WO2013093014A1 - Mangan enthaltende metallphosphate und verfahren zu deren herstellung - Google Patents
Mangan enthaltende metallphosphate und verfahren zu deren herstellung Download PDFInfo
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- WO2013093014A1 WO2013093014A1 PCT/EP2012/076669 EP2012076669W WO2013093014A1 WO 2013093014 A1 WO2013093014 A1 WO 2013093014A1 EP 2012076669 W EP2012076669 W EP 2012076669W WO 2013093014 A1 WO2013093014 A1 WO 2013093014A1
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- H—ELECTRICITY
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- 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
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- 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
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- C01B25/377—Phosphates of heavy metals of manganese
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- 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
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- C01G45/00—Compounds of manganese
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
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- C01P2004/32—Spheres
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- 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 further relates to a process for the preparation of the phosphate and its use.
- the cathode materials are lithium metal oxides such as LiCo0 2 , LiNi0 2 , LiNi
- lithium-containing phosphines with olivine structure such as LiFePO 4 (LFP)
- LFP lithium-containing phosphines with olivine structure
- cathode materials These materials are characterized by good performance, high specific capacity and very high stability.
- LFP containing lithium phosphates which are discussed as commercially useful cathode materials, such as LiMnP0 4, LiCoP0 4 or LiNiP0.
- LiFe x Mn y P0 4 and LiFe x Mn y M z PO 4 (LFMP), where M is a metal cation such as Mg, are discussed as suitable compounds for the replacement of pure LiFePO 4 (LFP) in cathode materials. Due to the higher working voltage of manganese or nickel or cobalt-containing compounds compared to iron-containing olivines, a higher energy storage density can be achieved.
- 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.
- thermal processes such as calcining
- a sufficiently high energy must generally be introduced into the reaction system in order to ensure efficient ion diffusion.
- an intensive mixing of all raw materials used upstream to reduce the energy and time required dry or wet mechanical processes, eg ball mills, are particularly suitable for mixing the raw materials.
- only mechanical mixtures of particles or crystals of different metal salts are obtained in this way. During the subsequent calcination, it must therefore be ensured that the ions required to build up the desired crystal phase diffuse beyond the primary grain boundaries.
- X, Y metal, eg Fe, Mn, etc.
- the introduction of certain metals in the form of their sulfates in equimolar amount to the phosphate usually requires that the product be subjected to an intensive washing process in order to reduce the sulfate content to a tolerable level.
- Sulphate is known to be an undesirable contaminant in lithium-ion batteries due to the corrosive action.
- the products obtained 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, whereby these substances burn or char / soot.
- the object of the present invention was to provide novel monometallic or mixed-metallic phosphates which are suitable, for example, for the production of cathode materials for lithium-ion batteries, in particular those with which cathode materials with high energy storage densities can be produced, and to provide a method for their production which is comparatively energy-efficient and is easy and with which the phosphates are produced in high purity, so that they are better than the prior art, for example, as precursor compounds (precursors) for the production of lithiated cathode materials for lithium ion batteries better.
- precursor compounds precursor compounds
- the manganese (Mn) -containing phosphate of the present invention has a novel structural type characterized by its peak positions in the powder X-ray diffraction pattern.
- the new structure type is also referred to herein as "Mn 3 (P0 4 ) 2 ⁇ 3 H 2 O-structure type".
- This type of structure is unknown in the literature. It can be-called with the above both as mono-metal phosphate of the type Mn 3 (P0 4) 2 ⁇ 3 H 2 0, as well as mixed metal phosphate of the type (Mn x Met y) 3 (P0 4) 2 ⁇ 3 H 2 0 obtained characteristic peak positions in the powder X-ray diffraction diagram.
- the individual peaks, depending on the composition of the metal components, may be subject to slight shifts within an angular range indicated by " ⁇ " given in degrees two-theta.
- the novel structure-type manganese (Mn) -containing phosphate of the present invention preferably has an orthorhombic unit cell with lattice parameters of 13, 2 ⁇ 0.2, 8.6 ⁇ 0.2 and 8.1 ⁇ 0.2 angstrom.
- the manganese (Mn) -containing phosphate is present as carbon composite and contains 1 to 10 wt .-% carbon, preferably 1.5 to 5 wt .-% carbon, more preferably 1.8 to 4 wt. % Carbon, based on the total weight of phosphate and carbon.
- Such phosphate-carbon composites are obtained by adding a carbon source during the preparation of the phosphate according to the invention, which is described in more detail below in connection with the process according to the invention.
- the inclusion of carbon in the product according to the invention allows an electrically conductive equipment of the material per se and / or the producible from the material products, for example, cathode materials for lithium ion batteries. Due to the amount and type of carbon source added in the preparation, the resulting carbon content and thus the conductivity can be adjusted freely within certain limits.
- One Too high a carbon content has the disadvantage of reducing the maximum possible amount of cathode active material in later use in lithium ion batteries. At a carbon content below 1 wt .-%, a sufficient conductivity increase is no longer achieved.
- the platelet-shaped morphology preferred according to the invention has particular advantages, for example when using the phosphate according to the invention for the production of lithiated (Li-containing) cathode material for Li-ion batteries.
- the platelet form with nanoscale platelet thickness of the primary crystallites ensures the lowest possible diffusion distances and diffusion times during lithiation via simple and inexpensive calcination processes.
- the ratio of Mn: (Mn + Met) denotes the atomic ratio of manganese to the sum of all metals included in the present invention including manganese.
- the ratio of Mn: (Mn + Met) can also be given by x: ( x + y).
- a manganese content in the mixed-metal phosphate of the new "Mn 3 (P0 4) 2 ⁇ 3 H 2 0-structure type" can not be obtained.
