CN105594025A

CN105594025A - Negative electrode active material and manufacturing method therefor, and negative electrode using negative electrode active material, and non-aqueous electrolyte secondary battery

Info

Publication number: CN105594025A
Application number: CN201480054169.3A
Authority: CN
Inventors: 西村健; 松下雅; 西久保英郎; 樋上俊哉; 打越昭成; 小见川祐; 中村健一; 佐佐木宏和; 山崎悟志
Original assignee: Furukawa Electric Co Ltd
Current assignee: Furukawa Electric Co Ltd
Priority date: 2013-10-30
Filing date: 2014-10-29
Publication date: 2016-05-18
Also published as: WO2015064633A1; KR20160063323A; JPWO2015064633A1

Abstract

Provided is a negative electrode active material characterized by a composition that includes silicon and an element (M) that can form a compound with silicon, and that first precipitates out a compound of silicon and the element (M) when the composition of silicon and the element (M) is cooled from a molten state, and then precipitates out pure silicon or solid-solution silicon when cooled further. The negative electrode active material is characterized, electrochemically, by a first phase having Li occlusion properties being dispersed in a second phase having Li conductivity properties, and the first phase further including a third phase with weaker Li occlusion properties than the first phase.

Description

Negative electrode active material and manufacture method thereof and utilize its negative pole and rechargeable nonaqueous electrolytic battery

Technical field

The present invention relates to the negative electrode active material and the manufacturer thereof that in negative pole that rechargeable nonaqueous electrolytic battery uses etc., useMethod, particularly, the particularly negative electrode active material of the lithium rechargeable battery of high power capacity, cycle characteristics, capacity dimension holdup excellenceMatter and manufacture method etc. thereof.

Background technology

So far, the various carbon-based materials such as native graphite, Delanium, amorphous carbon, mesocarbon are used as to negative poleThe rechargeable nonaqueous electrolytic battery of active material is practical. But the theoretical capacity of graphite is low to moderate 372mAh/g, furtherThere is limit in high capacity.

On the other hand, taking high capacity as target, develop the metal large as lithium compound theoretical capacity, alloy, spyIt not the negative pole that silicon and alloy thereof are used as the rechargeable nonaqueous electrolytic battery of negative electrode active material. For example Si has and exceedesThe theoretical capacity of 4000mAh/g.

Si, as in the situation of negative material, can be obtained to high power capacity. But, with occlusion, the disengaging volume together of LiChange greatly, crack and carry out the side reaction etc. of micronizing or generation and electrolyte, cycle characteristics is inadequate thus. Therefore, withIn the past be that the negative pole that active material forms is compared by carbon, the problem that average life is extremely short.

For silicon, because the dilation accompanying with the alloying of lithium, de-alloying reaction is large, therefore, in order to prevent producingRaw crackle, must make the particle that contains silicon is small particle diameter. By the liquation of silicon is cooling rapidly, can obtain fine silicon phase.But if make the crystallization of silicon by the liquation of the cooling silicon of common cooling method rapidly, the crystallization of silicon becomes hundreds of μThe size of about m, thus the silicon particle of enough small particle diameter can not be obtained. There is limit in the cooling velocity that improves melted silicon, passes throughThere is limit in the miniaturization that raising cooling velocity realizes silicon phase. So, require to form fine by cooling method rapidly in the pastThe method of silicon phase.

In addition, if silicon is carried out to discharging and recharging of lithium ion under the state contacting with electrolyte at silicon, pass through lithium ionBe called as SEI (SolidElectrolytelnterface, solid electricity with the side reaction of electrolyte at the Surface Creation of siliconSeparate matter interfacial film) overlay film. The generation of SEI is irreversible reaction, can not contribute to so generate the lithium ion of SEI in the time of chargingElectric discharge.

For silicon, the dilation accompanying with the alloying of lithium, de-alloying reaction is large. In order to prevent crackle, micro-Efflorescence, must make the particle that contains silicon is small particle diameter. But, if the particle diameter of the particle that contains silicon is reduced, per unit weightThe surface area of amount increases, and the amount of the SEI of Surface Creation increases, and coulombic efficiency reduces.

In addition, because the dilation of silicon is large, therefore, the SEI producing in the time of charging peels off from the silicon shrinking in the time of electric discharge.So, charge at every turn and just produce SEI on the surface of silicon, at the residual a large amount of SEI of negative terminal surface, become electrode thereby existThickness increase or internal resistance increase reason etc. problem.

For by repeating to discharge and recharge produced SEI, utilize Figure 22 to describe. Figure 22 (a) is the silicon grain before discharging and rechargingSon 100. As shown in Figure 22 (b), if the silicon particle 100 in electrolyte is charged, silicon particle 100 expands,Its surface forms a SEI101. In addition, on silicon particle 100, crack 103 when expansion. As shown in Figure 22 (c), if enteredRow electric discharge, silicon particle 100 shrinks, and a part of a SEI101 is from the sur-face peeling of silicon particle 100. As shown in Figure 22 (d),If carry out the charging of the 2nd time, silicon particle 100 expands once again, forms the 2nd SEI105 on its surface. In addition, when expansionOn silicon particle 100, produce the crackle 107 different from crackle 103. As shown in Figure 22 (e), if discharged, silicon particle 100Shrink, a part of the 2nd SEI105 is by the sur-face peeling of silicon particle 100. Its result, around silicon particle 100, remainsThe SEI101, the 2nd SEI105 that peel off, become the reason that the thickness increase of electrode or the resistance of negative pole raise. In addition, byIn with discharge and recharge the excessive electrolyte that expends together, therefore, it is violent that the consumption of electrolyte becomes, and causes lacking liquid and battery life is fallenLow.

So, do not disclose silicon particle has directly been used as to negative electrode active material, the intermetallic compound that comprises silicon and metal,Negative electrode active material (with reference to patent documentation 1) with the metallic matrix that contains Cu and Al.

In addition, disclose the crystal boundary of the crystal grain of the Si alloy phase fine in patent documentation 2, Si analyses with network-likeThe invention of the negative material that the composite alloy going out is used as lithium ion battery. Thus, even if in the time discharging and recharging, Si expands mutually, receiveContracting, also can suppress breaking off of micronizing, conductive network, and cycle characteristics is improved.

The lithium of the phase that comprises Si phase and contain Si, Al and Fe with the ratio of the atom % of 3:3:2 is disclosed in patent documentation 3The invention of the negative electrode active material that secondary cell is used. Thus, the Si content that carries out reversible reaction with lithium is increased, thereby make the initial stageDischarge capacity and cycle characteristics improve.

Prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2008-235276 communique

Patent documentation 2: TOHKEMY 2013-105655 communique

Patent documentation 3: TOHKEMY 2013-161786 communique

Summary of the invention

Invent problem to be solved

But, in the invention of recording in patent documentation 1, exist silicon mutually fine not, be easy to produce micronized problem points.According to Hall Page (Hall-Petch) rule, the finer destruction endurance of size of silicon phase and crystallite more improves and is difficult to micro mistChange. In addition, because use is easy to oxidized Cu alloy, therefore, exist and generate CuO, first inefficient problem points.

The related invention of patent documentation 2 is characterised in that, contain Si, Al, M1 (M1 be selected from except periodic law Biao 4 families,More than a kind metallic element in transition metal beyond the 5th family. ), (M2 is selected from 1 in periodic law Biao 4 families, the 5th family to M2Plant above metallic element. ) as Constitution Elements, form the Si-Al-M1-M2 alloy phase of fine crystal grain and described by havingThe alloy material that the crystal boundary of crystal grain is separated out the Si phase of network-like structure forms. In patent documentation 2, owing to being two-phase mutually, because ofThis, compared with situation about generating more than three-phase, it is large that the size of phase becomes, by causing with discharging and recharging the volumetric expansion followed and contractionProduce fine crackle, and produce Crack Extension and be easy to carry out micronizing. Therefore, cycle characteristics is easy to reduce.

The related invention of patent documentation 3 comprises the phase that contains Si, Al and Fe with the ratio of the atom % of 3:3:2(Si₃Al₃Fe₂Phase), due to Si₃Al₃Fe₂The ratio of mutually middle Fe is high to 25 atom %, therefore, makes foundry alloy cold rapidly even if compriseBut operation, also can Precipitation Temperature high, it is large that the size of Si phase is easy to become. Its result, is easy to running crack together with discharging and recharging,Cycle characteristics is inadequate.

Applicant's object is, provides: by suppressing by drawing with the volumetric expansion, the contraction that repeat to discharge and recharge Si togetherCrack Extension suppress the negative pole that the rechargeable nonaqueous electrolytic battery of micronizing, the cycle characteristics excellence of active material uses and liveProperty material and battery.

Be that the present application is:

(1) negative electrode active material, is characterized in that, contains silicon and can form with silicon the element M of compound, siliconWith the composition of described element M be when cooling from molten condition the compound of silicon and described element M separate out at first, further coolingThe composition that pure silicon or silicon solid solution are separated out.

(2) negative electrode active material, is characterized in that, contains silicon and can form with silicon the element M of compound, siliconWith the composition of described element M be the compound of silicon and described element M when cooling with speed more than 1000K/s from molten conditionThe composition of separate out at first, further cooling pure silicon or silicon solid solution being separated out.

(3) negative electrode active material according to (1) or (2), is characterized in that, described element M be selected from V, Nb, Ta,At least one element in Mo, W, Ti, Zr, Cr.

(4) according to the negative electrode active material described in any one in (1)～(3), it is characterized in that, silicon and described element MComposition is in hypereutectic region.

(5) according to the negative electrode active material described in any one in (1)～(4), it is characterized in that described negative electrode active materialThe silicide phase that has the silicon phase that comprises pure silicon or silicon solid solution and comprise silicon and the compound of described element M, described silicon is mutuallyMore than the 20wt% in described negative electrode active material.

