JP6112200B2 - Negative electrode active material for electric device and electric device using the same - Google Patents

Description

  The present invention relates to a negative electrode active material for electric devices and an electric device using the same. The negative electrode active material for an electric device and the electric device using the same according to the present invention include, for example, a driving power source and an auxiliary power source for a motor of a vehicle such as an electric vehicle, a fuel cell vehicle, and a hybrid electric vehicle as a secondary battery or a capacitor Used for.

  In recent years, in order to cope with air pollution and global warming, reduction of the amount of carbon dioxide has been strongly desired. In the automobile industry, there is a great expectation for reducing carbon dioxide emissions by introducing electric vehicles (EV) and hybrid electric vehicles (HEV). Electric devices such as secondary batteries for motor drive that hold the key to their practical application. Is being actively developed.

  As a secondary battery for driving a motor, it is required to have extremely high output characteristics and high energy as compared with a consumer lithium ion secondary battery used in a mobile phone, a notebook personal computer or the like. Therefore, lithium ion secondary batteries having the highest theoretical energy among all the batteries are attracting attention, and are currently being developed rapidly.

  Generally, a lithium ion secondary battery includes a positive electrode in which a positive electrode active material or the like is applied to both surfaces of a positive electrode current collector using a binder, and a negative electrode in which a negative electrode active material or the like is applied to both surfaces of a negative electrode current collector using a binder. However, it has the structure connected through an electrolyte layer and accommodated in a battery case.

Conventionally, carbon / graphite-based materials that are advantageous in terms of charge / discharge cycle life and cost have been used for negative electrodes of lithium ion secondary batteries. However, since carbon / graphite-based negative electrode materials are charged / discharged by occlusion / release of lithium ions into / from graphite crystals, the charge / discharge capacity of the theoretical capacity 372 mAh / g or more obtained from LiC ₆ which is the maximum lithium-introduced compound. There is a disadvantage that cannot be obtained. For this reason, it is difficult to obtain a capacity and energy density that satisfy the practical use level of the vehicle application with the carbon / graphite negative electrode material.

On the other hand, a battery using a material that is alloyed with Li for the negative electrode is expected as a negative electrode material for vehicle use because the energy density is improved as compared with a conventional carbon / graphite negative electrode material. For example, the Si material absorbs and releases _4.4 mol of lithium ions per mol as shown in the following reaction formula (A) in charge and discharge, and the theoretical capacity is 2100 mAh / in Li ₂₂ Si ₅ (= Li _4.4 Si). g. Furthermore, when calculated per Si weight, it has an initial capacity of 3200 mAh / g.

  However, a lithium ion secondary battery using a material that is alloyed with Li for the negative electrode has a large expansion and contraction in the negative electrode during charge and discharge. For example, when Li ions are occluded, the volume expansion is about 1.2 times in graphite materials, whereas in Si materials, when Si and Li are alloyed, transition from the amorphous state to the crystalline state causes a large volume change. (Approximately 4 times), there was a problem of reducing the cycle life of the electrode. In the case of the Si negative electrode active material, the capacity and the cycle durability are in a trade-off relationship, and there is a problem that it is difficult to improve the cycle durability while exhibiting a high capacity.

In order to solve such a problem, a negative electrode active material for a lithium ion secondary battery including an amorphous alloy having the formula: Si _x M _y Al _z has been proposed (for example, JP 2009-517850 A (international publication). No. 2007/064531)). Here, x, y, and z in the formula represent atomic percentage values, and x + y + z = 100, x ≧ 55, y <22, z> 0, M represents Mn, Mo, Nb, W, Ta, Fe, Cu, It is a metal composed of at least one of Ti, V, Cr, Ni, Co, Zr, and Y. In the invention described in the Japanese translations of PCT publication No. 2009-517850, paragraph “0008” describes that, by minimizing the content of the metal M, a good cycle life is exhibited in addition to high capacity. .

However, the formula described in JP-T 2009-517850 Patent Publication (WO _{2007/064531);} For Si _x M y Al _z lithium ion secondary battery using the anode having an amorphous alloy having a good Although it is said that the cycle durability can be exhibited, it cannot be said that the cycle durability is sufficient.

  Then, the objective of this invention is providing the negative electrode active material for electric devices, such as a lithium ion secondary battery, which has high cycle durability.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive research. As a result, it has been found that the above problem can be solved by using a ternary Si alloy having a predetermined composition and having a predetermined composition, and further supporting a carbon-based material on the surface of the alloy, The present invention has been completed.

  That is, the present invention relates to a negative electrode active material for electric devices. At this time, the negative electrode active material for an electric device has the following chemical formula (1):

(In the above chemical formula (1),
M is at least one metal selected from the group consisting of Ti, Zn, C, and combinations thereof;
A is an inevitable impurity,
x, y, z, and a represent mass% values, where 0 <x <100, 0 <y <100, 0 <z <100, and 0 ≦ a <0.5, and x + y + z + a = 100. )
It is characterized in that it contains an alloy represented by Another feature is that the carbon-based material is supported on the surface of the alloy.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view schematically showing an outline of a laminated flat non-bipolar lithium ion secondary battery which is a typical embodiment of an electric device according to the present invention. In FIG. 1, 10 is a lithium ion secondary battery (stacked battery); 11 is a negative electrode current collector; 12 is a positive electrode current collector; 13 is a negative electrode active material layer; 15 is a positive electrode active material layer; 17 indicates an electrolyte layer; 19 indicates a single battery layer; 21 indicates a power generation element; 25 indicates a negative electrode current collector plate; 27 indicates a positive electrode current collector plate; and 29 indicates a battery exterior material (laminate film). BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view schematically showing the appearance of a stacked flat lithium ion secondary battery that is a representative embodiment of an electric device according to the present invention. In FIG. 2, 50 is a lithium ion secondary battery (laminated battery); 57 is a power generation element; 58 is a negative electrode current collector plate; 59 is a positive electrode current collector plate; and 52 is a battery exterior material (laminate film). Are shown respectively. FIG. 3 is a ternary composition diagram plotting and showing alloy components formed in Reference Example A together with a preferable composition range of the Si—Sn—Ti alloy constituting the negative electrode active material for electric devices of the present invention. It is a ternary composition diagram showing a more preferable composition range of the Si—Sn—Ti based alloy constituting the negative electrode active material for electric devices of the present invention. It is a ternary composition diagram showing a more preferable composition range of the Si—Sn—Ti based alloy constituting the negative electrode active material for electric devices of the present invention. It is a ternary composition diagram showing a particularly preferable composition range of the Si—Sn—Ti based alloy constituting the negative electrode active material for electric devices of the present invention. It is a figure which shows the influence of a negative electrode active material alloy composition on the initial stage discharge capacity of the battery obtained by the reference example A. It is a figure which shows the influence of the negative electrode active material alloy composition which acts on the discharge capacity maintenance factor of the 50th cycle of the battery obtained by the reference example A. It is a figure which shows the influence of the negative electrode active material alloy composition which has on the discharge capacity maintenance factor of the 100th cycle of the battery obtained by the reference example A. It is a ternary composition diagram plotting and showing the alloy components formed in Reference Example B together with a preferable composition range of the Si—Sn—Zn-based alloy constituting the negative electrode active material for electric devices of the present invention. It is a ternary composition diagram showing a more preferable composition range of the Si—Sn—Zn-based alloy constituting the negative electrode active material for electric devices of the present invention. It is a ternary composition diagram showing a more preferable composition range of the Si—Sn—Zn-based alloy constituting the negative electrode active material for electric devices of the present invention. It is a ternary composition diagram showing a particularly preferable composition range of the Si—Sn—Zn-based alloy constituting the negative electrode active material for electric devices of the present invention. 4 is a drawing showing the influence of the negative electrode active material alloy composition on the initial discharge capacity of the battery obtained in Reference Example B. 4 is a drawing showing the relationship between the discharge capacity retention ratio at the 50th cycle and the negative electrode active material alloy composition of the battery obtained in Reference Example B. It is a figure which shows the relationship between the discharge capacity maintenance factor of the 100th cycle of a battery obtained in Reference Example B, and a negative electrode active material alloy composition. FIG. 3 is a ternary composition diagram plotting and showing alloy components formed in Reference Example C together with a preferable composition range of the Si—Sn—C based alloy constituting the negative electrode active material for an electric device of the present invention. It is a ternary composition diagram showing a more preferable composition range of the Si—Sn—C based alloy constituting the negative electrode active material for electric devices of the present invention. It is a ternary composition diagram showing a more preferable composition range of the Si-Sn-C based alloy constituting the negative electrode active material for electric devices of the present invention. It is a ternary composition diagram showing a particularly preferable composition range of the Si—Sn—C based alloy constituting the negative electrode active material for electric devices of the present invention. It is a figure which shows the influence of a negative electrode active material alloy composition on the initial stage discharge capacity of the battery obtained by the reference example C. It is a figure which shows the influence of the negative electrode active material alloy composition which acts on the discharge capacity maintenance factor of the 50th cycle of the battery obtained in Reference Example C. It is a figure which shows the influence of the negative electrode active material alloy composition which has on the discharge capacity maintenance factor of the 100th cycle of the battery obtained in Reference Example C. It is a color photograph which shows the mapping result by the Auger electron spectroscopy of the carbon coating Si alloy of Example 7.

  Hereinafter, embodiments of a negative electrode active material for an electric device of the present invention and an electric device using the same will be described with reference to the drawings. However, the technical scope of the present invention should be determined based on the description of the scope of claims, and is not limited to the following modes. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.

  Hereinafter, a basic configuration of an electric device to which the negative electrode active material for an electric device of the present invention can be applied will be described with reference to the drawings. In the present embodiment, a lithium ion secondary battery will be described as an example of an electric device. In the present invention, the “electrode layer” means a mixture layer containing a negative electrode active material, a binder, and, if necessary, a conductive additive, but is also referred to as a “negative electrode active material layer” in the description of this specification. Sometimes. Similarly, the electrode layer on the positive electrode side is also referred to as a “positive electrode active material layer”.

