JP5877025B2 - Porous silicon composite particles and method for producing the same - Google Patents

Porous silicon composite particles and method for producing the same Download PDF

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JP5877025B2
JP5877025B2 JP2011195751A JP2011195751A JP5877025B2 JP 5877025 B2 JP5877025 B2 JP 5877025B2 JP 2011195751 A JP2011195751 A JP 2011195751A JP 2011195751 A JP2011195751 A JP 2011195751A JP 5877025 B2 JP5877025 B2 JP 5877025B2
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intermediate alloy
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JP2012082126A (en
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吉田 浩一
浩一 吉田
三好 一富
一富 三好
久留須 一彦
一彦 久留須
俊夫 谷
俊夫 谷
耕二 幡谷
耕二 幡谷
西村 健
健 西村
秀実 加藤
秀実 加藤
武 和田
武 和田
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古河電気工業株式会社
株式会社 東北テクノアーチ
株式会社 東北テクノアーチ
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Description

  The present invention relates to porous silicon composite particles used for negative electrodes for lithium ion batteries and the like.

  Conventionally, lithium ion batteries using various carbon materials such as natural graphite, artificial graphite, amorphous carbon, and mesophase carbon, lithium titanate, tin alloy and the like as a negative electrode active material have been put into practical use. Also, a negative electrode is formed by kneading a negative electrode active material, a conductive aid such as carbon black, and a resin binder to prepare a slurry, and applying and drying on a copper foil. Yes.

  On the other hand, negative electrodes for lithium ion batteries using metals and alloys having a large theoretical capacity as lithium compounds, particularly silicon and alloys thereof as negative electrode active materials, have been developed with the aim of increasing the capacity. However, since the volume of silicon that occludes lithium ions expands to about 4 times that of silicon before occlusion, a negative electrode using silicon as a negative electrode active material repeats expansion and contraction during a charge / discharge cycle. For this reason, the negative electrode active material is peeled off, and there is a problem that the lifetime is extremely short compared to a negative electrode made of a conventional carbon-based active material.

As a conventional manufacturing method of a negative electrode using silicon, a technique of using silicon as a negative electrode material for a lithium battery by mechanically pulverizing silicon to a size of several micrometers and applying a conductive material thereto (for example, patent document) 1) is known.
In addition, as a conventional manufacturing method of a negative electrode using silicon, a method of forming a groove such as a slit by anodizing a silicon substrate, a method of crystallizing fine silicon in a ribbon-shaped bulk metal (for example, , See Patent Document 2).
In addition, polymer particles such as polystyrene and PMMA are deposited on a conductive substrate, a metal alloying with lithium is plated on the conductive substrate, and then the polymer particles are removed to remove a porous metal (porous) A technique (see, for example, Patent Document 3) for producing a material is also known.
Furthermore, a technique (for example, see Patent Documents 4 and 5) in which a material corresponding to a Si intermediate alloy which is an intermediate product of the present invention is used as a negative electrode material for a lithium battery is known.
In addition, a technique (for example, see Patent Document 6) in which this is heat-treated and used as a negative electrode material for a lithium battery is known.
Further, in connection with this technique, there is a technique (see, for example, Patent Document 7) in which element M is completely eluted and removed with an acid or alkali from a Si alloy of element M and Si produced by applying a rapid solidification technique. Are known.
Further, a technique for etching metallic silicon with hydrofluoric acid or nitric acid (for example, Patent Documents 8 and 9) is also known.

JP 2008-135364 A Japanese Patent No. 4172443 JP 2006-260886 A JP 2000-149937 A JP 2004-362895 A JP 2009-032644 A Japanese Patent No. 3827642 US Application Publication No. 2006/0251561 US Application Publication No. 2009/0186267

  However, the technique of Patent Document 1 forms a negative electrode by applying and drying a slurry of a negative electrode active material, a conductive additive, and a binder. In such a conventional negative electrode, the negative electrode active material and the current collector are bound with a binder of a resin having low conductivity, and the amount of resin used must be minimized so that the internal resistance does not increase. There is a weak binding force. Since silicon has a large volume change at the time of charge / discharge, in the technique of Patent Document 1, the negative electrode active material is pulverized from the negative electrode active material and peeled off from the negative electrode active material, generation of cracks in the negative electrode, A decrease in conductivity between substances occurs, resulting in a decrease in capacity. Therefore, there are problems that the cycle characteristics are poor and the life of the secondary battery is short.

  In addition, the technique of Patent Document 2 is a single crystal having a size of several micrometers obtained by pulverizing single crystal silicon, and a plate or powder in which silicon atoms have a layered or three-dimensional network structure is used for the negative electrode. It is used as a substance. Furthermore, in order to impart conductivity, silicon compounds (silicon carbide, silicon cyanide, silicon nitride, silicon oxide, silicon boride, silicon borate, silicon boronitride, silicon oxynitride, silicon alkali metal) One or more of a silicon compound group consisting of an alloy, a silicon alkaline earth metal alloy, and a silicon transition metal alloy). However, since silicon has a large volume change at the time of charge / discharge, the negative electrode active material described in Patent Document 2 is a fine powder of the negative electrode active material and peeling of the negative electrode active material, generation of cracks in the negative electrode, A decrease in electrical conductivity between the active materials occurs and the capacity decreases. Therefore, there are problems that the cycle characteristics are poor and the life of the secondary battery is short. In particular, silicon, which is expected to be put to practical use as a negative electrode material, has a problem that cracking easily occurs and charge / discharge cycle characteristics are poor because the volume change during charge / discharge is large.

  In the technique of Patent Document 3, polymer particles such as polystyrene and PMMA are deposited on a conductive substrate, a metal alloying with lithium is applied thereto by plating, and then the polymer particles are removed. A metal porous body (porous body) can be produced. However, in producing a Si porous body, it is extremely difficult to plate Si on polymer particles such as polystyrene and PMMA, and there is a problem that it cannot be applied industrially.

  Further, the technique of Patent Document 4 cools and solidifies the raw material melt constituting the alloy particles so that the solidification rate is 100 ° C./second or more, and at least partially surrounds the Si phase grains. Forming a negative electrode material for a non-aqueous electrolyte secondary battery, comprising: forming an alloy containing a Si-containing solid solution or an intermetallic compound phase. However, in this method, when Li reacts, it is necessary to diffuse and move through the included Si-containing solid solution, the reactivity is poor, and further, the practical application from the point that the content of Si that can contribute to charge and discharge is small. Has not reached.

  In addition, the technique of Patent Document 5 discloses silicon containing silicon (the silicon content is 22% by mass or more and 60% by mass or less) and one or more metal elements of copper, nickel, and cobalt. It is composed of alloy powder. By synthesizing this by a single roll method or an atomizing method, pulverization based on volume change due to occlusion / release of lithium ions or the like is suppressed. However, in this method, when Li reacts, it is necessary to diffuse and move through the included Si-containing solid solution, the reactivity is poor, and further, the practical application from the point that the content of Si that can contribute to charge and discharge is small. Has not reached.

  The technique of Patent Document 6 is selected from Si, Co, Ni, Ag, Sn, Al, Fe, Zr, Cr, Cu, P, Bi, V, Mn, Nb, Mo, In, and rare earth elements. It includes a step of rapidly cooling a molten alloy containing one or more elements and obtaining a Si-based amorphous alloy and a step of heat-treating the obtained Si-based amorphous alloy. By heat-treating the Si-based amorphous alloy, fine crystalline Si nuclei of about several tens of nm to 300 nm are precipitated. However, in this method, when Li reacts, it is necessary to diffuse and move through the included Si-containing solid solution, the reactivity is poor, and further, the practical application from the point that the content of Si that can contribute to charge and discharge is small. Has not reached.

The technique of Patent Document 7 is applied when producing an amorphous ribbon or fine powder, and solidifies at a cooling rate of 10 4 K / second or more. In the solidification of a general alloy, dendrites in which secondary dendrite grows while primary dendrite grows are taken. A special alloy system (Cu-Mg system, Ni-Ti system, etc.) can form an amorphous metal at 10 4 K / second or more, but other systems (for example, Si-Ni system) have a cooling rate. Even when solidified at a rate of 10 4 K / sec or more, an amorphous metal cannot be obtained and a crystalline phase is formed. The size of the crystal when this crystal phase is formed follows the relationship between the cooling rate (R: K / sec) and the dendrite arm spacing (DAS: μm).
DAS = A × R B (generally A: 40 to 100, B: −0.3 to −0.4)
Therefore, in the case of having a crystal phase, for example, when A: 60 and B: −0.35, DAS becomes 1 μm at R: 10 4 K / sec. The crystal phase is equivalent to this size, and a fine crystal phase of 10 nm or the like cannot be obtained. For these reasons, it is not possible to obtain a porous material composed of a fine crystalline phase with this rapid solidification technique alone with materials such as Si—Ni.

In the techniques of Patent Documents 8 and 9, metal silicon is etched using hydrofluoric acid or nitric acid to form fine holes on the surface. However, even though the BET specific surface area is 140 to 400 m 2 / g, the vacancies formed by etching are not uniformly dispersed, and vacancies do not exist uniformly from the particle surface to the center. Therefore, with the volume expansion and contraction during charging / discharging, there has been a problem that pulverization progresses inside the particles and the life is short.

  The present invention has been made in view of the above-described problems, and its object is to achieve <1> high capacity and good cycle characteristics, and <2> a conductive path made of a silicon compound inside the porous body. To obtain porous silicon composite particles suitable for a negative electrode material for a lithium ion battery.

  As a result of intensive studies to achieve the above-mentioned object, the present inventor has obtained a fine porous material by spinodal decomposition of silicon alloy (precipitation of silicon in the molten metal from the silicon alloy) and dealloying (dealloying). It has been found that silicon can be obtained. Since silicon is precipitated in the molten metal from the silicon alloy in a high-temperature molten metal, the primary particle diameter and porosity are large in the surface layer portion and the inside of the porous silicon particles obtained by dealloying (dealloying). Distribution is unlikely to occur. On the other hand, for example, in etching with an acid, the concentration inside the particle is restricted in the diffusion of decomponent elements, so the porosity of the particle surface layer portion increases and the porosity inside the particle decreases. Depending on the conditions, a Si core having no pores remains in the center of the particle, and the coarse Si in the center is pulverized during the reaction with Li, resulting in poor cycle characteristics. The present invention has been made based on this finding.

