DE102010006440A1 - Electrode material for rechargeable electrochemical cell, has cathode material containing lithium, sodium, magnesium, calcium, beryllium, aluminum and/or manganese, and iron, manganese, nickel, cobalt and/or their mixture - Google Patents

Abstract

An electrode material has a cathode material containing lithium, sodium, magnesium, calcium, beryllium, aluminum and/or manganese, and iron, manganese, nickel, cobalt and/or their mixture. An electrode material has a cathode material having compositional formula: Li qMe1 rMe2 sZO 4-xY' x. Me 1sodium, magnesium, calcium, beryllium, aluminum and/or manganese; Me 2iron, manganese, nickel, cobalt and/or their mixture; Y' : AR n; A : nitrogen, carbon or boron; R : H, or long-chain hydrocarbyl; Z : phosphorus, arsenic, antimony, silicon and/or sulfur; n : 0-4; q : 0.01-1; x : 10 ->2>0>to 2;and r+s+x : 10 ->2>0>.

Description

Field of the invention

The present invention relates to rechargeable (secondary) lithium-based batteries. Specifically, the invention relates to materials that can be used as electrodes in a lithium-ion battery. The invention includes chemical compounds from the group of amido and imido compounds, which is a formulation according to _Liq Me _Ir Me _IIs ZO _4-x Y _x where Y consists of the molecules NH, NH ₂ , NR; for R are conductive carbonaceous chains bonded directly to the nitrogen, and X is selected from the elements: phosphorus; Silicon, sulfur and boron and wherein Me _I and Me _II from the metal Mg, Ca, Be, Al, Mn or for Me _II metals of the first and second main group and further from the subgroups, in particular Fe, Mn, Ni, Co and is used as material or, in the case of a material mixture, as at least one component for at least one electrode of a rechargeable lithium battery. A lithium battery is understood in particular to mean a battery whose electrochemical functionality requires the presence of the lithium element.

State of the art

Rechargeable lithium batteries (synonym: lithium secondary batteries) according to the prior art use a solid reducing agent as the anode and a solid oxidizing agent as the cathode. Both the chemical and electrochemical processes at the anode and at the cathode must be reversibly designed to allow for rechargeability.

During the discharge, lithium ions leak out of the anode and into the electrolyte. At the same time, electrons are released from the anode into the outer-electrical consumer circuit (synonym: outer conductor circuit).

The cathode usually consists of an electrically conductive acceptor, which reversibly receives the Li + ions during the discharge process from the electrolyte and is electrically charge-neutralized by recombination with electrons from the outer conductor circuit.

During the discharge process, therefore, electrons flow from the anode into the outer conductor circuit, where they perform work on a consumer, for example an electric motor, and then flow back into the cathode, where they electrically recombine with Li + ions from the electrolyte.

During charging, the cathode is deprived of electrons by an external field. The resulting Li + ions pass from the cathode into the electrolyte via or from the electrolyte to the anode, where a renewed recombination with electrons from the outer conductor circuit takes place for charge neutralization. This restores the original material structure that existed before unloading.

Prior art rechargeable lithium ion batteries use on the anode side carbon in which the lithium is reversibly bound and a lithium compound on the cathode side, for example LiCoO 2, LiNiO 2, LiFePO 4 or manganese based compounds such as e.g. B. LiMn2O4, wherein the -Mn2O4 has a favorable spinel structure, which allows a reversible loading of lithium in the lattice interstices.

In this case, however, the small size of the oxygen ion limits the free volume available for the incorporation of Li + ions. As a result, the representable energy density of the electrodes and also the conductivity of the structure for Li-ion transport, which is primarily relevant for the maximum possible discharge speed, significantly limited.

An improvement can be achieved by replacing the oxygen ion with a larger sulfur ion, which can significantly increase the free volume. However, this reduces the output voltage of the unit cell significantly.

A further improvement results from the use of LiFePO4 as the cathode material. The use of this material results in further advantages in terms of storage capacity and ion transport speed due to a further increased available volume for the incorporation of Li ions in the interstitial lattice. [ EP0904607 ]

LiFePO4 has other major advantages over the other materials mentioned: it is inexpensive, environmentally safe and thermally stable in the charged state. The thermal stability is particularly noteworthy due to the structure: the oxygen atoms form a hexagonal dense structure (hdp). The iron atoms are arranged in so-called "zizag chains" as octahedrons in alternating basal planes; the lithium ions occupy the octahedral holes. The strong covalent bonds between the oxygen atoms and the phosphorus to phosphate ions (PO ₄ ) ^3- cause a stronger stabilization of the structure compared to the layer structures of LiCoO 2; LiNiO2 and LiMn2O4, in which the oxygen layers are weaker bound. The pronounced covalency stabilizes the state of bondage of the Fe ³⁺ / Fe ²⁺ state by Fe-OP inductive effects.

