Process for producing an electrode material for a rechargeable lithium battery, an electrode structural body for a rechargeable lithium battery, process for producing said electrode structural body, a rechargeable lithium battery in which said electrode structural body is used, and a process for producing said rechargeable lithium battery

Abstract

A process for producing an electrode material for a rechargeable lithium battery, comprising the steps of mixing a metal compound (a) of a metal (a′) capable of being electrochemically alloyed with lithium, a transition metal compound (b) of a transition metal (b′) and a complexing agent (c) with a solvent (d) to obtain a mixed solution, mixing a reducing agent (e) with said mixed solution to obtain a mixture, and oxidizing said reducing agent in said mixture to reduce ion of said metal (a′) and ion of said transition metal (b′) to obtain an amorphous alloy material capable of being electrochemically alloyed with lithium as said electrode material. An electrode structural body in which said electrode material is used, and a rechargeable lithium battery in which said electrode material is used.

1 - 80 . (canceled)  
     
     
         81 . A rechargeable lithium battery comprising at least an anode, a cathode, and an electrolyte and in which oxidation-reduction reaction of lithium is used, characterized in that said anode comprises an electrode structural body comprising: 
 a collector comprising a material incapable of being alloyed with lithium in an electrochemical reaction; and    an electrode material for a rechargeable lithium battery, produced by a process in which an oxidation-reduction reaction is used, said process comprising the steps of:    (1) mixing at least one kind of a metal compound (a) selected from the group consisting of metal salts of a metal (a′) and metal complexes of a metal (a′), at least one kind of a transition metal compound (b) selected from the group consisting of transition metal salts of a transition metal (b′) and transition metal complexes of a transition metal (b′), and a complexing agent (c) with a solvent (d) to obtain a mixed solution, said metal (a′) being capable of being electrochemically alloyed with lithium,    (2) mixing a reducing agent (e) with said mixed solution to obtain a mixture with a pH of less than 2, and    (3) oxidizing said reducing agent (e) contained in said mixture obtained in said step (2) to reduce an ion of said metal (a′) and an ion of said transition metal (b′), both of which are contained in said mixture obtained in step (2), by adding an alkali to said mixture obtained in said step (2) so that the pH value of said mixture obtained in step (2) is changed from less than 2 to a value in a range of from 3 to 12, whereby an amorphous alloy material capable of being electrochemically alloyed with lithium as said electrode material is obtained.    
     
     
         82 . A rechargeable lithium battery according to  claim 81 , wherein a layer comprising said electrode material is formed on said collector.  
     
     
         83 . A rechargeable lithium battery according to  claim 81 , wherein a layer comprising said electrode material and a binder is formed on said collector.  
     
     
         84 . A rechargeable lithium battery according to  claim 83 , wherein said binder comprises a water-soluble organic polymer material.  
     
     
         85 . A rechargeable lithium battery according to  claim 81 , wherein a layer comprising said electrode material, an electrically conductive auxiliary, and a binder is formed on said collector.  
     
     
         86 . A rechargeable lithium battery according to  claim 85 , wherein said binder comprises a water-soluble organic polymer material.  
     
     
         87 . A rechargeable lithium battery according to  claim 81 , wherein said cathode comprises a lithium-containing electrode material.  
     
     
         88 . A rechargeable lithium battery according to  claim 81 , wherein said amorphous alloy material is a powdery amorphous alloy material containing an amorphous metallic material.  
     
     
         89 . A rechargeable lithium battery according to  claim 88 , wherein said powdery amorphous alloy material has a main peak having a half width of more than 0.2° in X-ray diffraction using Kα-rays of Cu as a radiation source.  
     
     
         90 . A rechargeable lithium battery according to  claim 88 , wherein said powdery amorphous alloy material has a main peak having a half width of more than 0.5° in X-ray diffraction using Kα-rays of Cu as a radiation source.  
     
     
         91 . A rechargeable lithium battery according to  claim 88 , wherein said powdery amorphous alloy material has a peak appeared in a range of 2θ=25° to 50° in X-ray diffraction using Kα-rays of Cu as a radiation source, having a half width of more than 0.2°.  
     
