WO2010023129A2 - New alkali transition metal fluorophosphates - Google Patents
New alkali transition metal fluorophosphates Download PDFInfo
- Publication number
- WO2010023129A2 WO2010023129A2 PCT/EP2009/060657 EP2009060657W WO2010023129A2 WO 2010023129 A2 WO2010023129 A2 WO 2010023129A2 EP 2009060657 W EP2009060657 W EP 2009060657W WO 2010023129 A2 WO2010023129 A2 WO 2010023129A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- transition metal
- alkali transition
- lithium
- fluorophosphates
- alkali
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to new alkali transition metal fluorophosphates and to mixtures comprising these alkali transition metal fluorophosphates and at least one electrically conductive material, to a process for the preparation of these alkali transi- tion metal fluorophosphates and to methods of using these alkali transition metal fluorophosphates and these mixtures as electrode material in batteries.
- the invention relates to electrodes which comprise these alkali transition metal fluorophosphates or mixtures comprising these alkali transition metal fluorophosphates and at least one electrically conductive material.
- Cathode materials of modern secondary lithium ion batteries typically contain an electrically conducting material like carbon black or graphite and a solid compound with a lattice structure into which lithium ions can be reversibly inserted or intercalated.
- an electrically conducting material like carbon black or graphite
- lithium ions migrate into the lattice structure of the solid compound from which they can be removed again during charging.
- the anode is oxidized and lithium ions migrate through the electrolyte to the cathode.
- reduction occurs at the anode. Both during discharge and during recharging of the battery, the lithium ions generally migrate through a separator.
- the electrodes and the electrolyte have to have a high chemical and electrochemical stability. Since the ability of the cathode material to take up and release lithium ions is of greater importance for the stability and also the capacity of the cathode, it is an important object to develop new types of materials which, as a result of their structure, make long-term reversible migration of lithium ions into and out of the electrode possible.
- lithium cobalt oxide LiCo ⁇ 2
- lithium iron phosphate LiFePO 4
- lithium transition metal fluorophosphates e. g. Li 2 MPO 4 F, WO 03/038930, EP 1 277 248.
- Lithium iron phosphate LiFePO 4
- U2MPO4F Lithium transition metal fluorophosphates
- the object of the present invention is to provide new alkali transition metal fluorophosphates and methods of using them as electrode material in batteries. Moreover, it is another object of the present invention to provide a process for the preparation of these alkali transition metal fluorophosphates. Furthermore, it is another object of the present invention to provide mixtures comprising these alkali transition metal fluorophosphates and at least one electrically conductive material and methods of using these mixtures as electrode material in batteries. In addition, it is another object of the present invention to provide cathodes which comprise these alkali transition metal fluorophosphates or these mixtures.
- M 1 Li, Na, K, Rb, Cs,
- M 2 , M 3 Fe, Co, Ni, Mn, Cr, V, Ti,
- the alkali transition metal fluoro- phosphates of the general formula (1) give powder X-ray diffraction (XRD) patterns wherein the seven most intense reflexes occur at Bragg angels corresponding to distances between the planes in the atomic lattice and show relative intensities as given in brackets in percent of 5.51+0.4 (100+20), 5.45+0.4 (92+20), 3.83+0.3 (34+20), 2.75+0.3 (38+20), 2.72+0.3 (47+20), 2.68+0.3 (54+20) and 2.41+0.2 (39+20) Angstrom.
- XRD powder X-ray diffraction
- the alkali transition metal fluorophosphates of the general formula (1) give powder X-ray diffraction (XRD) patterns similar to those shown in Figures 1 and 2.
- M 1 in the general formula (1 ) is lithium.
- y in the general formula (1 ) is 0.
- M 1 is lithium and y is 0 in the general formula (1), i.e. the alkali transition metal fluorophosphates have the formula
- Another embodiment of the present invention is a process for the preparation of alkali transition metal fluorophosphates of the general formula Lii- x M 1 M 2 i-yM 3 y P ⁇ 4F (1), wherein 0,01 ⁇ x ⁇ 1 , comprising the step of reacting an alkali transition metal fluoro- phosphate of the general formula LiM 1 M 2 i- y M 3 y P ⁇ 4F (2) with an oxidizer.