LiFePO4 has a specific capacity of 170 mAh / g with good recyclability and a flat discharge potential curve at 3.2 to 3.4 V depending on the discharge condition.

However, the olivine structures have the disadvantage of extremely low electrical conductivity and low lithium diffusivity.

Basic electrochemical considerations and relationships

Overview of the abbreviations and formula symbols used P Electric power [W] n Num. speak. Charges per ion U Electric voltage [V] F Faraday I Current [A] E _g Energy gap between upper valence band and lowest conduction band R Resistance [ohm] μ _A Electrochemical potential anode HOMO Highest occupied molecular orbital μ _C Electrochem. Potential cathode LUMO Lowest unoccupied molecular orbital ε _F Fermi R _in (A) R _b Battery resistance R _in (C) R _el electrolyte resistance R _c (A) R _c (C) Capacitive resistance U _OCV Open circuit voltage σ _Li Conductance Li

The power output P of a battery is the product of the electrical voltage U at the poles of the battery and the electric current I supplied by the battery. P = U · I (1)

The electrical voltage under load is reduced compared to the open-circuit voltage U _OCV (Synonym: Open Circuit Voltage - OCV) by an overvoltage resulting from the internal resistance of the battery: U _load = U _OCV - R _Batt * I (2)

The open circuit voltage results

With the number of electrical charges n transported per ion and the Faraday constant F. The magnitude of the OCV is determined by the achievable difference in the electrochemical potential between anode and cathode or the energy gap between the uppermost valence band and the lowest one Conduction band of a solid electrolyte.

The chemical potential of the anode μ _A , which corresponds to the Fermi energy ε _{F of} a metal-reducing anode or the HOMO of a liquid or gaseous reducing agent, must lie between the LUMO of a liquid electrolyte or the conduction band of a solid electrolyte, so that the electrolyte thermodynamically stable with respect to Reduction by the reducing agent is.

Analogously, the chemical potential of the cathode μ _C , which corresponds to the LUMO of a liquid or gaseous oxidizer or the Fermi energy of a metal-oxidizing cathode must be above the HOMO of a liquid electrolyte or the valence band of a solid electrolyte, so that the electrolyte thermodynamically stable against oxidation by the oxidizing agent is.

Thermodynamic stability is therefore present when: μA - μC ≤ E _g (4) and also the E _{g of} the electrolyte to the chemical potentials μ _A and μ _C fits, so that the highest possible OCV results. In practice, this means that the representation of a high power output requires the highest possible OCV with the lowest possible internal battery resistance. R _b = R _el + R _in (A) + R _in (C) + R _c (A) + R _c (C) (6)

The electrolyte resistance R _{el of} the ionic current is proportional to the ratio of the effective thickness L to the geometric area A of the space between the electrodes, which is filled by an electrolyte having the ionic conductivity σ _i :

As the ions move by diffusion, the ionic conductivity increases with increasing temperature.

Typical conductivities of in practice under 0.1 S / cm at operating temperature of z. B. 25 ° C therefore necessarily lead to the use of a separator membrane between the electrodes with a large geometric area A and small thickness L.

The transport resistance of an ion through the electrode-electrolyte interface is proportional to the ratio of geometric area to contact area at each electrode.

Since the electrochemical process in the cell requires ionic transport across this interface, small particle size porous electrodes are particularly advantageous. The representation of a high electrode capacity, that is, the use of the highest possible proportion of the existing electrode material for the electrochemical process, also requires a good electronic contact - in the sense of electron conduction - between the electrode particles and a large contact area between the particles and the electrolyte for a good ion conduction over many charging and discharging cycles.

If the reversible cell reaction during charging or discharging is associated with a first-order phase change, the particles may break during repeated charging and discharging of the battery, the so-called cyclization, or lose the mutual electronic contact - in the sense of electron conduction. The loss of direct electronic contact between the particles prevents the electrochemical reaction and results in an irretrievable loss of storage capacity.

