CA2803760A1 - Cathode materials comprising rhombohedral nasicon for secondary (rechargeable) lithium batteries - Google Patents

Abstract

The invention relates to materials for use as electrodes in an alkali-ion secondary (rechargeable) battery, particularly a lithium-ion battery. The invention provides transition-metal compounds having the ordered-olivine or the rhombohedral NASICON structure and the polyanion (PO4)3- as at least one constituent for use as electrode material for alkali-ion rechargeable batteries.

Description

-i -DESCRIPTION

CATHODE MATERIALS COMPRISING RHOMBOHEDRAL
NASICON FOR SECONDARY (RECHARGEABLE) LITHIUM BATTERIES

BACKGROUND OF THE INVENTION
This is a division of Canadian patent application No. 2,755,356 filed on April 23, 1997.
1. Field of the Invention The present invention relates to secondary (rechargeable) alkali-ion batteries.
More specifically, the invention relates to materials for use as electrodes for an alkali-ion battery. The invention provides transition-metal compounds having the ordered olivine or the rhombohedral NASICON structure and containing the polyanion (PO4)3- as at least one constituent for use as electrode material for alkali-ion rechargeable batteries.

2. Description of the Related Art Present-day lithium batteries use a solid reductant as the anode and a solid oxidant as the cathode. On discharge, the metallic anode supplies Li+ ions to the Lition electrolyte and electrons to the external circuit. The cathode is typically an electronically conducting host into which Li4 ions are inserted reversibly from the electrolyte as a guest species and charge-compensated by electrons from the external circuit. The chemical reactions at the anode and cathode of a lithium secondary battery must be reversible. On charge, removal of electrons from the cathode by an external field releases Li+ ions back to the electrolyte to restore the parent host structure, and the addition of electrons to the anode by the external field attracts charge-compensating Li+ ions back into the anode to restore it to its original composition_ Present-day rechargeable lithium-ion batteries use a coke material into which lithium is inserted reversibly as the anode and a layered or framework transition-metal oxide is used as the cathode host material (Nishi et al., U.S. Patent 4,959,281). Layered oxides using Co and/or Ni are expensive and may degrade due to the incorporation of unwanted species from the electrolyte. Oxides such as Li 1,[Mn2)04, which has the [M2]04 spinel framework, provide strong bonding in three dimensions and an interconnected interstitial space for lithium insertion. However, the small size of the 02' ion restricts the free volume available to the Li + ions, which limits the power capability Of the electrodes. Although substitution of a larger S2" ion for the 02" ion increases the ro free volume available to the Li ions, it also reduces the output voltage of an elementary cell.
A host material that will provide a larger free volume for Lition motion in the interstitial space would allow realization of a higher lithium-ion conductivity au, and hence higher power densities. An oxide is needed for output voltage, and hence higher Is energy density. An inexpensive, non-polluting transition-metal atom would make the battery environmentally benign.
SUMMARY OF THE INVENTION
The present invention meets these goals more adequately than previously known secondary battery cathode materials by providing oxides containing larger tetrahedral 20 oxide polyanions forming 3D framework host structures with octahedral-site transition-metal oxidant cations, such as iron, that are environmentally benign.
The present invention provides electrode material for a rechargeable electrochemical cell comprising an anode, a cathode and an electrolyte. The cell may additionally include an electrode separator. As used herein, "electrochemical cell" refers 25 not only to the building block, or internal portion, of a battery but is also meant to refer to a battery in general. Although either the cathode or the anode may comprise the material of the invention, the material will preferably be useful in the cathode.
Generally, in one aspect, the invention provides an ordered olivine compound having the general formula LiMP04, where M is at least one first row transition-metal 30 cation. The alkali ion Li+ may be inserted/extracted reversibly from/to the electrolyte of the battery to/from the interstitial space of the host MPO4 framework of the ordered-olivine structure as the transition-metal M cation (or combination of cations) is reduced/oxidized by charge-compensating electrons supplied/removed by the external circuit of the battery in, for a cathode material, a discharge/charge cycle.
In particular, M
will preferably be Mn, Fe, Co, Ti, Ni or a combination thereof. Examples of combinations of the transition-metals for use as the substituent M include, but are not limited to, Fe1.Mn, and Fet,Ti, where 0 <x < 1.
Preferred formulas for the ordered olivine electrode compounds of the invention include, but are not limited to LiFePO4, LiMnPO4, LiCoPO4, LiNiPO4, and mixed to transition-metal comounds such as Li1..2õFe1jixPO4 or LiFe11Mn,PO4, where 0 <x < 1.
However, it will be understood by one of skill in the art that other compounds having the general formula LiMPO4 and an ordered olivine structure are included within the scope of the invention.
The electrode materials of the general formula LiMPO4 described herein typically have an ordered olivine structure having a plurality of planes defined by zigzag chains and linear chains, where the M atoms occupy the zigzag chains of octahedra and the Li atoms occupy the linear chains of alternate planes of octahedral sites.
