TW201522220A - Porous silicon-based particles, method of preparing the same, and lithium secondary battery including the porous silicon-based particles - Google Patents

Porous silicon-based particles, method of preparing the same, and lithium secondary battery including the porous silicon-based particles Download PDF

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TW201522220A
TW201522220A TW103130105A TW103130105A TW201522220A TW 201522220 A TW201522220 A TW 201522220A TW 103130105 A TW103130105 A TW 103130105A TW 103130105 A TW103130105 A TW 103130105A TW 201522220 A TW201522220 A TW 201522220A
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particles
porous
based particles
ruthenium
porous ruthenium
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TWI583624B (en
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Jung-Woo Yoo
Mi-Rim Lee
Yong-Ju Lee
Eun-Kyung Kim
Han-Ho Lee
Ji-Hyun Yoon
Byoung-Man Bang
Chang-Rae Lee
Il-Kyo Jeong
Mi-Kyeong Lee
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Lg Chemical Ltd
Sejin Innotech Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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

Abstract

Provided are a porous silicon-based particle including a silicon (Si) or SiOx(0 < x < 2) particle, wherein the particle includes a plurality of nonlinear pores, and the nonlinear pores are formed as open pores in a surface of the particle, and a method of preparing the porous silicon-based particles. Porous silicon-based particles according to an embodiment of the present invention may be more easily dispersed in an anode active material slurry, may minimize side reactions with an electrolyte, and may reduce volume expansion during charge and discharge. Also, according to an embodiment of the present invention, the shape, form, and size of pores formed in the porous silicon-based particle may be controlled by adjusting the type of a metal catalyst, the concentration of the catalyst, and etching time.

Description

多孔矽基粒子、製備彼等之方法、及包含多孔矽基粒子之鋰二次電池 Porous ruthenium-based particles, methods for preparing same, and lithium secondary batteries comprising porous ruthenium-based particles

本發明關於多孔矽基粒子、製備彼等之方法、及包含多孔矽基粒子之鋰二次電池。 The present invention relates to porous ruthenium-based particles, a method of preparing the same, and a lithium secondary battery comprising porous ruthenium-based particles.

最近，根據資訊及電信工業的發展，為了符合電子裝置之小型化、輕量化、薄型及可攜式趨勢，對於用作該等電子裝置的電源之高能量密度電池的需求增加。目前，已積極地進行研究作為可最佳滿足上述需求之電池的鋰二次電池。 Recently, in accordance with the development of the information and telecommunications industry, in order to meet the trend toward miniaturization, weight reduction, thinness, and portability of electronic devices, there has been an increase in demand for high energy density batteries used as power sources for such electronic devices. At present, research has been actively conducted as a lithium secondary battery which can best satisfy the above requirements.

各種類型之能夠嵌入/脫嵌鋰的碳基材料(其包含人造石墨、天然石墨或硬碳)已被用作鋰二次電池的陽極活性材料。碳基材料之中，因為石墨提供就鋰電池的能量密度而言的優點且由於極佳可逆性也保證鋰二次電池的長壽命，所以石墨已被最廣泛地使用。 Various types of carbon-based materials capable of intercalating/deintercalating lithium, which include artificial graphite, natural graphite or hard carbon, have been used as anode active materials for lithium secondary batteries. Among the carbon-based materials, graphite has been most widely used because it provides advantages in terms of the energy density of the lithium battery and also ensures long life of the lithium secondary battery due to excellent reversibility.

然而，因為石墨就電極的每單位體積之能量 密度而言可能具有低電容，且會促進在高放電電壓下與有機電解質之副反應，由於電池的故障和過充電而有火災或***的危險。 However, because graphite is the energy per unit volume of the electrode In terms of density, it may have a low capacitance and may promote a side reaction with an organic electrolyte at a high discharge voltage, which may cause a fire or explosion due to malfunction and overcharge of the battery.

因此，已研究金屬基陽極活性材料，諸如矽(Si)。已知矽金屬基陽極活性材料呈現約4,200mAh/g的高鋰電容。然而，矽金屬基陽極活性材料在與鋰反應之前或之後(即，在充電及放電期間)會造成300%或更大之最大值的體積改變。結果，電極中的導電網被破壞且粒子之間的接觸電阻增加。因此，有其中電池性能退化的現象。 Therefore, metal-based anode active materials such as bismuth (Si) have been studied. The base metal-based anode active material is known to exhibit a high lithium capacity of about 4,200 mAh/g. However, the base metal-based anode active material causes a volume change of a maximum of 300% or more before or after the reaction with lithium (i.e., during charging and discharging). As a result, the conductive mesh in the electrode is broken and the contact resistance between the particles is increased. Therefore, there is a phenomenon in which battery performance is degraded.

因此，已嘗試一種藉由將矽粒子之大小減少至奈米大小來根據體積改變減少直徑之實質改變的方法。然而，也有困難在於：開發合成均勻奈米矽陽極活性材料和將奈米矽陽極活性材料均勻分佈在漿料中之方法，及因為表面積最大化而與電解質之副反應可能會增加。 Therefore, a method of reducing the substantial change in diameter according to volume change has been attempted by reducing the size of the ruthenium particles to the size of the nanometer. However, there are also difficulties in developing a synthetic uniform nano-nano anode active material and a method of uniformly distributing the nano-nano anode active material in the slurry, and the side reaction with the electrolyte may be increased because the surface area is maximized.

因此，有需要開發一種可替代一般陽極活性材料且可解決與電解質之副反應、在充電及放電期間的體積膨脹、及二次電池之性能退化的限制之陽極活性材料。 Therefore, there is a need to develop an anode active material which can replace a general anode active material and which can solve a side reaction with an electrolyte, volume expansion during charging and discharging, and deterioration of performance of a secondary battery.

先前技術文獻 Prior technical literature [專利文獻] [Patent Literature]

韓國專利申請案公開第2012-0109080號 Korean Patent Application Publication No. 2012-0109080

本發明提供可更容易地分散在陽極活性材料漿料中、可將與電解質之副反應減至最少、及可減少在充電及放電期間的體積膨脹之多孔矽基粒子。 The present invention provides porous ruthenium-based particles which can be more easily dispersed in an anode active material slurry, can minimize side reactions with electrolytes, and can reduce volume expansion during charge and discharge.

本發明也提供一種製備多孔矽基粒子之方法。 The invention also provides a method of making porous sulfhydryl particles.

本發明也提供一種包含多孔矽基粒子之陽極活性材料。 The present invention also provides an anode active material comprising porous ruthenium-based particles.

本發明也提供一種包含陽極活性材料之陽極及鋰二次電池。 The present invention also provides an anode comprising an anode active material and a lithium secondary battery.

根據本發明之一方面，提供一種包含矽(Si)或SiOx(0<x<2)粒子之多孔矽基粒子，其中該粒子包含多個非線性孔，及該等非線性孔係在粒子的表面中形成為開孔。 According to an aspect of the invention, there is provided a porous ruthenium-based particle comprising cerium (Si) or SiO x (0<x<2) particles, wherein the particle comprises a plurality of nonlinear pores, and the nonlinear pores are in the particle The surface is formed as an opening.

根據本發明之另一方面，提供一種多孔矽基粒子，其包含：包含矽(Si)或SiOx(0<x<2)之核心部分；及在該核心部分上的包含多個非線性孔之Si或SiOx外殼部分，其中外殼部分之表面具有開孔。 According to another aspect of the present invention, there is provided a porous ruthenium-based particle comprising: a core portion comprising cerium (Si) or SiO x (0 < x <2); and a plurality of nonlinear pores on the core portion The Si or SiO x outer casing portion, wherein the surface of the outer casing portion has an opening.

根據本發明之另一方面，提供一種製備多孔矽基粒子之方法，該方法包括下列步驟：(i)使用蝕刻溶液移除存在於矽(Si)或SiOx(0<x<2)粒子之表面上的氧化物 層；及(ii)藉由以混合及攪拌包括Si或SiOx(0<x<2)粒子之蝕刻溶液與金屬觸媒來蝕刻Si或SiOx(0<x<2)粒子而在Si或SiOx(0<x<2)粒子中形成非線性孔。 According to another aspect of the present invention, there is provided a method of preparing a porous ruthenium-based particle, the method comprising the steps of: (i) removing an iridium (Si) or SiO x (0 < x < 2) particle using an etching solution; An oxide layer on the surface; and (ii) etching Si or SiO x by mixing and stirring an etching solution comprising Si or SiO x (0<x<2) particles with a metal catalyst (0<x<2) The particles form a nonlinear pore in the Si or SiO x (0 < x < 2) particles.

根據本發明之另一方面，提供一種包含多孔矽基粒子之陽極活性材料。 According to another aspect of the present invention, an anode active material comprising porous ruthenium-based particles is provided.

根據本發明之另一方面，提供一種包含陽極活性材料之陽極。 According to another aspect of the present invention, an anode comprising an anode active material is provided.

根據本發明之另一方面，提供一種包含陽極之鋰二次電池。 According to another aspect of the present invention, a lithium secondary battery including an anode is provided.

根據本發明之一具體實例的多孔矽基粒子藉由包含具有多個非線性孔之矽(Si)或SiOx(0<x<2)粒子之多孔矽基粒子而可更容易地分散在陽極活性材料漿料中、可將與電解質之副反應減至最少、及可減少在充電及放電期間的體積膨脹。 The porous ruthenium-based particles according to an embodiment of the present invention can be more easily dispersed in the anode by porous ruthenium-based particles comprising ruthenium (Si) or SiO x (0 < x < 2) particles having a plurality of nonlinear pores. In the active material slurry, side reactions with the electrolyte can be minimized, and volume expansion during charging and discharging can be reduced.

同樣，根據本發明之一具體實例，在多孔矽基粒子中所形成的孔之形狀、形式、及大小可藉由調節金屬觸媒的類型、觸媒的濃度、及蝕刻時間來控制。 Also, according to an embodiment of the present invention, the shape, form, and size of the pores formed in the porous ruthenium-based particles can be controlled by adjusting the type of the metal catalyst, the concentration of the catalyst, and the etching time.

下列說明書中所附圖式以實例方式顯示本發明的較佳實例，並用於使可與給予於下的本發明詳細描述一起進一步理解本發明的技術概念，且因此本發明不應只 用在該等圖式中的事項解釋。 The following description of the preferred embodiments of the present invention is intended to Explain what is used in the drawings.

圖1為顯示根據本發明之一具體實例的包含非線性孔之多孔矽基粒子的示意圖；圖2為顯示包含線性孔之多孔矽基粒子的示意圖；圖3為顯示本發明實例1至6中所製備的多孔矽基粒子之孔形狀根據蝕刻時間的掃描電子顯微鏡(SEM)影像；圖4為顯示本發明實例7中所製備的多孔矽基粒子之表面形狀的SEM影像；圖5為顯示本發明實例7中所製備的多孔矽基粒子之內剖面的SEM影像；圖6為顯示實例1中所製備的包含非線性孔之多孔矽基粒子的內剖面之SEM影像；及圖7為顯示實例1至6中所製備的多孔矽基粒子之透過根據本發明實驗例之水銀(Hg)孔隙度分析的孔分佈之圖。 1 is a schematic view showing a porous ruthenium-based particle containing a nonlinear pore according to an embodiment of the present invention; FIG. 2 is a schematic view showing a porous ruthenium-based particle containing a linear pore; and FIG. 3 is a view showing Examples 1 to 6 of the present invention. The shape of the pores of the prepared porous cerium-based particles was a scanning electron microscope (SEM) image according to the etching time; FIG. 4 is an SEM image showing the surface shape of the porous cerium-based particles prepared in Example 7 of the present invention; SEM image of the inner cross section of the porous ruthenium-based particles prepared in Inventive Example 7; FIG. 6 is an SEM image showing the internal cross section of the porous ruthenium-based particles containing the nonlinear pores prepared in Example 1; and FIG. 7 is a display example The pore-permeability of the porous sulfonium-based particles prepared in 1 to 6 was analyzed according to the pore distribution of the mercury (Hg) porosity analysis of the experimental example of the present invention.