  First, in a negative electrode for a lithium ion secondary battery, which is a typical embodiment of a negative electrode including a negative electrode active material for an electric device according to the present invention, and a lithium ion secondary battery using the same, a cell (single cell layer) ) Voltage is large, and high energy density and high power density can be achieved. Therefore, the lithium ion secondary battery using the negative electrode active material for the lithium ion secondary battery of the present embodiment is excellent as a vehicle driving power source or an auxiliary power source. As a result, it can be suitably used as a lithium ion secondary battery for a vehicle driving power source or the like. In addition to this, the present invention can be sufficiently applied to lithium ion secondary batteries for portable devices such as mobile phones.

  That is, the lithium ion secondary battery that is the subject of the present embodiment may be any one that uses the negative electrode active material for the lithium ion secondary battery of the present embodiment described below. It should not be restricted in particular.

  For example, when the lithium ion secondary battery is distinguished by form / structure, it can be applied to any conventionally known form / structure such as a stacked (flat) battery or a wound (cylindrical) battery. Is. By adopting a stacked (flat) battery structure, long-term reliability can be secured by a sealing technique such as simple thermocompression bonding, which is advantageous in terms of cost and workability.

  Moreover, when viewed in terms of electrical connection form (electrode structure) in a lithium ion secondary battery, it can be applied to both non-bipolar (internal parallel connection type) batteries and bipolar (internal series connection type) batteries. Is.

  When distinguished by the type of electrolyte layer in the lithium ion secondary battery, a solution electrolyte type battery using a solution electrolyte such as a nonaqueous electrolyte solution for the electrolyte layer, a polymer battery using a polymer electrolyte for the electrolyte layer, etc. It can be applied to any conventionally known electrolyte layer type. The polymer battery is further divided into a gel electrolyte type battery using a polymer gel electrolyte (also simply referred to as gel electrolyte) and a solid polymer (all solid) type battery using a polymer solid electrolyte (also simply referred to as polymer electrolyte). It is done.

  Therefore, in the following description, the non-bipolar (internal parallel connection type) lithium ion secondary battery using the negative electrode active material for the lithium ion secondary battery of this embodiment will be described very simply with reference to the drawings. However, the technical scope of the lithium ion secondary battery of the present embodiment should not be limited to these.

<Overall battery structure>
FIG. 1 schematically shows the overall structure of a flat (stacked) lithium ion secondary battery (hereinafter also simply referred to as “stacked battery”), which is a typical embodiment of the electrical device of the present invention. FIG.

  As shown in FIG. 1, the stacked battery 10 of the present embodiment has a structure in which a substantially rectangular power generation element 21 in which a charge / discharge reaction actually proceeds is sealed inside a laminate sheet 29 that is an exterior body. . Here, in the power generation element 21, the positive electrode in which the positive electrode active material layer 15 is disposed on both surfaces of the positive electrode current collector 12, the electrolyte layer 17, and the negative electrode active material layer 13 is disposed on both surfaces of the negative electrode current collector 11. It has a configuration in which a negative electrode is laminated. Specifically, the negative electrode, the electrolyte layer, and the positive electrode are laminated in this order so that one positive electrode active material layer 15 and the negative electrode active material layer 13 adjacent thereto face each other with the electrolyte layer 17 therebetween. .

  Thereby, the adjacent positive electrode, electrolyte layer, and negative electrode constitute one unit cell layer 19. Therefore, it can be said that the stacked battery 10 shown in FIG. 1 has a configuration in which a plurality of single battery layers 19 are stacked and electrically connected in parallel. The positive electrode current collector 15 located on both outermost layers of the power generation element 21 has the positive electrode active material layer 15 disposed only on one side, but the active material layers may be provided on both sides. . That is, instead of using a current collector dedicated to the outermost layer provided with an active material layer only on one side, a current collector having an active material layer on both sides may be used as it is as an outermost current collector. Further, by reversing the arrangement of the positive electrode and the negative electrode as compared with FIG. 1, the outermost negative electrode current collector is positioned on both outermost layers of the power generation element 21, and one side of the outermost negative electrode current collector or A negative electrode active material layer may be disposed on both sides.

  The positive electrode current collector 12 and the negative electrode current collector 11 are attached to the positive electrode current collector plate 27 and the negative electrode current collector plate 25 that are electrically connected to the respective electrodes (positive electrode and negative electrode), and are sandwiched between the end portions of the laminate sheet 29. Thus, it has a structure led out of the laminate sheet 29. The positive electrode current collector 27 and the negative electrode current collector 25 are ultrasonically welded to the positive electrode current collector 12 and the negative electrode current collector 11 of each electrode via a positive electrode lead and a negative electrode lead (not shown), respectively, as necessary. Or resistance welding or the like.

  The lithium ion secondary battery described above is characterized by a negative electrode. Hereinafter, main components of the battery including the negative electrode will be described.

<Active material layer>
The active material layer 13 or 15 contains an active material, and further contains other additives as necessary.

[Positive electrode active material layer]
The positive electrode active material layer 15 includes a positive electrode active material.

(Positive electrode active material)
Examples of the positive electrode active material include lithium metal, lithium-transition metal composite oxide, lithium-transition metal phosphate compound, lithium-transition metal sulfate compound, solid solution system, ternary system, NiMn system, NiCo system, spinel Mn system Etc.

Examples of the lithium-transition metal composite oxide include LiMn ₂ O ₄ , LiCoO ₂ , LiNiO ₂ , Li (Ni, Mn, Co) O ₂ , Li (Li, Ni, Mn, Co) O ₂ , LiFePO ₄ and Examples include those in which some of these transition metals are substituted with other elements.

As a solid solution system, xLiMO ₂ · (1-x) Li ₂ NO ₃ (0 <x <1, M is one or more transition metals having an average oxidation state of 3+ and N is an average oxidation state of 4+), LiRO _2- LiMn ₂ O ₄ (R = transition metal elements such as Ni, Mn, Co and Fe).

  Examples of the ternary system include nickel / cobalt / manganese (composite) positive electrode materials.

Examples of the NiMn system include LiNi _0.5 Mn _1.5 O ₄ .

Examples of the NiCo system include Li (NiCo) O ₂ .

Examples of the spinel Mn system include LiMn ₂ O ₄ .

General formula disclosed in JP 2012-185913 A: Li _{(2-0.5x) y} □ _{(2-0.5x) (1-y)} Mn _1-x M _1.5x O ₃ (wherein Li is lithium, □ is a vacancy in the crystal structure, Mn is manganese, M is Ni _α Co _β Mn _γ (Ni is nickel, Co is cobalt, Mn is manganese, α, β, and γ are 0 <α .Ltoreq.0.5, 0.ltoreq..beta..ltoreq.0.33, and 0 <.gamma..ltoreq.0.5. And a layered transition metal oxide having a crystal structure belonging to the space group C2 / m may be used as the positive electrode active material.

  In some cases, two or more positive electrode active materials may be used in combination. Preferably, a lithium-transition metal composite oxide is used as the positive electrode active material from the viewpoint of capacity and output characteristics. Of course, positive electrode active materials other than those described above may be used. When the optimum particle size is different for expressing the unique effect of each active material, the optimum particle size may be blended and used for expressing each unique effect. It is not always necessary to make the particle diameter uniform.

  The average particle diameter of the positive electrode active material contained in the positive electrode active material layer 15 is not particularly limited, but is preferably 1 to 30 μm, more preferably 5 to 20 μm from the viewpoint of increasing the output. In this specification, unless otherwise specified, “particle diameter” means active material particles (observation) observed using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). It means the maximum distance among the distances between any two points on the contour line. In the present specification, unless otherwise specified, the value of “average particle diameter” is within several to several tens of fields using observation means such as a scanning electron microscope (SEM) and a transmission electron microscope (TEM). The value calculated as the average value of the particle diameters of the observed particles is adopted. The particle diameters and average particle diameters of other components can be defined in the same manner.

  The positive electrode active material layer 15 can include a binder.

(Binder)
The binder is added for the purpose of maintaining the electrode structure by binding the active materials or the active material and the current collector. Although it does not specifically limit as a binder used for a positive electrode active material layer, For example, the following materials are mentioned. Polyethylene, polypropylene, polyethylene terephthalate (PET), polyether nitrile (PEN), polyacrylonitrile, polyimide, polyamide, polyamideimide, cellulose, carboxymethyl cellulose (CMC), ethylene-vinyl acetate copolymer, polyvinyl chloride, styrene / butadiene Rubber (SBR), isoprene rubber, butadiene rubber, ethylene / propylene rubber, ethylene / propylene / diene copolymer, styrene / butadiene / styrene block copolymer and hydrogenated product thereof, styrene / isoprene / styrene block copolymer and Thermoplastic polymers such as hydrogenated products, polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), tetrafluoroethylene hexafluoropropylene Copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene Fluororesin such as copolymer (ECTFE), polyvinyl fluoride (PVF), vinylidene fluoride-hexafluoropropylene-based fluororubber (VDF-HFP-based fluororubber), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene-based fluorine Rubber (VDF-HFP-TFE fluorine rubber), vinylidene fluoride-pentafluoropropylene fluorine rubber (VDF-PFP fluorine rubber), vinylidene fluoride-pentafluoropropylene-teto Fluoroethylene fluororubber (VDF-PFP-TFE fluororubber), vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene fluororubber (VDF-PFMVE-TFE fluororubber), vinylidene fluoride-chlorotrifluoroethylene Vinylidene fluoride-based fluororubbers such as epoxy-based fluororubbers (VDF-CTFE-based fluororubbers), and epoxy resins. Among these, polyvinylidene fluoride, polyimide, styrene / butadiene rubber, carboxymethyl cellulose, polypropylene, polytetrafluoroethylene, polyacrylonitrile, polyamide, and polyamideimide are more preferable. These suitable binders are excellent in heat resistance, have a very wide potential window, are stable at both the positive electrode potential and the negative electrode potential, and can be used for the active material layer. These binders may be used alone or in combination of two.

  The amount of the binder contained in the positive electrode active material layer is not particularly limited as long as it is an amount capable of binding the active material, but is preferably 0.5 to 15% by mass with respect to the active material layer. More preferably, it is 1-10 mass%.

  The positive electrode (positive electrode active material layer) can be applied by any one of a kneading method, a sputtering method, a vapor deposition method, a CVD method, a PVD method, an ion plating method, and a thermal spraying method in addition to a method of applying (coating) a normal slurry. Can be formed.

