WO2012008540A1 - Matériau d'électrode négative en alliage de si présentant une excellente conductivité électrique, et procédé de fabrication de celui-ci - Google Patents

Matériau d'électrode négative en alliage de si présentant une excellente conductivité électrique, et procédé de fabrication de celui-ci Download PDF

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Publication number
WO2012008540A1
WO2012008540A1 PCT/JP2011/066139 JP2011066139W WO2012008540A1 WO 2012008540 A1 WO2012008540 A1 WO 2012008540A1 JP 2011066139 W JP2011066139 W JP 2011066139W WO 2012008540 A1 WO2012008540 A1 WO 2012008540A1
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Prior art keywords
phase
electrode material
negative electrode
silicon
sicu
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PCT/JP2011/066139
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English (en)
Japanese (ja)
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友紀 廣野
哲朗 仮屋
柳本　勝
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山陽特殊製鋼株式会社
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Publication of WO2012008540A1 publication Critical patent/WO2012008540A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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

Definitions

  • the present invention relates to a Si-based alloy negative electrode material excellent in electrical conductivity of an electricity storage device such as a lithium ion secondary battery or a hybrid capacitor that accompanies movement of lithium ions during charge and discharge, and a method for producing the same.
  • lithium-ion secondary batteries as hybrid electric storage devices for automobiles and home use and hybrid capacitors in which the reaction mechanism is applied to the negative electrode are also actively developed.
  • a negative electrode material for such electricity storage devices carbonaceous materials such as natural graphite, artificial graphite, and coke that can occlude and release lithium ions are used.
  • Si has attracted attention as a material that can replace carbonaceous materials.
  • the reason is that since Si can form a compound represented by Li 22 Si 5 and occlude a large amount of lithium, the capacity of the negative electrode can be greatly increased compared to the case where a carbonaceous material is used, As a result, there is a possibility that the storage capacity of the lithium ion secondary battery or the hybrid capacitor can be increased.
  • the Si phase is pulverized by repeated expansion when alloying with lithium during charging and contraction when dealloying with lithium during discharging.
  • the lifetime of the electricity storage device is extremely short because problems such as the Si phase dropping off from the electrode substrate or the lack of electrical conductivity between the Si phases occur.
  • Si has poor electrical conductivity compared to carbonaceous materials and metal-based materials, and the efficient movement of electrons associated with charge / discharge is limited, so the negative electrode material supplements electrical conductivity such as carbonaceous materials.
  • the negative electrode material supplements electrical conductivity such as carbonaceous materials.
  • Patent Document 1 Japanese Patent Laid-Open No. 2001-297757
  • Patent Document 2 Japanese Patent Laid-Open No. 10-31804
  • Patent Document 3 Japanese Unexamined Patent Application Publication No. 2004-228059
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2005-44672
  • a material in which at least a part of a parent lithium phase such as Si is surrounded by an intermetallic compound is an industrially preferable process because a parent lithium phase and an intermetallic compound are formed during a solidification process after melting.
  • a parent lithium phase and an intermetallic compound are formed during a solidification process after melting.
  • the present inventors have formed an intermetallic compound with a Cu element, among other intermetallic compounds with the Si phase, to form SiCu 3 that is particularly excellent in electrical conductivity. I found out. Moreover, the present inventors have found that a composite phase consisting of Si phase and SiCu 3 alloy, utilizing the large discharge capacity of Si, and, SiCu 3 with excellent inherent low electrical conductivity Si electrical conductivity It has also been found that both the discharge capacity and the cycle life are improved when the average particle size of the Si phase is 10 ⁇ m or less.