Another, but reversible, capacity loss can be observed with increasing discharge currents. Depending on the geometry of the electrode, it may then happen that the diffusive transport process of the lithium ions can not take place fast enough to bring the required current. This means in practice that with increasing current level increasingly less of the existing particles can be actively used. The same effect occurs with decreasing ionic conductivity σi, for example due to decreasing working temperatures.

The relationship between the practical battery voltage and the load current I is shown in the so-called polarization curve. Analogously, the battery voltage is referred to as the discharge characteristic as a function of the state of charge. The resulting overvoltage U _η as a function of the current level depends on the internal battery resistance.

When charging the battery, the overvoltage results from the difference between the required charging voltage and the OCV.

The contact overvoltage U _η stabilizes to a constant value. Therefore, the slope of the polarization curve in this region of the curve increases dV / dI ≈ R _el + R _c (A) + R _c (C) (11)

The polarization curve is determined by the finite diffusion rate. At these currents, the transport of ions from / to the electrode / electrolyte phase boundaries is not fast enough to achieve a reaction equilibrium.

cathode materials

The cathode material according to the invention for use in a rechargeable (secondary) battery consists of a structure in which lithium can be stored reversibly.

The maximum power output of a cell at a given maximum current depends on the OCV and the overvoltage U _η (I) associated with this current: U _max = U _OCV - U _{η (I)} (12)

A powerful electrode therefore has a high OCV and a high electronic conductivity. In order to keep the overvoltage U _η as small as possible, the electrodes must also have a high ionic conductivity and have a low contact resistance for the mass transfer at the electrode / electrolyte interface. For the representation of high maximum currents, therefore, the largest possible specific electrode / electrolyte interface is required.

In areas where a two-phase boundary occurs at the electrode particle, for example, at the boundary (solid) electrode / (liquid) electrolyte, the, usually diffusion-controlled, mass transfer must be able to proceed fast enough across this interface to provide the desired current or to be able to maintain. This mechanism therefore reduces the lithium storage capability of the electrode with respect to practically usable lithium with increasing current density.

In practice, oxide storage structures are fabricated with tightly packed oxygen sublattices in layers, such as Li _1-x CoO ₂ [ Mizushima et al, 1980 ], or in stable three-dimensional structures such. The manganese spinel Li _1-x [Mn 2] O ₄ . [ Thackeray 1995 ], [ Thackeray et al 1983 ], [ Thackeray et al. 1984 ], [ Guyomard and Tarascon 1992 ], [ Masquelier et al. 1996 ].

The intercalation of Li into a van der Waals gap between strongly connected layers can lead to a fast transport mechanism but involves the risk of the participation of unwanted species from the liquid electrolyte in the process.

Likewise, the storage in a closely packed oxygen substructure as a three-dimensional structure, such. As a [Mn2] O4 spinel, not unproblematic, since the free volume for the embedded Li + ions is too small to allow at room temperature, a high ion mobility, whereby the maximum achievable current decreases. Although the said spinel structure brings due to the size of the free volume in the lattice space with a selectivity for the incorporation of Li ions; however, at the same time the Li-ion mobility and thus the Li + ion conductivity σ _{Li is} limited.

Consequently, the oxospinels have a sufficiently high Li + ion conductivity for use in commercial low-power cells [ Thackeray et al 1983 ], but are not sufficient in terms of their performance for high-power cells.

Through the use of LiFePO4 [ WO9740541A1 / Goodenough], there are advantages by using an electrode material having, for example, oxidic polyanions such as (PO ₄ ) ³ , which has a three-dimensional storage structure with octahedral oxidizer cations based on so-called transition metals. As mentioned above, LiFePO4 has other major advantages over the other materials mentioned: it is inexpensive, environmentally safe, and thermally stable in the charged state. The thermal stability is particularly noteworthy due to the structure: the oxygen atoms form a hexagonal dense structure (hdp). The iron atoms are arranged in "zizag chains" as octahedrons in alternating basal planes. The lithium ions occupy the octahedral holes. The strong covalent bonds between the oxygen atoms and the phosphorus to phosphate ions (PO ₄ ) ^3- cause a stronger stabilization of the structure compared to the layer structures of LiCoO 2; LiNiO2 and LiMn2O4, in which the oxygen layers are weaker bound. The pronounced covalency stabilizes the state of bonding of the Fe ³⁺ / Fe ²⁺ state by Fe-OP inductive effects.