[Negative electrode active material layer]
The negative electrode active material layer 13 includes a negative electrode active material.

(Negative electrode active material)
The negative electrode active material essentially contains a predetermined alloy.

By applying _a ternary Si _x Sn _y M _z A _a alloy and supporting a carbon-based material on the surface of the alloy, the anode active material can be refined by expansion and contraction during charge and discharge, The effect | action of suppressing reaction of this is acquired. As a result, the negative electrode using the negative electrode active material according to the present invention has a useful effect of having high cycle durability.

Alloy In this embodiment, the alloy is represented by the following chemical formula (1).

  In the chemical formula (1), M is at least one metal selected from the group consisting of Ti, Zn, C, and combinations thereof. A is an inevitable impurity. Furthermore, x, y, z, and a represent mass% values, where 0 <x <100, 0 <y <100, 0 <z <100, and 0 ≦ a <0.5. , X + y + z + a = 100. In the present specification, the “inevitable impurity” means an Si alloy that exists in a raw material or is inevitably mixed in a manufacturing process. The inevitable impurities are originally unnecessary impurities, but are a very small amount and do not affect the characteristics of the Si alloy.

  In the present embodiment, as the negative electrode active material, Sn as the first additive element and M (at least one metal selected from the group consisting of Ti, Zn, C, and combinations thereof) as the second additive element are used. By the selection, the cycle life can be improved by suppressing the phase transition of the amorphous-crystal during the Li alloying. This also makes the capacity higher than that of a conventional negative electrode active material, for example, a carbon-based negative electrode active material.

  Here, in the case of Li alloying, the amorphous-crystal phase transition is suppressed because, in the Si material, when Si and Li are alloyed, the amorphous state transitions to the crystalline state and a large volume change (about 4 times) occurs. This is because the particles themselves are broken and the function as an active material is lost. Therefore, by suppressing the amorphous-crystal phase transition, it is possible to suppress the collapse of the particles themselves, to maintain the function (high capacity) as an active material, and to improve the cycle life. By selecting the first and second additive elements, a Si alloy negative electrode active material having a high capacity and a high cycle durability can be provided.

As described above, M is at least one metal selected from the group consisting of Ti, Zn, C, and combinations thereof. Therefore, _{hereinafter, Si x Sn y Ti z A} a, the _{Si x Sn y Zn z A a} , and _{Si x Sn y C z A a} Si alloy will be described respectively.

_[Si x _Sn y _Ti z _Si alloys represented by _{A a]}
The _Si x _Sn y _Ti z _{A a,} as described above, and Sn is a first additional element, by selecting the Ti as the second additional element, when Li alloying, amorphous - crystalline phases The cycle life can be improved by suppressing the transition. This also makes the capacity higher than that of a conventional negative electrode active material, for example, a carbon-based negative electrode active material.

  In the composition of the alloy, the x, y, and z are represented by the following formula (1) or (2):

It is preferable to satisfy. That is, from the viewpoint of improving the above characteristics of the negative electrode active material, the first region has a silicon (Si) content of 35% by mass or more and 78% by mass or less, and 7% by mass or more, as indicated by reference symbol A in FIG. A region containing 30% by mass or less of tin (Sn) and more than 0% by mass and 37% by mass or less of titanium (Ti) is preferable. Moreover, as shown by the code | symbol B of FIG. 3, 2nd area | region is 35 mass% or more and 52 mass% or less of Si, 30 mass% or more of 51 mass% or less of Sn, more than 0 mass% and 35 mass% or less. A region containing Ti is preferable. When the content of each component is within the above range, an initial discharge capacity exceeding 1000 Ah / g can be obtained, and the cycle life can also exceed 90% (50 cycles).

  In addition, from the viewpoint of further improving the above characteristics of the negative electrode active material, it is desirable that the titanium content is in the range of 7% by mass or more. That is, as indicated by reference C in FIG. 4, the first region has a silicon (Si) content of 35% to 78% by mass, tin (Sn) of 7% to 30% by mass, and 7% by mass or more. A region containing 37 mass% or less of titanium (Ti) is preferable. Moreover, as shown by the code | symbol D of FIG. 4, 35 mass% or more and 52 mass% or less of Si, 30 mass% or more and 51 mass% or less of Sn, 7 mass% or more and 35 mass% or less of Ti It is preferable that it is the area | region containing. That is, the x, y, and z are represented by the following formula (3) or (4):

It is preferable to satisfy. As a result, as shown in a reference example described later, the discharge capacity retention rate after 50 cycles can be 43% or more.

  And from the viewpoint of ensuring better cycle durability, as shown by the symbol E in FIG. 5, the first region is 35 mass% to 68 mass% Si, 7 mass% to 30 mass%. A region containing Sn, 18 mass% or more and 37 mass% or less of Ti is preferable. 5, the second region includes 39% to 52% by mass of Si, 30% to 51% by mass of Sn, and 7% to 20% by mass of Ti. It is desirable that the region includes That is, the x, y, and z are represented by the following formula (5) or (6):

It is preferable to satisfy.

  From the viewpoint of initial discharge capacity and cycle durability, it is particularly preferable that the negative electrode active material of the present embodiment includes an alloy that includes a component in the region indicated by symbol G in FIG. In addition, the area | region shown with the code | symbol G is an area | region containing 46 mass% or more and 58 mass% or less of Si, 7 mass% or more and 21 mass% or less of Sn, and 24 mass% or more and 37 mass% or less of Ti. That is, the x, y, and z are represented by the following formula (7):

It is preferable to satisfy.

  As described above, A is an impurity (unavoidable impurity) other than the three components derived from the raw materials and the manufacturing method. The a is 0 ≦ a <0.5, and preferably 0 ≦ a <0.1.

[Si alloy represented by Si _x Sn _y Zn _z A _a ]
As described above, the Si _x Sn _y Zn _z Aa is selected from the first additive element Sn and the second additive element Zn. And the cycle life can be improved. This also makes the capacity higher than that of a conventional negative electrode active material, for example, a carbon-based negative electrode active material.

  In the composition of the alloy, x is more than 23 and less than 64, y is 4 or more and 58 or less, and z is more than 0 and less than 65. This numerical range corresponds to the range indicated by the symbol X in FIG. And this negative electrode active material of Si alloy is used for the negative electrode of an electrical device, for example, the negative electrode of a lithium ion secondary battery. In this case, the alloy contained in the negative electrode active material absorbs lithium ions when the battery is charged and releases lithium ions when discharged.

  More specifically, the negative electrode active material is a negative electrode active material of a Si alloy, and tin (Sn) as a first additive element and zinc (Zn) as a second additive element are added therein. Is. And, by appropriately selecting Sn as the first additive element and Zn as the second additive element, when alloying with lithium, the amorphous-crystal phase transition is suppressed and the cycle life is improved. Can do. In addition, this can make the capacity higher than that of the carbon-based negative electrode active material.

  Then, by optimizing the composition ranges of Sn and Zn as the first and second additive elements, respectively, a Si (Si—Sn—Zn) alloy having a good cycle life after 50 cycles and 100 cycles The negative electrode active material can be obtained.

  At this time, in the negative electrode active material made of a Si—Sn—Zn-based alloy, when x exceeds 23, a sufficient discharge capacity at the first cycle can be ensured. In addition, when y is 4 or more, a satisfactory discharge capacity retention rate at the 50th cycle can be sufficiently secured. When x, y, and z are within the range of the above composition, cycle durability is improved, and a satisfactory discharge capacity retention rate (for example, 50% or more) at the 100th cycle can be sufficiently secured.

  In addition, from the viewpoint of further improving the above characteristics of the Si alloy negative electrode active material, in the composition of the above alloy, reference numerals in FIG. 11 represented by 23 <x <64, 4 ≦ y <34, and 2 <z <65. A range indicated by A is desirable. Further, it is desirable that the range shown by the symbol B in FIG. 11 satisfying 23 <x <44, 34 <y <58, and 0 <z <43. As a result, as shown in Table 2, it is possible to obtain a discharge capacity maintenance rate of 92% or more in 50 cycles and over 55% in 100 cycles. From the standpoint of ensuring better cycle durability, it is desirable that the range shown by the symbol C in FIG. 12 satisfy 23 <x <64, 4 <y <34, and 27 <z <61. In addition, it is desirable that the range shown by the symbol D in FIG. 12 satisfy 23 <x <34, 34 <y <58, and 8 <z <43. As a result, cycle durability is improved, and as shown in Table 2, a discharge capacity maintenance rate exceeding 65% can be obtained in 100 cycles.

  Furthermore, the range indicated by the symbol E in FIG. 13 satisfying 23 <x <58, 4 <y <24, 38 <z <61, 23 <x <38, 24 ≦ y <35, and 27 <z <53 are satisfied. A range indicated by reference sign F in FIG. 13, a range indicated by reference sign G in FIG. 13 satisfying 23 <x <38, 35 <y <40, 27 <z <44, or 23 <x <29, 40 ≦ y <58, It is desirable that the range shown by the symbol H in FIG. 13 satisfying 13 <z <37. As a result, cycle durability is improved, and as shown in Table 2, a discharge capacity maintenance rate exceeding 75% can be obtained in 100 cycles.

  As described above, A is an impurity (unavoidable impurity) other than the three components derived from the raw materials and the manufacturing method. The a is 0 ≦ a <0.5, and more preferably 0 ≦ a <0.1.

[Si alloy represented by Si _x Sn _y C _z A _a ]
As described above, the Si _x Sn _y C _z A _a is selected from the first additive element Sn and the second additive element C, so that an amorphous-crystalline phase is formed during Li alloying. The cycle life can be improved by suppressing the transition. This also makes the capacity higher than that of a conventional negative electrode active material, for example, a carbon-based negative electrode active material.

  In the alloy composition, x is preferably 29 or more. This numerical range corresponds to the range indicated by the symbol A in FIG. By having the said composition, not only high capacity | capacitance is expressed but a high discharge capacity can be maintained also after 50 cycles after 100 cycles.

  From the viewpoint of further improving the above-described characteristics of the negative electrode active material, it is preferable that x is in the range of 29 to 63, y is 14 to 48, and z is 11 to 48. This numerical range corresponds to the range indicated by the symbol B in FIG.