- the process can be illustrated by the following scheme (A):
- M 1 Li, Na, K 1 Rb, Cs,
- M 2 , M 3 Fe, Co 1 Ni , Mn, Cr, V, Ti
- the alkali transition metal fluorophosphates of the general formula LiM 1 M 2 i -y M 3 y PO 4 F (2), that are according to scheme (A) employed as starting material in the process of the present invention, are known and can be prepared, for example, by solid state reaction between lithium fluoride LiF and the corresponding alkali transition metal phosphate M 1 M 2 i -y M 3 y PO 4 (e.g. Dutreilh, M. et al., J. Solid State Chem. 1999, Vol. 142, pages 1 to 5 for the synthesis of Li 2 NiPO 4 F).
- the oxidizer must have a redox potential sufficiently strong to oxidize the transition metal M 2 and/or M 3 to a higher oxidation state.
- suitable oxidizers include fluorine, chlorine, bromine, nitrosyl chloride, nitrosyl nitrate, nitrosyl hexafluorophos- phate and nitrosyl tetrahydroborate.
- a preferred oxidizer is nitrosyl nitrate.
- the oxidation is accompanied by an extraction of lithium ions from the starting material.
- the process according to the invention changes the structure of the starting alkali transition metal fluorophosphate (2) to that of the new alkali transition metal fluorophosphate (1 ) as described above.
- the process of the present invention is carried out in the presence of a solvent.
- the oxidizer and the starting material (2) are dissolved or dispersed in a solvent and stirred for a time sufficient to effect the desired reaction according to scheme (A).
- the reaction time is usually between 1 minute and 48 hours, preferably between 1 and 24 hours.
- the reaction temperature is generally between 0 0 C and 150 0 C, preferably between 10 0 C and 100°C, most preferred around ambient temperature.
- Suitable solvents are essentially inert against the oxidizer, allow to dissolve the oxidizer at least partially and do not react with the fluorophosphates (1) and (2).
- suitable solvents include hydrocarbons like pentane, hexane, benzene, toluene, ethers like diethylether, tetrahydrofuran, methyl-tert-butylether, acetonitril, dimethylformamid, dimethylsulfoxide and the like.
- a molar excess of the oxidizer is employed relative to the alkali transition metal fluorophosphate (2).
- the molar ratio of the oxidizer to the alkali transition metal fluorophosphates (2) is in the range of from 1 ,1 :1 to 100:1 , preferably in the range of from 1 ,5:1 to 50:1.
- the present invention further relates to alkali transition metal fluorophosphates of the general formula Lii- x M 1 M 2 i-yM 3 y P ⁇ 4F (1) as defined above, preparable by the process according to the present invention.
- the alkali transition metal fluorophosphates of the general formula Lii- x M 1 M 2 i-yM 3 y P ⁇ 4F (1 ) as defined above are particularly suitable for the use for the preparation of a cathode of a lithium-ion battery or an electrochemical cell. Therefore, the present invention also relates to the use of these alkali transition metal fluorophosphates of the general formula Lii- x M 1 M 2 i-yM 3 y P ⁇ 4F (1 ) for the preparation of a cathode of a lithium-ion battery or an electrochemical cell.
- the present invention further relates to a cathode for a lithium-ion battery or an electro- chemical cell, comprising at least one alkali transition metal fluorophosphate of the general formula Lii- x M 1 M 2 i-yM 3 y P ⁇ 4F (1) as defined above.
- a cathode for a lithium-ion battery or an electro- chemical cell, comprising at least one alkali transition metal fluorophosphate of the general formula Lii- x M 1 M 2 i-yM 3 y P ⁇ 4F (1) as defined above.
- the alkali transition metal fluorophosphates of the general formula Lii- x M 1 M 2 i-yM 3 y P ⁇ 4F (1 ) is mixed with at least one electrically conducting material, described for example in WO 2004/082047.
- Suitable electrically conducting materials are for example carbon black, graphite, carbon fibres, carbon nanofibres, carbon nanotubes or electrically conducting polymers. Typically 2 to 40% by weight of the at least one electrically conducting material are used together with the alkali transition metal fluorophosphates of the general formula Lii- ⁇ M 1 M 2 i- y M 3 y P ⁇ 4F (1) as defined above in the cathode.
- the electrically conducting material and the alkali transition metal fluorophosphates of the general formula Lii- x M 1 M 2 i-yM 3 y P ⁇ 4F (1) as defined above are mixed, optionally in the presence of an organic solvent and optionally in the presence of an organic binder, for example polyisobutene, and this mixture is optionally formed and dried.
- a temperature of 80 to 150 0 C is applied in the drying step.
