WO2014161742A1 - Phosphate de fer(iii) amorphisé - Google Patents

Phosphate de fer(iii) amorphisé Download PDF

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WO2014161742A1
WO2014161742A1 PCT/EP2014/055866 EP2014055866W WO2014161742A1 WO 2014161742 A1 WO2014161742 A1 WO 2014161742A1 EP 2014055866 W EP2014055866 W EP 2014055866W WO 2014161742 A1 WO2014161742 A1 WO 2014161742A1
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Prior art keywords
iron
iii
phosphate
orthophosphate
carbon composite
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PCT/EP2014/055866
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German (de)
English (en)
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Gunnar BÜHLER
Kilian Schwarz
Christian Graf
Michael RAPPHAHN
Manola Stay
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Chemische Fabrik Budenheim Kg
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Publication of WO2014161742A1 publication Critical patent/WO2014161742A1/fr

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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
    • C01B25/37—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
    • C01B25/45—Phosphates containing plural metal, or 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
    • H01M4/362—Composites
    • 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
    • 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
    • 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 invention relates to a novel structurally amorphous or amorphized iron (III) phosphate anhydrate and a carbon composite thereof and to a process for the preparation thereof.
  • the structurally amorphous or amorphized iron phosphate anhydrate is suitable for direct use as a cathode material for lithium-ion accumulators as well as a precursor for the production of chemically or thermally lithiated iron phosphate or carbon composite thereof.
  • the invention further relates to a lithiated iron phosphate and a carbon composite thereof and to a process for its preparation from the amorphous or amorphized iron (III) phosphate anhydrate or its carbon composite.
  • the product is suitable, among other things, as a cathode material for lithium ion accumulators.
  • Li-ion batteries are widespread energy storage devices, especially in the field of mobile electronics, since the Li-ion battery is characterized by a high energy density and can deliver a high nominal voltage, so that the lithium-ion battery with comparable performance significantly smaller and lighter than conventional accumulators.
  • cathode materials spinels such as UC0O2, LiNiCk, üNii- x Co x 02 and LiMn n 04 have been established.
  • LiFePC has been developed as a cathode material. This material is characterized by good performance, high specific capacity and high thermal stability during operation.
  • Iron orthophosphate is a starting material for the production of LiFePC cathode material for lithium ion accumulators.
  • Li iron phosphate has a poor electrical conductivity, which is why it is only partially usable in its pure form as a cathode material.
  • the products are also referred to as carbon composite of FOP and LFP and are herein abbreviated to FOP / C and LFP / C, respectively.
  • US 2009/0311597 describes the doping of LFP with different transition metals or transition metal compounds to produce cathode materials with acceptable electrical conductivities.
  • the dopants can be distributed homogeneously in the material in the sense of a mixed crystal or be present as a separate crystalline phase in addition to LFP.
  • the doping with transition metals or with lanthanide metals causes high costs for these dopants per se and also requires very complicated and costly process to achieve a Leitfä ⁇ ability increasing distribution and doping.
  • the method according to US 2009/031 1597 requires very high calcination temperatures of 800 ° C and long calcination times of up to 96 hours, which represents a major disadvantage economically.
  • the amorphous iron (III) orthophosphate dihydrate is prepared according to Wang et al. Although produced from inexpensive FeS04 x 7 H2Ü, this method requires a pH control, which can only be achieved by the addition of alkalis. The product therefore inevitably contains contaminations of alkali and / or alkaline earth metal cations and sulfate ions. Wang et al. describe, therefore, that the amorphous iron (III) orthophosphate dihydrate thus prepared must be washed several times in order to sufficiently remove these contaminations of sulfate ions and alkali and / or alkaline earth metal cations. That by Wang et al.
  • amorphous iron (III) orthophosphate dihydrate has particle sizes of 1 00 to 200 nm.
  • the high particle surface therefore offers a large adsorption surface for contaminating anions and cations, with the result that the washing processes have only a low efficiency.
  • further dopants in the form of their nitrate salts can be added, which in turn introduces further contamination with nitrate ions into the material.
  • the investigated iron phosphate materials were either commercially available or were prepared by precipitation from equimolar aqueous solutions of 0.025 mol / liter Fe (NH 4 ) 2 (SO 4 ) 2 x 6H 2 O and 0.025 mol / liter of NH 4 H 2 P0 4 , and hydrogen peroxide as the oxidant produced.
  • the products were subjected to thermal processes to adjust the desired water of hydration.
  • Iron (III) orthophosphates in different hydrate stages can also be used directly as cathode materials in electrochemical cells without prior lithiation.
  • the above works by Masquellier et al. and Hong et al. start from commercially available amorphous iron (III) phosphates in various hydrate stages.