In another aspect, the invention provides electrode materials for a rechargeable electrochemical cell comprising an anode, a cathode and an electrolyte, with or without an electrode separator, where the electrode materials comprise a rhombohedral NASICON material having the formula Y.X2(PO4)3, where 0 x 5. Preferably, the compounds of the invention will be useful as the cathode of a rechargeable electrochemical cell. The alkali ion Y may be inserted from the electrolyte of the battery to the interstitial space of the rhombohedral M2(X04)3 NASICON host framework as the transition-metal M cation (or combination of cations) is reduced by charge-compensating electrons supplied by the external circuit of the battery during dis9harge With the reverse process occurring during charge of the battery. While it is contemplated that the materials of the invention may consist of either a single rhombohedral phase or two phases, e.g. orthorhombic and monoclinic, the materials are preferably single-phase rhombohedral NASICON compounds. Generally, M will be at least one first-row transition-metal cation and Y will be Li or Na. In preferred compounds, M will be Fe, V.
Mn, or Ti and Y will be Li.
Redox energies of the host M cations can be varied by a suitable choice of the X04 polyanion, where X is taken from Si, P, As, or S and the structure may contain a combination of such polyanions. Tuning of the redox energies allows optimization of the battery voltage with respect to the electrolyte used in the battery. The invention replaces the oxide ion 02- of conventional cathode materials by a polyanion (X04)m- to take advantage of (1) the larger size of the polyanion, which can enlarge the free volume of the host interstitial space available to the alkali ions, and (2) the covalent X-0 bonding, io which stabilizes the redox energies of the M cations with M-0-X
bonding so as to create acceptable open-circuit voltages Voc with environmentally benign Fe3+/Fe2+
and/or Ti4+/Ti3+ or V N4+3+ redox couples.
Preferred formulas for the rhombohedral NASICON electrode compounds of the invention include, but are not limited to those having the formula Li3+õFe2(PO4)3, Li24õFeTi(PO4)3, Li1TiNb(PO4)3, and Lii.jeNb(PO4)3, where 0 <x <2. It will be understood by one of skill in the art that Na may be substituted for Li in any of the above = compounds to provide cathode materials for a Na ion rechargeable battery.
For example, one may employ Na34,Fe2(PO4)3, Na24eTi(PO4)3, NaxTiNb(PO4)3 or Nal.fxFeNb(PO4)3, where 0 < x < 2, in a Na ion rechargeable battery. In this aspect, Na+ is the working ion and the anode and electrolyte comprise a Na compound.
Compounds of the invention having the rhombohedral NASICON structure form a framework of MO6 octahedra sharing all of their corners with X04 tetrahedra (X = Si, P, As, or S), the X04 tetrahedra sharing all of their corners with octahedra.
Pairs of MO6 octahedra have faces bridged by three X04 tetrahedra to form "lantern" units aligned parallel to the hexagonal c-axis (the rnomobhedral [111] direction), each of these X04 tetrahedra bridging to two different "lantern" units. The Li+ or Na+ ions-occupy the interstitial space within the M2(X04)3 framework. Generally, YxM2(X04)3 compounds with the rhombohedral NASICON framework may be prepared by solid-state reaction of stoichiometric proportions of the Y, M, and X04 groups for the desired valence of the M
cation. Where Y is Li, the compounds may be prepared indirectly from the Na analog by ion exchange of Li+ for Na+ ions in a molten LiNO3 bath at 300 C. For example, rhombohedral LiTi2 may be prepared from intimate mixtures of Li2CO3 or LiOH=1120, TiO2 and NH4H2PO4.H20 calcined in air at 200 C to eliminate H20 and CO2 followed by heating in air for 24 hours near 850 C and a further heating for 24 hours near 950 C.
However, preparation of Li3Fe2(PO4)3 by a similar solid-state reaction gives the undesired monoclinic framework. To obtain the rhombohedral form, it is necessary to prepare rhombohedral Na3Fe2(PO4)3 by solid-state reaction of NaCO3 Fe (CH2COOH}2 and NH4H2P044120 for example. The rhombohedral form of Li3Fe2(PO4)3 is then obtained at 300 C by ion exchange of Li+ for Na+ in a bath of molten LiNO3. It will be understood by one of skill in the art that the rhombohedral Na compounds will be useful as cathode materials in rechargeable Na ion batteries.
In another aspect of the invention, the rhombohedral NASICON electrode compounds may have the general formula YM2(PO4)(X04)3.4. where 0 <y 5_ 3, M is a transition-metal atom, Y is Li or Na, and X = Si, As, or S and acts as a counter cation in the rhombohedral NASICON framework structure. In this aspect, the compound comprises a phosphate anion as at least part of an electrode material. In preferred embodiments, the compounds are used in the cathode of a rechargeable battery.
Preferred compounds having this general formula include, but are not limited to Li1+õFe2(SO4)2(PO4) where 0 x 5_ 2.
The rhombohedral NASICON compounds described above may typically be prepared by preparing an aqueous solution comprising a lithium compound, an iron compound, a phosphate compound and a sulfate compound, evaporating the solution to obtain dry material and heating the dry material to about 500 C. Preferably, the aqueous starting solution comprises FeC13 (NH4)2SO4 and LiH2PO4.
In a further embodiment, the invention provides electrode materials for a rechargeable electrochemical cell comprising an anode, a cathode and an electrolyte, with or without an electrode separator, where the electrode materials have a rhombohedral NASICON structure wit the general formula A In these compounds, A
may be Li, Na or a combination thereof and 0 x 5_ 2. In preferred embodiments, the compounds are a single-phase rhombohedral NASICON material. Preferred formulas for the rhombohedral NASICON electrode compounds having the general formula A3V2(PO4)3 include, but are not limited to those having the formula Li2NaV2(PO4)3, where 0 < x < 2.
The rhombohedral NASICON materials of the general formula A3,V2(PO4)3 may generally be prepared by ionic exchange from the monoclinic sodium analog Na3V2(PO4)3 . Alternatively, Li2NaV2(1)04)3 may be prepared by a direct solid-state reaction from LiCO3, NaCO3, NI-141-12PO4.H20 and V203.
In a further aspect, the invention provides a secondary (rechargeable) battery where an electrochemical cell comprises two electrodes and an electrolyte, with or without an electrode separator. The electrodes are generally referred to as the anode and the cathode. The secondary batteries of the invention generally comprise as electrode material, and preferably as cathode material, the compounds described above. More particularly, the batteries of the invention have a cathode comprising the ordered olivine compounds described above or the rhombohedral NASICON
compounds described above.

