CN1419303A - Negative electrode material for nonelectrolyte cell and making method, negative electrode and cell - Google Patents

Negative electrode material for nonelectrolyte cell and making method, negative electrode and cell Download PDF

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CN1419303A
CN1419303A CN02147000A CN02147000A CN1419303A CN 1419303 A CN1419303 A CN 1419303A CN 02147000 A CN02147000 A CN 02147000A CN 02147000 A CN02147000 A CN 02147000A CN 1419303 A CN1419303 A CN 1419303A
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mentioned
atom
nonaqueous electrolyte
mutually
negative material
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泽孝雄
坂本敏也
河野龙兴
高见则雄
松野真辅
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Toshiba Corp
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Toshiba Corp
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Priority claimed from JP2001336931A external-priority patent/JP3844676B2/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The object of the present invention is to provide a negative electrode material for a nonaqueous electrolyte battery with a high discharge capacity, long charge-discharge cycle life, and excellent rate characteristics. The characteristics of the negative electrode material is that it has a composition represented by a general formula (1):(Al<1-x>Si<x>)<a>M<b>M'<c>T<d>......(1) and is essentially composed of an amorphous phase.

Description

Nonaqueous electrolyte battery negative material and manufacture method, negative pole and battery
Technical field
The present invention relates to nonaqueous electrolyte battery and use the manufacture method of negative material with negative material, the negative pole that comprises above-mentioned negative material, the nonaqueous electrolyte battery that has above-mentioned negative pole, nonaqueous electrolyte battery.Nonaqueous electrolyte battery of the present invention comprises nonaqueous electrolyte primary cell and rechargeable nonaqueous electrolytic battery.
Background technology
In recent years, use lithium metal to cause concern as high energy density cells as the nonaqueous electrolyte battery of negative electrode active material.In positive active material, use manganese dioxide (MnO 2), fluorocarbons [(CF 2) n], thionyl chloride (SOCl 2) primary cell that waits has been used to the power supply of tiny computer, clock and the reserve battery of memory.In addition, in recent years, along with miniaturization, the lightweight of various electronic equipments such as VTR, communication equipment, possessing the more secondary cell of high-energy-density as its power requirement, is that the research of the lithium secondary battery of negative electrode active material is carried out just actively with the lithium.
As lithium secondary battery, studied the battery that possesses following formation.That is, comprise the negative pole of lithium metal, by at propene carbonate (PC), 1,2-dimethoxy-ethane (DME), gamma-butyrolacton (have dissolved LiClO in γ-BL), the oxolane nonaqueous solventss such as (THF) 4, LiBF 4, LiAsF 6The electrolyte that constitutes Deng the nonaqueous electrolytic solution of lithium salts or lithium conducting solid electrolyte, and comprise the compound (TiS for example that carries out topochemical reaction with lithium as positive active material 2, MoS 2, V 2O 5, V 6O 13, MnO 2Deng) positive pole.
But above-mentioned lithium secondary battery is practicability not also at present.Its main cause is lithium metal meeting micronizing in repeated charge of using in the negative pole, becomes the Li dendrite with reactivity, damages the fail safe of battery, causes battery breakage, short circuit, thermal explosion etc.In addition, because lithium metal deterioration, efficiency for charge-discharge reduces, the problem that exists cycle life to shorten.
Therefore, but propose the alternative metals lithium and use occlusion to discharge the carbide of lithium, for example coke, resin sintered body, carbon fiber, thermal decomposition gas-phase carbon etc.In recent years, commercial lithium rechargeable battery possesses the negative pole of carbide-containing and contains LiCoO 2Positive pole and nonaqueous electrolyte.Discharge when taking place in this lithium rechargeable battery, and the lithium ion that discharges from negative pole enters the nonaqueous electrolyte, and the lithium ion in the nonaqueous electrolyte is reacted by the negative pole occlusion during charging.
But,, wish that strongly battery capacity can be further improved along with the requirement that further miniaturization of electronic equipment and long-time continuous are used.Yet the raising of the charge/discharge capacity of existing material with carbon element limits to some extent, possesses the low-temperature sintering carbon of high power capacity because material density is little, so be difficult to increase the charge/discharge capacity of unit volume.Therefore, in the process of research high-capacity battery, need the new negative material of exploitation.
The spy opens and discloses the noncrystalline SnAX alloy that comprises with nonstoichiometric composition in the 2000-311681 communique is the negative electrode for lithium secondary battery electrode material of the particle of principal component.In the above-mentioned formula, A represents that at least a in the transition metal, X represent to be selected from least a of O, F, N, Mg, Ba, Sr, Ca, La, Ce, Si, Ge, C, P, B, Bi, Sb, Al, In, S, Se, Te, Zn.Wherein can not comprise X.The atomicity of each atom satisfies the relation of Sn/ (Sn+A+X)=20～80 atom % in the above-mentioned formula.
Open the 2000-311681 communique as the spy, in the alloy system of Sn, if Sn content then can not get high power capacity below 20 atom % as the basic element of Li occlusion capacity.In fact, in the table 1 with Sn 18Co 82In the amorphous alloy of expression, first efficiency for charge-discharge, discharge capacity and cycle life all are not so good as the amorphous alloy that Sn content surpasses 80 atom %.On the other hand, if Sn content surpasses 80 atom %, though capacity increases to some extent, cycle life shortens.In addition, even if the composition of capacity and cycle life relative equilibrium can not be realized the high power capacity and the long lifetime of battery.
On the other hand, in paragraph [0010]～[0012] of Te Kaiping 10-223221 communique, be the discharge capacity of realization secondary cell and the raising of charge and discharge circulation life, the binary system or the ternary system intermetallic compound that use transition metals such as comprising Ni, Co, Fe and Al are disclosed, and the technical scheme of the binary system intermetallic compound of Al and Mg.
But the nonaqueous electrolyte battery that uses the special intermetallic compound of opening flat 10-223221 communique record is discharge capacity and cycle life not only, and the discharge rate characteristic is all not ideal enough.
Be to realize the improvement of discharge capacity, coulombic efficiency and rate characteristic, the spy opens flat 10-302770 communique and discloses and use chemical formula AB xThe anode material for lithium-ion secondary battery that the compound of (0.5≤X≤3) expression constitutes.Wherein, A is one or more the element that is selected from Fe, Ni, Mn, Co, Mo, Cr, Nb, V, Cu and W, and B is one or more the element that is selected from Si, C, Ge, Sn, Pb, Al and P.
The Si that represents with B and the ratio Si of M (C, Ge, Sn, Pb, Al, P): M have been put down in writing in the paragraph of above-mentioned communique [0025] in the scope of 1: 0.2 (0.83: 0.17)～1: 0.
Yet, AB xEven in the Si that represents with B exist rate up to more than 0.83, can not obtain desirable discharge capacity, cycle life and discharge rate characteristic.
Patent documentation 1: the spy opens 2000-311681 communique (claim scope, table 1); Patent documentation 2: the spy opens flat 10-223221 communique (paragraph [0010]-[0012]); Patent documentation 3: the spy opens flat 10-302770 communique (claim scope, paragraph [0025]).
The present invention seeks to be provided at discharge capacity, charge and discharge circulation life and rate characteristic aspect superior nonaqueous electrolyte battery negative material and manufacture method, negative pole and nonaqueous electrolyte battery.
The object of the invention provides the nonaqueous electrolyte battery that can realize higher discharge capacity and superior rate characteristic with negative material and manufacture method, negative pole and nonaqueous electrolyte battery.
Summary of the invention
The present invention 1 provides a kind of nonaqueous electrolyte battery negative material, and this material has following general formula (1): (A1 1-xSi x) aM bM ' cT d(1) Biao Shi composition, constitute by amorphous phase in fact, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni, Cu and M, above-mentioned M ' is for being selected from least a element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x＜0.75.
The present invention 2 provides a kind of nonaqueous electrolyte battery negative material, and this material has following general formula (2): (Al 1-xA x) aM bM ' cT d(2) Biao Shi composition, constitute by amorphous phase in fact, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is for being selected from Fe, Co, Ni, at least a element of Cu and Mn, above-mentioned M ' is for being selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x≤0.9.
The present invention 3 provides a kind of nonaqueous electrolyte battery negative material, and this material comprises the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (3): (Al 1-xSi x) aM bM ' cT d(3) Biao Shi composition, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x＜0.75.
The present invention 4 provides a kind of nonaqueous electrolyte battery negative material, and this material comprises the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (4): (Al 1-xA x) aM bM ' cT d(4) Biao Shi composition, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x≤0.9.
The present invention 5 provides a kind of nonaqueous electrolyte battery negative material, and this material has following general formula (5): [(Al 1-xSi x) aM bM ' cT d] yLi z(5) Biao Shi composition, constitute by amorphous phase in fact, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni, Cu and Mn, above-mentioned M ' is for being selected from least a element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x＜0.75, y+z=100 atom %, 0＜z≤50 atom %.
The present invention 6 provides a kind of nonaqueous electrolyte battery negative material, and this material has following general formula (6): [(Al 1-xA x) aM bM ' cT d] yLi z(6) Biao Shi composition, constitute by amorphous phase in fact, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is for being selected from Fe, Co, Ni, at least a element of Cu and Mn, above-mentioned M ' is for being selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d, x, y, z satisfies a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x≤0.9, y+z=100 atom %, 0＜z≤50 atom %.
The present invention 7 provides a kind of nonaqueous electrolyte battery negative material, and this material comprises the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (7): [(Al 1-xSi x) aM bM ' cT d] yLi z(7) Biao Shi composition, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn structure, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x＜0.75, y+z=100 atom %, 0＜z≤50 atom %.
The present invention 8 provides a kind of nonaqueous electrolyte battery negative material, and this material comprises the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (8): [(Al 1-xA x) aM bM ' cT d] yLi z(8) Biao Shi composition, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x≤0.9, y+z=100 atom %, 0＜z≤50 atom %.
The present invention 9 provides a kind of nonaqueous electrolyte battery negative material, but this material occlusion discharges lithium, in programming rate is 10 ℃/minute differential scanning calorimetry (DSC), an exothermic peak appears in 200～450 ℃ scope at least, and in X-ray diffraction, the diffraction maximum based on crystalline phase appears.
The present invention 10 provides a kind of nonaqueous electrolyte battery negative material, this material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, 1 μ m 2The number of above-mentioned intermetallic compound crystalline particle be 10～2000, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, and above-mentioned second separates out with the state of imbedding between above-mentioned isolated crystalline particle.
The present invention 11 provides a kind of nonaqueous electrolyte battery negative material, this material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, average distance between above-mentioned intermetallic compound crystalline particle is below 500nm, and above-mentioned second separate out with the state of imbedding between above-mentioned isolated crystalline particle.
The present invention 12 provides a kind of nonaqueous electrolyte battery negative material, this material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, it is the antifluorite structure of 5.42～6.3_ that above-mentioned intermetallic compound crystalline particle has cubic system fluorite structure or the lattice constant that lattice constant is 5.42～6.3_, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, and above-mentioned second separates out with the state of imbedding between above-mentioned isolated crystalline particle.
The present invention 13 provides a kind of nonaqueous electrolyte battery negative material, this material possess comprise two or more can with the intermetallic compound of the element of lithium alloyage mutually, and based on can with the element of lithium alloyage second mutually, in powder x-ray diffraction is measured, when the d value is at least 3.1 3～3.64_ with 1.92～2.23_, occur, and when the d value is at least 2.31～2.40_, diffraction maximum occurs from above-mentioned second phase from above-mentioned intermetallic compound diffraction maximum mutually.
The present invention 14 provides a kind of nonaqueous electrolyte battery negative material, this material possess with the monomer of the element of lithium alloyage mutually with a plurality of intermetallic compound phases, above-mentioned a plurality of intermetallic compound at least two kinds in mutually comprise respectively with the element of lithium alloyage and not with the element of lithium alloyage, the element of above-mentioned and lithium alloyage and above-mentioned not different each other with the combination of the element of lithium alloyage.
The present invention 15 provides a kind of nonaqueous electrolyte battery negative material, this material possess with the monomer of the element of lithium alloyage mutually, intermetallic compound mutually and non-equilibrium phase.
The present invention 16 provides a kind of negative pole, and described negative pole comprises and has following general formula (1): (Al 1-xSi x) aM bM ' cT d(1) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni, Cu and M, above-mentioned M ' is for being selected from least a element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x＜0.75.
The present invention 17 provides a kind of negative pole, and described negative pole comprises and has following general formula (2): (Al 1-xA x) aM bM ' cT d(2) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is for being selected from Fe, Co, Ni, at least a element of Cu and Mn, above-mentioned M ' is for being selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x≤0.9.
The present invention 18 provides a kind of negative pole, and described negative pole comprises and possesses the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (3): (Al 1-xSi x) aM bM ' cT d(3) alloy of Biao Shi composition, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x＜0.75.
The present invention 19 provides a kind of negative pole, and described negative pole comprises and possesses the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (4): (Al 1-xA x) aM bM ' cT d(4) alloy of Biao Shi composition, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x≤0.9.
The present invention 20 provides a kind of negative pole, and described negative pole comprises and has following general formula (5): [(Al 1-xSi x) aM bM ' cT d] yLi z(5) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni, Cu and Mn, above-mentioned M ' is for being selected from least a element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x＜0.75, y+z=100 atom %, 0＜z≤50 atom %.
The present invention 21 provides a kind of negative pole, and described negative pole comprises and has following general formula (6): [(Al 1-xA x) aM bM ' cT d] yLi z(6) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is for being selected from Fe, Co, Ni, at least a element of Cu and Mn, above-mentioned M ' is for being selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d, x, y, z satisfies a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x≤0.9, y+z=100 atom %, 0＜z≤50 atom %.
The present invention 22 provides a kind of negative pole, and described negative pole comprises and possesses the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (7): [(Al 1-xSi x) aM bM ' cT d] yLi z(7) alloy of Biao Shi composition, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn structure, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x＜0.75, y+z=100 atom %, 0＜z≤50 atom %.
The present invention 23 provides a kind of negative pole, and described negative pole comprises and possesses the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (8): [(Al 1-xA x) aM bM ' cT d] yLi z(8) alloy of Biao Shi composition, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x≤0.9, y+z=100 atom %, 0＜z≤50 atom %.
But the present invention 24 provides and has comprised the negative pole that occlusion discharges the negative material of lithium, above-mentioned negative material is in programming rate is 10 ℃/minute differential scanning calorimetry (DSC), an exothermic peak appears in 200～450 ℃ scope at least, and in X-ray diffraction, the diffraction maximum based on crystalline phase appears.
The present invention 25 provides the negative pole that comprises negative material, above-mentioned negative material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, 1 μ m 2The number of above-mentioned intermetallic compound crystalline particle be 10～2000, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, and above-mentioned second separates out with the state of imbedding between above-mentioned isolated crystalline particle.
The present invention 26 provides the negative pole that comprises negative material, above-mentioned negative material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, average distance between above-mentioned intermetallic compound crystalline particle is below 500nm, and above-mentioned second separate out with the state of imbedding between above-mentioned isolated crystalline particle.
The present invention 27 provides the negative pole that comprises negative material, above-mentioned negative material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, it is the antifluorite structure of 5.42～6.3_ that above-mentioned intermetallic compound crystalline particle has cubic system fluorite structure or the lattice constant that lattice constant is 5.42～6.3_, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, and above-mentioned second separates out with the state of imbedding between above-mentioned isolated crystalline particle.
The present invention 28 provides the negative pole that comprises negative material, above-mentioned negative material possess comprise two or more can with the intermetallic compound of the element of lithium alloyage mutually, and based on can with the element of lithium alloyage second mutually, during powder x-ray diffraction is measured, when the d value is at least 3.13～3.64_ with 1.92～2.23_, occur, and when the d value is at least 2.31～2.40_, diffraction maximum occurs from above-mentioned second phase from above-mentioned intermetallic compound diffraction maximum mutually.
The present invention 29 provides the negative pole that comprises negative material, above-mentioned negative material possess with the monomer of the element of lithium alloyage mutually with a plurality of intermetallic compound phases, above-mentioned a plurality of intermetallic compound at least two kinds in mutually comprise respectively with the element of lithium alloyage and not with the element of lithium alloyage, the element of above-mentioned and lithium alloyage and above-mentioned not different each other with the combination of the element of lithium alloyage.
The present invention 30 provides the negative pole that comprises negative material, above-mentioned negative material possess with the monomer of the element of lithium alloyage mutually, intermetallic compound mutually and non-equilibrium phase.
The present invention 31 provides a kind of nonaqueous electrolyte battery, and this battery possesses negative pole, positive pole and nonaqueous electrolyte, and described negative pole comprises and has following general formula (1): (Al 1-xSi x) aM bM ' cT d(1) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni, Cu and M, above-mentioned M ' is for being selected from least a element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x＜0.75.
The present invention 32 provides a kind of nonaqueous electrolyte battery, and this battery possesses negative pole, positive pole and nonaqueous electrolyte, and described negative pole comprises and has following general formula (2): (Al 1-xA x) aM bM ' cT d(2) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is for being selected from Fe, Co, Ni, at least a element of Cu and Mn, above-mentioned M ' is for being selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x≤0.9.
The present invention 33 provides a kind of nonaqueous electrolyte battery, and this battery possesses negative pole, positive pole and nonaqueous electrolyte, and described negative pole comprises and possesses the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (3): (Al 1-xSi x) aM bM ' cT d(3) alloy of Biao Shi composition, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x＜0.75.
The present invention 34 provides a kind of nonaqueous electrolyte battery, and this battery possesses negative pole, positive pole and nonaqueous electrolyte, and described negative pole comprises and possesses the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (4): (A1 1-xA x) aM bM ' cT d(4) alloy of Biao Shi composition, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x≤0.9.
The present invention 35 provides a kind of nonaqueous electrolyte battery, and this battery possesses negative pole, positive pole and nonaqueous electrolyte, and described negative pole comprises and has following general formula (5): [(Al 1-xSi x) aM bM ' cT d] yLi z(5) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni, Cu and Mn, above-mentioned M ' is for being selected from least a element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x＜0.75, y+z=100 atom %, 0＜z≤50 atom %.
The present invention 36 provides a kind of nonaqueous electrolyte battery, and this battery possesses negative pole, positive pole and nonaqueous electrolyte, and described negative pole comprises and has following general formula (6): [(Al 1-xA x) aM bM ' cT d] yLi z(6) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is for being selected from Fe, Co, Ni, at least a element of Cu and Mn, above-mentioned M ' is for being selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d, x, y, z satisfies a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x≤0.9, y+z=100 atom %, 0＜z≤50 atom %.
The present invention 37 provides a kind of nonaqueous electrolyte battery, and this battery possesses negative pole, positive pole and nonaqueous electrolyte, and described negative pole comprises and possesses the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (7): [(Al 1-xSi x) aM bM ' cT d] yLi z(7) alloy of Biao Shi composition, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn structure, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x＜0.75, y+z=100 atom %, 0＜z≤50 atom %.
The present invention 38 provides a kind of nonaqueous electrolyte battery, and this battery possesses negative pole, positive pole and nonaqueous electrolyte, and described negative pole comprises and possesses the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (8): [(Al 1-xA x) aM bM ' cT d] yLi z(8) alloy of Biao Shi composition, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x≤0.9, y+z=100 atom %, 0＜z≤50 atom %.
The present invention 39 provides a kind of nonaqueous electrolyte battery, this battery possesses negative pole, positive pole and nonaqueous electrolyte, but described negative pole comprises the negative material that occlusion discharges lithium, above-mentioned negative material is in programming rate is 10 ℃/minute differential scanning calorimetry (DSC), an exothermic peak appears in 200～450 ℃ scope at least, and in X-ray diffraction, the diffraction maximum based on crystalline phase appears.
The present invention 40 provides a kind of nonaqueous electrolyte battery, this battery possesses negative pole, positive pole and the nonaqueous electrolyte that comprises negative material, above-mentioned negative material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, 1 μ m 2The number of above-mentioned intermetallic compound crystalline particle be 10～2000, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, and above-mentioned second separates out with the state of imbedding between above-mentioned isolated crystalline particle.
The present invention 41 provides a kind of nonaqueous electrolyte battery, this battery possesses the negative pole that comprises negative material, positive pole and nonaqueous electrolyte, above-mentioned negative material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, average distance between above-mentioned intermetallic compound crystalline particle is below 500nm, and above-mentioned second separate out with the state of imbedding between above-mentioned isolated crystalline particle.
The present invention 42 provides a kind of nonaqueous electrolyte battery, this battery possesses the negative pole that comprises negative material, positive pole and nonaqueous electrolyte, above-mentioned negative material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, it is the antifluorite structure of 5.42～6.3_ that above-mentioned intermetallic compound crystalline particle has cubic system fluorite structure or the lattice constant that lattice constant is 5.42～6.3_, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, and above-mentioned second separates out with the state of imbedding between above-mentioned isolated crystalline particle.
The present invention 43 provides a kind of nonaqueous electrolyte battery, this battery possesses negative pole, positive pole and the nonaqueous electrolyte that comprises negative material, above-mentioned negative material possess comprise two or more can with the intermetallic compound of the element of lithium alloyage reach mutually based on can with second phase of the element of lithium alloyage, during powder x-ray diffraction is measured, when the d value is at least 3.13～3.64_ with 1.92～2.23_, occur, and when the d value is at least 2.31～2.40_, diffraction maximum occurs from above-mentioned second phase from above-mentioned intermetallic compound diffraction maximum mutually.
The present invention 44 provides a kind of nonaqueous electrolyte battery, this battery possesses negative pole, positive pole and the nonaqueous electrolyte that comprises negative material, above-mentioned negative material possess with the monomer of the element of lithium alloyage mutually with a plurality of intermetallic compound phases, above-mentioned a plurality of intermetallic compound at least two kinds in mutually comprise respectively with the element of lithium alloyage and not with the element of lithium alloyage, the element of above-mentioned and lithium alloyage and above-mentioned not different each other with the combination of the element of lithium alloyage.
The present invention 45 provides a kind of nonaqueous electrolyte battery, and this battery possesses negative pole, positive pole and the nonaqueous electrolyte that comprises negative material, above-mentioned negative material possess with the monomer of the element of lithium alloyage mutually, intermetallic compound mutually and non-equilibrium phase.
The present invention 46 provides the manufacture method of nonaqueous electrolyte battery with negative material, the feature of this method is, the metallic solution that will comprise the first～the element is expelled on single roller, make thickness of slab reach 10～500 μ m by chilling, and make and comprise compound between high-melting point metal mutually and second mutually the metal structure curing, wherein, intermetallic compound comprises above-mentioned the first～the element mutually, second based on above-mentioned first element and lower than the fusing point of above-mentioned intermetallic compound phase, above-mentioned first element is for being selected from Al, In, Pb, Ga, Sb, Bi, Sn, at least a element of Zn, above-mentioned second element is for being selected from except that Al, In, Pb, Ga, Sb, Bi, Sn, beyond the Zn can be with the element of lithium alloyage at least a, above-mentioned element is the element that can form intermetallic compound with first element and second element.
The present invention 47 provides the manufacture method of nonaqueous electrolyte battery with negative material, the feature of this method is, to comprise Al, element N1, the metallic solution of element N2 and element N3 is expelled on single roller, make thickness of slab reach 10～500 μ m by chilling, and make and comprise compound between high-melting point metal mutually and second mutually the metal structure curing, wherein, intermetallic compound comprises Al mutually, element N1 and element N2, second based on Al and lower than the fusing point of above-mentioned intermetallic compound phase, above-mentioned element N1 is Si or Si and Mg, above-mentioned element N2 is at least a element that is selected from Ni and Co, above-mentioned element N3 is for being selected from In, Bi, Pb, Sn, Ga, Sb, Zn, Fe, Cu, Mn, Cr, Ti, Zr, Nb, at least a element of Ta and rare earth element, Al content in the above-mentioned metallic solution is h atom %, element N1 content in the above-mentioned metallic solution is i atom %, element N2 content in the above-mentioned metallic solution is j atom %, when the element N3 content in the above-mentioned metallic solution is k atom %, above-mentioned h, i, j, k satisfies 12.5≤h＜95 respectively, 0＜i≤71,5≤j≤40,0≤k＜20 the present invention 48 provide the manufacture method of nonaqueous electrolyte battery with negative material, the feature of this method is, possesses to make by single-roller method to have following general formula (9): X xTl yJ z(9) the metallic solution chilling of Biao Shi composition makes in fact the step of the alloy that is made of amorphous phase, and under the temperature more than the crystallized temperature of above-mentioned alloy above-mentioned alloy is implemented heat treated step; Wherein, above-mentioned X is at least two kinds of elements that are selected from Al, Si, Mg, Sn, Ge, In, Pb, P, C, above-mentioned Tl is at least a element that is selected from Fe, Co, Ni, Cr and Mn, above-mentioned J is at least a element that is selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, above-mentioned x, y, z satisfy x+y+z=100 atom % respectively, 50≤x≤90,10≤y≤33,0≤z≤10.
The present invention 49 provides the manufacture method of nonaqueous electrolyte battery with negative material, and the feature of this method is, possesses to make by single-roller method to have following general formula (10): Al aTl bJ cZ d(10) the metallic solution chilling of Biao Shi composition makes in fact the step of the alloy that is made of amorphous phase, and under the temperature more than the crystallized temperature of above-mentioned alloy above-mentioned alloy is implemented heat treated step; Wherein, above-mentioned Al is at least a element that is selected from Si, Mg and Al, above-mentioned Tl is at least a element that is selected from Fe, Co, Ni, Cr, Mn, above-mentioned J is at least a element that is selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, and above-mentioned Z is at least a element that is selected from C, Ge, Pb, P and Sn structure, and above-mentioned a, b, c, d satisfy a+b+c+d=100 atom % respectively, 50≤a≤95,5≤b≤40,0≤c≤10,0≤d＜20.
The present invention 50 provides the manufacture method of nonaqueous electrolyte battery with negative material, and the feature of this method is, possesses to make by single-roller method to have following general formula (11): Tl 100-a-b-c(A2 1-xJ ' x) aB bJ c(11) the metallic solution chilling of Biao Shi composition makes in fact the step of the alloy that is made of amorphous phase, and under the temperature more than the crystallized temperature of above-mentioned alloy above-mentioned alloy is implemented heat treated step; Wherein, above-mentioned Tl is at least a element that is selected from Fe, Co, Ni, Cu, Cr, Mn, above-mentioned A2 is at least a element that is selected from Al and Si, above-mentioned J is at least a element that is selected from Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, above-mentioned J ' is for being selected from least a element of C, Ge, Pb, P, Sn and Mg, above-mentioned a, b, c, x satisfy 10 atom %≤a≤85 atom % respectively, 0＜b≤35 atom %, 0≤c≤10 atom %, 0≤x≤0.3, Sn contains quantity not sufficient 20 atom % (comprising 0 atom %).
The present invention 51 provides the manufacture method of nonaqueous electrolyte battery with negative material, and the feature of this method is, possesses to make by single-roller method to have following general formula (12): (Mg 1-xA3 x) 100-a-b-c-d(RE) aTl bMl cA4 d(12) the metallic solution chilling of Biao Shi composition makes in fact the step of the alloy that is made of amorphous phase, and under the temperature more than the crystallized temperature of above-mentioned alloy above-mentioned alloy is implemented heat treated step; Wherein, above-mentioned A3 is at least a element that is selected from Al, Si and Ge, above-mentioned RE is at least a element that is selected from Y and rare earth element, above-mentioned Tl is at least a element that is selected from Fe, Co, Ni, Cu, Cr, Mn, above-mentioned M1 is at least a element that is selected from Ti, Zr, Hf, V, Nb, Ta, Mo, W, above-mentioned A4 is at least a element that is selected from Sn, Pb, Zn, P and C, above-mentioned a, b, c, d, x satisfy 0＜a≤40 atom % respectively, 0＜b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0≤x≤0.5.
The present invention 52 provides the manufacture method of nonaqueous electrolyte battery with negative material, and the feature of this method is, possesses to make by single-roller method to have following general formula (13): (Al 1-xA5 x) aTl bJ cZ d(13) the metallic solution chilling of Biao Shi composition makes in fact the step of the alloy that is made of amorphous phase, and under the temperature more than the crystallized temperature of above-mentioned alloy above-mentioned alloy is implemented heat treated step; Wherein, above-mentioned A5 is at least a element that is selected from Si and Mg, above-mentioned T1 is at least a element that is selected from Fe, Co, Ni, Cr, Mn, and above-mentioned J is at least a element that is selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, and above-mentioned Z is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x satisfy a+b+c+d=100 atom % respectively, 50≤a≤95,5≤b≤40,0≤c≤10,0≤d＜20,0＜x≤0.9.
Description of drawings
Fig. 1 is the sectional view of slim rechargeable nonaqueous electrolytic battery of an example of nonaqueous electrolyte battery of the present invention.
Fig. 2 is the A portion amplification sectional view of Fig. 1.
Fig. 3 is the X-ray diffractogram of the negative material of embodiment 1.
Fig. 4 is the X-ray diffractogram of the negative material of embodiment 15.
Fig. 5 is the metal structure ideograph of nonaqueous electrolyte battery of the present invention with negative material.
Fig. 6 is the X-ray diffractogram of the negative material of embodiment 52.
Fig. 7 is the transmission electron microphoto (multiplying power is 100,000 times) of the negative material of embodiment 52.
Fig. 8 is the DSC curve chart of differential scanning calorimetry of the negative material of embodiment 52.
Fig. 9 is the X-ray diffractogram of the negative material of embodiment 73.
Figure 10 is the X-ray diffractogram of the negative material of embodiment 89.
Symbol description:
1 is external packing component,
2 is electrode group,
3 is interlayer,
4 is anodal layer,
5 is positive electrode collector,
6 is anodal,
7 is negative electrode layer,
8 is negative electrode collector,
9 is negative pole,
10 is positive terminal,
11 is negative terminal.
Embodiment
The present invention 1～12 nonaqueous electrolyte battery negative material at first is described.
＜nonaqueous electrolyte battery negative material 1 〉
The present invention 1 nonaqueous electrolyte battery comprises with negative material and has following general formula (1): (Al 1-xSi x) aM bM ' cT d(1) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni, Cu and M, above-mentioned M ' is for being selected from least a element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x＜0.75.
As the metal structure that constitutes by amorphous phase in fact, can exemplify the tissue that in X-ray diffraction, does not occur based on the peak of crystalline phase.
(aluminium and Si)
Al and Si are the basic elements of occlusion lithium.The atomic ratio x of Si is 0.75 when above, can not get the metal structure that is made of amorphous phase in fact, reduces the cycle life of secondary cell.The better scope of atomic ratio x is more than 0.3 below 0.75.