That is, the following invention is provided.
(1) Porous silicon composite particles formed by bonding silicon fine particles and silicon compound particles, wherein the silicon compound particles are silicon, As, Ba, Ca, Ce, Co, Cr, Cu, Er, Fe. , Gd, Hf, Lu, Mg, Mn, Mo, Nb, Nd, Ni, Os, Pr, Pt, Pu, Re, Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Ti, Tm, U , V, W, Y, Yb, Zr, and a compound with one or more complex elements selected from the group consisting of Vr, W, Y, Yb, and Zr, and the average particle size of the porous silicon composite particles is 0.1 μm to 1000 μm The porous silicon composite particles, wherein the porous silicon composite particles have a three-dimensional network structure composed of continuous voids.
(2) The silicon fine particles have an average particle diameter or average column diameter of 2 nm to 2 μm, and the silicon fine particles are solid silicon fine particles containing 80 atomic% or more of silicon in a ratio of elements excluding oxygen. The porous silicon composite particle according to (1), which is characterized in that
(3) Solid silicon, wherein the silicon compound particles have an average particle size of 50 nm to 50 μm, and the silicon compound particles contain 50 to 90 atomic% of silicon in a ratio of elements excluding oxygen. The porous silicon composite particles according to (1) or (2), wherein the porous silicon composite particles are compound particles.
(4) The average particle diameter Ds of the silicon fine particles in the surface vicinity region of 50% or more in the radial direction of the porous silicon composite particles, and the particle internal region of 50% or less in the radial direction of the porous silicon composite particles The porous silicon composite according to any one of (1) to (3), wherein Ds / Di, which is the ratio of the average particle diameter Di of the silicon fine particles, is 0.5 to 1.5 particle.
(5) The porosity Xs of the region near the surface of 50% or more in the radial direction of the porous silicon composite particles and the porosity Xi of the particle internal region within 50% in the radial direction of the porous silicon composite particles. The porous silicon composite particle according to any one of (1) to (3), wherein the ratio Xs / Xi is 0.5 to 1.5.
(6) An alloy of silicon, one or more intermediate alloy elements listed in Table 1, and one or more complex elements listed in Table 1 below, wherein the ratio of the complex elements is 1 of the silicon. A silicon intermediate alloy that is ˜33 atomic%, the silicon content of the porous silicon composite is 10 atomic% or more, and is equal to or less than the maximum Si content in Table 1 corresponding to the intermediate alloy element contained A step (a) in which the silicon alloy particles are immersed in a melt of one or more melt elements corresponding to the intermediate alloy element in Table 1; A step (b) for separating the phase and a step (c) for removing the second phase, wherein the second phase is an alloy of the intermediate alloy element and the molten element and / or the molten element. Porous silica characterized by comprising Method of manufacturing the emission composite particles.
(7) In the step (a), silicon (X atom%), intermediate alloy element (Y atom%) and one or more complex elements (Z 1 , Z 2 , Z 3 ,... Atom%) However, the method for producing porous silicon composite particles according to (6), wherein a silicon intermediate alloy having a composition satisfying the following formula is prepared.
10 ≦ X <[maximum Si content] Formula (1)
10 ≦ a ÷ (a + Y) × 100 ≦ [maximum Si content] Formula (2)
However, a = X−1.5 × (Z 1 + Z 2 + Z 3 ,...)
[Si maximum content] is the Si maximum content in Table 1 corresponding to the intermediate alloy element to be contained.
(8) It is an alloy of silicon and one or more intermediate alloy elements described in Table 1, and the ratio of silicon is 10 atomic% or more of the whole. A step (a) of producing a silicon intermediate alloy having a maximum Si content of not more than the highest value, and a melt of one or more molten elements shown in Table 1 corresponding to the intermediate alloy element, One or more composite elements listed in Table 1 corresponding to the alloy elements are immersed in an alloy bath containing 10 atomic% or less, and a total of 20 atomic% or less, and silicon fine particles, silicon and composite element silicon compound particles, A step (b) for separating the second phase and a step (c) for removing the second phase, wherein the second phase is an alloy of the intermediate alloy element and the molten element and / or It is composed of the molten metal element, Method for producing a quality silicon composite particles.
(9) In the step (a), the silicon intermediate alloy is in a ribbon shape, foil piece shape or linear shape having a thickness of 0.1 μm to 2 mm, or in a powdery shape, granular shape or massive shape having a particle size of 10 μm to 50 mm. The method for producing porous silicon composite particles according to any one of (6) to (8), wherein:
(10) In the step (c), the second phase is dissolved and removed with at least one of an acid, an alkali and an organic solvent, or only the second phase is heated and reduced in pressure. The method for producing porous silicon composite particles according to any one of (6) to (9), comprising a step of evaporating and removing.
(11) The step (a) is a step of producing a ribbon-like or thin-plate-like silicon intermediate alloy by using a single roll casting machine or a twin roll casting machine with a molten metal of the silicon, the intermediate alloy element, and the composite element. The method for producing porous silicon composite particles according to any one of (6) to (10), wherein:
(12) The step (a) is a step of producing a powdery silicon intermediate alloy by using an atomization method of the molten silicon, the intermediate alloy element, and the composite element (6) )-(10) The manufacturing method of the porous silicon composite particle in any one of.
(13) The step (a) includes a step of producing a lump silicon intermediate alloy by cooling a molten metal of the silicon, the intermediate alloy element, and the complex element in a mold ( The manufacturing method of the porous silicon composite particle in any one of 6)-(10).
(14) The ratio of silicon to Cu (Y atomic%) is 10 to 30 atomic% (X atomic%) with respect to the whole, and As, Ba, Ca, Ce, Co, Cr, Er, Fe, Gd, and Hf. , Mn, Mo, Nb, Nd, Ni, Os, Pr, Pt, Pu, Re, Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Ti, Tm, U, V, W, Y, Yb , One or more complex elements (Z 1 , Z 2 , Z 3 ,... Atomic%) selected from the group consisting of Zr so as to satisfy the formulas (1) and (2) of (7) A step (a) for preparing a silicon intermediate alloy in a ribbon shape, foil piece shape, linear shape or a particle size of 10 μm to 50 mm in a powder shape, a granular shape or a lump shape with a thickness of 0.1 μm to 2 mm, and the silicon The intermediate alloy is at least one molten metal selected from the group consisting of Al, Be, Cd, Ga, In, Sb, Sn, and Zn. A step (b) of immersing in a molten metal containing the element as a main component to separate silicon fine particles, silicon and silicon compound particles of the complex element, and a second phase; and a step of removing the second phase ( c), wherein the second phase is composed of an alloy of the Cu and the molten metal element and / or the molten metal element, and the step (c) includes the second phase as an acid, an alkali, and an organic material. A porous silicon composite particle comprising: a step of dissolving and removing at least one solvent in a solvent; or a step of evaporating and removing only the second phase by increasing the temperature and pressure. Production method.
(15) Ribbon shape, foil piece shape, and linear shape with a thickness of 0.1 μm to 2 mm, in which Cu (Y atom%) is mixed with 10 to 30 atom% (X atom%) of silicon. Or a step (a) of producing a granular / lumped silicon intermediate alloy having a particle size of 10 μm to 50 mm, and the silicon intermediate alloy selected from the group consisting of Al, Be, Cd, Ga, In, Sb, Sn, Zn As a main component of the molten metal containing one or more molten elements, As, Ba, Ca, Ce, Co, Cr, Er, Fe, Gd, Hf, Mn, Mo, Nb, Nd, Ni, Os, Pr, Pt, Pu , Re, Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Ti, Tm, U, V, W, Y, Yb, Zr, each of one or more complex elements Soaked in an alloy bath prepared by adding 10 atomic percent or less and a total of 20 atomic percent or less. A step (b) for separating silicon fine particles, silicon and silicon compound particles of the complex element, and a second phase, and a step (c) for removing the second phase, The second phase is composed of an alloy of the Cu and the molten element and / or the molten element, and the step (c) includes at least one of the acid, alkali, and organic solvent in the second phase. A method for producing porous silicon composite particles, comprising a step of dissolving and removing, or a step of evaporating and removing only the second phase by heating and decompressing.
(16) The ratio of silicon to Mg (Y atom%) is 10 to 50 atom% (X atom%) with respect to the whole, and As, Ba, Ca, Ce, Cr, Co, Er, Fe, Gd, Hf , Mn, Mo, Nb, Nd, Ni, Os, Pr, Pt, Pu, Re, Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Ti, Tm, U, V, W, Y, Yb , One or more complex elements (Z 1 , Z 2 , Z 3 ,... Atomic%) selected from the group consisting of Zr so as to satisfy the formulas (1) and (2) of (7) A step (a) for preparing a silicon intermediate alloy in a ribbon shape, foil piece shape, linear shape or a particle size of 10 μm to 50 mm in a powder shape, a granular shape or a lump shape with a thickness of 0.1 μm to 2 mm, and the silicon The intermediate alloy is made of Ag, Al, Au, Be, Bi, Ga, In, Pb, Sb, Sn, Tl, Zn. A step (b) of immersing in a melt mainly composed of one or more molten metal elements selected from the above, and separating the silicon fine particles, silicon and silicon compound particles of the composite element, and the second phase; And (c) removing the second phase, wherein the second phase is composed of an alloy of the Mg and the molten element and / or the molten element, and the step (c) is the second phase. And a step of dissolving and removing at least one of an acid, an alkali and an organic solvent, or a step of evaporating and removing only the second phase by heating and depressurization. A method for producing porous silicon composite particles.
(17) Mg (Y atom%) is mixed with 10 to 50 atom% (X atom%) of silicon in the whole, and ribbons, foil pieces, and lines having a thickness of 0.1 μm to 2 mm Or a step (a) of producing a granular / lumped silicon intermediate alloy having a particle size of 10 μm to 50 mm, and the silicon intermediate alloy is made of Ag, Al, Au, Be, Bi, Ga, In, Pb, Sb, Sn, As a main component of one or more molten metal elements selected from the group consisting of Tl and Zn, As, Ba, Ca, Ce, Cr, Co, Er, Fe, Gd, Hf, Mn, Mo, Nb, Nd, Ni , Os, Pr, Pt, Pu, Re, Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Ti, Tm, U, V, W, Y, Yb, Zr. Add two or more complex elements for each 10 atomic percent or less, total 20 atomic percent or less A step (b) of immersing in the prepared alloy bath to separate silicon fine particles, silicon and silicon compound particles of the complex element, and a second phase; and a step (c) of removing the second phase. And the second phase is composed of an alloy of the Mg and the molten metal element and / or the molten metal element, and the step (c) includes the second phase of an acid, an alkali, or an organic solvent. A method for producing porous silicon composite particles, comprising: a step of dissolving and removing at least one or more, or a step of evaporating and removing only the second phase by heating and depressurizing. .
(18) The ratio of silicon to Ni (Y atom%) is 10 to 55 atom% (Y atom%), and As, Ba, Ca, Ce, Cr, Co, Er, Fe, Gd, Hf , Mn, Mo, Nb, Nd, Os, Pr, Pt, Pu, Re, Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Ti, Tm, U, V, W, Y, Yb, Zr One or more complex elements selected from the group consisting of (Z 1 , Z 2 , Z 3 ,... Atomic%) are blended so as to satisfy the formulas (1) and (2) of (7) (A) producing a ribbon-like, foil-like, linear or powdery / granular / lumped silicon intermediate alloy having a thickness of 0.1 μm to 2 mm, and the silicon intermediate alloy At least one molten element selected from the group consisting of Al, Be, Cd, Ga, In, Sb, Sn, and Zn. A step (b) of immersing in a molten metal as a main component to separate silicon fine particles, silicon and silicon compound particles of the complex element, and a second phase; and a step (c) of removing the second phase. And the second phase is composed of an alloy of Ni and the molten metal element and / or the molten metal element, and the step (c) includes the second phase of an acid, an alkali, or an organic solvent. A method for producing porous silicon composite particles, comprising: a step of dissolving and removing at least one or more, or a step of evaporating and removing only the second phase by heating and depressurizing. .
(19) Ni (Y atom%) is mixed with 10 to 55 atom% (Y atom%) of silicon relative to the whole, and a ribbon shape, foil piece shape, or linear shape with a thickness of 0.1 μm to 2 mm. Or a step (a) of producing a granular / lumped silicon intermediate alloy having a particle size of 10 μm to 50 mm, and the silicon intermediate alloy selected from the group consisting of Al, Be, Cd, Ga, In, Sb, Sn, Zn As a main component of the molten metal containing one or more molten elements, As, Ba, Ca, Ce, Cr, Co, Er, Fe, Gd, Hf, Mn, Mo, Nb, Nd, Os, Pr, Pt, Pu, Re 10 atoms each of one or more complex elements selected from the group consisting of Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Ti, Tm, U, V, W, Y, Yb, Zr % Or less, soaked in an alloy bath prepared by adding 20 atomic% or less in total, A step (b) for separating silicon fine particles, silicon and silicon compound particles of the complex element, and a second phase; and a step (c) for removing the second phase, and the second phase. Is composed of an alloy of Ni and the molten element and / or the molten element, and the step (c) comprises dissolving the second phase with at least one of an acid, an alkali, and an organic solvent. A method for producing porous silicon composite particles, comprising a step of removing, or a step of evaporating and removing only the second phase by heating and decompressing.
(20) The ratio of silicon to Ti (Y atom%) is 10 to 80 atom% (Y atom%) with respect to the whole, and As, Ba, Ca, Ce, Cr, Co, Er, Fe, Gd, Hf , Lu, Mg, Mn, Mo, Nb, Nd, Ni, Os, Pr, Pt, Pu, Re, Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Tm, U, V, W, Y , Yb, Zr selected from the group consisting of one or more complex elements (Z 1 , Z 2 , Z 3 ,... Atomic%) satisfying the formulas (1) and (2) of (7) A step (a) of preparing a silicon intermediate alloy in a ribbon shape, a foil piece shape, a linear shape having a thickness of 0.1 μm to 2 mm, or a powdery, granular, or massive shape having a particle size of 10 μm to 50 mm; The silicon intermediate alloy is made of Ag, Al, Au, Be, Bi, Cd, Ga, In, Pb, Sb, Sn, Zn. A step (b) of immersing in a melt mainly composed of one or more melt elements selected from the group consisting of silicon fine particles, silicon and silicon compound particles of the composite element, and a second phase; And (c) removing the second phase, wherein the second phase is composed of the alloy of Ti and the molten element and / or the molten element, and the step (c) includes the step (c). It comprises a step of dissolving and removing two phases with at least one of an acid, an alkali and an organic solvent, or a step of evaporating and removing only the second phase by heating and decompressing. A method for producing porous silicon composite particles.
(21) Ti (Y atom%) is mixed with 10 to 80 atom% (Y atom%) of silicon relative to the whole, and a ribbon shape, foil piece shape, or linear shape with a thickness of 0.1 μm to 2 mm Or a step (a) of producing a granular / lumped silicon intermediate alloy having a particle diameter of 10 μm to 50 mm, and the silicon intermediate alloy is made of Ag, Al, Au, Be, Bi, Cd, Ga, In, Pb, Sb, As a main component of one or more molten metal elements selected from the group consisting of Sn and Zn, As, Ba, Ca, Ce, Cr, Co, Er, Fe, Gd, Hf, Lu, Mg, Mn, Mo, Nb , Nd, Ni, Os, Pr, Pt, Pu, Re, Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Tm, U, V, W, Y, Yb, Zr One or more complex elements, each 10 atom% or less, total 20 atom% or less A step (b) of immersing in an added alloy bath to separate silicon fine particles, silicon and silicon compound particles of the complex element, and a second phase; and a step of removing the second phase ( c), wherein the second phase is composed of an alloy of Ti and the molten metal element and / or the molten metal element, and the step (c) includes the second phase as an acid, an alkali, and an organic material. A porous silicon composite particle comprising: a step of dissolving and removing at least one solvent in a solvent; or a step of evaporating and removing only the second phase by increasing the temperature and pressure. Production method.

