EP3233725A2 - Zur herstellung von kathoden für li-ionen-akkumulatoren geeignete phosphatverbindungen - Google Patents

Zur herstellung von kathoden für li-ionen-akkumulatoren geeignete phosphatverbindungen

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Publication number
EP3233725A2
EP3233725A2 EP15808375.8A EP15808375A EP3233725A2 EP 3233725 A2 EP3233725 A2 EP 3233725A2 EP 15808375 A EP15808375 A EP 15808375A EP 3233725 A2 EP3233725 A2 EP 3233725A2
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Prior art keywords
solution
metals
acid
aqueous solution
ppm
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EP15808375.8A
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German (de)
English (en)
French (fr)
Inventor
Christian Graf
Daniel Buchold
Schwarz KILIAN
Michael RAPPHAHN
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Chemische Fabrik Budenhiem KG
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Chemische Fabrik Budenhiem KG
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    • 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
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • C01B25/37—Phosphates of heavy metals
    • 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
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • 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
    • C01B25/37—Phosphates of heavy metals
    • C01B25/377—Phosphates of heavy metals of manganese
    • 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
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C01B25/451—Phosphates containing plural metal, or metal and ammonium containing metal and ammonium
    • 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
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/02—Amorphous compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/60—Compounds characterised by their crystallite size
    • 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
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • M1, M2 and M3 are metals from the group consisting of Mn, Fe, Co and Ni
  • M4 represent one or more metals from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Be, Mg, Ca, Sr, Ba, Al, Zr, La ,
  • Rechargeable Li-ion batteries are widely used energy storage devices, especially in the field of mobile electronics.
  • cathode materials have lithium metal oxides such as L1C0O2, LiNi02, LiNi-XCO x 02 and 4 LiMn2Ü established.
  • DE 10 201 1 056 812 describes a process for preparing a monometallic or mixed-metal phosphate of the type (M1 M2 M3... Mx) 3 (PO 4 ) 2 .aH 2 O by neutralizing a corresponding phosphoric acid solution containing metal ions.
  • the neutralization takes place in all cases with alkaline ion-containing basic solutions.
  • the alkali ions can occupy lattice sites of lithium ions in the later cathode material, they reduce the performance, lifetime and capacity of such a cathode material.
  • WO 97/40541 US Pat. No. 5,910,382 and WO 00/60680 describe the preparation of lithium mixed metal phosphates, wherein physical mixtures of different metal salts or organometallic compounds are generally first prepared, which are then used in a subsequent step with classical methods of solid-state synthesis calcination at high temperatures and, if necessary, atmospheric control. In most cases, the starting compounds are decomposed in such a way that only the desired ions remain to build up the target compound in the reaction system.
  • a disadvantage of these methods is the high energy input required for the implementation, combined with high process costs. Also, the product quality is often unsatisfactory, since no homogeneous distribution of the components is achieved and also the particle morphology is not controllable.
  • X, Y metal, eg Fe, Mn, etc.
  • the resulting products have to be calcined afterwards or additionally in order to ensure the necessary crystallinity.
  • the surface-active adjuvants must be removed quantitatively so as not to cause any negative effects in the subsequent application. This is also achieved by heating, which substances burn or carbonize or soot.
  • the object of the present invention was to provide a process for producing mixed metallic phosphates, which is comparatively energy efficient and simple and with which the phosphates in high purity, in particular with respect to interfering foreign ions, can be produced, so that they compared to the prior art, for example are more suitable as precursor compounds for the preparation of lithiated cathode materials for lithium-ion batteries.