(6) according to the negative electrode active material described in any one in (1)～(5), it is characterized in that, among described silicon phase, outerMore than footpath or width have the 50 volume % that occupy mutually described silicon phase of size of 10～300nm.

(7) according to the negative electrode active material described in any one in (1)～(6), it is characterized in that described negative electrode active materialFurther contain the element D different from described element M (be selected from Al, Cu, Fe, Co, Ni, Ca, Sc, Ti, V, Cr, Mn, Sr, La,At least one element in Ce, Nd, Dy, Sm, Pr, Y, Zr, Nb, Mo, Hf, Ta, W, Re, Os, Ir, Ru, Rh and Ba), described negativeUtmost point active material has the compound of silicon and described element D.

(8) negative electrode active material, is characterized in that, has in the conductive second-phase of Li and be dispersed with in electrochemistryHave the first-phase of Li occlusion, described first-phase further contains the third phase that lacks Li occlusion compared with first-phase.

(9) according to the negative electrode active material (8) described, it is characterized in that, first-phase is with respect to the area ratio of second-phaseBe 10～90%, further containing with respect to negative electrode active material material is the third phase of 1～40 atom %.

(10) according to the negative electrode active material (8) or (9) described, it is characterized in that, described first-phase is that pure silicon or silicon are solidSolution, the mean value of cross-sectional layers thickness is 20～2000nm.

(11) according to the negative electrode active material described in any one in (8)～(10), it is characterized in that, described second-phase is siliconCompound, the mean value of cross-sectional layers thickness is 20～2000nm.

(12) according to the negative electrode active material described in any one in (8)～(11), it is characterized in that, described second-phase containsSi and Al, further contain at least one element being selected from element D claimed in claim 6.

(13) according to the negative electrode active material described in any one in (8)～(12), it is characterized in that, described second-phase containsSi and Al, further contain at least one element being selected from Fe, Co, Mn, La, Ce, Nd, Pr, Sm and Dy.

(14) according to the negative electrode active material described in any one in (8)～(13), it is characterized in that, described second-phase containsLack the 4th phase of Li occlusion compared with first-phase.

(15) negative electrode active material of using according to the rechargeable nonaqueous electrolytic battery (14) described, is characterized in that, containsIt is the 4th phase of 1～50 atom % with respect to negative electrode active material material.

(16) according to the negative electrode active material described in any one in (8)～(15), it is characterized in that the cutting of described third phaseThe mean value of surface thickness is 1～100nm.

(17) according to the negative electrode active material described in any one in (8)～(16), it is characterized in that, described third phase containsBe selected from VSi₂、TaSi₂、MoSi₂、NbSi₂、WSi₂、TiSi₂、ZrSi₂、CrSi₂In at least one compound.

(18) according to the negative electrode active material described in any one in (8)～(17), it is characterized in that, described third phase containsBe selected from VSi₂、TaSi₂、NbSi₂In at least one compound.

(19) according to the negative electrode active material described in any one in (8)～(18), it is characterized in that described third phase or theFour contain mutually and are selected from SiO₂、TiO₂、Al₂O₃, at least one compound in ZnO, CaO, MgO.

(20) according to the negative electrode active material described in any one in (8)～(19), it is characterized in that, exist and form third phaseThe volume of particle occupy more than 10% region among the total volume of first-phase and third phase.

(21) anode for nonaqueous electrolyte secondary battery is the non-aqueous solution electrolysis on collector body with active material layerElectrolitc secondary cell negative pole,

It is characterized in that, described active material layer contains negative electrode active material and bonding agent, and described negative electrode active material containsHave silicon and can form with silicon the element M of compound, the composition of silicon and described element M be when cooling from molten condition silicon withThe composition that the compound of described element M separates out at first, further cooling pure silicon or silicon solid solution are separated out.

(22) rechargeable nonaqueous electrolytic battery, have can occlusion and emit the positive pole of lithium ion, on collector bodyThe division board that has the negative pole of active material layer and configure between described positive pole and described negative pole, it has lithium ion biographyIn the electrolyte of the property led, be provided with described positive pole, described negative pole and described division board,

It is characterized in that, the described active material layer of described negative pole contains negative electrode active material and bonding agent, described negative poleActive material contains silicon and can form with silicon the element M of compound, and the composition of silicon and described element M is from molten conditionThe composition that when cooling, the compound of silicon and described element M is separated out at first, further cooling pure silicon or silicon solid solution are separated out.

(23) manufacture method for negative electrode active material, is characterized in that, liquation is cold with speed more than 1000K/sBut, described liquation contains silicon and can form with silicon the element M of compound, and the composition of silicon and described element M is from moltenThe composition that when state is cooling, the compound of silicon and described element M is separated out at first, further cooling pure silicon or silicon solid solution are separated out.

(24) according to the manufacture method of the negative electrode active material (23) described, it is characterized in that, described liquation is by single rollerMethod, double roller therapy, melt spinning method, gas atomization or water atomization are cooling.

(25) anode for nonaqueous electrolyte secondary battery, it uses the non-water power described in any one in (8)～(20)Separate the negative electrode active material material used of electrolitc secondary cell and form.

(26) rechargeable nonaqueous electrolytic battery, its use (25) described anode for nonaqueous electrolyte secondary battery andForm.

(27) the negative electrode active material material that in a kind of (8)～(19), the rechargeable nonaqueous electrolytic battery described in any one is usedManufacture method, it is characterized in that, by contain Si, Al, element set D except Al (be selected from Cu, Fe, Co, Ni, Ca, Sc, Ti,At least one in V, Cr, Mn, Sr, La, Ce, Nd, Dy, Sm, Pr, Y, Zr, Nb, Mo, Hf, Ta, W, Re, Os, Ir, Ru, Rh and BaKind of element), after the alloy of element set M (being selected from least one element in V, Ta, Mo, Nb, W, Ti, Zr, Cr) dissolves, by listAny method in roller method, double roller therapy, melt spinning method, gas atomization and water atomization makes its cooling (1000K/ rapidlyMore than second) solidify, and temperature below 1000 DEG C makes Second Phase Precipitation.

Wherein, the element being selected from element set M and element set D is not identical element.

(28) manufacture method of the negative electrode active material material of using according to the rechargeable nonaqueous electrolytic battery (27) described, itsBe characterised in that, the element of the element set D except Al is to be selected from least one in Fe, Co, Mn, La, Ce, Nd, Pr, Sm and DyPlant element.

Invention effect

According to the present invention, guarantee to contribute to the first-phase of discharge capacity, and suppress with repeat to discharge and recharge accompany firstVolumetric expansion, the contraction of phase cause the Crack Extension producing, and can obtain thus the non-water power of high power capacity, cycle characteristics excellenceSeparate electrolitc secondary cell negative electrode active material.

Brief description of the drawings

Fig. 1 is the schematic diagram in the cross section of the related negative electrode active material of embodiments of the present invention 1.

Fig. 2 (a)～(d) is the showing of manufacture process that represents the related negative electrode active material of embodiments of the present invention 1Intention.

Fig. 3 (a)～(b) is the change that represents the manufacture process of the related negative electrode active material of embodiments of the present invention 1The schematic diagram of shape example.

Fig. 4 is the schematic diagram of the related gas atomization device of embodiments of the present invention 21.

Fig. 5 is the schematic diagram of the related single roller chilling apparatus 41 of embodiments of the present invention.

Fig. 6 is the schematic diagram of the related two roller chilling apparatus 51 of embodiments of the present invention.

Fig. 7 is the schematic diagram of the related melt spinning device of embodiments of the present invention 61.

Fig. 8 is the schematic diagram in the cross section of the related rechargeable nonaqueous electrolytic battery of embodiments of the present invention 71.

Fig. 9 is the binary system state diagram of vanadium and silicon.

Figure 10 is the binary system state diagram of niobium and silicon.

Figure 11 is the binary system state diagram of tantalum and silicon.

Figure 12 is the binary system state diagram of molybdenum and silicon.

Figure 13 is the binary system state diagram of tungsten and silicon.

Figure 14 is the binary system state diagram of titanium and silicon.

Figure 15 is the binary system state diagram of zirconium and silicon.

Figure 16 is the binary system state diagram of chromium and silicon.

Figure 17 is the scanning electron microscope photo in the cross section of the related negative electrode active material of embodiment 1.

Figure 18 is the XRD analysis result of the related negative electrode active material of embodiment 1.

Figure 19 is the scanning electron microscope photo in the cross section of the related negative electrode active material of comparative example 1.

Figure 20 is the XRD analysis result of the related negative electrode active material of comparative example 1.

Figure 21 is that the scanning electron microscope in the cross section of the negative electrode active material after 1 related circulation of comparative example 1 shinesSheet.

Figure 22 (a)～(e) is the figure that the SEI to forming around the silicon particle 100 in the past describes.

Figure 23 is the schematic diagram of the related negative electrode active material material of the present application.

Figure 24 is the BF-STEM (Bright-FieldScanning of the related Si-Fe-Al-V alloy of embodiment 11TransmissionElectronMicroscopy, light field scanning transmission electron microscope image)

Figure 25 is that (X-raydiffraction, X ray spreads out for the XRD of the related Si-Fe-Al-V alloy of embodiment 11Penetrate) analysis result.

Figure 26 is that (EnergyDispersiveX-raySpectrometer, energy divides the related EDS of embodiment 11Loose type x-ray spectrometer) draw.