進行本發明的模式 Carry out the mode of the present invention

在下文中，將更詳細描述本發明，以使更清楚地了解本發明。 In the following, the invention will be described in more detail in order to provide a clearer understanding of the invention.

應該理解的是，在說明書和申請專利範圍中所使用的詞語或術語不應解釋為常用字典中所定義的意 義。應進一步理解的是：詞語或術語應理解為具有與彼等在相關技術和本發明的技術思想範圍內一致的意義，根據該原則，發明者可適當定義詞語或術語的意義，以最佳地解釋本發明。 It should be understood that the words or terms used in the specification and claims should not be construed as meanings defined in the commonly used dictionary. Righteousness. It is to be further understood that words or terms are to be understood as having a meaning consistent with the scope of the related art and the technical idea of the present invention, according to which the inventor can appropriately define the meaning of the words or terms to optimally The invention is explained.

根據本發明之一具體實例的多孔矽基粒子包含矽(Si)或SiOx(0<x<2)粒子，其中該粒子包含多個非線性孔，及該等非線性孔係在粒子的表面中形成為開孔。 The porous ruthenium-based particles according to an embodiment of the present invention comprise cerium (Si) or SiO x (0<x<2) particles, wherein the particles comprise a plurality of nonlinear pores, and the nonlinear pores are on the surface of the particles Formed as an opening.

根據本發明之一具體實例，藉由包含具有多個非線性孔之矽(Si)或SiOx(0<x<2)粒子，多孔矽基粒子可更容易地分散在陽極活性材料漿料中、可將與電解質之副反應減至最少、及可減少在充電及放電期間的體積膨脹。 According to an embodiment of the present invention, the porous ruthenium-based particles can be more easily dispersed in the anode active material slurry by including ruthenium (Si) or SiO x (0 < x < 2) particles having a plurality of nonlinear pores. The side reaction with the electrolyte can be minimized, and the volume expansion during charging and discharging can be reduced.

此外，因為根據本發明之具體實例的多孔矽基粒子包含如圖1中所示之非線性孔及該等非線性孔包含在粒子之表面中的開孔，所以當多孔矽基粒子使用在鋰二次電池時，由於開孔存在於粒子之表面中而可抑制陽極活性材料在充電及/或放電期間之體積膨脹，且由於陽極活性材料的比表面積增加而可增加與電解質的接觸面積。因此，可改良包含上述陽極活性材料之鋰二次電池的壽命特性及速率特性。 Further, since the porous ruthenium-based particles according to the specific examples of the present invention contain non-linear pores as shown in FIG. 1 and the non-linear pores include openings in the surface of the particles, when the porous ruthenium-based particles are used in lithium In the case of the secondary battery, volume expansion of the anode active material during charging and/or discharging can be suppressed due to the presence of the opening in the surface of the particles, and the contact area with the electrolyte can be increased due to an increase in the specific surface area of the anode active material. Therefore, the life characteristics and rate characteristics of the lithium secondary battery including the above anode active material can be improved.

在此情況下，開孔的平均直徑係在約30nm至約500nm之範圍，且當在粒子之表面上觀察時，可在30nm至300nm之範圍。 In this case, the average diameter of the openings is in the range of from about 30 nm to about 500 nm, and may be in the range of from 30 nm to 300 nm when viewed on the surface of the particles.

根據本發明之一具體實例，該等非線性孔(例如)可具有非線性玉米型結構，其中該非線性孔的直徑以 多孔矽基粒子的中心之方向逐漸減小。 According to an embodiment of the invention, the non-linear apertures, for example, may have a non-linear corn-type structure, wherein the diameter of the non-linear aperture is The direction of the center of the porous ruthenium-based particles gradually decreases.

此外，根據本發明之一具體實例，該等非線性孔之至少二或多者可彼此連接。 Further, according to an embodiment of the present invention, at least two or more of the non-linear holes may be connected to each other.

非線性孔的深度可在0.1μm至5μm之範圍。在此情況下，非線性孔的深度表示在多孔矽基粒子之表面處所形成的開孔至孔之終端的長度(其中該孔直徑以粒子的中心之方向逐漸減小)，及非線性孔的深度(例如)可使用掃描電子顯微鏡(SEM)影像或水銀細孔計測量。 The depth of the nonlinear holes may range from 0.1 μm to 5 μm. In this case, the depth of the nonlinear pore means the length of the opening formed at the surface of the porous ruthenium-based particle to the end of the pore (where the diameter of the pore gradually decreases in the direction of the center of the particle), and the nonlinear pore The depth can be measured, for example, using a scanning electron microscope (SEM) image or a mercury pore meter.

此外，根據本發明之一具體實例，水銀侵入孔中之體積的變化率(其以多孔矽基粒子之水銀孔隙度測定法測量)可具有在30nm至2,500nm的平均孔徑範圍(例如，50nm至600nm)之峰值。於峰值處的總水銀侵入體積可在0.5mL/g至1.2mL/g之範圍。 Further, according to an embodiment of the present invention, the rate of change of volume in the mercury intrusion pore (which is measured by mercury porosimetry of porous ruthenium particles) may have an average pore diameter range of from 30 nm to 2,500 nm (for example, 50 nm to The peak of 600 nm). The total mercury intrusion volume at the peak can range from 0.5 mL/g to 1.2 mL/g.

“總水銀侵入體積”一詞表示使用水銀細孔計測量之浸入多個孔之水銀體積，且總水銀侵入體積為當孔的平均直徑及壓力之間的關係近似於下式時所測定之值：180/壓力=孔的平均直徑，其中水銀之表面張力及接觸角分別為485mN/m及130°。 The term "total mercury intrusion volume" means the volume of mercury immersed in a plurality of pores measured using a mercury porosimeter, and the total mercury intrusion volume is a value measured when the relationship between the average diameter of the pores and the pressure approximates the following formula. : 180 / pressure = average diameter of the pores, wherein the surface tension and contact angle of mercury are 485 mN / m and 130 °, respectively.

此外，水銀之侵入體積的變化率可具有得自水銀孔隙度測定法(mercury porosimetry)測量之結果的在30nm至2,500nm的平均孔徑範圍之峰值，表示分佈水銀之侵入體積的變化率以使具有上述得自水銀孔隙度測定法測量之結果的平均孔徑範圍內之峰值的向上凸曲線。 Further, the rate of change of the intrusion volume of mercury may have a peak value in the average pore diameter range of 30 nm to 2,500 nm as a result of measurement by mercury porosimetry, indicating a rate of change of the intrusion volume of the distributed mercury so as to have The above-mentioned upward convex curve of the peak within the average pore size range as a result of measurement by mercury porosimetry.

根據本發明之具體實例的多孔矽基粒子之平 均粒徑(D50)係在1μm至20μm之範圍，可在3μm至12μm之範圍，且例如，可在5μm至10μm之範圍。 The average particle diameter (D 50 ) of the porous ruthenium-based particles according to the specific examples of the present invention is in the range of 1 μm to 20 μm, may be in the range of 3 μm to 12 μm, and may be, for example, in the range of 5 μm to 10 μm.

在多孔矽基粒子的平均粒徑小於1μm的情況下，多孔矽基粒子可能難以分散在陽極活性材料漿料中。在其中多孔矽基粒子的平均粒徑大於20μm的情況下，因為由鋰離子的電荷導致的粒子膨脹可能變為嚴重，粒子間的黏著及粒子和集電器間的黏著會因重複充電及放電而降低。因此，循環特性可能會顯著退化。 In the case where the average particle diameter of the porous ruthenium-based particles is less than 1 μm, the porous ruthenium-based particles may be difficult to disperse in the anode active material slurry. In the case where the average particle diameter of the porous ruthenium-based particles is more than 20 μm, since the particle expansion caused by the charge of the lithium ions may become severe, the adhesion between the particles and the adhesion between the particles and the current collector may be caused by repeated charging and discharging. reduce. Therefore, the cycle characteristics may be significantly degraded.

在本發明中，粒子的平均粒徑可定義為在累積粒徑分佈中於50%之粒徑。例如，根據本發明之具體實例的粒子之平均粒徑(D50)可藉由使用雷射繞射方法測量。雷射繞射方法通常可測量範圍從亞微米級到數毫米的粒徑，且可獲得高可重複性和高解析度的結果。 In the present invention, the average particle diameter of the particles may be defined as a particle diameter of 50% in the cumulative particle size distribution. For example, the average particle diameter (D 50 ) of the particles according to the specific examples of the present invention can be measured by using a laser diffraction method. Laser diffraction methods typically measure particle sizes ranging from submicron to several millimeters and achieve high repeatability and high resolution results.

根據本發明之具體實例的多孔矽基粒子之比表面積(BET-SSA)可在5m2/g至50m2/g之範圍，及在藉由使用符合上述比表面積範圍之多孔矽基粒子作為陽極活性材料製備鋰二次電池的情況下，可改良該鋰二次電池之速率特性。 The porous sulfonium-based particles according to the specific examples of the present invention may have a specific surface area (BET-SSA) in the range of 5 m 2 /g to 50 m 2 /g, and as an anode by using porous cerium-based particles conforming to the above specific surface area range In the case of preparing a lithium secondary battery from an active material, the rate characteristics of the lithium secondary battery can be improved.

在比表面積大於50m2/g的情況下，與電解質之副反應由於大比表面積而會難以控制。在比表面積小於5m2/g的情況下，因為孔可能沒有充分地形成，所以在充電及放電期間體積膨脹不會有效地容納鋰。 In the case where the specific surface area is more than 50 m 2 /g, the side reaction with the electrolyte may be difficult to control due to a large specific surface area. In the case where the specific surface area is less than 5 m 2 /g, since the pores may not be sufficiently formed, volume expansion during charging and discharging does not efficiently accommodate lithium.

根據本發明之一具體實例，多孔矽基粒子的比表面積可藉由Brunauer-Emmett-Teller(BET)法測量。例 如，比表面積可以根據使用孔隙度測定分析儀(Bell日本公司的Belsorp-II mini)之氮氣吸附流方法的6點BET方法測量。 According to an embodiment of the present invention, the specific surface area of the porous ruthenium-based particles can be measured by the Brunauer-Emmett-Teller (BET) method. example For example, the specific surface area can be measured according to a 6-point BET method using a nitrogen adsorption flow method of a porosimetry analyzer (Belsorp-II mini of Bell Japan Co., Ltd.).

根據本發明之另一具體實例，所提供者為一種多孔矽基粒子，其包含：包含矽(Si)或SiOx(0<x<2)之核心部分；及在該核心部分上的包含多個非線性孔之Si或SiOx外殼部分，其中外殼部分之表面具有開孔。 According to another embodiment of the present invention, provided is a porous germanium-based particle comprising: a core portion comprising germanium (Si) or SiO x (0 < x <2); and a plurality of inclusions on the core portion A non-linear hole Si or SiO x outer casing portion, wherein the surface of the outer casing portion has an opening.

在多孔矽基粒子中，該核心部分的長度對外殼部分的長度之比率可在1：9至9：1之範圍。 In the porous ruthenium-based particles, the ratio of the length of the core portion to the length of the outer shell portion may range from 1:9 to 9:1.