  • M1, M2 and M3 are metals from the group consisting of Mn, Fe, Co and Ni
  • M4 is one or more metals from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu , Zn, Be, Mg, Ca, Sr, Ba, Al, Zr, La, and wherein the process is characterized by a) providing a first aqueous solution (I) containing divalent cations of at least one or more of the metals Contains M1, M2 and M3 and carboxylate anions,
  • At least one further metal M4 in the form of a metal compound selected from the group consisting of hydroxides, oxides, oxide hydroxides, oxide hydrates, carbonates, hydroxide carbonates, carboxylates, sulfates, chlorides and nitrates, the addition being in the form of an aqueous solution b) a second phosphoric acid aqueous solution (II) having a phosphoric acid concentration in the range from 5 to 85% by weight, which optionally contains divalent cations of at least one or more of the metals M1, M2 and M3,
  • divalent cations are introduced into the solution by dissolving at least one oxygen-containing metal compound selected from hydroxides, oxides, oxide hydroxides, hydrated oxides, carbonates and hydroxide carbonates of at least one or more of the metals M1, M2 and M3 in aqueous phosphoric acid, and
  • At least one further metal M4 in the form of a metal compound selected from the group consisting of hydroxides, oxides, oxide hydroxides, oxide hydrates, carbonates, hydroxide carbonates, carboxylates, sulfates, chlorides and nitrates, the addition being in the form of an aqueous solution the metal compound or as a solid, c) the solutions (I) and (II) with the precipitation of the phosphate compound of the type (M1 a M2 b M3 C M4 d ) 3 (P0 4 ) 2 ⁇ xH 2 0 united.
  • a metal compound selected from the group consisting of hydroxides, oxides, oxide hydroxides, oxide hydrates, carbonates, hydroxide carbonates, carboxylates, sulfates, chlorides and nitrates, the addition being in the form of an aqueous solution the metal compound or as a solid, c) the solutions (I) and (II) with the precipitation of the phosphat
  • the process according to the invention gives high-purity mixed-metal phosphates which can be used, in particular, as precursors for the further conversion to lithium metal phosphates for use. are suitable as cathode materials for lithium-ion batteries.
  • the process does not require the use of alkali ions containing basic solutions to raise the pH.
  • the buffer effect of the acids in the solutions (I) and (II) is exploited to increase the pH in the course of combining the solutions (I) and (II) in an optimum range for the precipitation reaction of the phosphate bring and keep there.
  • the metal ions (M 2+ ) dissolved in the carboxylic acid (HX) of solution (I) are then precipitated by combining with the phosphoric acid aqueous solution (II), the mixture of metal salt salt ⁇ M 2+ ; 2 X- ⁇ aq and free acid (HX) forms a buffer system which keeps the pH of the resulting solution substantially constant.
  • the resource-saving and cost-effective method according to the invention makes it possible to produce an alkali-free material of high purity.
  • This process is particularly economical in an embodiment in which an excess of dissolved metal ions is used and a stoichiometric amount of phosphoric acid is used to precipitate the desired phosphate.
  • the remaining or recovered carboxylic acid HX can then be recirculated to dissolve metal and to produce the solution (I) in the process.
  • the recycling of the carboxylic acid HX produces no or only small amounts of by-products or waste products, which makes a particularly economical and resource-saving process possible.
  • the mixed-metal phosphate of the invention (M1 a M2b M3 C M4d) 3 (P0 4) 2 ⁇ xH2O can be further reacted with an appropriate lithium source to a gemischtmetallischem lithium metal phosphate.
  • a carbon source can be introduced into the aqueous solution, which forms a homogeneous carbon layer during the thermal conversion of the material, which provides for improved electrochemical properties of the cathode material.
  • mixed crystalline-amorphous phosphate compound in the context of the present invention means that the phosphate compound is present as a mixture with crystalline and amorphous portions of the phosphate compound.
  • the crystallinity of a compound is usually judged by the X-ray diffractogram, with broad peaks of low intensities indicating lesser or inferior crystallinity than narrow peaks of higher intensities.
  • the width and intensity of the peaks can also be influenced by the morphology of the examined material.
  • a platelet-shaped morphology of the crystalline material with particle sizes in the nanometer range can lead to peak broadening and / or intensity reduction in comparison to other morphologies.
