0 < m, n, or 2; and 0 < e £ 1; and (d) the components of portions A, M, MI, Mil, X, Y, and Z, as well as the values for a, m, n, o and e, are selected to maintain the electroneutrality of the compound. In a particular submodality, A of the general formula (II) is Li, and XY4 = P04.

In another particular embodiment, the active material of the electrode has a rhombohedral NASICON (spatial group R-3) or monoclinic (spatial group Pbnc) structure, and is represented by the nominal general formula (V): Aa [Mm, MIn, MII0] (XY4) 3Ze, (V) wherein (a) the portions A, M, MI, Mil, X, Y and Z are as defined above herein; (b) at least one of M, MI, and Mil is an active redox element, and% [V (MI) + V (MII)] = V (M) where V (M) is the valence state of M , V (MI) is the valence state of MI, and V (MII) is the valence state of Mil; (c) 0 < at £ 5, 1 < m, n ,? £ 3; and O < e £ 4; and (d) the components of portions A, M, MI, Mil, X, Y, and Z, as well as the values for a, b, m, n, o and e, are selected to maintain the electroneutrality of the compound. In a particular submodality, A of the general formula (III) is Li, and XY4 = P04. Manufacturing Methods: The particular raw materials used will depend on the particular active material to be synthesized, the reaction method employed, and the desired byproducts. The active materials of the present invention are synthesized by reacting the alkali metal, M, MI, Mil, and the compounds containing XY4, at a temperature and for a sufficient time to form the desired reaction product. When used herein, the term "containing" includes compounds that contain the particular component, or that react to form the particular component so specified. Alkaline metal sources include any of a number of salts containing the alkali metal or ionic compounds. Compounds of lithium, sodium, and potassium are preferred, with lithium being particularly preferred. A wide range of such materials is well known in the field of inorganic chemistry Examples include fluorides, chlorides, bromides, iodides, nitrates, nitrites, sulfates, acid sulfates, sulfites, bisulfites, carbonates, bicarbonates, borates, phosphates , silicates, antimonatos, arsenatos, germanatos, oxides, acetates, oxalatos, that contain alkaline metals, and similars.The hydrates of the previous compounds also can be used, as well as the mixtures of the same.The mixtures can contain more than one metal alkaline so that a mixed alkali metal active material will be produced in the reaction.M, MI and Mil sources include fluorides, chlorides, bromides, iodides, nitrates, nitrites, sulfates, sulfates, sulphites, bisulfites, carbonates, bicarbonates , borates, phosphates, acid ammonium phosphates, diacid ammonium phosphates, silicates, antimonatos, arsenatos, germanatos, oxides, hydroxides, acetates, and oxalates d e the same. Hydrates can also be used. The element M, MI, and Mil in the raw material can have any oxidation state, depending on the oxidation state required in the desired product and the oxidizing and reducing conditions contemplated. It should be noted that any of the compounds noted above can also function as a source of the XY portion. As noted above, the active materials of the present invention may contain one or more XY4 groups, or may contain a phosphate group that is fully or partially substituted by one or more other portions of XY4, which will also be referred to as "replacements". of phosphate "or" modified phosphates ". Accordingly, the active materials are provided according to the invention wherein the XY4 portion is a phosphate group that is completely or partially replaced by portions such as Si04, Ge04 / V04, As04 / Sb04, S0, and mixtures thereof. Analogous elements of the above oxygenated anions wherein some or all of the oxygens are replaced by sulfur are also useful in the active materials of the invention, with the exception that the sulphate group can be completely replaced with sulfur. For example, the thiomonophosphates can also be used as a complete or partial replacement of the phosphate in the active materials of the invention. Such thiomonophosphates include the anions (P03S) 3", (P02S2) 3", (POS3) 3", and (PS) 3 ~, and are even more conveniently available as the sodium, lithium, or potassium derivative. Limitations of the monofluoromonocyphate sources include, without limitation, Na2P03F, K2P03F, (NH4) 2P03F-H20, LiNaP03F-H20, LiKP03F, LiNH4P03F, NaNH4P03F, NaK3 (P03F) 2 and CaP03F-2H20. Representative examples of compound sources of trifluorophosphate include, without limitation, NH4P02F2, NaP02F2, KP02F2, A1 (P02F2) 3, and Fe (P02F2) 3. Sources of the XY4 portion are common and readily available, for example, where X is Si sources Useful silicon include orthosilicates, pyrosilicates, cyclic silicates anions such as (Si309) 6 ~, (Si60? 