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WO2014092348A1 - Matériau actif d'électrode négative pour batterie secondaire au lithium - Google Patents

Matériau actif d'électrode négative pour batterie secondaire au lithium Download PDF

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Publication number
WO2014092348A1
WO2014092348A1 PCT/KR2013/010439 KR2013010439W WO2014092348A1 WO 2014092348 A1 WO2014092348 A1 WO 2014092348A1 KR 2013010439 W KR2013010439 W KR 2013010439W WO 2014092348 A1 WO2014092348 A1 WO 2014092348A1
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WIPO (PCT)
Prior art keywords
active material
negative electrode
electrode active
secondary battery
alloy
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Ceased
Application number
PCT/KR2013/010439
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English (en)
Korean (ko)
Inventor
김향연
배영산
임혜민
성민석
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Iljin Electric Co Ltd
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Iljin Electric Co Ltd
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Filing date
Publication date
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Publication of WO2014092348A1 publication Critical patent/WO2014092348A1/fr
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Ceased legal-status Critical Current

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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
    • 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
    • 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
    • H01M4/134—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
    • H01M4/386—Silicon or alloys based on silicon
    • 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 negative electrode active material for lithium secondary batteries, and more particularly, to a negative electrode active material for lithium secondary batteries having high charge and discharge capacity and excellent capacity retention rate.
  • Lithium metal is used as a negative electrode active material of a conventional lithium battery.
  • a carbon-based material is used as a negative electrode active material instead of lithium metal because a short circuit of the battery occurs due to the formation of dendrite. .
  • Examples of the carbon-based active material include crystalline carbon such as graphite and artificial graphite, and amorphous carbon such as soft carbon and hard carbon.
  • crystalline carbon such as graphite and artificial graphite
  • amorphous carbon such as soft carbon and hard carbon.
  • Graphite is typically used as the crystalline carbon, and has a theoretical limit capacity of 372 mAh / g, which has a high capacity, and is used as a negative electrode active material.
  • the graphite or carbon-based active material has a rather high theoretical capacity, it is only about 380 mAh / g, and there is a problem in that the above-described negative electrode cannot be used in the development of a high capacity lithium battery in the future.
  • the currently active research is a negative electrode active material of the metal-based or intermetallic compounds.
  • a negative electrode active material of the metal-based or intermetallic compounds.
  • lithium batteries using metals or semimetals such as aluminum, germanium, silicon, tin, zinc, and lead as negative electrode active materials have been studied.
  • Such a material has a high energy density and high energy density, and can absorb and release more lithium ions than a negative electrode active material using a carbon-based material, thereby manufacturing a battery having a high capacity and a high energy density.
  • Pure silicon for example, is known to have a high theoretical capacity of 4017 mAh / g.
  • the cycle characteristics are deteriorated, and it is still an obstacle to practical use.
  • the silicon is used as a lithium occlusion and emission material as a negative electrode active material, it is interposed between the active materials due to the volume change in the charging and discharging process. This is because the conductivity of the film is reduced or a phenomenon in which the negative electrode active material peels from the negative electrode current collector occurs. That is, the silicon or the like contained in the negative electrode active material expands to about 300 to 400% by occluding lithium by charging, and when lithium is discharged, the inorganic particles shrink.
  • Korean Laid-Open Patent No. 2004-0063802 relates to a "cathode active material for a lithium secondary battery, a manufacturing method thereof, and a lithium secondary battery” and used a method of eluting a metal after alloying other metals such as silicon and nickel.
  • Patent No. 2004-0082876 relates to "Method for Producing Porous Silicon and Nano-Sized Silicon Particles and Application to Cathode Material for Lithium Secondary Battery", and heat treatment by mixing a silicon precursor such as alkali metal or alkaline earth metal in powder state and silicon dioxide. Later, the technique of eluting with an acid was disclosed.
  • the patents may improve the initial capacity retention rate due to the buffering effect due to the porous structure.
  • the porous silicon particles having low conductivity are used, if the particles are not nano-sized, the conductivity between the particles may be lowered at the time of manufacturing the electrode. There is a problem that the retention characteristics are lowered.
  • a negative electrode active material for a lithium secondary battery in which the electrical change does not easily occur due to a small volume change during charge and discharge.
  • Another object of the present invention is to provide a negative electrode active material for a lithium secondary battery excellent in initial efficiency and capacity retention characteristics.
  • the present invention provides an alloy including Si, wherein an amorphous region or a microcrystalline region and an amorphous region exist on a matrix in the alloy, and the amorphous region or the microcrystalline region of the amorphous region exists. And it provides a negative electrode active material for a lithium secondary battery, characterized in that the amorphous area of the amorphous region is more than 30%.