     
         92 . A rechargeable lithium battery according to  claim 88 , wherein said powdery amorphous alloy material has a peak appeared in a range of 2θ25° to 50° in X-ray diffraction using Kα-rays of Cu as a radiation source having a half width of more than 0.5°.  
     
     
         93 . A rechargeable lithium battery according to  claim 88 , wherein said powdery amorphous alloy material has a crystallite size calculated from X-ray diffraction analysis, which is less than 50 nm.  
     
     
         94 . A rechargeable lithium battery according to  claim 88 , wherein said powdery amorphous alloy material has a crystallite size calculated from X-ray diffraction analysis, which is less than 20 nm.  
     
     
         95 . A rechargeable lithium battery according to  claim 81 , wherein said metal (a′) comprises at least one kind of a metal selected from the group consisting of Bi, In, Pb, Si, Ag, Sr, Ge, Zn, Sn, Cd, Sb, Tl, and Hg.  
     
     
         96 . A rechargeable lithium battery according to  claim 81 , wherein said metal (a′) comprises at least one kind of a metal selected from the group consisting of Bi, In, Pb, Zn, Sn, Sb and Tl.  
     
     
         97 . A rechargeable lithium battery according to  claim 81 , wherein said metal (a′) substantially comprises Sn.  
     
     
         98 . A rechargeable lithium battery according to  claim 97 , wherein said amorphous alloy material contains an amorphous Sn.A.X alloy with a substantially non-stoichiometric ratio composition, with A being at least one kind of a transition metal element, and X being at least one kind of an element selected from the group consisting of B, C, N, O, P, and S, where the element X is not always necessary to be contained, and said amorphous Sn.A.X alloy has a relationship of Sn/(Sn+A+X)=20 to 80 atomic percent in terms of the atom number of each element.  
     
     
         99 . A rechargeable lithium battery according to  claim 81 , wherein said transition metal (b′) comprises at least one kind of a transition metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Ti, V, Y, Sc, Zr, Nb, Hf, Ta, and W.  
     
     
         100 . A rechargeable lithium battery according to  claim 81 , wherein said transition metal (b′) comprises at least one kind of a transition metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au.  
     
     
         101 . A rechargeable lithium battery according to  claim 81 , wherein said transition metal (b′) comprises at least one kind of a transition metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, and Cu.  
     
     
         102 . A rechargeable lithium battery according to  claim 98 , wherein said amorphous alloy material has a peak appeared in a range of 2θ=25° to 50° in X-ray diffraction using Kα-rays of Cu as a radiation source, having a half width of more than 0.2°.  
     
     
         103 . A rechargeable lithium battery according to  claim 98 , wherein said amorphous alloy material has a peak appeared in a range of 2θ=25° to 50° in X-ray diffraction using Kα-rays of Cu as a radiation source, having a half width of more than 0.5°.  
     
     
         104 . A rechargeable lithium battery according to  claim 98 , wherein said amorphous alloy material has a crystallite size calculated from X-ray diffraction analysis, which is less than 50 nm.  
     
     
         105 . A rechargeable lithium battery according to  claim 98 , wherein said amorphous alloy material has a crystallite size calculated from X-ray diffraction analysis, which is less than 20 nm.  
     
     
         106 . A rechargeable lithium battery according to  claim 81 , wherein said amorphous alloy material has an average particle size in a range of from 0.1 to 2 μm.  
     
     
         107 . A rechargeable lithium battery according to  claim 81 , wherein said amorphous alloy material has an average particle size in a range of from 0.1 to 1 μm.  
     
     
         108 . A rechargeable lithium battery according to  claim 106 , wherein said amorphous alloy material has a particle size distribution in a range of from 0.01 to 20 μm.  
     
     
         109 . A rechargeable lithium battery according to  claim 106 , wherein said amorphous alloy material has a particle size distribution in a range of from 0.05 to 1 μm.  
     
     
         110 . A rechargeable lithium battery according to  claim 106 , wherein said amorphous alloy material has an average value of (longest length of particle)/(shortest length of particle), which is in a range of from 1.0 to 2.0.  
     