LiFePO4 has a specific capacity of 170 mAh / g with good recyclability and a flat discharge potential curve at 3.2 to 3.4 V depending on the discharge condition. Nevertheless, the olivine structures have the disadvantage of extremely low electrical conductivity and low lithium diffusivity.

Description of the present invention:

The present invention is intended to eliminate the disadvantages underlying the olivine or Nascion structures of low electrical conductivities and low lithium diffusivities. This happens because in the (PO ₄ ) ^y structure the oxygen is partially substituted. In a particularly preferred embodiment of the invention, this is done by nitrogen. In other preferred embodiments, substitution is by other metalloid elements such as carbon, boron, or fluorine, etc. In the present invention, astonishing results have been achieved by the partial substitution of nitrogen. These are compounds which, for example, contain a PN bond in the derivation from the oxo acids of the phosphors and formally represent the amido or imido compounds of the corresponding oxo acids.

In the corresponding salts, the oxygen atoms are replaced by isoelectronic groups, such as P = O by P = NH or P = NR or POP by P-NH-P or P-NR-P

There are a very large number of possible, inventive compounds that can be derived analogously from the structures. As with the polyanions of the oxo acids, the substituents can be used to formulate the corresponding polyanions in the salt:

With the introduction of the isoelectronic substituent into the oxo acids, two important advantages result for the application according to the invention as cathode material in a lithium battery:
The element with the weaker electronegativity weakens the strong electron localization compared to oxygen and increases the local lattice perturbation. This increases the vacancy concentration and thus the lithium diffusivity. The resulting lattice distortions lead to structural defects such as two-dimensional lattice defects in the form of step or screw dislocations. These usually develop perpendicular to the direction of the largest distortions in the lattice.

These distortions occur especially in the formation of FePO ₄ in the ac plane of LiFePO ₄ . The associated local lattice strains significantly increase the lithium mobility and can also increase the electronic conductivity. By the targeted substitution of oxygen by nitrogen on oxygen sites, an acceptor level is incorporated into the lattice. Depending on the concentration of nitrogen, this can influence the electronic conductivity.

According to the invention, with the introduction of the nitrogen into the oxygen sublattice, another important advantage results: the PO compounds can be replaced successively by the isoelectronic groups -NH ₂ , -NHR, -NR ₂ etc. or by = NH, = NR. R here stands for hydrocarbon compounds which contribute to the electrical conductivity with conjugated double bonds.

It has been shown that, LiFePO _4-x (NH) _x powder can be made highly conductive, if subsequently in a microwave plasma, the powder is first treated with nitrogen on the outer groups of the crystallites and then treated in a subsequent step in an ethene plasma becomes. The obvious advantage arises from the fact that the carbon is chemically bonded directly to the surface and thus the electron transfer between the amido or imidophosphate and the conductive surface layer can be barrier-free.

Another advantage of this approach is the high variability with which both the FePO _4-x (Y = NH, NR, ...) and other conductive surface compounds can be adjusted, such. B. highly conductive (CN) _x chains can be generated by deposition from a nitrogen-containing Kohlenhydrogen plasma. It should be emphasized that only a small window of the possibilities resulting from the concept is presented here. The presentation of further systems results analogously for the person skilled in the art. Of course, it is also conceivable to work with silicon-containing or boron-containing or metal-containing precursor gases, such as with titanium alcoholates or noble metal chlorides, etc.