The total atomic ratio of Al and Si is in the scope of 50～95 atom %.When adding up to atomic ratio less than 50 atom %, the lithium occlusion of negative material can reduce, and the discharge capacity of secondary cell, cycle life and rate characteristic are difficult to be further enhanced.On the other hand, when adding up to atomic ratio to surpass 95 atom %, cause the lithium release reaction in the negative material hardly.The better scope that adds up to atomic ratio be greater than 67 atom % less than 90 atom %, best is below the above 88 atom % of 70 atom %.
(element M)
These three kinds of elements of Al and Si and element M can promote decrystallized.Micronizing when element M can suppress occlusion in the negative material and discharges lithium.The atomic ratio b of element M is during less than 5 atom %, decrystallized difficulty.On the other hand, the atomic ratio b of element M is during greater than 40 atom %, and the discharge capacity of secondary cell significantly reduces.The better scope of the atomic ratio b of element M is 7～35 atom %.
(element M ')
As rare earth element, can exemplify La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu etc.Wherein be preferably La, Ce, Pr, Nd, Sm.
Contain element M with the atomic ratio below the 10 atom % ', can promote decrystallized.In addition, can reduce the delay of Li in alloy of occlusion, suppress charge/discharge capacity and descend.Better the scope of atomic ratio c is below the 8 atom %.Wherein, when the amount of atomic ratio c is less than 0.01 atom %, may can not get promoting effect decrystallized and that the inhibition charge/discharge capacity descends, so the lower limit of atomic ratio c is preferably 0.01 atom %.
(element T)
Element T can promote decrystallized.By pressing containing element T in the scope of atomic ratio d below 20 atom %, can improve capacity or increase the service life.But atomic ratio d is when 20 atom % are above, and cycle life reduces.The better scope of atomic ratio d is below the 15 atom %.
Rechargeable nonaqueous electrolytic battery with negative material of the present invention 1, the alloy composition that comprises in the above-mentioned negative material before enforcement discharges and recharges does not change, in case implement to discharge and recharge, causes sometimes that as the residual Li of irreversible capacity alloy composition changes.Alloy composition after the variation is represented with general formula described later (5).
＜nonaqueous electrolyte battery negative material 2 〉
Nonaqueous electrolyte battery comprises with negative material 2 and has following general formula (2): (Al 1-xA x) aM bM ' cT d(2) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is for being selected from Fe, Co, Ni, at least a element of Cu and Mn, above-mentioned M ' is for being selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x≤0.9.
As the metal structure that constitutes by amorphous phase in fact, can exemplify the tissue that in X-ray diffraction, does not occur based on the peak of crystalline phase.
(aluminium and elements A)
Al and elements A (Mg or Mg and Si) are the basic elements of occlusion lithium.The atomic ratio x of elements A can not get the metal structure that amorphous phase constitutes in fact 0.9 when above, also can reduce the cycle life and the rate characteristic of secondary cell.The better scope of atomic ratio x is 0.3≤x≤0.8.
The total atomic ratio of Al and elements A is in the scope of 50～95 atom %.When adding up to atomic ratio less than 50 atom %, the lithium occlusion of negative material can reduce, and the discharge capacity of secondary cell, cycle life and rate characteristic are difficult to improve.On the other hand, when adding up to atomic ratio to surpass 95 atom %, cause the lithium release reaction in the negative material hardly.Adding up to the better scope of atomic ratio is 70～90 atom %.
(element M)
These three kinds of elements of Al, elements A and element M can promote decrystallized.Micronizing when element M can suppress occlusion in the negative material and discharges lithium.The atomic ratio b of element M is during less than 5 atom %, decrystallized difficulty.On the other hand, the atomic ratio b of element M is during greater than 40 atom %, and the discharge capacity of secondary cell significantly reduces.The better scope of the atomic ratio b of element M is 7～35 atom %.
(element M ')
As rare earth element, with above-mentioned negative material 1 exemplified identical.Wherein be preferably La, Ce, Pr, Nd, Sm.
By containing element M by the atomic ratio below the 10 atom % ', can promote decrystallized.In addition, can also reduce the delay of Li in alloy of occlusion, suppress charge/discharge capacity and descend.Better the scope of atomic ratio c is below 8 atom %.But, when the amount of atomic ratio c is less than 0.01 atom %, may can not get promoting effect decrystallized and that the inhibition charge/discharge capacity descends, so the lower limit of atomic ratio c is preferably 0.01 atom %.
(element T)
Element T can promote decrystallized.By pressing the scope containing element T of atomic ratio d below 20 atom %, can improve capacity or increase the service life.But atomic ratio d is when 20 atom % are above, and cycle life reduces.The better scope of atomic ratio d is below 15 atom %.
Rechargeable nonaqueous electrolytic battery with negative material of the present invention 2, the alloy composition that comprises in the above-mentioned negative material before enforcement discharges and recharges does not change, in case implement to discharge and recharge, causes sometimes that as the residual Li of irreversible capacity alloy composition changes.Alloy composition after the variation is represented with general formula described later (6).
Negative material 1 and 2 can make by liquid quench method, machine-alloying or mechanical milling method.
(liquid quench method)
So-called liquid quench method is to be modulated to the method that cooling body (for example roller) that alloying metal solution that regulation forms injects to high speed rotating from small nozzle carries out chilling.The shape of the sample that the liquid quench method obtains comprises long thin ribbon shaped, laminar etc.When changing the sample composition, its fusing point changes, so specimen shape also can change according to the variation of forming.Metal structure comes down under the situation of amorphous phase formation, obtains long thin ribbon shaped easily.On the other hand, play main dominating role aspect the thickness of slab of the sample that cooling rate obtains at chilling, sample thickness roller rest material, roller rotating speed and nozzle bore are regulated.
Wettability with roller material and alloying metal solution decides best material, and it is desirable to Cu is the alloy (for example, Cu, TiCu, ZrCu, BeCu) of main component.
The roller rotating speed is formed decision by material, but easily realizes decrystallized at the range content of 20～60m/s.The roller rotating speed is during less than 20m/s, obtain easily crystallite mutually and the mixing of amorphous phase mutually.On the other hand, the roller rotating speed owing to be difficult to deposit alloying metal solution on the chill roll of high speed rotating, therefore makes cooling rate reduce during greater than 60m/s on the contrary, and crystallite is separated out mutually easily.Generally according to composition, obtain the target crystallite with the above roller rotating speed of general 10m/s.
Nozzle bore is preferably in the scope of 0.3～2mm.Nozzle bore is difficult to penetrate metallic solution from nozzle during less than 0.3mm.On the other hand, when nozzle bore surpasses 2mm,, be difficult to obtain sufficient cooling rate though obtain thicker sample easily.
Gap between roller and the nozzle is preferably in the scope of 0.2～10mm, when the gap surpasses 10mm, if flowing for laminar flow of metallic solution then can improve cooling rate equably.But, when adding broad gap, owing to obtain thicker sample, so the gap is wide more, cooling rate is slow more.
Need from alloying metal solution, to draw a large amount of heat in a large amount of the production, therefore preferably increase the thermal capacity of roller., more than the 300mm φ, better scope is more than 500mm φ to roller diameter more fortunately.The width of roller better is more than 50mm, is more preferably more than 100mm.
(machine-alloying and mechanical milling method)
So-called machine-alloying and mechanical milling method are meant in inert atmosphere gas packs in the crucible being modulated to powder that regulation forms, clamps powder by rotation with the spin in the crucible, with the method for the energy acquisition alloy of this moment
Can implement heat treatment to the alloy that constitutes by amorphous in fact that makes by liquid quench method, machine-alloying or mechanical milling method and make its embrittlement.From avoiding the viewpoint of controlled micro crystallization, heat treatment temperature is preferably in below the crystallized temperature.
Except that aforesaid liquid quench, machine-alloying, mechanical milling method, available gas atomization, rotating disk method, rotary electrode method etc. obtain Powdered sample.These methods can obtain spherical sample by alternative condition, so can the closeest filling negative material in the negative pole, realize the high capacity of battery.
＜nonaqueous electrolyte battery negative material 3 〉
Nonaqueous electrolyte battery comprises with negative material 3 and has following general formula (3): (Al 1-xSi x) aM bM ' cT d(3) Biao Shi composition, and the alloy that possesses the crystallite phase of average crystallite particle diameter below 500nm, wherein, above-mentioned M is for being selected from Fe, Co, at least a element of Ni and Mn, above-mentioned M ' is for being selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x＜0.75.
Negative material 3 can be made of mutually above-mentioned crystallite in fact, also can be made of mutually with the compound of amorphous phase mutually above-mentioned crystallite.
Crystallite can be made of intermetallic compound mutually, also can be made of the compound of nonstoichiometric composition, or is made of the alloy of nonstoichiometric composition, considers from useful life and capacity, preferably is made of a plurality of compounds or alloy phase.
The average crystallite particle diameter of crystallite phase is when 500nm is above, because the micronizing of negative material is carried out soon, when therefore making electrode, electrically contact minimizing between the negative material or between conductive auxiliary agent and the negative material, discharge capacity reduces, and causes discharging and recharging life-span cycle life and reduces.The better scope of average crystallite particle diameter is below the above 500nm of 5nm, and better scope is below the above 300nm of 5nm.
The average crystallite particle diameter can be obtained from the half value of x-ray diffraction line is wide according to the Scherrer formula.Can take transmission electron microscope (TEM) photo, will from the maximum particle diameter of optional 20 particles wherein on average as the average crystallite particle diameter.Preferably in transmission electron microscope (TEM) photo (for example 100,000 times), select 50 crystal grain adjacent one another are, the longest part of each crystal grain as particle diameter, measured its length, with its mean value as the average crystallite particle diameter.The multiplying power of TEM photo can be according to the particle size change of measuring.
Crystallite mutually and the ratio of the compound middle crystallite phase mutually of amorphous phase by (a) differential scanning calorimetry (DSC) or (b) X-ray diffraction record.
(a) differential scanning calorimetry (DSC)
When the alloy that amorphous phase is constituted by differential scanning calorimetry (DSC) is measured because heat release under crystallization temperature, therefore with this thermal discharge as the benchmark thermal discharge.Carry out differential scanning calorimetry (DSC) for the indefinite alloy of the ratio of crystallite phase, estimate crystallite ratio mutually by this thermal discharge relatively and benchmark thermal discharge.
(b) X-ray diffraction
Diffracted intensity with the highest peak in the X-ray diffractogram of the known alloy of the ratio of crystallite phase is a benchmark, estimates crystallite ratio mutually by the intensity of the same diffraction maximum of the indefinite alloy of ratio of crystallite phase relatively with benchmark intensity.
(aluminium and Si)
Al and Si are the basic elements of occlusion lithium.The atomic ratio x of Si reduces the cycle life of secondary cell 0.75 when above.The better scope of atomic ratio x is more than 0.3 below 0.75.
The total atomic ratio of Al and Si is in the scope of 50～95 atom %.When adding up to atomic ratio less than 50 atom %, the lithium occlusion of negative material can reduce, and the discharge capacity of secondary cell, cycle life and rate characteristic are difficult to improve.On the other hand, when adding up to atomic ratio to surpass 95 atom %, negative material causes the lithium release reaction hardly.The better scope that adds up to atomic ratio be greater than 67 atom % less than 90 atom %, be more preferably below the above 88 atom % of 70 atom %.
(element M)
These three kinds of elements of Al, Si and element M can promote the miniaturization of crystal grain.Micronizing when element M can suppress occlusion in the negative pole material and discharges lithium.The atomic ratio b of element M is during less than 5 atom %, the miniaturization difficulty of crystal grain.On the other hand, the atomic ratio b of element M is during greater than 40 atom %, and the discharge capacity of secondary cell significantly reduces.The better scope of the atomic ratio b of element M is 7～35 atom %.
(element M ')
As rare earth element, it is identical that its object lesson and above-mentioned negative material 1 are lifted.Wherein be preferably La, Ce, Pr, Nd, Sm.
By containing element M by the atomic ratio below the 10 atom % ', can promote the miniaturization of crystal grain.Reduce the delay of Li in alloy of occlusion, suppress charge/discharge capacity and reduce.Better the scope of atomic ratio c is below 8 atom %.But, when the amount of atomic ratio c is less than 0.01 atom %, may can not get promoting the miniaturization of crystal grain and suppressing the effect that charge/discharge capacity reduces, so the lower limit of atomic ratio c is preferably 0.01 atom %.
(element T)
Element T can promote the miniaturization of crystal grain.By pressing containing element T in the scope of atomic ratio d below 20 atom %, can improve capacity or increase the service life.But atomic ratio d is when 20 atom % are above, and cycle life reduces.The better scope of atomic ratio d is below 15 atom %.
Rechargeable nonaqueous electrolytic battery with negative material of the present invention 3, the alloy composition that comprises in the above-mentioned negative material before enforcement discharges and recharges does not change, in case implement to discharge and recharge, causes sometimes that as the residual Li of irreversible capacity alloy composition changes.Alloy composition after the variation is represented with general formula described later (7).
Negative material 3 can make with the described method in following (1)～(3).
(1) alloy that is made of amorphous phase in fact that aforesaid liquid quench, machine-alloying or mechanical milling method are made heats more than the crystallization temperature at it, heat-treats and separates out the crystallite phase, obtains negative material 3.
So-called crystallization temperature is meant when the heat of carrying out this material is analyzed, the temperature of obtaining from initial exothermic peak.Specifically just be to use differential scanning calorimetry, when measuring under 10 ℃/minute programming rate, not having the temperature of intersection point of the gradient steepest ascent of the extended line of the line that changes and exothermic peak is crystallization temperature.The element M that in negative material, contains trace ' time, can easily the average crystallite particle diameter be controlled at below the 500nm.In element M ' in a small amount of add Zr, Hf, Nb, Ta, Mo, W, 4d, the 4f of rare earth element, the 5d transition metal can obtain higher facilitation effect aspect the crystal grain miniaturization.Increase element M ' in the addition of Ti, V, Cr the time can obtain higher crystal grain micronized effect.
(2) can directly separate out crystallite with the liquid quench method.At this moment, by regulating the cooling rate of metallic solution, can separate out crystallization by proper proportion with suitable particle diameter.The thickness of slab of quench material relies on cooling rate, and the control of thickness of slab is by regulating rotating speed, roller material, the realizations such as (nozzle bores) of metallic solution quantity delivered of chill roll.The alloy enforcement heat treatment that the liquid quench method is made makes its embrittlement or control metal structure (adjustment of the size of particle diameter and the crystallite ratio of separating out mutually).
(3) can obtain negative material 3 by machine-alloying or mechanical milling method.
＜nonaqueous electrolyte battery negative material 4 〉
Nonaqueous electrolyte battery comprises with negative material 4 and has following general formula (4): (Al 1-xA x) aM bM ' cT d(4) Biao Shi composition, and the alloy that possesses the crystallite phase of average crystallite particle diameter below 500nm, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is for being selected from Fe, Co, at least a element of Ni and Mn, above-mentioned M ' is for being selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x≤0.9.
Negative material 4 can be made of mutually above-mentioned crystallite in fact, also can be made of mutually with the compound of amorphous phase mutually above-mentioned crystallite.
Crystallite can be made of intermetallic compound mutually, the compound of nonstoichiometric composition constitutes or be made of the alloy of nonstoichiometric composition, considers from useful life and capacity, preferably is made of a plurality of compounds or alloy phase.
The reason of average crystallite particle diameter below 500nm of crystallite phase is described identical with above-mentioned negative material 3.The better scope of average crystallite particle diameter is below the above 500nm of 5nm, and preferably scope is below the above 300nm of 5nm.
The average crystallite particle diameter can be obtained from the half value of x-ray diffraction line is wide according to the Scherrer formula.Can take transmission electron microscope (TEM) photo, will from the maximum particle diameter of optional 20 particles wherein on average as the average crystallite particle diameter.Preferably in transmission electron microscope (TEM) photo (for example 100,000 times), select 50 crystal grain adjacent one another are, the longest part of each crystal grain as particle diameter, measured its length, with its mean value as the average crystallite particle diameter.The multiplying power of TEM photo can be according to the particle size change of measuring.
Crystallite mutually and the ratio of the compound crystallite phase in mutually of amorphous phase can by (a) differential scanning calorimetry (DSC) or (b) X-ray diffraction mensuration finish.It is described identical with above-mentioned negative material 3 that differential scanning calorimetry (DSC) and X-ray diffraction are measured.
(aluminium and elements A)
Al and elements A (Mg or Mg and Si) are the basic elements of occlusion lithium.The atomic ratio x of elements A is 0.9 when above, and the controlled micro crystallization difficulty reduces the cycle life and the rate characteristic of secondary cell.The better scope of atomic ratio x is 0.3≤x≤0.8.
The total atomic ratio of Al and elements A is in the scope of 50～95 atom %.When adding up to atomic ratio less than 50 atom %, the lithium occlusion of negative material can reduce, and the discharge capacity of secondary cell, cycle life and rate characteristic are difficult to improve.On the other hand, when adding up to atomic ratio to surpass 95 atom %, negative material causes the lithium release reaction hardly.Adding up to the better scope of atomic ratio is 70～90 atom %.
(element M)
Can promote the miniaturization of crystal grain by three kinds of elements of Al and elements A and element M.Micronizing when element M can suppress occlusion in the negative material and discharges lithium.The atomic ratio b of element M is during less than 5 atom %, the miniaturization difficulty of crystal grain.On the other hand, the atomic ratio b of element M is during greater than 40 atom %, and the discharge capacity of secondary cell significantly reduces.The better scope of the atomic ratio b of element M is 7～35 atom %.
(element M ')
As rare earth element, its object lesson is described identical with above-mentioned negative material 1.Wherein be preferably La, Ce, Pr, Nd, Sm.
Reason based on same with above-mentioned negative material 3 is preferably by the atomic ratio below the 10 atom % and contains element M '.Better the scope of atomic ratio c is below 8 atom %.Based on the reason same with above-mentioned negative material 3, the lower limit of atomic ratio c is preferably 0.01 atom %.
(element T)
The reason of the atomic ratio d of element T below 20 atom % is described identical with above-mentioned negative material 3.The better scope of atomic ratio d is below 15 atom %.
Rechargeable nonaqueous electrolytic battery with negative material of the present invention 4, the alloy composition that comprises in the above-mentioned negative material before enforcement discharges and recharges does not change, in case implement to discharge and recharge, causes sometimes that as the residual Li of irreversible capacity alloy composition changes.Alloy composition after the variation is represented with general formula described later (8).
Negative material 4 can make with in (1)～(3) manufacture method of above-mentioned negative material 3 any.
Use the nonaqueous electrolyte battery negative material of the invention described above 1 or 2, discharge capacity can be made and charge and discharge circulation life increases, the discharge ratio can obtain higher discharge capacity when improving, and has realized with the less nonaqueous electrolyte battery that number of times obtains maximum discharge capacity that discharges and recharges.In addition, it is because its metal structure is made of amorphous phase in fact that negative material 1 or 2 can improve charge and discharge circulation life, to the extension of the single direction of lattice, has suppressed micronizing when having relaxed the lithium occlusion.
Use the nonaqueous electrolyte battery negative material of the invention described above 3 or 4, discharge capacity can be made and charge and discharge circulation life increases, the discharge ratio can obtain higher discharge capacity when improving, and has realized with the less nonaqueous electrolyte battery that number of times obtains maximum discharge capacity that discharges and recharges.In addition, it is owing to have a metal structure that comprises the crystallite phase of average crystallite particle diameter below 500nm that negative material 3 or 4 can improve charge and discharge circulation life, the lattice dilatation of having followed when this metal structure has relaxed the lithium occlusion and the distortion that causes has suppressed micronizing.
Do not comprise lithium because nonaqueous electrolyte battery constitutes in the element with the alloy of negative material 1～4, so element is handled simply when negative material is synthetic, danger such as do not strike sparks when adopting the liquid quench method to synthesize negative material is easy to large-scale production.Do not comprise in the alloy system of lithium alloy, amorphous phase, metastable phase is higher to the activation evergy of stable phase or the grain growth crystallite phase is slow, so crystalline texture itself is stable, and is favourable to the cycle life of electrode characteristic.In addition, be difficult to be subjected to the influence of the change of heat-treat condition, improved the fabrication yield of negative material.
Then, nonaqueous electrolyte battery of the present invention is described with negative material 5～8.
＜nonaqueous electrolyte battery negative material 5 〉
Nonaqueous electrolyte battery comprises with negative material 5 and has following general formula (5): [(Al 1-xSi x) aM bM ' cT d] yLi z(5) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni, Cu and Mn, above-mentioned M ' is for being selected from least a element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x＜0.75, y+z=100 atom %, 0＜z≤50 atom %.
As the metal structure that constitutes by amorphous phase in fact, can exemplify the tissue that in X-ray diffraction, does not occur based on the peak of crystalline phase.
(aluminium and Si)
Al and Si are the basic elements of occlusion lithium.The atomic ratio x of Si is described identical with above-mentioned negative material 1 in the reason below 0.75.The better scope of atomic ratio x is more than 0.3 below 0.75.
The reason of total atomic ratio in 0.50～0.95 scope of Al and Si is described identical with above-mentioned negative material 1.The better scope that adds up to atomic ratio is greater than 0.67 less than 0.90, and best is more than 0.7 below 0.88.
(element M)
The reason of atomic ratio b in 0.05～0.4 scope of element M is described identical with above-mentioned negative material 1.The better scope of the atomic ratio b of element M is 0.07～0.35.
(element M ')
As rare earth element, its object lesson is described identical with above-mentioned negative material 1.Wherein be preferably La, Ce, Pr, Nd, Sm.
Based on above-mentioned negative material 1 described identical reason, preferably contain element M by the atomic ratio below 0.1 '.Better the scope of atomic ratio c is below 0.08.Because and the same reason of above-mentioned negative material 1, the lower limit of atomic ratio c is preferably 0.0001.
(element T)
The atomic ratio d of element T is described identical with above-mentioned negative material 1 in the reason below 0.20.The better scope of atomic ratio d is below 0.15.
(Li)
Lithium is an element of bearing the electric charge transfer of nonaqueous electrolyte battery.Therefore, when comprising lithium, can improve the lithium occlusion burst size of negative pole, battery capacity and charge and discharge circulation life are increased as alloy formation element.Negative material 5 is compared easy activation with negative material 1, therefore can earlier obtain maximum discharge capacity in charge and discharge cycles.
But, as negative material 1, do not comprise under the situation of lithium in the formation element, need to use lithium-containing compounds such as lithium complex metal oxide in the positive active material.Negative material 5 can be used as positive active material with constituting the compound that does not comprise lithium in the element, so just can widen spendable positive active material kind.But, if lithium content z surpasses 50 atom %, then decrystallized difficulty.The better scope of lithium content z is below 25 atom %.
Negative material 5 can make by liquid quench method, machine-alloying, mechanical milling method, gas atomization, rotating disk method, rotary electrode method.These methods are implemented by above-mentioned negative material 1 described condition.
＜nonaqueous electrolyte battery negative material 6 〉
Nonaqueous electrolyte battery comprises with negative material 6 and has following general formula (6): [(Al 1-xA x) aM bM ' cT d] yLi z(6) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is for being selected from Fe, Co, Ni, at least a element of Cu and Mn, above-mentioned M ' is for being selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d, x, y, z satisfies a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x≤0.9, y+z=100 atom %, 0＜z≤50 atom %.
As the metal structure that constitutes by amorphous phase in fact, can exemplify the tissue that in X-ray diffraction, does not occur based on the peak of crystalline phase.
(aluminium and elements A)
Al and elements A are the basic elements of occlusion lithium.The atomic ratio x of elements A is described identical with above-mentioned negative material 2 in the reason below 0.9.The better scope of atomic ratio x is 0.3≤x≤0.8.
The reason of total atomic ratio in 0.50～0.95 scope of Al and elements A is described identical with above-mentioned negative material 2.Adding up to the better scope of atomic ratio is 0.7～0.9.
(element M)
The reason of atomic ratio b in 0.05～0.4 scope of element M is described identical with above-mentioned negative material 2.The better scope of the atomic ratio b of element M is 0.07～0.35.
(element M ')
As rare earth element, its object lesson is described identical with above-mentioned negative material 1.Wherein be preferably La, Ce, Pr, Nd, Sm.
Because and the same reason of above-mentioned negative material 2, preferably contain element M by the atomic ratio c below 0.1 '.Better the scope of atomic ratio c is below 0.08.Because and the same reason of above-mentioned negative material 2, the lower limit of atomic ratio c is preferably 0.0001.
(element T)
The atomic ratio d of element T is described identical with above-mentioned negative material 2 in the reason below 0.20.The better scope of atomic ratio d is below 0.15.
(Li)
When comprising lithium, can improve the lithium occlusion burst size of negative pole, battery capacity and charge and discharge circulation life are increased as alloy formation element.Negative material 6 is compared easy activation with negative material 2, therefore can earlier obtain maximum discharge capacity in charge and discharge cycles.
Negative material 6 can be used as positive active material with constituting the compound that does not comprise lithium in the element, has so just widened spendable positive active material kind.But, if lithium content z surpasses 50 atom %, then decrystallized difficulty.The better scope of lithium content z is below 25 atom %.
Negative material 6 can make by liquid quench method, machine-alloying, mechanical milling method, gas atomization, rotating disk method, rotary electrode method.These methods can with above-mentioned negative material 1 described same condition under implement.
＜nonaqueous electrolyte battery negative material 7 〉
Nonaqueous electrolyte battery comprises with negative material 7 and has following general formula (7): [(Al 1-xSi x) aM bM ' cT d] yLi z(7) Biao Shi composition, and the alloy that possesses the crystallite phase of average crystallite particle diameter below 500nm, wherein, above-mentioned M is for being selected from Fe, Co, at least a element of Ni and Mn, above-mentioned M ' is for being selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn structure, above-mentioned a, b, c, d, x, y, z satisfies a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤01,0≤d＜0.2,0＜x＜0.75, y+z=100 atom %, 0＜z≤50 atom %.
Negative material 7 can be made of mutually above-mentioned crystallite in fact, also can be made of mutually with the compound of amorphous phase mutually above-mentioned crystallite.
Crystallite can be made of intermetallic compound mutually, the compound of nonstoichiometric composition constitutes or be made of the alloy of nonstoichiometric composition, considers from useful life and capacity, preferably is made of a plurality of compounds or alloy phase.
The reason of average crystallite particle diameter below 500nm of crystallite phase is described identical with above-mentioned negative material 3.The better scope of average crystallite particle diameter is below the above 500nm of 5nm, and preferably scope is below the above 300nm of 5nm.
The average crystallite particle diameter can be obtained from the half value of x-ray diffraction line is wide according to the Scherrer formula.Can take transmission electron microscope (TEM) photo, will from the maximum particle diameter of optional 20 particles wherein on average as the average crystallite particle diameter.Preferably in transmission electron microscope (TEM) photo (for example 100,000 times), select 50 crystal grain adjacent one another are, the longest part of each crystal grain as particle diameter, measured its length, with its mean value as the average crystallite particle diameter.The multiplying power of TEM photo can be according to the particle size change of measuring.
Crystallite mutually and the ratio of the compound crystallite phase in mutually of amorphous phase can by (a) differential scanning calorimetry (DSC) or (b) X-ray diffraction mensuration finish.It is described identical with above-mentioned negative material 3 that differential scanning calorimetry (DSC) and X-ray diffraction are measured.
(aluminium and Si)
Al and Si are the basic elements of occlusion lithium.The reason that contains elements A with the atomic ratio x below 0.75 is described identical with above-mentioned negative material 3.The better scope of atomic ratio x is more than 0.3 below 0.75.
The reason of total atomic ratio in 0.50～0.95 scope of Al and Si is described identical with above-mentioned negative material 3.The better scope that adds up to atomic ratio is greater than 0.67 less than 0.90, is more preferably more than 0.70 below 0.88.
(element M)
The atomic ratio b of element M is described identical with above-mentioned negative material 3 in 0.05～0.40 reason.The better scope of the atomic ratio b of element M is 0.07～0.35.
(element M ')
As rare earth element, its object lesson is described identical with above-mentioned negative material 1.Wherein be preferably La, Ce, Pr, Nd, Sm.
Because the reason identical with above-mentioned negative material 3 contains element M by the atomic ratio below 0.1 ', the scope of better atomic ratio c is below 0.08.Because the reason identical with above-mentioned negative material 3, the lower limit of atomic ratio c is preferably 0.0001.
(element T)
The atomic ratio d of element T is described identical with above-mentioned negative material 3 in the reason below 0.20.The better scope of atomic ratio d is below 0.15.
(Li)
When comprising lithium, can improve the lithium occlusion burst size of negative pole, battery capacity and charge and discharge circulation life are increased as alloy formation element.Negative material 7 is compared easy activation with negative material 3, therefore can earlier obtain maximum discharge capacity in charge and discharge cycles.
Negative material 7 can be used as positive active material with constituting the compound that does not comprise lithium in the element, can widen spendable positive active material kind like this.But, if lithium content z surpasses 50 atom %, then controlled micro crystallization difficulty.The better scope of lithium content z is below 25 atom %.
Negative material 7 can make by in the manufacture method of above-mentioned negative material 3 described (1)～(3) any.
＜nonaqueous electrolyte battery negative material 8 〉
Nonaqueous electrolyte battery comprises with negative material 8 and has following general formula (8): [(Al 1-xA x) aM bM ' cT d] yLi z(8) Biao Shi composition, and the alloy that possesses the crystallite phase of average crystallite particle diameter below 500nm, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is for being selected from Fe, Co, at least a element of Ni and Mn, above-mentioned M ' is for being selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d, x, y, z satisfies a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x≤0.9, y+z=100 atom %, 0＜z≤50 atom %.
Negative material 8 can be made of mutually above-mentioned crystallite in fact, also can be made of mutually with the compound of amorphous phase mutually above-mentioned crystallite.
Crystallite can be made of intermetallic compound mutually, the compound of nonstoichiometric composition constitutes or be made of the alloy of nonstoichiometric composition, considers from useful life and capacity, preferably is made of a plurality of compounds or alloy phase.
The reason of average crystallite particle diameter below 500nm of crystallite phase is described identical with above-mentioned negative material 3.The better scope of average crystallite particle diameter is below the above 500nm of 5nm, and preferably scope is below the above 300nm of 5nm.