BRIEF DESCRIPTION OF THE DRAWINGS
The following drawings form part of the present specification and are included to demonstrate further certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments presented therein.
FIG. 1. FIG. 1 shows a typical polarization curve for the battery voltage V vs. the I delivered across a load. The voltage drop (V0,¨ V) of a typical curve is a measure of the battery resistance Rb(/). The interfacial voltage drops saturate in region (i). The slope of the curve in region (ii) is dV/dI Rd "f Rc (A) + Rc (C), the sums of the electrolyte resistance Rei and the current-collector resistances at the anode and cathode. Region (iii) is diffusion-limited. At the higher currents I, normal processes do not bring ions to or remove them from the electrode/electrolyte interfaces rapidly enough to sustain an equilibrium reaction.

FIG. 2A, 2B and 2C. FIG. 2A shows discharge/charge curves at 0.05 mA = cm-2 (0.95 mA = et) for the olivine Li i_x.FePO4 as cathode and lithium as anode. A
plateau at 3.4V corresponds to the Fe341Fe2+ redox couple relative to the lithium anode.
A plateau at 4.1 V corresponds to the Mn3+/Mn2+ couple. FIG. 2B shows discharge/charge curves at 0.05 mA = cm-2 (1.13 mA = et) for the olivine Li1Fe0.5Mn0.5PO4 as cathode relative to a lithium anode. FIG. 2C shows discharge/charge curves vs. lithium at 0.05 mA = cm-2 (0.95 mA = g-1) for the olivine LiõFePO4.
FIG. 3. FIG. 3 shows discharge/charge curves of an FePO4/LiC104 + PC +
DME/Li coin cell at 185 mA = g- for FePO4 prepared by chemical extraction of Li (delithiation) from LiFePO4.
FIG. 4. Schematic representation of the motion of LiFePO4/FePO4 interface on lithium insertion in to a particle of FePO4.
FIG. 5A and 5B. FIG. 5A shows the rhombohedral R3c (NASICON) as framework structure of Li3Fe2(PO4)3 prepared by ion exchange from Na3Fe2(PO4)3;
FIG. 5B shows the monoclinic P21/n framework structure of Li3Fe2(PO4)3 prepared by solid-state reaction.. The large, open three-dimensional framework of Fe06 octahedra and PO4 tetrahedra allows an easy diffusion of the lithium ions.
FIG. 6A and 6B. FIG. 6A shows discharge/charge curves vs. lithium at 0.1 mA = cm-2 for rhombohedral Li342.Fe2(PO4)3 where 0 <x <2. The shape of the curve for lithium insertion into rhombohedral Li3.,..Fe2(PO4)3 is surprisingly different from that for the monoclinic form. However, the average Voc at 2.8 V remains the same.
The Li+--ion distribution in the interstitial space appears to vary continuously with x with a high degree of disorder. FIG. 6B shows discharge/charge curves vs. lithium at 0.1 mA = cm-2 for monoclinic Li34e,2(1104)3 where 0 <x <2.
FIG. 7A and 7B. FIG. 7A shows discharge curves vs. a lithium anode at current densities of 0.05-0.5 mA = cm-2 for rhombohedral Li34.z.Fe2(PO4)3. A
reversible capacity loss on increasing the current density from 0.05 to 0.5 mA = cm-2 is shown.
This loss is much reduced compared to what is encountered with the monoclinic system.

FIG. 7B shows discharge curves at current densities of 0.05-0.5 mA-cm-2 for monoclinic Li3+xFe2(PO4)3.
FIG. 8. FIG. 8 shows discharge/charge curves at 0.05 mA-cm-2 (0.95 mA-g-l) for the rhombohedral LixNaV2(PO4)3. Rhombohedral Li2NaV004)3 reversibly intercalates 1.5 Li per formula unit for a discharge capacity of 100 mAh-g-1 with average closed-circuit voltage of 3.8 V vs. a lithium anode.
FIG. 9. FIG. 9 illustrates XRD patterns of Li2NaV2(PO4)3 having the rhombohedral NASICON framework, as resulting from the solid-state synthesis.
FIG. 10. FIG. 10 shows discharge/charge curves vs. lithium at 0.1 inkcm-2 for rhombohedral Lii õFe2(PO4)(SO4)2 where 0 < x < 2.

DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

Present-day secondary (rechargeable) lithium batteries use a solid reductant as the anode and a solid oxidant as the cathode. It is important that the chemical reactions at the anode and cathode of a lithium secondary battery be reversible. On discharge, the metallic anode supplies Li+ ions to the Li+- ion electrolyte and electrons to the external circuit. The cathode is a host compound into/from which the working Li+ ion of the electrolyte can be inserted/extracted reversibly as a guest species over a large solid-solubility range (Goodenough 1994). When the Li+ ions are inserted as a guest species into the cathode, they are charge-compensated by electrons from the external circuit. On charge, the removal of electrons from the cathode by an external field releases Li+ ions back to the electrolyte to restore the parent host structure. The resultant addition of electrons to the anode by the external field attracts charge-compensating Li+ ions back into the anode to restore it to its original composition.
The present invention provides new materials for use as cathodes in lithium secondary (rechargeable) batteries. It will be understood that the anode for use with the cathode material of the invention may be any lithium anode material, such as a reductant host for lithium or elemental lithium itself. Preferably, the anode material will be a reductant host for lithium. Where both the anode and cathode are hosts for -8a-the reversible insertion or removal of the working ion into/from the electrolyte, the electrochemical cell is commonly called a "rocking-chair cell. An implicit additional requirement of a secondary battery is maintenance not only of the electrode/electrolyte interfaces, but also of electrical contact between host particles, throughout repeated discharge/recharge cycles.
Since the volumes of the electrode particles change as a result of the transfer of atoms from one to another electrode in a reaction, this requirement normally excludes the use of a crystalline or glassy electrolyte with a solid electrode. A non-aqueous liquid or polymer electrolyte having a large energy-gap window between its highest occupied molecular orbital (HOMO) and its lowest unoccupied molecular orbital (LUMO) is used io with secondary lithium batteries in order to realize higher voltages. For example, practical quantities of very ionic lithium salts such as LiC104, LiBF4 and LiPF6 can be dissolved in empirically optimized mixtures of propylene carbonate (PC), ethylene carbonate (EC), or dimethyl carbonate (DMC) to provide acceptable electrolytes for use with the cathodes of the invention. It will be recogni7ed by those of skill in the art that 15 the (C104)- anion is explosive and not typically suitable for commercial applications.

General Design Considerations The power output P of a battery is the product of the electric current I
delivered by the battery and the voltage V across the negative and positive posts (equation 1).
P=Iv (1) The voltage V is reduced from its open-circuit value V., (I = 0) by the voltage drop /Rb due to the internal resistance Rb of the battery (equation 2).

V= Vo, ¨ IRb (2) The open-circuit value of the voltage is governed by equation 3.

Voc = (1.iA ¨ pj/(¨nF) <5V
(3) In equation 3, n is the number of electronic charges carried by the working ion and F is Faraday's constant. The magnitude of the open-circuit voltage is constrained to Tio, < 5V
not only by the attainable difference A ¨ tic of the electrochemical potentials of the anode reductant and the cathode oxidant, but also by the energy gap Eg between the to HOMO (highest occupied molecular orbital) and the LUMO (lowest unoccupied molecular orbital) of a liquid electrolyte or by the energy gap Eg between the top of the valence band and the bottom of the conduction band of a solid electrolyte_ The chemical potential A, which is the Fermi energy EF of a metallic-reductant anode or the HOMO of a gaseous or liquid reductant, must lie below the LUMO of a liquid electrolyte or the conduction band of a solid electrolyte to achieve thermodynamic stability against reduction of the electrolyte by the reductant. Similarly, the chemical potential tic, which is the LUMO Of a gaseous or liquid oxidant or the Fermi energy of a metallic-oxidant cathode, must lie above the HOMO of a liquid electrolyte or the valence band of a solid electrolyte to achieve thermodynamic stability against oxidation of the electrolyte by the oxidant Thermodynamic stability thus introduces the constraint ¨ Eg (4) as well as the need to match the "window" Eg of the electrolyte to the energies ttA and tic of the reactants to maximize V. It follows from equations 1 and 2 that realization of a high maximum power P (equation 5) requires, in addition to as high a V as possible, a low internal battery resistance Rb (see equation 6).