  • the data on the nominal water of hydration differed from the values experimentally determined by the authors. In one case, instead of the nominal hydrate water content FeP0 4 x 4 H2O, a water of hydration of 3.6 H 2 0 was determined, and in the other case, instead of FeP0 4 x 2 H 2 0, a hydration water content of 1.6 H 2 0 was determined. Prosini et al.
  • the object of the invention was therefore to provide a comparison with the prior art improved and easy and inexpensive accessible iron phosphate, which is by electrochemical or chemical Lithi réelle in a cathode material for lithium ion batteries or by thermal treatment at low temperatures and convert short calcination times into a lithium iron phosphate with improved properties over the prior art.
  • the invention encompasses a process for the preparation of an amorphous or amorphized iron (III) phosphate anhydrate or a carbon composite of amorphous or amorphized iron (III) phosphate anhydrate, which comprises iron (III) orthophosphate general formula FePÜ4 x 2 H2O or carbon composite of iron (III) orthophosphate of the general formula FePC x 2 H 2 O, wherein at least 80 wt .-% of iron (III) orthophosphats according to powder X-ray diffraction analysis with CuKa radiation in the phosphosiderite (Metastrengit II) crystal structure, at a temperature in the range of 140 to 250 to a residual water content of 0 to 1 wt .-%, which comprises both bound water of crystallization and free water, and up to a water of crystallinity ⁇ 0.2 H. 2 0 dehydrated.
  • At least 90% by weight, more preferably at least 95% by weight, very preferably at least 99% by weight, of the iron (III) orthophosphate are preferably present before the dehydration according to powder X-ray diffraction analysis with CuKa radiation in the phosphosiderite (US Pat. Metastrengite II) crystal structure.
  • the invention further comprises amorphous or amorphized iron (III) phosphate anhydrate or carbon composite of amorphous or amorphized iron (III) phosphate anhydrate, prepared or preparable by the method of the invention described herein.
  • the amorphous or amorphized iron (III) phosphate anhydrate or the carbon composite of amorphous or amorphized iron (III) phosphate anhydrate in the powder X-ray diffraction pattern has peaks at 15.9 ⁇ 0.5, 20.0 ⁇ 0.5, 20.95 ⁇ 0.5, 22.4 ⁇ 0.5, and 28.85 ⁇ 0.5 degrees two-theta based on CuKa radiation.
  • residual water content in the range from 0 to 1% by weight wherein the term residual water content comprises both bound water of crystallization and adsorbed water. Residual water contents of not more than 0.5% by weight are particularly advantageous.
  • the water of crystallization bound in phosphosiderite which is a dihydrate, is essentially completely removed. In this simple dehydration, the phosphosiderite completely or almost completely loses its original crystalline character to give an amorphous or amorphized iron (III) phosphate.
  • amorphized iron (III) phosphate anhydrate in the context of the present invention, denotes an iron (III) phosphate anhydrate which, in powder X-ray diffraction analysis, no longer shows the sharp peaks characteristic of a predominantly crystalline material, but at most relative low and sharply broadened peaks that show the skilled person that the material is predominantly amorphous.
  • An example of such a powder X-ray diffraction pattern of an amorphized iron (III) orthophosphate anhydrate according to the invention is shown in FIG. 3 and an amorphized iron (III) orthophosphate anhydrate carbon composite according to the invention in FIG.
  • a completely amorphous material shows no peaks in the powder X-ray diffraction pattern, as can be observed for the product according to the invention after chemical lithiation (see FIG. 10, diffractogram 3, with the exception of the reflex caused by graphite).
  • the crystalline starting material phosphosiderite exhibits characteristic reflections in the powder X-ray diffraction pattern with peaks at 13.68 ⁇ 0.05, 1.818 ⁇ 0.05, 24.75 ⁇ 0.05, 32.25 ⁇ 0.05, 32.35 ⁇ 0.05, 34.94 ⁇ 0.05, 35.22 ⁇ 0.05, 42.80 ⁇ 0.05, and 45.16 ⁇ 0.05 degrees two-theta, based on CuKa radiation.
  • These reflections characteristic of phosphosiderite can not be identified in the powder diffractogram of the amorphous iron (III) phosphate anhydrate according to the invention.
  • the iron (III) orthophosphate with phosphosiderite (Metastrengite II) crystal structure used according to the invention which can be produced by the processes of DE 10 2007 049 757, DE 10 2009 001 204 and DE 10 201 1 003 125, thus differs from the prior art by Reale et al. investigated material significantly in terms of its thermal dehydration behavior and phase formation.
  • the morphology of the primary particles of the phosphosiderite used according to the invention does not change during dehydration (see FIG. 7).
  • An essential advantage of the amorphous or amorphized iron (III) phosphate anhydrate or its carbon composite according to the invention is that it can be characterized unambiguously and completely with regard to its stoichiometry via the precursor of the crystalline phosphosiderite. This is not the case with the amorphous FePC hydrates described in the literature, since compounds which have not been defined at any time can be characterized here. There may be stoichiometric deviation, such. As described in the literature deviating water of crystallinity, which have a negative effect on the performance of the cathode material after further processing and in later use as a cathode material, due to the formation of unwanted secondary phases.