8) 12"and the like, and the pyrocenes represented by the formula [(Si03) 2] n, for example LiAl (SiO3) 2. Silica or SiO2 can also be used. Representative arsenate which can be used to prepare the active materials of the invention wherein X is As include H3As04 and the salts of the anions [H2As04] ~ and [HAs04] 2". Where X is Sb, the antimonate can be provided by antimony-containing materials such as Sb205, MJSb03 wherein M1 is a metal having an oxidation state 1 +, MI?:?: Sb04 wherein M111 is a metal having a state of oxidation 3+, and M?:? Sb207, wherein M11 is a metal that has an oxidation state of 2+. Additional sources of the antimonate include compounds such as Li3Sb04, NH4H2Sb04, and other mixed salts of alkali metals and / or ammonium of the [Sb04] 3 anion. "Where X is S, the sulfate compounds that may be used include the sulfates and alkali metal and transition metal disulfides as well as mixed metal sulfates such as (NH4) 2Fe (S04) 2, NH4Fe (S04) 2 and the like Finally, where X is Ge, a germanium containing compound such as Ge02 can be used to synthesize the active material Where Y 'of the portions X'04-xY'x, and X' 04-yY'2y is F, the sources of F include ionic compounds that contain a fluoride ion (F) or a hydrogen difluoride ion (HF2"). The cation can be any cation that forms a stable compound with the fluoride or hydrogen chloride dihydrogen. Examples include metal cations of 1+, 2+ and 3+, as well as ammonium and other nitrogen-containing cations. Ammonium is a preferred cation because it tends to form volatile by-products that are easily removed from the reaction mixture. Similarly, to produce X'04.xNx, raw materials containing "X" moles of a nitride ion source are provided. The nitride sources are among those known in the art including nitride salts such as Li3N and (NH4) 3N. As noted above, the active materials of the invention contain a mixture of A, M, MI, Mil, XY4 and (optionally) Z. A raw material can provide more than one of these components, as is evident in the above list. In various embodiments of the invention, the raw materials are caused to combine, for example, M and P04. As a general rule, there is sufficient flexibility to -allow the selection of raw materials containing any of the components of the alkali metal A, M, MI, Thousand, XY4, and (optionally) Z, depending on availability. Combinations of the raw materials provided by each of the components can also be used. In general, any counterion can be combined with A, M, MI, Mil, XY4, and (optionally) Z. It is preferred, however, to select raw materials with counterions that cause the formation of volatile by-products during the reaction. Accordingly, it is desirable to choose ammonium salts, carbonates, bicarbonates, oxides, hydroxides, and the like, where possible. Raw materials with these counterions tend to form volatile by-products such as water, ammonia, and carbon dioxide, which can be easily removed from the reaction mixture. Similarly, sulfur-containing anions such as sulfate, bisulfate, sulfite, bisulfite and the like tend to lead to volatile sulfur oxide byproducts. Nitrogen-containing anions such as nitrate and nitrite also tend to cause volatile N0X byproducts. A method for preparing the active materials of the present invention is by hydrothermal treatment of the raw materials required. In a hydrothermal reaction, the raw materials are mixed with a small amount of a liquid (for example water) and heated in a pressurized vessel or furnace at a temperature that is relatively lower when compared to the temperature necessary to produce the active material in an oven at ambient pressure. Preferably, the reaction is carried out at a temperature of about 150 ° C to about 450 ° C, under pressure, for a period of about 4 to about 48 hours, or until a reaction product is formed. The active materials of the present invention can also be synthesized by means of a reaction in the solid state, with or without the oxidation or simultaneous reduction of the oxidizable / reducible elements of M, MI and Mil, by heating the required raw materials at an elevated temperature for a given period of time, until the desired reaction product is formed. In a solid state reaction, the raw materials are provided in a particulate or powdered form, and are mixed together by any of a variety of processes, such as by grinding in a ball mill, combining in a mortar with the hand of the mortar, and the like. Typically, the raw materials are milled in a ball mill for 2 to 18 hours, rotating at a speed of 20 rpm. After this, the mixture of the pulverized raw materials can be compressed into a pellet and / or held together with a binder material which can also serve as a source of the reducing agent, to form a closely coherent reaction mixture. The reaction mixture is heated in an oven, generally at a temperature of about 400 ° C or higher, until a reaction product is formed. The reaction can be carried out under reducing or oxidizing conditions. The reducing