P max= max max (5) Rb = Re1 R1(A) + R(C) + R(A) + Re(C) (6) The electrolyte resistance 4 to the ionic current is proportional to the ratio of the effective thickness L to the geometrical area A of the interelectrode space that is filled with an electrolyte of ionic conductivity a; (equation 7).

= (liaiA) (7) Since ions move diffusively, ai (see equation 8) increases with temperature. A
a i 0.1 Scm-1 (the maximum al represents the room-temperature protonic conductivity crti in a strong acid) at an operating temperature 74 dictates the use of a membrane separator of large geometrical area A and small thickness L.

cru= (B/7)exp(¨EdkT) (8) The resistance to transport of the working ion across the electrolyte-electrode interfaces is proportional to the ratio of the geometrical and interfacial areas at each electrode:
Rin ¨ Al Ain (9) where the chemical reaction of the cell involves ionic transport across an interface, equation 9 dictates construction of a porous, small-particle electrode.
Achievement and retention of a high electrode capacity, i.e., utilization of a high fraction of the electrode material in the reversible reaction, requires the achievement and retention of good electronic contact between particles as well as a large particle-electrolyte interface area over many discharge/charge cycles. If the reversible reaction involves a first-order phase change, the particles may fracture or lose contact with one another on cycling to break a continuous electronic pathway to the current collector.
Loss of interparticle electrical contact results in an irreversible loss of capacity.
There may also be a reversible capacity fade. Where there is a two-phase process (or even a sharp guest-species gradient at a diffusion front) without fracture of the particles, the area of the interface (or diffusion front) decreases as the second phase penetrates the electrode particle. At a critical interface area, diffusion across the interface may not be fast enough to sustain the current /, so not all of the particle is accessible. The volume of inaccessible electrode increases with /, which leads to a diffusion-limited reversible capacity fade that increases with I. This problem becomes more important at lower ionic conductivity au.
The battery voltage V vs. the current / delivered across a load is called the polarization curve. The voltage drop (V., ¨ V) 71(/) of a typical curve, FIG.
1, is a measure of the battery resistance (see equation 10).

Rb(1) = 1(1)//
(10) On charging, i(/) = ¨ Voc) is referred to as an overvoltage. The interfacial voltage drops saturate in region (i) of FIG. 1; therefore in region (ii) the slope of the curve is dVIdl Ro+ R, (A) + R (C) (11) Region (iii) is diffusion-limited; at the higher currents I, normal processes do not bring ions to or remove them from the electrode/electrolyte interfaces rapidly enough to sustain an equilibrium reaction.
The battery voltage V vs. the state of charge, or the time during which a constant current I has been delivered, is called a discharge curve.

Cathode Materials The cathode material of the present invention, for use in a secondary lithium battery, consists of a host structure into which lithium can be inserted reversibly. The maximum power output, Pr. (see equation 5), that Can be achieved by a cell depends on the open-circuit voltage Voc = AEle and the overvoltage i(/) at the current Iõ,,õ of maximum power Vfl.õ = Voc ¨ ri(/) (12) AE is the energy difference between the work function of the anode (or the HOMO of the reductant) and that of the cathode (or the LUMO of the oxidant). In order to obtain a high Voc, it is necessary to use a cathode that is an oxide or a halide. It is preferable that the cathode be an oxide in order to achieve a large V and good electronic conductivity.
To minimize 1(4õõõ), the electrodes must be good electronic as well as ionic conductors and they must offer a low resistance to mass transfer across the electrode/electrolyte interface. To obtain a high /max, it is necessary to have a large electrode/electrolyte surface area. In addition, where there is a two-phase interface within the electrode particle, the rate of mass transfer across this interface must remain large enough to sustain the current. This constraint tends to limit the electrode capacity more as the current increases.
Oxide host structures with close-packed oxygen arrays may be layered, as in Li1,Co02 (Mizushima, et at 1980), or strongly bonded in three dimensions (3D) as in the manganese spinels Li1,[Mn2] 04 (Thackeray 1995; Thackeray et at 1983;

Thackeray et al. 1984; Guyomard and Tarascon 1992; and Masquelier et al.
1996). Li intercalation into a van der Waals gap between strongly bonded layers may be fast, but it can also be accompanied by unwanted species from a liquid electrolyte. On the other hand, strong 3D bonding within a close-packed oxygen array, as occurs in the spinel 5 framework [Mn2104, offers too small a free volume for the guest Li+ ions to have a high mobility at room temperature, which limits Imax. Although this constraint in volume of the interstitial space makes the spinet structure selective for insertion of Li+ ions, it reduces the Li-ion mobility and hence Li-ion conductivity au. The oxospinels have a sufficiently high au. to be used commercially in low-power cells (Thackeray et aL, io 1983) but would not be acceptable for the high power cells of the insertion.
The present invention overcomes these drawbacks by providing cathode materials containing larger tetrahedral polyanions which form 3D framework host structures with octahedral-site transition-metal oxidant cations. In the cathode materials of the invention having the NASICON structure, the transition-metal ions are separated by the 15 polyanions, so the electronic conductivity is polaronic rather than metallic. Nevertheless, the gain in au more than offsets the loss in electronic conductivity.
Variation of the energy of a given cation redox couple from one compound to another depends on two factors: (a) the magnitude of the crystalline electric field at the cation, which may be calculated for a purely ionic model by a Madelung summation of . . 20 the Coulomb fields from the other ions present, and (b) the covalent contribution to the bonding, which may be modulated by the strength of the covalent bonding at a nearest-neighbor counter cation. The stronger is the negative Madelung potential at a cation, the higher is a given redox energy of a cation. Similarly the stronger is the covalent bonding of the electrons at a transition-metal cation, the higher is a given redox energy of that 25 cation. The lower the redox energy of the cation host transition-metal ion, the larger is Voc.
The redox couples of interest for a cathode are associated with antibonding states of d-orbital parentage at transition-metal cations M or 4f-orbital parentage at rare-earth cations Ln in an oxide. The stronger is the cation-anion covalent mixing, the higher is 30 the energy of a given LUMO/HOMO redox couple. Modulation of the strength of the cation-anion covalence at a given M or Ln cation by nearest-neighbor cations that compete for the same anion valence electrons is known as the inductive effect.
Changes of structure alter primarily the Madelung energy as is illustrated by raising of the redox energy within a spinel [M2104 framework by about 1 eV on transfer of Li+ ions from tetrahedral to octahedral interstitial sites. Changing the counter cation, but not the structure, alters primarily the inductive effect, as is illustrated by a lowering of the Fe3+/Fe2+ redox energy by 0.6 eV on changing (Mo04)2- or (W04)2- to (SO4)2-polyanions in isostructural Fe-2(X04)3 compounds. Raising the energy of a given redox couple in a cathode lowers the voltage obtained from cells utilizing a common anode.
io Conversely, raising the redox energy of an anode raises the cell voltage with respect to a = common cathode.
The invention provides new cathode materials containing oxide polyanions, including the oxide polyanion (PO4)3- as at least one constituent, for use in secondary (rechargeable) batteries. For example, the cathode materials of the present invention may is have the general formula LiM(PO4) with the ordered olivine structure or the more open rhombohedral NASICON framework structure. The cathode materials of the present invention have the general formula LiM(PO4) for the ordered olivine structure, or Yx.M2(PO4)y(X04)31,, where 0 <y 3, M is a transition-metal atom, Y is Li or Na and X = Si, As or S and acts as a counter cation, for the rhombohedral NASICON
framework 20 structure.
The olivine structure of Mg2SiO4 consists of a slightly distorted array of oxygen atoms with Mg2+ ions occupying half the octahedral sites in two different ways. In alternate basal planes, they form zigzag chains of corner-shared octahedra running along the c-axis and in the other basal planes they form linear chains of edge-shared octahedra 25 running also along the c-axis.
In the ordered L1MPO4 olivine structures of the invention, the M atoms occupy the zigzag chains of octahedra and the Li atoms occupy the linear chains of the alternate planes of octahedral sites. In this embodiment of the present invention, M is preferably Mn, Fe, Co, Ni or combinations thereof. Removal of all of the lithium atoms leaves the 30 layered FePO4¨type structure, which has the same Pbnm orthorhombic space group.