- the present invention relates to mixtures comprising at least one alkali transition metal fluorophosphate of the general formula Lii- x M 1 M 2 i-yM 3 y P ⁇ 4F (1 ) as defined above and at least one electrically conducting material, selected from the group, consisting of carbon black, graphite, carbon fibres, carbon nanofibres, carbon nanotubes and electrically conducting polymers.
- Another embodiment of the present invention relates to the use of these mixtures as defined above for the preparation of a cathode of a lithium-ion battery or an electrochemical cell.
- the present invention also relates to a cathode for a lithium-ion battery or an electrochemical cell, comprising a mixture as defined above.
- binders For the preparation of a cathode comprising an alkali transition metal fluorophosphate of the general formula Lii- x M 1 M 2 i-yM 3 y P ⁇ 4F (1) as defined above or a mixture as de- fined above, in a preferred embodiment the following binders are used:
- Polyethylene oxide PEO
- cellulose polyethylene, polypropylene, polytetrafluoroethyl- ene, polyacrylonitrile-methylmethacrylate, styrene-butadiene-copolymers, tetrafluoro- ethylene-hexfluoropropylene-copolymers, polyvinylidenefluoride-hexafluoropropylene- copolymers (PVdF-HFP), perfluoroalkyl-vinylether-copolymers, vinylidenefluoride- chlorotrifluoroethylene-copolymers, ethylene-chlorofluoroethylene-copolymers, ethyl- ene-acrylic acid-copolymers (with and without sodium ions included), ethylene- methacrylic acid (with and without sodium ions included), polyimides and polyisobutene.
- PVdF-HFP polyvinylidenefluoride-hexafluoro
- the binder is normally added in an amount of 1 to 10% by weight, preferably 2 to 8% by weight, particularly preferred 3 to 7% by weight, in each case based on the whole cathode material.
- Figure 1 shows an X-ray diffraction (XRD) powder diagram of Li2- ⁇ Nio prepared according to example 1.
- Figure 2 shows an X-ray diffraction (XRD) powder diagram of Li2- ⁇ Nio67Feo33P ⁇ 4F, prepared according to example 2.
- Figure 3 shows a comparison of the X-ray diffraction (XRD) powder diagrams of Li2Nio75Feo25P ⁇ 4F and its oxidation product Li2- ⁇ Nio prepared according to example 1.
- XRD X-ray diffraction
- Figure 4 shows a comparison of the X-ray diffraction (XRD) powder diagrams of Li2Nio67Feo33P0 4 F and its oxidation product Li2- ⁇ Nio prepared according to example 2.
- XRD X-ray diffraction
- NONO3 nitrosyl nitrate
- Li2Nio67Feo33P04F 150 mg was added to 17 ml of 1 M nitrosyl nitrate (NONO3) solution and stirred for 24 h at ambient temperature (example 2).
- NONO3 nitrosyl nitrate
- the products were filtered, washed repeatedly with acetonitrile under nitrogen atmosphere, dried and analysed by powder X-ray diffraction.
- the XRD patterns of the light green powders are given in Figure 1 and 2, respectively.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Secondary Cells (AREA)
Abstract
Alkali transition metal fluorophosphates of the general Formula (1) Li1-χM1M 2
1-yM3
yPO4F (1), wherein 0 ≤ x ≤ 1, 0 ≤ y ≤1, M1 = Li, Na, K, Rb, Cs, M2, M3 = Fe, Co, Ni, Mn, Cr, V, Ti, which give powder X-ray diffraction (XRD) patterns wherein the seven most intense reflexes occur at Bragg angels corresponding to distances between the planes in the atomic lattice of 5.51+0.4, 5.45+0.4, 3.83+0.3, 2.75+0.3, 2.72+0.3, 2.68+0.3 and 2.41+0.2 Angstrom.
Description
New Alkali Transition Metal Fluorophosphates
Description
Field of the Invention
The present invention relates to new alkali transition metal fluorophosphates and to mixtures comprising these alkali transition metal fluorophosphates and at least one electrically conductive material, to a process for the preparation of these alkali transi- tion metal fluorophosphates and to methods of using these alkali transition metal fluorophosphates and these mixtures as electrode material in batteries. In addition, the invention relates to electrodes which comprise these alkali transition metal fluorophosphates or mixtures comprising these alkali transition metal fluorophosphates and at least one electrically conductive material.