  • a further advantage of the invention is that the amorphous or amorphized iron (III) phosphate anhydrate or its carbon composite and its starting compound according to the invention can be produced industrially and inexpensively and ecologically.
  • Another advantage of the invention is that the carbon composite of the amorphous or amorphized iron (III) phosphate anhydrate of the present invention retains its electrical conductivity at relatively low carbon levels. Subsequent coating of the amorphized material with carbon is not required.
  • the amorphized iron (III) phosphate anhydrate or its carbon composite according to the invention can also be prepared without difficulty during production by the choice of a high molecular weight. and can be introduced directly into the process described here for the production of LFP or LFP / C. So far, only carbon composites have been known in crystalline form.
  • a further advantage of the amorphous or amorphized iron (III) phosphate anhydrate according to the invention is that the material can be lithiated chemically and electrochemically.
  • the known crystalline material can only be lithiated thermally, which requires high temperatures and is associated with the known disadvantages, such as undesired crystal growth and sintering of the primary particles.
  • amorphous or amorphized iron (III) phosphate anhydrate according to the invention can be used directly in half-cells as the cathode material against a lithium anode or using a lithium-containing electrolyte with electrochemical lithiation. Initially no extraordinary activity of the mate- neck was found, but the material could easily be electrochemically lithiated and delithiated.
  • the amorphous or amorphized iron (III) phosphate anhydrate according to the invention showed a specific capacity increasing with increasing number of cycles.
  • amorphous or amorphized iron (III) phosphate anhydrate of the present invention over crystalline material in lithiation are believed to be due to structural differences in the materials.
  • iron (III) is converted to iron (II), and lithium ions are deposited in cavities of the structure to charge balance.
  • the amorphous or amorphized material according to the invention is metastable and presumably already has the required cavities in which the lithium ions can deposit relatively easily. In the case of crystalline material, these required cavities are initially absent or occupied by water of crystallization. Only at high temperatures, a thermal restructuring takes place, through which the cavities required for the storage of lithium ions are created.
  • novel amorphous or amorphized iron (III) phosphate anhydrate according to the invention can be lithiated directly electrochemically or chemically, which is not possible with a corresponding crystalline material according to the prior art.
  • the crystalline material can only be lithiated lithically.
  • a residual water content includes both bound water of crystallization and free water or free moisture or residual moisture.
  • the crystal water content refers only to the bound water of crystallization.
  • the residual water content is determined according to the invention by determining the loss on ignition of the material by heating to 800 ° C. for 10 minutes. The weight difference before and after this thermal treatment refers to the loss on ignition and thus the residual water content in the context of this invention.
  • the novel amorphous or amorphized iron (III) phosphate anhydrate according to the invention can be used directly as cathode material for lithium-ion accumulators.
  • the material can also be lithiated chemically and then used directly as a cathode material or, after conversion by calcination into a crystalline material, used as the cathode material.
  • the invention therefore further comprises a process for the preparation of a chemically lithiated iron orthophosphate or iron orthophosphate-carbon composite in which
  • At least 90% by weight, more preferably at least 95% by weight, most preferably at least 99% by weight, of the egg is present before dehydration.
  • a fine aqueous dispersion can be prepared on account of its special properties, simple stirring of the solid in water as matrix without addition of auxiliaries being completely sufficient.
  • various technologies such as the use of a wet mill, an ultraturrax, ultrasound and the like as well as the addition of surface-active substances, can positively influence the speed and quality of the dispersion formation.
  • surface-active substances it should be noted that no ionic contaminants are introduced, which later have a negative effect in a battery application.
  • the solids concentration of the dispersion is preferably in the range of 40 to 60 wt .-%.
  • step c) of the process according to the invention iron (III) is reduced to iron (II) using one or more reductones.
  • reductones are acidic. They have a strong reducing effect.
  • one electron equivalent of reductone refers to the amount of reductone required to reduce one mole of iron (III).
  • one equivalent of electron equivalent to one mole of iron (III) is equivalent to half a mole of reductone.
  • the color of the mixture immediately changes from white-yellowish to black in the case of the iron (III) phosphate anhydrate and from gray to black in the case of the carbon composite of iron ( lll) phosphate anhydrate.
  • the oxidation of the organic reducing agent takes place instead of intermediates in its oxidative degradation process.
  • the previously dispersed amorphous iron (III) phosphate anhydrate according to the invention is again divided into smaller units on the basis of primary particles during the reduction, as evidenced inter alia by the fact that the solid fraction obtained can neither be separated nor sedimented by customary filtration methods or by ultracentrifugation.