根據本發明之具體實例的該等非線性孔及開孔之形狀及孔之平均直徑係與上述相同，該形狀及平均直徑(例如)可藉由在製備多孔矽基粒子期間調整金屬觸媒的類型、觸媒的濃度、及蝕刻時間來控制。 The shape of the non-linear pores and openings and the average diameter of the pores according to a specific example of the present invention are the same as described above, and the shape and average diameter can be adjusted, for example, by adjusting the metal catalyst during the preparation of the porous ruthenium-based particles. Type, concentration of catalyst, and etching time are controlled.

一種製備根據本發明之一具體實例的多孔矽基粒子之方法可包括下列步驟：(i)使用蝕刻溶液移除存在於Si或SiOx(0<x<2)粒子之表面上的氧化物層；及(ii)藉由以混合及攪拌包含Si或SiOx(0<x<2)粒子之蝕刻溶液與金屬觸媒來蝕刻Si或SiOx(0<x<2)粒子而在Si或SiOx(0<x<2)粒子中形成非線性孔。 A method of preparing porous ruthenium-based particles according to an embodiment of the present invention may comprise the steps of: (i) removing an oxide layer present on the surface of Si or SiO x (0 < x < 2) particles using an etching solution And (ii) etching Si or SiO x (0<x<2) particles in Si or SiO by mixing and stirring an etching solution containing Si or SiO x (0<x<2) particles with a metal catalyst x (0<x<2) forms a nonlinear hole in the particle.

首先，步驟(i)可為使用蝕刻溶液移除存在於矽(Si)或SiOx(0<x<2)粒子之表面上的氧化物層之步驟。 First, step (i) may be a step of removing an oxide layer present on the surface of the cerium (Si) or SiO x (0 < x < 2) particles using an etching solution.

即，步驟(i)為移除存在於矽(Si)或SiOx(0<x<2)粒子之表面上的氧化物層之步驟，其中該氧化物層之移除可為一種進行表面處理以使使用無電金屬 沈積用金屬觸媒更平滑及均勻地塗佈Si或SiOx(0<x<2)粒子之方法。 That is, step (i) is a step of removing an oxide layer present on the surface of the cerium (Si) or SiO x (0 < x < 2) particles, wherein the removal of the oxide layer may be a surface treatment A method of coating Si or SiO x (0 < x < 2) particles more smoothly and uniformly using a metal catalyst for electroless metal deposition.

具體來說，將Si或SiOx(0<x<2)粒子浸漬在加熱至約20℃至約90℃之溫度的蝕刻溶液中，及然後攪拌約30分鐘至約3小時以移除存在於Si或SiOx(0<x<2)粒子的表面上之天然氧化物層。 Specifically, Si or SiO x (0<x<2) particles are immersed in an etching solution heated to a temperature of about 20 ° C to about 90 ° C, and then stirred for about 30 minutes to about 3 hours to remove the presence of A natural oxide layer on the surface of Si or SiO x (0 < x < 2) particles.

根據本發明之一具體實例可使用的蝕刻溶液可包括至少一種選自由下列所組成群組之溶液：氟化氫(HF)、氟矽酸(H2SiF6)、及氟化銨(NH4F)，及例如，蝕刻溶液可為氟化氫(HF)。 The etching solution which can be used according to an embodiment of the present invention may include at least one selected from the group consisting of hydrogen fluoride (HF), fluoroantimonic acid (H 2 SiF 6 ), and ammonium fluoride (NH 4 F). And, for example, the etching solution may be hydrogen fluoride (HF).

該蝕刻溶液的濃度可在5M至20M之範圍。 The concentration of the etching solution may range from 5M to 20M.

此外，步驟(ii)可為藉由以混合及攪拌包含Si或SiOx(0<x<2)粒子之蝕刻溶液與金屬觸媒來蝕刻Si或SiOx(0<x<2)粒子而在Si或SiOx(0<x<2)粒子中形成非線性孔之步驟。 Further, the step (ii) may be to etch Si or SiO x (0<x<2) particles by mixing and stirring an etching solution containing Si or SiO x (0<x<2) particles and a metal catalyst. A step of forming a nonlinear hole in the Si or SiO x (0 < x < 2) particles.

根據本發明之一具體實例，可在Si或SiOx(0<x<2)粒子中形之孔的平均粒徑及形狀可根據金屬觸媒的類型和濃度及蝕刻(攪拌)時間來控制。 According to an embodiment of the present invention, the average particle diameter and shape of the pores which can be formed in the Si or SiO x (0 < x < 2) particles can be controlled according to the type and concentration of the metal catalyst and the etching (stirring) time.

即，透過無電金屬沈積將金屬均勻沈積在Si或SiOx(0<x<2)粒子的表面上及同時，藉由將金屬觸媒加至包含具有從中移除氧化物層的Si或SiOx(0<x<2)粒子之蝕刻溶液，及混合及攪拌該溶液進行蝕刻。因此，可形成非線性孔。 That is, the metal is uniformly deposited on the surface of the Si or SiO x (0<x<2) particles by electroless metal deposition and at the same time, by adding the metal catalyst to the Si or SiO x containing the oxide layer removed therefrom. (0 < x < 2) etching solution of the particles, and mixing and stirring the solution for etching. Therefore, a nonlinear hole can be formed.

根據本發明之一具體實例可使用的金屬觸媒 可包括選自由下列所組成群組中任一者：銅(Cu)、鉑(Pt)、及鎳(Ni)、或彼等的二或多個元素，及例如，金屬觸媒可包括Cu。 Metal catalyst that can be used according to one embodiment of the present invention A second or more elements selected from the group consisting of copper (Cu), platinum (Pt), and nickel (Ni), or the like, and, for example, the metal catalyst may include Cu.

一般化學蝕刻方法中所使用之金屬觸媒可包含銀。當比較包含銅、鉑及鎳之金屬觸媒與包含銀之金屬觸媒時，相似性在於：只有與觸媒接觸的部分被蝕刻。然而，在使用包含銀之金屬觸媒的情況下，因為如圖2中所示之示意圖，蝕刻於垂直Si或SiOx(0<x<2)粒子的表面之方向發生，所以孔可線性地形成。 The metal catalyst used in the general chemical etching method may contain silver. When a metal catalyst containing copper, platinum, and nickel is compared with a metal catalyst containing silver, the similarity is that only the portion in contact with the catalyst is etched. However, in the case of using a metal catalyst containing silver, since the etching occurs in the direction of the surface of the vertical Si or SiO x (0<x<2) particles as shown in FIG. 2, the holes can be linearly form.

反之，在其中使用根據本發明之具體實例的包含銅、鉑或鎳之金屬觸媒的情況下，因為金屬觸媒之晶體形狀為矩形，所以沈積可以矩形的形式發生。此外，因為蝕刻不受Si或SiOx(0<x<2)的結晶性的影響，所以蝕刻可以無方向性之非線性孔的形式發生(參見圖1)。而且，因為蝕刻發生，其中當蝕刻部分(其為玉米形狀)逐漸移進Si或SiOx(0<x<2)粒子時，該等非線性孔的平均直徑可以粒子中心的方向逐漸減小。 On the other hand, in the case where a metal catalyst containing copper, platinum or nickel according to a specific example of the present invention is used, since the crystal shape of the metal catalyst is rectangular, the deposition may take place in a rectangular form. Further, since the etching is not affected by the crystallinity of Si or SiO x (0 < x < 2), the etching may occur in the form of non-directional nonlinear pores (see Fig. 1). Moreover, since etching occurs in which when the etched portion (which is a corn shape) is gradually moved into the Si or SiO x (0 < x < 2) particles, the average diameter of the nonlinear holes may gradually decrease in the direction of the particle center.

金屬觸媒沒有特別限制，只要其包括上述的金屬元素即可，但也可為包含上述金屬之鹽的形式。在此情況下，該鹽的陰離子可包括選自由下列所組成群組中之任一者：硝酸(NO3 -)、硫酸(SO4 2-)、碘(I-)、過氯酸鹽(ClO4 -)、及乙酸(CH3COO-)、或彼等的二或多者之混合物。 The metal catalyst is not particularly limited as long as it includes the above-described metal element, but may also be in the form of a salt containing the above metal. In this case, the anion of the salt may comprise one selected from the group consisting of nitric acid (NO 3 - ), sulfuric acid (SO 4 2- ), iodine (I - ), perchlorate ( ClO 4 - ), and acetic acid (CH 3 COO - ), or a mixture of two or more of them.

金屬觸媒的濃度可在5mM至100mM之範 圍。 The concentration of the metal catalyst can range from 5 mM to 100 mM. Wai.

根據本發明之一具體實例，蝕刻(攪拌)時間可在約3小時至約24小時之範圍，及該等非線性孔之形成度可由蝕刻時間改變。 According to one embodiment of the invention, the etching (stirring) time may range from about 3 hours to about 24 hours, and the degree of formation of the non-linear pores may be varied by etching time.

在該蝕刻時間小於3小時情況下，因為不形成本發明所要的孔，所以會無法獲得本發明所要的效果。在其中蝕刻時間大於24小時的情況下，因為由於蝕刻溶液的消耗而不再發生蝕刻，僅增加處理時間並且由於蝕刻時間而沒有效果。此外，因為在多孔矽基粒子的表面上觀察到龜裂和Si或SiOx(0<x<2)粒子被過度蝕刻，所以陽極活性材料的機械性質會劣化。 In the case where the etching time is less than 3 hours, since the pores of the present invention are not formed, the desired effects of the present invention cannot be obtained. In the case where the etching time is more than 24 hours, since the etching does not occur due to the consumption of the etching solution, only the processing time is increased and there is no effect due to the etching time. Further, since cracks and Si or SiO x (0 < x < 2) particles are excessively etched on the surface of the porous ruthenium-based particles, the mechanical properties of the anode active material may deteriorate.

根據本發明之一具體實例，該金屬觸媒的沈積可進行約1小時至約12小時。此外，就方法效率諸如時間及成本而言，該金屬觸媒的沈積及蝕刻二者可同時藉由混合及攪拌包含具有從中移除氧化物層的Si或SiOx(0<x<2)粒子之蝕刻溶液與金屬觸媒進行。 According to an embodiment of the invention, the deposition of the metal catalyst can be carried out for from about 1 hour to about 12 hours. In addition, in terms of method efficiency such as time and cost, both deposition and etching of the metal catalyst can simultaneously include Si or SiO x (0<x<2) particles having an oxide layer removed therefrom by mixing and stirring. The etching solution is carried out with a metal catalyst.

此外，根據本發明之一具體實例，在(ii)步驟中可將弱氧化劑進一步加至蝕刻溶液。在此情況下，弱氧化劑可增加化學蝕刻速率、透過矽的氧化可進一步形成另外的孔、及可促進蝕刻，以便使孔彼此連接。因此，弱氧化劑可增加由金屬觸媒所形成之孔的平均直徑。 Further, according to an embodiment of the present invention, a weak oxidizing agent may be further added to the etching solution in the step (ii). In this case, the weak oxidant can increase the chemical etch rate, further pores can be formed through the oxidation of the ruthenium, and the etching can be promoted to connect the pores to each other. Therefore, the weak oxidant can increase the average diameter of the pores formed by the metal catalyst.

在蝕刻方法中使用強氧化劑的情況下，因為該強氧化劑相較於弱氧化劑會過度增加化學蝕刻速率，所以矽連同金屬可被垂直蝕刻。因此，會難以形成本發明所 希望的非線性孔。 In the case where a strong oxidizing agent is used in the etching method, since the strong oxidizing agent excessively increases the chemical etching rate compared to the weak oxidizing agent, the germanium together with the metal can be vertically etched. Therefore, it may be difficult to form the present invention. The desired nonlinear hole.