Background of the Invention
Cathode materials of modern secondary lithium ion batteries typically contain an electrically conducting material like carbon black or graphite and a solid compound with a lattice structure into which lithium ions can be reversibly inserted or intercalated. When such a lithium ion battery is used (discharge), lithium ions migrate into the lattice structure of the solid compound from which they can be removed again during charging. During discharge of the battery the anode is oxidized and lithium ions migrate through the electrolyte to the cathode. When a lithium ion battery is recharged, reduction occurs at the anode. Both during discharge and during recharging of the battery, the lithium ions generally migrate through a separator.
To enable a battery to be used for a long time, the electrodes and the electrolyte have to have a high chemical and electrochemical stability. Since the ability of the cathode material to take up and release lithium ions is of greater importance for the stability and also the capacity of the cathode, it is an important object to develop new types of materials which, as a result of their structure, make long-term reversible migration of lithium ions into and out of the electrode possible.
A variety of materials has been suggested for use as cathode materials in lithium ion batteries, including, for example, lithium cobalt oxide (LiCoθ2), lithium vanadium oxide (Lii+χV3θ8, US 5013620), lithium iron phosphate (LiFePO4) and lithium transition metal fluorophosphates (e. g. Li2MPO4F, WO 03/038930, EP 1 277 248).
There is a strong demand for improved cathode materials for secondary lithium ion batteries which fulfil strict performance and safety requirements. The market dominating lithium cobalt oxide (LiCoO2) exhibits an insufficient thermal stability. Lithium iron phosphate (LiFePO4), a safer and thermally more stable material, is electrochemically
active at a lower voltage than UCOO2, why only lower energy densities can be reached. Lithium transition metal fluorophosphates (e. g. U2MPO4F) can be cycled a higher voltages than LiFePO4 and were therefore considered as a starting material for further improvements.
The object of the present invention is to provide new alkali transition metal fluorophosphates and methods of using them as electrode material in batteries. Moreover, it is another object of the present invention to provide a process for the preparation of these alkali transition metal fluorophosphates. Furthermore, it is another object of the present invention to provide mixtures comprising these alkali transition metal fluorophosphates and at least one electrically conductive material and methods of using these mixtures as electrode material in batteries. In addition, it is another object of the present invention to provide cathodes which comprise these alkali transition metal fluorophosphates or these mixtures.
Detailed Description of the Invention
The object of the present invention is achieved by alkali transition metal fluorophosphates of the general formula (1 )
Lii-χM1M2i-yM3 yPO4F (1 ),
wherein 0 < x < 1 , 0 < y < 1 ,
M1 = Li, Na, K, Rb, Cs,
M2, M3 = Fe, Co, Ni, Mn, Cr, V, Ti,
which give powder X-ray diffraction (XRD) patterns wherein the seven most intense reflexes occur at Bragg angels corresponding to distances between the planes in the atomic lattice of 5.5110.4, 5.4510.4, 3.83+0.3, 2.75+0.3, 2.72+0.3, 2.68+0.3 and 2.41+0.2 Angstrom.
In a preferred embodiment of the present invention the alkali transition metal fluoro- phosphates of the general formula (1) give powder X-ray diffraction (XRD) patterns wherein the seven most intense reflexes occur at Bragg angels corresponding to distances between the planes in the atomic lattice and show relative intensities as given in brackets in percent of 5.51+0.4 (100+20), 5.45+0.4 (92+20), 3.83+0.3 (34+20), 2.75+0.3 (38+20), 2.72+0.3 (47+20), 2.68+0.3 (54+20) and 2.41+0.2 (39+20) Angstrom. In a very preferred embodiment of the present invention the alkali transition metal fluorophosphates of the general formula (1) give powder X-ray diffraction (XRD) patterns similar to those shown in Figures 1 and 2.
In another preferred embodiment of the present invention M1 in the general formula (1 ) is lithium.
In another preferred embodiment of the present invention y in the general formula (1 ) is 0.