  • the entire mixture is dried by removing the water at elevated temperature and / or under reduced pressure.
  • a permanent mixing during the drying process is advantageous in order to produce no concentration gradients of any dissolved ingredients of the mixture and to ensure the highest possible homogeneity of the dried mixture.
  • Figures 8 and 9 show the present invention lithiated amorphous Fe (III) P04-anhydrate carbon composite after dispersion in water and addition of LiOH, acetic acid and ascorbic acid, and after drying at 1 10 ° C ( Figure 8) and at 200 ⁇ ( Figure 9 ).
  • the drying of the mixture can optionally be carried out under normal atmosphere and / or under protective atmosphere and / or under reduced pressure. In general, this is a thorough mixing of the mixture, for.
  • the drum dryer during the drying preferred to counteract demixing processes due to the solubility of some components in the aqueous phase. This ensures a homogeneous distribution of all components present in this mixture.
  • the formation of secondary phases due to concentration gradients with non-homogeneous distribution of the components during optional subsequent calcination can thus be completely suppressed.
  • the X-ray diffraction pattern of a calcined LFP / C produced according to the invention shows exclusively the reflections of LFP and an additional carbon reflex, which does not occur in LFP.
  • this is preferably a circulating air drying, it comes at higher temperatures from about 100 ° C, preferably 100 to 200 ° C product temperature, for the partial surface oxidation of previously reduced by the reductone iron (II).
  • the proportion of organic constituents introduced by the reductone can thereby be removed, since the oxidative degradation products and intermediates of the reductone are volatile at these temperatures. If this process is carried out under reduced pressure or reduced pressure at atmospheric pressure, oxidation can be prevented as far as possible. and the organic components can also be removed at lower temperatures.
  • This process is preferably used to produce low carbon LFP / C in the range of about 2 to 4 wt%.
  • the dried lithiated iron (III) phosphate anhydrate according to the invention or the carbon composite thereof is calcined at a temperature in the range of 400 to 800 ° C for a period of 1 to 24 hours.
  • the calcination of the dried product is carried out at a temperature in the range of 450 to 700, preferably 500 to 650 and / or for a period of 1 to 12 hours, preferably 2 to 6 hours.
  • Too high a calcination temperature has the disadvantage that crystal growth and sintering occur to a greater extent.
  • a too low calcining temperature has the disadvantage that non-crystalline areas may remain in the product and / or organic components may possibly remain in the product to a greater extent.
  • Organic constituents can have an electrically insulating effect.
  • an oxygen partial pressure can be set during the calcination.
  • the oxygen partial pressure can be adjusted so that a partial oxidation of Fe 2+ to Fe 3+ is compensated by the organic content present in the mixture.
  • organic additives in the form of z As hydrocarbons, carbohydrates, polymers or the like or graphite or other carbon modifications ensure efficient reduction of Fe 3+ to Fe 2+ in a calcination.
  • Calcination temperatures and residence times can be chosen to induce the formation of a pure LFP phase.
  • the experiments have shown that even at temperatures ⁇ 550 ° C pure LFP phases (see Figure 14) can be obtained.
  • calcining is only possible under a nitrogen atmosphere, ie no forming gas has to be used in order to prevent oxidation and the formation of secondary phases (see FIG. 13).
  • the X-ray diffraction pattern clearly shows reflections with high half-widths, which suggests small particles.
  • the calcination reflexes at 700 are much sharper (see Figure 15).
  • the resulting LFP or its carbon composite LFP / C may have a specific surface area of> 80 m 2 / g.
  • an LFP sample calcined at not more than 550 ° C has good performance at fast discharge rates. More than 50% of the energy that can be stored under C / 10 can be taken out at a discharge rate of 20C (discharge within 3 minutes).
  • a charging current of 1 C means that a cell whose capacity z. B. with 2 Ah, is charged with a charging current of 2 A for 1 hour and then contains the amount of energy 2 Ah.
  • Charging with C / 10 means that the cell was charged with a tenth of the charge current corresponding to its capacity, which, however, takes 10 times as long; H. 10 hours. This convention is commonly used to compare cells without taking into account real capacities.
  • Charging with C / 10 is common in stress tests, as this causes a particularly gentle and complete charge.
  • a discharge rate of 20C means that the discharge is for 1 / 20th-hour, ie. H. in 3 minutes.
  • the pH of the aqueous dispersion of dehydrated iron (III) phosphate or dehydrated th carbon composite of iron (III) phosphate before the addition of the lithium salt and before the addition of the reductone to a value ⁇ 7.0, preferably s 6.5, more preferably ⁇ 6.0 is set and / or buffered, wherein for adjusting and / or buffering the pH preferably organic carboxylic acids and / or their anhydrides and / or their lithium salts, particularly preferably formic acid, acetic acid, propionic acid, n-butanoic acid, pentanoic acid and / or their anhydrides and / or their lithium salts are used.
