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WO2015167167A1 - Matière d'anode de batterie au lithium-ion à base de si-fe-mo et son procédé de préparation - Google Patents

Matière d'anode de batterie au lithium-ion à base de si-fe-mo et son procédé de préparation Download PDF

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Publication number
WO2015167167A1
WO2015167167A1 PCT/KR2015/004060 KR2015004060W WO2015167167A1 WO 2015167167 A1 WO2015167167 A1 WO 2015167167A1 KR 2015004060 W KR2015004060 W KR 2015004060W WO 2015167167 A1 WO2015167167 A1 WO 2015167167A1
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Prior art keywords
negative electrode
ion battery
sifemo
present
fesi
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Ceased
Application number
PCT/KR2015/004060
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English (en)
Korean (ko)
Inventor
이희춘
최이식
문성환
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Sapphire Technology Co Ltd
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Sapphire Technology Co Ltd
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • 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
    • H01M4/44—Alloys based on cadmium
    • 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 SiFeMo lithium ion battery anode material, and more particularly, to improve the electrical conductivity, hardness, elasticity, corrosion resistance SiFeMo lithium ion battery anode material and improved charging capacity, charging and discharging efficiency, cycle characteristics and The manufacturing method is related.
  • carbon-based negative electrode active materials have been mainly applied to negative electrode materials of lithium ion batteries. Carbon-based active materials are largely classified into crystalline and amorphous active materials. Until now, graphite-based materials, which are crystalline active materials, have been applied to almost all lithium-ion batteries. The research on the system material has attracted much attention.
  • U.S. Patent No. 7,906,238 discloses SiMC (M is metal, C is carbon) used as an electrode of a lithium ion battery, which is a composition prepared by applying mechanical milling process technology. Where M and C are always greater than or equal to zero.
  • This mechanical milling process is a technique for dispersing Si crystals refined during milling onto a metal silicide matrix and adding carbon having excellent conductivity.
  • silicide which is an inactive phase with lithium
  • the concept of utilizing silicide, which is an inactive phase with lithium is known in the art [G.X.Wang, L.Sun, D.H.Bradhurst, S.Zhong, S.X. Dou, H.K. Liu, Journal of Power Sources 88 (2000) 278-281]
  • the high hardness and elastic properties of silicides allow the expansion / contraction of Si during charge and discharge.
  • the feature of this patent is simply a technique for improving the high electrical resistance of metal silicides by adding carbon.
  • SiMC added with carbon
  • carbon acts as a lubricant to reduce the coefficient of friction between powders or between powder and balls.
  • This patent has technical limitations because prolonged milling is a major contributor to contamination (impurities) coming from the mill vessel wall or milling media.
  • US Patent No. 8,071,2308 which is a similar patent, adds tin (Sn) to the existing SiMC composition and is based on the SiSnMC composition.
  • Sn tin
  • the reason for the addition of tin is to mitigate the volume change (shrinkage / expansion) that occurs when Si reacts with lithiation and delithiation.
  • tin it reacts with Li (active element), and the expansion rate when forming SnLi 4.4 is about 260%, which is lower than that of Si (320%).
  • the voltage for forming SiLi 4.4 is 0.4 V and SnLi 4.4 is 0.6 V, the fact that Si reacts preferentially with lithium in the process of voltage rise makes Sn actually relax the expansion / contraction of Si. It's hard to expect to.
  • the present inventors have performed a study to solve the problems of the prior art, and as a result, it is significantly different from the existing SiMC or SiSnMC composition, the method or expansion of adding carbon to improve the conductivity in the Si-Metal system Of the composite structure composed of silicide (FeSi 2 ) with high hardness and elasticity and silicide (MoSi 2 ) with low electrical resistance by forming a third silicide rather than a technical method of adding Sn, an active element to alleviate shrinkage.
  • the silicide matrix phase was formed.
  • SiFeMo cathode material was developed as a unique method of dispersing nano-sized Si crystals on such substrates. Based on the evaluation of the characteristics, we found that the battery capacity, cycle characteristics, and charge and discharge efficiency can be greatly improved. The invention has been completed.