根據本發明之具體實例可使用的弱氧化劑可包括選自由下列所組成群組中任一者：亞磷酸鹽、亞硫酸鹽、及磷酸鹽、或彼等的二或多者之混合物。例如，可使用亞磷酸鹽及該弱氧化劑的濃度可在0.25M至1.0M之範圍。 A weak oxidizing agent that can be used in accordance with specific embodiments of the present invention can include a mixture selected from the group consisting of phosphites, sulfites, and phosphates, or a mixture of two or more thereof. For example, the concentration of phosphite and the weak oxidant that can be used can range from 0.25 M to 1.0 M.

此外，根據本發明之一具體實例，在步驟(ii)中在Si或SiOx(0<x<2)粒子中形成該等非線性孔之後，可進一步包括移除殘留在粒子的金屬觸媒。 Further, according to an embodiment of the present invention, after forming the nonlinear pores in the Si or SiO x (0<x<2) particles in the step (ii), the metal catalyst remaining in the particles may be further removed. .

具有非線性孔形成於其中之Si或SiOx(0<x<2)粒子可與移除金屬的溶液接觸以移除金屬觸媒。 Si or SiO x (0 < x < 2) particles having nonlinear pores formed therein may be contacted with a metal removal solution to remove the metal catalyst.

可使用之移除金屬的溶液可包括選自由下列所組成群組中任一者：硝酸(HNO3)、硫酸(H2SO4)、及鹽酸(HCl)、或彼等的二或多者之混合物。 The solution in which the metal can be removed may include one selected from the group consisting of nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), and hydrochloric acid (HCl), or two or more of them. a mixture.

此外，多孔矽基粒子可進一步包含在該多孔矽基粒子上之碳塗層。 Further, the porous ruthenium-based particles may further comprise a carbon coating on the porous ruthenium-based particles.

一種形成碳塗層的方法可為一種使用碳前驅物的一般塗佈方法，及例如在蝕刻之後，形成碳塗層的方法可進一步包含藉由混合多孔矽基粒子與碳前驅物而用碳塗佈多孔矽基粒子的外表面，然後進行熱處理。 A method of forming a carbon coating may be a general coating method using a carbon precursor, and a method of forming a carbon coating, for example, after etching, may further include coating with carbon by mixing porous ruthenium particles with a carbon precursor. The outer surface of the porous ruthenium-based particles is then subjected to heat treatment.

可使用任何碳前驅物而沒有限制，只要其可藉由熱處理形成碳即可，且例如，可使用瀝青或烴基材料。烴基材料的例子可為糠醇或苯酚基樹脂。 Any carbon precursor can be used without limitation as long as it can form carbon by heat treatment, and for example, a pitch or a hydrocarbon-based material can be used. An example of the hydrocarbon-based material may be a decyl alcohol or a phenol based resin.

根據本發明之一具體實例，碳前驅物的用量以多孔矽基粒子的總重量為基準計可為10wt%至40wt%。 According to an embodiment of the present invention, the carbon precursor may be used in an amount of 10% by weight to 40% by weight based on the total mass of the porous cerium-based particles.

在碳前驅物的用量為小於10wt%的情況下，因為不會形成均勻塗層，所以導電率會降低。在其中碳前驅物的用量為大於40wt%的情況下，因為多孔矽基粒子的表面孔及內孔可用碳材料完全塗佈，所以可能無法獲得由多孔結構導致的性能改良效果且電量及初期效率由於額外不可逆反應的發生而會減少。 In the case where the amount of the carbon precursor is less than 10% by weight, since a uniform coating layer is not formed, the electrical conductivity is lowered. In the case where the amount of the carbon precursor is more than 40% by weight, since the surface pores and the inner pores of the porous ruthenium-based particles can be completely coated with the carbon material, the performance improvement effect by the porous structure and the electric quantity and initial efficiency may not be obtained. It will decrease due to the occurrence of additional irreversible reactions.

此外，例如，為了形成碳塗層，可使用四氫呋喃(THF)及醇作為溶劑，及該塗佈可藉由在300℃至1400℃的溫度範圍下進行熱處理來進行。 Further, for example, in order to form a carbon coating layer, tetrahydrofuran (THF) and an alcohol may be used as a solvent, and the coating may be carried out by heat treatment at a temperature ranging from 300 ° C to 1400 ° C.

根據本發明之具體實例的多孔矽基粒子之孔隙度以多孔矽基粒子的總體積為基準計係在5%至90%之範圍，可在10%至70%之範圍，及例如，可在10%至40%之範圍。 The porosity of the porous ruthenium-based particles according to the specific examples of the present invention is in the range of 5% to 90% based on the total volume of the porous ruthenium-based particles, may be in the range of 10% to 70%, and, for example, 10% to 40% range.

在此，孔隙度(%)可如下定義：孔隙度(%)={1-(多孔矽粒子的體密度/純矽粒子的體密度)}×100。 Here, the porosity (%) can be defined as follows: porosity (%) = {1 - (body density of porous cerium particles / bulk density of pure cerium particles)} × 100.

沒有特別限定孔隙度的測量。根據本發明之一具體實例，孔隙度(例如)可藉由BET方法或水銀(Hg)孔隙度測定法測定。 There is no particular limitation on the measurement of porosity. According to an embodiment of the invention, the porosity, for example, can be determined by a BET method or a mercury (Hg) porosimetry.

在多孔矽基粒子之孔隙度小於5%的情況下，可能不抑制在充電及放電期間陽極活性材料的體積膨脹。 在其中多孔矽基粒子之孔隙度就大於90%的情況下，機械強度由於陽極活性材料中所包括之多個孔而可能減小，且因此，陽極活性材料會在電池的製造方法(漿料混合、塗佈後擠壓、等等)期間斷裂。 In the case where the porosity of the porous ruthenium-based particles is less than 5%, the volume expansion of the anode active material during charging and discharging may not be inhibited. In the case where the porosity of the porous ruthenium-based particles is more than 90%, the mechanical strength may be reduced due to a plurality of pores included in the anode active material, and therefore, the anode active material may be in a battery manufacturing method (slurry) Breaking during mixing, extrusion after coating, etc.).

此外，本發明可提供一種包含多孔矽基粒子之陽極活性材料。 Further, the present invention can provide an anode active material comprising porous ruthenium-based particles.

根據本發明之一具體實例的陽極活性材料可進一步包括碳基材料。即，陽極活性材料可藉由混合多孔矽基粒子與通常使用之碳基材料而使用於二次電池中。 The anode active material according to an embodiment of the present invention may further include a carbon-based material. That is, the anode active material can be used in a secondary battery by mixing porous ruthenium-based particles with a commonly used carbon-based material.

通常使用之碳基材料可為至少一種選自由下列所組成群組中之至少一者：天然石墨、人造石墨、中間相碳微球(MCMB)、碳纖維、及碳黑。 The carbon-based material generally used may be at least one selected from the group consisting of natural graphite, artificial graphite, mesocarbon microbeads (MCMB), carbon fibers, and carbon black.

碳基材料包含量以100重量份的多孔矽基粒子為基準計可為0重量份至90重量份，例如，70重量份至95重量份。 The carbon-based material may be included in an amount of from 0 part by weight to 90 parts by weight, for example, from 70 parts by weight to 95 parts by weight based on 100 parts by weight of the porous sulfonium-based particles.

本發明也提供一種包含陽極活性材料之陽極。 The invention also provides an anode comprising an anode active material.

而且，本發明可提供一種包含陰極、陽極、配置在陰極和陽極之間的分隔膜，及鋰鹽溶解於其中之電解質的鋰二次電池，其中該陽極包括一包含多孔矽基粒子之陽極活性材料。 Moreover, the present invention can provide a lithium secondary battery comprising a cathode, an anode, a separator disposed between the cathode and the anode, and an electrolyte in which the lithium salt is dissolved, wherein the anode includes an anode active comprising porous cerium-based particles material.

如此製備之陽極活性材料可用於藉由該項技術中一般方法製備陽極。例如，根據本發明之具體實例的陽極活性材料與黏合劑、溶劑、及導電劑且如果需要的話 分散劑混合，及攪拌，以製備漿料。然後，可用有漿料塗佈集電器及擠壓，以製備陽極。 The anode active material thus prepared can be used to prepare an anode by a general method in the art. For example, an anode active material according to a specific example of the present invention is bonded to a binder, a solvent, and a conductive agent, and if necessary The dispersant is mixed and stirred to prepare a slurry. Then, the slurry can be coated with a current collector and extruded to prepare an anode.

各種類型的黏合劑聚合物，諸如偏二氟乙烯-六氟丙烯共聚物(PVDF-共-HEP)、聚偏二氟乙烯、聚丙烯腈、聚甲基丙烯酸甲酯、聚乙烯醇、羧甲基纖維素(CMC)、澱粉、羥丙基纖維素、再生纖維素、聚乙烯基吡咯啶酮、四氟乙烯、聚乙烯、聚丙烯、乙烯-丙烯-二烯單體(EPDM)、磺化EPDM、苯乙烯-丁二烯橡膠(SBR)、氟橡膠、聚丙烯酸和具有其氫以鋰(Li)、鈉(Na)及鈣(Ca)取代之聚合物可被用作黏合劑。N-甲基吡咯啶酮、丙酮或水可被用作溶劑。 Various types of binder polymers, such as vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HEP), polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl Cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomer (EPDM), sulfonation EPDM, styrene-butadiene rubber (SBR), fluororubber, polyacrylic acid, and polymers having hydrogen substituted with lithium (Li), sodium (Na), and calcium (Ca) can be used as the binder. N-methylpyrrolidone, acetone or water can be used as the solvent.

可使用任何導電劑而沒有特別的限制，只要其具有適當導電而不會在電池中造成不利的化學變化即可。例如，導電劑可包含導電材料諸如：石墨諸如天然和人造石墨；碳黑諸如乙炔黑、科琴黑(Ketjen black)、槽黑(channel black)、爐黑、燈黑、和熱碳黑(thermal black)；導電纖維諸如碳纖維和金屬纖維；導電管諸如碳奈米管；金屬粉末諸如氟碳粉末、鋁粉、和鎳粉；導電晶鬚諸如氧化鋅晶鬚和鈦酸鉀晶鬚；導電金屬氧化物諸如氧化鈦；或聚伸苯基衍生物。 Any conductive agent can be used without particular limitation as long as it has appropriate conductivity without causing adverse chemical changes in the battery. For example, the conductive agent may comprise a conductive material such as: graphite such as natural and artificial graphite; carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal carbon black (thermal Black); conductive fibers such as carbon fibers and metal fibers; conductive tubes such as carbon nanotubes; metal powders such as fluorocarbon powder, aluminum powder, and nickel powder; conductive whiskers such as zinc oxide whiskers and potassium titanate whiskers; A metal oxide such as titanium oxide; or a polyphenylene derivative.

水基分散劑或有機分散劑(諸如N-甲基-2-吡咯啶酮)可用作分散劑。 A water-based dispersant or an organic dispersant such as N-methyl-2-pyrrolidone can be used as the dispersing agent.

類似於陽極的製備，混合陰極活性材料、導電劑、黏合劑及溶劑以製備漿料，及然後可藉由用該漿料 直接塗佈金屬集電器或藉由將漿料澆鑄獨立載體上及將與載體膜分離之陰極活性材料膜層壓在金屬集電器而製得陰極。 Similar to the preparation of the anode, a cathode active material, a conductive agent, a binder, and a solvent are mixed to prepare a slurry, and then the slurry can be used The cathode is prepared by directly coating a metal current collector or by laminating a slurry on a separate carrier and laminating a cathode active material film separated from the carrier film on a metal current collector.

