Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B25/00—Phosphorus; Compounds thereof
  • C01B25/16—Oxyacids of phosphorus; Salts thereof
  • C01B25/26—Phosphates
  • C01B25/37—Phosphates of heavy metals
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B25/00—Phosphorus; Compounds thereof
  • C01B25/16—Oxyacids of phosphorus; Salts thereof
  • C01B25/26—Phosphates
  • C01B25/45—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
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0562—Solid materials
• • 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
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • 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
• • 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
  • H01M4/139—Processes of manufacture
  • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to phase-pure
• Lithium aluminum titanium phosphate a method for its
• Lithium aluminum titanium phosphate Lithium aluminum titanium phosphate
• lithium-ion accumulators also referred to as secondary lithium-ion batteries
• secondary lithium-ion batteries proved to be the most promising battery models for such
• lithium-ion batteries find diverse applications in fields such as power tools, computers, mobile phones, etc.
• cathodes and electrolytes there are the cathodes and electrolytes, but also the anodes
• LiMn 2 0 4 and LiCo0 2 are used as cathode materials. More recently, especially since the work of Goodenough et al. (US Pat. No. 5,910,382) doped or undoped mixed lithium transition metal phosphates, in particular LiFePO 4 .
• anode materials are usually, for example, graphite or, as already mentioned above
• Lithium compounds such as lithium titanates used in particular for large-volume batteries.
• lithium titanates in the present case the doped or non-doped lithium titanium spinels of the type Lii + x Ti 2 - x 04 with 0 ⁇ x ⁇ 1/3 of the space group Fd3m and all mixed titanium oxides of the generic formula Li x Ti y O (O ⁇ x, y ⁇ l) understood.
• Solid-state electrolytes but ceramic fillers such as nanoscale A1 2 0 3 and Si0 2 .
• Lithium titanophosphates have been mentioned as solid electrolytes for some time (JP A 1990 2-225310).
• lithium titanium phosphates have an increased lithium ion conductivity and a low electrical conductivity, which, in addition to their high hardness, also makes them very suitable solid electrolytes
• Aono et al. has the ionic (lithium) conductivity of doped and non-doped lithium titanium phosphates
• Lithium titanium phosphates as cathodes, anodes and electrolyte for lithium ion rechargeable batteries.
• Li 1 (3 Al 0 , 3 Tii (7 (P0 4 ) was proposed in EP 1 570 113 Bl as a ceramic filler in an "active" separator film having additional ionic conductivity for electrochemical devices.
• lithium titanium phosphates have a very complex synthesis by means of solid-state synthesis starting from solid phosphates, in which the usual way
• lithium titanium phosphate is contaminated by other foreign phases such as A1P0 4 or TiP 2 0. Phase pure lithium titanium phosphate or doped
• Lithium titanium phosphate was previously unknown.
• phase-pure lithium aluminum titanium phosphate since phase-pure lithium aluminum titanium phosphate combines the properties of a high lithium ion conductivity with a low electrical conductivity. Compared with non-phase-pure lithium aluminum titanium phosphate of the prior art, even better ionic conductivity due to the absence of foreign phases should be obtained.
• phase pure is understood in the present case that in X-ray powder diffraction (XRD) no reflections of
• Lithium aluminum titanate phosphates of the prior art Lithium aluminum titanate phosphates of the prior art.
• Lithium aluminum titanium phosphate only a very small
• Lithium aluminum titanium phosphates for magnetic iron or magnetic iron compounds are about 1 - 1000 ppm.
• Iron compounds cause, in addition to dendritic formation associated with voltage drop, the danger of short circuits within an electrochemical cell in which
• Lithium aluminum titanium phosphate is used as a solid electrolyte, significantly increased and thus represents a risk for the technical production of such cells. With the present pure phase lithium aluminum titanium phosphate this can be used as a solid electrolyte, significantly increased and thus represents a risk for the technical production of such cells. With the present pure phase lithium aluminum titanium phosphate this can be used as a solid electrolyte, significantly increased and thus represents a risk for the technical production of such cells. With the present pure phase lithium aluminum titanium phosphate this can be used as a solid electrolyte, significantly increased and thus represents a risk for the technical production of such cells. With the present pure phase lithium aluminum titanium phosphate this can be used as a solid electrolyte, significantly increased and thus represents a risk for the technical production of such cells. With the present pure phase lithium aluminum titanium phosphate this can be used as a solid electrolyte, significantly increased and thus represents a risk for the technical production of such cells. With the present pure phase lithium aluminum titanium phosphate this can be used as a solid
• phase-pure lithium aluminum titanium phosphate according to the invention further has a relatively high BET surface area of ⁇ 3.5 m 2 / g. Typical values are
• lithium aluminum titanium phosphates known from the literature have BET surface areas of less than 2 m 2 / g, in particular less than 1.5 m 2 / g.
• the lithium aluminum titanium phosphate according to the invention preferably has a particle size distribution of d 90 ⁇ 6 ⁇ , ⁇ 2.1 pm and dio ⁇ lpm, resulting in that the majority of the particles are particularly small and thus a particularly high ionic conductivity is achieved.