Detailed description of the invention

(negative electrode active material 1)

Based on the following drawings, embodiments of the present invention are at length described. For embodiments of the present invention instituteThe negative electrode active material 1 relating to describes. Fig. 1 is the schematic cross-section of negative electrode active material 1. Negative electrode active material 1 containsSilicon and can form with silicon the element M of compound. The composition of silicon and element M is silicon and element M when cooling from molten conditionThe composition that compound separates out at first, further cooling pure silicon or its solid solution (being denoted as below silicon phase) are separated out. As described later, logicalCross as such composition, in the time that silicon is separated out mutually, the compound of silicon and element M has been separated out, and therefore, the crystallization of silicon phase can be not significantlyGrowth, still keeps fine.

Particularly preferably element M is at least one element being selected from V, Nb, Ta, Mo, W, Ti, Zr, Cr. This is due to theseElement in the composition that contains in a large number silicon in MSi₂The hypereutectic region that the silicide of composition is separated out at first.

In addition, the composition of silicon and described element M is preferably in hypereutectic region. This be due to: as long as for hypereutectic region,The composition under the ratio silicon of element M and the eutectic point of element M is many, therefore, and when cooling from liquation state, by silicon and elementThe MSi that M forms₂The silicide of composition is first separated out mutually than silicon.

Preferably negative electrode active material 1 has the silicon phase 3 that comprises pure silicon or its solid solution and the chemical combination that comprises silicon and element MThe first silicide phase 5 of thing, silicon phase 3 is more than the 20wt% in negative electrode active material 1. Show and judge negative electrode active material 1That silicon is situation more than 20wt% mutually than the condition of the capacity of graphite electrode, SiO electrode discharge about 670mAh/g capacious.This is because: silicon 3 is participated in and reacted with discharging and recharging of lithium ion mutually, therefore, if the amount of silicon phase 3 is too few, with graphite in the pastThe charge/discharge capacity of the negative electrode active material of system becomes not too big difference, thereby has lost the advantage that uses silicon. In addition, silicon phaseAs long as 3 maintain the charge-discharge characteristics such as cycle characteristics, even if contain in a large number, also no problem.

In addition, silicon 3 is embedded in the first silicide phase 5 mutually. Therefore, by the silicide of high conductivity compared with silicon, negativeThe electric conductivity of utmost point active material 1 can raise, thereby can further suppress silicon 3 expansion, contraction mutually. In addition, due to silicationThing is a small amount of, but can occlusion, emit lithium, thereby keep the permeability of lithium, so, bury underground in 5 mutually at the first silicideSilicon mutually 3 can occlusion, emit lithium.

The contained multiple silicon of negative electrode active material 1 are mutually among 3, and external diameter or width have the silicon of the size of 10～300nm3 volume adds up to mutually, more than preferably occupying 50 volume % of silicon phase 3. If silicon phase 3 is excessive, according to Hall-Petch rule,Stress when discharging and recharging make silicon mutually 3 probability that generate crackles increase. Therefore, preferably account for silicon mutually 3 whole, be difficult to rawIt is over half becoming the ratio of silicon phase crackle, little.

At this, so-called silicon is 3 external diameter or width mutually, and the meaning is silicon its external diameter in 3 situations that are shape of particle mutually, the meaningBe: silicon mutually 3 has its thickness, silicon in the situation of two-dimentional platy structure and 3 has its section in the situation of club shaped structure of one dimension mutuallyThe diameter of face. , preferably silicon mutually among 3, the length of the one dimension scope in 10～300nm at least.

In negative electrode active material 1,3 profile, width can be by using electron microscope observation negative electrode active material 1 mutually for siliconCross section try to achieve. In addition, 3 volume ratio can be by will be in cross section mutually for silicon in negative electrode active material 1, given sizeThe silicon of the given size of exposing mutually 3 area, compare and try to achieve with the area of negative electrode active material 1 gross section.

(interpolation of element D)

And preferred described negative electrode active material contain the element D different from element M (be selected from Cu, Al, Fe, Co, Ni, Ca,At least one unit in Sc, Ti, V, Cr, Mn, Sr, Y, Zr, Nb, Mo, Ru, Rh, Ba, lanthanide series, Hf, Ta, W, Re, Os and IrElement), described negative electrode active material has the compound of silicon and element D. First, for the ternary system of silicon and element M and element DIn situation, can melting point depression and make liquation with low temperature, therefore, silicon is easy to become fine mutually. In addition, at negative electrode active materialIn 1, beyond the compound of silica removal and element M, be formed with the compound of silicon and element D or comprise silicon and element M and element DThe compound of ternary system silicide, silicon 3 more easily 5 is covered by the first silicide mutually mutually thus. Silicon is 3 involved elements mutuallyThe first silicide of the compound of M or element D and silicon 5 covers mutually, and therefore, negative electrode active material 1 becomes more high conductivity and energyEnough relax silicon 3 volumetric expansion mutually. As described later, cover silicon mutually 3 silicide be divided by the first silicide mutually beyond 5, also canContain the second silicide phase 7 grades and have multiple phases.

(preparation method of negative electrode active material)

For the manufacture process of the related negative electrode active material 1 of embodiments of the present invention, utilize Fig. 2 to describe.As shown in Fig. 2 (a), silicon is mixed with element M, be heated to high temperature, form thus liquation 11. In embodiment, adopt silicideCompare silicon and first separate out mutually the composition of kind, silicon and the element M of such element M. As shown in Fig. 2 (b), if by cooling liquation 11Get off, the kind of the silicon in liquation 11, element M, concentration are the scope of regulation, therefore, form silicide primary crystal by liquation 1113. If further carry out coolingly,, as shown in Fig. 2 (c), start to separate out as the silicon 15 of silicon crystallization. But, silicon 15 excessivelyGrowth is hindered by silicide primary crystal 13 the first silicide 17 of surrounding forming of growing, and therefore, as shown in Fig. 2 (d), obtains fineSilicon mutually 3. In addition, silicon mutually 3 is embedded in the first silicide that the first silicide 17 grows mutually in 5.

And, can form by appending the element D different from element M the binary system silicide of silica removal and element DThe ternary system silicide being formed by silicon and element M and element D in addition. Fig. 3 (a) is at the interior element D that further appends of liquation 11Situation, cooling along with carrying out from the state of Fig. 2 (c), the binary system silicide of silicon and element D or by silicon and element M andThe ternary system silicide that element D forms and the second silicide 19 of forming starts to separate out. But the undue growth of silicon 15 is by weekThe first silicide 17 or the second silicide 19 that enclose hinder, and therefore, obtain fine silicon phase 3 as shown in Fig. 3 (b). Fig. 3 (b)The second silicide mutually 7 can be the binary system silicide of silica removal and element D or formed by silicon and element M and element DBeyond ternary system silicide, multiple silicide that composition ratio is different.

Manufacture method for concrete negative electrode active material 1 describes. Silicon can be to contain B (boron), Ru (ruthenium) etc.Solid solution. First, be made into the liquation that contains silicon and can form with silicon the element M of compound. Silicon in liquation and elementThe composition of M is the group that silicon is separated out at first with the compound of element M when cooling from molten condition, further cooling silicon is separated out mutuallyBecome. Can in this liquation, further append element D. If this liquation is cooling with speed more than 1000K/s, cause siliconCompound is separated out with the silicon of following it and is separated out mutually, thereby forms negative electrode active material 1. Carry out more than 1000K/s more rapidlyCooling, therefore, can obtain fine silicon phase 3, the first silicide phase 5 and the second silicide phase 7. Negative electrode active material 1 is preferredForm by gas atomization or water atomization. Or can pass through any general in single-roller method, double roller therapy, melt spinning methodAfter liquation is cooling, by the sheet obtaining, band shape, tabular or thread alloy pulverizing, classification and form negative electrode active material 1.

(gas atomization, water atomization)

Gas atomization device 21 is as shown in Figure 4 the devices that form negative electrode active material 1 by gas atomization. Will beThe lysigenous liquation 11 of the interior silicon of crucible 23 and element M drips from nozzle 25, sprays upward from non-active gas, air are provided simultaneouslyDeng the gas injection stream 31 of gas spraying machine 29 of ejection gas 27, pulverize liquation 11, make it be solidified as drop and form powderThe negative electrode active material 1 of shape. Can in liquation 11, further append element D. Negative electrode active material 1 can by with gas mistCyclone, filter that gasifying device 21 connects, be classified into desirable particle size continuously. If provide water to replace ejectionGas 27, the water of spraying high pressure replaces gas injection stream 31, is water atomization.

(single-roller method)

Single roller chilling apparatus 41 is as shown in Figure 5 the dresses for the manufacture of the alloy 47 of the band shape based on single-roller method or sheetPut. For single roller chilling apparatus 41, the liquation that contains silicon and element M 11 in crucible 43 is penetrated towards single roller 45 of High Rotation SpeedGo out, and liquation 11 is cooling rapidly, can obtain thus and contain silicon phase 3 and the band shape of the first silicide phase 5 or the alloy of sheet47. Can in liquation 11, further append element D. Single roller chilling apparatus 41 can be by setting ejaculation amount, the list of liquation 11The rotating speed of roller 45 is controlled quenching speed, thereby can control silicon phase 3, the first silicide phase 5 and the second silicide chi of 7 mutuallyVery little. In addition, by as required the alloy of the band shape obtaining or sheet 47 being pulverized, classification, can obtain once desirableThe negative electrode active material 1 of the particle diameter of particle. For single-roller method, liquation 11 penetrates coverlet roller 45 instantaneous coolings from crucible 43, because ofThis, compared with gas atomization, quenching speed accelerates, thereby can obtain finer silicon mutually 3, the first silicide mutually 5 and theDisilicide phase 7.