陰極活性材料的例子可為層狀化合物，諸如鋰鈷氧化物(LiCoO2)、鋰鎳氧化物(LiNiO2)、Li[NixCoyMnzMv]O2(其中M係選自由下列所組成群組中之任一者：鋁(Al)、鎵(Ga)、及銦(In)、或彼等的二或多個元素；及0.3x<0.1，0y，z0.5，0v0.1，及x+y+z+v=1)、Li(LiaMb-a-b’M’b’)O2-cAc(其中0a0.2，0.6b1，0b’0.2，及0c0.2；M包含錳(Mn)及選自由下列所組成群組中之至少一者：Ni、鈷(Co)、鐵(Fe)、鉻(Cr)、釩(V)、Cu、鋅(Zn)及鈦(Ti)；M’為選自由下列所組成群組中之至少一者：Al、鎂(Mg)及硼(B)；及A為選自由下列所組成群組中之至少一者：磷(P)、氟(F)、硫(S)及氮(N))，或以一或多個過渡金屬取代的化合物；鋰錳氧化物諸如化學式Li1+yMn2-yO4(其中y範圍從0至0.33)、LiMnO3、LiMn2O3、及LiMnO2；鋰銅氧化物(Li2CuO2)；釩氧化物諸如LiV3O8、LiFe3O4、V2O5、和Cu2V2O7；以化學式LiNi1-yMyO2表示的Ni-位置型鋰鎳氧化物(其中M為Co、Mn、Al、Cu、Fe、Mg、B、或Ga，及y範圍從0.01至0.3)；以化學式LiMn2-yMyO2表示的鋰錳錯合氧化物(其中M為Co、Ni、Fe、Cr、Zn、或鉭(Ta)，及y範圍從0.01至0.1)或Li2Mn3MO8(其中M為Fe、Co、Ni、Cu、或Zn)；具有一部分Li以鹼土金屬離子取代之 LiMn2O4；二硫化合物；及Fe2(MoO4)3。然而，陰極活性材料不限於此。 An example of the cathode active material may be a layered compound such as lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), Li[Ni x Co y Mn z M v ]O 2 (wherein M is selected from the following Any of the group consisting of: aluminum (Al), gallium (Ga), and indium (In), or two or more of them; and 0.3 x<0.1,0 y,z 0.5,0 v 0.1, and x+y+z+v=1), Li(Li a M ba-b' M'b' )O 2-c A c (where 0 a 0.2, 0.6 b 1,0 b' 0.2, and 0 c 0.2; M comprises manganese (Mn) and is selected from at least one of the group consisting of Ni, cobalt (Co), iron (Fe), chromium (Cr), vanadium (V), Cu, zinc (Zn) And titanium (Ti); M' is at least one selected from the group consisting of: Al, magnesium (Mg), and boron (B); and A is at least one selected from the group consisting of: Phosphorus (P), fluorine (F), sulfur (S) and nitrogen (N)), or a compound substituted with one or more transition metals; lithium manganese oxide such as the chemical formula Li 1+y Mn 2-y O 4 ( Wherein y ranges from 0 to 0.33), LiMnO 3 , LiMn 2 O 3 , and LiMnO 2 ; lithium copper oxide (Li 2 CuO 2 ); vanadium oxide such as LiV 3 O 8 , LiFe 3 O 4 , V 2 O 5 And Cu 2 V 2 O 7 ; Ni-position type lithium nickel oxide represented by the chemical formula LiNi 1-y M y O 2 (wherein M is Co, Mn, Al, Cu, Fe, Mg, B, or Ga, And y range from 0.01 to 0.3); a lithium manganese complex oxide represented by the chemical formula LiMn 2-y M y O 2 (wherein M is Co, Ni, Fe, Cr, Zn, or yttrium (Ta), and y range From 0.01 to 0.1) or Li 2 Mn 3 MO 8 (wherein M is Fe, Co, Ni, Cu, or Zn); LiMn 2 O 4 having a portion of Li substituted with an alkaline earth metal ion; disulfide compound ; and Fe 2 (MoO 4 ) 3 . However, the cathode active material is not limited thereto.

用作一般分隔膜之一般多孔材料聚合物膜(例如，自以聚烯烴為主的聚合物(諸如乙烯均聚物、丙烯均聚物、乙烯/丁烯共聚物、乙烯/己烯共聚物，和乙烯/甲基丙烯酸酯共聚物)製造的多孔聚合物膜)可以單獨使用或與其層壓作為分隔器。此外，可使用一般多孔非織物，例如，高熔點玻璃纖維或聚對酞酸乙二酯纖維形成的非織物及具有其至少一個表面上塗佈有陶瓷的聚合物分隔膜基材。然而，本發明不限於此。 A general porous material polymer film used as a general separator film (for example, a polyolefin-based polymer (such as an ethylene homopolymer, a propylene homopolymer, an ethylene/butene copolymer, an ethylene/hexene copolymer, The porous polymer film produced by copolymerization with ethylene/methacrylate) can be used alone or laminated as a separator. Further, a general porous nonwoven fabric such as a non-woven fabric formed of high-melting glass fiber or polyethylene terephthalate fibers and a polymer separator film substrate having at least one surface coated with a ceramic may be used. However, the invention is not limited thereto.

在本發明之一具體實例中所使用的電解質溶液中，可使用可包括作為該電解質的鋰鹽而沒有限制，只要其通常用於二次電池之電解質溶液中即可。例如，可使用選自由下列所組成群組中之至少一者：F-、Cl-、I-、NO3 -、N(CN)2 -、BF4 -、ClO4 -、PF6 -、(CF3)2PF4 -、(CF3)3PF3 -、(CF3)4PF2 -、(CF3)5PF-、(CF3)6P-、CF3SO3 -、CF3CF2SO3-、(CF3SO2)2N-、(FSO2)2N-、CF3CF2(CF3)2CO-、(CF3SO2)2CH-、(SF5)3C-、(CF3SO2)3C-、CF3(CF2)7SO3 -、CF3CO2 -、CH3CO2 -、SCN-、及(CF3CF2SO2)2N-作為鋰鹽的陰離子。 In the electrolyte solution used in one embodiment of the present invention, a lithium salt which can be included as the electrolyte can be used without limitation as long as it is generally used in an electrolyte solution of a secondary battery. For example, at least one selected from the group consisting of F - , Cl - , I - , NO 3 - , N(CN) 2 - , BF 4 - , ClO 4 - , PF 6 - , ( CF 3 ) 2 PF 4 - , (CF 3 ) 3 PF 3 - , (CF 3 ) 4 PF 2 - , (CF 3 ) 5 PF - , (CF 3 ) 6 P - , CF 3 SO 3 - , CF 3 CF 2 SO 3 -, (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , (SF 5 ) 3 C - , (CF 3 SO 2 ) 3 C - , CF 3 (CF 2 ) 7 SO 3 - , CF 3 CO 2 - , CH 3 CO 2 - , SCN - , and (CF 3 CF 2 SO 2 ) 2 N - an anion as a lithium salt.

在本發明之一具體實例中所使用的電解質溶液中，可使用包括在該電解質中的有機溶劑而沒有限制，只要其通常用於該項技術中即可。通常，可使用選自由下列所組成群組中任一者：碳酸丙二酯、碳酸乙二酯、碳酸 二乙酯、碳酸二甲酯、碳酸甲乙酯、碳酸甲丙酯、碳酸二丙酯、碳酸氟乙二酯、二甲亞碸、乙腈、二甲氧乙烷、二乙氧乙烷、碳酸乙烯二酯、環丁碸、γ-丁內酯、亞硫酸丙二酯、四氫呋喃、甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸異丙酯、乙酸異戊酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、丁酸甲酯、及丁酸乙酯、或彼等的二或多者之混合物。 In the electrolyte solution used in one embodiment of the present invention, an organic solvent included in the electrolyte may be used without limitation as long as it is generally used in the art. Generally, any one selected from the group consisting of propylene carbonate, ethylene carbonate, carbonic acid can be used. Diethyl ester, dimethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, dipropyl carbonate, fluoroethylene carbonate, dimethyl hydrazine, acetonitrile, dimethoxyethane, diethoxyethane, carbonic acid Ethylene diester, cyclobutyl hydrazine, γ-butyrolactone, propylene sulfite, tetrahydrofuran, methyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isoamyl acetate, methyl propionate, C Ethyl acetate, propyl propionate, butyl propionate, methyl butyrate, and ethyl butyrate, or a mixture of two or more of them.

特別地，以碳酸酯為主的有機溶劑之中，碳酸乙二酯和碳酸丙二酯(環型碳酸酯)由於因高黏度有機溶劑之高介電常數而良好離解電解質中的鋰鹽，且因此，可使用環型碳酸酯。因為當環型碳酸酯與低黏度、低介電常數的直鏈碳酸酯(如碳酸二甲酯和碳酸二乙酯)以適當比例混合時可製備具有高導電性之電解質，所以例如可使用環型碳酸酯。 In particular, among the organic solvents mainly composed of carbonates, ethylene carbonate and propylene carbonate (cyclocarbonate) are excellent in dissociating the lithium salt in the electrolyte due to the high dielectric constant of the high viscosity organic solvent, and Therefore, a cyclic carbonate can be used. Since an electrolyte having high conductivity can be prepared when a cyclic carbonate is mixed with a low-viscosity, low-dielectric linear carbonate such as dimethyl carbonate and diethyl carbonate in an appropriate ratio, for example, a ring can be used. Type carbonate.

選擇性地，根據本發明儲存的電解質可進一步包括添加劑，諸如過充電抑制劑，即包括在一般電解質中。 Alternatively, the electrolyte stored according to the present invention may further include an additive such as an overcharge inhibitor, that is, included in a general electrolyte.

分隔膜配置在陰極及陽極之間以形成電極組件，該電極組件放置在圓柱形電池殼體或棱柱形電池殼體或鋁袋，及當電解質注入其中時，則完成二次電池。此外，將電極組件堆疊並用電解質溶液浸漬，及當如此得到的產物放入電池殼體及封口時，則完成二次電池。 A separator is disposed between the cathode and the anode to form an electrode assembly, which is placed in a cylindrical battery case or a prismatic battery case or an aluminum bag, and when the electrolyte is injected therein, the secondary battery is completed. Further, the electrode assembly is stacked and impregnated with an electrolyte solution, and when the product thus obtained is placed in the battery case and sealed, the secondary battery is completed.

根據本發明之鋰二次電池不僅可用於用作小型裝置的電源之電池單元，且也可用作在包括多個電池單 元之中型和大型電池模組中的單元電池。中型和大型裝置的較佳例子可為電動車、混合電動車、插電式混合電動車或電力存儲系統，但該中型和大型裝置不限於此。 The lithium secondary battery according to the present invention can be used not only as a battery unit used as a power source for a small device, but also as a plurality of battery sheets Unit cells in medium and large battery modules. A preferred example of the medium and large devices may be an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, or a power storage system, but the medium and large devices are not limited thereto.

在下文中，將根據特定實例詳細描述本發明。然而，本發明可以許多不同形式具體化且不應解釋為限於本文中所闡述之具體實例。而是，提供這些具體實例以使本說明將是徹底及完整的，並將本發明的概念範圍充分地傳達至熟習該項技術者。 Hereinafter, the present invention will be described in detail based on specific examples. However, the invention may be embodied in many different forms and should not be construed as being limited to the specific examples set forth herein. Instead, the specific examples are provided so that this description will be thorough and complete, and the scope of the present invention will be fully conveyed to those skilled in the art.