• the lithium aluminum titanium phosphate has the
• Lii i2 Tii, 8Alo, 2 (P0 4 ) 3 which has a very good total ion conductivity of approx. 5 x 1CT 4 S / cm at 298 K and - in the particularly phase-pure form - Li lr3 Ti 1 (7 Alo, 3 (P0 4 ) 3, which at 293 K is a particularly high
• Phosphoric acid i. typically an aqueous phosphoric acid can be used.
• the process according to the invention may also be referred to as a "hydrothermal process.”
• the use of a phosphoric acid enables a lighter one
• the first reaction step c) of the process according to the invention includes the otherwise reaction-inert TiO 2 and, via the intermediate product Ti 2 O (PO 4 ) 2 which is not necessarily to be isolated in the context of the process according to the invention, allows one
• the intermediate ⁇ 2 0 ( ⁇ 0 4 ) 2 does not necessarily have to be isolated, since the process according to the invention is preferably carried out as a "one-pot process.” It is also possible, however, in not quite so preferred developments of the invention, to use Ti 2 O (P0 4 ) 2 to isolate by methods known to those skilled in the art, such as precipitation, spray drying, etc., and optionally to purify and then the other
• Process control may be particularly recommended when using other phosphoric acids as ortho-phosphoric acid.
• Phosphoric acid or alternatively a phosphate may be added so that the final product has the correct stoichiometry.
• phosphoric acid is a dilute ortho-phosphoric acid, for example in the form of a 30% to 50% solution, although in less preferred further embodiments of the present invention other phosphoric acids may also be used, such as
• meta-phosphoric acid etc. All
• Oligophosphor Acid Among ring-shaped metaphosphoric acids (tri-, tetrametaphosphoric acid) up to the anhydride of phosphoric acid P 2 0 5 . It is important according to the invention only that all the aforementioned phosphoric acids in dilute form in solution, preferably in aqueous solution, are used.
• any suitable lithium compound can be used as the lithium compound, such as L1 2 CO 3 , LiOH, Li 2 O,
• step d the aluminum compound is added in step d), and the lithium compound is added only after 30 minutes to 1 hour. This reaction procedure is referred to herein as "cascade phosphating".
• oxygen-containing aluminum compound virtually any oxide or hydroxide or mixed oxide / hydroxide of aluminum may be used.
• Alumina Al 2 O 3 is preferred in the art for its ready availability. In the present case, however, it has been found that the best results are obtained with Al (OH) 3.
• Al (OH) 3 is even more cost effective compared to Al2O3 and also especially in the
• Al 2 O 3 may also be used in the process of the invention, although less preferably; in particular then takes however, calcination is longer compared to the use of Al (OH) 3.
• the step of heating the mixture of phosphoric acid and titanium dioxide (“phosphating") is carried out at a temperature of more than 100 ° C., in particular in a range of 140 to 200 ° C., preferably 140 to 180 ° C. This is a gentle reaction guaranteed to a homogeneous product, which can also be controlled.
• reaction product of step d) obtained according to the invention is subsequently purified by conventional methods, e.g. Evaporation or spray drying isolated. Spray drying is particularly preferred.
• the calcination is preferably carried out at temperatures of 850-950 ° C, most preferably at 880-900 ° C, since below 850 ° C, the risk of the occurrence of foreign phases is particularly large.
• the calcination is carried out over a period of 5 to 24 hours, preferably 10 to 18 hours, most preferably 12 to 15 hours. It was surprisingly
• the present invention also provides a phase-pure lithium aluminum titanium phosphate of the formula Li x Ti 2 - X Al X (PO 4 ) 3, where x is 0.4, which is obtainable by the process according to the invention and by the hydrothermal
• the invention also relates to the use of the pure lithium aluminum titanium phosphate according to the invention as a solid electrolyte in a secondary lithium ion battery.
• Solid electrolyte Due to its high lithium ion conductivity, the solid electrolyte is particularly suitable and, due to its phase purity and low iron content, particularly stable and also resistant to short circuits.
• the cathode of the invention In preferred embodiments of the present invention, the cathode of the invention
• doped lithium transition metal phosphate as a cathode, wherein the transition metal of the lithium transition metal phosphate is selected from Fe, Co, Ni, Mn, Cr and Cu. Particularly preferred is doped or undoped
• Lithium iron phosphate LiFePC Lithium iron phosphate LiFePC.
• the cathode material additionally contains a doped or non-doped mixed different from the lithium transition metal phosphate used
• Lithium transition metal oxo compound Lithium transition metal oxo compound.
• Lithium transition metal oxo compounds which are suitable according to the invention are, for example, LiMn 2 O 4 ,
• NCA LiNi 1.
• X _ y Co x Al y 0 2 eg LiNi 0 , 8Coo, i5 lo, o50 2
• NCM LiNii / 3Coi / 3M i / 30 2 .