• – Basis ist die Chemische Formulierung Li_qMe_IrMe_IIsZO_4-xY_x
• – Es liegt nahe, dass der Sauerstoff jeglichen oxidbasierten Kathoden- oder Anodenmaterial in ähnlicherweise durch stickstoff oder andere Metalloide teilsubstituiert werden kann wie z. B. in LiMn₂O₄, LiCoO₂, LiNiO_{2 ,} Li₄Ti₅O₁₂ und andere
• – Z besteht aus zumindest einem der Elemente: Phosphor; Silizium, Schwefel und Bor
• – Y steht für die Verbindung AR_n, wobei A aus mindestens einem der Metalloide: Stickstoff, Kohlenstoff, Bor besteht.
• – Me_I besteht aus zumindest einem der Metalle: Mg, Ca, Be, Al, Mn
• – Me_II besteht aus zumindest einem der Metalle: Metalle der ersten und zweiten Hauptgruppe sowie aus den Nebengruppen, insbesondere Fe, Mn, Ni, Co
• – Das entsprechende Material bzw. Materialgemisch ist zumindest eine Komponente für zumindest eine Elektrode einer wiederaufladbaren Lithiumbatterie.
• – In der ZO₄ ^δ– werden die Sauerstoffatome zumindest teilweise durch Amido- oder durch Imidogruppen ersetzt; die Konzentration liegt im Bereich der Dotierungskonzentration, insbesondere 10^–20, bis hin zur stöchiometrischen Konzentration gemäß -(ZO_4-xY_x)^3– mit x = 10^–20 oder größer, besonders bevorzugt 10^–20 <= x <= 2
• – Anstelle des Wasserstoffs können Kohlenwasserstoffketten, insbesondere langkettige Kohlenwasserstoffketten treten, zum Beispiel zur Erhöhung der elektronischen Leitfähigkeit.
• – In einer besonderen Ausführung lassen sich die unsubstituierten wie teilsubstituierten Phosphate (Sauerstoffsubstitution durch Amido bzw. Imidogruppe), beispielsweise in einem Stickstoffplasma, derart behandeln, dass lediglich Oberflächenatome oder oberflächennahe Atome entsprechend substituiert werden
• – Hieraus ergibt sich der zusätzliche Vorteil, dass in situ aus einem kohlenstoffhaltigen Plasma leitfähige Kohlenstoffketten an die Oberfläche angekoppelt werden. Durch die direkte chemische Verbindung zum Lithiumeisenphosphat bzw. Lithiumeisen-Amido(bzw. Imido)-phosphat kann der Elektronentransfer zwischen den Substanzen nahezu barrierefrei erfolgen

For clarity, here again the essential features of the present invention are summarized:

• - Based on the chemical formulation _Liq Me _Ir Me _IIs ZO _4-x Y _x
• It is obvious that the oxygen of any oxide-based cathode or anode material can similarly be partially substituted by nitrogen or other metalloids such as e.g. In LiMn ₂ O ₄ , LiCoO ₂ , LiNiO _{2 ,} Li ₄ Ti ₅ O ₁₂ and others
• - Z consists of at least one of the elements: phosphorus; Silicon, sulfur and boron
• Y is the compound AR _n , where A consists of at least one of the metalloids: nitrogen, carbon, boron.
• - Me _I consists of at least one of the metals: Mg, Ca, Be, Al, Mn
• Me _II consists of at least one of the metals: metals of the first and second main groups and of the subgroups, in particular Fe, Mn, Ni, Co
• - The corresponding material or material mixture is at least one component for at least one electrode of a rechargeable lithium battery.
• - In the ZO ₄ ^δ- the oxygen atoms are at least partially replaced by amido or imido groups; the concentration is in the range of the doping concentration, in particular 10 ^ -20, up to the stoichiometric concentration according to - (ZO _4-x Y _x ) ^3- with x = 10 ^ -20 or greater, particularly preferably 10 ^ -20 <= x <= 2
• Instead of the hydrogen, hydrocarbon chains, in particular long-chain hydrocarbon chains, can be used, for example to increase the electronic conductivity.
• In a particular embodiment, the unsubstituted and partially substituted phosphates (oxygen substitution by amido or imido group), for example in a nitrogen plasma, can be treated such that only surface atoms or near-surface atoms are correspondingly substituted
• This results in the additional advantage that conductive carbon chains are coupled to the surface in situ from a carbon-containing plasma. The direct chemical connection to the lithium iron phosphate or lithium iron amido (or imido) phosphate, the electron transfer between the substances can be almost barrier-free