conditions can be provided by effecting the reaction in a "reducing atmosphere" such as hydrogen, ammonia, carbon monoxide, methane or mixtures thereof, or other suitable reducing gas. Alternatively, or in addition thereto, the reduction can be carried out in situ by including in the reaction mixture a reducing agent that will participate in the reduction to reduce the M, MI, and / or Mil, and produce byproducts that will not interfere with the active material when they are subsequently used in an electrode or in an electrochemical cell. The reduction can also be effected by synthesizing the active materials of the present invention by means of a thermal reaction, wherein M, MI, and / or Mil is reduced by a granulated or powdered metal present in the reaction mixture. In one embodiment, the reducing agent is elemental carbon, wherein the reducing power is provided by the simultaneous oxidation of the carbon to carbon monoxide and / or carbon dioxide. An excess of carbon, which remains after the reaction, is intimately mixed with the active material of the product and functions as a conductive constituent in the formulation of the final electrode. Consequently, the excess carbon, of the order of 100% or greater, can be used. The presence of carbon particles in the starting materials also provides nucleation sites for the production of crystals of the product. The source of carbon reduction can also be provided by an organic material which forms a carbon-rich decomposition product, referred to herein as a "carbonaceous material", and other by-products during heating under the conditions of the reaction. At least a portion of the organic precursor, the carbonaceous material and / or the functions formed by the by-products before, during and / or after the organic precursor undergoes thermal decomposition, as a reduction during the synthesis reaction for the active material. Such precursors include any liquid or solid organic material (for example, sugars and other carbohydrates, including derivatives and polymers thereof). Although the reaction can be carried out in the presence of oxygen, the reaction is preferably carried out under an essentially non-oxidizing atmosphere so as not to interfere with the reduction reactions being carried out. An essentially non-oxidizing atmosphere can be achieved through the use of a vacuum, or through the use of inert gases such as argon, nitrogen, and the like. Preferably, the particulate starting materials are heated to a temperature below the melting point of the starting materials. The temperature should be about 400 ° C or higher, and desirably about 450 ° C or higher. The CO and / or C02 are produced during the reaction. Higher temperatures favor the formation of CO. Some of the reactions are carried out more desirably at temperatures greater than about 600 ° C; more desirably greater than about 650 ° C. Suitable ranges for many reactions are from about 500 to about 1200 ° C. At about 700 ° C the reactions of both C are occurring. CO as of C - > C02 . At temperatures closer to about 600 ° C, the reaction of C? C02 is the dominant reaction. At a temperature closer to about 800 ° C, the reaction of C-CO is dominant. Since the reducing effect of the C - »C02 reaction is greater, the result is that less carbon is needed per atomic unit of M1 and / or M11 to be reduced. The starting materials can be heated upwardly from a fraction of a degree to about 10 ° C per minute. In some cases, for example where continuously heated rotary furnaces are employed, the rising speed can be significantly higher. Once the desired reaction temperature is achieved, the reagents (starting materials) are maintained at a reaction temperature for a sufficient time for the reaction to occur. Typically, the reaction is carried out for several hours at the final reaction temperature.

After the reaction is complemented, the products are preferably cooled from the elevated temperature to room temperature (ie, about 10 ° C to about 40 ° C). It is also possible to shut off the products to achieve a higher cooling rate, for example, in the order of approximately 100 ° C / minute. Thermodynamic considerations such as the ease of reduction of the selected starting materials, the kinetic characteristics of the reaction, and the melting point of the salts will cause adjustment in the general procedure, such as the amount of the reducing agent, the temperature of the reaction, and the drying time. Electrochemical cells: To form an electrode, the active material of the present invention can be combined with a polymeric binder (e.g., polyvinylidene difluoride (PVdF) and hexafluoropropylene (HFP)) to form a cohesive mixture. The mixture is then placed in electrical communication with a current collector, which, in turn, provides electrical communication between the electrode and an external load. The mixture can be formed or