  • An object of the present invention is to solve the technical problem that it is difficult to refine the Si by the addition of carbon in the anode material based on the conventional SiMC (M is metal, C is carbon), using a high-energy milling process Nano Si crystals are embedded on a FeSi 2 + MoSi 2 matrix by forming a matrix of nanoscaled microstructures and at the same time forming a matrix consisting of a composite phase of FeSi 2 phase with excellent mechanical properties (hardness and modulus of elasticity) and MoSi 2 phase with low electrical resistance.
  • the present invention provides a SiFeMo-based lithium ion battery anode material and a method for manufacturing the same, which have excellent capacity and cycle characteristics without using carbon, thereby improving charge and discharge efficiency.
  • the present invention is a SiFeMo system, which is a cathode material of Si a Fe b Mo c that satisfies the conditions of 77 ⁇ a ⁇ 85at%, 10 ⁇ b ⁇ 19at%, 1 ⁇ c ⁇ 10at% Provided is a lithium ion battery negative electrode material.
  • a is 80at%
  • b is 14-17at%
  • c is 3-6at%.
  • the negative electrode material has a microstructure in which Si particles are dispersed in a matrix made of a mixed phase of FeSi 2 and MoSi 2 .
  • the negative electrode material is composed of FeSi 2 , MoSi 2 , Si phase, and the Si phase fraction is preferably 23% to 65%.
  • the present invention is to prepare a raw material powder of Si a Fe b Mo c that satisfies the conditions of 77 ⁇ a ⁇ 85at%, 10 ⁇ b ⁇ 19at%, 1 ⁇ c ⁇ 10at%; And inserting the raw material powder into a milling apparatus and performing a mechanical milling process to alloy the raw material powder to produce a negative ion material for a lithium ion battery, thereby providing a method for producing a negative electrode material for a LiFe-based lithium ion battery.
  • the SiFeMo lithium ion battery anode material of the present invention is to control the ratio of Fe and Mo by controlling the phase ratio of FeSi 2 and MoSi 2 , thereby improving the high electrical resistance and high electrical resistance of the disadvantages of FeSi 2 phase There is an advantage to this.
  • the SiFeMo lithium ion battery anode material of the present invention generates FeSi 2 and MoSi 2 composed of Fe and Mo and induces the refinement of Si grains during milling, so that the fine Si crystals are mechanically strong and have excellent electrical conductivity.
  • embedding (embedding) inside there is an effect that can improve the characteristics of the negative electrode material of the secondary battery than the conventional Fe silicide (FeSi 2 ) -based Si dispersion material.
  • the present invention mechanically milling the raw material powder of SiFeMo, by substituting Fe with Mo to adjust the phase fraction of MoSi 2 to effectively improve the high electrical resistance, which is a disadvantage of the FeSi 2 phase negative electrode having improved battery capacity and cycle characteristics Material may be provided.
  • FIG. 1 is a flow chart of the manufacturing process of SiFeMo-based negative electrode material according to the present invention.
  • SiFeMo-based negative electrode material is a graph showing the change of Si, FeSi 2 , MoSi 2 phase fraction according to the composition change of the SiFeMo-based negative electrode material.
  • 3A to 3C are graphs of absolute capacity and cycle characteristics according to the composition change of the SiFeMo-based negative electrode material and the comparative example according to the present invention.
  • 5a to 5d are scanning electron micrographs of the SiFeMo-based negative electrode material according to the present invention.
  • FIG. 6 is an X-ray diffraction diagram of a sample obtained according to the mechanical milling time according to the present invention.
  • the present invention provides a SiFeMo-based lithium ion battery negative electrode material which can improve the high electrical resistance, low hardness and elasticity, which are disadvantages of FeSi 2 , by controlling the phase ratio of FeSi 2 and MoSi 2 by controlling the component ratio of Fe and Mo. It is.
  • Such a method for manufacturing a SiFeMo-based lithium ion battery anode material according to the present invention can be implemented by performing (1) raw material powder manufacturing step and (2) mechanical milling step, as shown in FIG.
  • SiFeMo lithium ion battery anode material Si a Fe b Mo c satisfying the conditions of 77 ⁇ a ⁇ 85at%, 10 ⁇ b ⁇ 19at%, 1 ⁇ c ⁇ 10at% Prepare a powder.
  • the raw material powder may be a powder obtained by pulverizing an alloy of Si a Fe b Mo c .
  • a powder obtained by mixing Si powder, Fe powder, and Mo powder satisfying the above conditions may be used.
  • an alloy powder is obtained through a process of melting Si, Fe, and Mo in a high frequency induction melting furnace to form a mother alloy and grinding the mother alloy.