  From the viewpoint of ensuring better cycle durability, it is preferable that x is in the range of 29 to 44, y is in the range of 14 to 48, and z is in the range of 11 to 48. This numerical range corresponds to the range indicated by the symbol C in FIG.

  Furthermore, it is preferable that x is in the range of 29 to 40 and y is in the range of 34 to 48 (and therefore 12 ≦ z ≦ 37). This numerical range corresponds to the range indicated by the symbol D in FIG.

  As described above, A is an impurity (unavoidable impurity) other than the three components derived from the raw materials and the manufacturing method. The a is 0 ≦ a <0.5, and preferably 0 ≦ a <0.1.

(Carbon material support on Si alloy surface)
The Si alloy according to the present invention is characterized in that a carbon-based material is supported (coated) on the surface thereof. Lithium ion using a negative electrode active material including a Si alloy (hereinafter also simply referred to as “carbon-supported Si alloy” or “carbon-coated Si alloy”) in which a carbon-based material is supported (coated) on the surface having such characteristics. An electric device such as a secondary battery has high cycle durability.

  In this specification, “support” or “coating” means that the carbon-based material is chemically or physically bonded to at least a part of the surface of the Si alloy. Whether or not a carbon-based material is supported (coated) on the surface of the Si alloy depends on whether the carbon-based material adheres to the alloy particles in the carbon-supported Si alloy (negative electrode active material) that is manufactured or collected (separated) from the electrode. The case where the coverage of the alloy with the carbon-based material is 15 mol% or more is defined as “the carbon-based material is supported (coated) on the surface of the Si alloy”. For this reason, depending on the simple mixing of the negative electrode active material, the conductive auxiliary agent (carbon-based material) and the binder as conventionally performed, the conductive auxiliary agent is not supported on the negative electrode active material or depends on the carbon-based material of the alloy. It is supported only when the coverage is less than 15 mol%. In addition, the carrying | support (coating) state to the alloy surface of a carbonaceous material can be confirmed easily by well-known means, such as a scanning electron microscope (SEM).

  The detailed reason is unclear why the cycle durability of the electric device using the Si alloy having the above-described characteristics is improved, but the following reasons are conceivable.

As described above, since the Si alloy is severely expanded and contracted during charging and discharging, deterioration in cycle durability is a problem due to pulverization or reaction (oxidation) with the electrolyte accompanying an increase in surface area. In the lithium ion secondary battery using the negative electrode having the amorphous alloy having the formula: Si _x M _y Al _z described in Patent Document 1, even if the amorphous alloy has the formula: Si _x M _y Al _z Like the high purity Si active material, the expansion and contraction cannot be sufficiently suppressed. For this reason, the active material (particles) is refined due to expansion and contraction during charge and discharge, the specific surface area of the active material is increased, decomposition of the electrolyte is promoted, and side reactions are generated due to electrolyte depletion and electrolyte decomposition. An object is formed, which hinders conductivity.

  Moreover, since the amorphous alloy described in Patent Document 1 contains Si (semiconductor), sufficient conductivity is not ensured. For this reason, when the amorphous alloy is used as an active material, it is necessary to add a conductive additive. However, it is difficult to uniformly disperse the conventional conductive additive, and locally highly conductive. In many cases, the active material and the low active material are mixed. For these reasons, it has been difficult for conventional techniques to maintain high cycle characteristics.

In contrast, in the present invention, an alloy (particle) of Si _x Sn _y M _z A _a (M = Ti, Zn, C, or a combination thereof) is applied, and the surface of the alloy (particle) is carbon-based. The material is supported (coated). For this reason, the presence of the carbon-based material on the alloy surface can suppress the reactivity between the surface of the alloy (particles) and the electrolytic solution. It becomes possible to suppress. In addition, unlike conventional methods in which a conductive additive is added, a highly conductive carbon-based material exists on the surface of the alloy (particles), so that the conductivity of the alloy (particles) is ensured and the entire alloy has high conductivity. Can be granted. Thereby, for example, when applied to a lithium ion secondary battery, when Li ions are inserted, an effect of promoting uniform charge depth of the alloy particles is brought about, and Li ions are excessively inserted and easily deteriorated. Alloy particles can be eliminated.

  That is, since the negative electrode active material according to the present invention is not an alloy particle but a carbon-based material is in contact with the electrolytic solution, the decomposition reaction of the electrolytic solution (particularly due to silicon) can be suppressed, and the carbon-based material exists on the outermost surface. Thus, the conductivity can be improved. Therefore, the negative electrode active material according to the present invention can improve cycle characteristics, and further, initial capacity and cycle characteristics.

  In addition, the said mechanism is based on estimation and this invention is not restrict | limited to the said mechanism at all.

  A carbon-based material is supported (coated) on the surface of the alloy (particle). Here, the coverage (support rate) of the alloy with the carbon-based material is not particularly limited. Considering the effect of improving the cycle characteristics (cycle durability), the effect of improving the conductivity, the coverage of the alloy with the carbon-based material is preferably 50 to 400 mol%, more preferably 100 to 400 mol%, More preferably, it is 250-400 mol%.

  In this specification, a value measured and calculated by the following method is adopted as the “covering rate (support rate) of the alloy with the carbon-based material”. In the present specification, the “coverage (support rate) (mol%) of the alloy with a carbon-based material” is also simply referred to as “carbon coverage (mol%)”.

<Measurement of coverage (support rate) of alloy with carbon-based material>
The carbon coverage of the alloy on which the carbon-based material is supported is determined by measuring the molar ratio of silicon and the molar ratio of carbon using Auger electron spectroscopy under the following measurement conditions.

  Next, using the mole ratio of silicon and the mole ratio of carbon measured above, the mole ratio of carbon to the mole ratio of silicon was calculated according to the following formula, and the obtained value was expressed as the carbon coverage (Table 4 below). "Carbon coverage with respect to silicon")) (mol%).

  Here, the method for controlling the coverage (support rate) of the alloy with the carbon-based material within the above preferable range is not particularly limited. Specifically, a method is used in which an alloy and a carbon-based material are mixed in an appropriate ratio and then physically or chemically treated to chemically or physically bond (support) the carbon-based material on the alloy surface. it can.

  In the above method, the mixing ratio of the alloy and the carbon-based material is not particularly limited. Specifically, when the total amount of the carbon-based material and the alloy and the carbon-based material is 100 parts by weight, the ratio is preferably 1 to 25 parts by weight, more preferably 5 to 25 parts by weight. Especially preferably, it mixes with an alloy in the ratio of 10-25 weight part. According to such a mixing ratio, the coverage (support rate) of the alloy with the carbon-based material can be easily controlled within the preferable range as described above. Further, according to such a mixing ratio, the carbon-based material can be uniformly supported (coated) on the alloy surface.

  The carbon-based material is not particularly limited, and a carbon-based material that is usually used as a conductive additive can be used. Specific examples include acetylene black, furnace black, carbon black, channel black, and graphite. Of these, from the viewpoint of supporting and maintaining properties, the carbon-based material preferably has low crystallinity in which insertion or desorption of Li ions hardly occurs or does not occur, and it is more preferable to use acetylene black or carbon fiber. Further, the shape of the carbon-based material is not particularly limited, and may be in a particle form or a fiber form. From the viewpoint of easy loading, a particle form is preferable, and from a conductive point, a fiber form is preferable. The size of the carbon-based material is not particularly limited. For example, when the carbonaceous material is in the form of particles, the average particle size (secondary particle size) is preferably 10 to 200 nm, more preferably 20 to 150 nm. Moreover, when a carbonaceous material is a fiber form, a diameter becomes like this. Preferably it is 20-500 nm, More preferably, it is 50-300 nm, Length is preferably 5-20 micrometers, More preferably, it is 8- 15 μm. With such a size, the carbon-based material can be easily supported on the alloy surface. Moreover, if it is such a magnitude | size, a carbonaceous material can carry | support uniformly on the alloy surface.

  In the above method, the physical or chemical treatment method for chemically or physically bonding (supporting) the carbon-based material to the surface of the alloy is not particularly limited, and the carbon-based material is incorporated into the alloy by shearing. Examples thereof include a method of embedding at least a part, a method of chemically bonding via functional groups on the surface of the alloy and the carbon-based material, and the like. More specifically, a mechanochemical method, a liquid phase method, a sintering method, a vapor deposition (CVD) method, and the like can be given.

  The physical or chemical treatment conditions for chemically or physically bonding (supporting) the carbon-based material to the alloy surface are not particularly limited and can be appropriately selected depending on the method used. For example, when the mechanochemical method is used, the rotation speed (processing rotation speed) is preferably 3000 to 8000 rpm, more preferably 4000 to 7000 rpm. Further, the load power is preferably 200 to 400 W, more preferably 250 to 300 W. The treatment time is preferably 10 to 60 minutes, more preferably 20 to 50 minutes. Under such conditions, the carbon-based material can be supported (coated) on the alloy surface at the above preferable coverage (support rate). Further, the carbon-based material can be uniformly supported on the alloy surface.

(D50 value of secondary particle diameter of Si alloy)
The size of the Si alloy according to the present invention is not particularly limited, but the D50 value of the secondary particle diameter obtained by the laser diffraction method is preferably more than 0.01 μm and less than 20 μm. An electric device such as a lithium ion secondary battery using a negative electrode active material containing a Si alloy having such a size has high cycle durability. The D50 value of the secondary particle diameter is preferably 0.4 to 10 μm, more preferably 2.5 to 7 μm, from the viewpoint of cycle durability. With such an alloy particle size, the carbon-based material can be efficiently supported on the surface of the alloy particle, and it is effective that the supported carbon-based material is peeled off from the alloy surface by suppressing the expansion and contraction of the alloy. Can be suppressed and prevented.

  In the present invention, the D50 value is calculated based on the particle size distribution data calculated by a laser type particle size distribution meter, and D50; median diameter, that is, an intermediate particle diameter is calculated. In the present invention, the laser particle size distribution analyzer uses a laser diffraction / scattering particle size distribution measuring device (manufactured by Horiba, Ltd., model: LA-920).

(Si alloy)
The shape of the Si alloy is not particularly limited, and may be spherical, elliptical, cylindrical, polygonal, scaly, indefinite, or the like.

