Process for manufacture of negative electrode material for a non-aqueous electrolyte secondary battery
View Patent ↗A negative electrode material for a nonaqueous electrolyte secondary battery having a high discharge capacity and a good cycle life is made from alloy particles having an average particle diameter of 0.1-50 μm and including Si phase grains 40 and a phase of a solid solution or an intermetallic compound of Si and other element selected from Group 2A elements, transition elements, Group 3B elements, and Group 4B elements from the long form periodic table (for example, an NiSi 2 phase 42 and an [NiSi 2 +NiSi] phase 41 ) at least partially enveloping the Si phase grains. 5-99 wt % of this material is Si phase grains. The alloy particles can be manufactured by rapid solidification (such as atomization or roller quenching) of a melt including Si and the other element, or by adhering the other element to Si powder by electroless plating or mechanical alloying and then performing heat treatment. Even if rapid solidification is carried out, a negative electrode material having a good discharge capacity and cycle life is obtained without heat treatment.
1. A process for manufacturing a negative electrode material for a nonaqueous electrolyte secondary battery, which is made from alloy particles of a structure comprising one or more Si phase grains at least partially enveloped in a phase consisting essentially of an Si-containing solid solution or Si-containing intermetallic compound, the process comprising solidifying a melt of raw materials for the alloy particles by cooling so as to obtain a cooling rate of at least 100° C. per second and forming said alloy particles of a structure comprising one or more Si phase grains at least partially enveloped in a phase of a Si-containing solid solution or Si-containing intermetallic compound.
2. A process of manufacturing a negative electrode material for a nonaqueous electrolyte secondary battery as claimed in claim 1 , wherein the cooling at a rate of at least 100° C. per second is carried out by a method selected from the group consisting of the atomization method, the roller quenching method, and the rotating electrode method.
3. A process of manufacturing a negative electrode material for a nonaqueous electrolyte secondary battery as claimed in claim 1 , further including subjecting the alloy to heat treatment at a temperature at least 10° C. below the solidus temperature of the Si-containing solid solution or Si-containing intermetallic compound.
4. A process of manufacturing a negative electrode material for a nonaqueous electrolyte secondary battery as claimed in claim 1 , wherein the cooling rate is at least 1000° C. per second.
5. A process of manufacturing a negative electrode material for a nonaqueous electrolyte secondary battery as claimed in claim 1 , wherein the negative electrode material which is manufactured contains at least 5 wt. % and at most 99 wt. % of Si phase grains, and the average particle diameter of the alloy particles is at least 0.1 μm and at most 50 μm.
6. A process of manufacturing a negative electrode material for a nonaqueous electrolyte secondary battery as claimed in claim 1 , wherein the Si-containing solid solution or intermetallic compound is made from Si and at least one element selected from the group consisting of Group 2A elements, transition elements, Group 3B elements and Group 4B elements other than Si from the long form periodic table.
7. A nonaqueous electrolyte secondary battery equipped with a nonaqueous electrolyte and positive and negative electrodes which can reversibly occlude and release lithium, wherein the negative electrode is a negative electrode containing a negative electrode material manufactured by the process of claim 1 .
8. A process for manufacturing a negative electrode material for a nonaqueous electrolyte secondary battery, which is made from alloy particles of a structure comprising one or more Si phase grains at least partially enveloped in a phase consisting essentially of an Si-containing solid solution or Si-containing intermetallic compound, the process comprising forming an adhering layer of a material by a mechanical alloying method which contains an element capable of forming a solid solution or an intermetallic compound with Si, on the surface of a powder of metallic Si or an alloy having an Si phase, and subjecting the powder having the adhering layer to heat treatment at a temperature at least 10° C. below the solidus temperature of the solid solution or the intermetallic compound to convert the material forming the adhering layer to form an Si-containing solid solution or Si-containing intermetallic compound.
9. A process of manufacturing a negative electrode material for a nonaqueous electrolyte secondary battery as claimed in claim 8 , wherein the negative electrode material which is manufactured contains at least 5 wt. % and at most 99 wt. % of Si phase grains, and the average particle diameter of the alloy particles is at least 0.1 μm and at most 50 μm.
10. A process of manufacturing a negative electrode material for a nonaqueous electrolyte secondary battery as claimed in claim 8 , wherein the Si-containing solid solution or intermetallic compound is made from Si and at least one element selected from the group consisting of Group 2A elements, transition elements, Group 3B elements, and Group 4B elements other than Si from the long form periodic table.
11. A nonaqueous electrolyte secondary battery equipped with a nonaqueous electrolyte and positive and negative electrodes which can reversibly occlude and release lithium, wherein the negative electrode is a negative electrode containing a negative electrode material manufactured by the process of claim 8 .
12. A process of manufacturing a negative electrode for a nonaqueous electrolyte secondary battery, comprising adhering a powder of metallic Si or of an alloy containing an Si phase on a negative electrode substrate to form a powder layer on the substrate, plating the powder layer with a material comprising an element capable of forming a solid solution or intermetallic compound with Si, and thereafter performing heat treatment at a temperature at least 10° C. below the solidus temperature of the solid solution or intermetallic compound so as to convert the plating to form an Si-containing solid solution or Si-containing intermetallic compound.
13. A process of manufacturing a negative electrode for a nonaqueous electrolyte secondary battery as claimed in claim 12 , wherein the Si-containing solid solution or intermetallic compound is made from Si and at least one element selected from the group consisting of Group 2A elements, transition elements, Group 3B elements, and Group 4B elements other than Si from the long form periodic table.
14. A nonaqueous electrolyte secondary battery equipped with a nonaqueous electrolyte and positive and negative electrodes which can reversibly occlude and release lithium, wherein the negative electrode is a negative electrode manufactured by the process of claim 12 .
15. A process of manufacturing a negative electrode material for a nonaqueous electrolyte secondary battery as claimed in claim 8 , wherein the heat treatment is a diffusion heat treatment at a temperature no greater than at least 10° C. below the solidus temperature of the solid solution or the intermetallic compound.
16. A process of manufacturing a negative electrode for a nonaqueous electrolyte secondary battery as claimed in claim 12 , wherein the heat treatment is a diffusion heat treatment at a temperature no greater than at least 10° C. below the solidus temperature of the solid solution or the intermetallic compound.