     
         111 . A rechargeable lithium battery according to  claim 106 , wherein said amorphous alloy material has an average value of (longest length of particle)/(shortest length of particle), which is in a range of from 1.0 to 1.5.  
     
     
         112 . A rechargeable lithium battery according to  claim 81 , wherein said amorphous alloy material has a specific surface area of more than 10 m 2 /g.  
     
     
         113 . A rechargeable lithium battery according to  claim 81 , wherein said amorphous alloy material has a specific surface area of more than  30  m 2 /g.  
     
     
         114 . A rechargeable lithium battery according to  claim 81 , wherein said metal compound (a) is soluble in said solvent (d).  
     
     
         115 . A rechargeable lithium battery according to  claim 81 , wherein said metal compound (a) comprises at least one kind of a metal salt selected from a group consisting of chlorides, sulfates and nitrates of said metal (a′).  
     
     
         116 . A rechargeable lithium battery according to  claim 81 , wherein said metal compound (a) comprises at least one kind of a metal salt selected from a group consisting of chlorides, sulfates and nitrates of Sn.  
     
     
         117 . A rechargeable lithium battery according to  claim 81 , wherein said transition metal compound (b) is soluble in said solvent (d).  
     
     
         118 . A rechargeable lithium battery according to  claim 81 , wherein said transition metal compound (b) comprises at least one kind of a metal salt selected from the group consisting of chlorides, sulfates and nitrates of said transition metal (b′).  
     
     
         119 . A rechargeable lithium battery according to  claim 81 , wherein said complexing agent (c) comprises at least one kind of a compound selected from a group consisting of organic carboxylic acids and amines.  
     
     
         120 . A rechargeable lithium battery according to  claim 119 , wherein said complexing agent (c) comprises at least one kind of a compound selected from the group consisting of citric acids, ethylenedianminetetraacetic acid, and salts thereof.  
     
     
         121 . A rechargeable lithium battery according to  claim 81 , wherein said reducing agent (e) comprises a material having an electrode potential which is inferior by more than 0.1 V to that of said metal (a′) or said transition metal (b′) which is the lowest.  
     
     
         122 . A rechargeable lithium battery according to  claim 81 , wherein said reducing agent (e) comprises a material having an electrode potential which is inferior by more than 0.2 V to that of said metal (a′) or said transition metal (b′) which is the lowest.  
     
     
         123 . A rechargeable lithium battery according to  claim 81 , wherein said reducing agent (e) comprises a material having a property that an aqueous solution of said material maintained at 25° C. exhibits a normal electrode potential al of less than −0.2 V.  
     
     
         124 . A rechargeable lithium battery according to  claim 81 , wherein said reducing agent (e) comprises a material having a property that an aqueous solution of said material maintained at 25° C. exhibits a normal electrode potential of less than −0.5 V.  
     
     
         125 . A rechargeable lithium battery according to  claim 81 , wherein said reducing agent (e) comprises at least one kind of a compound selected from the group consisting of lower oxygen compounds selected from the group consisting of hypophosphorous acid, phosphorous acid, sulfurous acid, thiosulfuric acid, and dithionous acid; salts of these compounds; metal salts in the low valence state of Fe (II), Ti (III) and Cr (II); organic compounds selected from the group consisting of formaldehyde, formic acid, and oxalic acid; and salts of these organic compounds.  
     
     
         126 . A rechargeable lithium battery according to  claim 81 , wherein said reducing agent (e) is soluble in said solvent (d).  
     
     
         127 . A rechargeable lithium battery according to  claim 81 , wherein said solvent (d) comprises at least one kind of a solvent selected from the group consisting of water and polar solvents.  
     
     
         128 . A rechargeable lithium battery according to  claim 81 , wherein said polar solvent includes alcohol, ester compounds, amide compounds, nitrile compounds, amine compounds, halogen compounds, sulfur compounds, liquid ammonia, and glacial acetic acid.  
     
     
         129 . A rechargeable lithium battery according to  claim 81 , wherein said solvent comprises at least one kind of a solvent selected from a group consisting of water and alcohols.  
     
     
         130 . A rechargeable lithium battery according to  claim 81 , wherein said mixed solution obtained in said step (1) contains a complex formed by said metal (a′) and said complexing agent (c).  
     