- aqueous solution which contains at least divalent manganese cations (Mn 2+ ) and optionally one or more of the metals Fe, Co and / or Ni as divalent cations, by oxidic metal (II) -, metal (III) and / or metal (IV) compounds or mixtures thereof or compounds having mixed oxidation states selected from Hydroxides, oxides, oxide hydroxides, oxide hydrates, carbonates and hydroxide carbonates of at least one of Mn, Fe, Co and / or Ni together with the elemental forms or alloys of at least one of Mn, Fe, Co and / or Ni in a phosphoric acid containing aqueous medium and the oxidic metal compounds fertilize with the elemental forms or alloys of the metals (in a redox reaction) to the bivalent metal ions, wherein at least one of the oxide metal compounds and / or at least one of the elemental forms or alloys of metal comprises manganese,
- the aqueous solution (I) further at least one compound of at least one of the metals Met in the form of an aqueous solution or as a solid in the form of a salt, wherein the at least one compound is preferably selected from hydroxides, oxides, oxide hydroxides, oxide hydrates, carbonates, hydroxide carbonates, carboxylates, sulfates, chlorides or nitrates of the metals is selected,
- a phosphoric acid solution prepared by neutralization with an aqueous alkali hydroxide solution or a prepared from an aqueous solution of one or more Alkaliphosphate template solution (II) having a pH of 5 to 8, e) the aqueous solution (I) to the Added to template solution (II) and simultaneously a basic aqueous alkali metal hydroxide solution so metered that the pH of the resulting reaction mixture in the range of 5 to 8, preferably 6 to 7, is maintained, wherein the phosphate of the type Mn 3 (P0 4 ) 2 ⁇ a H 2 O or (Mn x Met y ) 3 (PO 4 ) 2 ⁇ a H 2 O is precipitated,
- the metals introduced into the solution (I) in step a) are also referred to herein as "main metals.”
- the main metals comprise at least manganese (Mn) and optionally Fe, Co and / or Ni which are optionally added to the solution in step (c).
- I) introduced metals selected from Fe, Co, Ni, Sc, Ti, V, Cr, Cu, Zn, Be, Mg, Ca, Sr, Ba, Al, Zr, Hf, Re, Ru, La, Ce, Pr , Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu are also referred to herein as "doping metals”.
- manganese (Mn) can be introduced in step c).
- the doping metals may be in the form of the divalent metal ions in the solution, but they may also be in the form of the trivalent or tetravalent metal ions in the solution. Some of the doping metals are preferably in the trivalent form. If, for example, the phosphate according to the invention is further processed into a cathode material, then these non-divalent metal ions constitute quasi-impurities in the structure, which may advantageously influence the performance of the cathode material.
- the process according to the invention for producing a monometallic or mixed-metal phosphate is simple and inexpensive compared to the prior art.
- Another advantage of the method according to the invention is that the aqueous phosphoric acid solution (I) only contains the desired metal cations and exclusively or predominantly phosphate anions or phosphoric acid. An expensive removal of foreign anions, such as sulfates, nitrates, chlorides or others, in the further course of the preparation of the products according to the invention is therefore not required.
- doping metals for example in the form of their sulfates, nitrates or chlorides, are introduced in stage c) of the process according to the invention, this takes place in small amounts which are still acceptable in the product to be produced and do not adversely affect the product properties or only to an acceptable extent.
- the phosphates according to the invention thus have a high purity, which makes them particularly suitable, for example, for the preparation of lithiated cathode materials.
- the lithiation can be carried out by a simple thermal reaction step (calcining), in which case a suitable lithium salt must be added depending on the type of phosphate material.
- the process according to the invention offers the possibility, by suitable choice of the precipitation conditions, such as pH, concentrations, temperature, etc., of certain material parameters, such as crystal phase and cation distribution, morphology, crystallite and secondary particle size and the chemical purity of the resulting products check. Preference is given to the products described above with platelet-shaped morphology, which have a uniform crystal phase and an isotropic distribution of the cations.
- the oxidic metal (II), metal (III) and / or metal (IV) compounds are reacted with elemental metal or alloys in phosphoric acid aqueous medium in a redox reaction to form the divalent metal ions.
- the course of the described redox reaction between the elemental metals and the oxidic components depends on their respective specific surface areas, since the electron transfer takes place at the interface.
- the formation of hydrogen gas is taken into account. This leads to the electron transfer from the elemental metal forms to protons with the formation of radicals, which form hydrogen gas by radical combination.
- the particle sizes of the elemental and oxidic metal forms used should therefore be matched to suppress the side reaction and to take maximum advantage of the dissolution of the inexpensive oxide metal mold. Generally, the finer the elemental metal form, the more likely the side reaction is favored if the oxic form does not provide a sufficiently high active surface area.
- unreacted components may remain as solid residues in the solution. If in the resulting reaction solution still solids are contained, they are preferably separated from the phosphoric acid aqueous solution.
- the separation of solids can be carried out by any suitable known methods for the separation of liquids and solids, for example filtration, centrifugation, sedimentation etc.
- the phosphate to be prepared according to the invention is a mixed-metal phosphate and, in addition to the metals introduced into the solution in step a), contains further metals selected under Met
- the aqueous solution (I) is added to the initial solution (II) in step e) before being metered.
- at least one compound of at least one of metals selected under Met, optionally also manganese, in the form of an aqueous solution or as a solid in the form of a salt said at least one compound preferably among hydroxides, oxides, oxide hydroxides, oxide hydrates, carbonates, hydroxide carbonates , Carboxylates, sulfates, chlorides or nitrates of the metals.
- doping metals is expediently carried out in stage c) of the process after any solids present have been separated off from the phosphoric acid aqueous solution (I).
- the described addition of the doping metals can also be carried out immediately after the preparation of the solution (I) in stage a) and before the separation of any solids present.
- the separation of optionally contained solids then takes place after the addition of the doping metals.
- the addition of the metals in the form of their sulfates, chlorides or nitrates may also be suitable for dopants, if the content of sulfates, chlorides or nitrates in the product does not exceed certain limits which are still considered acceptable for the particular application.