laminated on the stream collector, or an electrode film can be formed from the mixture where the stream collector is interleaved in the film. Suitable current collectors include cross-linked or sheet-shaped metals (eg aluminum, copper and the like). A diluent or electrically conductive agent (e.g., a carbon such as carbon black and the like) can be added to the mixture to increase the electrical conductivity of the electrode. In one embodiment, the electrode material is compressed on or around the current collector, thus eliminating the need for the polymeric binder. In one embodiment, the electrode contains 5 to 30% by weight of the electrically conductive agent, 3 to 20% by weight of the binder, and the remainder which is the active material of the electrode. To form an electrochemical cell, a solid electrolyte or an electrolyte permeable separator is interposed between the electrode and a counter-electrode. In one embodiment, the electrolyte contains a solvent selected from the group consisting of the electrolyte comprising a lithium salt and a solvent selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC) ), ethylmethyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, lactones, esters, glymes (dimethoxyethoes), sulfoxides, sulfoianes, and mixtures thereof; and 5 to 65% by weight of an alkali metal salt. Combinations of the preferred solvents include EC / DMC, EC / DEC, EC / DPC and EC / EMC. In one embodiment, the counter-electrode contains an active intercalation material selected from the group consisting of a transition metal oxide, a metal chalcogenide, carbon (for example "graphite), and mixtures thereof. of electrolytes, and methods for manufacturing them, among those useful herein, are disclosed in US patent 5,700,298, Shi et al., issued December 23, 1997; US patent 5,830,602, Barker et al., issued November 3, 1998, US Patent 5,418,091, Gozdz et al., Issued May 23, 1995, US Patent 5,508,130, Golovin, issued April 16, 1996, US Patent 5,541,020, Golovin et al. , issued July 30, 1996, US Patent 5,620,810, issued by Golovin et al., issued April 15, 1997, US Patent 5,643,695, issued by Barker et al., issued July 1, 1997; 5,712,059, Barker et al., Issued January 27, 1997 the U.S. 5,851,504, Barker et al., Issued December 22, 1998; the U.S. patent 6,020,087, from Gao, issued on February 1, 2001; and the U.S. patent 6,103,419, by Saidi et al., Issued August 15, 2000; all of which are incorporated herein for reference. Electrochemical cells composed of electrodes (including stacked cells of polymer type and cylindrical cells), electrolytes and other materials, among those useful here, are described in the following documents, all of which are incorporated for reference here: US patent 4,668,595, issued by Yoshino et al., May 26, 1987; the U.S. patent 4,792,504, Schwab et al., Issued December 20, 1998; the U.S. patent 4,830,939, Lee et al., Issued May 16, 1989; the U.S. patent 4,935,317, to Fauteaux et al., Issued June 19, 1980; the U.S. patent 4,990,413, Lee et al., Issued February 5, 1991; the U.S. patent 5,037,712, issued by Shackle et al., Issued August 6, 1991, US Pat. No. 5,262,253, issued by Golovin, issued November 16, 1993, and US Patent 5,300,373, issued by Shackle, issued April 5, 1994; US Patent 5,399,447, Chaloner-Gill et al., issued March 21, 1995; US Patent 5,411,820, issued by Chaloner-Gill, issued May 2, 1995; US Patent 5,435,054, issued by Tonder et al., issued on July 25, 1995, US Pat. No. 5,463,179, issued by Chaloner-Gill et al., issued on October 31, 1995, US Pat. No. 5,482,795, issued by Chaloner-Gill, issued on January 9, 1996; US Patent No. 5,660,948; , of Barker, issued September 16, 1995; US Patent No. 5,869,208, Miyasaka, issued February 9, 1999; US Patent No. 5,882,821, Miyasaka, issued March 16, 1999; US No. 5,616,436, issued to Sonobe et al., Issued April 1, 1997, and US Patent No. 6,306,215, issued to Larkin, issued October 23, 1997; 2001. The following non-limiting examples illustrate the compositions and methods of the present invention Example 1 An active material of the electrode having the formula Li [Fe2 + o.9? Cu + 0.o5 3 + o.? 5] P04 it is done as follows. The following raw materials are provided, and the synthesis reaction proceeds as follows. 