  According to the present invention, <1> a porous silicon composite suitable for a negative electrode material for a lithium ion battery, etc. that achieves high capacity and good cycle characteristics, and <2> secures a conductive path by a silicon compound inside the porous body Body particles can be obtained.

(A) The figure which shows the porous silicon composite particle 1 concerning this invention, (b) The figure which shows the surface vicinity area | region S and the particle | grain internal area | region I of the porous silicon composite particle 1. FIG. The figure which shows the outline of the 1st manufacturing method of (a)-(c) porous silicon composite particle 1. FIG. The figure explaining the manufacturing process of the ribbon-shaped silicon intermediate alloy 19 which concerns on this invention. The figure explaining the immersion process to the molten metal 23 of the ribbon-shaped silicon intermediate alloy 19 which concerns on this invention. (A) The figure which shows the gas atomizer 31 which concerns on this invention, (b) The figure which shows the rotary disk atomizer 41 concerning this invention. (A)-(c) The figure explaining the manufacturing process of the lump silicon intermediate alloy 57. FIG. (A), (b) The figure which shows the molten metal immersion apparatuses 61 and 71 concerning this invention. The figure which shows the outline of the 2nd manufacturing method of (a)-(c) porous silicon composite particle 1. FIG. 2 is an SEM photograph of the surface of porous silicon composite particles according to Example 1. FIG. 2 is an SEM photograph of a cross section inside porous silicon composite particles according to Example 1. FIG. 2 is an SEM photograph of the surface of porous silicon composite particles according to Example 1. FIG. 3 is an X-ray diffraction grating image of silicon fine particles of porous silicon composite particles according to Example 1. FIG. 4 is a TEM photograph of a silicon fine particle of a porous silicon composite particle according to Example 1 and a limited-field electron diffraction image (upper left).

(Porous silicon composite particles)
The porous silicon composite particles according to the present invention will be described with reference to FIG. As shown in FIG. 1A, the porous silicon composite particles 1 according to the present invention are formed by bonding silicon fine particles 3 and silicon compound particles 5, and the average particle size of the porous silicon composite particles 1 is 0. The average porosity of the porous silicon composite particles 1 is 15 to 93%, and it has a three-dimensional network structure composed of continuous voids.

  The three-dimensional network structure in the present invention means a structure in which pores are connected to each other, such as a co-continuous structure or a sponge structure generated in the spinodal decomposition process. The pores of the porous silicon composite particles have a pore diameter of about 0.1 to 300 nm.

In the porous silicon composite particle 1, the ratio Xs / Xi, which is the ratio of the porosity Xs of the region near the surface of 50% or more in the radial direction and the porosity Xi of the particle internal region within 50% in the radial direction, is 0.00. 5 to 1.5.
That is, the porous silicon composite particles according to the present invention have the same pore structure in the surface vicinity region and the particle internal region, and the whole particle has a substantially uniform pore structure.
The porosity Xs can be obtained by observing the surface of the porous silicon composite particle 1 with an SEM, and the porosity Xi is obtained by observing a portion corresponding to the particle internal region in the cross section of the porous silicon composite particle 1 with an SEM. Can be obtained.

  The silicon fine particles 3 have an average particle diameter or an average column diameter of 2 nm to 2 μm, preferably 10 to 500 nm, and more preferably 20 to 300 nm. Moreover, an average porosity is 15 to 93%, Preferably it is 50 to 80%, More preferably, it is 60 to 70%. The crystal structure of each silicon fine particle 3 is a single crystal having crystallinity. The silicon fine particles 3 are solid fine particles containing 80 atomic% or more of silicon in the ratio of elements excluding oxygen, and the rest are intermediate alloy elements, molten metal elements, and other inevitable impurities described later.

Further, as shown in FIG. 1B, the porous silicon composite particles 1 are divided into a surface vicinity region S of 50% or more in the radial direction and a particle inner region I of 50% or less in the radial direction. Ds / Di, where Ds is the average particle size of the silicon fine particles constituting the region near the surface of the porous silicon composite particles, and Di is the average particle size of the silicon fine particles constituting the particle internal region of the porous silicon composite particles Is 0.5 to 1.5.
The average particle diameter Ds can be obtained by observing the surface of the porous silicon composite particle 1 with an SEM, and the average particle diameter Di is obtained by SEM of a cross section of a portion corresponding to the particle internal region of the porous silicon composite particle 1. It can be obtained by observation.

  The silicon compound particles 5 have an average particle size of 50 nm to 50 μm, preferably 100 nm to 20 μm, and more preferably 200 nm to 10 μm. In terms of composition, As, Ba, Ca, Ce, Co, Cr, Cu, Er, Fe, Gd, Hf, Lu, Mg, Mn, Mo, Nb, Nd, Ni, Os, Pr, Pt, Pu One or more complex elements selected from the group consisting of: Re, Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Ti, Tm, U, V, W, Y, Yb, Zr; It is a particle having solid crystallinity composed of 50 to 90 atomic% of silicon and an intermediate alloy element, a molten metal element, and other inevitable impurities described later. In general, the silicon compound particles 5 are larger than the silicon fine particles 3.

Further, the surface of the porous silicon composite particle 1, that is, the silicon fine particle 3 or the silicon compound particle 5, is an oxide having a thickness of 20 nm or less, or a particle size ratio of each silicon fine particle 3 or silicon compound particle 5 of 10% or less. Even if the layer is formed, there is no problem in characteristics.
The oxide layer on the surface of the porous silicon composite particles 1 can be formed by immersing in 0.0001 to 0.1 N nitric acid after removing the second phase. Or after removing a 2nd phase, it can also form by hold | maintaining under the oxygen partial pressure of 0.00000001-0.02 MPa. When the oxide layer such as silicon is formed, the porous silicon composite particles 1 become extremely stable in the air and do not need to be handled in a glove box or the like.