- the template solution (II) for the subsequent precipitation of the phosphates according to the invention is likewise a phosphate solution having a pH in the range of 5 to 8 buffered.
- the initial solution is prepared either from an aqueous phosphoric acid solution by neutralization with an aqueous alkali metal hydroxide solution or directly from an aqueous solution of one or more alkali metal phosphates.
- the aqueous solution (I) is added to the pre-treatment solution (II). Due to the low pH of the phosphoric acid solution (I) metered at the same time adding a basic aqueous alkali hydroxide solution in order to keep the pH of the resulting reaction mixture in the range of 5 to 8. Too low a pH of the template solution (II) or of the resulting reaction mixture at a pH of 5 has the disadvantage that, in addition to the desired crystal phase according to the invention, it is also possible to form further crystal phases, eg. As metal hydrogen or Metalldihydrogenphosphate.
- An excessively high pH of the template solution (II) above a pH of 8 has the disadvantage that traces of metal hydroxides can form which represent undesired contamination in the products according to the invention.
- the basic aqueous alkali metal hydroxide solution is preferably added in such a way that a pH in the range from 6 to 7 is established in the reaction mixture when the solution (I) is metered in. This has the advantage that only the crystal phase according to the invention forms.
- the phosphate separated off from the reaction solution is then expediently dried, ie. H. dewatered.
- the drying can be carried out either under ambient atmosphere, under a protective gas atmosphere and / or under reduced pressure and / or elevated temperature (above room temperature, 25 ° C).
- the methods suitable for this purpose are familiar to the person skilled in the art and require no further description.
- free water is removed from the residue separated from the reaction solution. Depending on the desired product but also bound water of crystallization is removed by drying up to a desired hydrate level of the product.
- the manganese (Mn) -containing phosphate produced by the process according to the invention is a mixed-metal phosphate which contains at least one other metal (Met) in addition to manganese (Mn), the phosphate preferably containing not more than 7 different metals. In most cases it will be convenient to produce a mixed metal phosphate of the type according to the invention with two, three or four different metals.
- a mixed-metal phosphate which, in addition to manganese (Mn), contains one or two metals selected from Fe, Co and Ni in high proportions as so-called main metals and / or one or more metals in small proportions as so-called doping metals .
- Mn manganese
- a manganese containing as main metal according to the invention containing a small proportion of a further metal, for example Mg, Al, Cu or a Lanthanoidenmetalls, as demonstrated in the following examples.
- the manganese (Mn) -containing mixed-metal phosphate contains at least 40 at.% Mn, preferably at least 60 at.% Mn, more preferably at least 80 at.% Mn, most preferably at least 90 ath. -% Mn.
- the manganese (Mn) -containing phosphate produced by the process according to the invention is a monometallic phosphate which, in addition to process-related impurities, contains only manganese (Mn) as the metal.
- the process according to the invention has considerable advantages over the state of the art in terms of efficiency, process costs, energy consumption and product purity achievable, in particular in the production of mixed-metal phosphates.
- the proportions of the various metals in the mixed metal phosphate can be adjusted very easily and accurately.
- the process according to the invention makes it possible to control certain material parameters, such as crystal phase and cation distribution, morphology, crystallite and secondary particle size and the chemical purity of the products obtained, by suitably selecting the precipitation conditions, such as pH, concentrations, temperature, etc. ,
- the precipitation conditions such as pH, concentrations, temperature, etc.
- the manganese (Mn) -containing phosphate produced according to the invention particularly preferably has the novel "Mn 3 (PO 4 ) 2 .3 H 2 O structure type" described herein with peaks in the powder X-ray diffraction diagram at 10.96 ⁇ 0.05, 12, 78 ⁇ 0.17, 14.96 ⁇ 0.13, 17.34 ⁇ 0.15, 18.98 ⁇ 0.18, 21, 75 ⁇ 0.21, 22.07 ⁇ 0.11, 22.97 ⁇ 0.10, 25.93 ⁇ 0.25, 26.95 ⁇ 0.30, 27.56 ⁇ 0.10, 29.19 ⁇ 0.12, 29.84 ⁇ 0.21, 30.27 ⁇ 0, 12, 34.86 ⁇ 0.21, 35.00 ⁇ 0.20, 35.33 ⁇ 0.30, 35.58 ⁇ 0.10, 35.73 ⁇ 0.12, 42.79 ⁇ 0.45, 43.37 ⁇ 0.45, 44.70 ⁇ 0.15 and 44.93 ⁇ 0.20 degrees two-theta based on CuKa radiation.
- the precipitation of the manganese (Mn) -containing phosphate in step e) is carried out at a temperature in the range from 5 to 105.degree. C., preferably in the range from 10 to 40.degree.
- the temperature can be kept constant by a suitable control unit in the range +/- 5 ° C to the desired point. Higher temperatures generally result in a more pronounced crystallinity of the products. Temperatures below 5 ° C are possible, but require unnecessary cooling.
- the best solution is to carry out the precipitation at room temperature or at the reaction-dependent temperature. to lead. At temperatures above 105 ° C, the reaction mixture boils, which is undesirable and may be disadvantageous.
- the precipitation of the phosphate in step e) is carried out at a temperature in the range from 10 to 40 ° C., since this is the most cost-effective.
- a carbon source comprises elemental carbon or consists exclusively of elemental carbon and is preferably selected from Graphite, expanded graphite, carbon black or black carbon, carbon nanotubes (CNT), fullerenes, graphene, vitreous carbon, carbon fibers, activated carbon or mixtures thereof, or the aforesaid carbon source comprises organic compounds in addition to elemental carbon wherein the organic compounds are preferably selected from hydrocarbons, alcohols, aldehydes, carboxylic acids, surfactants, oligomers, polymers, carbohydrates or mixtures thereof.