  • the lithium salt is used in an amount of 0.9 to 1, 1, more preferably in an amount of 1, 0 to 1, 05 molar equivalents in the aqueous dispersion and / or the reductone in an amount from 1, 0 to 1, 05 electron equivalents of the aqueous dispersion used.
  • lithium salt is used in too high an amount, unwanted lithium-rich secondary phases may possibly form in a later calcination reaction. If the lithium salt is used in too low an amount, unwanted lithium-poor secondary phases may possibly form in a later calcination reaction.
  • reductone is used in excess, there is a risk that an excess of reductone will adversely affect the further course of the reactions. Moreover, this is an unnecessary cost aspect. If the reductone is used in an excessively low amount, there is a risk that the reduction of the Fe 3+ does not proceed completely and thus no stoichiometric amount of lithium ions is stored.
  • the lithium salt in the aqueous dispersion is selected from the group consisting of lithium hydroxide (LiOH), lithium carbonate (Li 2 C0 3 ), lithium acetate, lithium formate and mixtures thereof.
  • the use of these lithium salts has the advantage that the lithium salt does not introduce interfering anion contaminants into the final product, for example sulfate ions or nitrate ions.
  • Organic anions, such as acetate, are oxidized and / or expelled during later calcining.
  • the reductone is selected from the group consisting of tartronaldehyde (hydroxypropanedial), ascorbic acid, reductic acid (2,3-dihydroxy-2-cyclopentenone), acetylformoin and mixtures of the abovementioned ones the reductone is preferably ascorbic acid.
  • the drying of the reaction product in stage d) takes place with mixing. Permanent mixing during the drying process prevents the formation of concentration gradients in any dissolved substances and ensures a high homogeneity of the dried product.
  • the dehydrated iron (III) phosphate obtained in step a) or the dehydrated carbon composite of iron (III) phosphate in the powder X-ray diffraction pattern has peaks at 15.9 ⁇ 0.5, 20.0 ⁇ 0 , 5, 20.95 ⁇ 0.5, 22.4 ⁇ 0.5 and 28.85 ⁇ 0.5 degrees two-theta based on CuKa radiation.
  • This amorphized product has the advantages described herein.
  • iron (III) orthophosphate used here or the carbon composite of iron (III) orthophosphate with phosphosiderite (Metastrengite II) crystal structure a product prepared or preparable according to DE102007049757, DE 102009001204 or DE 10201 1003125.
  • the contents of DE102007049757, DE102009001204 and DE 10201 1003125 are intended to be encompassed by the disclosure of the disclosure of the present specification.
  • the production of iron (III) orthophosphate with phosphosiderite (Metastrengit II) crystal structure according to DE102007049757 comprises the following measures:
  • solid iron (III) orthophosphate separates from the reaction mixture.
  • the reaction of the iron compounds with phosphoric acid at a temperature in the range of 50 ° C to 180 ⁇ , preferably in the range of Q0 ° C to 1 5 nq C, more preferably carried out in the range of 70 ° C to 120 ° C.
  • reaction of the iron compounds with phosphoric acid is carried out with thorough mixing.
  • reaction of the iron compounds with phosphoric acid is carried out at a concentration in the range of 8% to 23%.
  • the iron (III) orthophosphate is dried after separation from the reaction mixture at elevated temperature and / or under reduced pressure.
  • the iron (III) orthophosphate at least in one dimension has a mean primary particle size ⁇ 1 ⁇ , preferably ⁇ 500 nm, more preferably ⁇ 100 nm.
  • the iron (III) orthophosphate has a bulk density> 600 g / l, preferably> 800 g / l, more preferably> 1000 g / l.
  • the iron (III) orthophosphate has a content of sodium and potassium of ⁇ 300 ppm each. 12. Further preferably, the iron (III) orthophosphate has a sulfur content ⁇ 300 ppm.
  • the iron (III) orthophosphate has a nitrate content ⁇ 100 ppm.
  • oxidic iron (II), iron (III) or mixed iron (II, III) compounds selected from hydroxides, oxides, oxide hydroxides, hydrated oxides, carbonates and Hydroxide carbonates together with elemental iron
  • an oxidizing agent is added to the phosphoric acid aqueous Fe 2+ solution in order to oxidize iron (II) in the solution, and iron (III) orthophosphate of the general formula FePO 4 .xNH 2 O precipitates.
  • Precipitation reagents are preferably added to the aqueous solution of phosphoric acid in order to precipitate solids out of the solution and to separate them from the aqueous phosphoric acid Fe 2+ solution, and / or to precipitate electrolytes dissolved in the phosphoric acid aqueous solution from the solution.