  • an object of the present invention is to make it possible to provide a secondary negative electrode material having both excellent discharge capacity and cycle life and excellent electrical conductivity.
  • a Si-based alloy negative electrode material having excellent electrical conductivity wherein the negative electrode material is Si base phase, which is a partially substituted Si phase in which the Si phase or a part of Si is substituted with one or more elements selected from the group consisting of C, Ge, Sn, Pb, Al and P
  • the negative electrode material is Si base phase, which is a partially substituted Si phase in which the Si phase or a part of Si is substituted with one or more elements selected from the group consisting of C, Ge, Sn, Pb, Al and P
  • a SixCuy phase made of an alloy having a composition of SixCuy (where x ⁇ y), which is an intermetallic compound of Si and Cu;
  • a powder composed of a composite phase of There is provided a Si-based alloy negative electrode material in which the Si base phase has a particle shape having an average particle size of 10 ⁇ m or less, and at least a part of the Si base phase is surrounded by a SixCuy phase.
  • a method for producing a Si-based alloy negative electrode material having excellent electrical conductivity Melting a SiCu-based alloy having the overall composition of the negative electrode material to form a molten metal; A step of quenching the molten metal by a gas atomizing method, a disk atomizing method or a liquid quenching method; A manufacturing method is provided comprising:
  • FIG. 1 shows a phase diagram of the Si—Cu binary system.
  • Si precipitates as the primary crystal when the liquidus temperature is reached (eg, 1200 ° C. in the case of Si: 64 atomic% —Cu: 36 atomic%).
  • This primary crystal precipitates as a granular crystal if the cooling rate is high as in the liquid quenching method or the atomizing method, and when the temperature reaches the solidus temperature (802 ° C.), a eutectic reaction between Si and SiCu 3 occurs and solidification is completed.
  • the phase diagram on the Si rich side it is a eutectic reaction between the Si phase and the SiCu 3 phase, and the Si phase surrounds the SiCu 3 phase.
  • combinations of elements for alloying other than Cu and Si include, for example, Fe—Si, Ni—Si, Mn—Si, Co—Si, Cr—Si, Si—W, Mo—Si, Nb—Si, and Si. -Ti, Si-V, etc. are conceivable. However, it will both FeSi 2, NiSi 2, CoSi 2 , CrSi 2, WSi 2, MoSi 2, MnSi 2, NbSi 2, TiSi 2, VSi 2 and the Si-rich composition remains than metal elements .
  • SiCu 3 has a metal-rich composition compared to other silicide compounds.
  • Cu 1.73 ⁇ 10 ⁇ 4 ⁇ ⁇ m
  • Fe 10 ⁇ 10 ⁇ 4 ⁇ ⁇ m
  • Ni 11.8 ⁇ 10 ⁇ 4 ⁇ ⁇ m
  • Co 9.71 ⁇ 10 ⁇ 4 ⁇ ⁇ m
  • simple substance Cu had a very low resistance value compared to other transition metal elements, and was a combination of Si and the transition metal having the lowest resistance value It is.
  • the combination of Si and transition metal element having the lowest resistance value among the transition metal silicide compounds is Si and Cu.
  • Si which is a raw material of a transition metal silicide compound, has an extremely low resistance value compared to other simple transition metal elements, and is never obtained by a combination of transition metal elements of Si phase and Si.
  • a metal-rich compound phase (SixCuy (x ⁇ y)), for example, an SiCu 3 phase between Cu and Cu elements.
  • SiCu 3 is an Si-rich intermetallic compound (FeSi 2 , NiSi 2 , CoSi 2 , CrSi 2 , WSi 2 , MoSi 2 , MnSi 2 , NbSi 2 , TiSi 2 , It can be seen that the electric conductivity is higher than that of VSi 2 ).
  • the SiCu 3 phase since the SiCu 3 phase is not alloyed with lithium, the SiCu 3 phase itself does not expand or contract even if it is repeatedly charged (lithium enters the negative electrode) -discharge (lithium comes out from the negative electrode). On the contrary, since the SiCu 3 phase has a lower hardness than Si, it can be a phase that relieves stress due to a large volume expansion and contraction of Si caused by the reaction between Si and lithium.