  • the present invention provides a negative electrode active material for a lithium secondary battery, characterized in that the alloy is an alloy consisting of the formula (1).
  • the present invention provides a negative electrode active material for a lithium secondary battery, characterized in that the transition metal is selected from the group consisting of Al, Cu, Ti and Fe.
  • the negative electrode active material for a lithium secondary battery according to the present invention has an effect of extending the service life because the electrical change does not occur because the volume change is small during charge and discharge when used in the secondary battery.
  • the negative electrode active material for a lithium secondary battery according to the present invention has an excellent initial efficiency and capacity retention characteristics when used in a secondary battery.
  • the negative electrode active material for a lithium secondary battery according to the present invention has an effect that the amount of voltage and current is maintained substantially constant even when repeated charging and discharging when used in the secondary battery.
  • Figure 1 shows the SEM measurement results of the negative electrode active material according to an embodiment of the present invention.
  • Figure 2 shows the XRD measurement results of the negative electrode active material according to an embodiment of the present invention.
  • Figure 3 shows the amorphousness measurement of the negative electrode active material according to an embodiment of the present invention.
  • Figure 4 shows the charge and discharge capacity of the negative electrode active material according to an embodiment of the present invention.
  • 5 is a charge and discharge cycle repeated up to 50 times at 0.5C of a battery manufactured using a negative electrode active material according to an embodiment of the present invention, the capacity change according to the cycle is measured.
  • an alloy including Si wherein an amorphous region or a microcrystalline region and an amorphous region exist on the matrix in the alloy, but the amorphous region or the amorphous region of the microcrystalline region and the amorphous region It is characterized by more than 30%.
  • an amorphous region or a microcrystalline region and an amorphous region exist on the matrix of the alloy to have a buffer effect against volume change, thereby changing the volume of the secondary battery during charging and discharging. Can be suppressed.
  • the alloy including Si of the present invention may be additionally Ni, there is an advantage in the high-strength matrix as the strength is excellent due to the presence of Ni.
  • the present invention is when the amorphous region without the microcrystalline region in the alloy when the amorphous region of the amorphous region of 30% or more in the matrix (Matt) or when the amorphous region and at the same time when the amorphous region is present in the alloy
  • the amorphous state of the microcrystalline region and the amorphous region is characterized in that more than 30%.
  • the amorphous degree is 30% or more, there is a characteristic that facilitates the diffusion of lithium.
  • the amorphous phase on the matrix is 30% or more, when the secondary battery is used as a negative electrode active material, volume expansion may be suppressed during charging.
  • the present invention may be made of an alloy consisting of the following formula (1).
  • Chemical Formula 1 exists within the above range, an amorphous region or a microcrystalline region and an amorphous region exist on a matrix in an alloy having an amorphous degree of 30% or more.
  • the transition metal is preferably selected from one or more from the group consisting of Al, Cu, Ti and Fe.
  • Figure 1 shows the SEM measurement results of the negative electrode active material according to an embodiment of the present invention
  • Figure 2 shows the XRD measurement results of the negative electrode active material according to an embodiment of the present invention.
  • Amorphization degree of the microcrystals in the range of ° ⁇ 100 ° to 30 to 45%, thereby having an effect that the volume expansion is suppressed when the alloy is charged in the secondary battery.
  • the amorphousness is 30 to 45%, volume expansion is suppressed so that electrical insulation is hardly generated.
  • Calculation of the degree of amorphousness used in the present invention is as follows, the expression can be obtained by looking at the area to measure the degree of amorphousness of FIG.
  • the high degree of amorphousness means that there are many microcrystalline or amorphous regions, and thus, a buffering function is performed in the microcrystalline region or amorphous region during charging to block a factor in which lithium ions may accumulate and expand in volume. Will be able to.
  • the method for preparing the negative electrode active material of the present invention is not particularly limited, and for example, various fine powder production techniques known in the art (gas atomizer method, centrifugal gas atomizer method, plasma atomizer method, rotation) Electrode method, mechanical etching method, etc.) can be used.
  • Si and the components constituting the matrix may be mixed, the mixture may be melted by an arc melting method or the like, and then applied to a single roll quench solidification method in which the melt is sprayed onto a rotating copper roll to prepare an active material. have.
  • the method applied in the present invention is not limited to the above method, and if a sufficient quenching speed can be obtained in addition to the single-roll quenching solidification method, the fine powder production technique (gas atomizer method, centrifugal gas atomizer method) presented above. , Plasma atomizer method, rotary electrode method, mechanical aligning method, and the like.