實例 Instance <多孔矽粒子的製備> <Preparation of porous ruthenium particles> 實例1 Example 1 <步驟(i)：使用蝕刻溶液移除存在於Si或SiOx(0<x<2)粒子的表面上之氧化物層> <Step (i): Removing an oxide layer existing on the surface of Si or SiO x (0 < x < 2) particles using an etching solution >

矽以粉末狀態浸漬在加熱至50℃的溫度之8.5M氟化氫中，且然後攪拌約30分鐘。透過上述方法移除以粉末狀態存在於矽的表面上之天然氧化物層(SiO2)。因此，藉由進行表面處理獲得從具有從中移除氧化物層的矽粒子，其可允許使用無電金屬沈積用金屬觸媒更平滑及均勻地塗佈Si或SiOx(0<x<2)粒子。 The crucible was impregnated in a powder state in 8.5 M hydrogen fluoride heated to a temperature of 50 ° C, and then stirred for about 30 minutes. The natural oxide layer (SiO 2 ) present on the surface of the crucible in a powder state is removed by the above method. Therefore, the ruthenium particles having the oxide layer removed therefrom are obtained by surface treatment, which allows the smooth or uniform coating of Si or SiO x (0<x<2) particles using the metal catalyst for electroless metal deposition. .

<步驟(ii)：藉由以混合及攪拌包含具有從中移 除氧化物層的Si或SiOx(0<x<2)粒子之蝕刻溶液與金屬觸媒來蝕刻Si或SiOx(0<x<2)粒子而在Si或SiOx(0<x<2)粒子中形成非線性孔> <Step (ii): etching Si or SiO x by mixing and stirring an etching solution containing a Si or SiO x (0<x<2) particle having an oxide layer removed therefrom and a metal catalyst (0<x) <2) Particles form nonlinear pores in Si or SiO x (0<x<2) particles>

將與氟化氫相同體積的所製得之15mM硫酸銅(CuSO4)水溶液加至步驟中(i)所獲得之包含具有從中移除氧化物層(SiO2)的矽之水溶液，其中混合8.5M氟化氫，及攪拌約3小時以進行蝕刻。透過上述方法將銅沈積在具有從中移除氧化物層(SiO2)的矽之表面上，且同時，進行蝕刻。 The same volume of the obtained 15 mM aqueous solution of copper sulfate (CuSO 4 ) as the hydrogen fluoride was added to the aqueous solution obtained in the step (i) containing ruthenium having the oxide layer (SiO 2 ) removed therefrom, wherein 8.5 M hydrogen fluoride was mixed. And stirring for about 3 hours for etching. Copper is deposited on the surface of the crucible having the oxide layer (SiO 2 ) removed therefrom by the above method, and at the same time, etching is performed.

在水溶液狀態，藉由使用能夠同時進行過濾、洗滌、及脫水的壓濾機將多孔矽粒子洗滌數次來移除其餘氟化氫。其後，將如此獲得之溶液過濾、脫水及在約150℃下進行乾燥約1小時以獲得其中非線性孔彼此連接之多孔矽粒子。 In the aqueous solution state, the remaining hydrogen fluoride is removed by washing the porous tantalum particles several times using a filter press capable of simultaneous filtration, washing, and dehydration. Thereafter, the solution thus obtained was filtered, dehydrated, and dried at about 150 ° C for about 1 hour to obtain porous tantalum particles in which nonlinear pores were connected to each other.

為了去除殘留在以上述方法製備之多孔矽粒子上的銅，將硝酸物加熱到50℃的溫度，且然後將多孔矽粒子浸漬在硝酸中約2小時以移除銅。 In order to remove copper remaining on the porous tantalum particles prepared in the above manner, the nitrate was heated to a temperature of 50 ° C, and then the porous tantalum particles were immersed in nitric acid for about 2 hours to remove copper.

實例2至6 Examples 2 to 6

以與實例1中相同的方式製備多孔矽粒子，除了將與氟化氫相同體積的所製得之15mM硫酸銅(CuSO4)水溶液加至步驟中(i)所獲得之包含具有從中移除氧化物層(SiO2)的矽之水溶液，其中混合8.5M氟化氫，及分別攪拌約6小時、9小時、12小時、18小時、及24 小時之外。 Porous cerium particles were prepared in the same manner as in Example 1, except that the same volume of the obtained 15 mM aqueous solution of copper sulphate (CuSO 4 ) as the hydrogen fluoride was added to the step (i) to obtain an oxide layer removed therefrom. An aqueous solution of (SiO 2 ) in which 8.5 M of hydrogen fluoride was mixed and stirred for about 6 hours, 9 hours, 12 hours, 18 hours, and 24 hours, respectively.

實例7 Example 7 <步驟(i)：使用蝕刻溶液移除存在於Si或SiOx(0<x<2)粒子的表面上之氧化物層> <Step (i): Removing an oxide layer existing on the surface of Si or SiO x (0 < x < 2) particles using an etching solution >

將粉末狀矽浸漬在加熱至50℃的溫度之17.5M氟化氫，且然後攪拌約30分鐘。透過上述方法移除存在於粉末狀矽的表面上之天然氧化物層(SiO2)。因此，藉由進行可允許使用無電金屬沈積以金屬觸媒更平滑及均勻地塗佈Si或SiOx(0<x<2)粒子之表面處理獲得具有從中移除氧化物層的矽粒子。 The powdery crucible was immersed in 17.5 M of hydrogen fluoride heated to a temperature of 50 ° C, and then stirred for about 30 minutes. The natural oxide layer (SiO 2 ) present on the surface of the powdery crucible is removed by the above method. Therefore, the ruthenium particles having the oxide layer removed therefrom are obtained by performing a surface treatment which allows the use of electroless metal deposition to coat the Si or SiO x (0 < x < 2) particles more smoothly and uniformly with the metal catalyst.

<步驟(ii)：藉由以混合及攪拌包含具有從中移除氧化物層的Si或SiOx(0<x<2)粒子之蝕刻溶液與金屬觸媒來蝕刻Si或SiOx(0<x<2)粒子而在Si或SiOx(0<x<2)粒子中形成非線性孔> <Step (ii): etching Si or SiO x by mixing and stirring an etching solution containing a Si or SiO x (0<x<2) particle having an oxide layer removed therefrom and a metal catalyst (0<x) <2) Particles form nonlinear pores in Si or SiO x (0<x<2) particles>

將與氟化氫相同體積的所製得之30mM硫酸銅(CuSO4)水溶液加至一水溶液，其中混合17.5M氟化氫及步驟(i)中所獲得之具有從中移除氧化物層(SiO2)的矽，及攪拌約1小時。透過上述方法將銅均勻地沈積在具有從中移除氧化物層(SiO2)的矽之表面上。 An aqueous solution of 30 mM copper sulfate (CuSO 4 ) prepared in the same volume as hydrogen fluoride was added to an aqueous solution in which 17.5 M of hydrogen fluoride was mixed and the ruthenium obtained in the step (i) having the oxide layer (SiO 2 ) removed therefrom And stir for about 1 hour. Copper is uniformly deposited on the surface of the crucible having the oxide layer (SiO 2 ) removed therefrom by the above method.

在包含具有從中移除氧化物層(SiO2)的矽之水溶液中，其中混合17.5M氟化氫，製備0.5M亞磷酸鹽 (H3PO3)水溶液以具有1/3體積之氟化氫，且然後加至在上述金屬沈積步驟中所得之包含銅沈積的矽之水溶液。當此混合物在50℃下混合約21小時時，用銅沈積之部分和以亞磷酸鹽氧化之表面只被化學蝕刻選擇性地蝕刻，且因此，製得其中非線性孔彼此連接之多孔矽。 In an aqueous solution containing ruthenium having an oxide layer (SiO 2 ) removed therefrom, 17.5 M of hydrogen fluoride is mixed therein to prepare a 0.5 M aqueous solution of phosphite (H 3 PO 3 ) to have 1/3 volume of hydrogen fluoride, and then added An aqueous solution containing copper-deposited ruthenium obtained in the above metal deposition step. When the mixture was mixed at 50 ° C for about 21 hours, the portion deposited with copper and the surface oxidized with phosphite were selectively etched only by chemical etching, and thus, porous ruthenium in which nonlinear pores were connected to each other was obtained.

在此情況下，使用沈積在矽上之銅作為觸媒來還原矽及使用亞磷酸鹽作為弱氧化劑氧化矽以增加化學蝕刻速率。 In this case, copper deposited on the crucible is used as a catalyst to reduce hydrazine and phosphite is used as a weak oxidant cerium oxide to increase the chemical etching rate.

即，亞磷酸鹽用作弱氧化劑可增加由銅所形成的孔之大小或可透過矽的氧化來形成另外的孔。 That is, the use of phosphite as a weak oxidant increases the size of the pores formed by copper or the oxidation of the ruthenium to form additional pores.

比較例1 Comparative example 1

以與實例1相同之方式製備多孔矽粒子，除了使用硝酸銀水溶液代替實例1之步驟(ii)中的硫酸銅(CuSO4)水溶液之外。 Porous cerium particles were prepared in the same manner as in Example 1 except that an aqueous solution of silver nitrate was used instead of the aqueous solution of copper sulphate (CuSO 4 ) in the step (ii) of Example 1.

比較例2 Comparative example 2

以與實例7中相同的方式製備多孔矽粒子，除了使用硝酸鐵(Fe(NO3)3)(或其他強氧化劑)替代實例7步驟(ii)中之0.5M亞磷酸鹽(H3PO3)水溶液之外。 Porous cerium particles were prepared in the same manner as in Example 7, except that ferric nitrate (Fe(NO 3 ) 3 ) (or other strong oxidizing agent) was used instead of 0.5 M phosphite (H 3 PO 3 in Example 7, step (ii). Outside the aqueous solution.

比較例3 Comparative example 3

以與實例1中相同的方式製備多孔矽粒子，除了在實例1之步驟(ii)中蝕刻進行28小時之外。 Porous cerium particles were prepared in the same manner as in Example 1, except that etching was carried out for 28 hours in the step (ii) of Example 1.

比較例4 Comparative example 4

以與實例1中相同的方式製備多孔矽粒子，除了在實例1之步驟(ii)中蝕刻進行1小時之外。 Porous cerium particles were prepared in the same manner as in Example 1 except that etching was carried out for 1 hour in the step (ii) of Example 1.

<二次電池的製備> <Preparation of secondary battery> 實例8 Example 8

使用實例1中所製備的多孔矽基粒子作為陽極活性材料。將陽極活性材料、作為導電劑的乙炔黑、及作為黏合劑的聚偏二氟乙烯以70：10：20的重量比混合，並將該混合物與N-甲基-2-吡咯啶酮溶劑混合，以製備漿料。用所製備的漿料塗佈銅集電器的一表面至30μm的厚度，乾燥及軋輥。然後，藉由衝壓成預定的尺寸而製備陽極。 The porous ruthenium-based particles prepared in Example 1 were used as an anode active material. The anode active material, acetylene black as a conductive agent, and polyvinylidene fluoride as a binder are mixed in a weight ratio of 70:10:20, and the mixture is mixed with a solvent of N-methyl-2-pyrrolidone To prepare a slurry. A surface of the copper current collector was coated with the prepared slurry to a thickness of 30 μm, dried and rolled. Then, an anode is prepared by punching into a predetermined size.