(double roller therapy)

Two roller chilling apparatus 51 shown in Fig. 6 are the dresses for the manufacture of the banded or tabular alloy 59 based on double roller therapyPut. Two roller chilling apparatus 51 can be clamped the liquation 11 of the silicon that contains in crucible 53 and element M and obtain with a pair of casting roll 55Banded or tabular alloy 59. Can in liquation 11, further append element D. And, can be at the outlet tool of casting roll 55There is the chilling apparatus 57 that banded or tabular alloy 59 is sprayed to water, air etc. For double roller therapy, be also that liquation 11 is from crucible 53Penetrate by a pair of casting roll 55 instantaneous coolings, therefore, can obtain fine silicon phase 3, the first silicide phase 5 and the second silicationThing phase 7.

(melt spinning method)

Melt spinning device 61 shown in Fig. 7 is for the manufacture of the thread or banded alloy 70 based on melt spinning methodDevice. Melt spinning device 61 is can limit cooling rapidly by the liquation in crucible 63 11 by a large amount of cooling fluids 67 in container 65And guide with guide roller 69, limit obtains thread or banded alloy 70. In melt spinning method, be also can liquation 11 is cold rapidlyBut, therefore, can obtain fine silicon phase 3, the first silicide phase 5 and the second silicide phase 7.

(element M)

As previously mentioned, preferred elements M is at least one element being selected from V, Nb, Ta, Mo, W, Ti, Zr, Cr.

Fig. 9 is the binary system state diagram of vanadium and silicon. The hypereutectic region of vanadium and silicon be Si/ (Si+V) be 52 % by weight～95 % by weight (67 atom %～97 atom %). If the composition having in the hypereutectic region of vanadium and silicon, at high temperature shapeWhen the liquation of state is cooling, VSi₂First separate out Deng silicide, thereafter, at the time point that becomes 1400 DEG C, start separating out of pure silicon, because ofThis, can hinder the crystalline growth of pure silicon.

(should illustrate, in figure, hypereutectic region is α, and eutectic point is β. Also be same for following figure)

Figure 10 is the binary system state diagram of niobium and silicon. The hypereutectic region of niobium and silicon is that Si/ (Si+Nb) is 38 % by weight～93.7 % by weight (67 atom %～98 atom %).

Figure 11 is the binary system state diagram of tantalum and silicon. The hypereutectic region of tantalum and silicon is that Si/ (Si+Ta) is 24 % by weight～94 % by weight (67 atom %～99 atom %).

Figure 12 is the binary system state diagram of molybdenum and silicon. The hypereutectic region of molybdenum and silicon is that Si/ (Si+Mo) is 37 % by weight～94.4 % by weight (67 atom %～98 atom %).

Figure 13 is the binary system state diagram of tungsten and silicon. The hypereutectic region of tungsten and silicon is that Si/ (Si+W) is 23 % by weight～94 % by weight (67 atom %～99 atom %).

Figure 14 is the binary system state diagram of titanium and silicon. The hypereutectic region of titanium and silicon is that Si/ (Si+Ti) is 52 % by weight～73 % by weight (65 atom %～82 atom %).

Figure 15 is the binary system state diagram of zirconium and silicon. The hypereutectic region of zirconium and silicon is that Si/ (Si+Zr) is 38 % by weight～80 % by weight (67 atom %～93 atom %).

Figure 16 is the binary system state diagram of chromium and silicon. The hypereutectic region of chromium and silicon is that Si/ (Si+Cr) is 52 % by weight～81 % by weight (67 atom %～86 atom %).

(about first-phase)

First-phase preferably has Li occlusion, has the material of large discharge capacity in electrochemistry. Particularly, can enumerateThe solid solution of Si, Si etc.

As described later, in second-phase, be dispersed with this first-phase and first-phase and contain shortage Li suction compared with first-phaseThe third phase of Tibetan property is the technical characteristics of the present application.

Should illustrate, the silicon phase 3 in Fig. 1 is equivalent to the first-phase of the present application.

The thickness of the cross-sectional layers of first-phase is preferably 20～2000nm. More than 20nm, be easy to stably manufacture if,If below 2000nm, little with the degree that discharges and recharges volumetric expansion together, contraction and be difficult to generate crackle, thereby excellentChoosing.

The shape of each phase can be taked the various forms such as point-like, spot shape, network shape, striated. Therefore, measure phase cross sectionThickness, the thickness that is cross-sectional layers by the scope dictates of the above analog value of each phase 50 volume %.

(about second-phase)

Second-phase must be Li conductibility in electrochemistry. As long as this is owing to having Li conductibility, having in electrochemistryA small amount of Li occlusion, thus Li can reversibly pass through second-phase. The migration of Li can be Li ionic conductivity, can be alsoLi alloying reaction. Therefore, can make Li arrive the first-phase scattering with the island of island structure in the inside of second-phase. Change speechIt, if second-phase is the metal of non-Li activity in the such electrochemistry of Cu, Ni, Li can not arrive with island scatter Si like thisFirst-phase, be therefore unfavorable for discharging and recharging, do not produce discharge capacity.

Should illustrate, in Fig. 1, the first silicide phase 5 is equivalent to the second-phase of the present application.

Second-phase particularly can be enumerated silicide etc.

The thickness of second-phase cross-sectional layers is preferably 20～2000nm. If more than 20nm, be easy to same with first-phaseStably manufacture, if below 2000nm, guarantee first-phase from being easy to ormal weight, be easy to guarantee that high discharge capacity aspect examinesConsider and preferably. As previously mentioned, in second-phase, be dispersed with first-phase.

For first-phase in second-phase preferably contain ratio, preferably with by SEM (ScanningElectronMicroscopy, scanning electron microscope) image analysis and area ratio count 10～90%, more preferably 20～80%, more preferably 30～70%.

And preferably second-phase contains Si and Al, and contain be selected from Cu, Fe, Co, Ni, Ca, Sc, Ti, V, Cr, Mn,At least one element in Sr, La, Ce, Nd, Dy, Sm, Pr, Y, Zr, Nb, Mo, Hf, Ta, W, Re, Os, Ir, Ru, Rh and Ba.At this, although have Ni generate crystallite composition inequality, easily sneak into thick crystallite this respect, from electric conductivity raising sideFace is considered preferably.

And, being easy to mutually miniaturization from the viewpoint of silicon phase and silicide, more preferably Fe, Co, Mn, from low melting point silicationThing is easy to generate, silicon phase is considered with the aspect that silicide is easy to miniaturization mutually, more preferably La, Ce, Nd, Pr, Sm and Dy.

(about third phase)

One of technical characterictic of the present application is in first-phase, to contain compared with first-phase to lack the of Li occlusionThree-phase.

Figure 23 is the schematic diagram of the negative electrode active material in the present application. The epimere of Figure 23 is illustrated in second-phase and dispersesThere is first-phase. If second-phase is sea, first-phase forms island structure existence. The stage casing of Figure 23 is a part, first for epimereEnlarged drawing with the boundary member of second-phase. The hypomere of Figure 23 is the figure that amplifies the multiplying power observation of stage casing first-phase.

By at the inner such fine structure of third phase that forms of first-phase, can be broken by the slide surface that makes first-phase dislocationContinuous third phase is suppressed at while discharging and recharging and causes by first-phase volumetric expansion, contraction the Crack Extension producing.

The mean value of the cross-sectional layers thickness of third phase is preferably 1～100nm, more preferably below 2～40nm. IfMore than 1nm, the supression power of Crack Extension is large, below 100nm, can guarantee stable first-phase if, therefore easyIn guaranteeing high discharge capacity.

And third phase can contain and is selected from VSi₂、TaSi₂、MoSi₂、NbSi₂、WSi₂、TiSi₂、ZrSi₂、CrSi₂、SiO₂、TiO₂、Al₂O₃, at least one compound in ZnO, CaO, MgO is as third phase.

In addition, third phase preferably contains 1～40 atom %. And more preferably contain 3～30 atom %. This be due to: asFruit is more than 3 atom %, and the effect of Crack Extension that suppresses first-phase is high, below 30 atom %, guarantees enough ifThe first-phase of amount, guarantees high discharge capacity.

(about the 4th phase)

Second-phase can contain the 4th phase that lacks Li occlusion compared with first-phase. At this, at second-phase and first-phaseThe phase separated out of border be also judged as the 4th phase that second-phase comprises.

In addition, as the 4th phase, can be 5～150nm left and right point-like, spot shape, banded shape, 30～150nm left sideRight roughly spherical shape. The composition of the 4th phase can contain and is selected from Al, the VSi identical with third phase₂、TaSi₂、MoSi₂、NbSi₂、WSi₂、TiSi₂、ZrSi₂，SiO₂、TiO₂、Al₂O₃, at least one compound in ZnO, CaO, MgO. Particularly due toAl can suppress the coarsening of phase thereby preferably. Infer that second-phase is owing to containing the 4th phase that mechanical property is different, thereby relaxWith discharge and recharge first-phase volumetric expansion together, shrink the stress influence producing together, thereby contribute to cycle characteristics.

In addition, preferably the 4th contain mutually 1～50 atom %. More preferably contain 2～30 atom %. If the 4th is 2 former mutuallyMore than sub-%, by with the discharging and recharging volumetric expansion together, shrink the crackle causing and be difficult to expand to second-phase of first-phase, press downOnly the effect of the Crack Extension of second-phase is high. In addition, if the 4th be 30 atom % mutually, guarantee first-phase q.s, guaranteeHigh discharge capacity.

Al drops in the situation of element, if the input amount of Al is more than 26 atom %, the generation of second-phase becomesFully, excessive Al separates out with the form of metal A l phase. For example, in the situation of Si-Fe-Al-V system, generate FeAl₃Si₂AsSecond-phase, if but the input amount of Al lower than 26 atom %, Fe element is excessive, with FeAl₃Si₂Compare FeSi₂Be easy to 300Under high temperature more than DEG C, separate out. Its result, causes containing the phase coarsening of the first-phase being formed mutually by Si and is difficult to guarantee Gao RongAmount sustainment rate. Namely, become and be easy to guarantee high power capacity sustainment rate by thering is the element of ormal weight.