Since the porous silicon composite particles according to the present invention are usually present in an aggregated state, the average particle size of the particles herein refers to the average particle size of the primary particles. The particle diameter is measured by using image information of an electron microscope (SEM) and a volume-based median diameter of a dynamic light scattering photometer (DLS). For the average particle size, the particle shape is confirmed in advance using an SEM image, the particle size is obtained using image analysis software (for example, “A Image-kun” (registered trademark) manufactured by Asahi Kasei Engineering), or DLS ( For example, it can be measured by Otsuka Electronics DLS-8000). If the particles are sufficiently dispersed and not agglomerated at the time of DLS measurement, almost the same measurement results can be obtained with SEM and DLS.
Further, since the silicon fine particles and the silicon compound particles constituting the porous silicon composite particles are bonded to each other, the average particle diameter is obtained mainly using a surface scanning electron microscope or a transmission electron microscope.
The average column diameter is defined as the column diameter of rod-shaped (columnar) silicon particles having an aspect ratio of 5 or more. Let the average value of this support | pillar diameter be an average support | pillar diameter. This strut diameter is obtained mainly by SEM observation of particles.

  The average porosity refers to the proportion of voids in the particles. Submicron or smaller pores can be measured by nitrogen gas adsorption, but when the pore size is wide, observation with an electron microscope or mercury porosimetry (JIS R 1655 “fine ceramics by mercury porosimetry) It is possible to measure by, for example, “a method for measuring the pore size distribution of a molded body”, derived from the relationship between pressure and mercury volume when mercury enters the void).

  The porous silicon composite particles 1 according to the present invention have a particle size of 0.1 μm to 1000 μm depending on the Si concentration of the Si intermediate alloy and the cooling rate when manufacturing the intermediate alloy. Note that the particle size is reduced by decreasing the Si concentration or increasing the cooling rate. When used as the negative electrode active material, the average particle diameter is preferably 0.1 to 50 μm, more preferably 1 to 30 μm, and further preferably 5 to 20 μm. For this reason, when the porous silicon composite particles are small, they are used as aggregates or granules. Further, when the porous silicon composite particles are large, there is no problem even if the porous silicon composite particles are roughly pulverized and used.

(Outline of first production method of porous silicon composite particles)
An outline of a method for producing the porous silicon composite particles 1 will be described with reference to FIG.
First, as shown in FIG. 2A, silicon, an intermediate alloy element, and a composite element are heated and melted to produce a silicon intermediate alloy 7. At this time, when silicon, the composite element, and the intermediate alloy element are melted and solidified, an intermediate alloy 7 of silicon, the composite element, and the intermediate alloy element, and silicon compound particles composed of silicon and the composite element are formed.

  Thereafter, the silicon intermediate alloy 7 is immersed in the molten metal element. When the silicon intermediate alloy 7 is immersed in the molten metal bath, the molten metal element penetrates into the silicon intermediate alloy 7. At this time, the intermediate alloy element forms an alloy solid phase with the molten element, and further forms a liquid phase when the molten element permeates. Silicon atoms and complex elements are left in the liquid phase region. When the silicon atoms and the composite elements are aggregated from the diffused state, the silicon fine particles 3 are precipitated, and an alloy network of silicon atoms and the composite elements is formed, and a three-dimensional network structure is formed. That is, as shown in FIG. 2B, the intermediate alloy element of the silicon intermediate alloy 7 is eluted into the molten metal to form the second phase 9, and silicon is precipitated as the silicon fine particles 3. The second phase 9 is an alloy of an intermediate alloy element and a molten metal element, or is composed of a molten metal element substituted for the intermediate alloy element. Further, the silicon compound particles 5 remain as they are without being influenced by the molten metal. These silicon fine particles 3 and silicon compound particles 5 are bonded to each other to form a three-dimensional network structure.

  In the immersion process in the molten metal bath, the silicon primary crystal of silicon alone or the compound of silicon and the complex element does not cause reaggregation of the silicon atom or complex element even if the molten metal penetrates, The silicon primary crystal and the compound of the complex element remain as they are. Therefore, it is preferable to control the particle size by increasing the cooling rate at the time of producing the silicon intermediate alloy 7.

  Thereafter, as shown in FIG. 2C, the porous silicon composite in which the silicon fine particles 3 and the silicon compound particles 5 are joined by removing the second phase 9 by a method such as decomponent corrosion using acid or alkali. Body particles 1 are obtained.

From the above steps, the following conditions are required for the intermediate alloy element, the composite element, and the molten element.
Condition 1: The melting point of the molten element is lower than the melting point of silicon by 50K or more.
If the melting point of the molten element and the melting point of silicon are close, when the silicon intermediate alloy is immersed in the molten molten element, silicon is dissolved in the molten metal, so condition 1 is necessary.
Condition 2: Si primary crystals do not occur when silicon and intermediate alloy elements are solidified.
When forming an alloy of silicon and an intermediate alloy element, when the silicon concentration increases, a coarse silicon primary crystal is formed in the hypereutectic region. This silicon primary crystal does not cause diffusion or re-aggregation of silicon atoms during the immersion process, and does not form a three-dimensional network structure.
Condition 3: The solubility of silicon in the molten metal element is lower than 5 atomic%.
This is because when the intermediate alloy element and the molten metal element form the second phase, it is necessary to prevent silicon from being included in the second phase.
Condition 4: The intermediate alloy element and the molten metal element do not separate into two phases.
When the intermediate alloy element and the molten metal element are separated into two phases, the intermediate alloy element is not separated from the silicon intermediate alloy, and silicon atoms do not diffuse and reaggregate. Furthermore, even if the treatment with an acid is performed, the intermediate alloy element remains in the silicon particles.

Condition 5: Silicon and complex elements do not separate into two phases.
In the case where silicon and the composite element are easily separated into two phases, finally, silicon compound particles composed of an alloy of silicon and the composite element cannot be obtained.
Condition 6: The intermediate alloy element corresponding to the molten metal element does not include a complex element in the selectable elements.
When the composite element is an element that can be selected as an intermediate alloy element and has the characteristics of the intermediate alloy element as described above, when the molten metal element and the composite element form the second phase and the treatment with the acid is performed The complex element is removed.

  Considering the above conditions 1 to 6, the intermediate alloy element that can be used for producing the porous silicon composite, the composite element, the combination of the molten metal element, and the porosity of the obtained porous silicon composite are: It becomes as follows. Further, the ratio of the composite element is 1 to 33 atomic% of silicon. Furthermore, the ratio of silicon is 10 atomic% or more with respect to the sum of silicon, the intermediate alloy element, and the complex element, and the value of the maximum Si content in Table 1 below corresponding to the intermediate alloy element (a plurality of intermediate elements) In the case of including an alloy element, the maximum Si content in Table 1 corresponding to each intermediate alloy element is a value that is prorated according to the ratio of the intermediate alloy element). When a plurality of intermediate alloy elements are included, a composite element and a molten element that can be used in common with each intermediate alloy element are used.

In the step of forming the silicon intermediate alloy 7, silicon (X atom%), an intermediate alloy element (Y atom%), and one or more complex elements (Z 1 , Z 2 , Z 3 ,... Atom%) However, it is preferable to produce a silicon intermediate alloy having a composition satisfying the following formula. [Si maximum content] is the value of the maximum Si content in Table 1 corresponding to the intermediate alloy element. When there are a plurality of intermediate alloy elements, the maximum Si content of each intermediate alloy element is It is a value prorated according to the ratio of the intermediate alloy element. In addition, when there are a plurality of intermediate alloy elements, Y atomic% is the sum of the ratio of the plurality of intermediate alloy elements.
10 ≦ X <[maximum Si content] (1)
10 ≦ a ÷ (a + Y) × 100 ≦ [maximum Si content] (2)
However, a = X−1.5 × (Z 1 + Z 2 + Z 3 ,...)

(First production method of porous silicon composite particles)
A method for producing porous silicon composite particles according to the present invention will be described.
First, silicon, one or more intermediate alloy elements selected from the group consisting of Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, P, Ti, and Zr described in Table 1, and intermediate alloy elements Using a corresponding one or more composite elements shown in Table 1, a mixture containing silicon, intermediate alloy elements, and composite elements is heated and melted in a vacuum furnace or the like. At this time, an alloy of silicon and an intermediate alloy element and a compound of silicon and a complex element are formed.
Thereafter, for example, using a single roll casting machine 11 as shown in FIG. 3, the molten silicon alloy 13 is dropped from the crucible 15 and solidified while in contact with the rotating steel roll 17 to form a ribbon-like silicon intermediate alloy 19. Alternatively, a linear silicon intermediate alloy is manufactured. The cooling rate during solidification of the silicon intermediate alloy is 10 K / s or more, preferably 100 K / s or more, more preferably 200 K / s or more. This increase in the cooling rate contributes to reducing the size of silicon compound particles generated in the initial stage of solidification microscopically. Making the size of the silicon compound particles fine contributes to shortening the heat treatment time in the next step. The thickness of the ribbon-like silicon intermediate alloy 19 or the linear silicon intermediate alloy is 0.1 μm to 2 mm, preferably 0.1 to 500 μm, and more preferably 0.1 to 50 μm. Alternatively, the silicon intermediate alloy may be in the form of a foil piece having a certain length, unlike a linear shape or a ribbon shape.

  Next, the silicon intermediate alloy is made of at least one of Ag, Al, Au, Be, Bi, Cd, Ga, In, Pb, Sb, Sn, Tl, and Zn corresponding to the intermediate alloy elements described in Table 1. Submerged in a metal bath of a selected molten metal element, Si is spinodal decomposed to form a second phase that is an alloy of the intermediate alloy element and the molten element or a second phase composed of the molten element replaced with the intermediate alloy element Let In the dipping process, for example, a ribbon-like silicon intermediate alloy 19 or a linear silicon intermediate alloy is dipped in a molten metal 23 of a molten element using a molten metal immersion device 21 as shown in FIG. Thereafter, the film is wound up via the sink roll 25 and the support roll 27. The molten metal 23 is heated to a temperature higher than the liquidus temperature of the molten element by 10K or more. Although immersion in the molten metal 23 depends on the molten metal temperature, it is preferably 5 seconds or more and 10,000 seconds or less. This is because coarse Si grains are produced when immersion is performed for 10,000 seconds or more. The ribbon-like silicon intermediate alloy 19 after being immersed is cooled in a non-oxidizing atmosphere to obtain a composite of silicon fine particles 3, silicon compound particles 5, and second phase 9.