0.5Li2CO3 + 0.025 Cu20 + 0.025 V203 + 0.45 Fe203 + 1.00 NH4H2P04 + 0.45 C? Li [Fe2 + o.90, CuYos, V3 + 0.05] PO + 0.5 C02 + 0.45 CO + NH3 + 1.5 H20 The reagents are pre-mixed according to the following proportions: The above raw materials are combined and ground in a ball mill to mix the particles. After this, the mixture of the particles is converted into pellets. The mixture converted into pellets is heated, preferably in an inert atmosphere which is in fluid movement (for example, argon), until a product of the reaction is formed. The sample is removed from the oven and cooled. A suitable electrochemical test cell containing the active Li material [Fe2 + 0.9o, Cu + 0.05, V3 + 0.05] PO4 is constructed as follows. The positive electrode is prepared by emptying in the solvent a suspension of the active material, the conductive carbon, the binder and the solvent. The conductive carbon used is Super P (commercially available from MMM Coal). Kynar Flex 2801 (commercially available from Elf Atochem Inc.) is used as the binder, and electronic grade acetone as the solvent. The suspension is cast on glass and a film of the self-supporting electrode is formed when the solvent evaporates. The electrode film contains the following components, expressed as a percentage by weight: 80% of the active material, 8% of Super P carbon, and 12% of the Kynar 2801 binder. The carbonaceous material capable of reversibly intercalating the alkali metal ions is employed as the negative electrode. The electrolyte consists of ethylene carbonate (EC) and methyl ethyl carbonate (EMC) in a weight ratio of 2: 1, and a 1 molar concentration of a salt containing the compatible alkali metal (for example LiPF6). A fiberglass separator interpenetrated by the solvent and salt is interposed between the positive and negative electrodes. When an accumulator that uses the active material of Li [Fe2 + o.9? ^ Cu + 0.o5r V3 + 0.05] PO4 as the positive electrode, the active material is loaded, the active material of Li [Fe2 + o.9? CU + O.O5? 3"O5] P04 undergoes the following reversible oxidation reaction: Li [Fe2 + 0.9o, CuYo5, V3 + o.? 5] P?" 4 [Fe3 + 0.90, Cu2 + o.05, V4 + o.? 5 ] P04 + 1.0 Li + + 1.0 e ~ "10 Example 2 An active electrode material having the formula Li [Fe2 + 0.90r? + O.os / V3 + 0.05] PO4 is made as follows The following raw materials are provided , and the synthesis reaction proceeds as follows: 15 0.5 Li2C03 + 0.025 K2C03 + 0.025 V203 + 0.45 Fe203 + 1.00 NH4H2P04 + 0.45 C? Li [Fe2 + o.90, K + 0.05, V3 + 0.05] PO4 + 0.525 C02 + 0.45 CO + NH3 + 1.5 H20 The reagents are pre-mixed according to the following proportions: 20 The mixture indicated above is subjected to the reaction conditions specified in Example 1 to form the active material of Li [Fe2 + o.9o, + o.05, V3 + o.os] P0. When an accumulator that uses the Li [Fe2 + o.9o, K + 0.o5r V3 + o.os] P04 as the electrode-positive, the active material is charged, the positive material of Li [Fe2 + 0.9o, K + o.? 5 / - V3 + 0.05] PO4 suffers from the following reversible oxidation reaction. LÍ [Fe2 + 0.9o, K + o.? 5, V3Yo53P04? [Fe3 + o.90, K + o.o5, V5 + o.05] P04 + 1.0 Li + + l.Oe "Example 3 An active material of the electrode having the formula Li [Fe2 + 0.8, Ag + o.? , Mn3 + 0.?] P04 is done as follows The following raw materials are provided, and the synthesis reaction proceeds as follows: 0.5 Li2C03 + 0.050 Ag20 + 0.050 Mn203 + 0.40 Fe203 + 1.00 NH4H2P04 + 0.4 C? Li [Fe2 + 0.8, Ag + o.?, Mn3 + o.?] P04 + 0.5 C02 + 0.4 CO + NH3 + 1.5 H20 Reagents are pre-mixed according to the following proportions: The above-mentioned mixture under the reaction conditions specified in Example 1 to form the active material of Li [Fe2 + o.g, Ag + o.?, Mn3 + 0.?] P04. When an accumulator that uses Li [Fe2 + o.8 ^ Ag + o.?, Mn3 + 0.?] P04 as the positive electrode, the active material is charged, the positive material of Li [Fe2 + 0.8, Ag + o.?,Mn3+0.?]P04 has the following reversible oxidation reaction. Li [Fe2 + o.8, Ag + o.?, Mn3 + o.?] P04? - [Fe3 + 0.8 / Ag2 + o.?, Mn4 + o.?] P? 4 + 1.0 Li + + 1. 0 e "Example 4 An active material of the electrode having the formula Li [Fe2 + 0_8r Ag + o.?, Ti3 + 0.?] PO4 is made as follows The following raw materials are provided, and the synthesis reaction proceeds as indicated below 0.5 Li2C03 + 0.050 Ag20 + 0.050 Ti203 + 0.40 Fe203 + 1.00 NH4H2P04 + 0.4 C? Li [Fe2 + 0.8, Ag + 0.?, Ti3 + or.?] P04 + 0.5 C02 + 0.4 CO + NH3 + 1.5 H20 The reagents are pre-mixed according to the following proportions: The above-mentioned mixture is subjected to the reaction conditions specified in Example 1 to form the active material of Li [Fe 2 + 0.8 / g "10", Ti 3"10"] P04. When an accumulator that uses Li [Fe2 + 0.8, Ag + 0.1, Ti3 + 0.?] PO4 as the positive electrode, the active material is charged, the active material of Li [Fe2 + 0.8, Ag + o.?, Ti3 + 0.?] P04 suffers the following reversible oxidation reaction. Li [Fe2 + o.8, Ag + 0.?, Ti3 + o.1] P04? [Fe3 + 0.8, Ag2 + o.!, Ti4 + 0.?] P04 + 1.0 Li + + 1.0 e "Los. ' examples and other embodiments described herein are exemplary and are not intended to limit in the description the full scope of the compositions and methods of this invention Changes, modifications and equivalent variations of the specific modalities, materials, compositions and methods can be made within of the scope of the present invention, with substantially similar results It is noted that with respect to this date, the best method known by the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention. .

