Patent EP-2746220-A2 (EP)
Inventor: GUNTOW UWE
IPC: H01M4/36
Filed: 2013-12-20
Abstract: 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.