These phases may be prepared from either end, e.g., LiFePO4 (triphylite) or FePO4 (heterosite), by reversible extraction or insertion of lithium.
FIG. 2A, FIG. 2B and FIG. 2C show discharge/charge curves vs. lithium at 0.05 rnA x cm-2 (0.95 mA x g-i and 1.13 rnA x CI, respectively) for Lii_xFePO4, Li1_Ye0.5Mn0.5PO4 and LiyePO4, respectively, where 0 5. A plateau at 3.4 V
corresponds to the Fe3+/Fe2+ re,dox couple and a plateau at 4.1 V corresponds to the Mn3+/Mn2+ couple. With LiC104 in PC and DME as the electrolyte, it is only possible to charge up a cathode to 4.3 V vs. a lithium anode, so it was not possible to extract lithium from LiMnPO4, LiCoPO4 and LiNiPO4 with this electrolyte. However, in the presence io of iron, the Mn3+1Mn2+ couple becomes accessible. The inaccessibility is due to the stability of the Mn3+/Mn2+, CO3+/CO2+ and Ni3+ /Ni2+ couples in the presence of the polyanion (PO4)3-. The relatively strong covalence of the PO4 tetrahedron of the compounds of the present invention.stabilizes the redox couples at the octahedral sites to give the high V's that are observed.
Insertion of lithium into FePO4 was reversible over the several cycles studied.
FIG. 3 shows discharge/charge curves of FePO4/LiC104 + PC + DME/Li coin cell at 185 mA = g-1 for FePO4 prepared by chemical extraction of Li (delithiation) from LiFePO4.
The LixFePO4 material of the present invention represents a cathode of good capacity and contains inexpensive, environmentally benign elements. While a nearly close¨packed-hexagonal oxide¨ion array apparently provides a relatively small free volume for Li¨ion motion, which would seem to support only relatively small current densities at room temperature, increasing the current density does not lower the closed¨circuit voltage V.
Rather, it decreases, reversibly, the cell capacity. Capacity is easily restored by reducing the current.As illustrated schematically in FIG. 4, lithium insertion proceeds from the surface of the particle moving inwards behind a two-phase interface. In the system shown, it is a Li2FePO4/Li1,FePO4 interface. As the lithiation proceeds, the surface area of the interface shrinks. For a constant rate of lithium transport per unit area across the interface, a critical surface area is reached where the rate of total lithium transported across the interface is no longer able to sustain the current. At this point, cell performance becomes diffusion¨limited. The higher the current, the greater is the total critical interface area and, hence, the smaller the concentration x of inserted lithium before the cell performance becomes diffusion¨limited. On extraction of lithium, the parent phase at the core of the particle grows back towards the particle surface. Thus, the parent phase is retained on repeated cycling and the loss in capacity is reversible on lowering the current density delivered by the cell. Therefore, this loss of capacity does not appear to be due to a breaking of the electrical contact between particles as a result of volume changes, a process that is normally irreversible.
The invention further provides new cathode materials exhibiting a rhombohedral ics NASICON framework. NASICON, as used herein, is an acronym for the framework . host of a sodium superionic conductor Naii.3õZr2(111õSix04)3. The compound Fe2(SO4)3 has two forms, a rhombohedral NASICON structure and a related monoclinic form (Goodenough et al. 1976; Long et al. 1979). Each structure contains units of two Fe06 octahedra bridged by three corner-sharing SO4 tetrahedra. These units form 3D
Is frameworks by the bridging SO4 tetrahedra of one unit sharing corners with Fe06 octahedra of neighboring Fe2(SO4)3 elementary building blocks so that each tetrahedron shares corners with only octahedra and each octahedron with only tetrahedra.
In the rhombohedral form, the building blocks are aligned parallel; while they are aligned nearly perpendicular to one another in the monoclinic phase. The collapsed monoclinic 20 form has a smaller free volume for Li+¨ion motion which is why the rhombohedral form is preferred. In these structures, the Fe06 octahedra do not make direct contact, so electron transfer from an Fe2+ to an Fe3+ ion is polaronic and therefore activated.