  • the reaction of the oxidic iron compounds is carried out together with elemental iron in aqueous medium containing phosphoric acid (stage a) at a temperature in the range of 15 ° to 90 ° C., preferably in the range of 20 ° C. to 75 ° C. more preferably in the range of 25 ° C to Q5 ° C, and / or with intensive mixing by.
  • the reaction of the oxidic iron compounds together with elemental iron in aqueous medium containing phosphoric acid for a period of 1 min to 120 min, preferably from 5 min to 60 min, more preferably from 20 min to 40 min by. 5.
  • the concentration of phosphoric acid in the aqueous medium is 5% to 85%, preferably 10% to 40%, particularly preferably 15% to 30%, based on the weight of the aqueous solution.
  • the oxidizing agent which is added to oxidize iron (II) in the solution an aqueous solution of hydrogen peroxide (H 2 0 2 ), preferably at a concentration of 15 to 50 wt .-%, particularly preferred From 30 to 40% by weight.
  • the oxidizing agent which is added to oxidize iron (II) in the solution is a gaseous medium selected from air, pure oxygen or ozone, which is injected into the aqueous solution.
  • the iron (III) orthophosphate is separated off after precipitation from the aqueous solution and it is preferably dried after separation at elevated temperature and / or under reduced pressure.
  • the iron (III) orthophosphate has an average primary particle size ⁇ 1 ⁇ m, preferably ⁇ 500 nm, particularly preferably ⁇ 300 nm, very particularly preferably ⁇ 100 nm, at least in one dimension.
  • the iron (III) orthophosphate has a bulk density> 400 g / l, preferably> 700 g / l, more preferably> 1000 g / l and / or a tamped density> 600 g / l, preferably> 750 g / l , particularly preferably> 1 100 g / l. 1 1.
  • the iron (III) orthophosphate 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 nitrate content of ⁇ 300 ppm, preferably ⁇ 200 ppm, more preferably ⁇ 100 ppm and / or a content of metals and transition metals, except iron, each ⁇ 300 ppm, preferably ⁇ 200 ppm, more preferably ⁇ 100 ppm.
  • the production of carbon composite of iron (III) orthophosphate with phosphosiderite (Meta-stritium II) crystal structure comprises the following measures: 1. Producing an iron (III) orthophosphate-carbon composite which iron (III) orthophosphate contains 2 0 (n ⁇ 2.5) of the general formula FePÜ4 x nH, wherein a carbon source in a phosphoric acid aqueous Fe one 2+ - ion-containing solution dispersed and with the addition of an oxidizing agent to the dispersion iron (III) orthophosphate-carbon composite (FOP / C) precipitates from the aqueous solution and separated.
  • the aqueous solution containing Fe 2+ ions is preferably prepared by reacting oxidic iron (II), iron (III) or mixed iron (III, III) compounds selected from hydroxides, oxides, oxide hydroxides, Oxide hydrates, carbonates and hydroxide carbonates, together with elemental iron in an aqueous medium containing phosphoric acid and brings Fe 2+ - ions in solution and Fe 3+ with elemental Fe (in a Komproportionierungsrepress) to Fe 2+ and then reacts with the phosphoric acid aqueous Separate Fe 2+ solution.
  • oxidic iron (II), iron (III) or mixed iron (III, III) compounds selected from hydroxides, oxides, oxide hydroxides, Oxide hydrates, carbonates and hydroxide carbonates
  • the carbon source comprises elemental carbon or consists solely of elemental carbon, wherein the elemental carbon is preferably selected from graphite, expanded graphite, carbon blacks or carbon blacks, carbon nanotubes (CNTs), fullerenes, graphene, glassy carbon (glassy carbon ), Carbon fibers, activated carbon or mixtures thereof.
  • elemental carbon is preferably selected from graphite, expanded graphite, carbon blacks or carbon blacks, carbon nanotubes (CNTs), fullerenes, graphene, glassy carbon (glassy carbon ), Carbon fibers, activated carbon or mixtures thereof.
  • the carbon source in addition to elemental carbon organic compounds, wherein the organic compounds are preferably selected from hydrocarbons, alcohols, aldehydes, carboxylic acids, surfactants, oligomers, polymers, carbohydrates or mixtures thereof.
  • the dispersion of the carbon source in the phosphate-containing aqueous Fe + ions-containing solution containing the carbon source in an amount of 1 to 10 wt .-% carbon, preferably 1, 5 to 5 wt .-% carbon, more preferably 1, 8 to 4% by weight of carbon, based on the weight of precipitated FOP.
  • the oxidizing agent which is added to the dispersion, an aqueous solution of hydrogen peroxide (H 2 0 2 ), preferably with a concentration of 15 to 50
  • the iron (III) orthophosphate-carbon composite is washed after precipitation and separation from the aqueous solution one or more times with water, aqueous and / or organic solvent and then dried at elevated temperature and / or under reduced pressure or as an aqueous dispersion having a solid content of 1 to 90% by weight.