  Thereafter, the second phase 9 which is an alloy of the intermediate alloy element and the molten metal element or the second phase 9 composed of the molten metal element replaced with the intermediate alloy element is dissolved in at least one of an acid, an alkali and an organic solvent. Remove only the second phase 9 and wash and dry. The acid may be any acid that dissolves the intermediate alloy element and the molten metal element and does not dissolve silicon, and examples thereof include nitric acid, hydrochloric acid, and sulfuric acid. Alternatively, the second phase 9 is removed by raising the temperature and reducing the pressure and evaporating and removing only the second phase.

  In addition, since the coarse aggregate of the porous silicon composite particle 1 is obtained after removing the second phase 9, it is pulverized with a ball mill or the like so that the average particle size of the aggregate becomes 0.1 μm to 20 μm. To.

(Another example of the first manufacturing method of the porous silicon composite particles 1)
As another example of the first manufacturing method of the porous silicon composite particles 1, a powdered, granular, or massive silicon intermediate alloy may be used in place of the linear or ribbon-like silicon intermediate alloy 19.
First, silicon, one or more intermediate alloy elements selected from the group consisting of Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, P, Ti, and Zr described in Table 1, and intermediate alloy elements Using a corresponding one or more complex elements shown in Table 1, a mixture containing silicon, intermediate alloy elements, and complex elements is heated and melted in a vacuum furnace or the like.
Thereafter, a massive ingot is obtained by a method of producing a substantially spherical particle / powdered silicon intermediate alloy by an atomizing method as shown in FIGS. 5A and 5B or by an ingot producing method shown in FIG. If necessary, a powdery, granular or massive silicon intermediate alloy is produced by a mechanical pulverization method.

  FIG. 5A shows a gas atomizing apparatus 31 that can produce a powdered silicon intermediate alloy 39 by a gas atomizing method. In the crucible 33, there is a silicon alloy 13 of silicon, an intermediate alloy element, and a composite element dissolved by induction heating or the like. The silicon alloy 13 is dropped from the nozzle 35 and at the same time, a jet gas 36 such as an inert gas or air is ejected. The gas jet flow 38 from the gas injector 37 supplied with is sprayed, the molten metal of the silicon alloy 13 is crushed and solidified as droplets to form a powdered silicon intermediate alloy 39.

  FIG. 5B shows a rotating disk atomizing device 41 that can manufacture the powdered silicon intermediate alloy 51 by the rotating disk atomizing method. In the crucible 43, there is a silicon alloy 13 of dissolved silicon, intermediate alloy element, and complex element. This silicon alloy is dropped from the nozzle 45, and the molten silicon alloy 13 is dropped onto a rotating disk 49 that rotates at high speed. Then, a shearing force is applied in the tangential direction to crush and form a powdery silicon intermediate alloy 51.

  FIG. 6 is a diagram illustrating a process of forming the massive silicon intermediate alloy 57 by the ingot manufacturing method. First, the molten silicon alloy 13 is put into the mold 55 from the crucible 53. Thereafter, the silicon alloy 13 is cooled in the mold 55 and solidified, and then the mold 55 is removed to obtain a bulk silicon intermediate alloy 57. The bulk silicon intermediate alloy 57 may be used as it is, or may be pulverized as necessary and used as a granular silicon intermediate alloy.

  The particle size of the powdered, granular or massive silicon intermediate alloy is preferably 10 μm to 50 mm, more preferably 0.1 to 10 mm, and further preferably 1 to 5 mm. The cooling rate during solidification of the silicon alloy is 0.1 K / s or more. If the thickness of the silicon intermediate alloy is increased to 50 mm or more, the heat treatment time becomes longer, which is not preferable because the particle diameter of the porous silicon composite particles grows and becomes coarse. In that case, the silicon intermediate alloy can be mechanically pulverized to reduce the thickness to 50 mm or less.

  Next, the silicon intermediate alloy is immersed in the melt of the molten element shown in Table 1 corresponding to the intermediate alloy element used to form the spinodal decomposition of silicon and the second phase which is an alloy of the intermediate alloy element and the molten element. . The oxygen in the molten metal is desirably reduced in advance to 100 ppm or less, preferably 10 ppm or less, more preferably 2 ppm or less. This is because dissolved oxygen in the molten metal reacts with silicon to form silica, and with this as a nucleus, silicon grows in a facet shape and becomes coarse. As a countermeasure, it can be reduced by a solid reducing material such as charcoal / graphite or a non-oxidizing gas, or an element having a strong affinity for oxygen may be added in advance. Silicon particles are formed for the first time in this dipping process.

  In the dipping process, a molten silicon immersion device 61 as shown in FIG. 7A is used, and the granular silicon intermediate alloy 63 is placed in a dipping basin 65 and immersed in a molten metal 69 of a molten element. At that time, as shown in FIG. 7A, the pressing cylinder 67 is moved up and down to give mechanical vibration to the silicon intermediate alloy or molten metal, or to give vibration by ultrasonic waves, as shown in FIG. The reaction can be advanced in a short time by stirring the molten metal using mechanical stirring using the mechanical stirrer 81 and gas injection using the gas blowing plug 83 or electromagnetic force. Then, it is pulled up in a non-oxidizing atmosphere and cooled. The molten metal 69 or 79 is heated to a temperature higher than the liquidus temperature of the molten element by 10K or more. The immersion in the molten metal depends on the molten metal temperature, but is preferably 5 seconds or longer and 10,000 seconds or shorter. This is because coarse Si grains are produced when immersion is performed for 10,000 seconds or more. The above-mentioned powdery, granular, and lump shapes of silicon intermediate alloys are simply called silicon powders, particles, and lumps with a small aspect ratio (aspect ratio of 5 or less) depending on the size. It is not strictly defined. Further, the granular silicon intermediate alloys 63, 73, and 93 are represented as granular silicon intermediate alloys on behalf of the aforementioned powdery, granular, and massive silicon intermediate alloys.

  Thereafter, in the same manner as in the first production method, the second phase is removed to obtain porous silicon composite particles.

(Second production method of porous silicon composite particles)
A second method for producing porous silicon composite particles according to the present invention will be described. In the second manufacturing method, as shown in FIG. 8A, a silicon intermediate alloy 111 made of silicon and an intermediate alloy element is formed. Thereafter, the silicon fine particles 3, the silicon compound particles 5, and the second phase 9 are formed as shown in FIG. 8B by immersing in a molten metal obtained by adding a complex element to a molten metal element. Then, as shown in FIG.8 (c), the 2nd phase 9 is removed and the porous silicon composite particle 1 is obtained.

Hereinafter, the second manufacturing method will be specifically described.
First, silicon powder and at least one intermediate alloy element powder selected from the group consisting of Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, P, Ti, and Zr described in Table 1 are used. Silicon (X atomic%) and intermediate alloy element (Y atomic%) are dissolved so as to satisfy the formula (3).
X ÷ (X + Y) × 100 ≦ [maximum Si content] (3)

  Thereafter, similarly to the first manufacturing method, a ribbon-like silicon intermediate alloy 19 or a linear silicon intermediate alloy, which is an alloy of silicon and an intermediate alloy element, is used by using a single roll casting machine 11 as shown in FIG. To manufacture. Alternatively, a powdery silicon intermediate alloy is manufactured by an atomizing method as shown in FIGS. Further, as shown in FIG. 6, a silicon intermediate alloy may be cast into an ingot, which may be mechanically pulverized into a granular shape.

  Next, the silicon intermediate alloy is made of at least one of Ag, Al, Au, Be, Bi, Cd, Ga, In, Pb, Sb, Sn, Tl, and Zn corresponding to the intermediate alloy elements described in Table 1. One or more complex elements corresponding to the intermediate alloy elements listed in Table 1 are added to the molten metal element in an amount of 10 atomic% or less, for a total of 20 atomic% or less. And forming a compound of Si and a composite element, and forming a second phase that is an alloy of an intermediate alloy element and a molten metal element and / or a second phase composed of the molten metal element replaced with the intermediate alloy element. The dipping process uses a molten metal dipping device 21 as shown in FIG. 4 to immerse the ribbon-like silicon intermediate alloy 19 or the linear silicon intermediate alloy in the molten metal 23 of the molten element, or as shown in FIG. Alternatively, the molten silicon processing apparatus is used to immerse the granular silicon intermediate alloy in the molten metal element. The molten metal 23 is heated to a temperature higher than the liquidus temperature of the molten element by 10K or more. Although immersion in the molten metal 23 depends on the molten metal temperature, it is preferably 5 seconds or more and 10,000 seconds or less. This is because coarse Si grains are produced when immersion is performed for 10,000 seconds or more. This is cooled in a non-oxidizing atmosphere to obtain a composite of silicon fine particles 3, silicon compound particles 5, and second phase 9.

  In addition, after immersing this silicon intermediate alloy in the bath of the molten element shown in Table 1 corresponding to the intermediate alloy element, the molten element shown in Table 1 corresponding to the intermediate alloy element corresponds to the intermediate alloy element. One or more composite elements selected from the group consisting of the composite elements described in Table 1 may be added to each of 10 atomic% or less, and a total of 20 atomic% or less, and immersed in an alloy bath.

  Then, only the 2nd phase 9 is removed similarly to the 1st manufacturing method, and the porous silicon composite particle 1 is obtained.

(Effect of porous silicon composite particles)
According to the present invention, porous silicon composite particles having an unprecedented three-dimensional network structure can be obtained.

  According to the present invention, it is possible to obtain porous silicon composite particles having a substantially uniform pore structure as a whole. This is because precipitation of silicon fine particles from the silicon intermediate alloy in the molten metal is performed in the molten metal at a high temperature, so that the molten metal penetrates into the particles.

  When the porous silicon composite particles according to the present invention are used as a negative electrode active material of a lithium ion battery, a negative electrode having a high capacity and a long life can be obtained. In particular, since the complex element is an element that does not absorb lithium as much as silicon, the complex element is difficult to expand during storage of lithium ions, so that expansion of silicon is suppressed and a longer-life negative electrode is obtained. Can do. In addition, since silicon compound particles, which are compounds of silicon and a composite element, have higher conductivity than silicon, the porous silicon composite particles according to the present invention are more rapidly charged / discharged than normal silicon particles. It can correspond to.