embodiments

• 1. The preparation of the abovementioned compounds according to the invention can be carried out in very different ways. In the following presentation two particularly preferred methods are described by means of a practical example:
• 1.1 Mechanochemical Method: Approx. 10 g of sol-gelated iron-III-phosphate is mixed with 12wt% ammonium nitrate and the stoichiometric amount of lithium carbonate and ground with a zirconium ball mill for 10 hours. The powder mixture is sintered at 700 ° C for 120 minutes under a nitrogen atmosphere. The composition of the powders are determined by SNMS analysis. The total nitrogen of the sample corresponds to a composition LiFePO _3.5 (NH) _0.5 ; The determined conductivity of the compound is at room temperature at λ ≈ 10 ^-4 to 10 ^-3 Scm ^-1 .
• 1.2 Plasmachemic method: First, the powder of iron oxalate, ammonium dihydrogen phosphate and lithium carbonate with the addition of polyethylene glycol (Mw = 2000) is prepared; The mixture is ball milled for 12 hours. The gel is dried at 120 ° C. under a nitrogen atmosphere and finally sintered in a temperature gradient program at 710 ° C. The purity of the powder is checked by means of SIMS and SNMS. The finished, nitrogen-free powder is treated in a vacuum system in a microwave nitrogen plasma at p = 100 Pa for 15 min. Before the "nitrification", the powder is first activated in an argon plasma for 1 minute. In a subsequent sequential treatment step, in the microwave plasma at the surface, a 20 nm thick carbon layer is deposited from an ethene atmosphere at 200-250 Pa. The mainly existing plasma 10% nitrogen are added, so as to deposit a highly conductive carbon layer. Other preparation methods which use the direct reaction of phosphoryl chlorides (POCl ₃ ) with metal amides (MeNH, Me = Na, K,...) Were tested in the course of the reaction according to the invention, but did not lead to the same surprisingly good results as above described method. Both of these first methods are characterized by their simplicity and allow the targeted incorporation of the substituents in the phosphate group. From the mechanochemically prepared powder, a cathode was prepared by subsequently treating the powder as described above by plasma treatment in a nitrogen-containing ethene plasma. The powder thus obtained was then mixed in a ball mill with 3% binder (PVDF, Dupont) and compressed to form a tablet of approximately 1.5 cm ² and measured in a three-electrode cell. A lithium foil serves as counterelectrode, the electrolyte is represented as DC / EC 1: 1 with 1 M lithium hexafluorophosphate and a PP separator (Celgrade 2400). The cyclization tests were carried out in a potential window of 2.2 V to 4.1 V with charge / discharge rates of 1C each. Furthermore, the cells were loaded with 3C. At this point, a further advantage of the plasma-chemical treatment should be additionally emphasized, namely that the hydrophobization of the powder can be done directly from the plasma, as by the application of fluoride-containing gases such as - (CF ₂ ) _n - or by the direct fluorination of the carbon-containing layers the powders.

literature

Delmas, C., and A. Nadiri, Mater. Res. Bull., 23, 63 (1988) ,
Goodenough, JB, HYP. Hong and JA Kafalas, Mater. Res. Bull. 11, 203, (1976) ,
Guyomard, D. and JM Tarascon, J. Electrochem. Soc., 139, 937 (1992) ,
Long, GJ, G. Longworth, P. Battle, AK Cheetham, RV Thundathil and D. Beveridge, Inorg. Chem., 18, 624 (1979) ,
Manthiram, A., and JB Goodenough, J. Power Sources, 26, 403 (1989) ,
Masquelier, C., M. Tabuchi, K. Ado, R. Kanno, Y. Kobayashi, Y. Maki, O. Nakamura and JB Goodenough, J. Solid State Chem., 123, 255 (1996) ,
Mizushima, K., PC Jones, PJ Wiseman and JB Goodenough, Mater. Res. Bull., 15, 783 (1980) ,
Nanjundaswamy, KS, et al., "Synthesis, redox potential evaluation and electrochemical characteristics of NASiCON-related 3D framework compounds," Solid State Ionics, 92 (1996) 1-10 ,
Nishi, Y., H. Azuma and A. Omaru, US Pat. 4,959,281 , September 25, 1990.
Okada, S., KS Nanjundaswamy, A. Manthiram and JB Goodenough, Proc. 36th Power Sources ConS, Cherry Hill at New Jersey (June 6-9, 1994).
Schoellhorn, R. and A. Payer, Agnew. Chem. (Int Ed. Engl.), 24, 67 (1985) ,
Sinha, S. and DW Murphy, Solid State Ionics, 20, 81 (1986) ,
Thackeray, MMWIF David, JB Goodenough and P. Groves, Mater. Res. Bull., 20, 1137 (1983) ,
Thackeray, MM, PJ Johnson, LA de Piciotto, PG Bruce and JB Goodenough, Mater. Res. BulL, 19, 179 (1984) ,
Thackeray, MM, WIF David, PG Bruce and JB Goodenough, Mater. Res. Bull. 18,461 (1983) ,
Wang, S., and SJ Hwu, Chem. Mater. 4, 589 (1992) ,