(the main method for making of the related negative electrode active material material of the alternate manner of the present application)

First, make the liquation that contains Si, Al and can form with Si the element set M of compound. In this liquation, enter oneStep is appended element set D. If this liquation is cooling with speed more than 1000K/s, cause third phase (DSi according to composition₂)Separate out and follow its first-phase (Si phase) and separate out, and the second-phase of low melting point (for example, in the situation that M is Fe isFeAl₃Si₂) separate out.

For negative electrode active material, can be through single-roller method, double roller therapy, melt spinning method, gas atomization and water atomizationIn any method liquation is cooling after, by the alloy of the band shape obtaining, tabular, thread, spherical or sheet is pulverized, pointLevel forms negative electrode active material. Si can be the Si solid solution that contains B, P etc.

The element set D using in liquation be preferably be selected from Cu, Fe, Co, Ni, Ca, Sc, Ti, V, Cr, Mn, Sr, La, Ce,At least one element in Nd, Dy, Sm, Pr, Y, Zr, Nb, Mo, Hf, Ta, W, Re, Os, Ir, Ru, Rh and Ba, element set M is excellentElect V, Ta, Mo, Nb, W, Ti, Zr, Cr (element wherein, being selected from element set M and element set D is not identical element) as.

And, due to SiO₂、TiO₂、Al₂O₃, ZnO, CaO, MgO fusing point separately of compound high to 1650 DEG C, 1640DEG C, 2054 DEG C, 1975 DEG C, 2613 DEG C, 2852 DEG C, therefore, in the stage that the raw material that forms first-phase, second-phase is dissolved, canDuring with difference, dissolve. SiO₂、TiO₂、Al₂O₃, ZnO, CaO, MgO compound use the primary particle of 2～200nm, in order to carryHigh treatability and be treated to the granulation body of 10～200 μ m. SiO₂、TiO₂、Al₂O₃, ZnO, CaO, MgO compound can makeUnder the state of plastochondria, put in liquation, in liquation, primary particle is dispersed and can mix with the element set in liquation.

As the ratio of components of each element (element set), Si is preferably 44～71 atom %, and Al is preferably 26～45 atom %,Element set D is preferably 2～12 atom %, and element set M is preferably 1～10 atom %.

If Si is more than 44 atom %, from the viewpoint of can fully ensureing discharge capacity preferably, if 71Below atom %, can prevent that crystallization from becoming thick, keeping capacity dimension holdup aspect and preferably.

If Al is more than 26 atom %, from can suitably adjust crystalline phase size, can keep capacity dimension holdupAspect considers and preferably, if below 45 atom %, from can assure Si addition, can guarantee the side of discharge capacityFace is considered and preferably.

If element set D is more than 2 atom %, below 12 atom %, adds from the Si that can be adjusted into common maximumDosage, the aspect that can keep the balance of capacity dimension holdup, discharge capacity are considered and preferably.

If there is a certain amount of element set M, that can guarantee to be defined by the double equilibrium diagram of Si and each element D is excessively commonThe separating out of the result in territory, crystalline region, silicide starts and can suitably be formed as third phase principal component at the temperature higher than SiSilicide (DSi₂) aspect consider and preferably.

(formation of anode for nonaqueous electrolyte secondary battery)

Anode for nonaqueous electrolyte secondary battery has active material layer in the one or two sides of collector body. Active material layerThe slurry coating that contains negative electrode active material 1 and bonding agent etc. is formed.

Collector body is to comprise the paper tinsel that is selected from least one metal in copper, nickel, stainless steel. Can use separately separately, alsoIt can be alloy separately. Thickness is preferably 4 μ m～35 μ m, further 6 μ m～18 μ m more preferably.

Bonding agent be selected from polyimides (PI), polybenzimidazoles (PBI), polyamidoimide, polyamide, styrene-More than one in butadiene rubber (SBR), Kynoar (PVdF), carboxymethyl cellulose (CMC), polyacrylic acid.

Bonding agent adds in slurry with the state dissolving in solvent, the state disperseing with form of emulsion. At slurryAfter coating, bonding agent by negative electrode active material 1 be bonded in collector body above.

In addition, conductive auxiliary agent can be joined in active material layer. By adding conductive auxiliary agent, the active material of negative poleThe electric conductivity of layer improves, and is easy to discharge and recharge. Conductive auxiliary agent is to comprise to be selected from least one in carbon, copper, tin, zinc, nickel, silver etc.Plant the powder of conductive material. Can be the monomer powders of carbon, copper, tin, zinc, nickel, silver, can be also the powder of alloy separately.The various shapes such as that the shape of conductive auxiliary agent can be used is spherical, dendroid, beads shape, indefinite form, flakey, wire. Be for exampleIn the situation of carbon, can use furnace black, acetylene carbon black, flaky graphite, CNT, carbon nanohorn, fullerene, graphiteThe common carbon blacks such as alkene sheet.

(manufacture method of anode for nonaqueous electrolyte secondary battery)

First, in mixer, drop into slurry feedstock, mixing formation slurry. Slurry feedstock is embodiments of the present invention instituteThe negative electrode active material 1 that relates to, conductive auxiliary agent, bonding agent, thickener, solvent etc.

In solid constituent in slurry, contain negative electrode active material 25～95 % by weight, conductive auxiliary agent 0～70 weightAmount %, bonding agent 1～30 % by weight, thickener 0～25 % by weight. Preferably count negative electrode active material 50～90 with solid constituentQuality %. For the ratio of conductive auxiliary agent 5～30 quality %, bonding agent 5～25 quality %. If bonding agent is very few, adhesivityReduce, be difficult to maintain the shape of granulation body and electrode. In addition, if bonding agent is too much, electric conductivity declines and is difficult to discharge and recharge.

Mixer can use the common muller using in slurry preparation, can use and be called as kneader, stirringMachine, dispersion machine, mixer etc. can be prepared the device of slurry. Can be by METHYLPYRROLIDONE as solvent.

Then, for example utilize the one side coating sizing-agent of coating machine at collector body. Coating machine can use and slurry can be coated withIn the common apparatus for coating of collector body, for example, be roll-coater, the coating machine that utilizes scraper, comma coating machine, mould coating machineDeng.

By preparation and slurry be coated on equably on collector body, thereafter, dry under 50～150 DEG C of left and right, forAdjust thickness, therefore pass through roll squeezer. Then, by polyimides as the situation of bonding agent 67 etc., as required 150 DEG C～Calcining at 350 DEG C, obtains anode for nonaqueous electrolyte secondary battery 61. Can form work on the two sides of collector body 63 as requiredProperty material layer 65.

(making of rechargeable nonaqueous electrolytic battery)

As the negative pole using in rechargeable nonaqueous electrolytic battery, use the related non-water power of embodiments of the present inventionSeparate electrolitc secondary cell negative pole.

(making of positive electrode for nonaqueous electrolyte secondary battery)

The positive pole of using as rechargeable nonaqueous electrolytic battery, positive active material, conductive auxiliary agent, bonding agent and solvent is mixedThe composition of the positive active material closing and obtain is directly coated with, is dried in the metal current collector such as aluminium foil, makes anodal.

As described positive active material, just all can use as long as normally used, be for example LiCoO₂、LiMn₂O₄、LiMnO₂、LiNiO₂、LiCo_1/3Ni_1/3Mn_1/3O₂、LiFePO₄Deng compound.

As conductive auxiliary agent, for example use carbon black, as bonding agent, for example, use Kynoar (PVdF), water-solubleAcrylic acid series binding agent, as solvent, uses METHYLPYRROLIDONE (NMP), water etc. Now, positive active material, leadThe content of electricity auxiliary agent, bonding agent and solvent is the level conventionally using in rechargeable nonaqueous electrolytic battery.

As division board, as long as there is the function of the anodal electrical conductivity with negative pole of insulation and be conventionally at non-aqueous solution electrolysisIn electrolitc secondary cell, use, just all can use. For example can use micro-porous polyolefin film, porous aromatic polyamides treeAdipose membrane, porous ceramics, nonwoven etc.

For electrolyte and electrolyte in rechargeable nonaqueous electrolytic battery, Li polymer battery etc., can use organicElectrolyte (non-aqueous electrolyte), inorganic solid electrolyte, polymer solid electrolyte etc.

As the concrete example of the solvent of organic electrolyte, can enumerate ethylene carbonate, propylene carbonate, carbonic acid AdenThe carbonic esters such as ester, diethyl carbonate, dimethyl carbonate, Methylethyl carbonic ester; Anaesthetie Ether, dibutyl ethers, glycol dinitrateThe ethers such as base ether, ethylene glycol bisthioglycolate ethylether, ethylene glycol bisthioglycolate butyl ether, diethylene glycol dimethyl ether; Benzonitrile, acetonitrile, oxolane,2-methyltetrahydrofuran, gamma-butyrolacton, dioxa penta encircle, 4-methyl dioxa penta ring, DMF, dimethylNon-protonic solvents such as acetamide, dimethylated chlorobenzene, nitrobenzene or two or more among these solvents are obtained by mixingMixed solvent.

For the electrolyte of organic electrolyte, can use and comprise LiPF₆、LiClO₄、LiBF₄、LiAlO₄、LiAlCl₄、LiSbF₆、LiSCN、LiCl、LiCF₃SO₃、LiCF₃CO₃、LiC₄F₉SO₃、LiN(CF₃SO₂)₂Deng one or more of lithium saltsThe material that electrolyte is obtained by mixing.