As a method for producing an alloy having a composition formula Si _x Sn _y M _{z A a} according to the manufacturing method according to this embodiment of the alloy is not limited in particular, be prepared by utilizing the manufacturing method of the conventionally known various it can. That is, since there is almost no difference in alloy state and characteristics depending on the manufacturing method, various manufacturing methods can be applied.

Specifically, for example, as a manufacturing method (alloying treatment method) of a particle form of an alloy having the composition formula Si _x Sn _y M _z A _a , there are a solid phase method, a liquid phase method, and a gas phase method. Further, a mechanical alloy method, an arc plasma melting method, or the like can be used.

  Further, the Si alloy according to the present invention may be subjected to a pulverization process and / or a firing process, if necessary, after the alloying process (for example, mechanical alloy method).

  When the pulverization treatment is performed after the alloying treatment, the pulverization conditions are not particularly limited. However, the pulverization conditions are usually 400 to 800 rpm, 5 minutes to 100 hours, preferably 30 minutes to 4 hours.

  In addition, the firing conditions when performing the firing treatment after the alloying treatment or the pulverization treatment are not particularly limited. In addition, the BET specific surface area of Si alloy falls by performing a baking process. Considering the BET specific surface area of the obtained Si alloy, the firing temperature is preferably 80 to 300 ° C. The firing time is preferably 0.5 to 3 hours. By performing the firing treatment under such conditions, the BET specific surface area of the Si alloy can be adjusted appropriately.

  In the method of manufacturing in the above particle form, a slurry is prepared by adding a binder and, if necessary, a conductive additive or a viscosity adjusting solvent to the particles (carbon-supported Si alloy), and a slurry electrode is formed using the slurry. Can be formed. Therefore, it is excellent in that it is easy to mass-produce (mass production) and to be practically used as an actual battery electrode.

As described above, the predetermined alloy included in the negative electrode active material layer has been described, but the negative electrode active material layer may contain other negative electrode active materials. Examples of the negative electrode active material other than the predetermined alloy include natural graphite, artificial graphite, carbon black, activated carbon, carbon fiber, coke, soft carbon, carbon such as hard carbon, pure metal such as Si and Sn, and the predetermined composition. Alloy-based active material out of ratio, or metal oxide such as TiO, Ti ₂ O ₃ , TiO ₂ , SiO ₂ , SiO, SnO ₂ , lithium such as Li _4/3 Ti _5/3 O ₄ or Li ₇ MnN And transition metal complex oxides, Li—Pb alloys, Li—Al alloys, Li, and the like. However, from the viewpoint of sufficiently exerting the effects exhibited by using the predetermined alloy as the negative electrode active material, the predetermined alloy (carbon-supported Si alloy) occupying 100% by mass of the total amount of the negative electrode active material. The content is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, particularly preferably 95 to 100% by mass, and most preferably 100% by mass.

  Subsequently, the negative electrode active material layer 13 includes a binder.

(Binder)
The binder is added for the purpose of maintaining the electrode structure by binding the active materials or the active material and the current collector. There is no restriction | limiting in particular also about the kind of binder used for a negative electrode active material layer, What was mentioned above as a binder used for a positive electrode active material layer can be used similarly. Therefore, detailed description is omitted here.

  The amount of the binder contained in the negative electrode active material layer is not particularly limited as long as it is an amount capable of binding the active material, but is preferably 0.5 to It is 20 mass%, More preferably, it is 1-15 mass%.

(Requirements common to the positive and negative electrode active material layers 15 and 13)
The requirements common to the positive and negative electrode active material layers 15 and 13 will be described below.

  The positive electrode active material layer 15 and the negative electrode active material layer 13 include a conductive additive, an electrolyte salt (lithium salt), an ion conductive polymer, and the like as necessary.

Conductive aid In the carbon-supported Si alloy according to the present invention, a carbon-based material is supported (coated) on the alloy surface in advance. For this reason, the negative electrode active material layer which concerns on this invention does not need to contain a conductive support agent. Here, the conductive auxiliary agent refers to an additive blended to improve the conductivity of the positive electrode active material layer or the negative electrode active material layer. Examples of the conductive assistant include carbon materials such as carbon black such as acetylene black, graphite, and vapor grown carbon fiber. When the active material layer contains a conductive additive, an electronic network inside the active material layer is effectively formed, which can contribute to improvement of the output characteristics of the battery.

  When the negative electrode active material layer or the positive electrode active material layer contains a conductive auxiliary agent, the content of the conductive auxiliary agent mixed into the active material layer is preferably 1% by mass or more with respect to the total amount of the active material layer. Is 3% by mass or more, more preferably 5% by mass or more. In addition, the content of the conductive additive mixed in the active material layer is 15% by mass or less, more preferably 10% by mass or less, and further preferably 7% by mass or less with respect to the total amount of the active material layer. is there. By defining the compounding ratio (content) of the conductive aid in the active material layer within the above range, the electronic conductivity of the active material itself is low and the electrode resistance can be reduced by the amount of the conductive aid. The That is, it is possible to sufficiently ensure the electronic conductivity without hindering the electrode reaction, to suppress the decrease in the energy density due to the decrease in the electrode density, and to improve the energy density due to the increase in the electrode density. .

  Moreover, the conductive binder having the functions of the conductive assistant and the binder may be used in place of the conductive assistant and the binder, or may be used in combination with one or both of the conductive assistant and the binder. . As the conductive binder, commercially available TAB-2 (manufactured by Hosen Co., Ltd.) can be used.

Electrolyte salt (lithium salt)
Examples of the electrolyte salt (lithium salt) include Li (C ₂ F ₅ SO ₂ ) ₂ N, LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiCF ₃ SO _{3 and the} like.

Ion conductive polymer Examples of the ion conductive polymer include polyethylene oxide (PEO) -based and polypropylene oxide (PPO) -based polymers.

  The compounding ratio of the components contained in the positive electrode active material layer and the negative electrode active material layer is not particularly limited. The mixing ratio can be adjusted by appropriately referring to known knowledge about the non-aqueous solvent secondary battery.

  There is no particular limitation on the thickness of each active material layer (active material layer on one side of the current collector), and conventionally known knowledge about the battery can be referred to as appropriate. For example, the thickness of each active material layer is usually about 1 to 500 μm, preferably 2 to 100 μm in consideration of the intended use of the battery (emphasis on output, energy, etc.) and ion conductivity.

<Current collector>
The current collectors 11 and 12 are made of a conductive material. The size of the current collector is determined according to the intended use of the battery. For example, if it is used for a large battery that requires a high energy density, a current collector having a large area is used.

  There is no particular limitation on the thickness of the current collector. The thickness of the current collector is usually about 1 to 100 μm.

  The shape of the current collector is not particularly limited. In the laminated battery 10 shown in FIG. 1, in addition to the current collector foil, a mesh shape (such as an expanded grid) can be used.

  In the case where the negative electrode active material is formed directly on the negative electrode current collector 12 by sputtering or the like, it is desirable to use a current collector foil.

  There is no particular limitation on the material constituting the current collector. For example, a metal or a resin in which a conductive filler is added to a conductive polymer material or a non-conductive polymer material can be employed.

  Specifically, examples of the metal include aluminum, nickel, iron, stainless steel, titanium, and copper. In addition to these, a clad material of nickel and aluminum, a clad material of copper and aluminum, or a plating material of a combination of these metals can be preferably used. Moreover, the foil by which aluminum is coat | covered on the metal surface may be sufficient. Of these, aluminum, stainless steel, copper, and nickel are preferable from the viewpoints of electronic conductivity, battery operating potential, and adhesion of the negative electrode active material by sputtering to the current collector.

  Examples of the conductive polymer material include polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyphenylene vinylene, polyacrylonitrile, and polyoxadiazole. Since such a conductive polymer material has sufficient conductivity without adding a conductive filler, it is advantageous in terms of facilitating the manufacturing process or reducing the weight of the current collector.

  Non-conductive polymer materials include, for example, polyethylene (PE; high density polyethylene (HDPE), low density polyethylene (LDPE), etc.), polypropylene (PP), polyethylene terephthalate (PET), polyether nitrile (PEN), polyimide (PI), polyamideimide (PAI), polyamide (PA), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyacrylonitrile (PAN), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA) , Polyvinyl chloride (PVC), polyvinylidene fluoride (PVdF), or polystyrene (PS). Such a non-conductive polymer material may have excellent potential resistance or solvent resistance.

  A conductive filler may be added to the conductive polymer material or the non-conductive polymer material as necessary. In particular, when the resin used as the base material of the current collector is made of only a non-conductive polymer, a conductive filler is inevitably necessary to impart conductivity to the resin.

  The conductive filler can be used without particular limitation as long as it is a substance having conductivity. For example, metals, conductive carbon, etc. are mentioned as a material excellent in electroconductivity, electric potential resistance, or lithium ion barrier | blocking property. The metal is not particularly limited, but at least one metal selected from the group consisting of Ni, Ti, Al, Cu, Pt, Fe, Cr, Sn, Zn, In, Sb, and K, or these metals It is preferable to contain an alloy or metal oxide containing. Moreover, there is no restriction | limiting in particular as electroconductive carbon. Preferably, it includes at least one selected from the group consisting of acetylene black, vulcan, black pearl, carbon nanofiber, ketjen black, carbon nanotube, carbon nanohorn, carbon nanoballoon, and fullerene.

  The amount of the conductive filler added is not particularly limited as long as it is an amount capable of imparting sufficient conductivity to the current collector, and is generally about 5 to 35% by mass.

<Electrolyte layer>
A liquid electrolyte or a polymer electrolyte can be used as the electrolyte constituting the electrolyte layer 17.

  The liquid electrolyte has a form in which a lithium salt (electrolyte salt) is dissolved in an organic solvent. Examples of the organic solvent include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), Examples include carbonates such as methylpropyl carbonate (MPC).

As the lithium _{salt, Li (CF 3 SO 2)} 2 N, Li (C 2 F 5 SO 2) 2 N, LiPF 6, LiBF 4, LiAsF 6, LiTaF 6, LiClO 4, LiCF 3 SO 3 , etc. A compound that can be added to the active material layer of the electrode can be employed.