- a carbon source to the aqueous solution (I) in the process according to the invention allows the production of phosphate-carbon composites, whereby an electrically conductive equipment of the material itself and / or the products can be made of the material possible, for example for the production of cathode materials for lithium ion batteries. Due to the added amount and type of carbon source directly to the solution (I), the resulting carbon content and thus the conductivity can be freely adjusted within certain limits.
- Too high a carbon content has the disadvantage of reducing the maximum possible amount of cathode active material in later use in lithium ion batteries. At a carbon content below 1 wt .-%, a sufficient conductivity increase is no longer achieved.
- the use of agitator ball mills is particularly suitable for this purpose.
- its average particle size or agglomerate size can also be modified.
- the mean grain size of a graphite can be reduced to ⁇ 300 nm.
- the dispersions obtained are very stable and have little tendency to sedimentation of the graphite solid even after several days, although this generally has initially hydrophobic material properties.
- the described treatment and an excess of free phosphate or phosphoric acid in the mixture modify the surfaces of the graphite and stabilize the solid in the dispersion.
- hydrophilization of carbon or graphite which are used advantageously can be, for example, the partial oxidation of the surface.
- the stability of the dispersion of the carbon source in the solution (I) can be improved with advantage by the addition of surface-active substances.
- the solution may be added in addition to other carbon sources or, alternatively, a polymer or biopolymer as carbon source. Advantages here provide soluble carbon sources under the acidic conditions prevailing in the solution (I). If the component is insoluble, the distribution in the solution can also be improved by the action of shear forces.
- the aqueous medium containing phosphoric acid for the preparation of the aqueous solution (I) contains the phosphoric acid in a molar excess in relation to the sum of the molar amounts of the metal cations of the oxidic metal compounds to be introduced into the solution the metals to be introduced in elemental form or as an alloy. Without an excess of phosphoric acid, the redox process does not proceed or at such a slow rate that the process may not be of interest to commercial application.
- the concentration of phosphoric acid in the aqueous solution (I) in stage a) is 5% to 85%, preferably 10% to 40%, more preferably 15% to 30%, most preferably 20% to 25% on the weight of the aqueous solution (I).
- the template solution (II) contains the phosphate ions, calculated as P 2 O 5 , in a concentration in the range from 0.35 to 1.85 mol / L.
- a concentration of phosphation below 0.35 mol / LP 2 0 5 has the disadvantage that it would unnecessarily dilute the reaction mixture and, in the case of a commercial application, would have to treat an unnecessarily large volume of filtrate.
- a phosphate concentration above 1.85 mol / LP 2 0 5 has the disadvantage that the reaction mixture can not be optimally mixed due to a high solids content and the resulting high viscosity. This can lead to local concentration gradients, which in turn can adversely affect the formation of the desired crystal phase.
- the reaction of the oxidic metal compounds with the elemental forms or alloys of the metals in stage a) is carried out at a temperature in the range from 5 ° C. to 105 ° C., preferably in the range from 10 ° C. to 75 ° ° C, more preferably in the range of 20 ° C to 50 ° C, by.
- the reaction with various metal components can be carried out smoothly and at a satisfactory speed, without the occurrence of oxidation phenomena with atmospheric oxygen.
- step a) it is advantageous to carry out the reaction of the oxidic metal compounds with the elemental forms or alloys of the metals in step a) with thorough mixing in order to achieve a uniform reaction and to avoid local excess concentrations within the reaction solution. This also applies to the subsequent precipitation stage.
- reaction time required for a sufficiently complete reaction depends on the reactants and the reaction conditions and can be easily determined by the skilled person by a few simple experiments. If the reaction time is too short, the reaction will generally not be sufficiently complete and will yield too much unreacted starting materials. The reaction time should also not be too long, since the process is then less economical.
- a complete reaction is desired to obtain a defined metal composition. As described above, the concentration of individual metals in the solution can optionally be adjusted by the addition of suitable metal salts. However, this means additional expense and increases the cost of the process and the risk of intolerable Anionenkontamination.
- the invention also encompasses the use of the phosphate according to the invention for the production of lithiated (Li-containing) cathode material for Li-ion accumulators, for example according to methods described in the literature.
- the use of the phosphate according to the invention as a precursor for the preparation of lithiated cathode material has the advantage over the use of the methods known for this purpose that in the phosphate according to the invention the various desired metal cations are already present in an ideally isotropically distributed form in a high-purity precursor which its crystal phase, composition and morphology can be clearly characterized by simple and well-known methods.
- the inventively preferred nanoscale platelet shape of the primary crystallites ensures the lowest possible diffusion distances and diffusion times in lithiation via simple and inexpensive calcination.
- the already ideal isotropic distribution of the metal ions also reduces the necessary calcination and calcination times, since no Matallionendiffusion across grain boundaries across is necessary.
- the defined crystal structure ensures clear and reproducible reaction paths during calcination and in the production of cathode materials.
- the effort in the precise production of Reisserormischept is significantly reduced compared to known methods, since the essential components are already present in a defined compound.
- the high purity of the phosphate according to the invention in particular the most extensive absence or very low levels of anionic impurities such as sulfates, nitrates, chlorides, etc., in a later battery application by a significantly higher cycle life and durability, which increases the efficiency of lithium-ion batteries and applications eg in electric vehicles.
- the invention further comprises a lithiated (Li-containing) cathode material for Li-ion accumulators, prepared using manganese (Mn) -containing phosphate according to the invention.
- the invention further comprises a Li-ion accumulator which contains the lithiated (Li-containing) cathode material according to the invention.