Hereinafter, the present invention will be specifically described using examples and comparative examples.
[Example 1]
Silicon powder (granular purity: 95.0% or more), iron powder (granular: 2 mm, purity: 99.999% or more) and magnesium powder (powder) at a ratio of Si: Fe: Mg = 25: 5: 70 (atomic%) (Purity: 98.0% or more) was added and dissolved at 1120 ° C. in an argon atmosphere. Thereafter, the ribbon was rapidly cooled using a single roll casting machine at a cooling rate of 800 K / s to produce a silicon alloy ribbon having a thickness of 40 μm. This was immersed in a molten bismuth at 500 ° C. for 1 minute, and immediately quenched with argon gas. By this treatment, a second phase composite made of silicon fine particles, silicon compound particles made of Si—Fe alloy, and Mg—Bi alloy or Bi was obtained. This composite was immersed in a 20% nitric acid aqueous solution for 5 minutes to obtain porous silicon composite particles.

[Examples 2-8, 10, 11]
The production conditions for each example and comparative example are summarized in Table 2. Examples 2-8, 10 and 11 are porous silicon in the same manner as in Example 1 except for the production conditions such as intermediate alloy elements, composite elements, and compounding ratios of each element shown in Table 2. A complex was obtained. In Example 4, since a continuous ribbon-shaped silicon alloy could not be formed and was cut at 1 to 2 cm, a foil piece-shaped silicon alloy was obtained. In the linear silicon intermediate alloy of Example 5, φ100 μm means that the diameter of the linear intermediate alloy is 100 μm. The same applies to the eighth embodiment.

[Example 9]
Silicon powder, vanadium powder, and phosphorus powder were blended at a ratio of Si: V: P = 40: 1: 59 (atomic%) and dissolved at 1439 ° C. in an argon atmosphere. After that, using a gas atomizer, a rapid cooling was performed at a cooling rate of 800 K / s to produce a granular silicon alloy having an average particle size of 40 μm. This was immersed in molten cadmium at 750 ° C. for 1 minute, and immediately quenched with argon gas. By this treatment, silicon fine particles, silicon compound particles made of an alloy of Si and V, and a second phase composite made of a P—Cd alloy or Cd were obtained. This composite was immersed in a 20% nitric acid aqueous solution for 5 minutes to obtain porous silicon composite particles. In addition, φ40 μm in the granular intermediate alloy means that the average particle diameter of the granular intermediate alloy is 40 μm.

[Example 12]
Silicon and magnesium were blended at a ratio of Si: Mg = 31: 69 (atomic%) and dissolved in an argon atmosphere. Then, it cooled in the casting_mold | template and produced the ingot made from a silicon alloy of a magnitude | size of 5 square mm. This was immersed in a molten bismuth containing 1 atomic% arsenic for 1 minute, and then immediately cooled with argon gas. By this treatment, silicon fine particles, silicon compound particles made of Si—As alloy, and a second phase composite made of Mg—Bi alloy or Bi were obtained. This composite was immersed in a 20% nitric acid aqueous solution for 50 minutes to obtain porous silicon composite particles.

[Examples 13 to 16]
In Examples 13 to 16, porous silicon composite particles were obtained in the same manner as in Example 12 except for the production conditions such as the intermediate alloy elements shown in Table 2 and the blending ratio of each element. In Examples 13, 15, and 16, the water cooling block is used to increase the cooling rate.

[Comparative Example 1]
Silicon powder, iron powder, and magnesium powder were blended at a ratio of Si: Fe: Mg = 55: 1: 44 (atomic%), and melted at 1195 ° C. in a vacuum furnace. Then, it cast using the copper block, and produced the 5 mm square silicon alloy block at the cooling rate: 1 K / s. This was immersed in a molten bismuth at 500 ° C. for 10 minutes, and then immediately cooled with argon gas. This two-phase composite was immersed in a 20% nitric acid aqueous solution for 50 minutes. This comparative example does not satisfy a ÷ (a + Y) × 100 ≦ [maximum Si content] in the formula (2).
[Comparative Example 2]
Silicon powder, iron powder, and magnesium powder were blended at a ratio of Si: Fe: Mg = 25: 11: 64 (atomic%), and dissolved at 1105 ° C. in a vacuum furnace. Then, it cast using the copper block, and produced the 5 mm square silicon alloy block at the cooling rate: 1 K / s. This was immersed in a molten bismuth at 500 ° C. for 10 minutes, and then immediately cooled with argon gas. This two-phase composite was immersed in a 20% nitric acid aqueous solution for 50 minutes. This comparative example does not satisfy 10 ≦ a ÷ (a + Y) × 100 of Expression (2).
[Comparative Example 3]
Silicon powder and magnesium powder were blended at a ratio of Si: Mg = 24: 76 (atomic%) and dissolved at 1095 ° C. in a vacuum furnace. Thereafter, casting was performed using a water-cooled copper block, and a 5 mm square silicon alloy block was produced at a cooling rate of 41 K / s. This was immersed in an alloy bath of bismuth 85 atomic% and nickel 15 atomic% at 500 ° C. for 10 minutes, and then immediately cooled with argon gas. This two-phase composite was immersed in a 20% nitric acid aqueous solution for 50 minutes. In this comparative example, the concentration of the single complex element in the alloy bath exceeds 10 atomic%.

[Comparative Example 4]
Silicon powder and iron powder were blended at a ratio of Si: Fe = 90: 10 (atomic%) and melted at 1390 ° C. in a vacuum furnace. Then, it cooled rapidly with the cooling rate: 110 K / s using the single roll casting machine, and produced the foil piece made from a silicon alloy. This was immersed in hydrofluoric acid for 10 minutes and then washed with water.
[Comparative Example 5]
Silicon powder and iron powder were blended at a ratio of Si: Fe = 66: 34 (atomic%) and melted at 1250 ° C. in a vacuum furnace. Thereafter, rapid solidification was performed with a gas atomizer to produce an FeSi 2 intermetallic compound. This was sieved to recover particles having a particle size distribution of 1 to 10 μm. These particles and silicon particles having an average particle size of 5 μm (SIE23PB, manufactured by High Purity Chemical Laboratory) were mixed at a ratio of 2: 1 and granulated using styrene butadiene rubber (SBR) as a binder.

[Evaluation]
The observation of the particle shape of the porous silicon composite particles was performed using a scanning transmission electron microscope (manufactured by JEOL Ltd., JEM 3100FEF). FIG. 9 shows an SEM photograph of the surface of the particle according to Example 1, FIG. 10 shows an SEM photograph of the cross section inside the particle according to Example 1, and FIG. 11 shows the surface of the particle according to Example 1. An SEM photograph is shown. In FIG. 9 and FIG. 10, it is observed that a large number of silicon fine particles having a particle diameter of 20 nm to 50 nm are joined together to form porous silicon composite particles. Moreover, it is observed in FIG. 9 and FIG. 10 that there is no big difference in the porosity and the particle size of the silicon fine particles. In FIG. 11, it is observed that small silicon particles are bonded to large silicide particles.

  FIG. 12 is an X-ray diffraction grating image of silicon fine particles constituting the silicon composite particles. A spot derived from a crystal of silicon is observed, and it can be seen that the silicon fine particle is a single crystal.

  FIG. 13 is a TEM photograph of silicon fine particles constituting the silicon composite particles, and the upper left is a limited-field electron diffraction image in the observation region of the TEM. In the TEM photograph, it can be seen that there is no grain boundary in one silicon fine particle and it is a single crystal. Further, in the limited-field electron diffraction image, a spot derived from a silicon crystal is observed, and it can be seen that the silicon fine particle is also a single crystal.

  The average particle size of the silicon fine particles and the silicon compound particles was measured by image information of an electron microscope (SEM). The porous silicon composite particles are divided into a surface vicinity region of 50% or more in the radial direction and a particle internal region of 50% or less in the radial direction, and the respective average particle diameters Ds and Di are obtained from the respective SEM photographs, These ratios were calculated. The values of Ds / Di were all in the range of 0.5 to 1.5 in the examples, but in Comparative Example 4 obtained by the etching method, the area near the surface was larger than the area inside the particle. The average particle size of the fine particles was small, and the value of Ds / Di was small. For the average particle diameter of the porous silicon composite particles, the above-described method using SEM observation and DLS was used.

  The Si concentration of silicon fine particles, the concentration of Si and complex elements in the porous silicon composite particles, and the like were measured with an ICP emission spectrometer. In any embodiment, the silicon fine particles contain 80 atomic% or more of silicon.

  The average porosity of the porous silicon composite particles was measured by a mercury intrusion method (JIS R 1655) using a 15 mL cell.

  Further, the porous silicon composite particles are divided into a surface vicinity region of 50% or more in the radial direction and a particle internal region of 50% or less in the radial direction, and an arbitrary portion in each region is analyzed with a surface scanning electron microscope. Observed, Xs and Xi were obtained as the average porosity, and the ratio of Xs and Xi was calculated. In the examples, the value of Xs / Xi is between 0.5 and 1.5, but in Comparative Example 4 obtained by the etching method, the pore structure in the region near the surface is larger than that in the particle inner region. Because of its development, Xs / Xi increased.

(Evaluation of cycle characteristics when particles are used for negative electrode)
(I) Preparation of Negative Electrode Slurry Silicon particles were pulverized into coarse particles by micronization pulverization and granulated to form a 1 to 20 μm porous body. The mixture was charged into a mixer at a ratio of 65 parts by mass of particles according to Examples and Comparative Examples and 20 parts by mass of acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd.). Furthermore, 5 mass parts of a styrene butadiene rubber (SBR) 5 mass% emulsion (manufactured by Zeon Corporation, BM400B) as a binder, and carboxymethylcellulose sodium (Daicel) as a thickener to adjust the viscosity of the slurry. A slurry was prepared by mixing a 1% by mass solution of Chemical Industry Co., Ltd. at a ratio of 10 parts by mass in terms of solid content.
(Ii) Production of negative electrode Using the automatic coating apparatus, the prepared slurry was applied to a 10 μm thick electrolytic copper foil for current collector (manufactured by Furukawa Electric Co., Ltd., NC-WS) with a thickness of 10 μm. After drying at 70 ° C., a negative electrode for a lithium ion battery was manufactured through a thickness adjustment step using a press.
(Iii) Characteristic evaluation A lithium ion battery negative electrode is cut out to φ20 mm, metal Li is used for a counter electrode and a reference electrode, and an electrolyte solution composed of a mixed solution of ethylene carbonate and diethyl carbonate containing 1 mol / L LiPF 6 is used as a medium. An electrochemical test cell was constructed. The electrochemical test cell was assembled in a glove box having a dew point of −60 ° C. or lower. The charge / discharge characteristics were evaluated by measuring the initial discharge capacity and the discharge capacity after 50 cycles of charge / discharge, and calculating the discharge capacity retention rate. The discharge capacity was calculated based on the total weight of silicide and active material Si effective for occlusion / release of lithium. First, in a 25 ° C. environment, charging is performed under a constant current condition of 0.1 C, and the voltage value is reduced to 0.02 V (the reference electrode Li / Li + oxidation-reduction potential is based on 0 V, the same applies hereinafter). At that point, charging was stopped. Next, discharging was performed under a condition of a current value of 0.1 C until the voltage with respect to the reference electrode became 1.5 V, and a 0.1 C initial discharge capacity was measured. In addition, 0.1 C is a current value that can be fully charged in 10 hours. Next, the above charge / discharge cycle was repeated 50 cycles at a charge / discharge rate of 0.1C. The ratio of the discharge capacity when charging / discharging was repeated 50 cycles with respect to the initial discharge capacity was obtained as a percentage, and the discharge capacity retention rate after 50 cycles was determined.