The average crystallite particle diameter can be obtained from the half value of x-ray diffraction line is wide according to the Scherrer formula.Can take transmission electron microscope (TEM) photo, will from the maximum particle diameter of optional 20 particles wherein on average as the average crystallite particle diameter.Preferably in transmission electron microscope (TEM) photo (for example 100,000 times), select 50 crystal grain adjacent one another are, the longest part of each crystal grain as particle diameter, measured its length, with its mean value as the average crystallite particle diameter.The multiplying power of TEM photo can be according to the particle size change of measuring.
Crystallite mutually and the ratio of the compound crystallite phase in mutually of amorphous phase can by (a) differential scanning calorimetry (DSC) or (b) X-ray diffraction mensuration finish.It is described identical with above-mentioned negative material 3 that differential scanning calorimetry (DSC) and X-ray diffraction are measured.
(aluminium and elements A)
A1 and elements A (Mg or Mg and Si) are the basic elements of occlusion lithium.The reason that contains elements A with the atomic ratio x below 0.9 is described identical with above-mentioned negative material 4.The better scope of atomic ratio x is 0.3≤x≤0.8.
The reason of total atomic ratio in 0.50～0.95 scope of Al and elements A is described identical with above-mentioned negative material 4.Adding up to the better scope of atomic ratio is 0.7～0.9.
(element M)
The atomic ratio b of element M is described identical with above-mentioned negative material 4 in 0.05～0.40 reason.The better scope of the atomic ratio b of element M is 0.07～0.35.
(element M ')
As rare earth element, its object lesson is described identical with above-mentioned negative material 1.Wherein be preferably La, Ce, Pr, Nd, Sm.
Because the reason identical with above-mentioned negative material 3 contains element M by the atomic ratio below 0.1 '.Better the scope of atomic ratio c is below 0.08.Because the reason identical with above-mentioned negative material 3, the lower limit of atomic ratio c is preferably 0.0001.
(element T)
The atomic ratio d of element T in the reason below 0.20 with identical described in the above-mentioned negative material 3.The better scope of atomic ratio d is below 0.15.
(Li)
When comprising lithium, can improve the lithium occlusion burst size of negative pole, battery capacity and charge and discharge circulation life are increased as alloy formation element.Negative material 8 is compared easy activation with negative material 4, therefore can earlier obtain maximum discharge capacity in charge and discharge cycles.
Negative material 8 can be used as positive active material with constituting the compound that does not comprise lithium in the element, has so just widened spendable positive active material kind.But, if lithium content z surpasses 50 atom %, then controlled micro crystallization difficulty.The better scope of lithium content z is below 25 atom %.
Negative material 8 can make by in the manufacture method of above-mentioned negative material 3 described (1)～(3) any.
Use the invention described above nonaqueous electrolyte battery negative material 5 or 6, discharge capacity can be made and charge and discharge circulation life increases, the discharge ratio also obtains higher discharge capacity when improving, and realizes with the less nonaqueous electrolyte battery that number of times obtains maximum discharge capacity that discharges and recharges.In addition, it is because its metal structure is made of amorphous phase in fact that negative material 5 or 6 can improve charge and discharge circulation life, to the extension of the single direction of lattice, has suppressed micronizing when having relaxed the lithium occlusion.
Use the invention described above nonaqueous electrolyte battery negative material 7 or 8, discharge capacity can be made and charge and discharge circulation life increases, the discharge ratio can obtain higher discharge capacity when improving, and has realized with the less nonaqueous electrolyte battery that number of times obtains maximum discharge capacity that discharges and recharges.In addition, it is owing to have a metal structure that comprises the crystallite phase of average crystallite particle diameter below 500nm that negative material 7 or 8 can improve charge and discharge circulation life, the lattice dilatation of having followed when this metal structure has relaxed the lithium occlusion and the distortion that causes has suppressed micronizing.
＜nonaqueous electrolyte battery negative material 9 〉
The present invention 9 nonaqueous electrolyte battery negative material is the negative material that a kind of occlusion discharges lithium, the feature of this material is, in programming rate is 10 ℃/minute differential scanning calorimetry (DSC), an exothermic peak appears in 200～450 ℃ scope at least, and in X-ray diffraction, the diffraction maximum based on crystalline phase appears.
According to differential scanning calorimetry (DSC), the thermal process of investigation from the nonequilibrium condition to the poised state.The thermal change that the exothermic peak correspondence that occurs during differential scanning calorimetry (DSC) produces when nonequilibrium condition is changed to than this phase stable status.It not is the non-equilibrium phase of amorphous phase that the diffraction maximum based on crystalline phase that occurs in the X-ray diffraction, above-mentioned X-ray diffraction measure that the negative material that occurs an exothermic peak when differential scanning calorimetry (DSC) is carried out by 10 ℃/minute programming rate in the back in 200～450 ℃ scope at least comprises, and can improve the charge and discharge circulation life of secondary cell.The improvement of charge and discharge circulation life may be because the diffusion velocity that above-mentioned non-equilibrium phase has improved lithium ion causes.For further improving charge and discharge circulation life, wish the temperature of exothermic peak to occur in 220～400 ℃ scope.
Therefore the number of exothermic peak does not limit especially according to composition and different.That is, according to composition, the process difference from the nonequilibrium condition to the poised state, so the qualification especially of its number of steps probably have 1～4 exothermic peak.
The contained non-equilibrium phase of the present invention 9 negative material has cubic system fluorite structure or antifluorite structure.The lattice constant of this crystalline phase is below the above 6.3_ of 5.42_.Its reason is, if lattice constant less than 5.42_, then may can not get high power capacity.On the other hand, if lattice constant greater than 6.3_, then is difficult to substantially improve charge and discharge circulation life.The better scope of lattice constant is 5.45～6_, is more preferably 5.5～5.9_.
Have the cubic system fluorite structure of the following lattice constant of the above 6.3_ of 5.42_ or the non-equilibrium phase of antifluorite structure, obtain easily when in non-equilibrium phase is formed, comprising Al, Si, Ni or comprising Al, Si, Co.Ni during this is formed or the displacement of available other elements of a part (for example, Fe, Nb, La) of Co obtain above-mentioned crystalline texture.Have in the non-equilibrium phase of this crystalline texture, be more preferably Si with other elements (for example, Co, Fe, Cu, Mn, Ti, Zr, Hf, Nb, Ta, Cr, La, Ce, Pr, Nd) displacement solid solution Al 2The Si of Ni phase, solid solution Al 2Co phase, above-mentioned Si 2The Ni of Ni phase or the part of Si, or replace above-mentioned Si with other elements (for example, Fe, Ni, Nb, La) 2The Co of Co phase or the part of Si.The kind of the non-equilibrium phase that comprises in the alloy can be one or more.
Contained in the present invention 9 the negative material is not that the average crystallite particle diameter of non-equilibrium phase of amorphous phase is in the scope of 5～500nm.Its reason is, the average crystallite particle diameter is during less than 5nm, and crystal grain is meticulous, and lithium occlusion difficulty can not get high power capacity.On the other hand, the average crystallite particle diameter is during greater than 500nm, the negative material micronizing, and charge and discharge circulation life reduces.The better scope of average crystallite particle diameter is 10～400nm.
The average crystallite particle diameter of non-equilibrium phase is in transmission electron microscope (TEM) photo (for example 100,000 times), selects 50 crystal grain adjacent one another are, and the maximum length of each crystal grain as particle diameter, is calculated its mean value and tried to achieve.The multiplying power of TEM photo can be according to the particle size change of measuring.
＜nonaqueous electrolyte battery negative material 10 〉
The present invention 10 nonaqueous electrolyte battery with negative material possess first mutually with second mutually, wherein, first be mutually comprise two or more can with the intermetallic compound of the element of lithium alloyage mutually, second based on can with the element of lithium alloyage, the feature of this material is, during powder x-ray diffraction is measured, when the d value is at least 3.13～3.64_ with 1.92～2.23_, display from above-mentioned intermetallic compound diffraction maximum (first phase) mutually, and when the d value is at least 2.31～2.40_, display diffraction maximum from above-mentioned second phase.
In powder x-ray diffraction is measured, be preferably first and diffraction maximum when the d value is at least 3.13～3.64_ and 1.92～2.23_, occurs.Simultaneously, second goes out diffraction maximum when the d value is at least 2.31～2.40_.When the arbitrary place in 3.13～3.64_, 1.92～2.23_, 2.31～2.40_ diffraction maximum do not occur, discharge capacity, charge and discharge circulation life or discharge rate characteristic descended.
From the discharge rate characteristic viewpoint of further raising battery, wish that first also occurs diffraction maximum respectively in powder x-ray diffraction is measured when the d value is 1.64～1.90_, 1.36～1.58_, 1.25～1.45_.Wish that second also occurs diffraction maximum respectively in powder x-ray diffraction is measured when the d value is 2.00～2.08_, 1.41～1.47_, 1.21～1.25_.
First mutually and the d value in second mutually the powder x-ray diffraction mensuration can be according to composition or quenched condition, thereafter technique change such as heat treatment.
＜nonaqueous electrolyte battery negative material 11 〉
The present invention 11 nonaqueous electrolyte battery with negative material possess first mutually with second mutually, wherein, first in mutually to comprise two or more can be isolated each other the separating out of at least a portion of the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, and above-mentioned second separate out with the state of imbedding between above-mentioned isolated crystalline particle.
Metal structure with reference to 5 couples of the present invention's 11 of figure negative material describes.
The metal structure of the present invention 11 negative material possesses separately and each other isolated first phase of separating out of intermetallic compound crystalline particle 21, and imbed these 21 isolated of intermetallic compound crystalline particles and separate out second mutually 22.It is the island structure that island, second phase 22 are equivalent to the sea that this metal structure possesses with isolated crystalline particle 21.Among Fig. 5, only express intermetallic compound crystalline particle 21 and isolate the island of separating out separately and each other, but also have plural intermetallic compound crystalline particle 21 adjacent situations about separating out (situation that the island more than 2 joins each other) in the metal structure.
Second mutually 22 when having continuous network configuration, owing to can improve the restraining force of first relative second phase, and the distortion that occurs so can obtain to suppress to follow the occlusion of the lithium of second phase to discharge.But, because having a plurality of intermetallic compound crystalline particles separates out with adjacent state or the second phase factor heat treatment and the tendency of aggegation, so the result of heat treatment aggegation second phase cuts off network configuration, the part of second phase 22 has isolated, and this situation is also contained among the present invention.When second phase 22 isolated, the number on the island of per unit area reduced, and the distance L between the island has the tendency of expansion.
(first phase)
With the average crystallite particle diameter of intermetallic compound crystalline particle be defined in the above-mentioned scope the reasons are as follows described.The average crystallite particle diameter makes lithium occlusion difficulty during less than 5nm owing to crystal grain is meticulous, can not get high power capacity.On the other hand, the average crystallite particle diameter is during greater than 500nm, and the lithium occlusion of following second phase discharges and the distortion that occurs is difficult to absorb mutually by intermetallic compound, so the very fast micronizing of negative material, causes charge and discharge circulation life to reduce.The better scope of average crystallite particle diameter is 10～300nm.
The average crystallite particle diameter of intermetallic compound crystalline particle is in transmission electron microscope (TEM) photo (for example 100,000 times), select 50 metalwork compound crystal particles adjacent one another are, measure the maximum length of each crystal grain, calculate its mean value and try to achieve.The multiplying power of TEM photo can be according to the particle size change of measuring.Under the situation that intermetallic compound crystalline particle more than 2 joins, the maximum length of each intermetallic compound crystalline particle that will disperse in the grain boundary is measured as particle diameter.
1 μ m 2In the number of intermetallic compound crystalline particle the reasons are as follows in 10～2000 scopes described.1 μ m 2In the number of intermetallic compound crystalline particle 10 when following, the restraining force of first relative second phase a little less than, the distortion of following the occlusion of the lithium of second phase to discharge is bigger, makes the very fast micronizing of negative material, causes charge and discharge circulation life to reduce.On the other hand, 1 μ m 2In the number of intermetallic compound crystalline particle 2000 when above, the lithium occlusion characteristic of negative material reduces, and can not get high power capacity.Make 1 μ m 2In the number of intermetallic compound crystalline particle in 10～2000 scope, can fully suppress to follow the lithium occlusion of second phase to discharge and the expansion contraction of appearance, suppress the micronizing of negative material, improve charge and discharge circulation life, better scope is 20～1800.
The mean value of the distance L between the intermetallic compound crystalline particle the reasons are as follows below 500nm is described.The mean value of the distance L between crystalline particle is during greater than 500nm, and first is difficult to retrain second phase mutually, and along with the lithium occlusion of second phase discharges, the very fast micronizing of negative material reduces charge and discharge circulation life.The mean value that makes the distance L between the intermetallic compound crystalline particle is below 500nm, surround second by the intermetallic compound crystalline particle and retrain second phase mutually, can fully suppress to follow the lithium occlusion of second phase to discharge and the expansion contraction of appearance, suppress the micronizing of negative material, improve charge and discharge circulation life.The mean value of the distance between crystalline particle is more preferably below 400nm, it is desirable to below 300nm especially.
The intermetallic compound crystalline particle has cubic system fluorite (CaF 2) antifluorite structure of structure or cubic system.The lattice constant of this crystalline particle is below the above 6.3_ of 5.42_.Its reason is, if lattice constant less than 5.42_, then may can not get high power capacity.On the other hand, if lattice constant greater than 6.3_, then is difficult to substantially improve charge and discharge circulation life.Make lattice constant below the above 6.3_ of 5.42_, can fully suppress to follow the lithium occlusion of second phase to discharge and the expansion contraction of appearance, therefore can suppress the micronizing of negative material, improve the charge and discharge circulation life of secondary cell.The better scope of lattice constant is 5.45～6_, preferably 5.5～5.9_.
Be preferably in the crystalline texture of intermetallic compound crystalline particle Al is solid-solubilized in fluorite (CaF 2) Si of type 2Crystalline texture A in the Ni lattice, and Al is solid-solubilized in fluorite type Si 2Crystalline texture B in the Co lattice.The Si of above-mentioned crystalline texture A 2Available other elements of a Ni in the Ni lattice or the part of Si (for example, Co, Fe, Cu, Mn, Ti, Zr, Hf, Nb, Ta, Cr, La, Ce, Pr, Nd) displacement.On the other hand, the Si of above-mentioned crystalline texture B 2Available other elements of a Co in the Co lattice or the part of Si (for example, Fe, Ni, Nb, La) displacement.The intermetallic compound crystalline particle that has crystalline texture A in the present invention 11 the negative material can coexist with the intermetallic compound crystalline particle with crystalline texture B.
First when carrying out differential scanning calorimetry (DSC) with 10 ℃/minute programming rate, expresses the non-equilibrium phase of an exothermic peak in 200～450 ℃ scope at least.This structure can improve the charge and discharge circulation life of secondary cell.The temperature range that exothermic peak occurs is 220～400 ℃.
(second phase)
The occupation rate of second phase in the negative material is more fortunately in 1～50% the scope.The occupation rate of second phase was less than 1% o'clock, and lithium occlusion difficulty can not get high power capacity.On the other hand, the occupation rate of second phase was difficult to suppress the micronizing of negative material greater than 50% o'clock, may can not get long useful life.The better scope of occupation rate is 5～40%.
The occupation rate of second phase in the negative material is measured with the method that the following describes.Promptly, (multiplying power changes according to particle diameter in a visual field of TEM photo, for example, multiplying power is 100,000 times) in, at least the area ratio (%) of first phase is obtained in the zone (area 100%) that comprises 50 intermetallic compound crystalline particles by image processing, from the area (100%) in whole zone, remove the area ratio (%) of first phase, obtain the area ratio of second phase, i.e. the occupation rate of second phase in the negative material.Under the situation that intermetallic compound crystalline particle more than 2 joins each other, its number is not done one, the intermetallic compound crystalline particle that looses in grain boundary punishment is counted.
First is preferably in the powder x-ray diffraction mensuration mutually, occurs diffraction maximum when the d value is at least 3.13～3.64_ and 1.92～2.23_.Simultaneously, second be preferably in mutually and occur diffraction maximum when the d value is at least 2.31～2.40_.This structure can further improve the discharge rate characteristic of battery.First in powder x-ray diffraction is measured, and preferably also occurs diffraction maximum when the d value is 1.64～1.90_, 1.36～1.58_, 1.25～1.45_ respectively.Second preferably occurs diffraction maximum respectively when the d value is 2.00～2.08_, 1.41～1.47_, 1.21～1.25_.
The present invention 10 and 11 nonaqueous electrolyte battery with negative material first mutually with second composition that preferably has the following stated mutually.
(composition of first phase)
As first comprise in mutually can with the element of lithium alloyage, better be Al, In, Pb, Ga, Mg, Sb, Bi, Sn, Zn.As can with the element that can form intermetallic compound with the element of lithium alloyage, use Ni or Co, or use Ni and Co simultaneously.Available other element substitutions of the part of Ni.As other elements, can use transition metals such as Co, Fe, Nb, and rare earth element such as La.On the other hand, other elements of a part as displacement Co comprise transition metals such as Fe and Nb, rare earth elements such as La.The kind of other elements is one or more.
(composition of second phase)
Second based on can with the element of lithium alloyage, other elements in addition can 10 atom % following amount solid solution.Can comprise Al, In, Pb, Ga, Mg, Sb, Bi, Sn, Zn etc. with the element of lithium alloyage.Wherein, be preferably Al.Second mutually in the element of solid solution be can be with the element of lithium alloyage the time, can improve the lithium occlusion burst size of second phase, this is desirable.M such as Ni, Co element and M ' element solid solution suppress the micronizing effect in second by improving mechanical strength.
The present invention 9～11 nonaqueous electrolyte battery negative material is to comprise Al, Si or Si and Mg as element N1, as element N2 be selected from least a of Ni and Co, as at least a alloy that is selected from In, Bi, Pb, Sn, Ga, Sb, Zn, Fe, Cu, Mn, Cr, Ti, Zr, Nb, Ta and rare earth element of element N3.Al content in this alloy is that the N1 content in h atom %, the alloy is that N2 content in i atom %, the alloy is that N3 content in j atom %, the alloy is when being k atom %, above-mentioned h, i, j, k satisfy 12.5≤h≤95 respectively, 0＜i≤71,5≤j≤40,0≤k＜20.
The content of Al in the alloy, element N1, element N2, element N3 be limited in the above-mentioned scope the reasons are as follows described.
(Al)
Al content h in the alloy is when 12.5 atom % are following, and separating out of second phase (sea) may become difficult, and charge and discharge circulation life may reduce.On the other hand, the Al content h in the alloy is when 95 atom % are above, and the formation of first phase (island) is few, and capacity and charge and discharge circulation life may reduce.The better scope of Al content is 20～85 atom %.
(element N1)
When not containing Si in the alloy, capacity significantly descends, and can not get high power capacity, simultaneously, does not separate out first phase (island) that is suitable for long lifetime, may can not get the long-life.On the other hand, when the element N1 content in the alloy surpasses 71 atom %,, may be difficult to form second phase (sea) though capacity increases to some extent.When not forming second phase (sea), charge and discharge circulation life reduces greatly, reaches charge and discharge cycles number of times or rate characteristic deterioration that heap(ed) capacity needs simultaneously.The better scope of element N1 content i is 10～60 atom %.
(element N2)
Element N2 content j in the alloy is during less than 5 atom %, and first forms difficulty mutually, and charge and discharge circulation life reduces.On the other hand, when element N2 content j surpasses 40 atom % in the alloy, form second phase hardly, all occupy mutually by first.At this moment, reach charge and discharge cycles number of times or the rate characteristic deterioration that heap(ed) capacity needs.The better scope of element N2 content i is 12～35 atom %.
(element N3)
If the element N3 content k 20 atom % in the alloy, then when element N3 was In, Bi, Pb, Sn, Ga, Mg, Sb or Zn, charge and discharge circulation life reduced.On the other hand, when element N3 was Fe, Cu, Mn, Cr, Ti, Zr, Nb, Ta, Cr and rare earth element, capacity reduced.The better scope of element N3 content k is below 15 atom %.
Be more preferably the composition that above-mentioned (3), (7) formula are represented in the alloy composition, elements A is the composition of Si and Mg in the composition that above-mentioned (4), (8) formula are represented, following (9) formula: (Al 1-m-nSi mM1 n) pM2 qM3 rM4 s(9) Biao Shi composition.
In the formula (9), above-mentioned M1 is for being selected from In, Bi, Pb, Sn, Ga, Mg, at least a element of Sb and Zn, above-mentioned M2 is at least a element that is selected from Ni and Co, above-mentioned M3 is for being selected from Fe, Cu, Mn, at least a element of Cr, above-mentioned M4 is for being selected from Ti, Zr, Nb, at least a element of Ta and rare earth element, above-mentioned atomic ratio m, n, p, q, r, s satisfies p+q+r+s=100 atom % respectively, 60 atom %≤p≤90 atom %, 10 atom %≤q≤40 atom %, 0≤r≤10 atom %, 0≤s≤10 atom %, 0＜m＜0.75,0≤n＜0.2.
＜nonaqueous electrolyte battery negative material 12 〉
The present invention 12 nonaqueous electrolyte battery possesses with negative material and comprises the crystallite phase of average crystallite particle diameter below 500nm, and has the alloy of the composition that the arbitrary general formula in above general formula (3), (4), (7) and (8) represents.But the elements A in the composition of general formula (4) and (8) expression is except the situation of Mg.
Comprise the negative material that constitutes mutually by above-mentioned crystallite in fact, in fact mutually and the compound negative material that constitutes mutually of amorphous phase and based on above-mentioned crystallite negative material mutually etc. as negative material 12 by above-mentioned crystallite.
Crystallite is made of intermetallic compound, also can be made of the compound of nonstoichiometric composition or be made of the alloy of nonstoichiometric composition.
The average crystallite particle diameter of crystallite phase is when 500nm is above, because the micronizing of negative material is carried out comparatively fast, therefore discharges and recharges life-span cycle life and reduces.Can suppress micronizing though the average crystallite particle diameter is less, when average crystallite particle diameter during less than 5nm, the occlusion of the lithium difficulty that becomes, the discharge capacity of secondary cell reduces.Therefore, the scope of average crystallite particle diameter below the above 500nm of 5nm is better, and better scope is below the above 300nm of 5nm.
The average crystallite particle diameter of crystallite phase is in transmission electron microscope (TEM) photo (for example 100,000 times), selects 50 crystal grain adjacent one another are, measures the maximum length of each crystal grain, calculates its mean value and tries to achieve.The multiplying power of TEM photo can be according to the particle size change of measuring.
Crystallite has cubic system fluorite (CaF mutually 2) structure or cubic system antifluorite structure.The lattice constant of this crystalline phase is below the above 6.3_ of 5.42_.Having lattice constant is not amorphous phase greater than 5.42_ less than the cubic system fluorite structure of 6.3_ and the crystallite of antifluorite structure mutually, but non-equilibrium phase, can improve the charge and discharge circulation life and the discharge capacity of secondary cell like this.Lattice constant may can not get high power capacity during less than 5.42_.On the other hand, lattice constant is difficult to substantially improve charge and discharge circulation life during greater than 6.3_.The better scope of lattice constant is 5.45～6_, preferably 5.5～5.9_.
Has cubic system fluorite (CaF 2) structure crystallite mutually in, be preferably the Si of solid solution Al 2The Si of Ni phase and solid solution Al 2The Co phase, above-mentioned Si 2Available other elements of the Ni of Ni phase or the part of Si (for example, Co, Fe, Cu, Mn, Ti, Zr, Hf, Nb, Ta, Cr, La, Ce, Pr, Nd) displacement, above-mentioned Si 2The Co of Co in mutually or available other elements of a part (for example, Fe, Ni, Nb, La) displacement of Si.These crystallites are not amorphous phases mutually, but non-equilibrium phase.These crystallites can improve the diffusion velocity of the lithium ion of negative material mutually, therefore can improve the charge and discharge circulation life of secondary cell.
When the present invention 12 negative material carried out differential scanning calorimetry (DSC) with 10 ℃/minute programming rate, the non-equilibrium phase of an exothermic peak appearred in 200～450 ℃ temperature range at least.This negative material can improve the charge and discharge circulation life of secondary cell.The temperature range that exothermic peak occurs is preferably 220～400 ℃.
The present invention 12 negative material is in powder x-ray diffraction is measured, diffraction maximum from Al appears when the d value is at least 2.31～2.40_, the diffraction maximum of the intermetallic compound of self-contained Al and Si appears coming simultaneously, when the d value is at least 3.13～3.64_ and 1.92～2.23_.The discharge capacity, cycle life and the discharge ratio aspect that possess the generation electrolyte secondary battery of this structure increase, and the charge and discharge cycles number of times that reaches heap(ed) capacity simultaneously reduces.
Consider from the discharge rate characteristic of further raising nonaqueous electrolyte battery, in powder x-ray diffraction is measured, when the d value is 2.00～2.08_, 1.41～1.47_, 1.21～1.25_, also wish to occur diffraction maximum from Al.When being 1.64～1.90_, 1.36～1.58_, 1.25～1.45_, the d value also wishes to occur the diffraction maximum of the intermetallic compound of self-contained Al and Si.
During powder x-ray diffraction was measured, the d value when diffraction maximum occurs changed according to the variation of composition, quenched condition or technologies such as heat treatment thereafter.
The metal structure of the present invention 12 negative material possess first mutually with second mutually, first comprises Al in mutually.At least a portion of the intermetallic compound crystalline particle of Si and above-mentioned element M is separated out each other isolatedly, and second to imbed between above-mentioned isolated crystalline particle and the A1 that separates out.Compare with first based on second of Al, lithium occlusion burst size is many, and the deflection when occlusion discharges also increases.The metal structure of said structure, because available first retrain second phase mutually, the distortion that occurs suppresses the micronizing of negative material so can relax that the lithium occlusion of following second phase discharges, and further improves charge and discharge circulation life.Based on second of Al can be below the 10 atom % in mutually amount solid solution Al beyond element.M such as Ni, Co element and M ' element suppress micronizing in second the solid solution in mutually by improving mechanical strength.
The present invention 9～12 negative material can make by following method.
The metallic solution that will comprise first element, second element and element injects on single roller, and chilling makes thickness of slab reach 10～500 μ m, compound between the refractory metal that comprises the first～the element is solidified mutually with based on first element and than the metal structure of mutually low-melting second phase of intermetallic compound, can obtain negative material 9～12.
First element is at least a element that is selected from Al, In, Pb, Ga, Mg, Sb, Bi, Sn, Zn, second element be selected from except that Al, In, Pb, Ga, Mg, Sb, Bi, Sn, Zn can with the element of lithium alloyage at least a, element is at least a element that can form intermetallic compound with first element and second element.
(composition of metallic solution)
Metallic solution can by following (a) or (b) described method obtain.
(a) atomic ratio (atom %) mixes the first～the element in accordance with regulations, and fusion gained mixture obtains metallic solution.
(b) use the first～the element, make the alloy with purpose composition by casting, fusion gained alloy obtains metallic solution.
In first element, be preferably Al.Use is under the situation of negative material of first element with Al, wishes with Si as second element.As the element that can form intermetallic compound, can use Ni and Co with Al and Si.The part of this Ni can be by other element substitutions.This other elements can use rare earth elements such as transition metals such as Co, Fe and Nb and La.On the other hand, as other elements of replacing section Co, can use rare earth elements such as transition metals such as Fe and Nb and La.The kind of other elements can be one or more.
Comprise in the metallic solution of the first～the element, be preferably and comprise A1, Si or Si and Mg as element N1, as element N2 be selected from least a of Ni and Co, as at least a metallic solution that is selected from In, Bi, Pb, Sn, Ga, Sb, Zn, Fe, Cu, Mn, Cr, Ti, Zr, Nb, Ta, Cr and rare earth element of element N3.Al content in the above-mentioned metallic solution is that the element N1 content in h atom %, the above-mentioned metallic solution is that element N2 content in i atom %, the above-mentioned metallic solution is that element N3 content in j atom %, the above-mentioned metallic solution is when being k atom %, above-mentioned h, i, j, k satisfy 12.5≤h＜95 respectively, 0＜i≤71,5≤j≤40,0≤k＜20.
Inject on single roller by the metallic solution that will have this composition, and chilling can make thickness of slab reach 10～500 μ m.Make again to possess compound phase between the refractory metal that comprises Al, element N1 and element N2, and solidify based on Al and than the metal structure of low-melting second phase of above-mentioned intermetallic compound.
Be preferably the composition that above-mentioned (3), (7) formula are represented in the composition of metallic solution, elements A is the composition of Si and Mg in the composition that above-mentioned (4) formula and (8) formula are represented, the composition that above-mentioned (9) formula is represented.
Composition by the represented metallic solution of above-mentioned (9) formula has fluorite (CaF 2) Si of type 2The Si of the intermetallic compound of the crystalline texture of solid solution Al phase or fluorite type in the Ni lattice 2The intermetallic compound of the crystalline texture of solid solution Al is separated out as primary crystal in the Co lattice.Simultaneously, can make particle diameter and the distance of intergranule and the number of die optimization of unit are of this intermetallic compound phase.
(intermetallic compound crystalline particle)
The intermetallic compound crystalline particle has at fluorite (CaF 2) Si of type 2The crystalline texture A of solid solution Al in the part of Ni lattice, and the Si that Al is solid-solubilized in fluorite type 2Crystalline texture B in the Co lattice.The Si of above-mentioned crystalline texture A 2Available other elements of a Ni in the Ni lattice or the part of Si (for example, Co, Fe, Cu, Mn, Ti, Zr, Hf, Nb, Ta, Cr, La, Ce, Pr, Nd) displacement.The Si of above-mentioned crystalline texture B 2Available other elements of a Co in the Co lattice or the part of Si (for example, Fe, Ni, Nb, La) displacement.
(second phase)
Second based on first element, but wherein can contain other following elements of 10 atom %.Especially when second contains second element with the amount below the 10 atom % in mutually, can increase the mhc monomer amount, therefore more satisfactory.The fusing point of second phase is lower than the fusing point of first phase, equates with the fusing point of intermetallic compound or more than it the time at the fusing point of second phase, and first separates out the comparison difficulty as primary crystal, is difficult to form island structure of the present invention.
Second is more preferably mutually based on Al.Based on Al second mutually in, comprise 10 atom % following M element and M ' elements such as Ni, Co.M such as Ni, Co element and M ' element solid solution suppress micronizing in second phase time by improving mechanical strength.
(chilling condition)
The roller material decides best material by the wettability with alloying metal solution, preferably based on the alloy (for example, Cu, TiCu, ZrCu, BeCu) of Cu with based on the alloy of Fe.In addition, can not use above-mentioned Cu alloy and Fe alloy, and plating Cr or Ni make thickness of slab reach 1～100 μ m on the roller surface.