Li,e2(SO4)3 has been reported to be a candidate material for the cathode of a Lit ion rechargeable battery with a Vs. = 3.6 V vs. a lithium anode (Manthiram and 25 Goodenough 1989). While the sulfates would seem to provide the desired larger free volume for Li, batteries using sulfates in the cathode material tend to exhibit phase-transition problems, lowering the electronic conductivity. The reversible lithium insertion into both rhombohedral and monoclinic Fe2(SO4)3 gives a flat closed-circuit voltage vs. a lithium anode of 3.6 V (Manthiram and Goodenough 1989; Okada et al.
30 1994; Nanjundaswamy et al. 1996). Neither parent phase has any significant solid solution with the orthorhombic lithiated phase Li2Fe2(SO4)3, which is derived from the rhombohedral form of Fe2(SO4)3 by a displacive transition that leaves the framework intact. Powder X-ray diffraction verifies that lithiation occurs via a two-phase process (Nanjundaswamy et al. 1996). Increasing the current density does not change significantly the closed-circuit voltage V, but it does reduce reversibly the capacity. The to reduction in capacity for a given current density is greater for the motion of the lithiated interface. The interstitial space of the framework allows fast Lit-ion motion, but the movement of lithium across the orthorhombic/monoclinic interface is slower than that across the orthorhombic/rhombohedral interface, which makes the reversible loss of capacity with increasing current density greater for the monoclinic than for the rhombohedral parent phase.
The cathode materials of the invention avoid the phase transition of known sulfate cathode materials by incorporating one or more phosphate ions as at least one of the constituents of the cathode material. The rhombohedral R3c (NASICON) and monoclinic P211 n framework structures of Li3Fe.2(PO4)3 are similar to those for the sulfates described above, as illustrated in FIG. 5A and FIG. 5B.
A further embodiment of the invention is a rhombohedral NASICON cathode material having the formula A3,V2(PO4)3, where A may be Li, Na or a combination thereof. Rhombohedral A3,V2(PO4)3 reversibly intercalates 1.5 Li per formula unit for a discharge capacity of 100 mAh = el with average closed-circuit voltage being 3.8 V vs. a lithium anode (see FIG. 8). The voltage and capacity performances of the rhombohedral A3_,V2(PO4)3 compounds of the invention are comparable to the high-voltage cathode materials LiMn204 (4.0 V), LiCo02 (4.0 V) and LiNi02 (4.0 V). The large, open three-dimensional framework of V06 octahedra and PO4 tetrahedra allows an easy diffusion of the lithium ions, making it attractive for high-power batteries. A further advantage of this material is that it includes a cheaper and less toxic transition-metal element (V) than the already developed systems using Co, Ni, or Mn.

EXAMPLES
Example 1. Ordered Olivine LiMPO4 Compounds The ordered-olivine compound LiFePO4 was prepared from intimate mixtures of stoichiometric proportions of Li2CO3 or L10H.H20, Fe(CH2COOH)2 and NH4H2PO4.1420; the mixtures were calcined at 300-350 C to eliminate NH3, H20, and 10 CO2 and then heated in Ar at about 800 C for 24 hours to obtain LiFe PO4. Similar solid-state reactions were used to prepare LiMnPO4, LiFe1.MnPO4, LiCoPO4 and LiNiPO4. FePO4 was obtained from LiFePO4 by chemical extraction of Li from LiFePO4. Charge/discharge curves for Li1_xFePO4 and discharge/charge cycles for LixFePO4 gave similar results with a voltage of almost 3.5 V vs. lithium for a capacity of = 15 0.6 Li/formula unit at a current density of 0.05 rnA=cm2- (See FIG. 2A and FIG. 2C).
The electrolyte used had a window restricting voltages to V <4.3 V. Li extraction was not possible from LiMnPO4, LiCoPO4, and LiNiPO4 with the electrolyte used because = these require a voltage V> 4.3 V to initiate extraction. However, Li extraction from = LiFeiri _x.MxPO4 was performed with 0 x 0.5, and the Mn3+/Mn2+ couple give a voltage 20 plateau at 4.0 V vs. lithium.
Example 2 Rhombohedral NASICON LixM2(PO4)3 Structures The inventors compared redox energies in isostructural sulfates with phosphates to obtain the magnitude of the change due to the different inductive effects of sulfur and phosphorus. Rhombohedral Li1.,õTi2(PO4)3 has been shown to-exhibit a flat open¨circuit 25 voltage V., = 2.5 V vs. lithium, which is roughly 0.8 V
below the Ti4+/Ti3+ level found for FeTi(SO4)3. The flat voltage V(x) is indicative of a two¨phase process. A
coexistence of rhombohedral and orthorhombic phases was found for x = 0.5 (Delmas and Nadiri 1988; Wang and Hwu 1992). Li2.,..FeTi(PO4)3 of the present invention remains single phase on discharge.
30 All three phosphates Li3M2(PO4)3, where M = Fe, Fe/V, or V, have the monoclinic Fe2(SO4)3 structure if prepared by solid-state reaction. The inventors have found that these compounds exhibit a rhombohedral structure when prepared by ion exchange in LiNO3 at 300 C from the sodium analog Na3Fe2(PO4)3. The discharge/charge curve of FIG. 6A for lithium insertion into rhombohedral Li34.,Fe2(PO4)3 exhibits an average Vo, of 2.8 V. This is surprisingly different from the curves for the monoclinic form (See FIG. 6B). The inventors have found that up to two lithiums per formula unit can be inserted into Li3Fe2(PO4)3, leading to Li5Fe2(PO4)3. The Li¨ion distribution in the interstitial space of Li3+.,Fe2(PO4)3, where 0 <x <2, appears to vary continuously with x with a high degree of disorder. FIG. 7A shows a reversible capacity loss on increasing the current density from 0.05 to 0.5 rnA = cm-2. A
reversible discharge capacity of 95 mAh = g-1 is still observed for rhombohedral Li3,F2(PO4)3 at a current density of 20 rnA = el. This is much reduced compared to what is encountered with the monoclinic system (See FIG. 7B). With a current density of 23 mA = el (or 1 mA = cni2), the initial capacity of 95 rnAh = el was maintained in a coin cell up to the 40th cycle.
Another cathode material of the present invention, Li2FeTi(PO4)3, having the NASICON framework was prepared by solid-state reaction. This material has a voltage ranging from 3.0 to 2.5 V.
Rhombohedral TiNb(PO4)3 can be prepared by solid-state reaction at about 1200 C. Up to three Li atoms per iormula unit can be inserted, which allows access to the Nb4+/Nb3 couple at 1.8 V vs. lithium for x> 2 in Liõ TiNb(PO4)3. Two steps are perhaps discernible in the compositional range 0 <x <2; one in the range of 0 <x < 1 corresponds to the Ti4+/Ti3+ couple in the voltage range 2.5 V < V < 2.7 V and the other for I < X < 2 to the Nbs+/Nb4+ couple in the range 2.2 V < V < 2.5 V. It appears that these redox energies overlap. This assignment is based on the fact that the Ti4+/Ti3+
couple in LiitcTi2(PO4)3 gives a flat plateau at 2.5 V due to the presence of two phases, rhombohedral LiTi2 (PO4)3 and orthorhombic Li3Ti2 (PO4)3. The presence of Nb in the structure suppresses the formation of the second phase in the range 0 <x <2.
Rhombohedral LiFeNb(PO4)3 and Li2FeTi(I'04)3 can be prepared by ion exchange with molten L1NO3 at about 300 C from NaFeNb(PO4)3 and -Na2FeTi(PO4)3, respectively. Two Li atoms per formula unit can be inserted reversibly into Li2jeTi(PO4)3 with a little loss of capacity at 0.5 rnA=cm-2. insertion of the first Li atom in the range 2.7 V<V<3.0 V corresponds to the Fe3+/Fe2+ redox couple and of the second Li atom in the range of 2.5 V<V:2.7 V to an overlapping Ti4+/Ti3+ redox couple.