  On the other hand, the polymer electrolyte is classified into a gel electrolyte containing an electrolytic solution and an intrinsic polymer electrolyte containing no electrolytic solution.

  The gel electrolyte has a configuration in which the liquid electrolyte (electrolytic solution) is injected into a matrix polymer made of an ion conductive polymer. The use of a gel polymer electrolyte as the electrolyte is superior in that the fluidity of the electrolyte is lost and it is easy to block ion conduction between the layers.

  Examples of the ion conductive polymer used as the matrix polymer include polyethylene oxide (PEO), polypropylene oxide (PPO), and copolymers thereof. In such polyalkylene oxide polymers, electrolyte salts such as lithium salts can be well dissolved.

  The ratio of the liquid electrolyte (electrolytic solution) in the gel electrolyte is not particularly limited, but is preferably about several mass% to 98 mass% from the viewpoint of ionic conductivity. In the present embodiment, the gel electrolyte having a large amount of electrolytic solution having a ratio of the electrolytic solution of 70% by mass or more is particularly effective.

  In the case where the electrolyte layer is composed of a liquid electrolyte, a gel electrolyte, or an intrinsic polymer electrolyte, a separator may be used for the electrolyte layer. Specific examples of the separator (including non-woven fabric) include a microporous film made of polyolefin such as polyethylene and polypropylene, a porous flat plate, and a non-woven fabric.

  The intrinsic polymer electrolyte has a structure in which a supporting salt (lithium salt) is dissolved in the matrix polymer, and does not include an organic solvent that is a plasticizer. Therefore, when the electrolyte layer is composed of an intrinsic polymer electrolyte, there is no fear of liquid leakage from the battery, and the reliability of the battery can be improved.

  The matrix polymer of the gel electrolyte or the intrinsic polymer electrolyte can exhibit excellent mechanical strength by forming a crosslinked structure. In order to form a crosslinked structure, thermal polymerization, ultraviolet polymerization, radiation polymerization, electron beam polymerization, etc. are performed on a polymerizable polymer (for example, PEO or PPO) for forming a polymer electrolyte using an appropriate polymerization initiator. A polymerization treatment may be performed.

<Current collector plate and lead>
A current collecting plate may be used for the purpose of taking out the current outside the battery. The current collector plate is electrically connected to the current collector and the lead, and is taken out of the laminate sheet that is a battery exterior material.

  The material which comprises a current collector plate is not specifically limited, The well-known highly electroconductive material conventionally used as a current collector plate for lithium ion secondary batteries can be used. As a constituent material of the current collector plate, for example, metal materials such as aluminum, copper, titanium, nickel, stainless steel (SUS), and alloys thereof are preferable, and aluminum is more preferable from the viewpoint of light weight, corrosion resistance, and high conductivity. Copper or the like is preferable. Note that the same material may be used for the positive electrode current collector plate and the negative electrode current collector plate, or different materials may be used.

  The positive terminal lead and the negative terminal lead are also used as necessary. As the material of the positive terminal lead and the negative terminal lead, a terminal lead used in a known lithium ion secondary battery can be used. It should be noted that the part taken out from the battery outer packaging material 29 has a heat insulating property so as not to affect the product (for example, automobile parts, particularly electronic devices) by contacting with peripheral devices or wiring and causing leakage. It is preferable to coat with a heat shrinkable tube or the like.

<Battery exterior material>
As the battery exterior material 29, a known metal can case can be used, and a bag-like case using a laminate film containing aluminum that can cover the power generation element can be used. For example, a laminate film having a three-layer structure in which PP, aluminum, and nylon are laminated in this order can be used as the laminate film, but the laminate film is not limited thereto. A laminate film is desirable from the viewpoint that it is excellent in high output and cooling performance, and can be suitably used for a battery for large equipment for EV and HEV.

In addition, said lithium ion secondary battery can be manufactured with a conventionally well-known manufacturing method.

<Appearance structure of lithium ion secondary battery>
FIG. 2 is a perspective view showing the appearance of a stacked flat lithium ion secondary battery.

  As shown in FIG. 2, the stacked flat lithium ion secondary battery 50 has a rectangular flat shape, and a positive current collector 59 for taking out power from both sides thereof, a negative current collector, and the like. The electric plate 58 is pulled out. The power generation element 57 is wrapped by the battery outer packaging material 52 of the lithium ion secondary battery 50 and the periphery thereof is heat-sealed. The power generation element 57 pulls out the positive electrode current collector plate 59 and the negative electrode current collector plate 58 to the outside. Sealed. Here, the power generation element 57 corresponds to the power generation element 21 of the lithium ion secondary battery (stacked battery) 10 shown in FIG. The power generation element 57 is formed by laminating a plurality of single battery layers (single cells) 19 including a positive electrode (positive electrode active material layer) 13, an electrolyte layer 17, and a negative electrode (negative electrode active material layer) 15.

  The lithium ion secondary battery is not limited to a laminated flat shape (laminate cell). In a wound type lithium ion battery, a cylindrical shape (coin cell), a prismatic shape (square cell), or such a cylindrical shape deformed into a rectangular flat shape Further, it may be a cylindrical cell, and is not particularly limited. The cylindrical or prismatic shape is not particularly limited, for example, a laminate film or a conventional cylindrical can (metal can) may be used as the exterior material. Preferably, the power generation element is covered with an aluminum laminate film. With this configuration, weight reduction can be achieved.

  Further, the removal of the positive electrode current collector plate 59 and the negative electrode current collector plate 58 shown in FIG. 2 is not particularly limited. The positive electrode current collector plate 59 and the negative electrode current collector plate 58 may be drawn out from the same side, or the positive electrode current collector plate 59 and the negative electrode current collector plate 58 may be divided into a plurality of parts and taken out from each side. It is not limited to the one shown in FIG. Further, in a wound type lithium ion battery, instead of the current collector plate, for example, a terminal may be formed using a cylindrical can (metal can).

  As described above, the negative electrode and the lithium ion secondary battery using the negative electrode active material for the lithium ion secondary battery of the present embodiment are large vehicles such as electric vehicles, hybrid electric vehicles, fuel cell vehicles, and hybrid fuel cell vehicles. It can be suitably used as a capacity power source. That is, it can be suitably used for a vehicle driving power source and an auxiliary power source that require high volume energy density and high volume output density.

  In the above embodiment, the lithium ion battery is exemplified as the electric device. However, the present invention is not limited to this, and can be applied to other types of secondary batteries and further to primary batteries. Moreover, it can be applied not only to batteries but also to capacitors.

  The invention is explained in more detail using the following examples. However, the technical scope of the present invention is not limited only to the following examples.

  First, as a reference example, performance evaluation was performed on the Si alloy represented by the chemical formula (1) constituting the negative electrode active material for an electric device according to the present invention.

(Reference Example _{A): Si x Sn y Ti} z A as the performance evaluation [1] Preparation sputtering apparatus of a negative electrode for _a, 3-way DC magnetron sputtering device independent control system (Yamato Equipment Industries Co., combinatorial sputter coating apparatus A thin film of a negative electrode active material alloy having each composition under the following conditions on a substrate (current collector) made of nickel foil having a thickness of 20 μm. Forty types of negative electrode samples were obtained by forming each film (Reference Examples 1-1 to 1-26 and Reference Examples 1′-1 to 1′-14).

(1) Target (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity: 4N)
Si: 50.8 mm diameter, 3 mm thickness (with 2 mm thick oxygen-free copper backing plate)
Sn: 50.8 mm diameter, 5 mm thickness Ti: 50.8 mm diameter, 5 mm thickness.

(2) Film formation conditions Base pressure: ˜7 × 10 ⁻⁶ Pa
Sputtering gas type: Ar (99.9999% or more)
Sputtering gas introduction amount: 10 sccm
Sputtering pressure: 30 mTorr
DC power supply: Si (185 W), Sn (0 to 40 W), Ti (0 to 150 W)
Pre-sputtering time: 1 min.
Sputtering time: 10 min.
Substrate temperature: room temperature (25 ° C.).

  That is, using the Si target, Sn target, and Ti target as described above, the sputtering time is fixed to 10 minutes, and the power of the DC power source is changed within the above range, whereby an amorphous alloy is formed on the Ni substrate. A thin film was formed, and negative electrode samples provided with alloy thin films having various compositions were obtained.

  In addition, if the example of sample preparation is shown about said (2), in the reference example 1-17, DC power supply 1 (Si target): 185W, DC power supply 2 (Sn target): 30W, DC power supply 3 (Ti target) : 150 W. In Reference Example 1'-2, the DC power source 1 (Si target): 185 W, the DC power source 2 (Sn target): 22 W, and the DC power source 3 (Ti target): 0 W. Further, in Reference Example 1'-7, the DC power source 1 (Si target): 185 W, the DC power source 2 (Sn target): 0 W, and the DC power source 3 (Ti target): 30 W.

  The component compositions of these alloy thin films are shown in Table 1 and FIG.

(3) Analysis method Composition analysis: SEM / EDX analysis (JEOL), EPMA analysis (JEOL)
Film thickness measurement (for sputter rate calculation): Film thickness meter (Tokyo Instruments)
Film state analysis: Raman spectroscopy (Bruker).

[2] Production of Battery Each negative electrode sample obtained above and a counter electrode made of lithium foil (Honjo Metal Co., Ltd., diameter: 15 mm, thickness: 200 μm) are opposed to each other through a separator (Celgard Cellguard 2400). Then, CR2032-type coin cells were produced by injecting an electrolyte solution.

As the above electrolyte solution, ethylene carbonate (EC) and diethyl carbonate (DEC) 1: in a mixed nonaqueous solvent were mixed at a volume ratio, the concentration of LiPF ₆ a (lithium hexafluorophosphate) 1M What was dissolved so that it might become was used.

[3] Battery Charging / Discharging Test The following charging / discharging test was performed on each battery obtained as described above.

  That is, using a charge / discharge tester (HJ0501SM8A manufactured by Hokuto Denko Co., Ltd.), in a thermostatic chamber (PFU-3K manufactured by Espec Co., Ltd.) set at a temperature of 300K (27 ° C), In a process of inserting Li into a certain negative electrode), the battery was charged from 2 V to 10 mV at 0.1 mA as a constant current / constant voltage mode. Thereafter, in the discharge process (Li desorption process from the negative electrode), the constant current mode was set, and discharge was performed from 0.1 mA, 10 mV to 2 V. The above charging / discharging cycle was made into 1 cycle, and this was repeated 100 times.