In a very preferred embodiment of the present invention M1 is lithium and y is 0 in the general formula (1), i.e. the alkali transition metal fluorophosphates have the formula
Another embodiment of the present invention is a process for the preparation of alkali transition metal fluorophosphates of the general formula Lii-xM1M2i-yM3 yPθ4F (1), wherein 0,01 < x < 1 , comprising the step of reacting an alkali transition metal fluoro- phosphate of the general formula LiM1M2i-yM3 yPθ4F (2) with an oxidizer. The process can be illustrated by the following scheme (A):
Oxidizer
LiM1M2i-yM3 y PO4F Lii-χM1M2i-yM3 yPO4F (A)
(2) (1 )
wherein
0.01 < x < 1 ,
0 < y < 1 ,
M1 = Li, Na, K1 Rb, Cs,
M2, M3 = Fe, Co1 Ni , Mn, Cr, V, Ti
The alkali transition metal fluorophosphates of the general formula LiM1M2i-yM3 yPO4F (2), that are according to scheme (A) employed as starting material in the process of the present invention, are known and can be prepared, for example, by solid state reaction between lithium fluoride LiF and the corresponding alkali transition metal phosphate M1M2i-yM3 yPO4 (e.g. Dutreilh, M. et al., J. Solid State Chem. 1999, Vol. 142, pages 1 to 5 for the synthesis of Li2NiPO4F).
The oxidizer must have a redox potential sufficiently strong to oxidize the transition metal M2 and/or M3 to a higher oxidation state. Examples of suitable oxidizers include fluorine, chlorine, bromine, nitrosyl chloride, nitrosyl nitrate, nitrosyl hexafluorophos- phate and nitrosyl tetrahydroborate. A preferred oxidizer is nitrosyl nitrate.
According to the invention the oxidation is accompanied by an extraction of lithium ions from the starting material. Moreover, the process according to the invention changes
the structure of the starting alkali transition metal fluorophosphate (2) to that of the new alkali transition metal fluorophosphate (1 ) as described above.
In a preferred embodiment the process of the present invention is carried out in the presence of a solvent. In one embodiment the oxidizer and the starting material (2) are dissolved or dispersed in a solvent and stirred for a time sufficient to effect the desired reaction according to scheme (A). The reaction time is usually between 1 minute and 48 hours, preferably between 1 and 24 hours. The reaction temperature is generally between 00C and 1500C, preferably between 100C and 100°C, most preferred around ambient temperature.
Suitable solvents are essentially inert against the oxidizer, allow to dissolve the oxidizer at least partially and do not react with the fluorophosphates (1) and (2). Examples of suitable solvents include hydrocarbons like pentane, hexane, benzene, toluene, ethers like diethylether, tetrahydrofuran, methyl-tert-butylether, acetonitril, dimethylformamid, dimethylsulfoxide and the like.
In one embodiment of the present invention a molar excess of the oxidizer is employed relative to the alkali transition metal fluorophosphate (2). In general the molar ratio of the oxidizer to the alkali transition metal fluorophosphates (2) is in the range of from 1 ,1 :1 to 100:1 , preferably in the range of from 1 ,5:1 to 50:1.
The present invention further relates to alkali transition metal fluorophosphates of the general formula Lii-xM1M2i-yM3 yPθ4F (1) as defined above, preparable by the process according to the present invention.
The alkali transition metal fluorophosphates of the general formula Lii-xM1M2i-yM3 yPθ4F (1 ) as defined above are particularly suitable for the use for the preparation of a cathode of a lithium-ion battery or an electrochemical cell. Therefore, the present invention also relates to the use of these alkali transition metal fluorophosphates of the general formula Lii-xM1M2i-yM3 yPθ4F (1 ) for the preparation of a cathode of a lithium-ion battery or an electrochemical cell.
The present invention further relates to a cathode for a lithium-ion battery or an electro- chemical cell, comprising at least one alkali transition metal fluorophosphate of the general formula Lii-xM1M2i-yM3 yPθ4F (1) as defined above. To obtain a cathode as mentioned above the alkali transition metal fluorophosphates of the general formula Lii-xM1M2i-yM3 yPθ4F (1 ) is mixed with at least one electrically conducting material, described for example in WO 2004/082047.
Suitable electrically conducting materials are for example carbon black, graphite, carbon fibres, carbon nanofibres, carbon nanotubes or electrically conducting polymers.
Typically 2 to 40% by weight of the at least one electrically conducting material are used together with the alkali transition metal fluorophosphates of the general formula Lii-χM1M2i-yM3 yPθ4F (1) as defined above in the cathode. To obtain the cathode the electrically conducting material and the alkali transition metal fluorophosphates of the general formula Lii-xM1M2i-yM3 yPθ4F (1) as defined above are mixed, optionally in the presence of an organic solvent and optionally in the presence of an organic binder, for example polyisobutene, and this mixture is optionally formed and dried. A temperature of 80 to 150 0C is applied in the drying step.