The thickness of the sample on the roller wishes to be set in the scope of 10～500 μ m.Its reason is, because the sample thickness of slab is during greater than 500 μ m, cooling rate is slack-off, therefore, is difficult to solid solution first element in the intermetallic compound that second element and element constitute.The sample thickness of slab is thin more, and cooling rate is fast more.When sample thickness of slab during less than 10 μ m, the alloy strength deficiency that obtains, alloy is difficult to handle.The optimum range of thickness of slab is 15～300 μ m.
Although the roller rotating speed is formed decision by material, general in the scope of 10～60m/s, easy so non-equilibriumization (forcing the non-equilibrium phase of solid solution, accurate crystallization to equate) of carrying out handled.
Nozzle bore is preferably in the scope of 0.3～1mm.Nozzle bore is difficult to penetrate metallic solution from nozzle during less than 0.3mm.On the other hand, when nozzle bore surpasses 1mm, obtain thicker sample easily, be difficult to obtain enough cooling rates.
Gap between roller and the nozzle is preferably in the scope of 0.2～10mm, but cooling rate if flowing of metallic solution is laminar flow, can be improved when surpassing 10mm equably in the gap.But, when adding broad gap, can obtain thicker sample, the wide more cooling rate in gap is slow more.
In a large amount of production, need from alloying metal solution, draw a large amount of heat, therefore preferably increase the thermal capacity of roller.The diameter of roller is preferably more than 300mm φ, is more preferably more than 500mm φ.The width of roller better is more than 50mm, is more preferably more than 100mm.
Below the nonaqueous electrolyte battery of the present invention 13 and 14 is described with negative material.
The present invention 13 nonaqueous electrolyte battery with negative material comprise with the monomer of the element of lithium alloyage mutually with a plurality of intermetallic compound phases.
At least two kinds (hereinafter referred to as two or more intermetallic compound phase X) in above-mentioned a plurality of intermetallic compound comprise respectively with the element of lithium alloyage (below be called element P) and not with the element of lithium alloyage (below be called element Q), the combination of above-mentioned element P and element Q differs from one another.
(element monomer phase)
As with the element of lithium alloyage, comprise Zn, Cd, Al, Ga, In, Si, Ge, Sn, Pb, P, Sb, Bi, S, Se, Te etc.Wherein be preferably Al, Sn, Si, Bi, Pb.
The element monomer can comprise in mutually and the element of lithium alloyage and constitute other elements of alloy.In most cases, other element solid solutions with the metal of lithium alloyage in.In addition, the content of other elements of element monomer in mutually exceeds not influence battery behavior, and is generally less, for example below 10at%.
The kind of the element monomer phase that comprises in the negative material 13 can be one or more.
(a plurality of intermetallic compound phase)
Above-mentioned two or more intermetallic compound phase X at first is described.
Two or more intermetallic compound phase X is respectively the metallic compound of stoichiometric composition.Here, the ratio that the metallic compound of stoichiometric composition refers to the atom of formation compares the intermetallic compound (diagram of representing with simple integer, metal material technical terms dictionary (the 2nd edition), metal material technical research institute compiles, Nikkan Kogyo Shimbun's distribution, issue date: on January 30th, 2000, the 394th page).
Identical as element described in element P that comprise and lithium alloyage and the above-mentioned element monomer phase among each intermetallic compound phase X.The element kind that constitutes element P can be one or more.On the other hand, as not with the element Q of lithium alloyage, comprise Cr, Mn, Fe, Co, Ni, Cu etc.Wherein, be preferably Fe, Ni, Cu, Cr.The element kind that constitutes element Q can be one or more.
Among the two or more intermetallic compound phase X, the whole element kinds that have element P and element Q concurrently differ from one another.This structure can increase the kind of the position of occlusion lithium, the lattice deformability in the time of therefore can relaxing the lithium occlusion.The combination of element P and element Q between intermetallic compound phase X, different needs constitutes the element kind difference of the element P of each intermetallic compound phase X, or the kind difference of formation element Q, or the element of formation element P is all different with the kind of the element that constitutes element Q.For improving charge and discharge circulation life, wish the kind difference of the element of the formation element P between intermetallic compound phase X.To contain among the element P than being easier to and store mutually as lithium with the intermetallic compound of the element of lithium alloyage, and the intermetallic compound that will contain difficult element with alloying so just can effectively relax the lattice deformability of following the lithium occlusion to discharge and occurring as the breakover point that the lithium occlusion discharges.
A plurality of intermetallic compounds mutually in except that above-mentioned two or more intermetallic compound phase X, also comprise the intermetallic compound phase of other kinds.As the intermetallic compound phase of other kinds, comprise that the intermetallic compound phase with stoichiometric composition beyond the intermetallic compound phase X, the intermetallic compound of nonstoichiometric composition equate.As the intermetallic compound phase beyond the intermetallic compound phase X, can use the kind that constitutes element identical but constitute the two or more intermetallic compound phase that the element ratio of components differs from one another with stoichiometric composition.
From the viewpoint of capacity and cycle life balance and rate characteristic, the average grain diameter of a plurality of intermetallic compound phases is preferably in the scope of 5～500nm.When average grain diameter surpasses 500nm, can not get long circulation life.Average grain diameter can not get superior rate characteristic during less than 5nm.The better scope of average grain diameter is 10～400nm.
The average crystallite particle diameter be the longest part of crystal grain that TEM (transmission electron microscope) is photographed as particle diameter, in the photo that utilizes tem observation to obtain (for example 100,000 times), measure 50 adjacent crystal grain, calculate its mean value.The multiplying power of TEM photo can change according to grain size.
The present invention 13 nonaqueous electrolyte battery with in the negative material except a plurality of intermetallic compounds mutually with the element monomer mutually, also comprise the such non-equilibrium phase of amorphous phase.
This negative material 13 has following (9)～(13) and (9) '～(13) ' described composition.
＜form 1 〉
X xTl yJ z……(9)
Wherein, above-mentioned X is at least two kinds of elements that are selected from Al, Si, Mg, Sn, Ge, In, Pb, P, C, above-mentioned T1 is at least a element that is selected from Fe, Co, Ni, Cr, Mn, above-mentioned J is at least a element that is selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, above-mentioned x, y, z satisfy x+y+z=100 atom % respectively, 50≤x≤90,10≤y≤33,0≤z≤10.
(element X)
The compatibility height of this element X and lithium is the basic element of occlusion lithium.Kind by making the element that constitutes element X is two or more, can alleviate because the lattice deformability that lithium occlusion release causes.With the atomic ratio x of element X be defined in the above-mentioned scope the reasons are as follows described.Atomic ratio x is during less than 50 atom %, when making negative material with liquid quench legal systems such as single-roller method and atomizations, separates out difficulty mutually with the monomer of the element of lithium alloyage.On the other hand, atomic ratio x is during greater than 90 atom %, and the lithium release characteristics when negative material discharges and recharges is impaired.Because atomic ratio x is big more, the easy more element monomer that causes is separated out mutually, thus the better scope of atomic ratio x be greater than 67 atom % less than 90 atom %, better scope is 70～90 atom %.
(element T l)
With the atomic ratio y of element T l be defined in the above-mentioned scope the reasons are as follows described.The atomic ratio y of element T l is during less than 10 atom %, decrystallized or ultra-fine crystallization difficulty, and cycle characteristics reduces.On the other hand, atomic ratio y is during greater than 33 atom %, and the discharge capacity of battery obviously reduces.The atomic ratio y of element T l can promote decrystallized and ultra-fine crystallization in the scope of 10～33 atom %, suppress the micronizing when occlusion discharges lithium in the negative material simultaneously.When especially comprising Al, Si or Mg among the element X, can further promote decrystallized and ultra-fine crystallization.The better scope of the atomic ratio y of element T l is 15～25 atom %.
(element J)
As rare earth element, comprise La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu etc.Wherein be preferably La, Ce, Pr, Nd, Sm.
By containing element J, can promote decrystallized and ultra-fine crystallization by the atomic ratio below the 10 atom %.Especially easily the average crystallite particle diameter with the crystallite phase is controlled at below the 500nm.A small amount of Zr, Hf, Nb, Ta, the 4d of Mo, W, 5d transition metal of adding can promote the crystal grain miniaturization in element J.Increase Ti and V among the element J, can improve the crystal grain micronized effect.Element J is also useful aspect the lithium that discharges institute's occlusion.Better the scope of atomic ratio z is below 8 atom %.But, under the kind of element T l is a kind of situation,, then may can not get promoting the effect of decrystallized and ultra-fine crystallization if the amount of atomic ratio z is less than 0.01 atom %, also can not get the effect that the capacity that suppresses to discharge and recharge reduces, so the lower limit of atomic ratio z is preferably 0.01 atom %.
Have the rechargeable nonaqueous electrolytic battery of the alloy of above-mentioned formula (9) expression, above-mentioned alloy composition does not change before enforcement discharges and recharges, in case implement to discharge and recharge, causes sometimes that as the residual Li of irreversible capacity above-mentioned alloy composition changes.Above-mentioned alloy composition after the variation is represented with general formula described later (9 ').
＜form 1 ' 〉
[X xTl yJ z] yLi w……(9’)
Wherein, above-mentioned X is the two or more at least element that is selected from Al, Si, Mg, Sn, Ge, In, Pb, P, C, above-mentioned Tl is at least a element that is selected from Fe, Co, Ni, Cr, Mn, above-mentioned J is at least a element that is selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, and above-mentioned x, y, z, v, w satisfy x+y+z=1 respectively, 0.5≤x≤0.9,0.1≤y≤0.33,0≤z≤0.1, v+w=100 atom %, 0＜w≤50.
With element X, element T l and element J atomic ratio x, y, z regulation separately is because and the same reason of explanation in the above-mentioned composition 1 in the above range.
(Li)
Lithium is an element of bearing the electric charge transfer of nonaqueous electrolyte battery.Therefore, when comprising lithium, can improve the lithium occlusion burst size of negative pole, battery capacity and charge and discharge circulation life are increased as alloy formation element.The negative material of composition 1 ' is compared with the negative material of the composition 1 that does not comprise lithium, and therefore activation easily earlier obtains maximum discharge capacity in charge and discharge cycles.
But, as the negative material of forming 1, do not comprise under the situation of lithium in the formation element, need to use lithium-containing compounds such as lithium complex metal oxide in the positive active material.The negative material of composition 1 ' can be used as positive active material with constituting the compound that does not comprise lithium in the element, so just can widen the kind of spendable positive active material.But, when lithium content w surpasses 50 atom %, decrystallized and ultra-fine crystallization difficulty.The better scope of lithium content w is below 25 atom %.
＜form 2 〉
Al aTl bJ cZ d……(10)
Wherein, above-mentioned Al is at least a element that is selected from Si, Mg and AL, above-mentioned Tl is at least a element that is selected from Fe, Co, Ni, Cr, Mn, above-mentioned J is at least a element that is selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, and above-mentioned Z is at least a element that is selected from C, Ge, Pb, P and Sn, and above-mentioned a, b, c, d satisfy a+b+c+d=100 atom % respectively, 50≤a≤95,5≤b≤40,0≤c≤10,0≤d＜20.
(element al)
Element al is the basic element of occlusion lithium.It is described that the atomic ratio a of element al is defined in the reasons are as follows of above-mentioned scope.Atomic ratio a is during less than 50 atom %, when making negative material with liquid quench legal systems such as single-roller method and atomizations, separates out difficulty mutually with the monomer of the element of lithium alloyage.On the other hand, atomic ratio a is during greater than 95 atom %, and the lithium release characteristics when negative material discharges and recharges is impaired.Because atomic ratio a is big more, the easy more element monomer that causes is separated out mutually, therefore, the better scope of atomic ratio a be greater than 67 atom % less than 95 atom %, better scope is 70～95 atom %.
(element T l)
With the atomic ratio b of element T l be defined in the above-mentioned scope the reasons are as follows described.The atomic ratio b of element T l is during less than 5 atom %, decrystallized or ultra-fine crystallization difficulty, and cycle characteristics reduces.On the other hand, atomic ratio b is during greater than 40 atom %, and the discharge capacity of battery obviously reduces.The atomic ratio b of element T l can promote decrystallized and ultra-fine crystallization in the scope of 5～40 atom %, suppress the micronizing when occlusion discharges lithium in the negative material simultaneously.The better scope of the atomic ratio b of element T l is 7～35 atom %.
(element J)
As rare earth element, comprise La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu etc.Wherein be preferably La, Ce, Pr, Nd, Sm.
By containing element J, can promote decrystallized and ultra-fine crystallization by the atomic ratio below the 10 atom %.Especially easily the average crystallite particle diameter with the crystallite phase is controlled at below the 500nm.A small amount of Zr, Hf, Nb, Ta, the 4d of Mo, W, 5d transition metal of adding can promote the crystal grain miniaturization in element J.When increasing the addition of Ti, V among the element J, can improve the crystal grain micronized effect.Element J is also useful aspect release occlusion lithium.Better the scope of atomic ratio c is below 8 atom %.But, under the kind of element T l is a kind of situation, when the amount of atomic ratio c is less than 0.01 atom %, may can not get promoting the effect of decrystallized and ultra-fine crystallization, also can not get suppressing the effect that charge/discharge capacity reduces, therefore, the lower limit of atomic ratio c is 0.01 atom %.
(element Z)
Element Z can promote decrystallized and ultra-fine crystallization.The content that makes element Z, can improve capacity or increases the service life below 20 atom % by atomic ratio d.But atomic ratio d reduces cycle life when 20 atom % are above.The better scope of atomic ratio d is below 15 atom %.
At the rechargeable nonaqueous electrolytic battery of the alloy with above-mentioned formula (10) expression, before enforcement discharged and recharged, above-mentioned alloy composition did not change, in case implement to discharge and recharge, caused sometimes that as the residual Li of irreversible capacity above-mentioned alloy composition changes.Above-mentioned alloy composition after the variation is represented with general formula described later (10 ').
＜form 2 ' 〉
[Al aTl bJ cZ d] yLi z……(10’)
Wherein, above-mentioned Al is at least a above element that is selected from Si, Mg and Al, above-mentioned T1 is at least a element that is selected from Fe, Co, Ni, Cr, Mn, above-mentioned J is at least a element that is selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, above-mentioned Z is at least a above element that is selected from C, Ge, Pb, P, Sn, above-mentioned a, b, c, d, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.20, y+z=100 atom %, 0＜z≤50
Atomic ratio a, the b of element al, element T l, element J and element Z, c, the reason of d separate provision in above-mentioned scope is described identical with above-mentioned composition 2.
(Li)
Lithium is an element of bearing the electric charge transfer of nonaqueous electrolyte battery.Therefore, when comprising lithium, can improve the lithium occlusion burst size of negative pole, battery capacity and charge and discharge circulation life are increased as alloy formation element.The negative material of composition 2 ' is compared easy activation with the negative material of the composition 2 that does not comprise lithium, therefore more early obtains maximum discharge capacity in charge and discharge cycles.
But, as the negative material of forming 2, in constituting element, do not comprise under the situation of lithium, need to use lithium-containing compounds such as lithium complex metal oxide in the positive active material.The negative material of composition 2 ' can be used as positive active material with constituting the compound that does not comprise lithium in the element, so just can widen the kind of spendable positive active material.But, if lithium content z surpasses 50 atom %, then decrystallized and ultra-fine crystallization difficulty.The better scope of lithium content z is below 25 atom %.
＜form 3 〉
Tl 100-a-b-c(A2 1-xJ’ x) aB bJ c……(11)
Wherein, above-mentioned Tl is at least a element that is selected from Fe, Co, Ni, Cu, Cr, Mn, above-mentioned A2 is at least a element that is selected from Al and Si, above-mentioned J is at least a element that is selected from Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, above-mentioned J ' is for being selected from least a element of C, Ge, Pb, P, Sn and Mg, above-mentioned a, b, c, x satisfy 10 atom %≤a≤85 atom % respectively, 0＜b≤35 atom %, 0≤c≤10 atom %, 0≤x≤0.3, Sn contains quantity not sufficient 20 atom % (comprising 0 atom %).
(elements A 2)
Element al and Si are the basic elements of occlusion lithium.With atomic ratio a be defined in the above-mentioned scope the reasons are as follows described.Atomic ratio a is during less than 10 atom %, and discharge capacity reduces.On the other hand, atomic ratio a is during greater than 85 atom %, and cycle life shortens.The better scope of atomic ratio a is 15～80 atom %.
(element J ')
Use the part of element J ' substitutional element A2, can prolong cycle life.Surpass at 0.3 o'clock at replacement amount x, discharge capacity reduces or can not get the effect of life-saving.When alloy added up to 100 atom %, the content of Sn was set in 20 atom % following (comprising 0 atom %).The content of Sn is when 20 atom % are above, and discharge capacity reduces or charge and discharge circulation life shortens.
(boron)
When atomic ratio b surpassed 35 atom %, discharge capacity and cycle life reduced, and the discharge capacity reduced rate when improving the discharge ratio increases, and in addition, reaches the needed increased frequency that discharges and recharges of maximum discharge capacity.Atomic ratio b can promote the miniaturization (ultra-fine crystallization) of crystal grain when 35 atom % are following, realize the raising of discharge capacity, cycle life and rate characteristic, and makes and reach the needed number of times that discharges and recharges of maximum discharge capacity and reduce.Therefore, decrystallized in order to promote, atomic ratio b below 30 atom % for well.The better scope of atomic ratio b is 0.1～28 atom %.Preferably scope is 1～25 atom %.
Boron is very big to the miniaturization influence of decrystallized and crystal grain, when containing boron and element T, can promote decrystallized significantly and miniaturization crystal grain.
(element J)
As rare earth element, comprise La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu etc.Wherein be preferably La, Ce, Pr, Nd, Sm.
Element J is the micronized effect that occurs promoting decrystallized and crystal grain miniaturization effective elements, have concurrently to suppress to follow the lithium occlusion to discharge.Also effective aspect the delay of the lithium that reduces occlusion in alloy, the capacity reduction that suppresses to discharge and recharge.But when atomic ratio c surpassed 10 atom %, discharge capacity reduced, so atomic ratio c better is below 10 atom %.The better scope of atomic ratio c is below 8 atom %, and preferably scope is below 5 atom %.
(element T l)
Element T l has the function of the lithium that discharges institute's occlusion, and simultaneously, it also is the element for promoting that decrystallized or crystal grain miniaturization need be used in combination with B.
Have the rechargeable nonaqueous electrolytic battery of the alloy of above-mentioned formula (11) expression, above-mentioned alloy composition does not change before enforcement discharges and recharges, in case implement to discharge and recharge, causes sometimes that as the residual Li of irreversible capacity above-mentioned alloy composition changes.Above-mentioned alloy composition after the variation is represented with general formula described later (11 ').
＜form 3 ' 〉
[Tl 1-a-b-c(A2 1-xJ’ x) aB bJ c] yLi z………………(11’)
Wherein, above-mentioned Tl is for being selected from Fe, Co, Ni, Cu, Cr, at least a element of Mn, above-mentioned A2 is at least a element that is selected from Al and Si, above-mentioned J is for being selected from Ti, Zr, Hf, V, Nb, Ta, Mo, at least a element of W and rare earth element, above-mentioned J ' is for being selected from C, Ge, Pb, P, at least a element of Sn and Mg, above-mentioned a, b, c, x, y, z satisfies 0.1≤a≤0.85 respectively, 0＜b≤0.35,0≤c≤0.1 atom %, 0≤x≤0.3,0＜z≤50 atom %, (y+z)=100 atom %, Sn contains quantity not sufficient 20 atom % (comprising 0 atom %).
The reason that atomic ratio a, b, c, the x of element T l, elements A 2, element J ', boron and element J is defined in the above-mentioned scope is described identical with above-mentioned composition 3.
(Li)
Lithium is an element of bearing the electric charge transfer of nonaqueous electrolyte battery.Therefore, when comprising lithium, can improve the lithium occlusion burst size of negative pole, battery capacity and charge and discharge circulation life are increased as alloy formation element.The negative material of composition 3 ' is compared with the negative material of the composition 3 that does not comprise lithium, and therefore activation easily earlier obtains maximum discharge capacity in charge and discharge cycles.The negative material of composition 3 ' can be used as positive active material with constituting the compound that does not comprise lithium in the element, has so just widened the kind of spendable positive active material.But, when lithium content z surpasses 50 atom %, decrystallized and ultra-fine crystallization difficulty.The better scope of lithium content z is below 25 atom %.
＜form 4 〉
(Mg 1-xA3 x) 100-a-b-c-d(RE) aTl bM1 cA4 d……(12)
Wherein, above-mentioned A3 is at least a element that is selected from Al, Si and Ge, above-mentioned RE is at least a element that is selected from Y and rare earth element, above-mentioned T1 is at least a element that is selected from Fe, Co, Ni, Cu, Cr, Mn, above-mentioned M1 is at least a element that is selected from Ti, Zr, Hf, V, Nb, Ta, Mo, W, above-mentioned A4 is at least a element that is selected from Sn, Pb, Zn, P and C, above-mentioned a, b, c, d, x satisfy 0＜a≤40 atom % respectively, 0＜b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0≤x≤0.5.
(magnesium and elements A 3)
Mg is the basic element of occlusion lithium.A part of available element A3 of Mg (be selected from Al, Si and Ge more than one element) displacement.But atomic ratio x surpasses at 0.5 o'clock, and cycle life shortens.
(RE element)
The RE element is to obtain amorphous phase or the necessary element of ultra-fine crystalline phase.The reason of atomic ratio a below 40 atom % be, if atomic ratio a when 40 atom % are above, then capacity reduces.In order to promote decrystallized and the raising capacity, atomic ratio a is preferably in the scope of 5～40 atom %, and better scope is 7～30 atom %.For promoting ultra-fine crystallization and raising capacity, atomic ratio a should be below 40 atom %, and better scope is 2～30 atom %.
(element T l)
Element T l and Mg and elements RE combination can promote decrystallized and miniaturization crystal grain.Atomic ratio b the reasons are as follows below 40 atom % is described.If atomic ratio b is when 40 atom % are above, then capacity reduces.For promoting decrystallized and the raising capacity, atomic ratio b is preferably 5～40 atom %, and better scope is 7～30 atom %.For promoting ultra-fine crystallization and raising capacity, atomic ratio b should be below 40 atom %, and better scope is 2～30 atom %.
(element M 1)
Element M 1 can promote crystal grain miniaturization and decrystallized.In the delay of lithium in alloy that reduces occlusion, the capacity reduction aspect that inhibition discharges and recharges is also effective.Better the scope of atomic ratio c is below 8 atom %.
(elements A 4)
The content that makes elements A 4, can improve capacity or increases the service life below 20 atom % with atomic ratio measuring.But atomic ratio d is when 20 atom % are above, and cycle life reduces.
Have the rechargeable nonaqueous electrolytic battery of the alloy of above-mentioned formula (12) expression, above-mentioned alloy composition does not change before enforcement discharges and recharges, in case implement to discharge and recharge, causes sometimes that as the residual Li of irreversible capacity above-mentioned alloy composition changes.Above-mentioned alloy composition after the variation is represented with general formula described later (12 ').
＜form 4 ' 〉
[(Mg 1-xA3 x) 1-a-b-c-d(RE) aTl bM1 cA4 d] yLi z……(12’)
Wherein, above-mentioned A3 is for being selected from Al, at least a element of Si and Ge, above-mentioned RE is at least a element that is selected from Y and rare earth element, above-mentioned Tl is for being selected from Fe, Co, Ni, Cu, Cr, at least a element of Mn, above-mentioned M1 is for being selected from Ti, Zr, Hf, V, Nb, Ta, Mo, at least a element of W, above-mentioned A4 is for being selected from Sn, Pb, Zn, at least a element of P and C, above-mentioned a, b, c, d, x, y and z satisfy 0＜a≤0.4 respectively, 0＜b≤0.4,0≤c≤0.1,0≤d＜0.2,0≤x≤0.5,0＜a≤50 atom %, (y+z)=100 atom %.
The reason that Mg, elements A 3, elements RE, element T l, element M 1, atomic ratio a, the b of elements A 4, c, d, x are defined in the above-mentioned scope is described identical with above-mentioned composition 4.
＜form 5 〉
(Al 1-xA5 x) aTl bJ cZ d……(13)
Wherein, above-mentioned A5 is at least a element that is selected from Si and Mg, above-mentioned Tl is at least a element that is selected from Fe, Co, Ni, Cr, Mn, and above-mentioned J is at least a element that is selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, and above-mentioned Z is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x satisfy a+b+c+d=100 atom % respectively, 50≤a≤95,5≤b≤40,0≤c≤10,0≤d＜20,0＜x≤0.9.
(aluminium and elements A 5)
When Si was used as elements A 5, atomic ratio x was preferably in the scope of 0＜x≤0.75.Because the atomic ratio x of Si surpasses at 0.75 o'clock, the cycle life of secondary cell reduces.The better scope of atomic ratio x is more than 0.2 below 0.6.
When Si was used as elements A 5, the total atomic ratio a of Al and Si was preferably in the scope of 50～95 atom %.Add up to atomic ratio when 50 atom % are following, the lithium occlusion capacity of negative material reduces, and the discharge capacity of secondary cell, cycle life and rate characteristic are difficult to improve.On the other hand, add up to atomic ratio when 95 atom % are above, negative material causes the lithium release reaction hardly.The better scope that adds up to atomic ratio be greater than 67 atom % less than 90 atom %, preferably scope is 70～90 atom %.
When using Mg or Mg and Si as A5, atomic ratio x is preferably in the scope of 0＜x≤0.9.If the atomic ratio x of elements A 5 surpasses 0.9, then the cycle life of secondary cell and rate characteristic can reduce.The better scope of atomic ratio x is 0.3≤x≤0.8.
When using Mg or Mg and Si as A5, the total atomic ratio a of Al and elements A 5 is preferably in the scope of 50～95 atom %.Add up to atomic ratio when 50 atom % are following, the lithium occlusion capacity of negative material reduces, and the discharge capacity of secondary cell, cycle life and rate characteristic are difficult to improve.On the other hand, add up to atomic ratio when 95 atom % are above, negative material causes the lithium release reaction hardly.The better scope that adds up to atomic ratio be greater than 67 atom % less than 90 atom %, preferably scope is 70～85 atom %.
(element T l)
It is described that the atomic ratio b of element T l is defined in the reasons are as follows of above-mentioned scope.The atomic ratio b of element T l is during less than 5 atom %, and decrystallized and ultra-fine crystallization is very difficult.On the other hand, when the atomic ratio b of element T l surpassed 40 atom %, the discharge capacity of secondary cell significantly reduced.The scope of the atomic ratio b of element T l is set at 10～33 atom %, can promotes decrystallized and ultra-fine crystallization, suppress the micronizing when occlusion discharges lithium in the negative material simultaneously.The better scope of the atomic ratio b of element T l is 15～30 atom %.
(element J)
As rare earth element, comprise La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu etc.Wherein be preferably La, Ce, Pr, Nd, Sm.
By containing element J, can promote decrystallized and ultra-fine crystallization by the atomic ratio below the 10 atom %.Reduce the delay of Li in alloy of occlusion, suppress charge/discharge capacity and reduce.Better the scope of atomic ratio c is below 8 atom %.Wherein, the kind of element T l is under a kind of situation, when the amount of atomic ratio c is less than 0.01 atom %, may can not get promoting the effect of decrystallized and ultra-fine crystallization and suppressing the effect that charge/discharge capacity reduces, so the lower limit of atomic ratio c is preferably 0.01 atom %.
(element Z)
Element Z can promote decrystallized and ultra-fine crystallization.The content that makes element Z, can improve capacity or increases the service life below 20 atom % by atomic ratio d.But atomic ratio d is when 20 atom % are above, and cycle life can shorten.The better scope of atomic ratio d is below 15 atom %.
Have the rechargeable nonaqueous electrolytic battery of the alloy of above-mentioned formula (13) expression, above-mentioned alloy composition does not change before enforcement discharges and recharges, in case implement to discharge and recharge, causes sometimes that as the residual Li of irreversible capacity above-mentioned alloy composition changes.Above-mentioned alloy composition after the variation is represented with general formula described later (13 ').
＜form 5 ' 〉
[(Al 1-xA5 x) aTl bJ cZ d] yLi z……(13’)
Wherein, above-mentioned A5 is at least a element that is selected from Si and Mg, above-mentioned Tl is at least a element that is selected from Fe, Co, Ni, Cr, Mn, above-mentioned J is at least a element that is selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, above-mentioned Z is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x≤0.9, y+z=100 atom %, 0＜z≤50 atom %.
The reason that elements A 5, element T l, element J, atomic ratio a, the b of element Z, c, d, x are defined in the above-mentioned scope is described identical with above-mentioned composition 5.The reason that the atomic ratio z of Li is defined in the above-mentioned scope is described identical with above-mentioned composition 5.
Have the nonaqueous electrolyte battery negative material of the composition that (9), (10), (11), (12) or (13) formula represent, owing to do not comprise lithium in the formation element of its alloy, therefore, the element when negative material is synthetic is handled simple.Danger such as do not strike sparks when adopting the synthetic negative material of liquid quench method is easy to large-scale production.Do not comprise in the alloy system of lithium alloy, the activation evergy height of amorphous phase, metastable phase trend stable phase, perhaps the grain growth of crystallite phase is slow, and therefore, crystalline texture itself is stable, and is favourable to the cycle life of electrode characteristic.In addition, the influence of heat-treat condition change can be subjected to hardly, the fabrication yield of negative material can be improved.
Use the present invention 13 nonaqueous electrolyte battery negative material, can make discharge capacity and charging capacity cycle life is not impaired, can improve rate characteristic, the rechargeable nonaqueous electrolytic battery that discharge capacity, charge and discharge circulation life and rate characteristic meet the demands simultaneously.This secondary cell reaches the needed number of times that discharges and recharges of maximum discharge capacity to be reduced to some extent.
That is,, can improve capacity with when the monomer of the element of lithium alloyage improves lithium occlusion rate of release mutually.On the other hand, intermetallic compound is also effective aspect the improving of lithium occlusion rate of release.The a plurality of intermetallic compounds that comprise two or more intermetallic compound phase X mutually in, there is significant difference in the lithium occlusion easness of intermetallic compound phase, therefore will store phase as lithium than what be easier to cause lithium occlusion reaction, with the difficult breakover point that discharges as the lithium occlusion that causes lithium occlusion reaction, thus the lattice deformability when relaxing the lithium occlusion and discharging.Consequently, can not have influence on discharge capacity and charge and discharge circulation life, rate characteristic is made moderate progress, reach the needed number of times that discharges and recharges of maximum discharge capacity and reduce.