  • the iron (III) orthophosphate-carbon composite preferably has an average primary particle size ⁇ 1 ⁇ m, preferably ⁇ 500 nm, particularly preferably ⁇ 300 nm, very particularly preferably ⁇ 100 nm, at least in one dimension.
  • the iron (III) orthophosphate-carbon composite has a bulk ⁇ density> 400 g / l, preferably> 700 g / l, more preferably> 1000 g / l and / or a tapped density> 600 g / l , preferably> 750 g / l, more preferably> 1 100 g / l.
  • the present invention further comprises a lithiated iron phosphate or a lithiated iron phosphate-carbon composite prepared as described herein.
  • the invention also encompasses the use of the amorphous or amorphized iron (III) phosphate anhydrate or the carbon composite thereof or the lithiated iron phosphate or the carbon composite thereof according to this invention as a cathode material for lithium-ion secondary batteries.
  • FIG. 2 X-ray diffraction pattern of iron (III) orthophosphate dihydrate (Fe)
  • FIG. 3 X-ray diffraction pattern of amorphous iron (III) orthophosphate
  • Anhydrate (FOP) prepared by heating to 200 ° C of the iron II) orthophosphate dihydrate (FePÜ4 x 2 H 2 0) according to Figure 1.
  • Electron micrograph (3730-fold magnification above and 2130-fold magnification below) of agglomerates of iron (III) orthophosphate dihydrate (FeP0 4 x 2 H 2 0) -Kohlenstoffkomposit (FOP / C), prepared according to DE 10 201 1 003 1 25 Phosphosiderite (Metastrengit II) crystal structure with platelet-shaped morphology of the primary particles.
  • Diffractogram 1 iron (III) orthophosphate-carbon composite (FOP / C) with
  • Diffractogram 2 produced by heating the substance in accordance with the diffractogram 1) to 200 q C amorphous Fe (III) P04 anhydrate-carbon composite;
  • Diffractogram 3 according to the invention from the substance according to diffractogram 2) prepared amorphous Fe (III) PO 4 anhydrate
  • Diffractogram 4 according to the invention from the substance according to diffractogram 3) produced Fe (III) P04 anhydrate-carbon composite after further drying at 200 ⁇ ⁇ (according to Figure 9);
  • Diffractogram 5 according to the invention from the substance according to diffractogram 3) prepared lithiated Fe (III) PO 4 anhydrate
  • FIG. 17 X-ray diffraction pattern of lithium iron (III) orthophosphate anhydrate (LFP) prepared according to the comparative example in ethanol, calcined at 55 ° C. under N 2 atmosphere and peak list according to PDF maps 40-1499 and 76-1 762 (below).
  • iron oxide magnetite; FesC
  • FOP iron fluoride orthophosphate
  • the turbidity was removed by filtration and the filtrate with 40 ml H 2 O 2 solution (35 wt .-%) at 85 ° C added. There was a change in color over intense red to light pink, the product precipitated as a fine solid with a light pink color. The yield was 83.5% (60.0 g).
  • Example 8 Preparation of iron fluoride orthophosphate (FOP) according to DE 10 2009 001 204 20 g Fe304, 7 g Fe, 250 g H 2 O and 204 g 75% phosphoric acid were combined at RT. The density of dilute phosphoric acid in the batch was 1.32 g / ml at 20 ° G. There was a slight gas evolution that persisted throughout the reaction period. Within 10 minutes, the temperature rose to 53 ⁇ 0, and the color of the suspension changed to brown. It was immediately cooled to 50 ° C with the help of an ice bath. After a further 40 minutes at 50 ° C, a green solution was present, which had a very low turbidity. Further gas evolution was no longer observed.
  • FOP iron fluoride orthophosphate
  • the turbidity was removed by filtration and the filtrate with 40 ml H 2 0 2 solution (35 wt .-%) at 85 ° C added. There was a change in color over intense red to light pink, the product precipitated as a coarse solid with a light pink color. The yield was 85.8% (61.6 g).
  • Example 11 Preparation of an iron end orthophosphate-carbon composite (FOP / C) with 7.3% graphite according to DE 10 2011 003 125
  • the solids content of the mixture was separated with a Nutsche filter and then resuspended twice in each 1, 5 L of deionized water and filtered. After drying in a circulating air drying oven at 100 ° C., 273 g of a gray solid were obtained.
  • the XRD analysis of the product showed the characteristic reflections for phosphosiderite and graphite.
  • Ketjenblack ® EC-300J (Messrs. Akzo Nobel) were an Fe 2+ solution added in portions within 15 minutes to 5600 g (about 4.5 L).
  • the solution was pumped through a stirred ball mill (LabStar, Fa. Netzsch), equipped with grinding balls of 0.8-1, 0 mm, in recycle mode. After 3 hours, the dispersion was collected in a beaker.