- Figure 1 X-ray powder diffraction pattern of the product from Example 4 with CuK a radiation
- FIG. 6 Electron micrograph of the product from Example 18;
- Figure 7 X-ray powder diffraction pattern of the product of Example 17 with CuK a radiation, fully indexed by PDF 75-1186 (Fe 3 (P0 4) 2 8 x H 2 0) and 41-0375 (Co 3 (P0 4) 2 x 8 H 2 O);
- Figure 8 X-ray powder diffraction pattern of the product of Example 16 with CuK a radiation, fully indexed by PDF 75-1186 (Fe 3 (P0 4) 2 8 x H 2 0) (or 46-1388 (Ni 3 P0 4) 2 x 8H 2 0);
- Figure 9 Powder X-ray diffraction pattern of the product from Example 3 with CuK a radiation.
- a phosphoric acid solution (I) was prepared from 80 g of 75% H 3 PO 4 and 160 g of deionized water. Into this solution (I) was added 14.3 g of Mn 3 O 4 and 3.5 g of Fe. The solution (I) was stirred for 90 minutes at room temperature and then filtered to remove any remaining residue from the solution.
- a basic solution of 40g NaOH and 1000g deionized water was prepared.
- 25 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- the Me 2+ phosphoric acid solution (I) and the basic solution were simultaneously metered in with stirring so that the pH of the template solution (II) was always kept between 6.5 and 7.
- the solution was stirred for a further 5 minutes.
- the precipitated solid was then filtered with suction using a Nutsche filter and washed with deionized water.
- the filter cake was dried at 120 ° C in a convection oven.
- a basic solution of 120g NaOH and 3000g deionized water was prepared.
- 25 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the original solution (II).
- the Me 2+ phosphoric acid solution (I) and the basic solution were simultaneously metered in with stirring so that the pH of the template solution (II) was always kept between 6.5 and 7.
- the solution was stirred for a further 5 minutes.
- the precipitated solid was then removed with the aid of a Suction filter filtered off and washed with deionized water.
- the filter cake was dried at 90 ° C in a convection oven.
- a phosphoric acid solution (I) was prepared from 80 g of 75% H 3 PO 4 and 160 g of deionized water. Into this solution (I), 14.3 g of Mn 3 O 4 and 3.8 g of Co were added. The solution (I) was stirred for 60 minutes at 60 ° C and then filtered to remove any remaining residue from the solution. Furthermore, a basic solution of 40.4 g NaOH and 229 g water was prepared. Subsequently, 25 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- the Me 2+ phosphoric acid solution (I) and the basic solution were simultaneously metered in with stirring so that the pH of the template solution (II) was always kept between 6.5 and 7. After completion of the addition, the solution was stirred for a further 5 minutes. The precipitated solid was then filtered with suction using a Nutsche filter and washed with deionized water. The filter cake was dried at 70 ° C in a convection oven.
- a phosphoric acid solution (I) was prepared from 80 g of 75% H 3 PO 4 and 160 g of deionized water. Into this solution (I) was added 14.1 g of Mn 3 O 4 and 4.5 g of Mn. The solution (I) was stirred for 90 minutes at 20 ° C and then filtered to remove any remaining residue from the solution. Furthermore, a basic solution of 17.6 g of NaOH and 158.7 g of water was prepared. Subsequently, 10 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- a phosphoric acid solution (I) was prepared from 80 g of 75% H 3 PO 4 and 160 g of deionized water. Into this solution (I) was added 14.3 g of Mn 3 O 4 and 3.5 g of Fe. The solution (I) was stirred for 90 minutes at room temperature and then 17.7 g of CoSO 4 -6H 2 0 dissolved in 20 g of water was added. Subsequently, the resulting solution was filtered to remove any remaining residue. Furthermore, a basic solution of 40g NaOH and 1000g water was prepared. Subsequently, 25 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- the Me 2+ phosphoric acid solution (I) and the basic solution were simultaneously metered in with stirring so that the pH of the template solution (II) was always kept between 6.5 and 7. After completion of the addition, the solution was stirred for a further 5 minutes. The precipitated solid was then filtered with suction using a Nutsche filter and washed with deionized water. The filter cake was dried at 80 ° C in a convection oven.
- a phosphoric acid solution (I) was prepared from 80 g of 75% H 3 PO 4 and 160 g of deionized water. Into this solution (I) was added 14.3 g of Mn 3 O 4 and 3.5 g of Fe. The solution (I) was stirred for 90 minutes at 60 ° C and then added 2.6g Mg (acetate) 2 -6H 2 0 dissolved in 20g of water. Subsequently, the resulting solution was filtered to remove any remaining residue.
- a basic solution of 50g NaOH and 450g water was prepared.
- 10 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- the Me 2+ phosphoric acid solution (I) and the basic solution were simultaneously metered in with stirring so that the pH of the template solution (II) was always kept between 6.5 and 7.
- the solution was stirred for a further 5 minutes.
- the precipitated solid was then filtered with suction using a Nutsche filter and washed with deionized water.
- the filter cake was dried at 80 ° C in a convection oven.
- a phosphoric acid solution (I) was prepared from 80 g of 75% H 3 PO 4 and 160 g of deionized water. Into this solution (I), 14.3 g of Mn 3 O 4 and 2.2 g of Fe and 1.5 g of Co were added. The solution (I) was stirred for 90 minutes at room temperature and then filtered to remove any remaining residue from the solution.
- a basic solution of 40g NaOH and 1000g deionized water was prepared.
- 25 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- the Me 2+ phosphoric acid solution (I) and the basic solution were simultaneously metered in with stirring so that the pH of the template solution (II) was always kept between 6.5 and 7.
- the solution was stirred for a further 5 minutes.
- the precipitated solid was then sucked with the aid of a Nutsche filter and with washed deionized water.
- the filter cake was divided and one part each dried at 60 ° C or 120 ° C in a convection oven.
- a phosphoric acid solution (I) was prepared from 80 g of 75% H 3 PO 4 and 160 g of deionized water. Into this solution (I), 14.3 g of Mn 3 O 4 and 2.2 g of Fe and 1.5 g of Co were added. The solution (I) was stirred for 90 minutes at room temperature and then filtered to remove any remaining residue from the solution. To this solution then added with 2.6 g of Mg (acetate) -6H 2 0 dissolved in 20 g of water.