  The evaluation results are summarized in Table 3. In Examples 13 to 16 and Comparative Example 3, since silicon particles are large, characteristics were evaluated using particles that were pulverized and reduced in a mortar. For example, the average particle size 130⇒33 of the porous silicon composite particles of Example 13 is obtained by pulverizing the porous silicon composite particles having an average particle size of 130 μm to obtain the porous silicon composite particles having an average particle size of 33 μm. Means that

As shown in the table, each example has a higher capacity retention rate after 50 cycles than each comparative example, and the rate of decrease in discharge capacity due to repeated charge and discharge is small, so the battery life is expected to be long. .
In each example, since the negative electrode active material is a porous silicon composite particle having a three-dimensional network structure, volume change of expansion / contraction occurs due to alloying / dealloying of Li and Si during charge / discharge. However, the silicon composite particles are not cracked or pulverized, and the discharge capacity retention rate is high.

When compared in more detail, in Comparative Example 1, pure Si crystallized as an initial crystal when the intermediate alloy was produced, and a eutectic structure (Si and Mg 2 Si) was generated at the end of solidification. The primary crystal Si was as coarse as about 10 μm. Even if it was immersed in molten bismuth, it did not become finer and remained as it was even after the etching process. Therefore, when repeating the intrusion / release of Li, Si alone, including coarse Si, is unable to follow the volume change of expansion / contraction due to charge / discharge = Li / Si alloying / dealloying. It is thought that the rate at which the current collection path and electrode function were lost increased and the battery life was shortened.

  In Comparative Example 2, the amount of iron, which is a complex element, was larger than that of silicon, and since most silicon formed silicide, the discharge capacity was small.

  In Comparative Example 3, the amount of Ni as a complex element added to the immersed molten metal was large, and most of the silicon had formed silicide, so the discharge capacity was small.

  In Comparative Example 4, since the pore structure was formed by etching with hydrofluoric acid or nitric acid, a portion where no pore was formed was formed at the center of the particle. This core portion cannot follow the volume change due to charging / discharging and is considered to have poor cycle characteristics.

  In Comparative Example 5, since it is a simple particle having no pore structure, it cannot follow the volume change due to charging / discharging, and the cycle characteristics are considered to be poor.

  The preferred embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to such examples. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the technical idea disclosed in the present application, and these are naturally within the technical scope of the present invention. Understood.

  The porous silicon composite particles according to the present invention can be used not only for a negative electrode of a lithium ion battery but also as a negative electrode of a lithium ion capacitor, a solar battery, a light emitting material, and a filter material.

DESCRIPTION OF SYMBOLS 1 ......... Porous silicon composite particle 3 ......... Silicon fine particle 5 ......... Silicon compound particle S ......... Surface vicinity region I ......... Particle internal region 7 ......... Silicon intermediate alloy 9 ......... Second Phase 11 ......... Single roll casting machine 13 ......... Silicone alloy 15 ......... Crucible 17 ......... Steel roll 19 ......... Ribbon-like silicon intermediate alloy 21 ......... Melting device 23 ......... Melting metal 25 ... ... Sink roll 27 ...... Support roll 31 ......... Gas atomizing device 33 ... …… Crucible 35 ... …… Nozzle 36 ......... Gas jet 37 ... …… Gas jet 38 ... …… Gas jet flow 39 ... …… Powder Silicon intermediate alloy 41 ......... Rotating disc atomizer 43 ......... Crucible 45 ... …… Nozzle 49 ... …… Rotating disc 51 ... …… Powdered silicon alloy 53 ... …… Crucible 55 ... …… Mold 7 ......... Lumped silicon intermediate alloy 61 ......... Mixed silicon immersion device 63 ......... Granular silicon intermediate alloy 65 ......... Immersion rod 67 ......... Pushing cylinder 69 ...... Melted metal 71 ......... Mold immersion device 73 ... …… Particulate silicon intermediate alloy 75 ………… Immersion bowl 79 ………… Melt 81 ………… Mechanical stirrer 83 ………… Gas blowing plug 111 ………… Silicon intermediate alloy

Claims (20)

  1. Porous silicon composite particles formed by bonding silicon fine particles and silicon compound particles,
    The silicon compound particles include silicon, As, Ba, Ca, Ce, Co, Cr, Cu, Er, Fe, Gd, Hf, Lu, Mg, Mn, Mo, Nb, Nd, Ni, Os, Pr, and Pt. , Pu, Re, Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Ti, Tm, U, V, W, Y, Yb, Zr, one or more complex elements And a compound with
    The silicon compound particles have an average particle size of 100 nm to 20 μm,
    The average particle diameter of the porous silicon composite particles is 0.1 μm to 1000 μm,
    A porous silicon composite particle, wherein the porous silicon composite particle has a three-dimensional network structure composed of continuous voids.
  2. The average particle diameter or average column diameter of the silicon fine particles is 2 nm to 2 μm,
    The porous silicon composite particle according to claim 1, wherein the silicon fine particle is a solid silicon fine particle containing 80 atomic% or more of silicon in a ratio of an element excluding oxygen.
  3. Before Symbol silicon compound particles, the ratio of elements other than oxygen, according to claim 1 or 2, characterized in that the particles of solid silicon compound characterized in that it comprises 50 to 90 atomic% of silicon Porous silicon composite particles.
  4.   The average particle diameter Ds of the silicon fine particles in the surface vicinity region of 50% or more in the radial direction of the porous silicon composite particles, and the silicon in the particle inner region within 50% in the radial direction of the porous silicon composite particles The porous silicon composite particle according to any one of claims 1 to 3, wherein Ds / Di, which is a ratio of the average particle diameter Di of the fine particles, is 0.5 to 1.5.
  5.   The ratio between the porosity Xs of the surface vicinity region of 50% or more in the radial direction of the porous silicon composite particles and the porosity Xi of the particle internal region within 50% in the radial direction of the porous silicon composite particles. Xs / Xi is 0.5-1.5, The porous silicon composite particle of any one of Claims 1-3 characterized by the above-mentioned.
  6. It is an alloy of silicon, one or more intermediate alloy elements listed in the following Table 1, and one or more complex elements listed in the following Table 1, and the ratio of the complex elements is 1 to 33 of the silicon. A silicon intermediate alloy that is atomic%, the silicon content of the porous silicon composite is 10 atomic% or more, and is equal to or less than the maximum Si content value in Table 1 below corresponding to the intermediate alloy element to be contained. Producing step (a);
    A step of immersing in a melt of one or more melt elements shown in Table 1 below corresponding to the intermediate alloy element to separate into silicon fine particles, silicon compound particles of silicon and complex elements, and a second phase ( b) and
    And (c) removing the second phase,
    The second phase is composed of an alloy of the intermediate alloy element and the molten element and / or the molten element ;
    In the step (a),
    Silicon (X atom%), an intermediate alloy element (Y atom%) and one or more complex elements (Z 1 , Z 2 , Z 3 ,... Atom%) satisfy the following formula: A method for producing porous silicon composite particles, comprising producing an intermediate alloy having silicon .
    10 ≦ X <[maximum Si content] Formula (1)
    10 ≦ a ÷ (a + Y) × 100 ≦ [maximum Si content] Formula (2)
    However, a = X−1.5 × (Z 1 + Z 2 + Z 3 ,...)
    [Si maximum content] is the Si maximum content in Table 1 corresponding to the intermediate alloy element to be contained.