Claims (65)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property. An accumulator, characterized in that it comprises: (A) a first electrode comprising a compound represented by the nominal general formula: Aa [Mra, MIn, MII0] (XY4) dZe, wherein: (i) A is selected from the group which consists of the elements of Group I of the Periodic Table, and mixtures thereof, and 0 < to £ 9; (ii) at least one of M, -MI, and Mil is a redox active element, 0 < m, n, or £ 4, and% [V (MI) + V (MII)] = V (M), where V (M) is the valence state of M, V (MI) is the valence state of MI, and V (MII) is the valence state of Mil, and where MI is selected from the group consisting of Li1 + K1 +, Na1 +, Ru1 +, Cs1 +, and mixtures thereof; (iii) XY is selected from the group consisting of X'fO ^^ Y'x], X '[04.y, Y'2y], X''S4, [Xz "', X '? - z] 04 , and mixtures thereof, wherein: (a) X 'and X' '' are each independently selected from the group consisting of P, As, Sb, Si, Ge, V, S, and mixtures thereof; (b) X "is selected from the group consisting of P, As, Sb, Si, Ge, V, and mixtures thereof; (c) Y 'is selected from the group consisting of a halogen, S, N, and mixtures thereof; and (d)? £ X £ 3,? £ and £ 2,? £ Z £ l, and l £ d £ 3; and (iv) Z is selected from the group consisting of a hydroxyl (OH), a halogen, and mixtures thereof, and 0 £ e £ 4; where A, M, MI, Thousand X, Y, Z, a, m, n, o, d, and e are selected to maintain the electroneutrality of the compound; (B) the accumulator further comprises a second electrode; and (C) an electrolyte.
2. 2. The accumulator according to claim 1, characterized in that A is selected from the group consisting of Li, K, Na, and mixtures thereof.
3. 3. The accumulator according to claim 1, characterized in that A is Li.
4. The accumulator according to claim 1, characterized in that at least one of M and Mil is an active element that is not redox.
5. 5. The accumulator according to claim 1, characterized in that one of M and Mil is an active element that is not redox.
6. 6. An accumulator, characterized in that it comprises: (A) a first electrode comprising a compound represented by the nominal general formula: Aa [Mm, MI? A, MII0] (XY4) dZe, wherein: (i) A is selected from the group which consists of the elements of Group I of the Periodic Table, and mixtures thereof, and 0 < to £ 9; (ii) at least one of M, MI and Mil is a redox active element, 0 <m, n, or £ 4, and [V (MI) + V (MII)] = V (M), where V (M) is the valence state of M, V (MI) is the valence state of MY; (iii) XY4 is selected from the group consisting of X '[04.x, Y'x], X' [04.y, Y'2y], X "S4, [Xz '", X'? - z] 04, and mixtures thereof, wherein: (a) X 'and X' '' are each independently selected from the group consisting of P, As, Sb, Si, Ge, V, S, and mixtures thereof; (b) X "is selected from the group consisting of P, As, Sb, Si, Ge, V, and mixtures thereof; (c) Y 'is selected from the group consisting of a halogen, S, N, and mixtures thereof; and (d)? £ X £ 3,? £ and £ 2, 0 < z 1, and l £ d £ 3; and (iv) Z is selected from the group consisting of a hydroxyl (OH), a halogen, and mixtures thereof, and 0 £ e £ 1; where A, M, MI, Thousand X, Y, Z, a, m, n, o, d, and e are selected to maintain the electroneutrality of the compound; (B) the accumulator further comprises a second electrode; and (C) an electrolyte.
7. The accumulator according to claim 6, characterized in that A is selected from the group consisting of Li, K, Na, and mixtures thereof.
8. 8. The accumulator according to claim 6, characterized in that A is Li.
9. 9. The accumulator according to claim 6, characterized in that M, MI and Mil are each a redox active element.
10. The accumulator according to claim 9, characterized in that MI is selected from the group consisting of redox active elements with an oxidation state 1+, an oxidation state 2+, an oxidation state 3+ and mixtures thereof .
11. The accumulator according to claim 6, characterized in that at least one of M and Mil is an active element that is not redox.
12. 12. The accumulator according to claim 6, characterized in that MI is selected from the group consisting of CuI +, Ag1 + and mixtures thereof.
13. 13. The accumulator according to claim 12, characterized in that at least one of M and Thousand is an active element that is not redox.