The present invention 13 nonaqueous electrolyte battery is represented with the general formula of above-mentioned (9)～(13) and (9 ')～(13 ') with the composition of negative material, can be improved discharge capacity, charge and discharge circulation life and the rate characteristic of nonaqueous electrolytic solution secondary battery.Wherein, the composition of general formula (13) and (13 ') expression can further improve charge and discharge circulation life, is optimal.
＜nonaqueous electrolyte battery negative material 14 〉
The present invention 14 nonaqueous electrolyte battery with negative material comprise with the monomer of the element of lithium alloyage mutually, intermetallic compound mutually and non-equilibrium phase.
(element monomer phase)
This element monomer is described identical with negative material 13 with above-mentioned nonaqueous electrolyte battery.
(intermetallic compound phase)
The kind of the intermetallic compound phase that negative material 14 comprises can be one or more.
Intermetallic compound comprise with the element of lithium alloyage and not with the element of lithium alloyage.With the element of lithium alloyage and the object lesson with the element of lithium alloyage is described not identical with above-mentioned negative material 13.From improving the viewpoint of charge and discharge circulation life, the kind of the element of hope and lithium alloyage is two or more.
Intermetallic compound has stoichiometric composition mutually.The intermetallic compound of this stoichiometric composition comprises above-mentioned negative material 13 described intermetallic compound phases (two or more intermetallic compound phase X) mutually, it is identical and constitute two or more intermetallic compound phase that the ratio of components of element differs from one another, do not have the multiple intermetallic compound of particular kind of relationship etc. between forming to constitute the element kind.
Based on the reason identical with above-mentioned negative material 13, the average grain diameter of intermetallic compound phase is in the scope of 5～500nm.The better scope of average grain diameter is 10～400nm.
(non-equilibrium phase)
As non-equilibrium phase, comprise that the intermetallic compound of amorphous phase, accurate crystalline phase, nonstoichiometric composition equates.Non-equilibrium phase can be single-phase, also can be compound phase.
The affirmation of non-equilibrium phase is undertaken by following method.
At first, the anticathode material carries out hot assay determination, confirms whether to occur exothermic peak.Exothermic peak occurring when (for example,, exothermic peak occurring), comprise non-equilibrium phase in the negative material at 200～700 ℃ with 10 ℃/minute speed.Then, the micro organization by X-ray diffraction or transmission electron microscope observation non-equilibrium phase.Comprise in the X-ray diffraction of negative material of non-equilibrium phase, detection is less than the diffraction data of known intermetallic deposits yields, after the temperature that exothermic peak occurs is heat-treated, when carrying out X-ray diffraction mensuration once more, can confirm the diffraction maximum of known intermetallic deposits yields.
As the composition of the present invention 14 negative material, can exemplify the composition of above-mentioned general formula (9)～(13 ') expression.Wherein, the composition of general formula (13), (13 ') expression can further improve charge and discharge circulation life.
Use the present invention 14 nonaqueous electrolyte battery negative material, can not influence discharge capacity and charge and discharge circulation life, rate characteristic makes moderate progress, therefore can provide discharge capacity, charge and discharge circulation life and rate characteristic all good nonaqueous electrolytic solution secondary batteries, and make this secondary cell reach the needed number of times that discharges and recharges of maximum discharge capacity to reduce.
That is, when improving the occlusion rate of release of lithium, can improve capacity with intermetallic compound mutually with the monomer of the element of lithium alloyage.On the other hand, non-equilibrium phase has the crystalline texture distortion in advance, therefore, can alleviate the distortion when inserting lithium, suppresses the micronizing of negative material.Consequently do not damage discharge capacity and charge and discharge circulation life, can realize the rate characteristic improvement and reach the needed minimizing that discharges and recharges number of times of maximum discharge capacity.
The present invention 13 and 14 negative material can pass through liquid quench method, machine-alloying or mechanical milling method to be made.
(liquid quench method)
So-called liquid quench method is will be modulated into alloying metal solution that regulation forms to inject to the method for carrying out chilling on the cooling body (for example, roller) of high speed rotating from less nozzle.The shape of utilizing the sample that the liquid quench method obtains can be a long thin ribbon shaped, laminar etc.When changing sample and forming and since its fusing point and amorphous phase form can or crystallite form mutually can be different, so tendency of the with good grounds composition change of specimen shape.On the other hand.Play main dominating role aspect the thickness of slab of the sample that cooling rate obtains at chilling, sample thickness roller rest material, roller rotating speed and nozzle bore are regulated.
Metallic solution can be any in the composition represented of above-mentioned (9)～(13) and (9 ')～(13 ') formula.
The material of roller is by deciding best material with the wettability of alloying metal solution, preferably based on the alloy (for example, Cu, TiCu, ZrCu, BeCu) of Cu.
The roller rotating speed is according to forming decision, and general roller rotating speed more than 10m/s can obtain crystallite.The roller rotating speed is during less than 20m/s, obtain easily crystallite mutually and the mixing of amorphous phase mutually.On the other hand, the roller rotating speed owing to be difficult to deposit alloying metal solution on the chill roll of high speed rotating, therefore makes cooling rate reduce during greater than 60m/s on the contrary, and crystallite is separated out mutually easily.Therefore, though the roller rotating speed can generally in the scope of general 20～60m/s, be easy to realize decrystallized according to forming decision.
Nozzle bore is preferably in the scope of 0.3～2mm.Nozzle bore is difficult to penetrate metallic solution from nozzle during less than 0.3mm.On the other hand, when nozzle bore surpasses 2mm, obtain thicker sample easily, be difficult to obtain sufficient cooling rate.
Gap between roller and the nozzle is preferably in the scope of 0.2～10mm, but cooling rate if flowing of metallic solution is laminar flow, then can be improved when surpassing 10mm equably in the gap.But, when adding broad gap, obtain thicker sample, so the gap is wide more, cooling rate is slow more.
In a large amount of the production, need from alloying metal solution, draw a large amount of heat, therefore preferably increase the thermal capacity of roller.Owing to these reasons, wish to increase roller diameter, and widen the roller width.Specifically, more than the 300mm φ, better scope is more than 500mm φ to roller diameter more fortunately.The width of roller better is more than 50mm, and better scope is more than 100mm.
(mechanical alloying, mechanical lapping)
So-called mechanical alloying and mechanical lapping are to pack in the crucible (pot) being modulated to powder that regulation forms in inert atmosphere gas, clamp powder by rotation with the spin in the crucible, carry out the method for alloying with energy at this moment.
The alloy that liquid quench method, machine-alloying or mechanical milling method are made can be implemented the heat treatment of embrittlement.From suppressing the viewpoint that crystallization carries out, be under one the situation in exothermic peak, heat treatment temperature be from hanging down 50 ℃ temperature than its ascending temperature (crystallized temperature) to than in the high 50 ℃ temperature range of this temperature.Exist under the situation of a plurality of exothermic peaks, better be more than the temperature than low 50 ℃ of the ascending temperature of minimum exothermic peak, be positioned at the temperature range below the temperature of exothermic peak of highest temperature side.
Except that aforesaid liquid quench, machine-alloying, mechanical milling method, available gas atomization, rotating disk method, rotary electrode method etc. obtain Powdered sample.Select certain condition to use these methods can obtain spherical sample, so can the closeest filling negative material in the negative pole, the high capacity of battery improved.
Nonaqueous electrolyte battery of the present invention possess comprise at least a negative pole, the positive pole in the negative material 1～14 and be configured in positive pole and negative pole between non-aqueous electrolyte layer.
1) negative pole
Negative pole possesses collector body and form at least a negative electrode layer that comprises in the negative material 1～14 on the single or double of collector body.
This negative pole is by in the presence of organic solvent, the powder of mixing negative material and adhesive, the outstanding absurd creature that obtains be coated on the collector body and drying after carry out compacting and make.
When obtaining the powder of negative material 1,2,5,6,13 and 14, embrittlement is carried out in the heat treatment of implementing under the temperature below the crystallized temperature 0.1～24 hour before pulverizing.As breaking method, can adopt pin type grinder, jet mill, hammer mill and ball mill.
On the other hand, for negative material 3,4,7,8,13 and 14, temporary transient decrystallized sample under the situation that its heat treatment of carrying out more than crystallization temperature 0.1～24 hour is synthesized, is wished that pulverization process carries out after heat treatment.By decrystallized sample is heat-treated the making negative material at it more than the crystallization temperature, can reduce the manufacturing cost of negative material.The crystallization temperature of decrystallized sample can be obtained from the exothermic peak of the differential scanning calorimetry (DSC) of 10 ℃/minute programming rate.Specifically, detected exothermic peak is under one the situation, measures the transition temperature that the amorphous phase sample shifts to equilibrium phase from this exothermic peak, the transition temperature that obtains as crystallization temperature.On the other hand, under detected exothermic peak is a plurality of situation, measure the transition temperature of sample from the detected exothermic peak of lowest temperature side, with the transition temperature that obtains as crystallization temperature.Determine transition temperature from exothermic peak, the method that illustrates in can the differential scanning calorimetry by embodiment 52 described later is carried out.Can separate out crystallite by quench and come to synthesize sample mutually, at this moment, have or not the heat treatment before pulverizing all harmless.
With reducing mechanisms such as jet mill, pin type grinder, hammer mills sample being pulverized is the particle of average grain diameter 5～80 μ m.The mensuration of average grain diameter can be undertaken by little rail method of using laser.In the sample that the present invention uses, have approximate dull and stereotyped shape, in the mensuration of above-mentioned little rail method, also be assumed that sphere near the sample of writing board shape, carry out data processing, obtain average grain diameter.
As above-mentioned adhesive, can use polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), ethylene-propylene-diene copolymer (EPDM), styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC) etc.
The cooperation ratio of negative material and adhesive preferably negative material is that 90～98 weight %, adhesive are 1～10 weight %.
As collector body,, it is not particularly limited so long as electric conducting material gets final product.Can use paper tinsel that copper, stainless steel or nickel constitutes, screen cloth, perforated metal, lath metal etc.
2) positive pole
Positive pole possesses collector body and is formed at the single face of collector body or the positive electrode active material layer that contains positive active material on two sides.
This positive pole is coated on the collector body surface by positive active material, conductive agent and adhesive suitably are suspended in the solvent with the outstanding absurd creature that obtains, and dry then, compacting makes.
But positive active material if when battery discharge alkali metal such as occlusion lithium, when charging, can discharge alkali metal and get final product, it is not particularly limited.As this positive active material, comprise various oxides and sulfide, for example, manganese dioxide (MnO 2), complex Li-Mn-oxide (for example, LiMn 2O 4, LiMnO 2), lithium nickel composite oxide (for example, LiNiO 2), lithium cobalt composite oxide (for example, LiCoO 2), lithium/nickel/cobalt composite oxide (for example, LiNi 1-xCo xO 2), lithium manganese cobalt composite oxide (for example, LiMn xCo 1-xO 2), barium oxide (V 2O 5) etc.In addition, also comprise organic materials such as conductive polymer material, disulphide based polymer material.Positive active material comprises the high complex Li-Mn-oxide of cell voltage (for example, LiMn preferably 2O 4), lithium nickel composite oxide (for example, LiNiO 2), lithium cobalt composite oxide (for example, LiCoO 2), lithium/nickel/cobalt composite oxide (for example, LiNi 0.8Co 0.2O 2), lithium manganese cobalt composite oxide (for example, LiMn xCo 1-xO 2) etc.
As adhesive, comprise polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorubber etc.
As conductive agent, comprise acetylene black, carbon black, graphite etc.
Positive active material, adhesive. the mix proportion of conductive agent preferably positive active material is that 80～95wt%, conductive agent are that 3～20wt%, adhesive are 2～7wt%.
As collector body,, it there is not special restriction so long as electric conducting material gets final product.But use collector body as anodal, be difficult to the material of oxidation when preferably using cell reaction, for example, aluminium, stainless steel, titanium etc.
3) non-aqueous electrolyte layer
Non-aqueous electrolyte layer can provide the ionic conductivity between positive pole and the negative pole.
As non-aqueous electrolyte layer, comprise the dividing plate that keeps nonaqueous electrolytic solution, gluey non-aqueous electrolyte layer, the dividing plate that keeps gluey nonaqueous electrolyte, solid macromolecule electrolyte layer, inorganic solid electrolytic layer etc.
As dividing plate, can utilize porous material.The material of this dividing plate comprises nonwoven fabrics that synthetic resin makes, polyethylene porous membrane, polypropylene porous film etc.
Nonaqueous electrolytic solution can be modulated by dissolving electrolyte in nonaqueous solvents.
As nonaqueous solvents, can use ethylene carbonate (EC), propylene carbonate cyclic carbonates such as (PC), based on the nonaqueous solvents of the mixed solvent of these cyclic carbonates and the nonaqueous solvents lower than cyclic carbonate viscosity.As the low nonaqueous solvents of above-mentioned viscosity, comprise that linear carbonate (for example, dimethyl carbonate, carbonic acid methyl ethyl ester, diethyl carbonate etc.), gamma-butyrolacton, acetonitrile, methyl propionate, ethyl propionate, cyclic ether (for example, tetrahydrofuran, 2-methyltetrahydrofuran etc.), chain ether (for example, dimethoxy-ethane, diethoxyethane etc.).
As electrolyte, use lithium salts.Specifically, comprise lithium hexafluoro phosphate (LiPF 6), boron lithium fluoride (LiBF 4), hexafluoro arsenic lithium (LiAsF 6), lithium perchlorate (LiClO 4), trifluoromethanesulfonic acid lithium (LiCF 3SO 3) etc.Wherein be preferably lithium hexafluoro phosphate (LiPF 6), boron lithium fluoride (LiBF 4).
The meltage that electrolyte is summed up at nonaqueous solvents is preferably 0.5～2mol/L.
Gluey nonaqueous electrolyte can be by obtaining nonaqueous electrolyte and compoundization of macromolecular material.As macromolecular material, comprise polyacrylonitrile, poly-propionic ester, polyvinylidene fluoride (PVdF), polyoxyethylene monomers such as (PECO) condensate or with the copolymer of other monomers.
The solid macromolecule electrolyte layer can by with electrolyte dissolution in macromolecular material and be cured and obtain.As this macromolecular material, comprise polyacrylonitrile, polyvinylidene fluoride (PVdF), polyoxyethylene monomers such as (PEO) condensate or with the copolymer of other monomers.
As inorganic solid electrolyte, comprise containing the lithium ceramic material.Object lesson bag Li 3N, Li 3PO 4-Li 2S-SiS 2, LiI-Li 2S-SiS 2Glass etc.
Describe slim rechargeable nonaqueous electrolytic battery in detail with reference to figure 1 and Fig. 2 as an example of nonaqueous electrolyte battery of the present invention.
Figure 1 shows that the sectional view of slim rechargeable nonaqueous electrolytic battery of an example of nonaqueous electrolyte battery of the present invention, Fig. 2 is the amplification sectional view of the A portion of presentation graphs 1.
As shown in Figure 1, the electrode group 2 of in the external packing component 1 that stacked film constitutes, packing into.Above-mentioned electrode group 2 has the structure that the sandwich that positive pole, dividing plate and negative pole are constituted is wound as flat.(from the figure downside) as shown in Figure 2, the stacked in order dividing plate 3 of above-mentioned sandwich, positive pole 6 with anodal layer 4, positive electrode collector 5 and anodal layer 4, dividing plate 3, negative pole 9 with negative electrode layer 7, negative electrode collector 8 and negative electrode layer 7, dividing plate 3 has the positive pole 6 of anodal layer 4, positive electrode collector 5 and anodal layer 4, dividing plate 3 has the negative pole 9 of negative electrode layer 7 and negative electrode collector 8.Above-mentioned electrode group 2 is placed above-mentioned negative electrode collector 8 at outermost layer.Strip-shaped positive electrode 10 1 ends that go between are connected with the above-mentioned positive electrode collector 5 of above-mentioned electrode group 2, and the other end extends from above-mentioned external packing component 1.On the other hand, banded negative wire 11 1 ends are connected with the above-mentioned negative electrode collector 8 of above-mentioned electrode group 2, and the other end extends from above-mentioned external packing component 1.
The described example that is wound as the electrode group of flat for positive pole and non-aqueous electrolyte layer and negative pole use of above-mentioned Fig. 1, Fig. 2, but the electrode group that the sandwich that also is applicable to anodal and non-aqueous electrolyte layer and negative pole constitutes, sandwich anodal and non-aqueous electrolyte layer and negative pole bends the electrode group of the structure more than 1 time.
Describe embodiments of the invention in detail below with reference to accompanying drawing.
(embodiment 1～10)
The making of＜negative pole 〉
Each element that adds ratio shown in the hotlist 1, make its fusion after, in inert atmosphere gas, obtain the thin ribbon shaped alloy by single-roller method.Specifically, the nozzle bore from 0.6mm φ in inert atmosphere gas injects metallic solution to the chill roll of the BeCu alloy manufacturing of rotating by the speed of 40m/s, and chilling obtains the thin ribbon shaped alloy.Atmosphere gas during chilling is atmosphere, perhaps makes inert gas flow to spray nozzle front end and all can obtain same alloy.
The crystallinity of the alloy of the embodiment 1～10 that obtains is measured with X-ray diffraction method, confirms not observe the peak based on crystalline phase.X-ray diffractogram (the X ray of the alloy of expression embodiment 1 among Fig. 3; CuK α).
For the thin ribbon shaped alloy of embodiment 1～3,7～8, block the back and pulverize the alloy powder of making average grain diameter 10 μ m with the injecting type grinder.Thin ribbon shaped alloy for embodiment 4～6,9～10, block the back as 250 ℃ of heat treated of carrying out 3 hours under the temperature below the crystallization temperature, former state is kept amorphous phase and embrittlement, and then pulverizes with the injecting type grinder, makes the alloy powder of average grain diameter 10 μ m.
Mix this alloy powder of 94wt%, the powdered graphite of 3wt%, the styrene butadiene ribber of 2wt%, the carboxymethyl cellulose of 1wt%, it is dispersed in the outstanding absurd creature of modulation in the water as organic solvent as adhesive as conductive material.This outstanding absurd creature is coated on the Copper Foil as the thickness 18 μ m of collector body, is dried the back compacting and makes negative pole.
＜anodal making 〉
Mix the lithium cobalt oxide powder of 91wt%, the powdered graphite of 6wt%, the polyvinylidene fluoride of 3wt%, it is distributed in the N-N-methyl-2-2-pyrrolidone N-, be modulated into slurry.With this slurry be coated on as on the aluminium foil of collector body and dry back compacting make positive pole.
The making of＜lithium rechargeable battery 〉
Prepare the dividing plate that polyethylene porous membrane constitutes.Between positive pole and negative pole, insert dividing plate, be wound as vortex shape simultaneously and make electrode group.To be dissolved in the mixed solvent (volume ratio is 1: 2) of ethylene carbonate and carbonic acid methyl ethyl ester by 1mol/L as electrolytical lithium hexafluoro phosphate, be modulated into nonaqueous electrolytic solution.
After electrode group is enclosed in stainless steel and is shaped in the round-ended cylinder shape container, inject nonaqueous electrolyte liquid, seal processing, be assembled into cylindric lithium rechargeable battery.
(embodiment 11～12)
Make the alloy of forming shown in the following table 1 of machine-alloying.The crystallinity that obtains alloy is measured with X-ray diffraction method.Confirm not observe peak based on crystalline phase.And then pulverize with the injecting type grinder, make the alloy powder of average grain diameter 10 μ m.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(embodiment 13～14)
Each element that adds the ratio of hotlist 2 expressions, after making its fusion, inject alloying metal solution from the nozzle bore of 0.8mm φ to the chill roll by the BeCu alloy manufacturing of the speed rotation of rotating speed 45m/s by single-roller method in inert atmosphere gas, chilling obtains thin ribbon shaped or laminar alloy.The crystallinity of gained alloy is measured with X-ray diffraction method, confirms not observe the peak based on crystalline phase.Atmosphere gas during chilling is atmosphere, or makes inert gas flow to spray nozzle front end all can to obtain same alloy.
This alloy is blocked after 1 hour the heat treatment carrying out in inert atmosphere gas under 300 ℃ more than the crystallization temperature, pulverize with the injecting type grinder again, make the alloy powder of average grain diameter 10 μ m.
1) ratio measuring of the crystallite phase in the alloy
To having and the thermal discharge of the same alloy measuring of forming and constituting by amorphous phase of embodiment 13～14 under 10 ℃/minute of programming rates, obtain the benchmark thermal discharge by differential scanning calorimetry (DSC).Alloy for the embodiment 13～14 of the unknown proportion of crystallite phase utilizes differential scanning calorimetry (DSC), is determined at the thermal discharge under 10 ℃/minute of the programming rates, obtains thermal discharge.By relatively this thermal discharge and benchmark thermal discharge, measure the ratio of crystallite phase, its result is shown in the following Table 2.
2) mensuration of the average crystallite particle diameter of crystallite phase
Take transmission electron microscope (TEM) photo,, measure the maximum gauge of each crystal grain, its mean value as the average crystallite particle diameter, be the results are shown in the following table 2 for 50 crystal grain adjacent one another are.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(embodiment 15～16)
Each element that adds the ratio of hotlist 2 expression, make its fusion after, in inert atmosphere gas, obtain alloy by single-roller method.Specifically, the nozzle bore from 0.8mm φ in inert atmosphere gas injects alloying metal solution to the chill roll of the BeCu alloy manufacturing of rotating by the speed of rotating speed 25m/s, and chilling obtains laminar alloy.Block this alloy, pulverize, make the alloy powder of average grain diameter 10 μ m with the injecting type grinder.
For the gained alloy, carry out the crystallite ratio measuring mutually and the mensuration of the average crystallite particle diameter of crystallite phase equally with the foregoing description 13, its result is represented in the following Table 2.Fig. 4 represents the X-ray diffractogram (X ray of the alloy of embodiment 15; CuK α).As can be seen from Figure 4, the peak based on crystalline phase appears in the alloy of embodiment 15 in X-ray diffractogram.Among Fig. 4, near the peak P1 2 θ are 40 ° is from Al monomer phase, and near near the peak P3 of the peak P2 2 θ are 30 ° with 45 ° from crystallite mutually.As can be known, the crystalline texture of the crystallite phase that comprises in the alloy of embodiment 15 is that lattice constant is the fluorite structure of 5.52_ from the X-ray diffractogram of Fig. 4.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(embodiment 17～18)
Each element that adds the ratio of hotlist 2 expression, make its fusion after, in inert atmosphere gas, obtain alloy by single-roller method.Specifically, the nozzle bore from 0.8mm φ in inert atmosphere gas injects alloying metal solution to the chill roll of the BeCu alloy manufacturing of rotating by the speed of rotating speed 25m/s, and chilling obtains laminar alloy.Metal structure is adjusted in the heat treatment of under 300 ℃ this alloy being carried out 1 hour.Then, block this alloy, pulverize, make the alloy powder of average grain diameter 10 μ m with the injecting type grinder.
For the gained alloy, carry out the crystallite ratio measuring mutually and the mensuration of the average crystallite particle diameter of crystallite phase equally with the foregoing description 13, its result is represented in the following Table 2.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(embodiment 19～20)
Each element that adds the ratio of hotlist 2 expression, make its fusion after, in inert atmosphere gas, obtain alloy by single-roller method.Specifically, the nozzle bore from 0.6mm φ in inert atmosphere gas injects alloying metal solution to the chill roll of the BeCu alloy manufacturing of rotating by the speed of rotating speed 40m/s, and chilling obtains thin ribbon shaped or laminar alloy.With the crystallinity of X-ray diffraction method mensuration gained alloy, confirm the peak that does not observe based on crystalline phase.Atmosphere gas during chilling is atmosphere, or makes inert gas flow to spray nozzle front end all can to obtain same alloy.
In 300 ℃ inert atmosphere gas, this alloy carried out block after 1 hour the heat treatment, pulverize with the injecting type grinder, make the alloy powder of average grain diameter 10 μ m.
1) ratio measuring of the crystallite phase in the alloy
And have with embodiment 19～20 same form and crystallite mutually ratio be that the diffracted intensity of highest peak of the X-ray diffractogram of 100% alloy is a benchmark, by the relatively intensity and the benchmark intensity of the same diffraction maximum of the alloy of the embodiment 19～20 of crystallite phase unknown proportion, estimate the ratio of crystallite phase, its result is shown in the following Table 2.
2) mensuration of the average crystallite particle diameter of crystallite phase
Same with the foregoing description 13, carry out the mensuration of the average crystallite particle diameter of crystallite phase, its result is represented in the following Table 2.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(embodiment 21～22)
Each element that adds the ratio of hotlist 2 expression, make its fusion after, in inert atmosphere gas, obtain alloy by single-roller method.Specifically, the nozzle bore from 0.7mm φ in inert atmosphere gas injects alloying metal solution to the chill roll of the BeCu alloy manufacturing of rotating by the speed of rotating speed 20m/s, and chilling obtains laminar alloy.Crystallinity with X-ray diffraction method mensuration gained alloy observes the peak based on crystalline phase.
Under 300 ℃, this alloy is carried out 1 hour heat treatment and blocks after the embrittlement, pulverize with the injecting type grinder, make the alloy powder of average grain diameter 10 μ m.
Gained alloy and the foregoing description 13 are carried out the crystallite ratio measuring mutually and the mensuration of the average crystallite particle diameter of crystallite phase equally, its result is represented in the following Table 2.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(embodiment 23～24)
Make the alloy of forming shown in the following table 2 of machine-alloying.And then pulverize with the injecting type grinder, make the alloy powder of average grain diameter 10 μ m.
Gained alloy and the foregoing description 19 are carried out the crystallite ratio measuring mutually and the mensuration of the average crystallite particle diameter of crystallite phase equally, its result is represented in the following Table 2.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(embodiment 25～27)
After adding each element and fusion of ratio of hotlist 2 expression, in inert atmosphere gas, obtain alloy by single-roller method.Specifically, the nozzle bore from 0.5mm φ in inert atmosphere gas injects alloying metal solution to the chill roll of the BeCu alloy manufacturing of rotating by the speed of rotating speed 40m/s, and chilling obtains thin ribbon shaped or laminar alloy.With the crystallinity of X-ray diffraction method mensuration gained alloy, confirm not observe peak based on crystalline phase.
In 300 ℃ inert atmosphere gas, this alloy carried out block after 1 hour the heat treatment, pulverize with the injecting type grinder, make the alloy powder of average grain diameter 10 μ m.
Gained alloy and the foregoing description 13 are carried out the crystallite ratio measuring mutually and the mensuration of the average crystallite particle diameter of crystallite phase equally, its result is represented in the following Table 2.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(comparative example 1)
(fiber diameter is 10 μ m, and average fiber length is 25 μ m, and face is d at interval through heat treated mesophase pitch based carbon fiber down at 3250 ℃ to remove the use of instead of alloy powder 002Be 0.3355nm, the specific area that the BET method obtains is 3m 2Beyond/g) the carbon dust, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(comparative example 2)
Except that the instead of alloy powder used the Al powder of average grain diameter 10 μ m, other operations were described identical with the foregoing description 1, make lithium rechargeable battery.
(comparative example 3)
With machine-alloying through making Sn in 100 hours 30Co 70Alloy.The logical X-ray diffraction of gained alloy is confirmed decrystallized.Except that using this alloy, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(comparative example 4～6)
As negative material, make Si with single-roller method 33Ni 67Alloy, (Al 0.1Si 0.9) 33Ni 67Alloy, Cu 50Ni 25Sn 25Alloy.The roller material is the BeCu alloy, and the roller rotating speed is 25m/s.The gained alloy is confirmed controlled micro crystallization with X-ray diffraction method.Calculate average grain diameter with the Scherrer formula, its result represents in the following Table 3.Except that using this alloy, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(comparative example 7)
As negative material, make Fe by polishing 25Si 75Alloy.Calculate average grain diameter with the Scherrer formula, the average crystallite particle diameter is 300nm.Except that using this alloy, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(comparative example 8～10)
Each element that adds the ratio of hotlist 3 expressions, after making its fusion, inject alloying metal solution by single-roller method from the nozzle bore of 0.7mm φ on by the chill roll of the speed rotation of rotating speed 30m/s (the roller material is the BeCu alloy) in inert atmosphere gas, chilling obtains thin ribbon shaped or laminar alloy.With the crystallinity of X-ray diffraction method mensuration gained alloy, confirm not observe peak based on crystalline phase.
In 300 ℃ inert atmosphere gas, this alloy carried out block after 1 hour the heat treatment, pulverize with the injecting type grinder, make the alloy powder of average grain diameter 10 μ m.
Gained alloy and the foregoing description 13 are carried out the crystallite ratio measuring mutually and the mensuration of the average crystallite particle diameter of crystallite phase equally, its result is represented in the following Table 2.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
For the secondary cell of embodiment 1～27 and comparative example 1～10, carry out following charge and discharge cycles test.That is, under 20 ℃, carry out charging in 2 hours with the charging current of 1.5A, reach 4.2V after, discharge into 2.7V with 1.5V, measure discharge capacity than and the capacity sustainment rate of 300 circulation times, its result is illustrated in following table 1～3.Discharge capacity represents that than the ratio that with the discharge capacity of comparative example 1 is at 1 o'clock capacity sustainment rate maximum discharge capacity is that the discharge capacity of 300 circulation times of 100% o'clock is represented.
Under 20 ℃, the 4.2V that carried out 1 hour with the ratio of 1C decides electric current, decide the charging of voltage after, under 0.1 ratio, measure the discharge capacity when discharging into 3.0V, obtain the discharge capacity of 0.1C.After charging under the same condition, the discharge capacity when mensuration discharges into 3.0V by the 1C ratio obtains the discharge capacity under the 1C.As 100% discharge capacity of representing under the 1C, its result is presented in the following table 1～3 as rate characteristic with the discharge capacity under the 0.1C.
For the secondary cell of embodiment 1～27 and comparative example 1～10, mensuration reaches the cycle-index that maximum discharge capacity needs when carrying out charge and discharge cycles with 1C, its result is illustrated in following table 1～3.