  • the average particle size of the Si phase or Si phase having Si as the main phase is 10 ⁇ m or less, preferably 8 ⁇ m or less, more preferably 5 ⁇ m or less, still more preferably 3 ⁇ m or less, and most preferably 2 ⁇ m or less. This is because if the average particle size is large, the cycle life is reduced.
  • the reaction between Si and lithium occurs at the contact portion of the electrolyte.
  • “average particle diameter” refers to a number-based D50 particle diameter. For large Si particles having a maximum particle size exceeding 10 ⁇ m, the reaction with lithium during the initial charging reaction stops only at the surface part of the Si particle in contact with the electrolytic solution, and it takes time until the electrolytic solution penetrates. The internal reaction will not be performed.
  • Si is a main phase, and is a group of phases composed of one or more elements that can reversibly combine and segregate with Li.
  • this phase one or two or more elements selected from the group consisting of C, Ge, Sn, Pb, Al, and P, which are such elements, are substituted as a part of Si and partially substituted Si phase may be used.
  • the composition ratio is not particularly limited, but the ratio of C, Ge, Sn, Pb, Al, and P is replaced by Si when Si is 1 when these are M.
  • the total amount of M is preferably less than 0.5, more preferably less than 0.2, even more preferably less than 0.1, and most preferably less than 0.05.
  • the composition of the SixCuy phase needs to be x ⁇ y.
  • FeSi 2 does not become Fe rich. Since an alloy of Fe element and Si forms a Si-rich compound phase, the electrical conductivity is inferior, and the electrical conductivity between Si phases is prevented from being lowered due to the refinement of Si caused by repeated charge and discharge. Therefore, the composition of the SixCuy phase is set to x ⁇ y.
  • FIG. 2 shows a cross-sectional SEM image of the Si—Cu alloy powder.
  • the black portion is the embedded resin 1
  • the gray portion is the Si phase 2
  • the white portion is the SiCu 3 phase 3. Focusing particularly on the central Si—Cu particles, the gray Si phase 2 is surrounded by the white SiCu 3 phase in the portion A inside the particles. However, it can be seen that in the portion B of the particle surface portion, the gray Si phase 2 is exposed on the particle surface. Thus, at least a part of the Si phase is surrounded by the SixCuy phase.
  • the negative electrode material of the present invention as a whole is one or more selected from the group consisting of 10 to 50% Cu, 0 to 10% C, Ge, Sn, Pb, Al and P in at%. , And the balance Si and inevitable impurities, more preferably selected from the group consisting of 18-36% Cu, 0-3% C, Ge, Sn, Pb, Al and P It has the composition which consists of 1 type (s) or 2 or more types and balance Si and an unavoidable impurity. These preferable overall compositions also apply to the SiCu-based alloy as a starting material for producing the negative electrode material of the present invention.
  • a negative electrode material powder having the composition shown in Table 1 was prepared by a liquid quenching method, a gas atomizing method, or a disk atomizing method as described below.
  • a raw material having a predetermined composition is placed in a quartz tube having pores at the bottom, melted at a high frequency in an Ar atmosphere to form a molten metal, and after the molten metal is discharged on the surface of a rotating copper roll, the copper roll A quenching ribbon was produced by the quenching effect. Thereafter, the produced ribbon was sealed in a zirconia pot container together with zirconia balls in an Ar atmosphere, and powdered by mechanical milling.
  • a raw material of a predetermined structure is placed in a quartz crucible having pores at the bottom, heated and melted in a high-frequency induction melting furnace in an Ar gas atmosphere, and then gas is injected and discharged in the Ar gas atmosphere, followed by rapid cooling.
  • the desired gas atomized fine powder was obtained by solidification.
  • a raw material having a predetermined structure is placed in a quartz crucible having pores at the bottom, heated and melted in a high-frequency induction melting furnace in an Ar gas atmosphere, and then on a rotating disk (40000 to 60000 r) in an Ar gas atmosphere. P.m.) and then rapidly solidified by cooling to obtain the desired disc atomized fine powder.