14. 14. The accumulator according to claim 6, characterized in that MI is selected from the group consisting of Ti2 +, V +, _Cr2 +, Mn2 +, Fe2 +, Co2 +, Ni +, Cu2 +, Mo2 +, _ Si2 + Sn2 +, Pb2 +, and mixtures thereof. same.
15. 15. The accumulator according to claim 14, characterized in that at least one of M and Mil is an active element that is not redox.
16. 16. The accumulator according to claim 6, characterized in that MI is selected from the group consisting of Ti3 +, V3 +, Cr3 +, Mn3 +, Fe3 +, Co3 +, Ni3 +, Mo3 +, Nb3 +, and mixtures thereof.
17. The accumulator according to claim 16, characterized in that at least one of M and Mil is an active element that is not redox.
18. The accumulator according to claim 6, characterized in that MI is selected from the group consisting of active elements which are not redox with an oxidation state 1+, an oxidation state 2+, an oxidation state 3+ and mixtures thereof.
19. 19. The accumulator according to claim 18, characterized in that one of M and Mil is an active element that is not redox.
20. 20. The accumulator according to claim 18, characterized in that MI is selected from the group consisting of Li1 +, K1 +, Na1 +, Ru1 +, Cs1 +, and mixtures thereof.
21. 21. The accumulator according to claim 20, characterized in that one of MI and Mil is an active element that is not redox.
22. 22. The accumulator according to claim 18, characterized in that MI is selected from the group consisting of Be2 +, Mg2 +, Ca2 +, Sr2 +, Ba2 +, Zn2 +, Cd2 +, C2 +, Ge2 +.
23. 23. The accumulator according to claim 22, characterized in that one of M and Mil is an active element that is not redox.
24. 24. The accumulator according to claim 18, characterized in that MI is selected from the group consisting of Be2 +, Mg2 +, Ca2 +, Sr2 +, Ba2 +, and mixtures thereof.
25. 25. The accumulator according to claim 18, characterized in that MI is selected from the group consisting of Zn2 +, Cd2 +, and mixtures thereof.
26. 26. The accumulator according to claim 18, characterized in that MI is selected from the group consisting of C2 +, Ge2 +, and mixtures thereof.
27. 27. The accumulator according to claim 18, characterized in that MI is selected from the group consisting of Sc3 +, Y3 +, B3 +, Al3 +, Ga3 +, and mixtures thereof.
28. 28. The accumulator according to claim 6, characterized in that one of M and Mil is an active element that is not redox.
29. 29. An accumulator, characterized in that it comprises: (A) a first electrode comprising a compound represented by the nominal general formula: Aa [Mm, MIn, MII0] (XY4) 3Ze, wherein: (i) A is selected from the group which consists of the elements of Group I of the Periodic Table, and mixtures thereof, and 0 < to £ 5; (ii) at least one of M, MI and Mil is a redox active element, 1 < m, n, or £ 3, and [V (MI) + V (MII)] = V (M), where V (M) is the valence state of M, V (MI) is the valence state of MY; (iii) XY4 is selected from the group consisting of X '[? -x, yX], X '[04-y, Y'2y], X''S4, [XX > ', X'a-z] 04, and mixtures thereof, wherein: (a) X' and X '' 'are each independently selected from the group consisting of P, As, Sb, Si, Ge, V , S, and mixtures thereof; (b) X "is selected from the group consisting of P, As, Sb, Si, Ge, V, and mixtures thereof; (c) Y 'is selected from the group consisting of a halogen, S, N, and mixtures thereof; and (d)? £ X £ 3,? £ and £ 2, and? £ Z £ l; and (iv) Z is selected from the group consisting of a hydroxyl (OH), a halogen, and mixtures thereof, and 0 £ e < '- where A, M, MI, Thousand X, Y, Z, a, m, n, o, d, and e are selected to maintain the electroneutrality of the compound; (B) the accumulator further comprises a second electrode; and (C) an electrolyte.
30. 30. The accumulator according to claim 29, characterized in that A is selected from the group consisting of Li, K, Na, and mixtures thereof.
31. 31. The accumulator according to claim 29, characterized in that A is Li.
32. 32. The accumulator according to claim 29, characterized in that M, MI and Mil are each a redox active element.
33. 33. The accumulator according to claim 32, characterized in that MI is selected from the group consisting of redox active elements with an oxidation state 1+, an oxidation state 2+, an oxidation state 3+ and mixtures thereof.
34. 34. The accumulator according to claim 29, characterized in that at least one of M and Mil is an active element that is not redox ..
35. 35. The accumulator according to claim 29, characterized in that MI is selected from the group consisting of of Cu1 +, Ag1 + and mixtures thereof.