The insertion of lithium into Lii,õ-Fenb(PO4)3 gives a V vs. x curve that further verifies the location of the relative positions of the Fe3+/Fe2+, Nb54-/Nb4+ redox energies in phosphates with NASICON-related structures. It is possible to insert three lithium atoms into the structure; and there are three distinct plateaus corresponding to Fe3 /Fe2+ at 2.8 V, Nb5+/Nb4+ at 2.2 V, and Nb471\1b5+ at 1.7 V vs. lithium in the discharge curve.
The rhombohedral A3V2(PO4)3 compounds of the invention can be prepared by ionic exchange from the monoclinic sodium analog Na3V2(PO4)3. The inventors were also able to prepare the rhombohedral Li2NaV2(PO4)3 with the NASICON
framework by a direct solid-state reaction (FIG. 9). The discharge/charge curves at 0.05 mA = cm-2 (0.95 mA = g-1) for the rhombohedral Li1NaV2(PO4)3 are shown in FIG. 8.
The rhombohedral LiFe2(SO4)2(PO4) may be prepared by obtaining an aqueous solution comprising FeCl3, (NH4)2SO4, and LiH2PO4, stirring the solution and evaporating it to dryness, and heating the resulting dry material to about 500 C.
Discharge/charge curves vs. lithium at 0.1 mA = cm-2 for rhombohedral Li1,,Fe2(PO4)(SO4)2, wherein 0 <x < 3, are shown in FIG. 10.
While the compositions and methods of this invention have been described in terms of preferred embodiments, the scope of the claims should not be limited by the preferred embodiments set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole.

REFERENCES
Delmas, C., and A. Nadiri. Mater. Res. Bull., 23, 63 (1988).
Goodenough, J.B., H.Y.P. Hong and J.A. Kafalas, Mater. Res. Bull. 11, 203 (1976).
Guyomard, D. and J.M. Tarascon. J. Electrochem. Soc., 139, 937 (1992).
Long, G.J., G. Longworth, P. Battle, A.K. Cheetham, R.V. Thundathil and D.
Beveridge, Inorg. Chem. 18, 624 (1979).
Manthiram, A., and J. B. Goodenough, J. Power Sources, 26, 403 (1989).
Masquelier, C., M. Tabuchi, K. Ado, R. Kann , Y. Kobayashi, Y. Maki, 0.
Nakamura and J. B. Goodenough, J. Solid State Chem., 123, 255 (1996).
Mizushima, K., P.C. Jones, P.J. Wiseman and J.B. Goodenough, Mater. Res.
Bull., 15, 783 (1980).
Nanjundaswamy, K.S., et al., Synthesis, redox potential evaluation and electrochemical characteristics of NAS ICON-related 3D framework compounds , Solid State Ionics, 92 (1996) 1-10.
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Okada, S., K.S. Nanjundaswamy, A. Manthiram and J.B. Goodenough, Proc. 36"
Power Sources Conf, Cherry Hill at New Jersey (June 6-9, 1994).
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Sinha, S. and D.W. Murphy, Solid State Ionics, 20,81 (1986).
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Goodenough, Mater. Res. Bull., 19, 179 (1984).
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Claims (50)

1. A cathode material for a rechargeable electrochemical cell, said cell also comprising an anode and an electrolyte, the cathode material comprising a rhombohedral NASICON material having the formula Y x M2(PO4)3, where M is at least one first-row transitionmetal cation and 0 <= x <= 5 and Y
is Li or Na.

2. The cathode material of claim 1, where M is selected from the group consisting of Fe, V, Mn, and Ti.

3. The cathode material of claim 2, wherein the cathode material has the formula

4. The cathode material of claim 2, wherein the cathode material has the formula Li3Fe2(P0 4)3.
Li3+x Fe2(PO4)3, where 0 <= x <= 2.

5. The cathode material of claim 2, having the formula Li1+x Ti2(P0 4)3.

6. The cathode material of claim 2, having the formula Li2FeTi(PO4)3.

7. The cathode material of claim 2, having the formula Li x TiNb(PO4)3, where

8. The cathode material of claim 2, having the formula Li1+x FeNb(PO4)3 where

9. The cathode material of claim 2, prepared by the process comprising the steps:
(a) preparing Na2Fe2(PO4)3; and (b) contacting said Na2Fe2(PO4)3 with a molten lithium salt, such that an ionic exchange reaction occurs.

10. The cathode material of claim 2, prepared by a direct solid state reaction.

11. A cathode material for a rechargeable electrochemical cell also comprising an anode and an electrolyte, the cathode comprising a rhombohedral NASICON
material having the formula A3-x V2(PO4)3, where A may be Li, Na or a combination thereof

12. The cathode material of claim 11, wherein the cathode material has the and 0 <= x <= 2.

13. The cathode material of claim 11, prepared by the process comprising the formula Li2-x NaV2(PO4)3, where 0 <= x <= 2.
steps:

(a) preparing Na3V2(PO4)3; and (b) contacting said Na3V2(PO4)3 with a molten lithium salt, such that an ionic exchange reaction occurs.

14. The cathode material of claim 11, prepared by a direct solid-state reaction.

15. A secondary battery comprising an anode, a cathode and an electrolyte, said cathode comprising a rhombohedral NASICON material having the formula Y is Li or Na, other than Li2+x FeTi(PO4)3.