將10wt%碳酸氟乙二酯(以電解質溶液的總重量為基準計)加至混合溶劑中，其包括1.0M LiPF6及以30：70的重量比混合碳酸乙二酯及碳酸二乙酯製備之有機溶劑，以製備非水性電解質溶液。 10 wt% of fluoroethylene carbonate (based on the total weight of the electrolyte solution) was added to a mixed solvent comprising 1.0 M LiPF 6 and a mixture of ethylene carbonate and diethyl carbonate in a weight ratio of 30:70. An organic solvent to prepare a non-aqueous electrolyte solution.

使用鋰箔作為相對電極，在二個電極之間配置聚烯烴分隔膜，及然後藉由注入該電解質溶液以製備硬幣型半電池。 A lithium foil was used as a counter electrode, a polyolefin separator film was disposed between the two electrodes, and then a coin type half cell was prepared by injecting the electrolyte solution.

實例9至14 Examples 9 to 14

以與實例8中相同的方式製備硬幣型半電池，除了使用實例2至7中所製備的多孔矽基粒子作為陽極活性材料，而不是使用實例1中所製備的多孔矽基粒子之外。 A coin-type half-cell was prepared in the same manner as in Example 8, except that the porous ruthenium-based particles prepared in Examples 2 to 7 were used as the anode active material instead of the porous ruthenium-based particles prepared in Example 1.

實例15 Example 15

以與實例8中相同的方式製備一硬幣型半電池，除了用10wt%的碳塗佈實例5中所製備之多孔矽粒子及使用其中碳塗佈之多孔矽粒子和石墨係以50：50之比率混合的陽極活性材料之外。 A coin-type half-cell was prepared in the same manner as in Example 8, except that the porous tantalum particles prepared in Example 5 were coated with 10% by weight of carbon and the porous tantalum particles and graphite in which carbon coating was used were 50:50. The ratio is mixed outside the anode active material.

比較例5 Comparative Example 5

以與實例8中相同的方式製備一硬幣型半電池，除了使用純Si粒子作為陽極活性材料，而不是使用實例1中所製備的多孔矽基粒子之外。 A coin-type half-cell was prepared in the same manner as in Example 8 except that pure Si particles were used as the anode active material instead of the porous ruthenium-based particles prepared in Example 1.

比較例6至9 Comparative Examples 6 to 9

以與實例8中相同的方式製備一硬幣型半電池，除了使用比較例1至4中所製備的多孔矽基粒子作為陽極活性材料，而不是使用實例1中所製備的多孔矽基粒子之外。 A coin-type half-cell was prepared in the same manner as in Example 8 except that the porous ruthenium-based particles prepared in Comparative Examples 1 to 4 were used as the anode active material instead of the porous ruthenium-based particles prepared in Example 1. .

比較例10 Comparative Example 10

以與實例8中相同的方式製備一硬幣型半電 池，除了用10wt%的碳塗佈比較例4中所製備之多孔矽粒子及使用其中碳塗佈之多孔矽粒子和石墨係以50：50之比率混合的陽極活性材料之外。 A coin type semi-electricity was prepared in the same manner as in Example 8. The pool was prepared except that the porous tantalum particles prepared in Comparative Example 4 were coated with 10 wt% of carbon and the anode active material in which carbon coated porous tantalum particles and graphite were mixed at a ratio of 50:50.

實驗例1 Experimental example 1 <掃描電子顯微鏡(SEM)影像> <Scanning Electron Microscope (SEM) Image>

包含在實例1至6中所得之多孔矽基粒子中的非線性孔之表面形態根據蝕刻時間用SEM鑑定。其結果示於圖3中。 The surface morphology of the nonlinear pores contained in the porous sulfhydryl particles obtained in Examples 1 to 6 was identified by SEM according to the etching time. The result is shown in Fig. 3.

參照圖3，可確認：實例1之多孔矽基粒子的表面中形成孔，其中蝕刻進行3小時，及在粒子中所形成之孔的形成度和直徑傾向於隨刻時間增加到如在實例2至6中之6小時、9小時、12小時、18小時、及24小時而增加。 Referring to Fig. 3, it was confirmed that pores were formed in the surface of the porous ruthenium-based particles of Example 1, in which etching was performed for 3 hours, and the degree of formation and diameter of pores formed in the particles tend to increase with time as in Example 2 Increased to 6 hours, 9 hours, 12 hours, 18 hours, and 24 hours.

此外，可確認：包含在實例2至6(其中蝕刻進行6小時或更久)之多孔矽基粒子中的非線性孔之至少二個或多個孔係彼此連接。 Further, it was confirmed that at least two or more pores of the nonlinear pores contained in the porous ruthenium-based particles of Examples 2 to 6 in which etching was performed for 6 hours or longer were connected to each other.

關於實例6(其中蝕刻進行約24小時)，可確認：包含在多孔矽基粒子中之非線性孔幾乎彼此連接，且也證實：孔的深度在實例6(其中蝕刻進行約24小時)中為最大。 With respect to Example 6 (where the etching was carried out for about 24 hours), it was confirmed that the nonlinear pores contained in the porous ruthenium-based particles were almost connected to each other, and it was also confirmed that the depth of the pores was in Example 6 (where etching was performed for about 24 hours). maximum.

據認為：粒子之非線性孔的深度增加，因為作為金屬觸媒之沉積在矽的表面上之銅的大小隨蝕刻時間 增加而被氟化氫增加。 It is believed that the depth of the nonlinear pores of the particles increases because the size of the copper deposited on the surface of the crucible as a metal catalyst varies with the etching time. Increased and increased by hydrogen fluoride.

用SEM鑑定實例7(其中使用亞磷酸鹽(H3PO3)作為弱氧化劑進行蝕刻)之多孔矽粒子的表面形態。其結果出示於圖4中。 The surface morphology of the porous cerium particles of Example 7 in which phosphite (H 3 PO 3 ) was used as a weak oxidizing agent was identified by SEM. The results are shown in Figure 4.

如圖4中所示，可觀察到：在整個多孔矽粒子上形成多個非線性孔，且該等非線性孔係形成為在粒子的表面中之開孔。此外，確認：該等非線性孔的平均直徑是在約幾十至幾百奈米的範圍。 As shown in FIG. 4, it can be observed that a plurality of nonlinear pores are formed on the entire porous tantalum particles, and the nonlinear pores are formed as openings in the surface of the particles. Further, it was confirmed that the average diameter of the nonlinear holes was in the range of about several tens to several hundreds of nanometers.

當相較於用銀作為觸媒之一般化學蝕刻方法，相似性在於：僅有接觸觸媒的部分被蝕刻。然而，在使用銀作為觸媒的情況下，因為蝕刻發生在垂直於矽的表面之方向，所以可形成直線形式的孔(參見圖2及6)。 When compared to the general chemical etching method using silver as a catalyst, the similarity is that only the portion contacting the catalyst is etched. However, in the case where silver is used as the catalyst, since the etching occurs in a direction perpendicular to the surface of the crucible, a hole in a straight line form can be formed (see Figs. 2 and 6).

相比之下，在其中在本發明具體實例中使用銅作為觸媒情況下，可確認：因為銅晶體的形狀為矩形，所以銅沉積可以矩形的形式發生。亦可確認，因為蝕刻不受矽的結晶性影響，所以蝕刻可以無方向性之非線性孔的形式發生。 In contrast, in the case where copper is used as a catalyst in the specific example of the present invention, it can be confirmed that since the shape of the copper crystal is a rectangle, the copper deposition can occur in a rectangular form. It was also confirmed that since etching is not affected by the crystallinity of germanium, etching can occur in the form of non-directional nonlinear pores.

圖5為顯示實例7中所得多孔矽粒子切片後之內剖面的電子顯微鏡影像。 Fig. 5 is an electron microscope image showing the inner cross section of the porous ruthenium particles obtained in Example 7.

為了鑑定實例7中所製備的多孔矽粒子之內剖面的形態，用氬(Ar)-離子銑切裝置將多孔矽粒子橫剖開並用電子顯微鏡分析內剖面。 In order to identify the morphology of the inner cross section of the porous tantalum particles prepared in Example 7, the porous tantalum particles were cross-sectioned by an argon (Ar)-ion milling device and the inner cross section was analyzed by an electron microscope.

參照圖5，確認：形成實例7中所製備的多孔矽粒子之孔最多至粒子的內側，並可確認：無方向性之非 線性孔在多孔矽粒子中彼此連接。 Referring to Fig. 5, it was confirmed that the pores of the porous tantalum particles prepared in Example 7 were formed up to the inside of the particles, and it was confirmed that: The linear pores are connected to each other in the porous tantalum particles.

當比較在多孔矽粒子的內側/外側中形成的孔之平均直徑時，確認：在其內側形成之孔的平均直徑傾向於小於在其外側形成之孔的平均直徑。 When the average diameter of the pores formed in the inner side/outer side of the porous tantalum particles was compared, it was confirmed that the average diameter of the pores formed on the inner side thereof tends to be smaller than the average diameter of the pores formed on the outer side thereof.

據認為：由於矽的結晶方向而對銅觸媒沒有影響，蝕刻無方向性發生，且當其以多孔矽粒子的中心之方向逐漸移動，發生其中蝕刻部分為非線性玉米的形狀之蝕刻。 It is considered that there is no influence on the copper catalyst due to the crystal orientation of the crucible, etching non-directionality occurs, and when it is gradually moved in the direction of the center of the porous crucible particles, etching in which the etching portion is in the shape of nonlinear corn occurs.

此外，可評估：相較於多孔矽粒子的表面，由於藉由亞磷酸鹽的額外孔形成及孔之間活性連接，內孔的平均直徑傾向於以粒子的中心方向逐漸減小。 Furthermore, it can be evaluated that the average diameter of the inner pores tends to gradually decrease in the center direction of the particles due to the extra pore formation by the phosphite and the active connection between the pores compared to the surface of the porous tantalum particles.

相比之下，參照顯示實例1中所製備的矽基粒子之內剖面的圖6，可確認：因為蝕刻以垂直於矽的表面之方向發生，所以孔可線性地形成。 In contrast, referring to Fig. 6 showing the inner cross section of the ruthenium-based particles prepared in Example 1, it was confirmed that the holes were linearly formed because the etching occurred in the direction perpendicular to the surface of the ruthenium.

實驗例2：多孔矽基粒子之物理性質的測量 Experimental Example 2: Measurement of Physical Properties of Porous Bismuth Particles

測量實例1至6中所製備的多孔矽基粒子之敲緊密度(g/cc)、總水銀侵入體積(mL/g)、體密度(g/cc)、及孔隙度(%)且其結果出示於下表1中。 The knock-tightness (g/cc), total mercury intrusion volume (mL/g), bulk density (g/cc), and porosity (%) of the porous sulfhydryl particles prepared in Examples 1 to 6 were measured and the results were measured. Shown in Table 1 below.

<敲緊密度測量> <knock tightness measurement>

將實例1至6中所得之多孔矽基粒子分別裝入容器中，且作為粒子的敲緊密度，藉由在預定條件下振動測量粒子的視密度。 The porous sulfhydryl particles obtained in Examples 1 to 6 were separately charged into a container, and as the knocking degree of the particles, the apparent density of the particles was measured by vibration under predetermined conditions.

<水銀孔隙度測定法> < Mercury Porosimetry>

使用水銀孔隙計(AutoPore VI 9500,Micromerities,USA)測量總水銀侵入體積(mL/g)。 Total mercury intrusion volume (mL/g) was measured using a mercury porosimeter (AutoPore VI 9500, Micromerities, USA).