     
         131 . A rechargeable lithium battery according to  claim 81 , wherein said mixed solution obtained in said step (1) contains a complex formed by said transition metal (b′) and said complexing agent (c).  
     
     
         132 . A rechargeable lithium battery according to  claim 81 , wherein the step (2) of mixing the reducing agent (e) with the mixed solution obtained in the step (1) is performed under condition with a temperature of −10 to 100° C.  
     
     
         133 . A rechargeable lithium battery according to  claim 81 , wherein the step (2) of mixing the reducing agent (e) with the mixed solution obtained in the step (1) is performed under condition with a temperature of 10 to 90° C.  
     
     
         134 . A rechargeable lithium battery according to  claim 81 , wherein the step (3) of oxidizing the reducing agent (e) contained in the mixture obtained in the step (2) is performed under condition with a temperature of −10 to 100° C.  
     
     
         135 . A rechargeable lithium battery according to  claim 81 , wherein the step (3) of oxidizing the reducing agent (e) contained in the mixture obtained in the step (2) is performed under condition with a temperature of 10 to 90° C.  
     
     
         136 . A rechargeable lithium battery according to  claim 81 , wherein the addition of said alkali in the step (3) is performed so that the pH value of the mixture is changed from less than 2 to a value in at range of from 5 to 10.  
     
     
         137 . A rechargeable lithium battery according to  claim 81 , wherein the alkali comprises at least one kind of a compound selected from the group consisting of hydroxides of alkali metals, hydroxides of alkaline earth metals, amines, and ammonia.  
     
     
         138 . A rechargeable lithium battery according to  claim 81 , wherein the step (2) is performed in an atmosphere comprising at least one kind of a gas selected from the group consisting of hydrogen gas, nitrogen gas, and inert gas selected from the group consisting of argon gas and helium gas.  
     
     
         139 . A rechargeable lithium battery according to  claim 81 , wherein the step (3) is performed in an atmosphere comprising at least one kind of a gas selected from the group consisting of hydrogen gas, nitrogen gas, and inert gas selected from the group consisting of argon gas and helium gas.  
     
     
         140 . A rechargeable lithium battery according to  claim 81 , wherein the metal compound (a) and the transition metal compound (b) are used respectively in such an amount that (the number of moles of the metal (a′) in the metal compound (a))/(the number of moles of the transition metal (b′) in the transition metal compound (b)) falls in a range of from 0.1 to 10.  
     
     
         141 . A rechargeable lithium battery according to  claim 81 , wherein the metal compound (a) and the transition metal compound (b) are used respectively in such an amount that (the number of moles of the metal (a′) in the metal compound (a))/(the number of moles of the transition metal (b′) in the transition metal compound (b)) falls in a range of from 0.2 to 5.  
     
     
         142 . A rechargeable lithium battery according to  claim 81 , wherein the complexing agent (c) is used in such an amount that (the number of moles of the complexing agent (c))/(the number of moles of the metal compound (a)+the number of moles of the transition metal compound (b)) falls in a range of from 1 to 5.  
     
     
         143 . A rechargeable lithium battery according to  claim 81 , wherein the completing agent (c) is used in such an amount that (the number of moles of the complexing agent (c))/(the number of moles of the metal compound (a)+the number of moles of the transition metal compound (b)) falls in a range of from 2 to 5.  
     
     
         144 . A rechargeable lithium battery according to  claim 81 , wherein the reducing agent (e) is used in an amount which is 1 to 3 times versus the sum of the equivalence point of the metal compound (a) and that of the transition metal compound (b).  
     
     
         145 . A rechargeable lithium battery according to  claim 81 , wherein the reducing agent (e) is used in an amount which is 1 to 2 times versus the sum of the equivalence point of the metal compound (a) and that of the transition metal compound (b).  
     
     
         146 . A rechargeable lithium battery according to  claim 81 , which further includes a step of washing said amorphous alloy material.  
     
     
         147 . A rechargeable lithium battery according to  claim 81 , which further includes a step of drying said amorphous alloy material.  
     
     
         148 . A rechargeable lithium battery according to  claim 81 , which further includes a step of grinding said amorphous alloy material.