Table 1
Negative material Battery behavior
Alloy composition Metal structure The discharge capacity ratio Capacity sustainment rate (%) Rate characteristic (%) Discharge and recharge number of times
Embodiment 1 (Al 0.75Si 0.25) 80Ni 14Co 4C 2 Amorphous ????1.5 ????85 ????97 ????7
Embodiment 2 (Al 0.95Si 0.05) 84Ni 13Nb 2Cr 1 Amorphous ????1.6 ????85 ????97 ????7
Embodiment 3 (Al 0.85Si 0.15) 84Ni 10Co 3Mo 2W 1 Amorphous ????1.6 ????86 ????94 ????7
Embodiment 4 (Al 0.8Si 0.2) 80Ni 15Fe 3Zr 1La 1 Amorphous ????1.5 ????90 ????94 ????7
Embodiment 5 (Al 0.7Si 0.3) 79Ni 15Cu 2Ta 3Hf 1 Amorphous ????1.4 ????91 ????95 ????7
Embodiment 6 (Al 0.65Si 0.35) 76Ni 10Mn 1Ti 2V 1Fe 10 Amorphous ????1.4 ????89 ????97 ????7
Embodiment 7 [(Al 0.8Si 0.05Ni 0.1Co 0.04C 0.01)] 80Li 20 Amorphous ????1.7 ????86 ????98 ????3
Embodiment 8 [(Al 0.9Si 0.1) 0.84Ni 0.13Nb 0.02Cr 0.01] 80Li 20 Amorphous ????1.7 ????87 ????97 ????3
Embodiment 9 [(Al 0.8Si 0.2) 0.84Ni 0.1Co 0.03Mo 0.02W 0.01] 85Li 15 Amorphous ????1.7 ????88 ????96 ????3
Embodiment 10 [(Al 0.7Si 0.3) 0.8Ni 0.15Fe 0.03Zr 0.02] 85Li 15 Amorphous ????1.6 ????92 ????96 ????3
Embodiment 11 [(Al 0.6Si 0.4) 0.78Ni 0.1Cu 0.08Ta 0.03Hf 0.01] 90Li 10 Amorphous ????1.5 ????92 ????95 ????3
Embodiment 12 [(Al 0.5Si 0.5) 0.76Ni 0.15Fe 0.05Mn 0.01Ti 0.02V 0.01] 88Li 12 Amorphous ????1.5 ????90 ????95 ????3
Table 2
Negative material Battery behavior
Alloy composition The crystallite phase The discharge capacity ratio Capacity sustainment rate (%) Rate characteristic (%) Discharge and recharge number of times
Ratio (%) Average grain diameter (nm)
Embodiment 13 (Al 0.8Si 0.2) 85Ni 10Co 3Nb 2 ????30 ????30 ????1.6 ????86 ????97 ????7
Embodiment 14 (Al 0.7Si 0.3) 84Ni 10Fe 2Nb 2Cr 1P 1 ????60 ????50 ????1.8 ????85 ????97 ????7
Embodiment 15 (Al 0.5Si 0.5) 78Ni 10Fe 7W 2Mo 1Ge 2 ????80 ????70 ????1.4 ????87 ????94 ????7
Embodiment 16 (Al 0.6Si 0.4) 80Ni 10Co 7Ta 1Pb 1Ce 1 ????50 ????50 ????1.5 ????84 ????94 ????7
Embodiment 17 (Al 0.7Si 0.3) 77Ni 14Cu 4Zr 3Hf 1Sn 1 ????100 ????80 ????1.5 ????86 ????95 ????7
Embodiment 18 (Al 0.6Si 0.4) 80Ni 10Mn 1Co 5Ti 3V 1 ????100 ????120 ????1.6 ????85 ????97 ????7
Embodiment 19 [(Al 0.7Si 0.3) 0.8Ni 0.12Co 0.05Nb 0.03)] 80Li 20 ????20 ????40 ????1.7 ????87 ????98 ????3
Embodiment 20 [(Al 0.8Si 0.2) 0.84Ni 0.1Fe 0.02Nb 0.02Cr 0.01P 0.01] 80Li 20 ????50 ????70 ????1.9 ????86 ????97 ????3
Embodiment 21 [(Al 0.6Si 0.4) 0.77Ni 0.1Fe 0.08W 0.02Mo 0.01Ge 0.02] 85Li 15 ????100 ????90 ????1.5 ????91 ????96 ????3
Embodiment 22 [(Al 0.5Si 0.5) 0.8Ni 0.1Co 0.07Ta 0.02Pb 0.01] 85Li 15 ????90 ????80 ????1.6 ????85 ????96 ????3
Embodiment 23 [(Al 0.75Si 0.25) 0.77Ni 0.14Cu 0.04Zr 0.03Hf 0.01Sn 0.01] 90Li 10 ????80 ????80 ????1.6 ????87 ????95 ????3
Embodiment 24 [(Al 0.8Si 0.2) 0.8Ni 0.1Mn 0.01Co 0.05Ti 0.03V 0.01] 88Li 12 ????100 ????120 ????1.8 ????86 ????95 ????3
Embodiment 25 (Al 0.7Si 0.3) 75Fe 10Ni 10Cr 5 ????20 ????30 ????1.5 ????87 ????96 ????7
Embodiment 26 (Al 0.5Si 0.5) 75Fe 10Ni 10Cr 5 ????30 ????60 ????1.7 ????85 ????96 ????7
Embodiment 27 (Al 0.3Si 0.7) 75Fe 10Ni 10Cr 5 ????50 ????90 ????1.8 ????82 ????96 ????7
Table 3
Negative material Battery behavior
Alloy composition The crystallite phase The discharge capacity ratio Capacity sustainment rate (%) Rate characteristic (%) Discharge and recharge number of times
Ratio (%) Average grain diameter (nm)
Comparative example 1 ?C ??- ????5000 ????1 ????70 ????80 ????7
Comparative example 2 ?Al ??100 ????10000 ????3 ????2 ????40 Can not measure
Comparative example 3 ?Sn 30CO 70 Amorphous ????- ????1.1 ????80 ????82 ????9
Comparative example 4 ?Si 33Ni 67 ??100 ????40 ????1.0 ????82 ????85 ????9
Comparative example 5 ?(Al 0.1Si 0.9) 33Ni 67 ??100 ????300 ????1.0 ????55 ????70 ????7
Comparative example 6 ?Cu 50Ni 25Sn 25 ??100 ????200 ????1.0 ????70 ????75 ????8
Comparative example 7 ?Si 25Fe 75 ??100 ????300 ????0.7 ????65 ????70 ????7
Comparative example 8 ?Ni(Si 0.8Al 0.2) 2 ??100 ????400 ????1.2 ????60 ????65 ????5
Comparative example 9 ?(Al 0.1Si 0.9) 75Fe 10Ni 10Cr 5 ??80 ????150 ????1.5 ????60 ????80 ????7
Comparative example 10 ?Si 75Fe 10Ni 10Cr 5 ??100 ????300 ????1.2 ????55 ????70 ????6
From table 1 to table 3 as can be known, the secondary cell of embodiment 1～27 is all superior aspect the capacity sustainment rate of discharge capacity, 300 circulation times and rate characteristic.
In contrast, with carbide as the secondary cell of the comparative example 1 of negative material compare with embodiment 1～27 aspect the capacity sustainment rate of discharge capacity, 300 circulation times and the rate characteristic all poor.The Al metal is compared the discharge capacity height as the secondary cell of the comparative example 2 of negative material with embodiment 1～27, but the capacity sustainment rate and the rate characteristic of 300 circulation times are poor.The rate characteristic of the secondary cell of comparative example 3～7 is not as embodiment 1～27.
Observe the negative pole behind the cycle charge-discharge 300 times, alloy be can't see variation in the negative material that embodiment 1～24 uses, and separates out the dendrite of Al in the negative pole of comparative example 2.Separate out Al dendrite and can infer the initial cells discharge capacity height of the secondary cell that comparative example 2, the capacity sustainment rate after 300 circulations significantly reduces.Easy and the electrolyte reaction of Al dendrite, so battery security reduces.
By embodiment 25～27 comparison, less than 0.75 o'clock, can improve the capacity sustainment rate and the rate characteristic of 300 circulation times at the atomic ratio x of Si with comparative example 9～10.
On the other hand, use to have the secondary cell of comparative example 8 that the spy opens the alloy of the composition of putting down in writing in the flat 10-302770 communique and be low to moderate 60% at 300 circulation time capacity sustainment rates, rate characteristic degrades to 65%.
(embodiment 28～37)
The making of＜negative pole 〉
Add each element of the ratio of hotlist 4 expressions, after its fusion, in inert atmosphere gas, obtain alloy by single-roller method.That is, the nozzle bore from 0.6mm φ in inert atmosphere gas injects alloying metal solution to the chill roll of the BeCu alloy manufacturing of rotating by the speed of rotating speed 40m/s, and chilling is made the thin ribbon shaped alloy.Atmosphere gas during chilling is atmosphere, or makes inert gas flow to spray nozzle front end all can to obtain same alloy.
The crystallinity of the alloy of gained embodiment 28～37 is measured with X-ray diffraction method, confirms not observe the peak based on crystalline phase.
For the thin ribbon shaped alloy of embodiment 28～30,36～37, block the back and pulverize with the injecting type grinder, make the alloy powder of average grain diameter 10 μ m.For the thin ribbon shaped alloy of embodiment 31～35, after blocking, 300 ℃ of heat treated of carrying out 5 hours below crystallization temperature, former state is kept amorphous phase and embrittlement, and then pulverizes with the injecting type grinder, makes the alloy powder of average grain diameter 10 μ m.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(embodiment 38～39)
Make the alloy of forming shown in the following table 4 of machine-alloying.The crystallinity of gained alloy is measured with X-ray diffraction method.Confirm not observe peak based on crystalline phase.And then pulverize with the injecting type grinder, make the alloy powder of average grain diameter 10 μ m.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(embodiment 40～41)
Each element that adds the ratio of hotlist 5 expression, make its fusion after, in inert atmosphere gas, obtain alloy by single-roller method.That is, the nozzle bore from 0.6mm φ in inert atmosphere gas injects alloying metal solution to the chill roll of the BeCu alloy manufacturing of rotating by the speed of rotating speed 45m/s, and chilling makes thin ribbon shaped or laminar alloy.The crystallinity of gained alloy is measured with X-ray diffraction method, confirms not observe the peak based on crystalline phase.
In 350 ℃ the inert atmosphere gas more than crystallization temperature, alloy is implemented to block after the heat treatment in 1 hour, pulverize, make the alloy powder of average grain diameter 10 μ m with the injecting type grinder.
For the alloy that obtains, carry out the crystallite ratio measuring mutually and the mensuration of the average crystallite particle diameter of crystallite phase equally with the foregoing description 13, its result is illustrated in the following table 5.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(embodiment 42～43)
Each element that adds the ratio of hotlist 5 expression, make its fusion after, in inert atmosphere gas, obtain alloy by single-roller method.That is, in inert atmosphere gas, the chill roll of making to the BeCu alloy of the speed rotation of pressing rotating speed 40m/s from the nozzle bore of 0.7mm φ penetrates alloying metal solution, and chilling makes laminar alloy.Block this alloy, pulverize, make the alloy powder of average grain diameter 10 μ m with the injecting type grinder.
For the alloy that obtains, carry out the crystallite ratio measuring mutually and the mensuration of the average crystallite particle diameter of crystallite phase equally with the foregoing description 13, its result is illustrated in the following table 5.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(embodiment 44～45)
After adding each element and fusion of ratio of hotlist 5 expression, in inert atmosphere gas, obtain alloy by single-roller method.That is, the chill roll of making to the BeCu alloy of the speed rotation of pressing rotating speed 40m/s from the nozzle bore of 0.7mm φ in inert atmosphere gas penetrates alloying metal solution, and chilling makes laminar alloy.Under 300 ℃, this alloy is implemented heat treatment in 1 hour carry out the adjustment of metal structure.And then block this alloy, and pulverize with the injecting type grinder, make the alloy powder of average grain diameter 10 μ m.
For the alloy that obtains, same with the foregoing description 13, carry out the mensuration of ratio measuring with the crystallite average crystallite particle diameter mutually of crystallite phase, its result is illustrated in the following table 5.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(embodiment 46～47)
After adding each element and fusion of ratio of hotlist 5 expression, in inert atmosphere gas, obtain alloy by single-roller method.That is, the chill roll of making to the BeCu alloy of the speed rotation of pressing rotating speed 35m/s from the nozzle bore of 0.5mm φ in inert atmosphere gas penetrates alloying metal solution, and chilling makes thin ribbon shaped or laminar alloy.The crystallinity of gained alloy is measured with X-ray diffraction method, confirms not observe the peak based on crystalline phase.
In 300 ℃ inert atmosphere gas, this alloy is implemented to block after the heat treatment in 1 hour, pulverize, make the alloy powder of average grain diameter 10 μ m with the injecting type grinder.
For the alloy that obtains, carry out the crystallite ratio measuring mutually and the mensuration of the average crystallite particle diameter of crystallite phase equally with the foregoing description 13, its result is illustrated in the following table 5.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(embodiment 48～49)
After adding each element and fusion of ratio of hotlist 5 expression, in inert atmosphere gas, obtain alloy by single-roller method.That is, the nozzle bore from 0.45mm φ in inert atmosphere gas injects alloying metal solution to the chill roll of the BeCu alloy manufacturing of rotating by the speed of rotating speed 45m/s, and chilling makes laminar alloy.
Under 300 ℃, this alloy is implemented heat treatment in 1 hour and blocked after the embrittlement, pulverize with the injecting type grinder, make the alloy powder of average grain diameter 10 μ m.
For the gained alloy, carry out the crystallite ratio measuring mutually and the mensuration of the average crystallite particle diameter of crystallite phase equally with the foregoing description 13, its result is illustrated in the following table 5.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(embodiment 50～51)
Make the alloy of the composition shown in the following table 5 of machine-alloying.And then pulverize with the injecting type grinder, make the alloy powder of average grain diameter 10 μ m.
For the gained alloy, carry out the crystallite ratio measuring mutually and the mensuration of the average crystallite particle diameter of crystallite phase equally with the foregoing description 13, its result is illustrated in the following table 5.
Except that using this alloy powder, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(comparative example 11～13)
As negative material, make Al with single-roller method 3Mg 4Alloy, Al 8Mg 5Alloy, Cu 3Mg 2The Si alloy.The roller material is the BeCu alloy, and the roller rotating speed is 30m/s.The gained alloy is confirmed controlled micro crystallization with X-ray diffraction.Calculate average grain diameter with the Scherrer formula, all expressions in the table 6 below.Except that use this alloy with, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
Secondary cell for embodiment 28～51 that obtains and comparative example 11～13, with same evaluation discharge capacity ratio, capacity sustainment rate, the rate characteristic of the foregoing description 1 explanation with reach the number of times that discharges and recharges of heap(ed) capacity, its result is illustrated in following table 4～6.Have the result of above-mentioned comparative example 3 and 6 in the table 6 concurrently.
Table 4
Negative material Battery behavior
Alloy composition Metal structure The discharge capacity ratio Capacity sustainment rate (%) Rate characteristic (%) Discharge and recharge number of times
Embodiment 28 (Al 0.9Mg 0.1) 87Ni 8Co 4C 1 Amorphous 1.5 ?85 ?95 ????7
Embodiment 29 (Al 0.95Mg 0.05) 84Ni 13Nb 2Cr 1 Amorphous 1.5 ?85 ?97 ????7
Embodiment 30 (Al 0.85Mg 0.15) 84Ni 10Co 3Mo 2W 1 Amorphous 1.5 ?86 ?96 ????7
Embodiment 31 (Al 0.8Mg 0.2) 80Ni 15Fe 3Zr 1Pr 1 Amorphous 1.4 ?90 ?98 ????7
Embodiment 32 (Al 0.75Mg 0.15Si 0.1) 77Ni 16Co 3Cu 1Ta 2Hf 1 Amorphous 1.3 ?91 ?95 ????7
Embodiment 33 (Al 0.75Mg 0.15Si 0.1) 76Ni 17Fe 2Mn 1Ti 3V 1 Amorphous 1.3 ?89 ?97 ????7
Embodiment 34 [(Al 0.9Mg 0.1) 0.87Ni 0.08Co 0.04C 0.01] 80Li 20 Amorphous 1.6 ?86 ?98 ????3
Embodiment 35 [(Al 0.95Mg 0.05) 0.84Ni 0.13Nb 0.02Cr 0.01] 80Li 20 Amorphous 1.6 ?87 ?94 ????3
Embodiment 36 [(Al 0.85Mg 0.15) 0.84Ni 0.1Co 0.03Mo 0.02W 0.01] 85Li 15 Amorphous 1.6 ?88 ?94 ????3
Embodiment 37 [(Al 0.8Mg 0.2) 0.8Ni 0.1Fe 0.08Zr 0.02] 85Li 15 Amorphous 1.5 ?92 ?94 ????3
Embodiment 38 [(Al 0.75Mg 0.25) 0.78Ni 0.15Co 0.03Cu 0.02Ta 0.01Hf 0.01] 90Li 10 Amorphous 1.4 ?92 ?96 ????3
Embodiment 39 [(Al 0.75Mg 0.25) 0.76Ni 0.14Fe 0.05Mn 0.01Ti 0.03V 0.01] 88Li 12 Amorphous 1.4 ?90 ?98 ????3
Table 5
Negative material Battery behavior
Alloy composition The crystallite phase The discharge capacity ratio Capacity sustainment rate (%) Rate characteristic (%) Discharge and recharge number of times
Ratio (%) Average grain diameter (nm)
Embodiment 40 (Al 0.7Mg 0.3) 80Ni 12Co 5Nb 2Nd 1 ?90 ??40 ??1.5 ????86 ????96 ????7
Embodiment 41 (Al 0.8Mg 0.2) 79Ni 15Fe 2Nb 2Cr 1P 1 ?70 ??60 ??1.7 ????85 ????95 ????7
Embodiment 42 (Al 0.5Mg 0.5) 76Ni 11Fe 10W 1Mo 1Ge 1 ?90 ??80 ??1.3 ????87 ????95 ????7
Embodiment 43 (Al 0.8Mg 0.2) 80Ni 10Co 7Ta 2Pb 1 ?60 ??60 ??1.4 ????84 ????96 ????7
Embodiment 44 (Al 0.75Mg 0.25) 77Ni 14Cu 4Zr 3Hf 1Sn 1 ?100 ??50 ??1.4 ????86 ????94 ????7
Embodiment 45 (Al 0.6Mg 0.4) 80Ni 10Mn 1Co 5Ti 3V 1 ?100 ??90 ??1.5 ????85 ????92 ????7
Embodiment 46 [(Al 0.8Mg 0.2) 08Ni 0.12Co 0.05Nb 0.03)] 80Li 20 ?100 ??60 ??1.6 ????87 ????91 ????3
Embodiment 47 [(Al 0.7Mg 0.3) 0.82Ni 0.12Fe 0.02Nb 0.02Cr 0.01P 0.01] 80Li 20 ?90 ??80 ??1.8 ????86 ????92 ????3
Embodiment 48 [(Al 0.9MG 0.1) 0.78Ni 0.1Fe 0.07W 0.02Mo 0.01Ge 0.02] 85Li 15 ?100 ??110 ??1.4 ????91 ????91 ????3
Embodiment 49 [(Al 0.7Mg 0.3) 0.8Ni 0.1Co 0.07Ta 0.02Pb 0.01] 85Li 15 ?90 ??100 ??1.5 ????85 ????93 ????3
Embodiment 50 [(Al 0.7Mg 0.3) 0.77Ni 0.14Cu 0.04Zr 0.03Hf 0.01Sn 0.01] 90Li 10 ?90 ??90 ??1.5 ????87 ????93 ????3
Embodiment 51 [(Al 0.8Mg 0.2) 0.8Ni 0.1Mn 0.01Co 0.05Ti 0.03V 0.01] 88Li 12 ?100 ??150 ??1.7 ????86 ????92 ????3
Table 6
Negative material Battery behavior
Alloy composition The crystallite phase The discharge capacity ratio Capacity sustainment rate (%) Rate characteristic (%) Discharge and recharge number of times
Ratio (%) Average grain diameter (nm)
Comparative example 3 ?Sn 30Co 70 Amorphous ????- ????1.2 ????80 ????82 ????9
Comparative example 6 ?Cu 50Ni 25Sn 25 ??100 ????200 ????1.1 ????70 ????75 ????8
Comparative example 11 ?Al 3Mg 4 ??100 ????500 ????1.0 ????60 ????75 ????8
Comparative example 12 ?Al 8Mg 5 ??100 ????600 ????1.0 ????70 ????75 ????8
Comparative example 13 ?Cu 3Mg 2Si ??100 ????400 ????0.9 ????75 ????77 ????8
From table 4 to table 6 as can be known, the secondary cell of embodiment 28～51 is all superior aspect the capacity sustainment rate of discharge capacity, 300 circulation times and rate characteristic.
In contrast, comparative example 3 and 6 the secondary cell that uses Sn content to surpass the alloy of 20 atom % aspect the capacity sustainment rate of discharge capacity, 300 circulation times and rate characteristic, compare with embodiment 28～51 all poor.Use the comparative example 11 of the binary system alloy of Al and Mg to compare with embodiment 28～51 with the secondary cell of the comparative example 13 of the ternary alloy of Si with use Cu, Mg with 12 secondary cell, the capacity sustainment rate and the rate characteristic of its 300 circulation times are all poor.
(embodiment 52～53)
Heating has the foundry alloy of the composition of table 7 expression, make its fusion after, in inert atmosphere gas, obtain alloy by single-roller method.Promptly, in inert atmosphere gas, be that (the roller material is the BeCu alloy to the chill roll by the speed rotation of rotating speed 25m/s for the nozzle bore (0.5mm φ) of 0.5mm from being configured to gap between roller and the nozzle, roller diameter is 500mm, the roller width is 150mm) on inject alloying metal solution, obtaining the sample thickness of slab is 15 μ m, and chilling makes the thin ribbon shaped alloy.
For the alloy of the embodiment 52～53 that obtains, carry out the described evaluation test in following (1)～(4), its result is illustrated in following table 7～8.
(1) X-ray diffraction
The gained alloy is carried out powder x-ray diffraction measures, as shown in table 7 obtain based on the diffraction maximum of intermetallic compound with based on second mutually the diffraction maximum.The X-ray diffractogram of embodiment 52 as shown in Figure 6.Specifically, can confirm based on Al second mutually with intermetallic compound existing mutually.In the X-ray diffractogram of Fig. 6, being 38.44 °, 44.74 °, the 65.04 ° peaks of locating to detect from the Al metal at 2 θ, is 27.76 °, 46.22 °, 54.80 °, the 67.48 ° Si that locate to detect from solid solution Al at 2 θ 2The peak of Ni phase.Face interval d presses 2dsin θ=λ, and (the θ angle of diffraction, λ: the wavelength of X ray) experimental data of formula is asked for.Infer that from X-ray diffractogram the intermetallic compound of first phase is fluorite (CaF 2) structure, basically at Si 2Solid solution Al in the Ni lattice.Confirm other constitute elements be also contained in this mutually in.The formation element of the TEM-EDX of second phase is shown in the following Table 8.Calculate the lattice constant of fluorite structure from the X-ray diffractogram that obtains, its result is illustrated in the following table 7.
On the other hand, the foundry alloy that uses for the alloy of making embodiment 52 and 53 comprises Al 3Ni phase and Si 2Ni phase (not solid solution Al) and Al phase.X-ray diffractogram by this foundry alloy relatively from Si 2The angle of diffraction at the peak of Ni and the X-ray diffractogram of Fig. 6 from Si 2The angle of diffraction at the peak of Ni can be confirmed the Si that the alloy of embodiment 52 and 53 comprises 2Ni mutually in solid solution Al.
According to the fluorite structure of intermetallic compound the relative intensity ratio of strong diffracted intensity is changed according to alloy composition, by Al at Si 2Ni phase or Si 2Moving appears in the solid solution ratio of Co in mutually, angle of diffraction.The foundry alloy that uses for the alloy of making each embodiment is under the situation based on AlSi, by Al 3Ni phase, Si 2Ni phase (not solid solution Al) and Al constitute mutually, wherein also comprise Al according to forming 3Ni 2Phase.On the other hand, based under the situation of AlSiCo by Al 9Co 2Phase, Si 2Co reaches Al mutually and constitutes mutually.The maximum gauge of the crystal grain in the foundry alloy all surpasses 500nm, all is the micron number magnitude under all situations.
(2) observation of transmission electron microscope (TEM)
Confirm metal structure by taking TEM photo (100,000 times), at least a portion of intermetallic compound crystalline particle is isolated to be separated out, and is that second of main body is imbedded mutually because of separating out between the island that forms and separated out with the element of lithium alloyage.The transmission electron microscope of the alloy of embodiment 52 (TEM) photo as shown in Figure 7.Among Fig. 7, isolated crystal grain (black) is intermetallic compound crystalline particle 21, and the phase (grey) that is embedded in 21 of this isolated crystal grain is second phase 22.The network of second phase is cut off as can be seen from Figure 7, and the part of second phase is isolated out.
For 50 intermetallic compound crystalline particles adjacent one another are of TEM photo, measure the maximum gauge of each crystalline particle, with its mean value as the average crystallite particle diameter.Be respectively 100nm and 60nm among the embodiment 52 and 53.Here, under the situation that the intermetallic compound crystalline particle more than 2 joins, the maximum length of each intermetallic compound crystalline particle that will disperse in the grain boundary is decided to be the crystallization particle diameter.
In addition, measure spacing between any 50 intermetallic compound crystalline particles for 50 intermetallic compound crystalline particles adjacent one another are of TEM photo, with the spacing of its mean value, be respectively 60nm, 30nm among the embodiment 52 and 53 as the intermetallic compound crystalline particle.
In the visual field of TEM photo, at least comprise in the zone (area 100%) of 50 intermetallic compound crystalline particles, obtain the area ratio (%) of first phase by image processing, remove the area ratio (%) of first phase from the area (100%) in whole zone, obtain the area ratio of second phase, i.e. the occupation rate of second phase in the negative material.Be respectively 17%, 30% among the embodiment 52 and 53.Here, under the situation that the intermetallic compound crystalline particle more than 2 joins each other, its number is not done one, the intermetallic compound crystalline particle that looses in grain boundary punishment is counted.
Then, measure per 1 μ m of alloy with method described below 2The intermetallic compound crystal grain subnumber of area, consequently, embodiment 52 and 53 alloy are respectively 80 and 205.
That is, number goes out 1 μ m in the visual field of TEM photo 2Scope in the island number of intermetallic compound.At this moment, it is 1 with the island number on the boundary line of 1 μ m * 1 μ m of distinguishing.
Its result is illustrated in the table 10,, under the situation that the intermetallic compound crystalline particle more than 2 joins each other, its number is not done one here, and the intermetallic compound crystalline particle that looses in grain boundary punishment is counted.
(3) differential scanning calorimetry
The differential scanning calorimetry uses differential scanning calorimetry (DSC) to measure under the programming rate of 10 ℃/min and inert atmosphere gas, the temperature that shifts to equilibrium phase from non-equilibrium phase with the exothermic peak evaluation.The DSC curve of the alloy of embodiment 52 as shown in Figure 8.The intersection point of the ruling grade of line of change minimum (baseline) and exothermic peak is a transition temperature in the exothermic peak, in the following Table 8 expression.In 293 ℃, embodiment 53, see initial exothermic peak among the embodiment 52 at 267 ℃.The transition temperature of obtaining by this method is the temperature of comparison near the rising of exothermic peak.
(4) TEM-EDX (energy dispersive X-ray diffraction)
With TEM-EDX confirm each alloy second mutually in other elements of ratio solid solution below the 10 atom %.Second of the alloy of embodiment 52 comprises the Si of 3 atom % and the Ni of 2.5 atom % in mutually, and second of the alloy of embodiment 53 comprises the Si of 2.2 atom % and the Ni of 1.9 atom % in mutually.
(1)～(4) after the evaluation, pulverizes with the injecting type grinder after blocking the alloy of embodiment 52 and 53, make the alloy powder of average grain diameter 10 μ m.
Except that using the alloy powder that obtains, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(embodiment 54～72)
After heating the foundry alloy and fusion of composition with table 8 and table 9 expression, in inert atmosphere gas, be that (the roller material is the BeCu alloy to the chill roll by the speed rotation of rotating speed 25m/s for the nozzle bore (0.5mm φ) of 0.5mm from being configured to gap between roller and the nozzle by single-roller method, roller diameter is 500mm, the roller width is 150mm) go up and penetrate alloying metal solution, obtaining the sample thickness of slab is 15 μ m, and chilling makes the thin ribbon shaped alloy.
For the alloy of the embodiment 54～72 that obtains, carry out each evaluation test of (1) X-ray diffraction, (2) tem observation, (3) TEM-EDX composition analysis equally with embodiment 52 and 53, its result is illustrated in following table 8～11.
(1)～(4) after the evaluation, pulverizes with the injecting type grinder after blocking the alloy of embodiment 54～72, make the alloy powder of average grain diameter 10 μ m.
Except that using the alloy powder that obtains, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(comparative example 14)
Remove and use the Si of lattice constant as the antifluorite structure of 5.4_ 66.7Ni 33.3Outside negative material, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(comparative example 15)
Remove and use the Mg of lattice constant as the fluorite structure of 6.35_ 66.7Si 33.3Outside negative material, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
(comparative example 16)
Form metallic solution at Ar atmosphere gas medium-high frequency dissolving raw material, this metallic solution is injected tundish after, go up the pore that is provided with by the tundish bottom and form the metallic solution thread, to this metallic solution thread spraying high pressure Ar gas, carry out powdered.
By the cross section of the powder of gained negative material being observed with SEM (scanning electron microscope) and each EPMA mutually analyzes, affirmation consists of Co 42Si 58, CoSi separates out as primary crystal, and Si forms lamellar eutectic with a CoSi part mutually mutually.Average out to 0.1～2 μ m of the thickness of Si layer (minor axis particle diameter).
Except that using this negative material, other operations are described identical with the foregoing description 1, make lithium rechargeable battery.
Secondary cell for gained embodiment 54～72 and comparative example 14～16, carry out with described identical discharge capacity ratio, capacity sustainment rate, the rate characteristic of the foregoing description 1 and reach the mensuration that discharges and recharges number of times of heap(ed) capacity, its result is illustrated in following table 8～11.