In still another embodiment the present invention relates to mixtures comprising at least one alkali transition metal fluorophosphate of the general formula Lii-xM1M2i-yM3 yPθ4F (1 ) as defined above and at least one electrically conducting material, selected from the group, consisting of carbon black, graphite, carbon fibres, carbon nanofibres, carbon nanotubes and electrically conducting polymers.
Another embodiment of the present invention relates to the use of these mixtures as defined above for the preparation of a cathode of a lithium-ion battery or an electrochemical cell.
The present invention also relates to a cathode for a lithium-ion battery or an electrochemical cell, comprising a mixture as defined above.
For the preparation of a cathode comprising an alkali transition metal fluorophosphate of the general formula Lii-xM1M2i-yM3 yPθ4F (1) as defined above or a mixture as de- fined above, in a preferred embodiment the following binders are used:
Polyethylene oxide (PEO), cellulose, polyethylene, polypropylene, polytetrafluoroethyl- ene, polyacrylonitrile-methylmethacrylate, styrene-butadiene-copolymers, tetrafluoro- ethylene-hexfluoropropylene-copolymers, polyvinylidenefluoride-hexafluoropropylene- copolymers (PVdF-HFP), perfluoroalkyl-vinylether-copolymers, vinylidenefluoride- chlorotrifluoroethylene-copolymers, ethylene-chlorofluoroethylene-copolymers, ethyl- ene-acrylic acid-copolymers (with and without sodium ions included), ethylene- methacrylic acid (with and without sodium ions included), polyimides and polyisobutene.
The binder is normally added in an amount of 1 to 10% by weight, preferably 2 to 8% by weight, particularly preferred 3 to 7% by weight, in each case based on the whole cathode material.
Figures:
Figure 1 shows an X-ray diffraction (XRD) powder diagram of Li2-χNio
prepared according to example 1.
Figure 2 shows an X-ray diffraction (XRD) powder diagram of Li2-χNio67Feo33Pθ4F, prepared according to example 2.
Figure 3 shows a comparison of the X-ray diffraction (XRD) powder diagrams of Li2Nio75Feo25Pθ4F and its oxidation product Li2-χNio
prepared according to example 1.
Figure 4 shows a comparison of the X-ray diffraction (XRD) powder diagrams of Li2Nio67Feo33P04F and its oxidation product Li2-χNio
prepared according to example 2.
Examples
The present invention is further illustrated by the following examples without limitation of the same:
Synthesis of Li2NiI-XFexPO4F
At first, phosphates, LiNii-xFexPθ4 (x=0.25, 0.33) were synthesized. To prepare about 2 g of phosphate with desirable composition appropriate amount of initial reagents (Tablei ) were thoroughly grinded in mortar (acetone-medium, for 30 to 40 minutes) and pelletized.
Table 1 :
Prepared pellets were annealed at 3700C for 10 hours in the argon atmosphere (with a heating rate of ~120°C/h). Then obtained products were grinded again (under acetone, for 30 to 40 minutes), pelletized and annealed at 7000C for 60 hours with one intermediate regrinding. XRD patterns were indexed in the space group Pnma with following cell parameters:
Obtained phosphates were used to synthesize corresponding fluorophosphates. The stoichiometric amounts of LiNii-xFexPθ4 and LiF (Table 2) were grinded carefully for 40 minutes and pelletized.
Table 2:
Pellets were placed into the corundum crucible covered with Nickel-foil and heated in the furnace under Argon flow. The following temperature profile was applied: heating to 6700C in 4 hours, annealing at 6700C for 1 hour and then quenching to room temperature. XRD patterns of obtained grey samples were indexed in the space group Pnma with following cell parameters:
Chemical oxidation of Li2Nii-xFexPθ4F
1 M nitrosyl nitrate (NONO3) solution was prepared by dissolving 3.68 g of N2O4 in 40 ml of acetonitrile. For oxidation the appropriate amount of fluorophosphate was stirred in 1 M NONO3 solution for 24 hours at ambient temperature.
1 15 mg of Li2Nio 75Fe025PO4F was added to 15 ml of 1 M nitrosyl nitrate (NONO3) solution and stirred for 24 h at ambient temperature (example 1 ).
150 mg of Li2Nio67Feo33P04F was added to 17 ml of 1 M nitrosyl nitrate (NONO3) solution and stirred for 24 h at ambient temperature (example 2).