Y x M2(PO4)3 where M is at least one first-row transition-metal cation and 0 <= x <= 5 and

16. The battery of claim 15, where M is selected from the group consisting of Fe, V, Mn, and Ti.

17. The battery of claim 16, wherein the cathode material has the formula

18. The battery of claim 17, wherein the cathode material has the formula Li3Fe2(PO4)3.

19. The battery of claim 16, wherein the cathode material has the formula Li2FeTi(PO4)3.

Li3+x Fe2(PO4)3, where 0 <= x <= 2.

20. The battery of claim 16, wherein the cathode material has the formula Li x TiNb(PO4)3, where0 <= x <= 2.

21. The battery of claim 16, wherein the cathode material has the formula

22. A secondary battery comprising an anode, a cathode and an electrolyte, said Li1+x FeNb(PO4)3, 0 <= x <= 2.
cathode comprising a rhombohedral NASICON material having the formula A3-x V2(PO4)3, where A may be Li, Na or a combination thereof and 0 <= x <= 2.

23. The battery of claim 22, wherein the cathode material has the formula

24. A rechargeable electrochemical cell of the rocking-chair type, comprising:

- an anode;
Li2+x NaV2(PO4)3, where 0 <= x <= 2.- a cathode; and - an electrolyte, wherein:

- both the anode and cathode are host for the reversible insertion or removal of the working ion into or from the electrolyte, - the cathode comprises a compound having an ordered olivine structure and the general formula LiMPO4, wherein M is at least one first-row transition-metal cation selected from the group consisting of Mn, Fe and Ni or a combination thereof, and - the anode material is a reductant host for the reversible insertion or removal of the working lithium-ion into or from the electrolyte.

25. A rechargeable electrochemical cell according to claim 24, wherein M is

26. A rechargeable electrochemical cell according to claim 24, wherein the cathode material has the general formula LiFePO4.

Fe1-x Mn x or Fe1-x Ti x and 0 < x < 1.

27. A rechargeable alkali-ion cell according to any one of claims 24 to 26, wherein the cathode material is obtainable by a direct solid state reaction.

28. A rechargeable electrochemical cell of the rocking-chair type, comprising:

- an anode;

- a cathode; and - an electrolyte, wherein:

- both the anode and cathode are host for the reversible insertion or removal of the working ion into or from the electrolyte, - the cathode comprises a compound having an ordered olivine structure with a plurality of planes defined by zig-zag chains and linear chains and the general formula LiMPO4 where the M atoms occupy the zigzag chains of octahedral sites and the lithium atoms occupy the linear chains of alternate planes of octahedral sites, M being at least one first-row transition-metal cation selected from the group consisting of Mn, Fe and Ni or a combination thereof, and - the anode material is a reductant host for the reversible insertion or removal of the working lithium-ion into or from the electrolyte.

29. A rechargeable electrochemical cell according to claim 28, wherein M is

30. A rechargeable electrochemical cell according to claim 29, wherein the cathode material has the formula LiFePO4 and a discharge plateau of 3.4 Volts versus Fe1-x Mn x or Fe1-x Ti x and 0 < x < 1.
lithium, corresponding to the Fe+3/Fe+2 couple.

31. A rechargeable electrochemical cell according to claim 30, wherein the cathode material may be prepared from either LiFePO4, the triphylite, or from FePO4, the heterosite, by reversible extraction or insertion of lithium.

32. A rechargeable electrochemical cell according to any one of claims 28, 30 and 31, wherein the lithium insertion, into a particle of FePO4, proceeds through a LiFePO4/FePO4 two-phase interface.

33. A rechargeable electrochemical cell according to claim 28 or 29, wherein M
is Fe and Mn haying a plateau at 3.4 Volts versus lithium, corresponding to the Fe+3/Fe+2 couple, and a second discharge plateau at 4.1 Volts versus lithium, corresponding to the Mn+3/Mn+2 couple.

34. A rechargeable alkali-ion cell according to any one of claims 28 to 33, wherein the cathode material is obtainable by a direct solid state reaction.

35. A cathode material for a rechargeable electrochemical cell, said cathode material comprising a porous material having particle sizes on the nanometer scale, the porous material comprising one or more compounds, at least one compound with an ordered olivine structure comprising the general formula LiMPO4, where M is one or more first-row transition-metals selected from the group consisting of Fe, Mn, Ni, Ti, and combinations thereof.

36. The cathode material of claim 35, wherein the cathode material comprises a nanoparticle comprising one or more compounds, at least one compound with an ordered olivine structure comprising the general formula LiMPO4, where M is one or more first-row transition-metals selected from the group consisting of Fe, Mn, Ni, Ti, and combinations thereof.

37. The cathode material of claim 35 or 36, where M comprises Fe.

38. The cathode material of claim 35 or 36, where M comprises Mn.

39. The cathode material of claim 35 or 36, where M is a combination of first row transition-metals selected from the group consisting of Mn, Fe, Ti, Fe1-x Mn x and Fe1-x Ti x where 0 < x < 1.

40. The cathode material of claim 39, where the compound comprises the formula LiFe1-x Mn x PO4 and 0 < x < 1.

41. The cathode material of claim 35, wherein the cathode material further comprises a second compound.

42. A cathode material according to any one of claims 35 to 41, wherein the cathode material is porous.

43. A cathode material according to claim 42, whrerein the particle size of the porous cathode is on the nanometer scale.

44. A rechargeable electrochemical cell comprising a cathode, wherein the cathode comprises a porous material having particle sizes on the nanometer scale, the porous material comprising one or more compounds, at least one compound with an olivine structure comprising the general formula LiMPO4, where M is one or more first-row transition-metals selected from the group consisting of Fe, Mn, Ni, Ti, and combinations thereof.

45. The rechargeable electrochemical cell of claim 44, wherein the cathode comprises a nanoparticle comprising one or more compounds, at least one compound with an olivine structure comprising the general formula LiMPO4, where M is one or more first-row transition-metals selected from the group consisting of Fe, Mn, Ni, Ti, and combinations thereof.

46. The rechargeable electrochemical cell of claim 44, where M comprises Fe.

47. The rechargeable electrochemical cell of claim 44, where M comprises Mn.

48. The rechargeable electrochemical cell of claim 44, where M is a combination of first row transition-metals selected from the group consisting of Mn, Fe, Ti, Fe1-x Mn x and Fe1-x Ti x, where 0 < x < 1.

49. The rechargeable electrochemical cell of claim 48, wherein the compound comprises the formula LiFe1-x Mn x PO4, where 0 < x < 1.

50. The rechargeable electrochemical cell of claim 44, wherein the cathode further comprises a second compound.