  • those skilled in the art are aware of this.
  • the concentration of phosphoric acid in solution (II) is in the range of 5 to 85% by weight. If the concentrations are too low, the metal ions optionally contained in solution (II) may not be dissolved. If the concentration is too high, the process can be technically complicated due to a high viscosity of the solution and therefore may become uneconomical.
  • the carboxylic acid (HX) in step a) is selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid and acrylic acid, where the carboxylic acid (HX) in step a) is preferably acetic acid.
  • the carboxylic acid (HX) in stage a) is used in the form of an aqueous solution with a concentration of 5 to 50% by weight, preferably 10 to 30% by weight of carboxylic acid.
  • concentration ranges of the aqueous carboxylic acid solution have proven to be advantageous for a rapid and substantially complete dissolution of the divalent metal cations M1, M2 and / or M3. If the concentration of the aqueous carboxylic acid solution is too low, the divalent metal cations may not be dissolved completely and not at an acceptable rate. Too high a concentration of the aqueous carboxylic acid solution may lead to a decrease in the yield and precipitation of impure phases in the final product. The dissolution of the metal cations in the aqueous carboxylic acid solution can bring about technical difficulties at too high a concentration, since the reaction is exothermic and runs faster with higher concentration of the carboxylic acid solution.
  • the solution (I) or (II) presents and added the other solution (II) or (I) to the solution submitted.
  • the presentation of a too small volume may have procedural disadvantages when homogenizing and recording measured variables. It was also found that the dosing rate seems to have an influence on the formation of the phases.
  • a metered addition of one solution to that of the other solution within a period of about 10 to 20 minutes has proved to be advantageous.
  • a carbon source is added to one or both of the solutions (I) and (II) prior to combining in step c), or a mixture is added in combining the solutions (I) and (II) in step c)
  • Carbon source in the form of a separate solution, dispersion or suspension the carbon source being selected from the group consisting of elemental carbon, organic compounds or mixtures thereof, preferably consisting of graphite, expanded graphite, carbon black, carbon black, carbon nanotubes (CNT), Fullerenes, graphene, glassy carbon, carbon fibers, activated carbon, hydrocarbons, alcohols, aldehydes, carboxylic acids, surfactants, oligomers, polymers, carbohydrates or mixtures thereof.
  • the carbon source is expediently added in an amount which comprises from 1 to 10% by weight of carbon, preferably from 1 to 5% by weight of carbon, particularly preferably from 1 to 8% by weight of carbon, based on the product. weight of precipitated phosphate compound.
  • the phosphoric acid aqueous solution (II) is prepared with a phosphoric acid concentration in the range from 5 to 70%, preferably from 10 to 60%, particularly preferably from 15 to 40%. This has advantages in terms of process and product properties, such as yield, solids content, particle size distribution and chemical composition.
  • the method according to the invention separates the c) precipitated phosphate compound of the type (M 1 a M 2 b M 3 C M4d) 3 (P0 4) 2 ⁇ xH2O by filtration, centrifugation or sedimentation from the solution and leads in stage of the Phosphate compound liberated solution (filtrate, centrifugate) in the stage a) of the process.
  • the first aqueous solution (I) prepared in stage a), the second phosphoric acid aqueous solution (II) prepared in stage b) or of both solutions (i) and (II) are separated prior to the combination in step c) undissolved solids.
  • the concentration of the metals M 1, M 2 and M 3 in the first aqueous solution (I) is adjusted so that the solution (I) contains the metal ions prior to step c) in a concentration of 0.2 to 3.5 mol / l, preferably 0.8 to 2.0 mol / l, more preferably 1, 0 to 1, 7 mol / 1, particularly preferably 1, 1 to 1, 3 mol / 1 contains.
  • This has advantages in terms of the morphology and particle size of the product.
  • the phosphate compound has a platelet-shaped morphology with an average thickness of the crystallites of ⁇ 1000 nm, preferably ⁇ 500 nm, more preferably ⁇ 100 nm, most preferably ⁇ 50 nm.