In addition, can replace above-mentioned organic electrolyte with the lithium ion conduction body of solid shape. For example can useComprise the solid macromolecule electrolyte that is mixed with described lithium salts in the polymer such as PEO, PPOX, polyaziridine,The polymer gel electrolyte that makes electrolyte infiltration be processed into gel in macromolecular material and to obtain.

And, also can be by lithium nitride, lithium halide, oxyacid lithium salts, Li₄SiO₄、Li₄SiO₄-LiI-LiOH、Li₃PO₄-Li₄SiO₄、Li₂SiS₃、Li₃PO₄-Li₂S-SiS₂, the inorganic material such as phosphoric sulfide compound is as inoganic solids electrolysisMatter.

(assembling of rechargeable nonaqueous electrolytic battery)

Configuration isolation plate between foregoing positive pole and negative pole, forms cell device. Reel or stacked such electricityPond element injects electrolyte after being encased in columnar battery box, square battery box, forms nonaqueous electrolyte secondaryBattery.

One example (sectional view) of rechargeable nonaqueous electrolytic battery of the present invention is shown in to Fig. 8. For nonaqueous electrolyte secondaryBattery 71, be situated between, negative pole 75 anodal 73 with the sequential cascade configuration of division board-positive pole-division board-negative pole by division board 77, with justThe mode that the utmost point 73 is inner side is reeled and is formed pole plate group, is inserted in battery can 79. Then, can be situated between by positive pole anodal 73Lead-in wire 81 is situated between and is connected respectively with battery can 79 by negative wire 85 with positive terminal 83, negative pole 75, will be at nonaqueous electrolyte secondaryThe inner chemical energy producing of battery 71 is fetched into outside with the form of electric energy. Then, can be in the mode to cover pole plate groupAfter the interior filling electrolyte 87 of battery can 79, be situated between by ring-type insulation spacer, install by justifying in the upper end of battery can 79 (peristome)The positive terminal 83 on shape cover plate and its top forms, is built-in with the seal body 89 of relief valve mechanism therein, manufactures the present inventionRechargeable nonaqueous electrolytic battery 71.

(effect of the related rechargeable nonaqueous electrolytic battery of embodiments of the present invention)

Use the rechargeable nonaqueous electrolytic battery of the related negative electrode active material 1 of embodiments of the present invention to contain negative poleIn active material 1, contained silicon phase 3 contains the higher silicon of capacity of per unit volume and per unit weight compared with carbon, because ofThis, compared with rechargeable nonaqueous electrolytic battery in the past, capacity is larger.

In addition, for the related negative electrode active material 1 of embodiments of the present invention, fine silicon 3 is embedded in first mutuallyIn silicide phase 5 or the second silicide phase 7, therefore, suppress and discharge and recharge silicon powder together, cycle characteristics improves. In addition,Directly do not contact with electrolyte by silicon, the side reaction of electrolyte and lithium, can prevent at silicon 3 the excessive formation in surface SEI mutually.So, use the negative pole coulombic efficiency of negative electrode active material 1 high, therefore, the non-aqueous solution electrolysis that embodiments of the present invention are relatedElectrolitc secondary cell is long-life.

Embodiment

For the present invention, utilize embodiment and comparative example to describe particularly below.

[embodiment 1]

(making of negative electrode active material)

By the granular feedstock of silicon and vanadium and iron and aluminium by the mode of counting Si:V:Fe:Al=62:7:12:19 with weight ratioMix, with vacuum arc melting plant (NEV-AD03 processed of Xin Jiyan Co., Ltd.) making foundry alloy. To be ground into, thereafterThe ladle refining of the size of 5mm left and right is to the interior crucible of liquid quench coagulation system (NEV-A1 processed of Xin Jiyan Co., Ltd.)In, be heated to 1650 DEG C with high frequency coil and make after its melting, its liquation is utilized to the copper list of the single roller chilling apparatus shown in Fig. 5Roller quenching, obtains laminar negative electrode active material thus. Vanadium is corresponding with element M. Vanadium and silicon generate VSi₂Form the first siliconCompound, iron and silicon and aluminium generate FeAl₃Si₂Form the second silicide. Excessive interpolation aluminium in the composition of embodiment 1, therefore, generatesDo not form the phase of the metal shape aluminium of silicide.

The laminar negative electrode active material planetary ball mill solidifying through single roller quenching and obtain is pulverized, and is 20 by meshThe sieve of μ m obtains pulverous negative electrode active material material.

(making of anode for nonaqueous electrolyte secondary battery)

(i) preparation of cathode size

Ratio taking the CNT amount of negative electrode active material material 70 mass parts and carbon nano tube dispersion liquid as 18 mass partsRate is put in mixer. Further by the polybenzimidazoles taking N methyl pyrrolidone as solvent by being scaled with solid constituentThe ratio of 12 mass parts is mixed as bonding agent, makes slurry.

(ii) making of negative pole

The slurry utilization preparing is automatically coated with to scraper that frock puts and is coated on the thickness of 15 μ m the current collection of thickness 10 μ m(Furukawa electrical industry (strain) system, NC-WS) is upper for electrolytic copper foil for body, after making it dry at 100 DEG C, through utilizing the tune of compactingAfter thick operation, at 330 DEG C, through 2 hours heat treatment steps, manufacture anode for nonaqueous electrolyte secondary battery.

(evaluation of cycle characteristics)

With anode for nonaqueous electrolyte secondary battery, containing the LiPF of 1.3mol/L₆Ethylene carbonate, carbonic acid diethylThe electrolyte, the metal Li paper tinsel that in the mixed solution of ester, ethyl-methyl carbonic ester, are added with vinylene carbonate form lithium to electrodeIon secondary battery, investigation charge-discharge characteristic.

First,, under 25 DEG C of environment, to make current value be 0.1C, make magnitude of voltage to 0.02V (vs.Li/Li⁺) at constant-current constantUnder voltage conditions, charge, the time point that is reduced to 0.05C at current value stops charging. Then be, 0.1C at current valueUnder condition, discharge until voltage is 1.5V (vs.Li/Li⁺). Should illustrate that so-called 1C can be full of with 1 hour electricCurrent value. In addition, charging and discharging all carries out under 25 DEG C of environment. Then, repeat above-mentioned filling with the speed that discharges and recharges under 0.2CElectric discharge is until 50 circulations. The evaluation of characteristic represents after 50 circulations with respect to putting for the first time by first discharge capacity with percentageThe capacity dimension holdup of the discharge capacity of capacitance carries out.

[comparative example 1]

(making of negative electrode active material)

Si powder is mixed by the mode taking weight ratio as Si:Fe:Al=68:12:20 with aluminium powder with iron powder, will doDry mixed-powder in crucible, be heated to 1500 DEG C it is dissolved after, utilize single roller chilling apparatus of Fig. 5 rapid this liquationCold, obtain thus negative electrode active material.

Operation beyond it is identical with embodiment 1.

(evaluation that negative electrode active material forms)

As shown in Figure 17 and Figure 19, for the cross section of embodiment 1 and the related negative electrode active material of comparative example 1, utilizeScanning electron microscope is observed secondary electron image. As shown in figure 17, cutting at the related negative electrode active material of embodiment 1On face, known black, external diameter or the width of being is that the silicon of about 10～300nm 91 is embedded in the silicide that is white in color mutually in 93 mutually.In addition, observe cross section, result external diameter or width are that 91 to account for the whole ratio of alloy be 50 volume % mutually for the silicon of about 10～300nmAbove. And, as shown in figure 18, carry out XRD parsing, carry out determining of crystalline phase. Its result, confirms silicon phase, vanadium silicideVSi₂The first silicide phase, comprise 3 yuan of system silicide (FeAl₃Si₂) the second silicide phase, aluminium phase. This active materialSi is about 43wt% mutually. In addition, the result of electrode evaluation shows first discharge capacity 1480mAh/g. Capacity dimension after 50 circulationsHoldup is 86%, demonstrates excellent cycle characteristics.

And mutually quantitative according to the silicon that utilizes XRD to resolve, discharge capacity is roughly proportional with the weight rate of Si phase,The little degree to ignoring of capacity of aluminium, silicide.

On the other hand, as shown in figure 19, on the cross section of the related negative electrode active material of comparative example 1, known be black,External diameter or width are that silicon more than 400nm 91 forms mutually continuously, and the size of silicon phase is large compared with embodiment 1. External diameter or width areThe silicon of 10～300nm left and right accounts for the mutually whole ratio of silicon mutually lower than 50 volume %. In addition, as shown in figure 20, carry out XRD parsing,Carry out determining of crystalline phase. Its result, confirms silicon phase, comprises 3 yuan of system silicide (FeAl₃Si₂) silicide phase, aluminium phase. RatioThe Si of the active material of example 1 is about 60wt% mutually, and the result that electrode is evaluated is known, demonstrates first discharge capacity 1530mAh/The enough capacity of g, but comparative example 1 50 circulation after capacity dimension holdup be 78%, poorer than embodiment 1 cycle characteristics. Figure 21 isThe scanning electron in the cross section of negative electrode active material that utilizes the electrode of the active material of comparative example 1 to discharge and recharge for the first time after (1 circulation)Microphotograph. The part 91 that Figure 21 is dark is silicon phase, and brighter part 93 is silicide (FeAl₃Si₂) phase. With about 400nmThe silicon of above size is mutually for starting point is observed crackle. Think that this is: external diameter or width are continuous silicone phase more than 400nm and discharge and rechargeTogether, produce micronizing and a part for active material comes off or shows new formation that is caused the silicon producing by crackle from electrodeOn face, generate by causing with the side reaction of electrolyte the SEI producing, thereby capacity dimension holdup reduces.