  • Si preferably satisfies 77 to 85 at%. If Si is less than 77at%, there is a problem that the characteristics of the lithium ion battery is lowered with a low charge capacity, showing a charging capacity of less than 800 mAh / g, when Si exceeds 85at%, the fraction of Si phase is excessively large, Since the particle size is also coarsened so that the fraction of silicide matrix is relatively small, there is a disadvantage in that the matrix phase, which is intended to accommodate the volume change in the reaction between Si and Li, is lost.
  • the amount of Mo added preferably satisfies 1 to 10 at%. If Mo is less than 1at%, the fraction of MoSi 2 phase is theoretically less than 10at%, so it is difficult to expect the effect of Mo addition substantially. If it exceeds 10at%, the MoSi 2 phase fraction is too large and the base phase becomes excessively strong, reacting with Li. It is not preferable because it can lead to destruction of Si-Li compound which expands upon time.
  • the raw material powder prepared in step (1) is placed in a milling apparatus, and the raw powder is alloyed by performing a mechanical milling process.
  • the ratio of the raw material powder to the milling ball can be set in the range of 1: 5 to 1:30. If milling is performed outside this range, the efficiency is low and the balls collide to cause contamination. Can be. And milling is performed suitably in the range of several hours to several tens of hours.
  • Si a Fe b Mo c satisfying the conditions of 77 ⁇ a ⁇ 85at%, 10 ⁇ b ⁇ 19at%, 1 ⁇ c ⁇ 10at%
  • the cathode material of can be manufactured.
  • the raw powder is forcibly homogenized and alloyed as a powerful ball mill to create a state where nano-sized Si particles are dispersed on a matrix composed of a mixed phase of FeSi 2 and MoSi 2 .
  • composition change of the SiFeMo-based negative electrode material according to the present invention is implemented by performing the processes of (1) and (2) described above, and the Si, FeSi 2 , MoSi 2 phase fraction change on the alloyed matrix Measured.
  • the composition of the SiFeMo-based anode material is Si 77 Fe 18 Mo 5 , Si 80 Fe 19 Mo 1 , Si 80 Fe 17 Mo 3 , Si 80 Fe 16 Mo 4 , Si 80 Fe 14 Mo 6
  • Si 80 Fe 12 Mo 8 , Si 80 Fe 10 Mo 10 , and Si 85 Fe 10 Mo 5 SiFeMo lithium ion battery anode material had a Si phase fraction as the Si content increased from 77at% to 85at% It increased from 23% to 65%, it can be seen that the phase fraction of Si is more dependent on the composition change of (Fe + Mo).
  • the SiFeMo lithium ion battery anode material of the present invention can effectively improve high electrical resistance, which is a disadvantage of FeSi 2, by controlling the phase fraction of MoSi 2 by replacing Fe with Mo.
  • the SiFeMo-based lithium ion battery anode material of the present invention can lower the electrical resistance and increase the elasticity, include MoSi 2 having excellent corrosion resistance, and can improve the capacity and charge / discharge efficiency of the lithium ion battery with micronized Si grains. It is.
  • the electrical resistance of MoSi 2 is 100 ⁇ -cm, which is about 800 times lower than that of FeSi 2 of 80,000 ⁇ -cm, and the low electrical resistance contributes to increased capacity by increasing the movement of electrons produced during charging and discharging. do.
  • FIG. 3A to 3C are graphs of absolute capacity and cycle characteristics according to the composition change of the SiFeMo-based negative electrode material and the comparative example according to the present invention
  • FIG. 4 is the average charge / discharge according to the composition change of the SiFeMo-based negative electrode material and the comparative example according to the present invention. It is a characteristic diagram.
  • the absolute capacity was better than that of the SiFe-based negative electrode material graph of Si 77 Fe 23 (I), Si 80 Fe 20 (J), and Si 85 Fe 15 (K) in FIG. 3C of the comparative example, and the capacity retention rate was shown in 100 cycles of charge and discharge. .
  • the negative electrode materials of Si 80 Fe 16 Mo 4 (D) and Si 80 Fe 14 Mo 6 (E) had a capacity of 850 mAh / g or more at 100 cycles of charging and discharging, showing a maximum capacity retention rate.
  • the SiFeMo-based negative electrode material of the present invention showed an average charge and discharge efficiency of 99% or more
  • the SiFe-based negative electrode material of the comparative example showed an average charge and discharge efficiency of 98% or less.
  • FIG. 5A to 5D are scanning electron micrographs of SiFeMo-based negative electrode materials according to the present invention
  • FIG. 6 is an X-ray diffraction diagram of a sample obtained according to the mechanical milling time according to the present invention.
  • the Si peak intensity is relatively weakened by the mechanical milling, the FeSi 2 peak is strengthened, and the mechanical milling can promote the refinement of Si.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Silicon Compounds (AREA)