  • the phosphate compound has a content of sodium and potassium of ⁇ 300 ppm, preferably ⁇ 200 ppm, more preferably ⁇ 100 ppm and / or a sulfur content of ⁇ 300 ppm, preferably
  • ⁇ 200 ppm more preferably ⁇ 100 ppm and / or a chlorine content of ⁇ 300 ppm, preferably ⁇ 200 ppm, more preferably ⁇ 100 ppm and / or a nitrate content of
  • ⁇ 300 ppm preferably ⁇ 200 ppm, more preferably ⁇ 100 ppm.
  • the invention further comprises the use of the phosphate compound according to the invention as described herein as a precursor compound for the production of cathode material for Li-ion accumulators.
  • the invention further comprises a process for producing a cathode material for Li ion batteries, in which one reacts a Li compound with a phosphate compound according to the invention.
  • the invention also comprises a process for the preparation of crystalline, amorphous or mixed crystalline-amorphous phosphate compounds of the type NH 4 (M1a M2b M3 C M4d) P0 4 ⁇ xH2O according to claim 15 as well as a product manufactured by the method according to claim 15 product.
  • Advantageous embodiments of the method according to claim 15 and the product produced thereafter result analogously to claims 2 to 10 as well as 12 and 13.
  • Example 2 Preparation of ⁇ ( ⁇ 4) 2'3 ⁇ 2 ⁇ with recycling of the carboxylic acid
  • the filtrate from example 1 was admixed with 37.1 g of elemental Mn in the form of chips and stirred for 2 h.
  • the obtained Mn 2+ acetate solution was mixed with 55.7 g of a 75% phosphoric acid. Again, a light pink precipitate formed, which was subsequently separated from the solution by suction suction. The precipitate was washed and dried under air atmosphere for 12 h at 120 ° C. The yield was 72.9 g of a dry pink product.
  • the product was identified as Mn 3 (PO 4) 2-3H 2 O.
  • Example 1 Although less elemental Mn was added in this example than in Example 1, the yield was the same as in Example 1. The reason for this is an excess of Mn 2+ ions in the precipitation in Example 1, so that in the solution (the Filtrate) after separation of the precipitated product nor Mn 2+ ions were included. Therefore, when the filtrate was recycled, a smaller amount of Mn had to be used to obtain the same Mn concentration in the Mn 2+ acetate solution. After the subsequent precipitation with phosphoric acid, Mn remained in the solution again, which explains that the same yield as in Example 1 was achieved.
  • the precipitate was washed and dried under air atmosphere for 12 h at 120 ° C.
  • the yield was 151.2 g of a dry pink product.
  • the ratio of Fe: Mn in the sample determined by XRF analysis was 0.3.
  • the product was identified by electron microscopic ( Figure 2a) and X-ray ( Figure 2b) studies as (Feo.25Mno.75) 3 (P04) 2-3H20.
  • the filtrate from Example 3 was made up to 1200 g with 12.5% acetic acid and mixed with 50 g Mn chips and stirred for 2 h.
  • a phosphoric acid Fe 2+ solution having an iron content of 6.2% and a phosphoric acid concentration of 30% was prepared from 13 g of Fe 2 O 3 and 8 g of Fe.
  • the phosphoric acid Fe solution was heated to 80 ° C and the Mn-acetate solution added slowly. After complete addition, the reaction solution was boiled for 10 minutes. Again, a yellowish-green precipitate formed, which was then separated from the solution by means of a suction filter. The precipitate was washed and dried under air atmosphere for 12 h at 120 ° C. The yield was 148.0 g of a dry pink product. Analogously to Example 3, the product was identified as (Feo.25Mno.75) 3 (PO 4) 2-3H 2 O.