  And the discharge capacity of 50th cycle and 100th cycle was calculated | required, and the maintenance factor with respect to the discharge capacity of 1st cycle was computed. The results are also shown in Table 1. At this time, the discharge capacity indicates a value calculated per alloy weight. The “discharge capacity (mAh / g)” is per pure Si or alloy weight, and when Li reacts with Si—Sn—M alloy (Si—M alloy, pure Si or Si—Sn alloy). Indicates capacity. In addition, what is described as “initial capacity” in this specification corresponds to “discharge capacity (mAh / g)” of the initial cycle (first cycle).

  The “discharge capacity maintenance ratio (%)” at the 50th or 100th cycle represents an index of “how much capacity is maintained from the initial capacity”. The calculation formula of the discharge capacity retention rate (%) is as follows.

  The results are also shown in Table 1. FIG. 7 shows the relationship between the discharge capacity at the first cycle and the alloy composition. Further, FIG. 8 and FIG. 9 show the relationship between the discharge capacity retention rate and the alloy composition at the 50th and 100th cycles, respectively. The discharge capacity indicates a value calculated per alloy weight.

  As a result, the battery of Reference Example A (see Table 1) using the Si—Sn—Ti-based alloy in which each component is in a specific range, that is, in the range A or the range B shown in FIG. As shown in FIG. 7, it has an initial capacity of at least 1000 mAh / g. Then, as shown in FIGS. 8 and 9, it was confirmed that the discharge capacity retention rate was 91% or more after 50 cycles and 43% or more after 100 cycles.

(Reference Example B): Performance Evaluation for Si _x Sn _y Zn _z A _a [1] Production of Negative Electrode “Ti: 50.8 mm diameter, 5 mm thickness” of the target in (1) of Reference Example A was changed to “Zn: “50.8 mm diameter, 3 mm thickness”. Furthermore, “Ti (0 to 150 W)” of the DC power source in (2) was changed to “Zn (0 to 150 W)”. Except for the above changes, 46 negative electrode samples were produced in the same manner as in Reference Example A (Reference Examples 2-1 to 2-32 and Reference Examples 2′-1 to 2′-14).

  That is, the Si target, Sn target, and Zn target as described above were used, the sputtering time was fixed at 10 minutes, and the power of the DC power source was changed within the above range. In this manner, an amorphous alloy thin film was formed on the Ni substrate, and negative electrode samples provided with alloy thin films having various compositions were obtained.

  As for the DC power source in (2), if several examples of sample preparation conditions are shown, in Reference Example 2-4, the DC power source 1 (Si target) is 185 W, the DC power source 2 (Sn target) is 22 W, and the DC power source. 3 (Zn target) was 100 W. In Reference Example 2'-2, the DC power source 1 (Si target) was 185 W, the DC power source 2 (Sn target) was 30 W, and the DC power source 3 (Zn target) was 0 W. Furthermore, in Reference Example 2'-5, the DC power source 1 (Si target) was 185 W, the DC power source 2 (Sn target) was 0 W, and the DC power source 3 (Zn target) was 25 W.

  Table 2 shows the component compositions of these alloy thin films. The obtained alloy thin film was analyzed by the same analysis method and analysis apparatus as in Reference Example A.

[2] Production of Battery A CR2032-type coin cell was produced in the same manner as in Reference Example A.

[3] Battery Charge / Discharge Test A battery charge / discharge test was performed in the same manner as in Reference Example A. The results are also shown in Table 2.

  As a result, in the battery of Reference Example B (see Table 2) using the Si—Sn—Zn-based alloy in which each component is in a specific range, that is, in the range X shown in FIG. 14 has an initial capacity of at least 1000 mAh / g. As shown in FIGS. 15 and 16, the negative electrode active material of the Si—Sn—Zn-based alloy in the range X of FIG. 10 has a discharge exceeding 92% after 50 cycles and exceeding 50% even after 100 cycles. It was confirmed that the capacity retention rate was exhibited (see Reference Examples 2-1 to 2-32).

(Reference Example C): Performance Evaluation for Si _x Sn _y C _z A _a [1] Production of Negative Electrode “Ti: 50.8 mm diameter, 5 mm thickness” of the target in (1) of Reference Example A was changed to “C: 50.8 mm diameter, 3 mm thickness (with 2 mm thick oxygen-free copper backing plate) ”. Also, “Ti (0 to 150 W)” of the DC power source in (2) was changed to “C (0 to 150 W)”. Except for the above changes, 34 negative electrode samples were produced in the same manner as in Reference Example A (Reference Examples 3-1 to 3-22 and Reference Examples 3′-1 to 3′-12).

  Regarding (2), if several examples of sample preparation are shown, in Reference Example 3-16, the DC power source 1 (Si target) is 185 W, the DC power source 2 (Sn target) is 35 W, and the DC power source 3 (C target) ) Was 110 W. In Reference Example 3'-2, the DC power source 1 (Si target) was 185 W, the DC power source 2 (Sn target) was 22 W, and the DC power source 3 (C target) was 0 W. Furthermore, in Reference Example 3'-7, the DC power source 1 (Si target) was 185 W, the DC power source 2 (Sn target) was 0 W, and the DC power source 3 (C target) was 30 W.

  The component compositions of these alloy thin films are shown in Table 3 and FIG.

[2] Production of Battery A CR2032-type coin cell was produced in the same manner as in Reference Example A.

[3] Battery Charge / Discharge Test A battery charge / discharge test was performed in the same manner as in Reference Example A. The results are also shown in Table 3.

  As a result, in the battery of Reference Example C (see Table 3) using Si—Sn—C alloy containing 29 mass% or more of Si, that is, within the range B shown in FIG. 18, as the negative electrode active material. Has an initial capacity of at least 1000 mAh / g as shown in FIG. As shown in FIGS. 22 and 23, the negative electrode active material of the Si—Sn—C alloy within the range B shown in FIG. 18 is 92% or more after 50 cycles and 45% or more after 100 cycles. (See Reference Examples 3-1 to 3-22).

Next, as an example, performance evaluation was performed on a negative electrode for an electric device having a negative electrode active material layer using a Si alloy (Si ₆₀ Sn ₂₀ Ti ₂₀ ) produced in the same manner as in Reference Example A as a negative electrode active material. It was.

The Si ₆₀ Sn ₂₀ Ti ₂₀ and other alloys used in the present invention (Si _x Sn _y Ti _z A _a , Si _x Sn _y Zn _z A _a , and Si _x Sn _y C _z A _a , For Si ₆₀ Sn ₂₀ Ti ₂₀ other than Si ₆₀ Sn ₂₀ Ti ₂₀ , the same or similar results as in the following examples using Si ₆₀ Sn ₂₀ Ti ₂₀ are obtained. This is because, in order to improve the cycle durability of the Si alloy, it is important to coat the alloy with a carbon-based material. Further, in addition to the coating of the carbon-based material on the alloy, it is considered that the progress of Si amorphization in the active material is important for improving the cycle durability of the Si alloy, and Ti, Zn and C (second The additive element) is for alloying the Si material to facilitate the progress of the amorphous state. Therefore, it is considered that the cycle durability improves as the amorphous state of Si progresses even with Si _x Sn _y Zn _z A _a using Zn and C other than Ti, and Si _x Sn _y C _z A _a. . That is, when an alloy having such similar characteristics is used, the same result can be obtained even if the type of the alloy is changed.

Example 1
[Manufacture of Si alloy]
The Si alloy was manufactured by a mechanical alloy method (or arc plasma melting method). Specifically, using a planetary ball mill device P-6 manufactured by Fricht, Germany, zirconia pulverized balls and raw material powders of each alloy were charged into a zirconia pulverized pot and alloyed at 600 rpm for 24 hours (alloys). ), And then pulverization was performed at 400 rpm for 1 hour. The average particle diameter (D50) of the obtained Si alloy was 6 μm.

[Production of negative electrode]
75 parts by mass of the Si alloy produced above (Si ₆₀ Sn ₂₀ Ti ₂₀ , average particle diameter (D50): 6 μm) and 25 parts by mass of acetylene black (average particle diameter: 30 nm) as a carbon-based material are mechanochemical composite Carbon support treatment was performed for 30 minutes under the conditions of a treatment rotational speed of 6000 rpm and a load power of 300 W using a chemical conversion device (manufactured by Hosokawa Micron). The carbon coating state was observed with a scanning electron microscope (SEM). For the carbon-coated Si alloy obtained here, the carbon coverage was measured using the following Auger electron spectroscopy, and the results are shown in Table 4 below.

  85 parts by mass of the carbon-coated Si alloy produced above as a negative electrode active material and 15 parts by mass of polyamideimide as a binder were mixed and dispersed in N-methylpyrrolidone to obtain a negative electrode slurry. Next, the obtained negative electrode slurry was uniformly applied to both surfaces of a negative electrode current collector made of copper foil so that the thickness of the negative electrode active material layer was 30 μm, and dried in a vacuum for 24 hours. Obtained.

[Production of positive electrode]
Li _1.85 Ni _0.18 Co _0.10 Mn _0.87 O ₃ which is a positive electrode active material was produced by the method described in Example 1 (paragraph 0046) of JP2012-185913. Then, 90 parts by mass of the positive electrode active material, 5 parts by mass of acetylene black as a conductive auxiliary agent, and 5 parts by mass of polyvinylidene fluoride as a binder are mixed and dispersed in N-methylpyrrolidone to obtain a positive electrode slurry. It was. Next, the obtained positive electrode slurry was uniformly applied to both surfaces of a positive electrode current collector made of aluminum foil so that the thickness of the positive electrode active material layer was 30 μm, and dried to obtain a positive electrode.

[Production of battery]
The positive electrode produced above and the negative electrode were made to face each other, and a separator (polyolefin, film thickness: 20 μm) was disposed therebetween. Next, the laminate of the negative electrode, the separator, and the positive electrode was disposed on the bottom side of a coin cell (CR2032, material: stainless steel (SUS316)). Furthermore, in order to maintain insulation between the positive electrode and the negative electrode, a gasket is attached, the following electrolyte is injected with a syringe, a spring and a spacer are stacked, the upper side of the coin cell is overlapped, and sealed by caulking. Thus, a lithium ion secondary battery was obtained.