  • a secondary battery may be manufactured using a negative electrode active material according to an embodiment of the present invention, and the positive electrode of the secondary battery may include a ritated intercalation compound, and also inorganic sulfur (S8). Also, elemental sulfur and sulfur compounds may be used.
  • the kind of electrolyte included in the secondary battery of the present invention is not particularly limited either, and general means known in the art may be employed.
  • the electrolyte may include a non-aqueous organic solvent and a lithium salt.
  • the lithium salt may be dissolved in an organic solvent to serve as a source of lithium ions in the battery and to promote the movement of lithium ions between the positive electrode and the negative electrode.
  • lithium salts examples include LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 4 , LiAlCl 4 , LiN (C x F 2x + 1 SO 2 ) (C y F 2y + 1 SO 2 ), where x and y are natural numbers, LiCl, LiI, and lithium It includes the one or more kinds of bisoxalate borate (lithium bisoxalate borate) or the like as a supporting electrolyte salt.
  • the concentration of lithium salt in the electrolyte which can vary depending on the application, is typically used within the range of 0.1M to 2.0M.
  • the organic solvent serves as a medium to move ions involved in the electrochemical reaction of the battery, for example, benzene, toluene, fluorobenzene, 1,2-difluorobenzene, 1, 3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1, 3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, iodobenzene, 1,2-diiobenzene, 1, 3-diiobenzene, 1,4-diiobenzene, 1,2,3-triiobenzene, 1,2,4-triiobenzene, fluorotoluene, 1,2-difluorotoluene , 1,3-di
  • the secondary battery of the present invention may further include conventional elements such as a separator, a can, a battery case or a gasket, and the specific types thereof are not particularly limited.
  • the secondary battery of the present invention may be manufactured in a conventional manner and shape in the art, including such elements.
  • Examples of the shape that the secondary battery of the present invention may have include a cylindrical shape, a horn shape, a coin shape, or a pouch shape, but are not limited thereto.
  • the method for preparing the negative electrode active material of the present invention is not particularly limited, and for example, various fine powder production techniques known in the art (gas atomizer method, centrifugal gas atomizer method, plasma atomizer method, rotary electrode method, Mechanical alignment, etc.) may be used.
  • gas atomizer method centrifugal gas atomizer method, plasma atomizer method, rotary electrode method, Mechanical alignment, etc.
  • Si and the components constituting the matrix were mixed, the mixture was melted by an arc melting method or the like, and then applied to a single roll quench solidification method in which the melt was sprayed onto a rotating copper roll to prepare an active material.
  • the method applied in the present invention is not limited to the above method, and if a sufficient quenching speed can be obtained in addition to the single-roll quenching solidification method, the fine powder manufacturing technique (gas atomizer method, centrifugal gas atomizer method, plasma method) presented above. It can also be manufactured by the atomizer method, the rotating electrode method, the mechanical etching method and the like.
  • a composite alloy was prepared in which the transition metal was Cu 65.40 Ni 25.69 Cu 8.91 in the Si x Ni y M z alloy, and the degree of amorphousness of the alloy was measured. In preparing, it was used as a negative electrode active material.
  • Example 2 It carried out similarly to Example 1 except having set the transition metal as Ti in Si x Ni y M z alloy, and set it as Si 65.41 Ni 25.69 Ti 8.90 .
  • Example 2 It carried out similarly to Example 1 except having set the transition metal to Fe in the alloy of Si x Ni y M z to Si 65.40 Ni 25.69 Fe 8.91 .
  • Example 2 It carried out similarly to Example 1 except having set the transition metal to Al in Si x Ni y M z alloy, and set it as Si 65.40 Ni 25.70 Al 8.90 .
  • Si 60 Fe 14 Al 26 was prepared. At this time, Si 60 Fe 14 Al 26 was prepared and used as a negative electrode active material.
  • Si x Ni y M z of a transition in the alloy with the metal of Fe was carried out in the same manner as in Example 1 except that Si 45 Ni 25 Fe 30.
  • Example 2 The same procedure as in Example 1 was carried out except that Si 48 Ni 30 Al 22 was prepared using Al as a transition metal in the alloy of Si x Ni y M z .
  • SEM Scanning Electron Microscopy
  • the Si phase was uniformly dispersed and precipitated on the matrix.
  • Cu k ⁇ -ray XRD measurements were performed on the negative active materials prepared in Examples 1 to 4, and the results are shown in FIG. 2.
  • the measurement angle was set at 20 degrees to 100 degrees, and the measurement speed was set at 5.7 degrees per minute.
  • Coin-shaped secondary batteries were prepared using the negative electrode active materials prepared in Examples 1 to 4 and Comparative Examples 1 to 4, and after the charge and discharge evaluations, the results are shown in FIG. 4.
  • the mixing ratio of the active material, the conductive agent (Super P-based conductive agent), and the binder (PI-based binder) is 77: 15: 2: 6 (active material: additive: conductive agent: binder). It was prepared as possible. Charged and discharged after performing once at 0.5C for the prepared electrode plate was measured, as shown in Table 1 below.
  • the amorphousness measurement can be obtained by using the formula of the amorphousness degree using the XRD pattern of the alloy.
  • the degree of amorphousness was less than 30%, and thus, it is judged that the volume expansion is higher than that of the Examples.
  • Charge and discharge was repeated 50 times at 0.5C and measured, and the result is as shown in FIG.
  • the charge and discharge method was performed according to the charge and discharge method for the active material for a lithium secondary battery generally known in the art.