• Lithium transition metal phosphate in such a combination is in the range of 1 to 60% by weight. Preferred proportions are, for example, 6-25 wt .-%, preferably 8-12 wt .-% at a LiCo0 2 / LiFeP0 4 mixture and 25-60 wt% in a LiNi0 2 / LiFeP0 4 mixture.
• the anode material of the secondary lithium ion battery of the invention contains a doped or not
• Li 4 Ti 5 0i 2 typically doped or undoped Li 4 Ti 5 0i 2 , so that, for example, a potential of 2 volts over the
• preferred cathode can be achieved from lithium transition metal phosphate.
• Doping is carried out with at least one other metal or with several, which in particular to an increased
• Preferred as a doping material are metal ions such as Al, B, Mg, Ga, Fe, Co, Sc, Y, Mn, Ni, Cr, V, Sb, Bi, Nb or more of these ions, which in the lattice structure of the cathode or anode material
• the lithium titanates are usually preferably rutile-free and thus also phase-pure.
• the doping metal cations are in the aforementioned
• Lithium transition metal phosphates or lithium titanates in an amount of 0.05 to 3 wt .-%, preferably 1 to 3 wt .-% based on the total mixed lithium transition metal phosphate or lithium titanate present. Based on the
• Transition metal (indicated in at%) or in the case of
• Lithium titanate based on lithium and / or titanium is the amount of doping metal cation (s) up to 20 at%, preferably 5-10 at%.
• the doping metal cations either occupy the lattice sites of the metal or of the lithium. Exceptions to this are mixed Fe, Co, Mn, Ni, Cr, Cu, lithium transition metal phosphates containing at least two of the aforementioned elements, in which larger amounts of doping metal cations may be present, in extreme cases up to 50 wt .-%.
• secondary lithium ion battery are in addition to the active material, that is, the lithium transition metal phosphate or the lithium titanate still Leitruße and a binder.
• Binder such as polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVDF), polyvinylidene difluoride hexafluoropropylene copolymers (PVDF-HFP), ethylene propylene terpolymers (EPDM), tetrafluoroethylene-hexafluoropropylene copolymers, polyethylene oxides (PEO), can be used here as binders.
• PTFE polytetrafluoroethylene
• PVDF polyvinylidene difluoride
• PVDF-HFP polyvinylidene difluoride hexafluoropropylene copolymers
• EPDM ethylene propylene terpolymers
• PEO polyethylene oxides
• PAN Polyacrylonitriles
• PMMA polyacrylmethacrylates
• CMC carboxymethylcelluloses
• Electrode material in the context of the present invention are preferably 80 to 98 parts by weight of active composition
• Electrode material 10 to 1 parts by weight lead carbon and 10 to 1 parts by weight binder.
• preferred cathodes / solid electrolyte / anode combinations 10 to 1 parts by weight lead carbon and 10 to 1 parts by weight binder.
• Fig. 1 shows the structure of the phase-pure according to the invention
• Lithium aluminum titanium phosphate Lithium aluminum titanium phosphate
• Fig. 2 is an XRD spectrum of an inventive
• Lithium aluminum titanium phosphate Lithium aluminum titanium phosphate
• Lithium aluminum titanium phosphate Lithium aluminum titanium phosphate
• Lithium aluminum titanium phosphate Lithium aluminum titanium phosphate
• the BET surface area was determined according to DIN 66131. (DIN-ISO 9277)
• the particle size distribution was determined by means of laser granulometry with a Malvern Mastersizer 2000 device in accordance with DIN 66133.
• X-ray powder diffraction was measured with an X 'Pert PRO diffractometer, PANalytical: goniometer theta / theta, Cu anode PW 3376 (maximum power 2.2kW), detector X'Celerator, X' Pert software.
• the content of magnetic constituents in the lithium aluminum titanium phosphate according to the invention is determined by separation by means of magnets and subsequent acid digestion and with
• the lithium aluminum titanium phosphate powder to be tested is placed in ethanolic suspension and a magnet of a defined size (diameter 1.7 cm, length 5.5 cm ⁇ 6000 gauss).
• the ethanolic suspension is in a
• the magnetic impurities are solubilized by acid digestion and analyzed by ICP (Ion Chromatography) analysis to determine the exact amount and composition of the magnetic impurities.
• ICP Ion Chromatography
• the device for ICP analysis was an ICP EOS, Varian Vista Pro 720-ES.
• the finely ground premix was within six
• X-ray diffractogram (XRD spectrum) can be detected. Subsequently, the product was sintered at 900 ° C for six hours and then finely ground in a ball mill with porcelain balls.
• the comparative example prepared had an amount of 2.79 ppm and of magnetic iron or
• the three-dimensional Li + channels of the crystal structure and a simultaneously very low activation energy of 0.30 eV for the Li migration in these channels cause a high
• Li1.3Alo.3Ti1.7 (P0 4 ) 3 is the solid state electrolyte with the highest Li + ion conductivity known from the literature.
• FIG. 3 shows a comparison in comparison

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• 2009
  • 2009-10-16 DE DE102009049694A patent/DE102009049694A1/de not_active Ceased
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