- a basic solution of 40g NaOH and 1000g deionized water was prepared.
- 25 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- the Me 2+ phosphoric acid solution (I) and the basic solution were simultaneously metered in with stirring so that the pH of the template solution (II) was always kept between 6.5 and 7.
- the solution was stirred for a further 5 minutes.
- the precipitated solid was then filtered with suction using a Nutsche filter and washed with deionized water.
- the filter cake was divided and one part each dried at 60 ° C or 120 ° C in a convection oven.
- a phosphoric acid solution (I) was prepared from 1090 g of 75% H 3 PO 4 and 2380 g of deionized water. Into this solution (I) was added 209 g of Mn 3 O 4 and 51 g of Fe. The solution (I) was stirred for 90 minutes at room temperature and then to 100 g of this solution 1, 94g Al 2 (S0 4 ) 3 -18H 2 0 dissolved in 20 ml of water was added to the solution and filtered to any remaining residue from the solution to remove.
- a basic solution of 50g NaOH and 450g water was prepared.
- 10 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- the Me 2+ phosphoric acid solution (I) and the basic solution were simultaneously metered in with stirring so that the pH of the template solution (II) was always kept between 6.5 and 7.
- the solution was stirred for a further 5 minutes.
- the precipitated solid was then filtered with suction using a Nutsche filter and washed with deionized water.
- the filter cake was dried at 80 ° C in a convection oven.
- a phosphoric acid solution (I) was prepared from 1090 g of 75% H 3 PO 4 and 2380 g of deionized water. Into this solution (I) was added 209 g of Mn 3 O 4 and 51 g of Fe. The solution (I) was stirred at room temperature for 90 minutes and then 0.65 g of Cu were added to 100 g of this solution. CO 3 Cu (OH) 2 0.5H 2 O dissolved in 20 ml dilute HCl added to the solution and filtered to remove any remaining residues from the solution.
- a basic solution of 50g NaOH and 450g water was prepared.
- 10 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- the Me 2+ phosphoric acid solution (I) and the basic solution were simultaneously metered in with stirring so that the pH of the template solution (II) was always kept between 6.5 and 7.
- the solution was stirred for a further 5 minutes.
- the precipitated solid was then sucked off with the aid of a suction filter and washed with deionized water.
- the filter cake was dried at 80 ° C in a convection oven.
- the Me 2+ phosphoric acid solution (I) and the basic solution were simultaneously metered in with stirring so that the pH of the template solution (II) was always kept between 6.5 and 7. After completion of the addition, the solution was stirred for a further 5 minutes. The precipitated solid was then filtered with suction using a Nutsche filter and washed with deionized water. The filter cake was dried at 80 ° C in a convection oven.
- a phosphoric acid solution (I) was prepared from 1090 g of 75% H 3 PO 4 and 2380 g of deionized water. Into this solution (I) was added 209 g of Mn 3 O 4 and 51 g of Fe. The solution (I) was stirred for 90 minutes at room temperature and then to 100 g of this solution 1, 12g EuCl 3 -7H 2 0 dissolved in 20ml of water was added to the solution and filtered to remove any remaining residue from the solution.
- a basic solution of 50g NaOH and 450g water was prepared.
- 10 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- the Me 2+ phosphoric acid solution (I) and the basic solution were simultaneously metered in with stirring so that the pH of the template solution (II) was always kept between 6.5 and 7 has been.
- the solution was stirred for a further 5 minutes.
- the precipitated solid was then filtered with suction using a Nutsche filter and washed with deionized water.
- the filter cake was dried at 80 ° C in a convection oven.
- a phosphoric acid solution (I) was prepared from 1090 g of 75% H 3 PO 4 and 2380 g of deionized water. Into this solution (I) was added 209 g of Mn 3 O 4 and 51 g of Fe. The solution (I) was stirred for 90 minutes at room temperature, and then this solution, 0.66 g of SnCl 2 -2H 2 0 were dissolved in 20ml of dilute HCl added to the solution and filtered to remove any remaining residue from the solution to 100 g.
- a basic solution of 50g NaOH and 450g water was prepared.
- 10 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- the Me 2+ phosphoric acid solution (I) and the basic solution were simultaneously metered in with stirring so that the pH of the template solution (II) was always kept between 6.5 and 7.
- the solution was stirred for a further 5 minutes.
- the precipitated solid was then filtered with suction using a Nutsche filter and washed with deionized water.
- the filter cake was dried at 80 ° C in a convection oven.
- a phosphoric acid solution (I) was prepared from 1090 g of 75% H 3 PO 4 and 2380 g of deionized water. Into this solution (I) was added 209 g of Mn 3 O 4 and 51 g of Fe. The solution (I) was stirred for 90 minutes at room temperature and then 0.95 g of ZrOCl 2 dissolved in 20 ml of dilute HCl was added to the solution to 100 g of this solution and filtered to remove any remaining residue from the solution.
- a basic solution of 50g NaOH and 450g water was prepared.
- 10 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- the Me 2+ phosphoric acid solution (I) and the basic solution were simultaneously metered in with stirring so that the pH of the template solution (II) was always kept between 6.5 and 7.
- the solution was stirred for a further 5 minutes.
- the precipitated solid was then filtered with suction using a Nutsche filter and washed with deionized water.
- the filter cake was dried at 80 ° C in a convection oven.
- a phosphoric acid solution (I) was prepared from 1090 g of 75% H 3 PO 4 and 2380 g of deionized water. Into this solution (I) was added 209 g of Mn 3 O 4 and 51 g of Fe. The solution (I) was stirred at room temperature for 90 minutes, and then to 100 g of this solution was added 0.33 g of CaCl 2 dissolved in 20 ml of dilute HCl added to the solution and filtered to remove any remaining residues from the solution.