  • Example 3 The product of Example 3 was mixed with L12CO3, NH4H2PO4 and sucrose in the ratio 2: 3: 2: 1. The mixture was then annealed at 700 ° C for 12 hours under forming gas. A black powder was obtained which could be identified as LiFeo.25Mno.75P04 by electron microscopy (Figure 3a) and X-ray analysis ( Figure 3b). This was treated with polyvinylidene fluoride (PVDF), carbon black and N-methyl-2-pyrrolidone (NMP) to a dispersion and then applied to aluminum foil. The resulting electrodes were used as a cathode in combination with a lithium electrode as an anode in button cells and electrochemically examined (Figure 3c, Figure 3d).
  • PVDF polyvinylidene fluoride
  • NMP N-methyl-2-pyrrolidone
  • phosphoric acid Fe solution was mixed with Mn acetate solution. This resulted in a yellowish-green precipitate, which was filtered off.
  • the solid was washed and then 8.69 g of the solid was suspended in 10.3 g of 20% phosphoric acid. To the suspension an aqueous, saturated LiOH solution was added, which had been prepared from 2.65 g LiOH * H20. This formed a white precipitate.
  • the solid components were separated by a suction filter, washed and dried at 120 ° C for 12 h under air atmosphere.
  • Example 6 The product obtained in Example 6 was annealed at 700 ° C for 12 hours under forming gas. A black powder was obtained which could be identified as LiFeo.25Mno.75P04 by electron microscopy ( Figure 4a) and X-ray analysis ( Figure 4b).
  • Example 2 Analogously to Example 1, a 15% acetic acid was mixed with Mn chips and stirred until a clear solution had formed. To remove suspended matter, the solution was filtered. Out Ammonia and phosphoric acid, an ammonium phosphate solution was prepared. Subsequently, the ammonium phosphate solution was mixed with the Mn solution and heated to 80 ° C. It formed a yellowish green precipitate, which was then sucked off and washed well. Subsequently, the precipitate was dried at 120 ° C for at least 12 h under air atmosphere. The product was identified as NhUMnPC HfeO by electron microscopic (FIG. 5a) and X-ray diffraction (FIG. 5b) examinations.
  • FIG. 1 a Scanning electron micrograph (SEM) of the product from Example 1;
  • FIG. 1 b Powder X-ray diffraction diagram of the product from Example 1;
  • FIG. 2 a Scanning electron micrograph (SEM) of the product from Example 3;
  • FIG. 2 b powder X-ray diffraction diagram of the product from example 3;
  • FIG. 3 a Scanning electron micrograph (SEM) of the product from example 5;
  • FIG. 3 b powder X-ray diffraction diagram of the product from example 5;
  • FIG. 3 c voltammetric measurement of material from Example 5;
  • FIG. 3 d Konstantstromzykltechnik of material from Example 5
  • FIG. 4 a Scanning electron micrograph (SEM) of the product from Example 7;
  • FIG. 4b powder X-ray diffraction diagram of the product from Example 7;
  • FIG. 5 a Scanning electron micrograph (SEM) of the product from Example 8.
  • FIG. 5 b Powder X-ray diffraction diagram of the product from Example 8.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
EP15808375.8A 2014-12-17 2015-12-09 Zur herstellung von kathoden für li-ionen-akkumulatoren geeignete phosphatverbindungen Withdrawn EP3233725A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014118907.8A DE102014118907A1 (de) 2014-12-17 2014-12-17 Zur Herstellung von Kathoden für Li-Ionen-Akkumulatoren geeignete Phosphatverbindungen
PCT/EP2015/079060 WO2016096555A2 (de) 2014-12-17 2015-12-09 Zur herstellung von kathoden für li-ionen-akkumulatoren geeignete phosphatverbindungen

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EP3233725A2 true EP3233725A2 (de) 2017-10-25

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WO2016096555A2 (de) 2016-06-23
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TW201638000A (zh) 2016-11-01
US20180346334A1 (en) 2018-12-06
WO2016096555A3 (de) 2016-10-27

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