Table 7
Embodiment Form X-ray diffraction peak d (_) based on first phase X-ray diffraction peak d (_) based on second phase The lattice constant (_) of intermetallic compound
?52 (Al 0.65Si 0.35) 75Ni 25 3.2101 ?1.9658 ?1.6764 ?1.3902 ?1.2756 ?2.3399 ?2.0239 ?1.4328 ?1.2211 ?5.560
?53 (Al 0.8Si 0.2) 80Ni 20 ?3.3311 ?2.0389 ?1.7380 ?1.4420 ?1.3210 ?2.3434 ?2.0308 ?1.4332 ?1.2244 ?5.770
Table 8
Alloy composition Second phase composition Intermetallic compound Lattice constant (_) Transition temperature (℃) Element monomer occupation rate (%)
Embodiment 52 (Al 0.65Si 0.35) 75Ni 25 Al main body+Si+Ni ?CaF 2Structure ????5.56 ??293 ????17
Embodiment 53 (Al 0.8Si 0.2) 80Ni 20 Al main body+Si+Ni ?CaF 2Structure ????5.77 ??267 ????30
Embodiment 54 (Al 0.55Si 0.45) 77.5Co 17.5Ni 5 Al main body+Si+Co+Ni ?CaF 2Structure ????5.51 ??350 ????15
Embodiment 55 (Al 0.6Si 0.4) 77Ni 20Co 3 Al main body+Si+Ni+Co ?CaF 2Structure ????5.54 ??290 ????18
Embodiment 56 (Al 0.6Si 0.4) 77Ni 20Fe 3 Al main body+Si+Ni+Fe ?CaF 2Structure ????5.54 ??320 ????22
Embodiment 57 (Al 0.7Si 0.3) 76Ni 22Nb 2 Al main body+Si+Ni ?CaF 2Structure ????5.72 ??365 ????8
Embodiment 58 (Al 0.7Si 0.3) 76Ni 18Co 5Ta 1 Al main body+Si+Ni+Co ?CaF 2Structure ????5.67 ??310 ????10
Embodiment 59 (Al 0.7Si 0.3) 76Ni 18Co 5La 1 Al main body+Si+Ni+Co ?CaF 2Structure ????5.64 ??340 ????13
Embodiment 60 (Al 0.5In 0.1Si 0.4) 76Ni 18Co 5Ce 1 Al main body+Si+In+Ni ?CaF 2Structure ????5.82 ??262 ????12
Embodiment 61 (Al 0.5Bi 0.1Si 0.4) 76Ni 18Co 6 Al main body+Si+Bi+Ni ?CaF 2Structure ????5.79 ??270 ????11
Embodiment 62 (Al0 .5Pb 0.1Si 0.4) 76Ni 18Mn 6 Al main body+Si+Pb+Ni ?CaF 2Structure ????5.88 ??285 ????9
Embodiment 63 (Al 0.5Zn 0.1Si 0.4) 76Ni 18Cu 6 Al main body+Si+Zn+Ni ?CaF 2Structure ????5.56 ??295 ????16
Embodiment 64 (Al 0.5Ga 0.1Si 0.4) 76Ni 18Co 4Ti 2 Al main body+Si+Ga+Ni ?CaF 2Structure ????5.50 ??248 ????23
Embodiment 65 (Al 0.5Sb 0.1Si 0.4) 76Ni 18Co 5Zr 1 Al main body+Si+Sb+Ni ?CaF 2Structure ????5.55 ??288 ????15
Embodiment 66 (Al 0.5Mg 0.1Si 0.4) 76Ni 18Co 5Hf 1 Al main body+Si+Mg+Ni ?CaF 2Structure ????5.80 ??285 ????15
Embodiment 67 (Al 0.5Sn 0.1Si 0.4) 76Ni 18Co 4Cr 2 Al main body+Si+Sn+Ni ?CaF 2Structure ????5.63 ??270 ????20
Table 9
Alloy composition Second phase composition Intermetallic compound Lattice constant (_) Transition temperature (℃) Element monomer occupation rate (%)
Embodiment 68 [(Al 0.65Si 0.35) 75Ni 25] 90Li 10 Al main body+Si+Ni+Li ?CaF 2Structure ??5.52 ??263 ????19
Embodiment 69 [(Al 0.8Si 0.2) 80Ni 20] 90Li 10 Al main body+Si+Ni+Li ?CaF 2Structure ??5.73 ??257 ????33
Embodiment 70 [(Al 0.55Si 0.45) 77.5Co 1.75Ni 5] 88Li 12 Al main body+Si+Co+Ni+Li ?CaF 2Structure ??5.47 ??330 ????18
Embodiment 71 [(Al 0.65Si 0.35) 77Ni 20Co 3] 92Li 8 Al main body+Si+Ni+Co+Li ?CaF 2Structure ??5.50 ??270 ????21
Embodiment 72 [(Al 0.6Si 0.4) 76Ni 20Fe 4] 90Li 10 Al main body+Si+Ni+Fe+Li ?CaF 2Structure ??5.50 ??300 ????25
Comparative example 14 Si 66.7Ni 33.3 ?- Antifluorite structure ??5.4 ???- ????-
Comparative example 15 Mg 66.7Si 33.3 ?- ?CaF 2Structure ??6.35 ???- ????-
Comparative example 16 Co 42Si 58 ?- ?CoSi 2Phase+CoSi phase ??5.35 ???- 15 (Si phases)
Table 10
First phase Battery behavior
Average crystallite particle diameter (nm) Number of die (individual) Intercrystalline average distance (nm) The discharge capacity ratio Capacity sustainment rate (%) Rate characteristic (%) Discharge time when reaching heap(ed) capacity
Embodiment 52 ????100 ????80 ????60 ????1.6 ????89 ????97 ????7
Embodiment 53 ????60 ????205 ????30 ????1.6 ????89 ????96 ????7
Embodiment 54 ????80 ????120 ????60 ????1.5 ????91 ????95 ????7
Embodiment 55 ????50 ????280 ????35 ????1.7 ????90 ????92 ????7
Embodiment 56 ????120 ????65 ????70 ????1.6 ????89 ????94 ????7
Embodiment 57 ????60 ????350 ????30 ????1.5 ????93 ????94 ????7
Embodiment 58 ????40 ????800 ????20 ????1.4 ????94 ????93 ????7
Embodiment 59 ????50 ????320 ????30 ????1.5 ????93 ????95 ????7
Embodiment 60 ????50 ????300 ????35 ????1.7 ????90 ????93 ????7
Embodiment 61 ????50 ????320 ????30 ????1.7 ????89 ????93 ????7
Embodiment 62 ????50 ????340 ????30 ????1.6 ????89 ????92 ????7
Embodiment 63 ????50 ????280 ????40 ????1.6 ????89 ????92 ????7
Embodiment 64 ????80 ????100 ????70 ????1.6 ????90 ????91 ????7
Embodiment 65 ????60 ????250 ????40 ????1.5 ????91 ????92 ????7
Embodiment 66 ????60 ????270 ????35 ????1.5 ????90 ????91 ????7
Embodiment 67 ????50 ????290 ????30 ????1.6 ????90 ????92 ????7
Table 11
First phase Battery behavior
Average crystallite particle diameter (nm) Number of die (individual) Intercrystalline average distance (nm) The discharge capacity ratio Capacity sustainment rate (%) Rate characteristic (%) Discharge time when reaching heap(ed) capacity
Embodiment 68 ????90 ????100 ????50 ????1.6 ????87 ????94 ????2
Embodiment 69 ????60 ????205 ????30 ????1.6 ????87 ????93 ????2
Embodiment 70 ????80 ????120 ????60 ????1.5 ????90 ????92 ????2
Embodiment 71 ????50 ????280 ????35 ????1.7 ????87 ????90 ????2
Embodiment 72 ????120 ????65 ????70 ????1.6 ????89 ????91 ????2
Comparative example 14 ????2000 ????1 ????- ????0.8 ????40 ????20 ????-
Comparative example 15 ????3000 ????1 ????- ????1 ????65 ????80 ????8
Comparative example 16 ????800 ????2 ????200 ????1 ????70 ????80 ????8
From table 8～table 11 as can be known, the secondary cell of embodiment 52～72 is compared with the secondary cell of comparative example 14～16, and discharge capacity, capacity sustainment rate and rate characteristic are more superior, and the number of times that discharges and recharges that reaches maximum discharge capacity reduces.
＜the characteristic that comprises the alloy of amorphous phase and comprise crystallite alloy mutually relatively 〉
The embodiment 2,3,10 of the alloy that amorphous phase constitutes and 11 secondary cell from the foregoing description 1～51, have been selected to have used, and used the embodiment 17 of the alloy that crystallite constitutes mutually and 18 secondary cell, make the secondary cell of embodiment 52,54,55,68 and 71.
Adopt with the foregoing description 1 described same method and make alloy (embodiment 73) with composition shown in the following table 12.Adopting with the foregoing description 1 described same method then utilizes this alloy to make the lithium rechargeable battery of embodiment 73.
Under room temperature and 60 ℃, adopt with the foregoing description 1 described same condition and carry out the charge and discharge cycles test for these secondary cells.The discharge capacity of circulation after 100 times under the room temperature is decided to be 100%, 60 ℃ of discharge capacities after following 100 circulations are shown, its result is illustrated in the following table 12 as high-temperature cycle.In the charge and discharge cycles test under 60 ℃, obtain the discharge capacity that maximum discharge capacity is made as 300 circulation times of 100% o'clock, its result is illustrated in the following table 12 as the capacity sustainment rate under 60 ℃.
Table 12
Negative pole Battery behavior
Alloy composition Metal structure The discharge capacity ratio Capacity sustainment rate in the time of 60 ℃ High-temperature cycle (%)
Embodiment 2 (Al 0.95Si 0.05) 84Ni 13Nb 2Cr 1 Amorphous ????1.6 ????68 ????90.8
Embodiment 3 (Al 0.85Si 0.15) 84Ni 10Co 3Mo 2W 1 Amorphous ????1.6 ????65 ????88.4
Embodiment 10 [(Al 0.7Si 0.2) 0.8Ni 0.15Fe 0.03Zr 0.02] 85Li 15 Amorphous ????1.6 ????63 ????86.5
Embodiment 11 [(Al 0.6Si 0.4) 0.78Ni 0.1Cu 0.08Ta 0.03Hf 0.01] 90Li 10 Amorphous ????1.5 ????66 ????85.5
Embodiment 73 (Al 0.8Si 0.2) 82Ni 16Nb 2 Amorphous ????1.6 ????70 ????89.1
Embodiment 17 (Al 0.7Si 0.3) 77Ni 14Cu 4Zr 3Hf 1Sn 1 Crystallite ????1.5 ????80 ????95.8
Embodiment 18 (Al 0.6Si 0.4) 80Ni 10Mn 1Co 5Ti 3V 1 Crystallite ????1.6 ????77 ????95.5
Embodiment 52 (Al 0.65Si 0.35) 75Ni 25 Crystallite ????1.6 ????77 ????96.5
Embodiment 54 (Al 0.55Si 0.45) 77.5Co 17.5Ni 5 Crystallite ????1.5 ????82 ????97.2
Embodiment 55 (Al 0.6Si 0.4) 77Ni 20Co 3 Crystallite ????1.7 ????81 ????97.4
Embodiment 68 [(Al 0.65Si 0.35) 75Ni 25] 90Li 10 Crystallite ????1.6 ????79 ????95.2
Embodiment 71 [(Al 0.65Si 0.35) 77Ni 20Co 3] 92Li 8 Crystallite ????1.7 ????79 ????94.9
As known from Table 12, possess the embodiment 17,18,52,54,55,68 of the alloy that comprises the crystallite phase and 71 secondary cell, the charge under 60 ℃ is better than the secondary cell of the embodiment 2,3,10,11 that possesses the alloy that comprises amorphous phase and 73.
(embodiment 73～88)
The making of＜negative pole 〉
The foundry alloy that the atom % ratio of table 13 expression is modulated press in heating, make its fusion after, in inert atmosphere gas, obtain alloy by single-roller method.That is, the nozzle bore from 1.0mm φ in inert atmosphere gas injects alloying metal solution to the chill roll of the BeCu alloy manufacturing of rotating by the speed of rotating speed 40m/s, and chilling makes the thin ribbon shaped alloy.Atmosphere gas during chilling is atmosphere or makes inert gas flow to spray nozzle front end all can to obtain same alloy.These alloys carry out heat treatment in 1.5 hours in 450 ℃ nitrogen atmosphere gas.
The crystallinity of the alloy of gained embodiment 73～88 is measured with X-ray diffraction method, confirms not observe the peak based on crystalline phase.
Crystallinity to the alloy of embodiment 73～88 is measured with X-ray diffraction method, confirm the monomer Al phase or the Mg phase mutually of the element of conduct and lithium alloyage, and the existence with two or more intermetallic compound phase X of stoichiometric composition shown in the following table 13.When comparing the composition between the intermetallic compound phase X, discovery differs from one another with the kind of the element of lithium alloyage.
Fig. 9 represents the X-ray diffractogram (X ray, CuK α) of the alloy of embodiment 73.Al monomer phase (using zero symbolic representation), Al appear respectively among Fig. 9 3Ni phase (using the symbolic representation), Si monomer phase (usefulness * symbolic representation) and Si 2The diffracted ray of Ni phase (using the △ symbolic representation).
Then, pulverize with the injecting type grinder after blocking the thin ribbon shaped alloy of embodiment 73～88, make the alloy powder of average grain diameter 10 μ m.
Mix this alloy powder of 94wt%, the powdered graphite of 3wt%, the styrene butadiene ribber of 2wt%, the carboxymethyl cellulose of 1wt%, it is dispersed in the outstanding absurd creature of modulation in the water as organic solvent as adhesive as conductive material.This outstanding absurd creature is coated on the Copper Foil as the thickness 18 μ m of collector body, is dried the back compacting and makes negative pole.
＜anodal making 〉
Mix the lithium cobalt oxide powder of 91wt%, the powdered graphite of 6wt%, the polyvinylidene fluoride of 3wt%, it is distributed in the N-N-methyl-2-2-pyrrolidone N-is modulated into slurry.With this slurry be coated on as on the aluminium foil of collector body and dry back compacting make positive pole.
The making of＜lithium rechargeable battery 〉
Prepare the dividing plate that polyethylene porous membrane constitutes.Between positive pole and negative pole, insert dividing plate, be wound as vortex shape simultaneously and make electrode group.To be dissolved in the mixed solvent (volume ratio is 1: 2) of ethylene carbonate and carbonic acid methyl ethyl ester by 1mol/L as electrolytical lithium hexafluoro phosphate, modulate nonaqueous electrolytic solution.
With electrode group pack into the stainless steel manufacturing have in the round-ended cylinder shape container after, inject nonaqueous electrolyte liquid, implement to seal processing, be assembled into cylindric lithium rechargeable battery.
(embodiment 89～104)
The foundry alloy that the atom % ratio of table 14 expression is modulated press in heating, make its fusion after, in inert atmosphere gas, obtain alloy by single-roller method.That is, the chill roll of making to the BeCu alloy of the speed rotation of pressing rotating speed 30m/s from the nozzle bore of 1mm φ in inert atmosphere gas penetrates alloying metal solution, and chilling makes the thin ribbon shaped alloy.The alloy that obtains carries out heat treatment in 1 hour in 350 ℃ nitrogen atmosphere gas.
To the alloy of gained embodiment 89～104, carry out hot assay determination under the following conditions, observe exothermic peak, confirm to comprise non-equilibrium phase at 200～350 ℃.
＜thermoanalytical condition determination 〉
Use heat to analyze differential scanning calorimetry and under the programming rate of 10 ℃/min, inert atmosphere gas, measure, obtain from the exothermic peak of non-equilibrium phase when equilibrium phase changes.
Measure the metal structure of the alloy of embodiment 89～104 with X-ray diffraction method, confirm the monomer Al phase mutually of the element of conduct and lithium alloyage, and the existence with two kinds of intermetallic compound phases of stoichiometric composition shown in the following table 14.When comparing the composition between the intermetallic compound phase, discovery differs from one another with the kind of the element of lithium alloyage.Figure 10 represents the X-ray diffractogram (X ray, CuK α) of the alloy of embodiment 89.Occur respectively among Figure 10 based on the Al phase peak (using zero symbolic representation), based on Si 2The peak of Ni phase (using the △ symbolic representation), based on Al 3Peak (using the symbolic representation) from non-equilibrium phase (being fluorite structure substantially) appears in the peak of Ni phase (usefulness * symbolic representation) simultaneously.
Except that using this alloy powder, other operations are described identical with the foregoing description 73, make lithium rechargeable battery.
(comparative example 17)
(fiber diameter is 10 μ m, and average fiber length is 25 μ m, and face is d at interval through heat treated mesophase pitch based carbon fiber down at 3250 ℃ to remove the use of instead of alloy powder 002Be 0.3355nm, the specific area that the BET method obtains is 3m 2Beyond/g) the carbon dust, other operations are described identical with the foregoing description 73, make lithium rechargeable battery.
(comparative example 18)
Except that the instead of alloy powder used the Al powder of average grain diameter 10 μ m, other operations were described identical with the foregoing description 73, make lithium rechargeable battery.
(comparative example 19)
With machine-alloying to make Sn in 100 hours 30Co 70Alloy.The gained alloy is confirmed decrystallized by X-ray diffraction.Except that using this alloy, other operations are described identical with the foregoing description 73, make lithium rechargeable battery.
(comparative example 20～22)
As negative material, make Si with single-roller method 33Ni 67Alloy, (Al 0.1Si 0.9) 33Ni 67Alloy, Cu 50Ni 25Sn 25Alloy.The roller material is the BeCu alloy, and the roller rotating speed is 25m/s.The gained alloy is confirmed controlled micro crystallization with X-ray diffraction.The result who calculates average grain diameter with the Scherrer formula represents in the following Table 15.Except that using this alloy, other operations are described identical with the foregoing description 73, make lithium rechargeable battery.
(comparative example 23)
As negative material, make Fe by polishing 25Si 75Alloy.Calculating the average crystallite particle diameter with the Scherrer formula is 300nm.Except that using this alloy, other operations are described identical with the foregoing description 73, make lithium rechargeable battery.
(comparative example 23)
Fusion AlNi 2Behind the alloy that Ti represents, use the single-roller method chilling, obtain the sample of comparative example 24.Manufacturing conditions is to use the Cu roller of diameter 200mm, carries out in Ar atmosphere gas.Carry out X-ray diffraction and measure, it is single-phase to confirm as amorphous.Pulverize the gained sample, make the alloy powder of average grain diameter 9 μ m.Except that using this alloy powder, other operations are described identical with the foregoing description 73, make lithium rechargeable battery.
(comparative example 25～27)
Make Ni (Si by gas atomization 1-xAl x) 2X=0.1 in the alloy of expression, 0.2 and 0.25 three kinds.The gained sample is not heat-treated the powder of classification 15～45 μ m.Except that using this negative material, other operations are described identical with the foregoing description 73, make lithium rechargeable battery.
(comparative example 28)
Ratio modulation Al and Mo in 12: 1 carry out alloying by the electric arc fusion.Cooling rate after the dissolving is controlled to be and obtains Al phase, Al 12Mo reaches Al mutually 5The Mo phase.
Pulverize this alloy, making average grain diameter is the negative material of 20 μ m.Except that using this negative material, other operations are described identical with the foregoing description 73, make lithium rechargeable battery.
Secondary cell for gained embodiment 73～104 and comparative example 17～28 carries out following evaluation test, and its result is recorded in following table 13～15 together.
1) mensuration of the average crystallite particle diameter of crystallite phase
Shown in table 13～table 15, the alloy of embodiment 73～104 comprises the mixed microcrystalline phase that essence is made of mutually element monomer phase and intermetallic compound.Alloy to embodiment 73～104, the longest part of the crystal grain that TEM (transmission electron microscope) photograph taking is arrived is as particle diameter, in the photo (for example 100,000 times) that tem observation photographs, measure 50 adjacent crystalline particles, with their mean value as the average crystallite particle diameter of intermetallic compound phase.Monomer phase marine floated under the situation on island of intermetallic compound phase, only uses the size on island (crystal grain) to estimate.The multiplying power of TEM photo changes according to grain size.
2) the capacity sustainment rate of discharge capacity ratio and 300 circulation times
To each secondary cell, carry out following charge and discharge cycles test.That is, after 20 ℃ of charging currents with 1.5A are carried out charging in 2 hours, reached 4.2V, discharge into 2.7V with 1.5A again, measure the capacity sustainment rate of discharge capacity ratio and 300 circulation times.Discharge capacity represents that than the ratio that with the discharge capacity of comparative example 1 is at 1 o'clock capacity sustainment rate maximum discharge capacity is that the discharge capacity of 300 circulation times of 100% o'clock is represented.
3) rate characteristic
To each secondary cell, after the charging in 1 hour of pressing 1C ratio enforcement 4.2V constant-current constant-voltage under 20 ℃, the discharge capacity when mensuration discharges into 3.0V by the 0.1C ratio obtains the discharge capacity under the 0.1C.After the charging, the discharge capacity when mensuration discharges into 3.0V by 1C obtains the discharge capacity under the 1C under similarity condition.As the discharge capacity under the 100% expression 1C, its result is as rate characteristic with the discharge capacity under the 0.1C.
4) number of times that discharges and recharges that reaches heap(ed) capacity is measured and is reached the required cycle-index of maximum discharge capacity when each battery carries out charge and discharge cycles with 1C.
Table 13
Negative pole Battery behavior
Alloy composition Precipitated phase Average crystallite particle diameter (nm) The discharge capacity ratio Capacity sustainment rate (%) Rate characteristic (%) Reach the number of times that discharges and recharges of heap(ed) capacity
Embodiment 73 (Al 0.4Si 0.6) 77Ni 22Nb 1 ?Al+Al 3Ni+Si 2Ni+Si ????280 ??1.6 ??85 ????91 ????6
Embodiment 74 (Al 0.3Si 0.7) 78Ni 19Ti 2Mo 1 ?Al+Al 3Ni+Si 2Ni ????250 ??1.5 ??87 ????92 ????6
Embodiment 75 (Al 0.5Si 0.5) 76Ni 21V 2Ta 1 ?Al+Al 3Ni+Si 2Ni ????300 ??1.7 ??83 ????93 ????6
Embodiment 76 (Al 0.4Si 0.6) 80Ni 17Cr 2W 1 ?Al+Al 3Ni+Si 2Ni ????320 ??1.4 ??85 ????92 ????6
Embodiment 77 (Al 0.5Si 0.5) 80Fe 15Co 2Ta 1Pb 1 ?Al+Al 3Fe+Si 2Fe ????300 ??1.4 ??86 ????91 ????6
Embodiment 78 (Al 0.5Ge 0.5) 79Ni 16Fe 4Nb 1 ?Al+Al 3Ni+GeNi ????320 ??1.6 ??85 ????91 ????6
Embodiment 79 (Al 0.6Ge 0.4) 81Cu 14Ni 4Mo 1 ?Al+Al 2Cu+Ga 2Cu ????350 ??1.4 ??87 ????88 ????6
Embodiment 80 (Al 0.5In 0.5) 76Ni 23Zr 1 ?Al+Al 3Ni+In 3Ni 2 ????360 ??1.5 ??83 ????88 ????6
Embodiment 81 (Al 0.5Si 0.4Ge 0.1) 80Ni 15?Co 4Nb 1 ?Al+Al 3Ni+Si 2Ni ?+GeNi ????270 ??1.6 ??85 ????86 ????6
Embodiment 82 (Al 0.6Bi 0.4) 80Ni 18Nb 2 ?Al+Al 3Ni+Bi 3Ni ????250 ??1.4 ??84 ????88 ????6
Embodiment 83 (Al 0.4Si 0.6) 76Fe 20B 4 ?Al+Al 3Fe+Si 2Fe ????180 ??1.5 ??80 ????84 ????6
Embodiment 84 (Al 0.6Si 0.4) 72Ni 20Cr 2B 6 ?Al+Al 3Ni+Si 2Ni+ ?Al 3Ni 2 ????150 ??1.4 ??79 ????85 ????6
Embodiment 85 (Al 0.5Si 0.5) 74Ni 20Co 2B 4 ?Al+Al 3Ni+Si 2Ni ????140 ??1.5 ??80 ????85 ????6
Embodiment 86 (Mg 0.9Si 0.1) 75La 6Ni 18Nb 1 ?Mg+Si 2Ni+Mg 2Ni ????200 ??1.4 ??83 ????84 ????6
Embodiment 87 (Mg 0.7Al 0.3) 74Ce 10Cu 14Zr 2 ?Mg+AlCu+Mg 2Cu ????180 ??1.4 ??82 ????86 ????6
Embodiment 88 (Mg 0.8Si 0.2) 73Pr 8Ni 18Mo 1 ?Mg+Si 2Ni+Mg 2Ni ????230 ??1.4 ??83 ????85 ????6
Table 14
Negative pole Battery behavior
Alloy composition Precipitated phase Average crystallite particle diameter (nm) The discharge capacity ratio Capacity sustainment rate (%) Rate characteristic (%) Reach the number of times that discharges and recharges of heap(ed) capacity
Embodiment 89 (Al 0.5Si 0.5) 75Ni 20Cr 2Fe 2Cu 1 ?Al+Al 3Ni+Si 2The Ni+ non-equilibrium phase ????230 ????1.7 ????86 ????93 ????6
Embodiment 90 (Al 0.55Si 0.45) 75Ni 20Nb 1Mn 3Cr 1 ?Al+Al 3Ni+Si 2The Ni+ non-equilibrium phase ????220 ????1.7 ????88 ????91 ????6
Embodiment 91 (Al 0.5Si 0.5) 74Ni 14Co 3Nb 1Cu 2 ?Al+Al 3Ni+Si 2The Ni+ non-equilibrium phase ????200 ????1.6 ????89 ????90 ????6
Embodiment 92 (Al 0.55Si 0.45) 76Ni 14Fe 3W 1Co 3?Cu 3 ?Al+Al 3Ni+Si 2The Ni+ non-equilibrium phase ????190 ????1.6 ????87 ????90 ????6
Embodiment 93 (Al 0.5Si 0.5) 80Ni 12Mn 5Ta 1Fe 2 ?Al+Al 3Ni+Si 2The Ni+ non-equilibrium phase ????190 ????1.4 ????90 ????90 ????6
Embodiment 94 (Al 0.5Si 0.4Sn 0.1) 76Ni 19Mo 1Cu 2?Cr 2 ?Al+Al 3Ni+Si 2The Ni+ non-equilibrium phase ????180 ????1.5 ????90 ????90 ????6
Embodiment 95 (Al 0.55Si 0.25Ge 0.2) 76Ni 17Cu 5?Nb 1Mo 1 ?Al+Al 3Ni+Si 2The Ni+ non-equilibrium phase ????160 ????1.6 ????89 ????91 ????6
Embodiment 96 (Al 0.4Si 0.5Ga 0.1) 75Ni 19Co 3Nb 1?Mn 2 ?Al+Al 3Ni+Si 2The Ni+ non-equilibrium phase ????210 ????1.4 ????89 ????91 ????6
Embodiment 97 (Al 0.5Si 0.45Zn 0.05) 78Ni 14Fe 5Zr 1?Cu 2 ?Al+Al 3Ni+Si 2The Ni+ non-equilibrium phase ????180 ????1.5 ????89 ????92 ????6
Embodiment 98 (Al 0.55Si 0.45) 76Ni 18Cu 2Nb 1Co 3 ?Al+Al 3Ni+Si 2The Ni+ non-equilibrium phase ????200 ????1.5 ????90 ????93 ????6
Embodiment 99 (Al 0.5Si 0.5) 80Ni 11Cr 4B 5 ?Al+Al 3Ni+Si 2The Ni+ non-equilibrium phase ????150 ????1.5 ????84 ????86 ????6
Embodiment 100 (A 0.6Si 0.4) 77Ni 15Cu 3B 5 ?Al+Al 3Ni+Si 2The Ni+ non-equilibrium phase ????130 ????1.5 ????83 ????86 ????6
Embodiment 101 (Al 0.55Si 0.45) 82Ni 11Co 3B 4 ?Al+Al 3Ni+Si 2The Ni+ non-equilibrium phase ????160 ????1.5 ????84 ????87 ????6
Embodiment 102 (Mg 0.6Si 0.1Al 0.3) 76La 9Ni 13Cr 2 ?Mg+Al 3Ni+Si 2The Ni+ non-equilibrium phase ????160 ????1.6 ????84 ????84 ????6
Embodiment 103 (Mg 0.5Si 0.2Al 0.3) 77Ce 8Ni 13Fe 2 ?Mg+Al 3Ni+Si 2The Ni+ non-equilibrium phase ????160 ????1.4 ????84 ????86 ????6
Embodiment 104 (Mg 0.6Si 0.2Al 0.2) 76Nd 7Ni 3Cu 2?Nb 1 ?Mg+Al 3Ni+Si 2The Ni+ non-equilibrium phase ????120 ????1.4 ????84 ????85 ????6
Table 15
Negative pole Battery behavior
Alloy composition Precipitated phase Average crystallite particle diameter (nm) The discharge capacity ratio Capacity sustainment rate (%) Rate characteristic (%) Reach the number of times that discharges and recharges of heap(ed) capacity
Comparative example 17 ?C - ??5000 ??1 ??70 ??80 ????7
Comparative example 18 ?Al - ??10000 ??3 ??2 ??40 Can not measure
Comparative example 19 ?Si 30Co 70 - Amorphous ??1.1 ??80 ??82 ????9
Compare 20 ?Sn 33Ni 67 - ??40 ??1.0 ??82 ??85 ????9
Comparative example 21 ?(Al 0.1Si 0.9) 33Ni 67 - ??300 ??1.0 ??55 ??70 ????7
Comparative example 22 ?Cu 50Ni 25Sn 25 - ??200 ??1.0 ??70 ??75 ????8
Comparative example 23 ?Si 75Fe 25 - ??300 ??1.2 ??30 ??50 ????7
Comparative example 24 ?AlNi 2Ti (roller quench) AlNi 2Ti ??300 ??0.7 ??85 ??80 ????8
Comparative example 25 ?Ni(Si 0.9Al 0.1) 2(gas atomization) Si 2Ni+AlNi ??600 ??1.3 ??75 ??75 ????7
Comparative example 26 ?Ni(Si 0.8Al 0.2) 2(gas atomization) Si 2Ni+AlNi ??700 ??1.2 ??77 ??75 ????7
Comparative example 27 ?Ni(Si 0.75Al 0.25) 2(gas atomization) Si 2Ni+AlNi ??600 ??1.1 ??79 ??75 ????7
Comparative example 28 AlMo is alloy (slow cooling) Al+Al 12Mo+A l5Mo ??800 ??1.0 ??70 ??75 ????8
As known from Table 13, embodiment 73～78,80 and 81 alloy composition belong to above-mentioned general formula (9), (10) and (13), the alloy composition of embodiment 83～85 belongs to above-mentioned general formula (11), and the secondary cell of the alloy composition of embodiment 86～88 belongs to above-mentioned general formula (12).The group of alloys Chengdu of embodiment 73～88 comprise with the monomer of the element of lithium alloyage mutually with two or more intermetallic compound X mutually, therefore the discharge capacity ratio is more than 1.4, the capacity sustainment rate of 300 circulation times is more than 79%, rate characteristic is more than 84%, and the number of times that discharges and recharges that reaches heap(ed) capacity lacks to 6 times.Wherein, the secondary cell of embodiment 73～78 is compared with embodiment 79～88, and its rate characteristic is better.