- a basic solution of 50g NaOH and 450g water was prepared.
- 10 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- the Me 2+ phosphoric acid solution (I) and the basic solution were simultaneously metered in with stirring so that the pH of the template solution (II) was always kept between 6.5 and 7.
- the solution was stirred for a further 5 minutes.
- the precipitated solid was then sucked off with the aid of a suction filter and washed with deionized water.
- the filter cake was dried at 80 ° C in a convection oven.
- a phosphoric acid solution (I) was prepared from 80 g of 75% H 3 PO 4 and 160 g of deionized water. Into this solution (I) was added 14.1 g of Fe 3 O 4 and 3.5 g of Fe. The solution (I) was stirred at 60 ° C. for 60 minutes and then 33.1 g of NiSO 4 -6H 2 O dissolved in 100 g of water were added. The resulting solution was filtered to remove any remaining residue.
- a phosphoric acid solution (I) was prepared from 80 g of 75% H 3 PO 4 and 160 g of deionized water. Into this solution (I) was added 14.1 g of Fe 3 O 4 and 3.8 g of Co. The solution (I) was stirred for 60 minutes at 60 ° C and then filtered to remove any remaining residue from the solution.
- a basic solution of 50g NaOH and 500g water was prepared.
- 10 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- the Me 2+ phosphoric acid solution (I) and the basic solution were simultaneously metered in with stirring so that the pH of the template solution (II) was always kept between 6.5 and 7.
- the solution was stirred for a further 5 minutes. The favored The solid was then sucked off with the aid of a suction filter and washed with deionized water.
- the filter cake was dried at 70 ° C in a convection oven.
- a phosphoric acid solution (I) was prepared from 80 g of 75% H 3 PO 4 and 160 g of deionized water. Into this solution (I) was added 14.4 g of Co 3 O 4 and 3.8 g of Co. The solution (I) was stirred for 60 minutes at room temperature and then filtered to remove any remaining residue from the solution. Furthermore, a basic solution of 41.9 g of NaOH and 376.8 g of water was prepared. Subsequently, 10 g of H 3 PO 4 were introduced with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- a basic solution of 17.6 g of NaOH and 158.7 g of water was prepared.
- 10 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- 100 g of the Me 2+ phosphoric acid solution (I) and the basic solution were added simultaneously to the neutralized original solution (II) with stirring so that the pH of the original solution (II) was always between 6.5 and 7 has been.
- the solution was stirred for a further 5 minutes.
- the precipitated solid was then filtered with suction using a Nutsche filter and washed with deionized water.
- the filter cake was dried at 80 ° C in a convection oven.
- a phosphoric acid solution (I) was prepared from 80 g of 75% H 3 PO 4 and 160 g of deionized water. Into this solution (I) was added 14.4 g of Co 3 O 4 and 3.5 g of Fe. The solution (I) was stirred for 60 minutes at room temperature and then filtered to remove any remaining residue from the solution. Furthermore, a basic solution of 41.9 g of NaOH and 376.8 g of water was prepared. Subsequently, 10 g of H 3 PO 4 were charged with 100 g of water in a reaction vessel and neutralized with the basic solution to a pH of 7 to obtain the template solution (II).
- the Me 2+ phosphoric acid solution (I) and the basic solution were simultaneously metered in with stirring so that the pH of the template solution (II) was always kept between 6.5 and 7. After completion of the addition, the solution was stirred for a further 5 minutes. The precipitated solid was then filtered with suction using a Nutsche filter and washed with deionized water. The filter cake was dried at 80 ° C. in a circulating air drying cabinet.
- Examples (comparative examples) 16 to 20 show that monom etal or mixed metal phosphates are obtained by the comparable method but without the addition of elemental manganese (Mn) or manganese-containing oxidic compounds which do not contain the "Mn 3 (P0 4 ) 2 ⁇ 3 H 2 0 structure type ".
- Mn elemental manganese
- the products of Examples 16 to 20 could all be assigned to the vivanite crystal structure type [Fe 3 (PO 4 ) 2 8 H 2 O] or its dehydration stages.
- the drying temperature had an influence on the content of bound water of crystallization.
- a reduced water partial pressure accelerated the drying.
- the products according to the invention of Examples 1 to 15 all show the same analytical X-ray diffraction pattern in the powder X-ray diffraction diagram with Pea ks be i 10, 96 ⁇ 0.05, 12.78 ⁇ 0.17, 14.96 ⁇ 0.13, 17.34 ⁇ 0.15, 18.98 ⁇ 0.18, 21, 75 ⁇ 0.21, 22.07 ⁇ 0, 1 1, 22.97 ⁇ 0.10, 25.93 ⁇ 0.25, 26 , 95 ⁇ 0.30, 27.56 ⁇ 0.10, 29, 19 ⁇ 0.12, 29.84 ⁇ 0.21, 30.27 ⁇ 0.12, 34.86 ⁇ 0.21, 35.00 ⁇ 0.20, 35.33 ⁇ 0.30, 35.58 ⁇ 0.10, 35.73 ⁇ 0.12, 42.79 ⁇ 0.45, 43.37 ⁇ 0.45, 44.70 ⁇ 0.15 and 44, 93 ⁇ 0.20 degrees two-theta, based on CuKa radiation.
- the powder X-ray analysis and electron diffraction analyzes in the transmission electron microscope prove for the products of Examples 1 to 15 an orthorhom bische unit cell with axial lengths of 13.2 +/- 0.2; 8.6 +/- 0.2 and 8.1 +/- 0.2 Angstroms.
- the powder X-ray diffraction diagrams obtained for the products according to the invention with the abovementioned peaks and the product cells intended for the products with the said parameters and slightly varying within the given ranges depending on the composition of the metal components are for compounds of composition Mn 3 (P0 4 ) 2 ' 3H 2 0 and their (pseudo) binary, (pseudo) ternary or (pseudo) quaternary variants in the relevant databases are not yet known.