  7. It is an alloy of silicon and one or more intermediate alloy elements shown in Table 1, the ratio of silicon is 10 atomic% or more of the whole, and the maximum Si content in Table 1 corresponding to the intermediate alloy element contained Producing a silicon intermediate alloy that is less than or equal to the highest value in the amount; and
    A melt of one or more molten elements shown in Table 1 corresponding to the intermediate alloy element, wherein one or more complex elements shown in Table 1 corresponding to the intermediate alloy element are each 10 atomic% or less, for a total of 20 A step (b) of immersing in an alloy bath containing at most atomic% to separate into silicon fine particles, silicon compound particles of silicon and complex elements, and a second phase;
    Removing the second phase (c);
    Comprising
    The method for producing porous silicon composite particles, wherein the second phase is composed of an alloy of the intermediate alloy element and the molten metal element and / or the molten metal element.
  8. In the step (a),
    The silicon intermediate alloy, ribbon-like thickness 0.1Myuemu~2mm, or a foil-like or linear, particle size 10μm~50mm powdered or claim 6, characterized in that a granular or bulk 8. The method for producing porous silicon composite particles according to 7 .
  9. The step (c)
    Removing the second phase, acid, alkali, dissolved in one or more and less organic solvent,
    Alternatively, the method for producing porous silicon composite particles according to any one of claims 6 to 8 , further comprising a step of evaporating and removing only the second phase by heating and depressurizing.
  10. The step (a)
    7. A step of producing a ribbon-like or thin-plate-like silicon intermediate alloy from a molten metal of the silicon, the intermediate alloy element, and the complex element by a single roll casting machine or a twin roll casting machine. 10. The method for producing porous silicon composite particles according to any one of 9 above.
  11. The step (a)
    Wherein a melt of the said silicon intermediate alloy element and said composite element, in any one of claims 6-9, characterized in that the step of producing a powdery silicon intermediate alloy with atomizing method Of producing porous silicon composite particles.
  12. The step (a)
    The molten silicon of the silicon, the intermediate alloy element, and the composite element is cooled in a mold to produce a lump silicon intermediate alloy, according to any one of claims 6 to 9. A method for producing the described porous silicon composite particles.
  13. The percentage of silicon in Cu (Y atom%) is 10 to 30 atom% (X atom%) with respect to the whole, and As, Ba, Ca, Ce, Co, Cr, Er, Fe, Gd, Hf, Mn, From Mo, Nb, Nd, Ni, Os, Pr, Pt, Pu, Re, Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Ti, Tm, U, V, W, Y, Yb, Zr One or more complex elements (Z 1 , Z 2 , Z 3 ,... Atomic%) selected from the group consisting of the following groups are blended so as to satisfy the formulas (1) and (2) of claim 6. A step (a) of producing a silicon intermediate alloy having a thickness of 0.1 μm to 2 mm in a ribbon shape, a foil piece shape, a linear shape, or a powdery shape, a granular shape, and a lump shape having a particle size of 10 μm to 50 mm;
    The silicon intermediate alloy is immersed in a melt mainly composed of one or more molten elements selected from the group consisting of Al, Be, Cd, Ga, In, Sb, Sn, and Zn, and silicon fine particles, silicon, A step (b) of separating the silicon compound particles of the complex element and the second phase;
    And (c) removing the second phase,
    The second phase is composed of an alloy of the Cu and the molten element and / or the molten element,
    Wherein step (c), the second phase, acid, alkali, a step of removing dissolved in one or more and less organic solvent, or heating under reduced pressure to evaporate only the second phase A method for producing porous silicon composite particles, comprising the step of removing.
  14. Cu (Y atom%) is blended with 10 to 30 atom% (X atom%) of silicon relative to the whole, and ribbons, foil pieces, wires, or grains having a thickness of 0.1 μm to 2 mm A step (a) of producing a granular and massive silicon intermediate alloy having a diameter of 10 μm to 50 mm;
    The silicon intermediate alloy is changed to As, Ba, Ca, Ce, Co, Cr, as a main component of one or more molten metal elements selected from the group consisting of Al, Be, Cd, Ga, In, Sb, Sn, and Zn. Er, Fe, Gd, Hf, Mn, Mo, Nb, Nd, Ni, Os, Pr, Pt, Pu, Re, Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Ti, Tm, U , V, W, Y, Yb, Zr are immersed in an alloy bath prepared by adding one or more complex elements selected from the group consisting of V, W, Y, Yb, and Zr to each of 10 atomic percent or less, and a total of 20 atomic percent or less. And (b) separating silicon, silicon compound particles of the complex element, and a second phase;
    And (c) removing the second phase,
    The second phase is composed of an alloy of the Cu and the molten element and / or the molten element,
    Wherein step (c), the second phase, acid, alkali, a step of removing dissolved in one or more and less organic solvent, or heating under reduced pressure to evaporate only the second phase A method for producing porous silicon composite particles, comprising the step of removing.
  15. In Mg (Y atom%), the ratio of silicon is 10 to 50 atom% (X atom%) with respect to the whole, and As, Ba, Ca, Ce, Cr, Co, Er, Fe, Gd, Hf, Mn, From Mo, Nb, Nd, Ni, Os, Pr, Pt, Pu, Re, Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Ti, Tm, U, V, W, Y, Yb, Zr One or more complex elements (Z 1 , Z 2 , Z 3 ,... Atomic%) selected from the group consisting of the following groups are blended so as to satisfy the formulas (1) and (2) of claim 6. A step (a) of producing a silicon intermediate alloy having a thickness of 0.1 μm to 2 mm in a ribbon shape, a foil piece shape, a linear shape, or a powdery shape, a granular shape, and a lump shape having a particle size of 10 μm to 50 mm;
    The silicon intermediate alloy is immersed in a melt mainly composed of one or more molten elements selected from the group consisting of Ag, Al, Au, Be, Bi, Ga, In, Pb, Sb, Sn, Tl, and Zn. Separating the silicon fine particles, silicon and silicon compound particles of the complex element, and the second phase (b),
    And (c) removing the second phase,
    The second phase is composed of an alloy of the Mg and the molten element and / or the molten element,
    Wherein step (c), the second phase, acid, alkali, a step of removing dissolved in one or more and less organic solvent, or heating under reduced pressure to evaporate only the second phase A method for producing porous silicon composite particles, comprising the step of removing.
  16. Mg (Y atom%) is mixed with 10 to 50 atom% (X atom%) of silicon relative to the whole, and ribbons, foil pieces, lines, or grains having a thickness of 0.1 μm to 2 mm A step (a) of producing a granular and massive silicon intermediate alloy having a diameter of 10 μm to 50 mm;
    The silicon intermediate alloy is changed to As, Ba, as a main component of one or more molten elements selected from the group consisting of Ag, Al, Au, Be, Bi, Ga, In, Pb, Sb, Sn, Tl, and Zn. , Ca, Ce, Cr, Co, Er, Fe, Gd, Hf, Mn, Mo, Nb, Nd, Ni, Os, Pr, Pt, Pu, Re, Rh, Ru, Sc, Sm, Sr, Ta, Te , Th, Ti, Tm, U, V, W, Y, Yb, an alloy prepared by adding one or more complex elements selected from the group consisting of 10% by atom or less and a total of 20 atom% or less A step (b) of immersing in a bath and separating into silicon fine particles, silicon and silicon compound particles of the complex element, and a second phase;
    And (c) removing the second phase,
    The second phase is composed of an alloy of the Mg and the molten element and / or the molten element,
    In the step (c), the second phase is dissolved and removed with at least one of an acid, an alkali, and an organic solvent, or only the second phase is evaporated and removed by heating and decompression. A process for producing porous silicon composite particles, comprising a step.
  17. Ni (Y atom%) is 10 to 55 atom% ( X atom%) relative to the whole, As, Ba, Ca, Ce, Cr, Co, Er, Fe, Gd, Hf, Mn, Mo, Nb, Nd, Os, Pr, Pt, Pu, Re, Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Ti, Tm, U, V, W, Y, Yb, Zr One or more selected complex elements (Z 1 , Z 2 , Z 3 ,... Atomic%) are blended so as to satisfy the formulas (1) and (2) of claim 6 , A step (a) of producing a silicon intermediate alloy in a ribbon shape, foil piece shape, linear shape having a thickness of 0.1 μm to 2 mm, or a powdery, granular, or massive shape having a particle size of 10 μm to 50 mm;
    The silicon intermediate alloy is immersed in a melt mainly composed of one or more molten elements selected from the group consisting of Al, Be, Cd, Ga, In, Sb, Sn, and Zn, and silicon fine particles, silicon, A step (b) of separating the silicon compound particles of the complex element and the second phase;
    And (c) removing the second phase,
    The second phase is composed of an alloy of the Ni and the molten element and / or the molten element,
    Wherein step (c), the second phase, acid, alkali, a step of removing dissolved in one or more and less organic solvent, or heating under reduced pressure to evaporate only the second phase A method for producing porous silicon composite particles, comprising the step of removing.
  18. Ni (Y atom%) is mixed with 10 to 55 atom% ( X atom%) of silicon relative to the whole, and ribbons, foil pieces, lines, or grains having a thickness of 0.1 μm to 2 mm A step (a) of producing a granular and massive silicon intermediate alloy having a diameter of 10 μm to 50 mm;
    The silicon intermediate alloy is changed to As, Ba, Ca, Ce, Cr, Co, or the like as a main component of one or more molten metal elements selected from the group consisting of Al, Be, Cd, Ga, In, Sb, Sn, and Zn. , Er, Fe, Gd, Hf, Mn, Mo, Nb, Nd, Os, Pr, Pt, Pu, Re, Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Ti, Tm, U, V , One or more complex elements selected from the group consisting of W, Y, Yb, and Zr are each immersed in an alloy bath prepared by adding 10 atomic percent or less, a total of 20 atomic percent or less, and silicon fine particles; A step (b) of separating silicon, silicon compound particles of the complex element, and a second phase;
    And (c) removing the second phase,
    The second phase is composed of an alloy of the Ni and the molten element and / or the molten element,
    Wherein step (c), the second phase, acid, alkali, a step of removing dissolved in one or more and less organic solvent, or heating under reduced pressure to evaporate only the second phase A method for producing porous silicon composite particles, comprising the step of removing.
  19. The proportion of silicon in Ti (Y atom%) is 10 to 80 atom% ( X atom%) with respect to the whole, and As, Ba, Ca, Ce, Cr, Co, Er, Fe, Gd, Hf, Lu, Mg, Mn, Mo, Nb, Nd, Ni, Os, Pr, Pt, Pu, Re, Rh, Ru, Sc, Sm, Sr, Ta, Te, Th, Tm, U, V, W, Y, Yb, One or more complex elements (Z 1 , Z 2 , Z 3 ,... Atomic%) selected from the group consisting of Zr so as to satisfy the formulas (1) and (2) of claim 6 (A) which mix | blends and produces the intermediate | middle silicon | silicone alloy of a powder form, a granular form, and a lump shape of a ribbon shape, foil piece shape, linear shape, or a particle size of 10 micrometers-50 mm with a thickness of 0.1 micrometer-2 mm,
    The silicon intermediate alloy is immersed in a melt mainly composed of one or more molten elements selected from the group consisting of Ag, Al, Au, Be, Bi, Cd, Ga, In, Pb, Sb, Sn, and Zn. Separating the silicon fine particles, silicon and silicon compound particles of the complex element, and the second phase (b),
    And (c) removing the second phase,
    The second phase is composed of an alloy of the Ti and the molten element and / or the molten element,
    Wherein step (c), the second phase, acid, alkali, a step of removing dissolved in one or more and less organic solvent, or heating under reduced pressure to evaporate only the second phase A method for producing porous silicon composite particles, comprising the step of removing.
  20. Ti (Y atom%) is mixed with 10 to 80 atom% ( X atom%) of silicon relative to the whole, and ribbons, foil pieces, lines, or grains having a thickness of 0.1 μm to 2 mm A step (a) of producing a granular and massive silicon intermediate alloy having a diameter of 10 μm to 50 mm;
    The silicon intermediate alloy is changed to As, Ba, as a main component of one or more molten elements selected from the group consisting of Ag, Al, Au, Be, Bi, Cd, Ga, In, Pb, Sb, Sn, and Zn. , Ca, Ce, Cr, Co, Er, Fe, Gd, Hf, Lu, Mg, Mn, Mo, Nb, Nd, Ni, Os, Pr, Pt, Pu, Re, Rh, Ru, Sc, Sm, Sr , Ta, Te, Th, Tm, U, V, W, Y, Yb, Zr are added at least 10 atomic% each, and a total of 20 atomic% or less is added. A step (b) of immersing in an alloy bath to separate silicon fine particles, silicon and silicon compound particles of the complex element, and a second phase;
    And (c) removing the second phase,
    The second phase is composed of an alloy of the Ti and the molten element and / or the molten element,
    Wherein step (c), the second phase, acid, alkali, a step of removing dissolved in one or more and less organic solvent, or heating under reduced pressure to evaporate only the second phase A method for producing porous silicon composite particles, comprising the step of removing.
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