  • a so-called bipolar coin-type cell using lithium metal as a counter electrode was used.
  • a negative electrode active material Si—Cu, etc.
  • a conductive material acetylene black
  • a binder polyvinylidene fluoride
  • a dispersion N-methylpyrrolidone
  • the solvent was evaporated by drying under reduced pressure with a vacuum dryer, and then punched into a shape suitable for a coin cell.
  • lithium for the counter electrode was punched into a shape suitable for the coin cell.
  • a 1: 7 mixed solvent of ethylene carbonate and dimethyl carbonate was used, and 1 mol of LiPF 6 (lithium hexafluorophosphate) was dissolved in the electrolyte as a supporting electrolyte to prepare an electrolyte for use in a lithium ion battery. . Since this electrolyte solution must be handled in an inert atmosphere with dew point control, all the cells were assembled in a glove box with an inert atmosphere. The separator was cut out into a shape suitable for a coin cell, and then held in the electrolyte for several hours under reduced pressure in order to sufficiently permeate the electrolyte into the separator. Thereafter, the negative electrode, separator, and counter electrode lithium punched in the previous step were combined in that order, and the battery was fully filled with the electrolyte.
  • LiPF 6 lithium hexafluorophosphate
  • the charge capacity and discharge capacity were measured at a temperature of 25 ° C. Charging is performed at a current density of 0.50 mA / cm 2 until the potential is equal to that of the metal lithium electrode (0 V), while discharging is performed up to 1.5 V at the same current value (0.50 mA / cm 2 ).
  • One cycle of charge-discharge The charge capacity at the first cycle at this time was evaluated as the initial capacity value. Further, as the cycle life, the discharge capacity of the first cycle was measured, and the discharge capacity of the negative electrode using the negative electrode material was measured. The discharge capacity of the 100th cycle was measured, and used as a measure of the cycle life.
  • Nos. 1 to 14 are examples of the present invention. 15 to 26 show comparative examples.
  • Invention Example No. 1 to 14 are powders composed of a composite phase of a SixCuy phase composed of a SixCuy alloy which is an intermetallic compound of Si phase and Si and Cu, and the composition of the SixCuy phase is x ⁇ y, and Si is the main phase. Since the average particle size of the Si phase is 10 ⁇ m or less, the condition of the present invention is satisfied. Moreover, the discharge capacity of the 1st cycle showed 1000 mAh / g or more. In addition, due to the improvement in electrical conductivity by the intermetallic compound phase SixCuy phase where x ⁇ y, the discharge capacity after 100 cycles was 372 mAh / g or more, which is the capacity of the current graphite electrode.
  • Comparative Example No. Nos. 15 to 16 are examples of the present invention. As in 1-2, it is a powder composed of a composite phase of a SixCuy phase composed of a SixCuy alloy which is an intermetallic compound of Si phase and Si and Cu, and the composition of the SixCuy phase is x ⁇ y.
  • the average particle size of the Si phase used as the phase is Comparative Example No. 15 and 12 ⁇ m, Comparative Example No. 16 exceeds 20 ⁇ m and 10 ⁇ m, so the conditions of the present invention are not satisfied.
  • the discharge capacity in the first cycle is the same as that in Comparative Example No. 15 at 1080 mAh / g, Comparative Example No.
  • Comparative Example No. 16 showed 1090 mAh / g and 1000 mAh / g or more, but the discharge capacity after 100 cycles was Comparative Example No. 15 and 200 mAh / g, Comparative Example No. 16 was 170 mAh / g, which was lower than the current capacity of the graphite electrode, 372 mAh / g.
  • the metal-rich SiCu 3 phase is excellent in electrical conductivity, and further has an excellent effect of improving both the charge / discharge capacity and the charge / discharge life due to the synergistic effect of making the average particle size of the Si phase 10 ⁇ m or less. It plays.
  • an alloy is melted to form a molten metal, and the molten metal is quenched by a gas atomizing method, a disk atomizing method, or a liquid quenching method, thereby enabling a method for producing a Si-based alloy negative electrode material having excellent electrical conductivity. .