The products were filtered, washed repeatedly with acetonitrile under nitrogen atmosphere, dried and analysed by powder X-ray diffraction. The XRD patterns of the light green powders are given in Figure 1 and 2, respectively.
Claims
1. Alkali transition metal fluorophosphates of the general formula (1 )
Lii-χM1M2i-yM3 yPO4F (1 ),
wherein 0 < x < 1 ,
0 < y < 1 ,
M1 = Li, Na, K, Rb, Cs, M2, M3 = Fe, Co, Ni, Mn, Cr, V, Ti,
which give powder X-ray diffraction (XRD) patterns wherein the seven most intense reflexes occur at Bragg angels corresponding to distances between the planes in the atomic lattice of 5.5110.4, 5.4510.4, 3.8310.3, 2.7510.3, 2.7210.3,
2.6810.3 and 2.4110.2 Angstrom.
2. Alkali transition metal fluorophosphates according to claim 1 , which give powder X-ray diffraction (XRD) patterns wherein the seven most intense reflexes occur at Bragg angels corresponding to distances between the planes in the atomic lattice and show relative intensities as given in brackets in percent of 5.5110.4 (100120),
5.4510.4 (92120), 3.8310.3 (34120), 2.7510.3 (38120), 2.7210.3 (47120), 2.6810.3 (54120) and 2.4110.2 (39120) Angstrom.
3. Alkali transition metal fluorophosphates according to claim 1 or 2, wherein M1 is lithium.
4. Alkali transition metal fluorophosphates according to any of claims 1 to 3, wherein y is 0.
5. Process for the preparation of alkali transition metal fluorophosphates of the general formula Lii-xM1M2i-yM3 yPθ4F (1 ) as defined in claim 1 , wherein 0,01 < x < 1 , comprising the step of reacting an alkali transition metal fluorophosphate of the general formula LiMW-i-ylvPyPCuF (2) with an oxidizer.
6. Process according to claim 5, wherein the oxidizer comprises fluorine, chlorine, bromine, nitrosyl chloride, nitrosyl nitrate, nitrosyl hexafluorophosphate or nitrosyl tetrahydroborate.
7. Process according to claim 5 or 6, wherein to process is carried out in the presence of a solvent.
8. Alkali transition metal fluorophosphates of the general formula Lii-χM1M2i-yM3 yPθ4F (1) as defined in claim 1 , wherein 0,01 < x < 1 , preparable by a process according to any of claims 5 to 7.
9. Use of an alkali transition metal fluorophosphate according to any of claims 1 to 4 for the preparation of a cathode of a lithium-ion battery or an electrochemical cell.
10. Cathode for a lithium-ion battery or an electrochemical cell, comprising at least one alkali transition metal fluorophosphate according to any of claims 1 to 4.
1 1. Mixture comprising at least one alkali transition metal fluorophosphate of the gen- eral formula Lii-xM1M2i-yM3 yPθ4F (1 ) as defined in claim 1 and at least one electrically conducting material, selected from the group, consisting of carbon black, graphite, carbon fibres, carbon nanofibres, carbon nanotubes and electrically conducting polymers.
12. Use of a mixture according to claim 11 for the preparation of a cathode of a lithium-ion battery or an electrochemical cell.