- a new "Mn 3 (PO 4 ) 2 .3H 2 O structure type" was identified. The structure is observed when the product according to the invention exclusively contains Mn as metal (see Example 3), but also when other metals are present.
- the products according to the invention predominantly have a platelet-shaped morphology of the primary crystallites, it being possible to determine the platelet thickness in the order of about 10 to 50 nm in the scanning electron microscope.
- the platelet-shaped morphology of the products according to the invention allows, in principle, a dense packing of the crystallites, i. the platelets can stack at a lower cut-off volume than is the case with round spherical particles. Layered aggregates or agglomerates of this material can be easily converted by conventional methods under the action of shear forces in dispersions of the primary particles.
- the small thickness of the crystal platelets of the product according to the invention ensures a high reaction rate in the lithiation of the phosphates to active cathode materials, since the Lithium ions in the implementation of only short diffusion paths must cover. This also leads to a better performance of the finished cathode material, since the diffusion distances and times of Li ions can be significantly reduced compared to a conventional material.
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US14/367,531 US9350020B2 (en) | 2011-12-21 | 2012-12-21 | Metal phosphate containing manganese and method for its production |
RU2014129527A RU2616063C2 (ru) | 2011-12-21 | 2012-12-21 | Марганецсодержащие фосфаты металлов и способ их получения |
BR112014012066A BR112014012066A8 (pt) | 2011-12-21 | 2012-12-21 | fostatos metálicos contendo manganes e processo para a sua produção |
JP2014548071A JP6097306B2 (ja) | 2011-12-21 | 2012-12-21 | マンガン含有金属リン酸塩及びその製造方法 |
IN962KON2014 IN2014KN00962A (de) | 2011-12-21 | 2012-12-21 | |
KR20147018138A KR20140110892A (ko) | 2011-12-21 | 2012-12-21 | 망간을 함유하는 금속 포스페이트 및 그의 제조 방법 |
MYPI2014001162A MY185281A (en) | 2011-12-21 | 2012-12-21 | Metal phosphates containing manganese and method for its production |
CN201280063651.4A CN104039693B (zh) | 2011-12-21 | 2012-12-21 | 含锰金属磷酸盐及其制备方法 |
EP12809277.2A EP2794472A1 (de) | 2011-12-21 | 2012-12-21 | Mangan enthaltende metallphosphate und verfahren zu deren herstellung |
CA2851432A CA2851432A1 (en) | 2011-12-21 | 2012-12-21 | Manganese-bearing metal phosphates and process for the production thereof |
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DE201110056816 DE102011056816A1 (de) | 2011-12-21 | 2011-12-21 | Mangan enthaltende Metallphosphate und Verfahren zu deren Herstellung |
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WO2016096555A3 (de) * | 2014-12-17 | 2016-10-27 | Chemische Fabrik Budenheim Kg | Zur herstellung von kathoden für li-ionen-akkumulatoren geeignete phosphatverbindungen |
CN115124010A (zh) * | 2022-07-15 | 2022-09-30 | 湖北万润新能源科技股份有限公司 | 一种磷酸锰(ii)纳米片和磷酸锰铁锂正极材料及其制备方法 |
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DE102011056812A1 (de) * | 2011-12-21 | 2013-06-27 | Chemische Fabrik Budenheim Kg | Metallphosphate und Verfahren zu deren Herstellung |
DE102014100026A1 (de) * | 2014-01-02 | 2015-07-02 | Chemische Fabrik Budenheim Kg | Gemischtmetallische kristalline Orthophosphate für die zeitlich kontrollierte Freisetzung von Spurenelementen im rhizodermalen und epidermalen Bereich von Pflanzen |
US10173897B2 (en) | 2016-05-10 | 2019-01-08 | Guiqing Huang | Method of synthesizing phosphate salt of high purity |
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- 2012-12-21 WO PCT/EP2012/076669 patent/WO2013093014A1/de active Application Filing
- 2012-12-21 KR KR20147018138A patent/KR20140110892A/ko not_active Application Discontinuation
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Cited By (4)
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WO2016096555A3 (de) * | 2014-12-17 | 2016-10-27 | Chemische Fabrik Budenheim Kg | Zur herstellung von kathoden für li-ionen-akkumulatoren geeignete phosphatverbindungen |
CN105226245A (zh) * | 2015-08-27 | 2016-01-06 | 北大先行科技产业有限公司 | 一种锂离子电池正极材料及其制备方法 |
CN105226245B (zh) * | 2015-08-27 | 2018-03-09 | 青海泰丰先行锂能科技有限公司 | 一种锂离子电池正极材料及其制备方法 |
CN115124010A (zh) * | 2022-07-15 | 2022-09-30 | 湖北万润新能源科技股份有限公司 | 一种磷酸锰(ii)纳米片和磷酸锰铁锂正极材料及其制备方法 |
Also Published As
Publication number | Publication date |
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CN104039693B (zh) | 2017-03-01 |
BR112014012066A8 (pt) | 2017-06-20 |
EP2794472A1 (de) | 2014-10-29 |
BR112014012066A2 (pt) | 2017-06-13 |
TW201343542A (zh) | 2013-11-01 |
CA2851432A1 (en) | 2013-06-27 |
KR20140110892A (ko) | 2014-09-17 |
RU2616063C2 (ru) | 2017-04-12 |
DE102011056816A1 (de) | 2013-08-01 |
US20150108412A1 (en) | 2015-04-23 |
TWI576312B (zh) | 2017-04-01 |
US9350020B2 (en) | 2016-05-24 |
JP6097306B2 (ja) | 2017-03-15 |
IN2014KN00962A (de) | 2015-10-09 |
CN104039693A (zh) | 2014-09-10 |
RU2014129527A (ru) | 2016-02-10 |
JP2015502911A (ja) | 2015-01-29 |
MY185281A (en) | 2021-04-30 |
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