  • amorphous or amorphized iron (III) phosphate anhydrate or its carbon composites was carried out by simply annealing iron (III) orthophosphate (FOP) or iron (III) orthophosphate-carbon composite (FOP / C) having a phosphosiderite structure according to Examples 1 to 14 at 150 ° C to 220 ⁇ for 8 to 20 hours under normal atmosphere, protective atmosphere or under vacuum.
  • Example 16 Preparation of Lithiated Iron Phosphate Supporter (LFP) 45.46 g of LiOH x 1 H 2 O were dissolved in 300 ml of H 2 O and then 100 ml of 96% acetic acid were added. In this solution, 100 g of ascorbic acid were dissolved and then added 156 g of amorphous iron (III) phosphate anhydrate according to Example 14 was added. The resulting dispersion was stirred for 2 hours at 60 ° C and then dried at 60 * 0 in a vacuum oven for 14 hours. Alternatively, the drying can be carried out at 1 10 ° C or at 210 * 0 in the circulating air drying cabinet for 14 hours.
  • Example 17 Calcination of Lithiated Iron (III) Phosphate Anhydrate (LFP)
  • Example 1 6 A prepared according to Example 1 6 lithiated iron (III) phosphate anhydrate or carbon composite thereof was heated in a rotary kiln with quartz reaction tube under nitrogen atmosphere within 1.5 hours to ⁇ ' ⁇ and then for 1 hour at this temperature held. The heater was then turned off and the reaction tube allowed to cool to room temperature.
  • a lithiated iron (III) phosphate anhydrate or carbon composite thereof prepared in Example 1 6 was heated to 700 ° C. in a rotary tube furnace with quartz reaction tube under a nitrogen atmosphere for 1.5 hours and then at that temperature for 1 hour held. The heater was then turned off and the reaction tube allowed to cool to room temperature.
  • a lithiated iron (III) phosphate anhydrate or carbon composite thereof prepared according to Example 16 was heated to 700 ° C over 2 hours under a flow of 5% by volume of hydrogen in a nitrogen atmosphere, followed by 2 hours maintained this temperature. The heater was then turned off and the reaction tube allowed to cool to room temperature.
  • a lithiated iron (III) phosphate anhydrate or carbon composite thereof prepared according to Example 16 was heated to 300 ° C over 2 hours under a flow of 5% by volume of hydrogen in a nitrogen atmosphere, followed by 2 hours held at this temperature, then heated to 600 ° C within 2 hours and then held at this temperature for 1 hour. The heater was then turned off and the reaction tube allowed to cool to room temperature.
  • a lithiated iron (III) phosphate anhydrate or carbon composite thereof prepared according to Example 16 was heated to 350 ° C under vacuum for 1.5 hours and then held at this temperature for 1 hour. No condensation products could be observed in the intermediate cold trap. Subsequently, the vacuum was exchanged for a flow of 5% by volume of hydrogen in a nitrogen atmosphere and the material was heated to 700 ° C. in the course of 1.5 hours and kept at this temperature for 1 additional hour. The heating was then switched off and the reaction tube was allowed to cool to room temperature.

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Abstract

L'invention concerne un procédé pour produire du phosphate de fer(III) anhydre amorphe ou amorphisé ou bien un composite carboné de phosphate de fer(III) anhydre amorphe ou amorphisé, caractérisé en ce qu'on traite de l'orthophosphate de fer(III) de formule générale FePO4 x 2 H2O ou un composite carboné de l'orthophosphate de fer(III) de formule générale FePO4 x 2 H2O, au moins 80 % en poids d'orthophosphate de fer(III) étant présents dans la structure cristalline de la phosphosidérite (métastrengite-II) selon analyse par diffraction X sur poudre par rayonnement CuKa, à une température située dans la plage de 140 à 250°C jusqu'à obtenir une teneur en eau résiduelle de 0 à 1 % en poids, qui comprend aussi bien de l'eau de cristallisation liée que de l'eau libre, et que l'on déshydrate jusqu'à obtenir une teneur en eau de cristallisation < 0,2 de H2O.
PCT/EP2014/055866 2013-04-04 2014-03-24 Phosphate de fer(iii) amorphisé WO2014161742A1 (fr)

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CN110182780A (zh) * 2019-05-13 2019-08-30 江苏亨利锂电新材料有限公司 一种致密化球形磷酸铁锂及其制备方法
CN110182780B (zh) * 2019-05-13 2023-07-14 四川乾元电子材料有限公司 一种致密化球形磷酸铁锂及其制备方法
CN114684801A (zh) * 2022-03-08 2022-07-01 四川大学 一种利用硫铁矿烧渣制备高纯磷酸铁的方法
CN114684801B (zh) * 2022-03-08 2023-09-01 四川大学 一种利用硫铁矿烧渣制备高纯磷酸铁的方法

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