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

Abstract

La présente invention concerne un matériau actif d'électrode négative pour une batterie secondaire au lithium, et plus particulièrement, fournit un matériau actif d'électrode négative pour une batterie secondaire au lithium, le matériau étant caractérisé en ce qu'il comprend un alliage comprenant Si, et en ce qu'il possède une région amorphe ou une région microcristalline et une région amorphe sur la matrice dans l'alliage, le degré d'amorphisation de la région amorphe ou le degré d'amorphisation de la région microcristalline et de la région amorphe étant d'au moins 30 %.
PCT/KR2013/010439 2012-12-12 2013-11-18 Matériau actif d'électrode négative pour batterie secondaire au lithium Ceased WO2014092348A1 (fr)

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KR10-2012-0144160 2012-12-12
KR20120144160A KR20140080579A (ko) 2012-12-12 2012-12-12 리튬 이차 전지용 음극활물질

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018225971A1 (fr) * 2017-06-07 2018-12-13 한국생산기술연구원 Matériau actif d'anode destiné à une batterie secondaire au lithium, anode destinée à une batterie secondaire au lithium, et batterie secondaire au lithium comprenant une telle anode

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001338646A (ja) * 2000-05-26 2001-12-07 Sanyo Electric Co Ltd リチウム二次電池用負極
KR20050090220A (ko) * 2004-03-08 2005-09-13 삼성에스디아이 주식회사 리튬 이차 전지용 음극 활물질, 그의 제조 방법 및 그를포함하는 리튬 이차 전지
KR20060074808A (ko) * 2004-12-27 2006-07-03 삼성에스디아이 주식회사 리튬 이차 전지
KR20080009269A (ko) * 2005-03-23 2008-01-28 파이오닉스 가부시키가이샤 리튬이차전지용 음극 활물질 입자와 음극 및 그들의 제조방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001338646A (ja) * 2000-05-26 2001-12-07 Sanyo Electric Co Ltd リチウム二次電池用負極
KR20050090220A (ko) * 2004-03-08 2005-09-13 삼성에스디아이 주식회사 리튬 이차 전지용 음극 활물질, 그의 제조 방법 및 그를포함하는 리튬 이차 전지
KR20060074808A (ko) * 2004-12-27 2006-07-03 삼성에스디아이 주식회사 리튬 이차 전지
KR20080009269A (ko) * 2005-03-23 2008-01-28 파이오닉스 가부시키가이샤 리튬이차전지용 음극 활물질 입자와 음극 및 그들의 제조방법

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018225971A1 (fr) * 2017-06-07 2018-12-13 한국생산기술연구원 Matériau actif d'anode destiné à une batterie secondaire au lithium, anode destinée à une batterie secondaire au lithium, et batterie secondaire au lithium comprenant une telle anode

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