In addition, as said electrolyte solution, hexafluorophosphoric acid which is a supporting salt in the organic solvent which mixed ethylene carbonate (EC) and diethyl carbonate (DEC) in the ratio of EC: DEC = 1: 2 (volume ratio). lithium (LiPF _6), was used as the concentration was such that 1 mol / L.

(Example 2)
In the production of the negative electrode, a negative electrode and a battery were produced in the same manner as in Example 1 except that the amounts of acetylene black as the Si alloy and the carbon-based material were changed to 80 parts by weight and 20 parts by weight, respectively. For the obtained carbon-coated Si alloy, the carbon coverage was measured using the following Auger electron spectroscopy, and the results are shown in Table 4 below.

(Example 3)
In the production of the negative electrode, a negative electrode and a battery were produced in the same manner as in Example 1 except that the amounts of the Si alloy and acetylene black (carbon-based material) were changed to 85 parts by weight and 15 parts by weight, respectively. For the obtained carbon-coated Si alloy, the carbon coverage was measured using the following Auger electron spectroscopy, and the results are shown in Table 4 below.

Example 4
In the production of the negative electrode, a negative electrode and a battery were produced in the same manner as in Example 1 except that the amounts of the Si alloy and acetylene black (carbon-based material) were changed to 90 parts by weight and 10 parts by weight, respectively. For the obtained carbon-coated Si alloy, the carbon coverage was measured using the following Auger electron spectroscopy, and the results are shown in Table 4 below.

(Example 5)
In the production of the negative electrode, a negative electrode and a battery were produced in the same manner as in Example 1, except that the amounts of the Si alloy and acetylene black (carbon-based material) were changed to 95 parts by weight and 5 parts by weight, respectively. For the obtained carbon-coated Si alloy, the carbon coverage was measured using the following Auger electron spectroscopy, and the results are shown in Table 4 below.

(Example 6)
In the production of the negative electrode, a negative electrode and a battery were produced in the same manner as in Example 1 except that the amounts of the Si alloy and acetylene black (carbon-based material) were changed to 99 parts by weight and 1 part by weight, respectively. For the obtained carbon-coated Si alloy, the carbon coverage was measured using the following Auger electron spectroscopy, and the results are shown in Table 4 below.

(Example 7)
In the production of the negative electrode, the same method as in Example 1 was used except that a carbon material (carbon fiber having a diameter of 200 nm and a length of 10 μm) produced by a vapor deposition method was used instead of acetylene black as the carbon-based material. A negative electrode and a battery were produced. For the obtained carbon-coated Si alloy, the carbon coverage was measured using the following Auger electron spectroscopy, and the results are shown in Table 4 below. Further, FIG. 24 shows the mapping result obtained by the Auger electron spectroscopy measurement of the obtained carbon-coated Si alloy.

(Comparative Example 1)
In the same manner as in [Production of Si alloy] in Example 1, a Si alloy (Si ₆₀ Sn ₂₀ Ti ₂₀ , average particle diameter (D50): 6 μm) was produced.

  90 parts by mass of the Si alloy (carbon non-coated) produced above and 10 parts by mass of acetylene black were dry mixed. In addition, about the Si alloy obtained after dry-mixing, the carbon coverage was measured using the following Auger electron spectroscopy, and the result is shown in Table 4 below.

  85 parts by mass of the mixture obtained above as a negative electrode active material and 15 parts by mass of polyamideimide as a binder were mixed and dispersed in N-methylpyrrolidone to obtain a negative electrode slurry. Next, the obtained negative electrode slurry was uniformly applied to both surfaces of a negative electrode current collector made of copper foil so that the thickness of the negative electrode active material layer was 30 μm, and dried in a vacuum for 24 hours. Obtained.

(Comparative Example 2)
In the same manner as in [Production of Si alloy] in Example 1, a Si alloy (Si ₆₀ Sn ₂₀ Ti ₂₀ , average particle diameter (D50): 6 μm) was produced.

  95 parts by mass of the Si alloy (carbon uncoated) produced above and 5 parts by mass of acetylene black were dry mixed. In addition, about the Si alloy obtained after dry-mixing, the carbon coverage was measured using the following Auger electron spectroscopy, and the result is shown in Table 4 below.

  85 parts by mass of the mixture obtained above as a negative electrode active material and 15 parts by mass of polyamideimide as a binder were mixed and dispersed in N-methylpyrrolidone to obtain a negative electrode slurry. Next, the obtained negative electrode slurry was uniformly applied to both surfaces of a negative electrode current collector made of copper foil so that the thickness of the negative electrode active material layer was 30 μm, and dried in a vacuum for 24 hours. Obtained.

<Performance evaluation>
[Measurement of Si Alloy Carbon Coverage (Carbon Coverage)]
For the carbon coverage, the molar ratio of silicon and the molar ratio of carbon were measured using Auger electron spectroscopy under the following measurement conditions.

  Next, using the mole ratio of silicon and the mole ratio of carbon measured above, the mole ratio of carbon to the mole ratio of silicon was calculated according to the following formula, and the obtained value was expressed as the carbon coverage (Table 4 below). "Carbon coverage with respect to silicon")) (mol%).

[Average particle diameter of Si alloy (D50)]
The particle size distribution data was measured using a laser diffraction / scattering type particle size distribution measuring apparatus (manufactured by Horiba, Ltd., model: LA-920), and based on the data, the average particle diameter (D50; median of Si alloy) Diameter) is calculated.

[Evaluation of cycle durability]
The cycle durability of each lithium ion secondary battery produced above was evaluated by the following method. Each battery was charged to 4.2 V in a constant current and constant voltage method (CCCV, current: 0.1 C, terminated in 20 hours) in an atmosphere of 30 ° C., paused for 10 minutes, and then constant current (CC, current : 0.1 C) to 2 V, and rested for 10 minutes after the discharge. This charge and discharge process is the first cycle, and the charge and discharge conditions are the same as those for the first cycle except that the charge and discharge are 0.5C for the second and subsequent cycles. The charge / discharge test was performed up to 50 cycles. The ratio of the discharge capacity at the 50th cycle to the discharge capacity at the 1st cycle (discharge capacity retention rate [%]) is shown in Table 4 below.

  From the results of Table 4 above, it is understood that the negative electrode active material having the Si alloy surface supported by a carbon-based material exhibits high energy density and high cycle durability.

  This application is based on the JP Patent application number 2013-123981 for which it applied on June 12, 2013, The content of an indication is referred and is incorporated as a whole.

Claims (19)

The following chemical formula (1):
(In the above chemical formula (1),
M is Ti,
A is an inevitable impurity,
x, y, z, and a represent mass% values, where 0 <x <100, 0 <y <100, 0 <z <100, and 0 ≦ a <0.5, and x + y + z + a = 100. )
A negative electrode active material for an electrical device comprising an alloy represented by:
A carbon-based material is supported on the surface of the alloy,
Said x, y, and z are following formula (3) or (4) :
Satisfying negative electrode active material for electrical devices. The x, y, and z are represented by the following formula (5) or (6):
The negative electrode active material for an electric device according to claim 1 , wherein The x, y, and z are the following formula (7):
The negative electrode active material for an electric device according to claim 2 , wherein The following chemical formula (1):
(In the above chemical formula (1),
M is Zn;
A is an inevitable impurity,
x, y, z, and a represent mass% values, where 0 <x <100, 0 <y <100, 0 <z <100, and 0 ≦ a <0.5, and x + y + z + a = 100. )
A negative electrode active material for an electrical device comprising an alloy represented by:
A carbon-based material is supported on the surface of the alloy,
The negative electrode active material for an electric device, wherein x is more than 23 and less than 64, y is 4 or more and less than 34, and z is more than 0 and less than 65. (In the above chemical formula (1),
M is Zn;
A is an inevitable impurity,
x, y, z, and a represent mass% values, where 0 <x <100, 0 <y <100, 0 <z <100, and 0 ≦ a <0.5, and x + y + z + a = 100. )
A negative electrode active material for an electrical device comprising an alloy represented by:
A carbon-based material is supported on the surface of the alloy,
The negative electrode active material for an electric device, wherein x is more than 23 and less than 44, y is 34 or more and 58 or less, and z is more than 0 and less than 65. The negative electrode active material for an electric device according to claim 4 , wherein the z is greater than 27 and less than 61. The negative electrode active material for an electric device according to claim 5 , wherein x is less than 34. The negative electrode active material for an electric device according to claim 6 , wherein the y is less than 24 and the z exceeds 38. The negative electrode active material for an electric device according to claim 6 , wherein the x is 24 or more and less than 38. The negative electrode active material for an electric device according to claim 5 , wherein the x is less than 38, the y is less than 40, and the z exceeds 27. The negative electrode active material for an electric device according to claim 5 , wherein x is less than 29 and y is 40 or more. The following chemical formula (1):
(In the above chemical formula (1),
M is C,
A is an inevitable impurity,
x, y, z, and a represent mass% values, where 0 <x <100, 0 <y <100, 0 <z <100, and 0 ≦ a <0.5, and x + y + z + a = 100. )
A negative electrode active material for an electrical device comprising an alloy represented by:
A carbon-based material is supported on the surface of the alloy,
The negative electrode active material for electric devices whose said x is 29 or more. The negative electrode active material for an electric device according to claim 12 , wherein the x is 63 or less, the y is 14 or more and 48 or less, and the z is 11 or more and 48 or less. The negative electrode active material for an electric device according to claim 13 , wherein x is 44 or less. The negative electrode active material for an electric device according to claim 14 , wherein x is 40 or less and y is 34 or more. The negative electrode active material for an electrical device according to any one of claims 1 to 15 , wherein a coverage of the alloy with a carbon-based material is 50 to 400 mol%. The negative electrode active material for an electric device according to claim 16 , wherein a coverage of the alloy with a carbon-based material is 100 to 400 mol%. The negative electrode active material for an electric device according to claim 17 , wherein a coverage of the alloy with a carbon-based material is 250 to 400 mol%. To any one of claims 1 to 18 containing a negative electrode active material for an electric device according electrical device