36. 36. The accumulator according to claim 35, characterized in that at least one of M and Mil is an active element that is not redox.
37. 37. The accumulator according to claim 29, characterized in that MI is selected from the group consisting of Ti2 +, V2 +, Cr2 +, Mn2 +, Fe2 +, Co2 +, Ni2 +, Cu2 +, Mo2 +, Si2 + Sn2 +, Pb2 +, and mixtures thereof.
38. 38. The accumulator according to claim 37, characterized in that at least one of M and Mil is an active element that is not redox.
39. 39. The accumulator according to claim 29, characterized in that MI is selected from the group consisting of Ti3 +, V3 +, Cr3 +, Mn3 +, Fe3 +, Co3 +, Ni3 +, Mo3 +, Nb3 +, and mixtures thereof.
40. 40. The accumulator according to claim 39, characterized in that at least one of M and Mil is an active element that is not redox.
41. 41. The accumulator according to claim 29, characterized in that MI is selected from the group consisting of active elements that are not redox with an oxidation state 1+, an oxidation state 2+, an oxidation state 3+ and mixtures thereof.
42. 42. The accumulator according to claim 41, characterized in that one of M and Mil is an active element that is not redox.
43. 43. The accumulator according to claim 41, characterized in that MI is selected from the group consisting of Li1 +, K1 +, Na1 +, Ru1 +, Cs1 +, and mixtures thereof.
44. 44. The accumulator according to claim 43, characterized in that one of M and Mil is an active element that is not redox.
45. 45. The accumulator according to claim 41, characterized in that MI is selected from the group consisting of Be2 +, Mg2 +, Ca2 +, Sr2 +, Ba2 +, Zn2 +, Cd2 +, C2 +, Ge2 +.
46. 46. The accumulator according to claim 45, characterized in that One of M and Mil is an active element that is not redox.
47. 47. The accumulator according to claim 41, characterized in that MI is selected from the group consisting of Be2 +, Mg2 +, Ca2 +, Sr2 +, Ba2 +, and mixtures thereof.
48. 48. The accumulator according to claim 41, characterized in that MI is selected from the group consisting of Zn2 +, Cd2 +, and mixtures thereof.
49. 49. The accumulator according to claim 41, characterized in that MI is selected from the group consisting of C2 +, Ge +, and mixtures thereof.
50. 50. The accumulator according to claim 41, characterized in that MI is selected from the group consisting of Sc3 +, Y3 +, B3 +, Al3 +, Ga3 +, and mixtures thereof.
51. 51. The accumulator according to claim 29, characterized in that one of M and Mil is an active element that is not redox.
52. 52. The accumulator according to any of claims 1 to 51, characterized in that XY4 is selected from the group consisting of P04, As04, Sb04, Si04, Ge04, V04, S04, and mixtures thereof.
53. 53. The accumulator according to any of claims 1 to 51, characterized in that XY4 is P04.
54. 54. The accumulator according to any of claims 1 to 51, characterized in that Z is selected from the group consisting of OH, F, Cl, Br, and mixtures thereof.
55. 55. The accumulator according to any of claims 1 to 51, characterized in that Z is F.
56. 56. The accumulator according to any of claims 5 and 29 to 51, characterized in that e = 0.
57. 57. The accumulator of according to any of claims 1 to 28, characterized in that the compound is represented by the nominal general formula: Aa [Mm_n_0, MIn, MII0] (X_Y4) dZß.-
58. 58. The accumulator according to any of claims 1 to 28 , characterized in that the compound is represented by the nominal general formula: A »tM or ° -Ml n 'M" «x dZ .. (" O m V (M) V (M) V (MI) V (M1I)
59. 59. The accumulator according to any of claims 1 to 28, characterized in that d = 1; A is Li; and XY4 = P0.
60. 60. The accumulator according to any of claims 1 to 28, characterized in that d = 3; A is Li; and XY4 = P04.
61. 61. The accumulator according to any of claims 1 to 51, characterized in that the second electrode comprises an active insertion material.
62. 62. The accumulator according to any of claims 1 to 51, characterized in that the active insertion material is selected from the group consisting of a metal oxide, metal chalcogenide, carbon, graphite, and mixtures thereof.
63. 63. The accumulator according to any of claims 1 to 51, characterized in that the active insertion material is graphite.
64. 64. The accumulator according to claim 63, characterized in that the electrolyte comprises a lithium salt and a solvent selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethylmethyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, lactones, esters, glymes, sulfoxides, sulfoienes, and mixtures thereof.
65. 65. The accumulator according to claim 64, characterized in that the electrolyte comprises a solvent selected from the group consisting of EC / DMC, EC / DEC, EC / DPC and EC / EMC.