Then,, for other embodiment of the present invention, utilize embodiment to describe particularly.

[embodiment 11]

(making of negative electrode active material)

Silicon is mixed by the mode taking atomic ratio measuring as Si:V:Fe:Al=66:3:4:27 with the ingot of aluminium with iron with vanadium, useVacuum arc melting plant (NEV-AD03 processed of Xin Jiyan Co., Ltd.) is made foundry alloy. To be ground into about 5mm, thereafterThe ladle refining of particle diameter arrives in the crucible in liquid quench coagulation system (NEV-A1 processed of Xin Jiyan Co., Ltd.), uses high-frequency lineCircle is heated to 1650 DEG C to be made after its melting, and the copper list roller of its liquation utilization list roller chilling apparatus is quenched to and has Li conductibilityThe temperature (1000 DEG C following) of Second Phase Precipitation, obtain thus laminar negative electrode active material. In the present embodiment, vanadium and unitD is corresponding for element. Vanadium and silicon are made the VSi that is equivalent to third phase₂, make the FeAl that iron and silicon and aluminium are equivalent to second-phase₃Si₂. RealExecute excessive interpolation aluminium in the composition of example 1, therefore, generate metallic aluminium as the 4th phase. To solidify through single roller quenching andLaminar negative electrode active material is pulverized with planetary ball mill, and the sieve that is 20 μ m by mesh obtains pulverous negative electrode active materialMaterial. The composition ratio of negative electrode active material material is by utilizing emitted lights such as ICP (InductivelyCoupledPlasma)Analysis of spectrum is confirmed.

(making of anode for nonaqueous electrolyte secondary battery)

(i) preparation of cathode size

Ratio taking the CNT amount of negative electrode active material material 70 mass parts and carbon nano tube dispersion liquid as 18 mass partsRate is put in mixer. Further by the polybenzimidazoles taking 1-METHYLPYRROLIDONE as solvent by being scaled with solid constituentThe ratio of 12 mass parts is mixed as bonding agent, makes slurry.

(ii) making of negative pole

(evaluation of cycle characteristics)

First,, under 25 DEG C of environment, to make current value be 0.1C, make magnitude of voltage to 0.02V (vs.Li/Li⁺) at constant-current constantUnder voltage conditions, charge, the time point that is reduced to 0.05C at current value stops charging. Then be, 0.1C at current valueUnder condition, discharge until voltage is 1.5V (vs.Li/Li⁺). Should illustrate that so-called 1C can be full of with 1 hour electricCurrent value. In addition, charging and discharging all carries out under 25 DEG C of environment. Then, repeat above-mentioned filling with the speed that discharges and recharges under 0.2CElectric discharge is until 100 circulations. The evaluation of characteristic with first discharge capacity (mAh/g) and 100 circulation after discharge capacity with respect at the beginning ofThe percentage of inferior discharge capacity carries out as capacity dimension holdup.

[embodiment 12～19]

As shown in table 1, change composition, ratio of components, in addition, adopt method for making, the evaluation method identical with embodiment 1.

[comparative example 11]

(making of negative electrode active material)

Si powder is mixed by the mode taking atomic ratio measuring as Si:Fe:Al=67:7:26 with aluminium powder with iron powder, willThe mixed-powder being dried in crucible, be heated to 1500 DEG C it is dissolved after, by single roller chilling apparatus quenching for its liquation, obtainObtain negative electrode active material. Operation beyond it is identical with embodiment 11.

[comparative example 12]

As shown in table 1, change composition, ratio of components, in addition, use method for making, the evaluation method identical with comparative example 1.The scope of 1500～2000 DEG C of being dissolved in of mixed-powder is carried out.

(the formation evaluation of negative electrode active material)

As shown in figure 24, observe the BF-STEM image in the cross section of negative electrode active material.

Further carry out as shown in figure 25 XRD parsing, carry out determining of crystalline phase. Its result, confirmed silicon phase (Figure 24'sWhite portion, first-phase), comprise 3 yuan of system silicide (FeAl₃Si₂) second-phase (the black part of Figure 24), comprise vanadium siliconCompound VSi₂Third phase (the grey color part of Figure 24), aluminium phase. As shown in figure 26, element distributes and measures by EDS. Second-phase(FeAl₃Si₂) in circular configuration be that the 4th phase (is mainly VSi₂)。

By the position relationship of this results verification crystalline phase, the inclusion relation of island structure, calculate raw in conjunction with XRD analysis resultBecome the composition of thing. The results are shown in table 1.

(state of third phase)

Area ratio, the volume ratio of third phase in the particle diameter of third phase or thickness, first-phase and third phase are shown in to table1. The thickness of third phase, by the analytical Calculation of SEM or TEM image, is to cut by the scope dictates of the above analog value of each phase 50 volume %The thickness of surface layer. Area ratio is calculated by image analysis software (" A is as the monarch " of the Engineering of Asahi Chemical Industry exploitation).

The calculating of volume ratio is undertaken building based on the three-dimensional of CutandSee by image information, can be by image solutionAnalysing process software calculates. Method based on CutandSee is that sample is become to every 10nm left and right by Repeated Cutting such as ion beamsThe thickness of regulation, the method for observing section S EM image or TEM image. Observe third phase sometimes roughly even in first-phaseGround becomes point-like, is inhomogeneous spot shape, network-like, ribbon sometimes, in the certain volume of three dimensional constitution, utilizes image analysisSoftware calculates, and calculates thus volume ratio.

Should illustrate, in table 1, the area ratio metewand of third phase is as follows.

◎: area ratio is more than 20%

〇: area ratio is more than 10%, lower than 20%

△: although can confirm the existence of third phase, area ratio is lower than 10%

-: can not confirm third phase

Should illustrate, for volume ratio metewand in table 1, as follows.

〇: volume ratio is more than 10%

△: although can confirm the existence of third phase, volume ratio is lower than 10%

-: can not confirm third phase

(performance evaluation of the secondary cell forming about utilizing negative electrode active material)

The result that method shown in the evaluation of the making by secondary battery cathode and cycle characteristics is evaluatedBe shown in table 1.

Should illustrate, for the metewand of capacity dimension holdup after 100 circulations in table 1, as follows.

◎: capacity dimension holdup is more than 72%

〇: capacity dimension holdup is more than 68%, lower than 72%

△: capacity dimension holdup is more than 64%, lower than 68%

×: capacity dimension holdup is lower than 64%

Practicality is considered in the evaluation of cycle characteristics, and in 100 circulations, capacity dimension holdup more than 64% is qualified.

Should illustrate, about capacity dimension holdup in 50 circulations, all embodiment all meets more than 72% (◎).

[table 1]

Known for embodiment 11～19, in first-phase, generate the VSi as third phase₂、TaSi₂、NbSi₂. Mutually reallyFixed by XRD resolves, section S EM observation, EPMA, STEM-EDS also with carrying out. Below, more specifically enter for assay methodRow explanation. The composition that quantitatively passes through icp analysis, product of feedstock composition is by the life of XRD parsing, first-phase and second-phaseThe shape and size of the shape and size that become thing by the product of SEM and SEM-EDX, third phase and the 4th phase by TEM andThe drawing of STEM-EDX, product entirety is undertaken by EPMA.

The size of third phase in embodiment 11～19 (thickness of cross-sectional layers) by the observed result of BF-STEM image be 1～100nm. Think owing to there being third phase, thereby can suppress by splitting of causing with discharging and recharging Si volumetric expansion together producingLine expansion, result, can guarantee the capacity dimension holdup under high power capacity. Should illustrate, as observed the arriving of observation example of Figure 26,VSi₂、TaSi₂、NbSi₂A part can be distributed in the 4th mutually in.

On the other hand, for comparative example 11 and comparative example 12, guarantee that the Si that becomes first-phase is mutually for equal with embodiment 16Or exceed some amount, guarantee the first discharge capacity of high several times of graphite. In addition, known for comparative example 11 and comparative example 12,Although guarantee that second-phase is also roughly equal amount with embodiment 16, the capacity dimension holdup after 50 circulations guarantees more than 64%,Can not confirm to generate third phase, therefore can not guarantee, 100 circulation after capacity dimension holdup be to become practicality judgment standard64％。

In embodiment 11,12, the input amount as many as 3at%～10at% of M group element, third phase separate out 9at%～30at%. In addition, also confirm that the 4th mutually contained metal A l separates out.

For embodiment 13～15, the input amount of M group element is fewer than embodiment 11,12, and the amount of separating out of third phase is also than realityExecute example 11,12 few. In addition, also confirm that the mutually contained metal A l of the 4th phase separates out. Embodiment 11～15 confirms the first～tetra-phaseExistence, wherein, high discharge capacity and the capacity dimension holdup of a large amount of embodiment 11 that exist of third phase 9at% are good. For realityExecute example 12,14,15, the first-phase larger with discharging and recharging volumetric expansion, shrinkage ratio is together suppressed to 22at%, with graphite-phaseRatio, guarantees sufficiently high discharge capacity, and capacity dimension holdup is good. Embodiment 13, compared with embodiment 12,14,15, dischargesCapacity approaches 3 times of levels, and therefore capacity dimension holdup is lower, but capacity dimension holdup self keeps more than 68%.

In embodiment 16, confirm third phase by the input of M group element, but the input amount of Al element is 20at%, not reallyRecognizing metal A l separates out mutually. Therefore, compared with embodiment 1～5, the ratio of thick phase increases, and capacity dimension holdup is 64%～68%Scope.

For embodiment 17, the input amount of M group element and embodiment 3～5 are same degree, but Ta, Nb be compared with V, mistakeEutectic regions is in a small amount of side, even if therefore M group element is few, also can guarantee that third phase is ormal weight. The part that M group element tails offObtain the discharge capacity of being brought by first-phase, can guarantee capacity dimension holdup with high power capacity compared with V.