Abstract

La présente invention se rapporte à une matière d'anode de batterie au lithium-ion à base de Si-Fe-Mo et à son procédé de préparation, laquelle matière d'anode est une matière d'anode de SiaFebMoc satisfaisant les relations suivantes : 77 ≤ a ≤ 85 % atomique, 10 ≤ b ≤ 19 % atomique, et 1 ≤ c ≤ 10 % atomique.
PCT/KR2015/004060 2014-04-29 2015-04-23 Matière d'anode de batterie au lithium-ion à base de si-fe-mo et son procédé de préparation Ceased WO2015167167A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2014-0051682 2014-04-29
KR1020140051682A KR101597570B1 (ko) 2014-04-29 2014-04-29 SiFeMo계 리튬이온전지 음극재료 및 그 제조방법

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WO2015167167A1 true WO2015167167A1 (fr) 2015-11-05

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KR20220127448A (ko) 2021-03-11 2022-09-20 현대자동차주식회사 리튬이온전지용 복합음극 제조방법
KR20240066977A (ko) 2022-11-08 2024-05-16 고려대학교 산학협력단 리튬 이온 전지용 전이금속 산화물 기반 바인더 프리 전극 및 이의 제조 방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4173687A (en) * 1978-06-20 1979-11-06 Occidental Research Corporation Current generating cell with alloy anode
KR20080072025A (ko) * 2005-12-01 2008-08-05 쓰리엠 이노베이티브 프로퍼티즈 컴파니 규소 함량이 높은 비결정성 합금을 기재로 하는 전극조성물
JP2009521792A (ja) * 2005-12-23 2009-06-04 スリーエム イノベイティブ プロパティズ カンパニー リチウム−イオン電池の電極に有用なシリコン含有合金
JP2013161786A (ja) * 2012-02-01 2013-08-19 Samsung Sdi Co Ltd 負極活物質とその製造方法、これを含むリチウム二次電池用の負極及びこれを採用したリチウム二次電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4173687A (en) * 1978-06-20 1979-11-06 Occidental Research Corporation Current generating cell with alloy anode
KR20080072025A (ko) * 2005-12-01 2008-08-05 쓰리엠 이노베이티브 프로퍼티즈 컴파니 규소 함량이 높은 비결정성 합금을 기재로 하는 전극조성물
JP2009521792A (ja) * 2005-12-23 2009-06-04 スリーエム イノベイティブ プロパティズ カンパニー リチウム−イオン電池の電極に有用なシリコン含有合金
JP2013161786A (ja) * 2012-02-01 2013-08-19 Samsung Sdi Co Ltd 負極活物質とその製造方法、これを含むリチウム二次電池用の負極及びこれを採用したリチウム二次電池

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KR101597570B1 (ko) 2016-02-25
KR20150124747A (ko) 2015-11-06

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