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 0904607 [0010]
• WO 9740541 [0041]
• US Pat. No. 4,959,281 [0052]

Cited non-patent literature

• Mizushima et al., 1980 [0037]
• Thackeray 1995 [0037]
• Thackeray et al 1983 [0037]
• Thackeray et al. 1984 [0037]
• Guyomard and Tarascon 1992 [0037]
• Masquelier et al. 1996 [0037]
• Thackeray et al 1983 [0040]
• Delmas, C., and A. Nadiri, Mater. Res. Bull., 23, 63 (1988) [0052]
• Goodenough, JB, HYP. Hong and JA Kafalas, Mater. Res. Bull. 11, 203, (1976) [0052]
• Guyomard, D. and JM Tarascon, J. Electrochem. Soc., 139, 937 (1992) [0052]
• Long, GJ, G. Longworth, P. Battle, AK Cheetham, RV Thundathil and D. Beveridge, Inorg. Chem., 18, 624 (1979) [0052]
• Manthiram, A., and JB Goodenough, J. Power Sources, 26, 403 (1989) [0052]
• Masquelier, C., M. Tabuchi, K. Ado, R. Kanno, Y. Kobayashi, Y. Maki, O. Nakamura and JB Goodenough, J. Solid State Chem., 123, 255 (1996) [0052]
• Mizushima, K., PC Jones, PJ Wiseman and JB Goodenough, Mater. Res. Bull., 15, 783 (1980) [0052]
• Nanjundaswamy, KS, et al., "Synthesis, redox potential evaluation and electrochemical characteristics of NASiCON-related 3D framework compounds," Solid State Ionics, 92 (1996) 1-10 [0052]
• Okada, S., KS Nanjundaswamy, A. Manthiram and JB Goodenough, Proc. 36th Power Sources ConS, Cherry Hill at New Jersey (June 6-9, 1994). [0052]
• Schoellhorn, R. and A. Payer, Agnew. Chem. (Int Ed. Engl.), 24, 67 (1985) [0052]
• Sinha, S. and DW Murphy, Solid State Ionics, 20, 81 (1986) [0052]
• Thackeray, MMWIF David, JB Goodenough and P. Groves, Mater. Res. Bull., 20, 1137 (1983) [0052]
• Thackeray, MM, PJ Johnson, LA de Piciotto, PG Bruce and JB Goodenough, Mater. Res. BulL, 19, 179 (1984) [0052]
• Thackeray, MM, WIF David, PG Bruce and JB Goodenough, Mater. Res. Bull. 18,461 (1983) [0052]
• Wang, S., and SJ Hwu, Chem. Mater. 4, 589 (1992) [0052]

Claims (9)

Electrode material for a rechargeable electrochemical cell, characterized in that the cathode material consists at least in part of material according to the formula _Liq Me _Ir Me _IIs ZO ₄ -xY _x where Me _I consists of one of the metals: Na, Mg, Ca, Be, Al, Mn or a combination thereof and Me _II consists of at least one of the metals: Fe, Mn, Ni, Co or a combination thereof and Y is the compound AR _n , where A is at least one of the metalloids: nitrogen, carbon , Boron, R is hydrogen or a long-chain hydrocarbon or a hydrogen-free carbon chain and Z is at least one of the elements: P, As, Sb, Si, S and the index n is between 0 and 4 and the index q is between 0.01 and 1 and the index x can take values between 10 ^-20 and 2, and the sum of the indicia r + s + x> 10 ^ -20. The electrode material of claim 1 is characterized in that metals alone form the compound or as a combination of the cations, the composition according to the invention occur The electrode material of claim 1, characterized in that metals of the 4th and 5th subgroup are included The electrode material of claim 1, characterized in that metals of the 3rd main group of the PSE are included. The electrode material according to claim 1 is characterized in that the long-chain carbon chains contain nitrogen The electrode material according to claim 1 is characterized in that the long-chain compounds additionally contain at least one of the elements: oxygen, sulfur, phosphorus and boron The electrode material according to claim 1 is characterized in that the long-chain compounds are electrically conductive The electrode material according to claim 1 is characterized in that the long-chain compounds are coupled only to the surface of the grains The cathode material according to claim 1 for rechargeable electrochemical cells is characterized in that in the formula also sodium can replace lithium partially or completely.