For embodiment 18～19, the lower limit of Si element and M group element is shown, select the composition model in hypereutectic regionEnclose, thus, can guarantee high power capacity sustainment rate and discharge capacity.

Above, limit is with reference to accompanying drawing, and limit is illustrated for the preferred embodiment of the present invention, but the present invention is not limited toRelated example. As long as those skilled in the art, will clearly in the disclosed technological thought category of the application, can thinkTo various modification or fixed cases, and can recognize for these and naturally also belong to technical scope of the present invention.

[explanation of symbol]

1 ... negative electrode active material

3 ... silicon phase

5 ... the first silicide phase

7 ... the second silicide phase

11 ... liquation

13 ... silicide primary crystal

15 ... silicon

17 ... the first silicide

19 ... the second silicide

21 ... gas atomization device

23 ... crucible

25 ... nozzle

27 ... ejection gas

29 ... gas spraying machine

31 ... gas injection stream

41 ... single roller chilling apparatus

43 ... crucible

45 ... single roller

47 ... alloy

51 ... two roller chilling apparatus

53 ... crucible

55 ... casting roll

57 ... chilling apparatus

59 ... alloy

61 ... melt spinning device

63 ... crucible

65 ... container

67 ... cooling fluid

69 ... guide roller

70 ... alloy

71 ... rechargeable nonaqueous electrolytic battery

73 ... anodal

75 ... negative pole

77 ... division board

79 ... battery can

81 ... positive wire

83 ... positive terminal

85 ... negative wire

87 ... electrolyte

89 ... seal body

91 ... silicon phase

93 ... silicide (FeAl₃Si₂)

100 ... silicon particle

101 ... the one SEI

103 ... crackle

105 ... the 2nd SEI

107 ... crackle

111 ... first-phase

112 ... second-phase

113 ... third phase

114 ... first-phase

115 ... second-phase

116 ... third phase

117 ... first-phase

118 ... second-phase

120 ... negative electrode active material

Claims

1. a negative electrode active material, is characterized in that, contain silicon and can form with silicon the element M of compound, silicon with described inThe composition of element M be when cooling from molten condition the compound of silicon and described element M separate out at first, further cooling pure siliconOr the silicon solid solution composition of separating out.

2. a negative electrode active material, is characterized in that, contain silicon and can form with silicon the element M of compound, silicon with described inThe composition of element M is that the compound of silicon and described element M is analysed at first when cooling with speed more than 1000K/s from molten conditionThe composition of go out, further cooling pure silicon or silicon solid solution being separated out.

3. negative electrode active material according to claim 1 and 2, is characterized in that, described element M be selected from V, Nb, Ta,At least one element in Mo, W, Ti, Zr, Cr.

4. according to the negative electrode active material described in any one in claim 1～3, it is characterized in that the group of silicon and described element MBecome in hypereutectic region.

5. according to the negative electrode active material described in any one in claim 1～4, it is characterized in that described negative electrode active materialThe silicide phase that has the silicon phase that comprises pure silicon or silicon solid solution and comprise silicon and the compound of described element M, described silicon is mutuallyMore than the 20wt% in described negative electrode active material.

6. according to the negative electrode active material described in any one in claim 1～5, it is characterized in that, among described silicon phase, external diameterOr more than width has the 50 volume % that occupy mutually described silicon phase of size of 10～300nm.

7. according to the negative electrode active material described in any one in claim 1～6, it is characterized in that described negative electrode active materialFurther contain the element D different from described element M, described negative electrode active material has the compound of silicon and described element D, itsIn, element D be selected from Al, Cu, Fe, Co, Ni, Ca, Sc, Ti, V, Cr, Mn, Sr, La, Ce, Nd, Dy, Sm, Pr, Y, Zr, Nb, Mo,At least one element in Hf, Ta, W, Re, Os, Ir, Ru, Rh and Ba.

8. a negative electrode active material, is characterized in that, has in the conductive second-phase of Li and be dispersed with and have in electrochemistryThe first-phase of Li occlusion, described first-phase further contains the third phase that lacks Li occlusion compared with first-phase.

9. negative electrode active material according to claim 8, is characterized in that, first-phase is with respect to the area ratio of second-phaseBe 10～90%, further containing with respect to negative electrode active material material is the third phase of 1～40 atom %.

10. negative electrode active material according to claim 8 or claim 9, is characterized in that, described first-phase is pure silicon or silicon solid solutionBody, the mean value of cross-sectional layers thickness is 20～2000nm.

Negative electrode active material in 11. according to Claim 8～10 described in any one, is characterized in that, described second-phase is siliconCompound, the mean value of cross-sectional layers thickness is 20～2000nm.

Negative electrode active material in 12. according to Claim 8～11 described in any one, is characterized in that, described second-phase containsSi and Al, further contain at least one element being selected from element D claimed in claim 6.

Negative electrode active material in 13. according to Claim 8～12 described in any one, is characterized in that, described second-phase containsSi and Al, further contain at least one element being selected from Fe, Co, Mn, La, Ce, Nd, Pr, Sm and Dy.

Negative electrode active material in 14. according to Claim 8～13 described in any one, is characterized in that, described second-phase containsLack the 4th phase of Li occlusion compared with first-phase.

The negative electrode active material that 15. rechargeable nonaqueous electrolytic batteries according to claim 14 are used, is characterized in that, containsIt is the 4th phase of 1～50 atom % with respect to negative electrode active material material.

Negative electrode active material in 16. according to Claim 8～15 described in any one, is characterized in that, described third phase cutThe mean value of surface thickness is 1～100nm.

Negative electrode active material in 17. according to Claim 8～16 described in any one, is characterized in that, described third phase containsBe selected from VSi₂、TaSi₂、MoSi₂、NbSi₂、WSi₂、TiSi₂、ZrSi₂、CrSi₂In at least one compound.

Negative electrode active material in 18. according to Claim 8～17 described in any one, is characterized in that, described third phase containsBe selected from VSi₂、TaSi₂、NbSi₂In at least one compound.

Negative electrode active material in 19. according to Claim 8～18 described in any one, is characterized in that, described third phase orFour contain mutually and are selected from SiO₂、TiO₂、Al₂O₃, at least one compound in ZnO, CaO, MgO.

Negative electrode active material in 20. according to Claim 8～19 described in any one, is characterized in that, exists and forms third phaseThe volume of particle occupy more than 10% region among the total volume of first-phase and third phase.

21. 1 kinds of anode for nonaqueous electrolyte secondary battery are the nonaqueous electrolytes two on collector body with active material layerPrimary cell negative pole,

It is characterized in that, described active material layer contains negative electrode active material and bonding agent, described negative electrode active material contain silicon,With the element M that can form with silicon compound, the composition of silicon and described element M is silicon and described unit when cooling from molten conditionThe composition that the compound of element M separates out at first, further cooling pure silicon or silicon solid solution are separated out.

22. 1 kinds of rechargeable nonaqueous electrolytic batteries, having can occlusion and emit the positive pole of lithium ion, on collector body, have workThe negative pole of property material layer and the division board configuring between described positive pole and described negative pole, it has lithium-ion-conductingIn electrolyte, be provided with described positive pole, described negative pole and described division board,

It is characterized in that, the described active material layer of described negative pole contains negative electrode active material and bonding agent, described negative electrode activeMaterial contains silicon and can form with silicon the element M of compound, and the composition of silicon and described element M is cooling from molten conditionTime silicon and described element M the composition that compound is separated out at first, further cooling pure silicon or silicon solid solution are separated out.

The manufacture method of 23. 1 kinds of negative electrode active materials, is characterized in that, liquation is cooling with speed more than 1000K/s, instituteState the element M that liquation contains silicon and can form with silicon compound, the composition of silicon and described element M is cold from molten conditionBut the composition that time, the compound of silicon and described element M is separated out at first, further cooling pure silicon or silicon solid solution are separated out.

The manufacture method of 24. negative electrode active materials according to claim 23, is characterized in that, described liquation is by single rollerMethod, double roller therapy, melt spinning method, gas atomization or water atomization are cooling.

25. 1 kinds of anode for nonaqueous electrolyte secondary battery, its right to use requires the non-aqueous solution electrolysis described in any one in 8～20The negative electrode active material material that electrolitc secondary cell is used and forming.

26. 1 kinds of rechargeable nonaqueous electrolytic batteries, its right to use requires the anode for nonaqueous electrolyte secondary battery described in 25And form.

The manufacturer of the negative electrode active material material that the rechargeable nonaqueous electrolytic battery described in 27. 1 kinds of claims 8～19 is usedMethod, is characterized in that, after the alloy that contains Si, Al, element set D, element set M except Al is dissolved, by single-roller method, twoAny method in roller method, melt spinning method, gas atomization and water atomization makes it anxious with speed more than 1000K/ secondSpeed cooled and solidified, and temperature below 1000 DEG C makes Second Phase Precipitation,

Wherein, element set D for be selected from Cu, Fe, Co, Ni, Ca, Sc, Ti, V, Cr, Mn, Sr, La, Ce, Nd, Dy, Sm, Pr, Y, Zr,At least one element in Nb, Mo, Hf, Ta, W, Re, Os, Ir, Ru, Rh and Ba, element set M for be selected from V, Ta, Mo, Nb, W,At least one element in Ti, Zr, Cr, and the element being selected from element set M and element set D is not identical element.

The manufacture method of the negative electrode active material material that 28. rechargeable nonaqueous electrolytic batteries according to claim 27 are used,It is characterized in that, the element of the element set D except Al is to be selected from Fe, Co, Mn, La, Ce, Nd, Pr, Sm and Dy at leastA kind of element.