As known from Table 14, embodiment 89～95 and 98 alloy composition belong to above-mentioned general formula (9), (10) and (13), the alloy composition of embodiment 99～101 belongs to above-mentioned general formula (11), and the secondary cell of the alloy composition of embodiment 102～104 belongs to above-mentioned general formula (12).The composition of the alloy of embodiment 89～104 all comprise with the monomer of the element of lithium alloyage mutually, intermetallic compound reaches non-equilibrium phase X mutually, therefore the discharge capacity ratio is more than 1.4, the capacity sustainment rate of 300 circulation times is more than 83%, rate characteristic is more than 84%, and the number of times that discharges and recharges that reaches heap(ed) capacity simultaneously lacks to 6 times.
In contrast, as known from Table 15, with carbide as the secondary cell of the comparative example 17 of negative material all poor aspect the capacity sustainment rate of discharge capacity, 300 circulation times and the rate characteristic than embodiment 73～104.Though the Al metal is compared discharge capacity as the secondary cell of the comparative example 18 of negative material with embodiment 73～104 high, the capacity sustainment rate of 300 circulation times and rate characteristic deterioration.
The secondary cell discharge capacity of comparative example 19～20 is higher than embodiment 73～104.Comparative example 21～23 and 25～28 secondary cell rate characteristic are lower than embodiment 73～104.In addition, the discharge capacity of the secondary cell of comparative example 24 is lower than embodiment 73～104 and compares.What the secondary cell of comparative example 17～28 (wherein except that comparative example 18 can not be measured) reached heap(ed) capacity discharges and recharges number of times all than embodiment more than 73～104.
Negative pole when observing repeatedly 300 cycle charge-discharges is not observed alloy and is changed, and separates out Al dendrite in the negative pole of comparative example 18 in the negative pole that uses among the embodiment 73～104.The initial cells discharge capacity of separating out the secondary cell that can infer comparative example 18 of Al dendrite is higher, but the capacity sustainment rate after 300 circulations obviously reduces.In addition, therefore easy the and electrolyte reaction of Al dendrite causes battery security to reduce.
In the foregoing description, the example that is applicable to the cylindrical shape rechargeable nonaqueous electrolytic battery has been described, but has been equally applicable to square rechargeable nonaqueous electrolytic battery, slim rechargeable nonaqueous electrolytic battery.
In the foregoing description, the example that is applicable to rechargeable nonaqueous electrolytic battery has been described, but has been applicable to the nonaqueous electrolyte primary cell, can improve its discharge capacity and discharge rate characteristic.
As above explanation the invention provides all superior nonaqueous electrolyte battery of discharge capacity, charge and discharge circulation life and discharge rate characteristic negative material and manufacture method, negative pole and nonaqueous electrolyte battery.
The invention provides the two all superior nonaqueous electrolyte battery of discharge capacity and rate characteristic negative material and manufacture method, negative pole and nonaqueous electrolyte battery.

Claims (63)

1. the nonaqueous electrolyte battery negative material is characterized in that, described material has following general formula (1): (Al 1-xSi x) aM bM ' cT d(1) Biao Shi composition, constitute by amorphous phase in fact, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni, Cu and M, above-mentioned M ' is for being selected from least a element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x＜0.75.
2. the nonaqueous electrolyte battery negative material is characterized in that, described material has following general formula (2): (A1 1-xA x) aM bM ' cT d(2) Biao Shi composition, constitute by amorphous phase in fact, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is for being selected from Fe, Co, Ni, at least a element of Cu and Mn, above-mentioned M ' is for being selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x≤0.9.
3. the nonaqueous electrolyte battery negative material is characterized in that, described material comprises the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (3): (Al 1-xSi x) aM bM ' cT d(3) Biao Shi composition, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x＜0.75.
4. nonaqueous electrolyte battery negative material as claimed in claim 3, its feature are that also described average crystallite particle diameter is more than the 5nm, below the 500nm.
5. nonaqueous electrolyte battery negative material as claimed in claim 3, its feature also is, in powder x-ray diffraction is measured, come the diffraction maximum of the intermetallic compound of self-contained Al and Si when the d value is at least 3.13～3.64_ and 1.92～2.23_, to occur, when the d value is at least 2.31～2.40_, occur from the diffraction maximum of Al.
6. nonaqueous electrolyte battery negative material as claimed in claim 3, its feature also is, described crystallite is a lattice constant in the cubic system fluorite structure more than the 5.42_, below the 6.3_ or lattice constant at the antifluorite structure more than the 5.42_, below the 6.3_ mutually.
7. nonaqueous electrolyte battery negative material as claimed in claim 3, its feature also be, in programming rate is 10 ℃/minute differential scanning calorimetry (DSC), occurs an exothermic peak at least in 200～450 ℃ scope.
8. nonaqueous electrolyte battery negative material as claimed in claim 3, its feature also is, aforementioned crystallite is the metal compound phase mutually that comprises Al, SI and aforementioned elements M mutually, at least a portion of the crystalline particle of compound phase is isolated each other between aforementioned metal separates out, and aforementioned nonaqueous electrolyte battery also possesses second phase of the Al that separates out based on the state of imbedding between above-mentioned isolated crystalline particle with negative material.
9. the nonaqueous electrolyte battery negative material is characterized in that, described material comprises the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (4): (A1 1-xA x) aM bM ' cT d(4) Biao Shi composition, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x≤0.9.
10. the nonaqueous electrolyte battery negative material is characterized in that, described material has following general formula (5): [(Al 1-xSi x) aM bM ' cT d] yLi z(5) Biao Shi composition, constitute by amorphous phase in fact, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni, Cu and Mn, above-mentioned M ' is for being selected from least a element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x＜0.75.y+z=100 atom %, 0＜z≤50 atom %.
11. nonaqueous electrolyte battery negative material, its feature are that also described material has following general formula (6): [(A1 1-xA x) aM bM ' cT d] yLi z(6) Biao Shi composition, constitute by amorphous phase in fact, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is for being selected from Fe, Co, Ni, at least a element of Cu and Mn, above-mentioned M ' is for being selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d, x, y, z satisfies a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x≤0.9, y+z=100 atom %, 0＜z≤50 atom %.
12. the nonaqueous electrolyte battery negative material is characterized in that, described material comprises the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (7): [Al 1-xSi x) aM bM ' cT d] yLi z(7) Biao Shi composition, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn structure, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x＜0.75, y+z=100 atom %, 0＜z≤50 atom %.
13. the nonaqueous electrolyte battery negative material is characterized in that, described material comprises the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (8): [(Al 1-xA x) aM bM ' cT d] yLi z(8) Biao Shi composition, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x≤0.9, y+z=100 atom %, 0＜z≤50 atom %.
14. nonaqueous electrolyte battery negative material, but described negative material occlusion discharges lithium, it is characterized in that, in programming rate is 10 ℃/minute differential scanning calorimetry (DSC), an exothermic peak appears in 200～450 ℃ scope at least, and in X-ray diffraction, the diffraction maximum based on crystalline phase appears.
15. nonaqueous electrolyte battery negative material, it is characterized in that, described material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, 1 μ m 2The number of above-mentioned intermetallic compound crystalline particle be 10～2000, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, and above-mentioned second separates out with the state of imbedding between above-mentioned isolated crystalline particle.
16. nonaqueous electrolyte battery negative material, it is characterized in that, described material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, average distance between above-mentioned intermetallic compound crystalline particle is below 500nm, and above-mentioned second separate out with the state of imbedding between above-mentioned isolated crystalline particle.
17. nonaqueous electrolyte battery negative material, it is characterized in that, described material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, it is the antifluorite structure of 5.42～6.3_ that above-mentioned intermetallic compound crystalline particle has cubic system fluorite structure or the lattice constant that lattice constant is 5.42～6.3_, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, and above-mentioned second separates out with the state of imbedding between above-mentioned isolated crystalline particle.
18. nonaqueous electrolyte battery negative material, described material possess comprise two or more can with the intermetallic compound of the element of lithium alloyage mutually, and based on can with the element of lithium alloyage second mutually, it is characterized in that, during powder x-ray diffraction is measured, when the d value is at least 3.13～3.64_ with 1.92～2.23_, occur, and when the d value is at least 2.31～2.40_, diffraction maximum occurs from above-mentioned second phase from above-mentioned intermetallic compound diffraction maximum mutually.
19. nonaqueous electrolyte battery negative material, it is characterized in that, possess with the monomer of the element of lithium alloyage mutually with a plurality of intermetallic compound phases, above-mentioned a plurality of intermetallic compound at least two kinds in mutually comprise respectively with the element of lithium alloyage and not with the element of lithium alloyage, the element of above-mentioned and lithium alloyage and above-mentioned not different each other with the combination of the element of lithium alloyage.
20. the nonaqueous electrolyte battery negative material is characterized in that, possess with the monomer of the element of lithium alloyage mutually, intermetallic compound mutually and non-equilibrium phase.
21. nonaqueous electrolyte battery negative material as claimed in claim 20, its feature are that also the average crystallite particle diameter of above-mentioned a plurality of intermetallic compound phases is in the scope of 5～500nm.
22. nonaqueous electrolyte battery negative material as claimed in claim 20, its feature also are to have following general formula (9): X xT1 yJ z(9) Biao Shi composition, wherein, above-mentioned X is at least two kinds of elements that are selected from Al, Si, Mg, Sn, Ge, In, Pb, P, C, above-mentioned T1 is at least a element that is selected from Fe, Co, Ni, Cr and Mn, above-mentioned J is at least a element that is selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, and above-mentioned x, y, z satisfy x+y+z=100 atom %, 50≤x≤90 respectively, 10≤y≤33,0≤z≤10.
23. nonaqueous electrolyte battery negative material as claimed in claim 20, its feature also are to have following general formula (10): A1 aT1 bJ cZ d(10) Biao Shi composition, wherein, above-mentioned A1 is at least a element that is selected from Si, Mg and Al, above-mentioned T1 is at least a element that is selected from Fe, Co, Ni, Cr, Mn, above-mentioned J is at least a element that is selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, above-mentioned Z is at least a element that is selected from C, Ge, Pb, P and Sn structure, above-mentioned a, b, c, d satisfy a+b+c+d=100 atom % respectively, 50≤a≤95,5≤b≤40,0≤c≤10,0≤d＜20.
24. nonaqueous electrolyte battery negative material as claimed in claim 20, its feature also are to have following general formula (11): T1 100-a-0(A2 1-xJ ' x) aB bJ c(11) Biao Shi composition, wherein, above-mentioned T1 is for being selected from Fe, Co, Ni, Cu, Cr, at least a element of Mn, above-mentioned A2 is at least a element that is selected from Al and Si, above-mentioned J is for being selected from Ti, Zr, Hf, V, Nb, Ta, Mo, at least a element of W and rare earth element, above-mentioned J ' is for being selected from C, Ge, Pb, P, at least a element of Sn and Mg, above-mentioned a, b, c, x satisfies 10 atom %≤a≤85 atom % respectively, 0＜b≤35 atom %, 0≤c≤10 atom %, 0≤x≤0.3, Sn contains quantity not sufficient 20 atom % (comprising 0 atom %).
25. nonaqueous electrolyte battery negative material as claimed in claim 20, its feature also are to have following general formula (12): (Mg 1-xA3 x) 100-a-b-c-d(RE) aT1 bM1 cA4 d(12) Biao Shi composition, wherein, above-mentioned A3 is for being selected from Al, at least a element of Si and Ge, above-mentioned RE is at least a element that is selected from Y and rare earth element, above-mentioned T1 is for being selected from Fe, Co, Ni, Cu, Cr, at least a element of Mn, above-mentioned M1 is for being selected from Ti, Zr, Hf, V, Nb, Ta, Mo, at least a element of W, above-mentioned A4 is for being selected from Sn, Pb, Zn, at least a element of P and C, above-mentioned a, b, c, d, x satisfies 0＜a≤40 atom % respectively, 0＜b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0≤x≤0.5.
26. nonaqueous electrolyte battery negative material as claimed in claim 20, its feature also are to have following general formula (13): (A1 1-xA5 x) aT1 bJ cZ d(13) Biao Shi composition, wherein, above-mentioned A5 is at least a element that is selected from Si and Mg, above-mentioned T1 is at least a element that is selected from Fe, Co, Ni, Cr, Mn, above-mentioned J is at least a element that is selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, above-mentioned Z is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x satisfy a+b+c+d=100 atom % respectively, 50≤a≤95,5≤b≤40,0≤c≤10,0≤d＜20,0＜x≤0.9.
27. a negative pole is characterized in that, described negative pole comprises and has following general formula (1): (Al 1-xSi x) aM bM ' cT d(1) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni, Cu and M, above-mentioned M ' is for being selected from least a element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x＜0.75.
28. a negative pole is characterized in that, described negative pole comprises and has following general formula (2): (A1 1-xA x) aM bM ' cT d(2) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is for being selected from Fe, Co, Ni, at least a element of Cu and Mn, above-mentioned M ' is for being selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atoms, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x≤0.9.
29. a negative pole is characterized in that, described negative pole comprises and possesses the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (3): (Al 1-xSi x) aM bM ' cT d(3) alloy of Biao Shi composition, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x＜0.75.
30. a negative pole is characterized in that, described negative pole comprises and possesses the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (4): (A1 1-xA x) aM bM ' cT d(4) alloy of Biao Shi composition, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x≤0.9.
31. a negative pole is characterized in that, described negative pole comprises and has following general formula (5): [(Al 1-xSi x) aM bM ' cT d] yLi z(5) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni, Cu and Mn, above-mentioned M ' is for being selected from least a element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x＜0.75, y+z=100 atom %, 0＜z≤50 atom %.
32. a negative pole is characterized in that, described negative pole comprises and has following general formula (6): [(Al 1-xA x) aM bM ' cT d] yLi z(6) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is for being selected from Fe, Co, Ni, at least a element of Cu and Mn, above-mentioned M ' is for being selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d, x, y, z satisfies a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x≤0.9, y+z=100 atom %, 0＜z≤50 atom %.
33. a negative pole is characterized in that, described negative pole comprises and possesses the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (7): [(Al 1-xSi x) aM bM ' cT d] yLi z(7) alloy of Biao Shi composition, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn structure, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x＜0.75, y+z=100 atom %, 0＜z≤50 atom %.
34. a negative pole is characterized in that, described negative pole comprises and possesses the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (8): [(Al 1-xA x) aM bM ' cT d] yLi z(8) alloy of Biao Shi composition, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x≤0.9, y+z=100 atom %, 0＜z≤50 atom %.
35. negative pole, but comprise the negative material that occlusion discharges lithium, it is characterized in that, above-mentioned negative material is in programming rate is 10 ℃/minute differential scanning calorimetry (DSC), an exothermic peak appears in 200～450 ℃ scope at least, and in X-ray diffraction, the diffraction maximum based on crystalline phase appears.
36. negative pole, comprise negative material, it is characterized in that, above-mentioned negative material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, 1 μ m 2The number of above-mentioned intermetallic compound crystalline particle be 10～2000, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, and above-mentioned second separates out with the state of imbedding between above-mentioned isolated crystalline particle.
37. negative pole, comprise negative material, it is characterized in that, above-mentioned negative material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, average distance between above-mentioned intermetallic compound crystalline particle is below 500nm, and above-mentioned second separate out with the state of imbedding between above-mentioned isolated crystalline particle.
38. negative pole, comprise negative material, it is characterized in that, above-mentioned negative material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, it is the antifluorite structure of 5.42～6.3_ that above-mentioned intermetallic compound crystalline particle has cubic system fluorite structure or the lattice constant that lattice constant is 5.42～6.3_, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, and above-mentioned second separates out with the state of imbedding between above-mentioned isolated crystalline particle.
39. negative pole, comprise negative material, it is characterized in that, above-mentioned negative material possess comprise two or more can with the intermetallic compound of the element of lithium alloyage mutually, and based on can with the element of lithium alloyage second mutually, during powder x-ray diffraction is measured, when the d value is at least 3.13～3.64_ with 1.92～2.23_, occur, and when the d value is at least 2.31～2.40_, diffraction maximum occurs from above-mentioned second phase from above-mentioned intermetallic compound diffraction maximum mutually.
40. negative pole, comprise negative material, above-mentioned negative material possess with the monomer of the element of lithium alloyage mutually with a plurality of intermetallic compound phases, it is characterized in that, above-mentioned a plurality of intermetallic compound at least two kinds in mutually comprise respectively with the element of lithium alloyage and not with the element of lithium alloyage, the element of above-mentioned and lithium alloyage and above-mentioned not different each other with the combination of the element of lithium alloyage.
41. a negative pole is characterized in that, comprises negative material, above-mentioned negative material possess with the monomer of the element of lithium alloyage mutually, intermetallic compound mutually and non-equilibrium phase.
42. nonaqueous electrolyte battery is characterized in that, possesses negative pole, positive pole and nonaqueous electrolyte, described negative pole comprises and has following general formula (1): (Al 1-xSi x) aM bM ' cT d(1) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni, Cu and M, above-mentioned M ' is for being selected from least a element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x＜0.75.
43. nonaqueous electrolyte battery is characterized in that, possesses negative pole, positive pole and nonaqueous electrolyte, described negative pole comprises and has following general formula (2): (A1 1-xA x) aM bM ' cT d(2) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is for being selected from Fe, Co, Ni, at least a element of Cu and Mn, above-mentioned M ' is for being selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x≤0.9
44. nonaqueous electrolyte battery is characterized in that, possesses negative pole, positive pole and nonaqueous electrolyte, described negative pole comprises and possesses the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (3): (Al 1-xSi x) aM bM ' cT d(3) alloy of Biao Shi composition, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x＜0.75.
45. nonaqueous electrolyte battery is characterized in that, possesses negative pole, positive pole and nonaqueous electrolyte, described negative pole comprises and possesses the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (4): (Al 1-xA x) aM bM ' cT d(4) alloy of Biao Shi composition, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d and x satisfy a+b+c+d=100 atom % respectively, 50 atom %≤a≤95 atom %, 5 atom %≤b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0＜x≤0.9.
46. nonaqueous electrolyte battery is characterized in that, possesses negative pole, positive pole and nonaqueous electrolyte, described negative pole comprises and has following general formula (5): [(A1 1-xSi x) aM bM ' cT d] yLi z(5) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni, Cu and Mn, above-mentioned M ' is for being selected from least a element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x＜0.75, y+z=100 atom %, 0＜z≤50 atom %.
47. nonaqueous electrolyte battery is characterized in that, possesses negative pole, positive pole and nonaqueous electrolyte, described negative pole comprises and has following general formula (6): [(A1 1-xA x) aM bM ' cT d] yLi z(6) Biao Shi composition, the alloy that constitutes by amorphous phase in fact, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is for being selected from Fe, Co, Ni, at least a element of Cu and Mn, above-mentioned M ' is for being selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, at least a element of W and rare earth element, above-mentioned T is for being selected from C, Ge, Pb, at least a element of P and Sn, above-mentioned a, b, c, d, x, y, z satisfies a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x≤0.9, y+z=100 atom %, 0＜z≤50 atom %
48. nonaqueous electrolyte battery is characterized in that, possesses negative pole, positive pole and nonaqueous electrolyte, described negative pole comprises and possesses the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (7): [(Al 1-xSi x) aM bM ' cT d] yLi z(7) alloy of Biao Shi composition, wherein, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn structure, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x＜0.75, y+z=100 atom %, 0＜z≤50 atom %.
49. nonaqueous electrolyte battery is characterized in that, possesses negative pole, positive pole and nonaqueous electrolyte, described negative pole comprises and possesses the crystallite phase of average crystallite particle diameter below 500nm, and has following general formula (8): [(Al 1-xA x) aM bM ' cT d] yLi z(8) alloy of Biao Shi composition, wherein, above-mentioned A is Mg or Si and Mg, above-mentioned M is at least a element that is selected from Fe, Co, Ni and Mn, above-mentioned M ' is for being selected from least a element of Cu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and rare earth element, above-mentioned T is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x, y, z satisfy a+b+c+d=1 respectively, 0.5≤a≤0.95,0.05≤b≤0.4,0≤c≤0.1,0≤d＜0.2,0＜x≤0.9, y+z=100 atom %, 0＜z≤50 atom %.
50. nonaqueous electrolyte battery, possess negative pole, positive pole and nonaqueous electrolyte, but described negative pole comprises the negative material that occlusion discharges lithium, it is characterized in that, above-mentioned negative material is in programming rate is 10 ℃/minute differential scanning calorimetry (DSC), in 200～450 ℃ scope, occur an exothermic peak at least, and in X-ray diffraction, diffraction maximum occurs based on crystalline phase.
51. nonaqueous electrolyte battery, possess the negative pole, positive pole and the nonaqueous electrolyte that comprise negative material, it is characterized in that, above-mentioned negative material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, 1 μ m 2The number of above-mentioned intermetallic compound crystalline particle be 10～2000, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, and above-mentioned second separates out with the state of imbedding between above-mentioned isolated crystalline particle.
52. nonaqueous electrolyte battery, possesses the negative pole that comprises negative material, positive pole and nonaqueous electrolyte, it is characterized in that, above-mentioned negative material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, average distance between above-mentioned intermetallic compound crystalline particle is below 500nm, and above-mentioned second separate out with the state of imbedding between above-mentioned isolated crystalline particle.
53. nonaqueous electrolyte battery, possesses the negative pole that comprises negative material, positive pole and nonaqueous electrolyte, it is characterized in that, above-mentioned negative material possess first mutually with second mutually, wherein, first comprises mutually that to contain two or more can be the intermetallic compound crystalline particle of 5～500nm with the average crystallite particle diameter of the element of lithium alloyage, second based on can with the element of lithium alloyage, it is the antifluorite structure of 5.42～6.3_ that above-mentioned intermetallic compound crystalline particle has cubic system fluorite structure or the lattice constant that lattice constant is 5.42～6.3_, at least a portion of above-mentioned intermetallic compound crystalline particle is isolated each other to be separated out, and above-mentioned second separates out with the state of imbedding between above-mentioned isolated crystalline particle.
54. nonaqueous electrolyte battery, possess the negative pole, positive pole and the nonaqueous electrolyte that comprise negative material, it is characterized in that, above-mentioned negative material possess comprise two or more can with the intermetallic compound of the element of lithium alloyage reach mutually based on can with second phase of the element of lithium alloyage, during powder x-ray diffraction is measured, when the d value is at least 3.13～3.64_ with 1.92～2.23_, occur, and when the d value is at least 2.31～2.40_, diffraction maximum occurs from above-mentioned second phase from above-mentioned intermetallic compound diffraction maximum mutually.
55. nonaqueous electrolyte battery, possess the negative pole, positive pole and the nonaqueous electrolyte that comprise negative material, above-mentioned negative material possess with the monomer of the element of lithium alloyage mutually with a plurality of intermetallic compound phases, it is characterized in that, above-mentioned a plurality of intermetallic compound at least two kinds in mutually comprise respectively with the element of lithium alloyage and not with the element of lithium alloyage, the element of above-mentioned and lithium alloyage and above-mentioned not different each other with the combination of the element of lithium alloyage.
56. nonaqueous electrolyte battery is characterized in that, possesses the negative pole, positive pole and the nonaqueous electrolyte that comprise negative material, above-mentioned negative material possess with the monomer of the element of lithium alloyage mutually, intermetallic compound mutually and non-equilibrium phase.
57. the nonaqueous electrolyte battery manufacture method of negative material, it is characterized in that, the metallic solution that will comprise the first～the element is expelled on single roller, make thickness of slab reach 10～500 μ m by chilling, and make and comprise compound between high-melting point metal mutually and second mutually the metal structure curing, intermetallic compound comprises above-mentioned the first～the element mutually, second based on above-mentioned first element and lower than the fusing point of above-mentioned intermetallic compound phase, wherein, above-mentioned first element is for being selected from Al, In, Pb, Ga, Sb, Bi, Sn, at least a element of Zn, above-mentioned second element is for being selected from except that Al, In, Pb, Ga, Sb, Bi, Sn, beyond the Zn can be with the element of lithium alloyage at least a, above-mentioned element is the element that can form intermetallic compound with first element and second element.
58. the nonaqueous electrolyte battery manufacture method of negative material, it is characterized in that, to comprise Al, element N1, the metallic solution of element N2 and element N3 is expelled on single roller, make thickness of slab reach 10～500 μ m by chilling, and make and comprise compound between high-melting point metal mutually and second mutually the metal structure curing, intermetallic compound comprises Al mutually, element N1 and element N2, second based on Al and lower than the fusing point of above-mentioned intermetallic compound phase, wherein, above-mentioned element N1 is Si or Si and Mg, above-mentioned element N2 is at least a element that is selected from Ni and Co, above-mentioned element N3 is for being selected from In, Bi, Pb, Sn, Ga, Sb, Zn, Fe, Cu, Mn, Cr, Ti, Zr, Nb, at least a element of Ta and rare earth element, Al content in the above-mentioned metallic solution is h atom %, element N1 content in the above-mentioned metallic solution is i atom %, element N2 content in the above-mentioned metallic solution is j atom %, when the element N3 content in the above-mentioned metallic solution is k atom %, above-mentioned h, i, j, k satisfies 12.5≤h＜95 respectively, 0＜i≤71,5≤j≤40,0≤k＜20.
59. nonaqueous electrolyte battery is characterized in that with the manufacture method of negative material, possesses to make by single-roller method to have following general formula (9): X xT1 yJ z(9) the metallic solution chilling of Biao Shi composition makes in fact the step of the alloy that is made of amorphous phase, and under the temperature more than the crystallized temperature of above-mentioned alloy above-mentioned alloy is implemented heat treated step; Wherein, above-mentioned X is at least two kinds of elements that are selected from Al, Si, Mg, Sn, Ge, In, Pb, P, C, above-mentioned T1 is at least a element that is selected from Fe, Co, Ni, Cr and Mn, above-mentioned J is at least a element that is selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, above-mentioned x, y, z satisfy x+y+z=100 atom % respectively, 50≤x≤90,10≤y≤33,0≤z≤10.
60. nonaqueous electrolyte battery is characterized in that with the manufacture method of negative material, possesses to make by single-roller method to have following general formula (10): A1 aT1 bJ cZ d(10) the metallic solution chilling of Biao Shi composition makes in fact the step of the alloy that is made of amorphous phase, and under the temperature more than the crystallized temperature of above-mentioned alloy above-mentioned alloy is implemented heat treated step; Wherein, above-mentioned A1 is at least a element that is selected from Si, Mg and Al, above-mentioned T1 is at least a element that is selected from Fe, Co, Ni, Cr, Mn, above-mentioned J is at least a element that is selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, and above-mentioned Z is at least a element that is selected from C, Ge, Pb, P and Sn structure, and above-mentioned a, b, c, d satisfy a+b+c+d=100 atom % respectively, 50≤a≤95,5≤b≤40,0≤c≤10,0≤d＜20.
61. nonaqueous electrolyte battery is characterized in that with the manufacture method of negative material, possesses to make by single-roller method to have following general formula (11): Tl 100-a-b-c(A2 1-xJ ' x) aB bJ c(11) the metallic solution chilling of Biao Shi composition makes in fact the step of the alloy that is made of amorphous phase, and under the temperature more than the crystallized temperature of above-mentioned alloy above-mentioned alloy is implemented heat treated step; Wherein, above-mentioned T1 is at least a element that is selected from Fe, Co, Ni, Cu, Cr, Mn, above-mentioned A2 is at least a element that is selected from Al and Si, above-mentioned J is at least a element that is selected from Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, above-mentioned J ' is for being selected from least a element of C, Ge, Pb, P, Sn and Mg, above-mentioned a, b, c, x satisfy 10 atom %≤a≤85 atom % respectively, 0＜b≤35 atom %, 0≤c≤10 atom %, 0≤x≤0.3, Sn contains quantity not sufficient 20 atom % (comprising O atom %).
62. nonaqueous electrolyte battery is characterized in that with the manufacture method of negative material, possesses to make by single-roller method to have following general formula (12): (Mg 1-xA3 x) 100-a-b-c-d(RE) aT1 bM1 cA4 d(12) the metallic solution chilling of Biao Shi composition makes in fact the step of the alloy that is made of amorphous phase, and under the temperature more than the crystallized temperature of above-mentioned alloy above-mentioned alloy is implemented heat treated step; Wherein, above-mentioned A3 is at least a element that is selected from Al, Si and Ge, above-mentioned RE is at least a element that is selected from Y and rare earth element, above-mentioned T1 is at least a element that is selected from Fe, Co, Ni, Cu, Cr, Mn, above-mentioned M1 is at least a element that is selected from Ti, Zr, Hf, V, Nb, Ta, Mo, W, above-mentioned A4 is at least a element that is selected from Sn, Pb, Zn, P and C, above-mentioned a, b, c, d, x satisfy 0＜a≤40 atom % respectively, 0＜b≤40 atom %, 0≤c≤10 atom %, 0≤d＜20 atom %, 0≤x≤0.5.
63. nonaqueous electrolyte battery is characterized in that with the manufacture method of negative material, possesses to make by single-roller method to have following general formula (13): (A1 1-xA5 x) aT1 bJ cZ d(13) the metallic solution chilling of Biao Shi composition makes in fact the step of the alloy that is made of amorphous phase, and under the temperature more than the crystallized temperature of above-mentioned alloy above-mentioned alloy is implemented heat treated step; Wherein, above-mentioned A5 is at least a element that is selected from Si and Mg, above-mentioned T1 is at least a element that is selected from Fe, Co, Ni, Cr, Mn, and above-mentioned J is at least a element that is selected from Cu, Ti, Zr, Hf, V, Nb, Ta, Mo, W and rare earth element, and above-mentioned Z is at least a element that is selected from C, Ge, Pb, P and Sn, above-mentioned a, b, c, d, x satisfy a+b+c+d=100 atom % respectively, 50≤a≤95,5≤b≤40,0≤c≤10,0≤d＜20,0＜x≤0.9.
CN02147000A 2001-09-28 2002-09-28 Negative electrode material for nonelectrolyte cell and making method, negative electrode and cell Pending CN1419303A (en)

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