13. Cathode for a lithium-ion battery or an electrochemical cell, comprising a mixture according to claim 11.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08163301 | 2008-08-29 | ||
| EP08163301.8 | 2008-08-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2010023129A2 true WO2010023129A2 (en) | 2010-03-04 |
| WO2010023129A3 WO2010023129A3 (en) | 2010-06-03 |
Family
ID=41396185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2009/060657 WO2010023129A2 (en) | 2008-08-29 | 2009-08-18 | New alkali transition metal fluorophosphates |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2010023129A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014110412A3 (en) * | 2013-01-11 | 2014-10-16 | Massachusetts Institute Of Technology | Design of multi-electron li-ion phosphate cathodes by mixing transition metals |
| CN109188298A (en) * | 2018-08-21 | 2019-01-11 | 天津力神电池股份有限公司 | A kind of evaluation method of the embedding lithium state of negative electrode of lithium ion battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003038930A2 (en) * | 2001-10-26 | 2003-05-08 | Valence Technology, Inc. | Alkali/transition metal halo-and hydroxy-modified phosphates and related electrode active materials |
| US6645452B1 (en) * | 2000-11-28 | 2003-11-11 | Valence Technology, Inc. | Methods of making lithium metal cathode active materials |
| EP1277248B1 (en) * | 2000-04-27 | 2006-02-01 | Valence Technology, Inc. | Lithium metal fluorophosphate materials and preparation thereof |
-
2009
- 2009-08-18 WO PCT/EP2009/060657 patent/WO2010023129A2/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1277248B1 (en) * | 2000-04-27 | 2006-02-01 | Valence Technology, Inc. | Lithium metal fluorophosphate materials and preparation thereof |
| US6645452B1 (en) * | 2000-11-28 | 2003-11-11 | Valence Technology, Inc. | Methods of making lithium metal cathode active materials |
| WO2003038930A2 (en) * | 2001-10-26 | 2003-05-08 | Valence Technology, Inc. | Alkali/transition metal halo-and hydroxy-modified phosphates and related electrode active materials |
Non-Patent Citations (1)
| Title |
|---|
| BARKER J ET AL: "Structural and electrochemical properties of lithium vanadium fluorophosphate, LiVPO4F" JOURNAL OF POWER SOURCES, ELSEVIER SA, CH LNKD- DOI:10.1016/J.JPOWSOUR.2005.03.126, vol. 146, no. 1-2, 26 August 2005 (2005-08-26), pages 516-520, XP025269075 ISSN: 0378-7753 [retrieved on 2005-08-26] * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014110412A3 (en) * | 2013-01-11 | 2014-10-16 | Massachusetts Institute Of Technology | Design of multi-electron li-ion phosphate cathodes by mixing transition metals |
| CN109188298A (en) * | 2018-08-21 | 2019-01-11 | 天津力神电池股份有限公司 | A kind of evaluation method of the embedding lithium state of negative electrode of lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010023129A3 (en) | 2010-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10756341B2 (en) | Metallate electrodes | |
| US9608269B2 (en) | Condensed polyanion electrode | |
| KR101323385B1 (en) | Synthesis of cathode active materials | |
| US8647773B2 (en) | Niobium oxide compositions and methods for using same | |
| KR101061702B1 (en) | Manufacturing method of positive electrode material for lithium battery and lithium battery | |
| US20100314577A1 (en) | Cathode materials for secondary (rechargeable) lithium batteries | |
| KR20120099383A (en) | Mixed metal olivine electrode materials for lithium ion batteries having improved specific capacity and energy density | |
| JP2013529830A (en) | Method for producing lithium or sodium battery | |
| US10205168B2 (en) | Sodium transition metal silicates | |
| US20200052298A1 (en) | High power electrode materials | |
| JP4773964B2 (en) | Boron-substituted lithium insertion compounds, electrode active materials, batteries and electrochromic devices | |
| Yang et al. | Realizing the performance of LiCoPO4 cathodes by Fe substitution with off-stoichiometry | |
| US20170237118A1 (en) | Cubic ionic conductor ceramics for alkali ion batteries | |
| KR20170018843A (en) | Tin-containing compounds | |
| EP3595061B1 (en) | Positive electrode active material for potassium secondary battery and potassium secondary battery containing same | |
| KR101752814B1 (en) | Nitrogen-containing hydride anodes, and galvanic elements containing nitrogen-containing hydride anodes | |
| EP2822905B1 (en) | V2O5-LiBO2, V2O5-NiO-LiBO2 GLASSES AND THEIR COMPOSITES OBTAINED BY NITROGEN DOPING AND REDUCED GRAPHITE OXIDE BLENDING AS CATHODE ACTIVE MATERIALS | |
| EP2607319A1 (en) | H4V3O8, a new vanadium(IV) oxide electroactive material for aqueous and non aqueous batteries | |
| WO2013165953A1 (en) | Cubic ionic conductor ceramics for alkali ion batteries | |
| WO2010023129A2 (en) | New alkali transition metal fluorophosphates | |
| EP3412631B1 (en) | High power electrode materials | |
| WO2023209113A1 (en) | New nasicon-type high voltage sodium vanadium phosphates materials for na-ion batteries | |
| WO2020049104A1 (en) | Method of producing a rechargeable high-energy battery having an anionically redox-active composite cathode | |
| Zhu et al. | A Strategy of High Entropy Enabling Advanced Nasicon Sodium-Ion Cathodes with High Stabilization and Multicationic Redox |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09781940 Country of ref document: EP Kind code of ref document: A2 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 09781940 Country of ref document: EP Kind code of ref document: A2 |