Abstract

L'invention concerne un matériau d'électrode négative en alliage de Si présentant une excellente conductivité électrique, et dont la capacité de décharge et la durée de vie sont toutes deux satisfaisantes. Ce matériau d'électrode négative consiste en une poudre constituée d'une phase composite avec une phase SixCuy constituée d'un alliage qui est composé de SixCuy (dans la formule, x<y). Cet alliage composé de SixCuy consiste en un composé intermétallique d'une phase de groupe Si, de Si et de Cu. Dans cette phase de groupe Si, une phase Si ou une partie de Si consiste en une phase de Si partiellement substitué par un ou plusieurs éléments choisis dans un groupe constitué de C, Ge, Sn, Pb, Al et P. La phase de groupe Si présente une forme de particules dont le diamètre moyen est inférieur ou égal à 10µm, et une phase SixCuy entoure au moins une partie de la phase de groupe Si.
PCT/JP2011/066139 2010-07-16 2011-07-14 Matériau d'électrode négative en alliage de si présentant une excellente conductivité électrique, et procédé de fabrication de celui-ci WO2012008540A1 (fr)

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JP2010-161308 2010-07-16
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JP2011105109A JP2012038708A (ja) 2010-07-16 2011-05-10 導電性に優れるＳｉ系合金負極材料およびその製造方法
JP2011-105109 2011-05-10

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012064316A (ja) * 2010-09-14 2012-03-29 Sanyo Special Steel Co Ltd Ｓｉ系合金負極電極の製造方法
JP2013179033A (ja) * 2012-02-01 2013-09-09 Sanyo Special Steel Co Ltd Ｓｉ系合金負極材料
WO2016052643A1 (fr) * 2014-10-02 2016-04-07 山陽特殊製鋼株式会社 Poudre pour charges conductrices
JP2016072192A (ja) * 2014-10-02 2016-05-09 山陽特殊製鋼株式会社 導電フィラー用粉末
JP2016110773A (ja) * 2014-12-04 2016-06-20 山陽特殊製鋼株式会社 導電フィラー用粉末
CN114695864A (zh) * 2022-04-25 2022-07-01 安徽工业大学 一种锂离子电池磷掺杂硅铜合金负极材料的制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6076772B2 (ja) * 2013-02-19 2017-02-08 山陽特殊製鋼株式会社 蓄電デバイス用Ｓｉ系合金負極材料およびそれを用いた電極
US10840506B2 (en) 2016-06-16 2020-11-17 Nissan Motor Co., Ltd. Negative electrode active material for electrical device and electrical device using the same

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WO2006129415A1 (fr) * 2005-06-03 2006-12-07 Matsushita Electric Industrial Co., Ltd. Batterie rechargeable avec un électrolyte non aqueux et procédé de production d’une électrode négative
JP2007149685A (ja) * 2005-11-29 2007-06-14 Samsung Sdi Co Ltd リチウム２次電池用負極活物質及び、これを含むリチウム２次電池
JP2009032644A (ja) * 2007-06-26 2009-02-12 Daido Steel Co Ltd リチウム二次電池用負極活物質およびリチウム二次電池

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001297757A (ja) * 2000-04-14 2001-10-26 Sumitomo Metal Ind Ltd 非水電解質二次電池用負極材料およびその製造方法
JP2004362895A (ja) * 2003-06-03 2004-12-24 Sony Corp 負極材料およびそれを用いた電池
JP2005011650A (ja) * 2003-06-18 2005-01-13 Sony Corp 負極材料およびそれを用いた電池
WO2006129415A1 (fr) * 2005-06-03 2006-12-07 Matsushita Electric Industrial Co., Ltd. Batterie rechargeable avec un électrolyte non aqueux et procédé de production d’une électrode négative
JP2007149685A (ja) * 2005-11-29 2007-06-14 Samsung Sdi Co Ltd リチウム２次電池用負極活物質及び、これを含むリチウム２次電池
JP2009032644A (ja) * 2007-06-26 2009-02-12 Daido Steel Co Ltd リチウム二次電池用負極活物質およびリチウム二次電池

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012064316A (ja) * 2010-09-14 2012-03-29 Sanyo Special Steel Co Ltd Ｓｉ系合金負極電極の製造方法
JP2013179033A (ja) * 2012-02-01 2013-09-09 Sanyo Special Steel Co Ltd Ｓｉ系合金負極材料
WO2016052643A1 (fr) * 2014-10-02 2016-04-07 山陽特殊製鋼株式会社 Poudre pour charges conductrices
JP2016072192A (ja) * 2014-10-02 2016-05-09 山陽特殊製鋼株式会社 導電フィラー用粉末
JP2016110773A (ja) * 2014-12-04 2016-06-20 山陽特殊製鋼株式会社 導電フィラー用粉末
CN114695864A (zh) * 2022-04-25 2022-07-01 安徽工业大学 一种锂离子电池磷掺杂硅铜合金负极材料的制备方法
CN114695864B (zh) * 2022-04-25 2023-09-08 安徽工业大学 一种锂离子电池磷掺杂硅铜合金负极材料的制备方法

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