Particles with a large surface coated with an intercalation material, method for the production thereof and use of the particles in hybrid electrodes and high capacity double layer capacitors and quick batteries

• Main Authors: UEBE, JOCHEN, GUNTOW, UWE, ANFIMOVAITE, VILIJA, KAPUSCHINSKI, MARTINA
• Format: Patent
• Language: English; French; German
• Published: 25.06.2014
• Subjects: BASIC ELECTRIC ELEMENTS; CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES ORLIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE; CHEMISTRY; COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSESC01D OR C01F; COMPOUNDS THEREOF; ELECTRICITY; INORGANIC CHEMISTRY; METALLURGY; NON-METALLIC ELEMENTS; PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSIONOF CHEMICAL INTO ELECTRICAL ENERGY

Producing a first particulate hybrid material in a negative electrode of lithium batteries and -accumulators, comprises (a) mixing a water- or alcohol-soluble titanium compound, at least one acetate compound or ion M, an organic diol, lithium hydroxide, at least one hydroxides or the ion A with a solvent and/or suspending agents, (b) adding carbon particles to the solution of step (a), (c) treating the resulting suspension in an autoclave, (d) depressurizing the autoclave, (e) separating the resulting particles from the solvent, (f) drying the particles, and (g) tempering the particles. Producing a first particulate hybrid material in a negative electrode of lithium batteries and -accumulators, comprises particles with a basic back bone made of carbon, which is provided with a phase-pure coating made of lithium-titanium alloy of formula (Li 4 - yA yTi 5 - xM xO 1 2) (I), comprises (a) mixing a water- or alcohol-soluble titanium compound, at least one acetate compound or ion M (in which x is not equal to 0), an organic diol, lithium hydroxide, at least one hydroxides of the ion A (in which x is not equal to 0) with a solvent and/or suspending agents comprising 1-5C alcohols and/or water and adding water, (b) adding carbon particles to the solution of step (a), which exhibits a surface area of at least 1000 m 2>g -> 1>, (c) treating the resulting suspension in an autoclave at over 100[deg] C for many hours, (d) depressurizing the autoclave, cooling the mixture, (e) separating the resulting particles from the solvent, (f) drying the particles at an elevated temperature, and (g) tempering the particles at temperatures up to 500[deg] C in air and/or up to 600[deg] C under an inert gas, preferably nitrogen or argon. The solvent does not comprise water. The solution of the step (a) is insoluble in the solvent. A : 1/2Mg,1/2Ca and/or 1/3Al; M : 4/aGe, Co, Fe, Co, Ni, Mn, Cr, Zr, Mo, V and/or Ta; A : oxidation number of transition metal ion; x : 0 or greater than 0 to 4; and y : 0 or greater than 0 to 3. Independent claims are also included for: (1) producing a second particulate hybrid material in a positive electrode of lithium batteries and -accumulators having particles with basic back bone made of carbon, which is provided with a phase-pure coating made of lithium-titanium alloy of formula (Li 1 - yA1 y 1Fe 1 - x 1B 1 x 1PO 4) (II), comprising (a1) mixing phosphoric acid, at least one hydroxide or ion A1 (x1 is not equal to 0), at least one hydroxide or sulfates or cation (B1) (y1 = is not equal to 0), lithium hydroxide iron (II) sulfate, an antioxidant, a complexing agent in an aqueous solution and/or suspension agents comprising water or aqueous 1-5C alcohol, (b1) adding carbon particles to the solution of step (a1), which exhibits a surface area of at least 1000 m 2>g -> 1>, (c1) treating the resulting suspension in the step (b1) in an autoclave at over 100[deg] C for many hours, (d1) depressurizing the autoclave, cooling the mixture, (e1) separating the resulting particles from the solvent, and (f1) drying the particles, where the solvent does not comprise water; (2) the first particulate hybrid material; and (3) using the first particulate hybrid material in a positive or negative electrode material comprising a binder and optionally carbon black. A1 : alkali metal ion, 1/2 alkaline earth metal ion or 1/3 ion comprising La, Ce, Gd, Pr, Nd, Sm or E; B1 : cation comprising 2/a1 Ni, Mn, V, Co, Sn, Ti, Cr, Cu, Sr, Ca, Ba and/or Zn; A : oxidation number of transition metal ion; x1 : 0 or greater than 0 to 0.8; y1 : 0 or greater than 0 to 1; a : oxidation number of transition metal; and a1 : oxidation number of cation B1. Die Erfindung betrifft ein Verfahren zum Herstellen eines partikelförmigen Hybridmaterials zum Einsatz in der negativen Elektrode von Lithiumbatterien und -akkumulatoren, umfassend Teilchen mit einem Grundgerüst aus Kohlenstoff, die mit einer phasenreinen Beschichtung aus Li 4-y A y Ti 5-x M x O 12 , versehen sind, worin das Ion A ausgewählt ist unter ½ Mg, ½ Ca, 1/3 Al oder Mischungen davon, das Übergangsmetallion M ausgewählt ist unter 4/a Ge, Co, Fe, Co, Ni, Mn, Cr, Zr, Mo, V, Ta oder Mischungen davon, wobei a die Oxidationszahl des Übergangsmetallions bedeutet, x 0 oder eine beliebige Zahl von >0 bis 4 ist und y 0 oder eine ungerade oder gerade Zahl von >0 bis 3 bedeutet, oder Teilchen mit einem Grundgerüst aus Kohlenstoff, die mit einer phasenreinen Beschichtung aus Li 1-y A y Fe 1-x B x PO 4 , versehen sind, worin A ein Alkaliion, ½ Erdalkalimetallion oder 1/3 Ion, ausgewählt unter den Ionen der Lanthaniden La, Ce, Gd, Pr, Nd, Sm, Er ist, B ein Kation ist, ausgewählt unter 2/a Ni, Mn, V, Co, Sn, Ti, Cr, Cu, Sr, Ca, Ba, Zn und Mischungen davon, wobei a die Oxidationszahl des Kations B bedeutet, und x von 0 oder eine beliebige Zahl von >0 bis 0,8 und y von 0 oder eine beliebige Zahl von >0 bis 1 bedeuten, wobei die Herstellung durch Solvothermal-Synthese in Gegenwart eines Komplexbildners erfolgt, bei dem es sich im ersten Falle um ein Diol handelt.