該水銀孔隙度測定法使用一種液體藉其滲入細孔中之毛細現象。當從外部施加壓力時，非潤濕液體(諸如水銀)可滲入，及孔的大小較小，需要較高的壓力。該測量結果可以根據壓力(或孔隙的大小)所侵入的水銀之累積體積的函數來表示。 The mercury porosimetry uses a capillary phenomenon in which a liquid penetrates into the pores. When pressure is applied from the outside, a non-wetting liquid such as mercury can penetrate, and the pore size is small, requiring a high pressure. The measurement can be expressed as a function of the cumulative volume of mercury invaded by the pressure (or the size of the pores).

操作原理 Principle of operation

將多孔矽粒子放入穿透計並密封，且然後施加真空及填充水銀。當壓力施加至穿透計，水銀滲入多孔矽粒子的孔中，以減少穿透計的水銀高度。當以壓力的函數測定減少，可以得到滲入孔中的水銀體積。水銀侵入的結果可以每樣品重量之孔半徑或入侵壓力及累積侵入體積來表示。 The porous tantalum particles are placed in a penetrator and sealed, and then vacuum is applied and mercury is filled. When pressure is applied to the penetrator, mercury penetrates into the pores of the porous tantalum particles to reduce the mercury level of the penetrator. When measured as a function of pressure, the volume of mercury that penetrates the pores can be obtained. The results of mercury intrusion can be expressed as the pore radius or intrusive pressure and cumulative intrusion volume per sample weight.

因為當壓力低時，水銀侵入粒子之間的孔中，所以孔的大小可隨壓力增加而減少。在多孔粉末所形成的樣品中，累積侵入曲線由於這些孔而可為雙峰曲線。 Because mercury invades the pores between the particles when the pressure is low, the size of the pores can decrease as the pressure increases. In the samples formed by the porous powder, the cumulative intrusion curve can be a bimodal curve due to these pores.

<體密度測量> <Body density measurement>

多孔矽基粒子之體密度可藉由使用在水銀孔隙度測定法期間當壓力為最大時(即，當水銀侵入不再發 生時)的總侵入體積獲得。 The bulk density of the porous ruthenium-based particles can be used when the pressure is maximized during mercury porosimetry (ie, when mercury intrusion is no longer emitted) The total invasive volume of the time) was obtained.

<孔隙度測量> <Porosity measurement>

使用下列方程式1計算實例1至6中所得之多孔矽基粒子的孔隙度。 The porosity of the porous ruthenium-based particles obtained in Examples 1 to 6 was calculated using the following Equation 1.

[方程式1]孔隙度(%)={1-(實例1至6之多孔矽粒子的體密度/純矽粒子的體密度)}×100。 [Equation 1] Porosity (%) = {1 - (body density of porous cerium particles of Examples 1 to 6 / bulk density of pure cerium particles)} × 100.

如表1中所示，實例1至6之多孔矽基粒子 的孔隙度(其中非線性孔藉由蝕刻3小時至24小時而形成)係在約11%至約39%之範圍。特別是，關於實例6之多孔矽基粒子(其中非線性孔藉由蝕刻24小時而形成)，相較於其中不進行形成孔的處理之純Si粒子，孔隙度接近約40%。 As shown in Table 1, the porous sulfhydryl particles of Examples 1 to 6 The porosity (where the non-linear pores are formed by etching for 3 hours to 24 hours) is in the range of about 11% to about 39%. In particular, with respect to the porous ruthenium-based particles of Example 6, in which the nonlinear pores were formed by etching for 24 hours, the porosity was close to about 40% as compared with the pure Si particles in which the treatment for forming the pores was not performed.

Si粒子具有1.02(g/cc)的敲緊密度及0.85(g/cc)的體密度。相比之下，實例1至6之多孔矽基粒子具有低於上述敲緊密度及體密度之敲緊密度及體密度。 The Si particles have a knock-tightness of 1.02 (g/cc) and a bulk density of 0.85 (g/cc). In contrast, the porous sulfhydryl particles of Examples 1 to 6 have knocking and bulk densities lower than the above-described knock-out and bulk density.

此外，Si粒子之總水銀侵入體積為0.53g/cc及實例1至6的多孔矽基粒子之總水銀侵入體積係在0.64g/cc至1.19g/cc之範圍。因此，相較於的Si粒子的總水銀侵入體積，實例1至6的多孔矽基粒子之總水銀侵入體積顯著增加。 Further, the total mercury intrusion volume of the Si particles was 0.53 g/cc and the total mercury intrusion volume of the porous sulfonium-based particles of Examples 1 to 6 was in the range of 0.64 g/cc to 1.19 g/cc. Therefore, the total mercury intrusion volume of the porous sulfhydryl particles of Examples 1 to 6 was significantly increased compared to the total mercury intrusion volume of the Si particles.

特別是，關於其中分別進行18小時及24小時蝕刻之實例5及6，總水銀侵入體積分別為1.05g/cc及1.19g/cc。因此，相較於Si粒子的總水銀侵入體積，該總水銀侵入體積增加2倍或更高。 In particular, with respect to Examples 5 and 6 in which etching was performed for 18 hours and 24 hours, respectively, the total mercury intrusion volumes were 1.05 g/cc and 1.19 g/cc, respectively. Therefore, the total mercury intrusion volume is increased by a factor of 2 or more compared to the total mercury intrusion volume of the Si particles.

相比之下，關於其中蝕刻時間與實例1相同但使用硝酸銀水溶液之比較例1，孔隙度為9.5%，且因此，可理解的是相較於實例1之孔隙度，該孔隙度顯著降低。 In contrast, with respect to Comparative Example 1 in which the etching time was the same as in Example 1 but using an aqueous silver nitrate solution, the porosity was 9.5%, and therefore, it is understood that the porosity was remarkably lowered as compared with the porosity of Example 1.

關於比較例3(其中蝕刻進行28小時)，只消耗蝕刻溶液，但由於過度的蝕刻時間而沒有作用。關於比 較例4(其中蝕刻只進行1小時)，孔隙度為7.1%，且因此，孔並沒有充分形成。 Regarding Comparative Example 3 (where the etching was performed for 28 hours), only the etching solution was consumed, but it did not function due to excessive etching time. About ratio Compared to Example 4 (where the etching was carried out for only 1 hour), the porosity was 7.1%, and therefore, the pores were not sufficiently formed.

此外，因為相較於純Si粒子，本發明實例1至6之敲緊密度和體密度減少及其總水銀侵入體積增加，所以據認為：所形成之非線性孔的深度增加及根據蝕刻時間增加而形成多個非線性孔。 In addition, since the knocking compactness and bulk density of Examples 1 to 6 of the present invention and the total mercury intrusion volume are increased as compared with the pure Si particles, it is considered that the depth of the formed nonlinear pores increases and increases according to the etching time. A plurality of nonlinear holes are formed.

為了鑑定實例7(其中使用弱氧化劑進行蝕刻)中所得多孔矽粒子之物理性質，測量敲緊密度(g/cc)、BET比表面積(m2/g)、及粒徑分佈，且其結果出示於在表2中。 In order to identify the physical properties of the obtained porous cerium particles in Example 7 in which etching with a weak oxidizing agent was used, the knock tightness (g/cc), the BET specific surface area (m 2 /g), and the particle size distribution were measured, and the results were shown. In Table 2.

<敲緊密度測量> <knock tightness measurement>

在此情況下，以與實例1至6之多孔矽基粒子相同之方式進行敲緊密度測量。 In this case, the knock tightness measurement was performed in the same manner as the porous sulfhydryl particles of Examples 1 to 6.

<比表面積測量> <Specific surface area measurement>

實例7之多孔矽基粒子的比表面積可以BET方法測量。例如，以根據使用孔隙度測定分析儀(Bell日本公司的Belsorp-II mini)之氮氣吸附流方法的6點BET方法測量比表面積。 The specific surface area of the porous sulfhydryl particles of Example 7 can be measured by the BET method. For example, the specific surface area is measured in accordance with a 6-point BET method using a nitrogen adsorption flow method using a porosimetry analyzer (Belsorp-II mini of Bell Japan Co., Ltd.).

<粒徑分佈測量> <particle size distribution measurement>

Dmin、D10、D50、D90、及Dmax係對於實例7之多孔矽基粒子的粒徑分佈測量為多孔矽基粒子之平均粒 徑分佈及Dmin、D10、D50、D90、及Dmax分別在累積平均粒徑分佈中表示為小於10%、10%、50%、90%、及大於90%之平均粒徑。 D min , D 10 , D 50 , D 90 , and D max are measured for the particle size distribution of the porous ruthenium-based particles of Example 7 as the average particle size distribution of the porous ruthenium-based particles and D min , D 10 , D 50 , D 90 and D max are each expressed as an average particle diameter of less than 10%, 10%, 50%, 90%, and more than 90% in the cumulative average particle size distribution.

使用雷射繞射法(Microtrac MT 3000)測量實例7之多孔矽基粒子的粒徑分佈。 The particle size distribution of the porous ruthenium-based particles of Example 7 was measured using a laser diffraction method (Microtrac MT 3000).

如表2中所示，實例7中所得多孔矽粒子的敲緊密度為0.61g/cc及Si粒子的敲緊密度為1.02g/cc。因此，可確認：實例7之多孔矽粒子的敲緊密度相較於Si粒子的敲緊密度減少約0.41g/cc。 As shown in Table 2, the porous ruthenium particles obtained in Example 7 had a knock-tightness of 0.61 g/cc and the Si particles had a knock-tightness of 1.02 g/cc. Therefore, it was confirmed that the knocking degree of the porous cerium particles of Example 7 was reduced by about 0.41 g/cc as compared with the knocking degree of the Si particles.

因此，如實驗例1的SEM影像中所示，可評估：在實例7中所得多孔矽粒子中形成孔。 Therefore, as shown in the SEM image of Experimental Example 1, it was evaluated that pores were formed in the obtained porous cerium particles in Example 7.

如表2中所示，實例7中所得多孔矽粒子之BET比表面積為20.87m2/g，及Si粒子之BET比表面積為1.56m2/g。因此，實例7中所製備的多孔矽粒子之BET比表面積相較於Si粒子的BET比表面積增加約13倍。 As shown in Table 2, the porous cerium particles obtained in Example 7 had a BET specific surface area of 20.87 m 2 /g, and the Si particles had a BET specific surface area of 1.56 m 2 /g. Therefore, the BET specific surface area of the porous cerium particles prepared in Example 7 was increased by about 13 times as compared with the BET specific surface area of the Si particles.

因為實例7及Si粒子呈現相同的粒徑分佈，據認為：比表面積之增加是由於孔之形成。 Since Example 7 and Si particles exhibited the same particle size distribution, it is believed that the increase in specific surface area is due to the formation of pores.

實驗例3：Hg孔隙度測定法分析 Experimental Example 3: Analysis of Hg Porosimetry

圖7顯示過透水銀孔隙度測定法分析之實例1至6中所製備的多孔矽基粒子之孔分佈。 Figure 7 shows the pore distribution of the porous ruthenium-based particles prepared in Examples 1 to 6 of the analysis of mercury permeability porosimetry.

參照圖7，侵入孔中之水銀體積的變化率(其藉由多孔矽基粒子之水銀孔隙度測定法測量)具有在約30nm至約2,500nm之平均孔徑範圍的峰值。 Referring to Figure 7, the rate of change of mercury volume in the intrusion pores, as measured by mercury porosimetry of porous sulfhydryl particles, has a peak in the average pore size range from about 30 nm to about 2,500 nm.

當檢查實例7中之圖的二個放大圖時，峰值分別出現在800nm至2,000nm及50nm至600nm之平均孔徑範圍。在此，在800nm至2,000nm的平均孔徑範圍內之峰值為對應於多孔矽粒子之間的孔之峰值及在50nm至600nm內的平均孔徑範圍之峰值為對應於該等包括在多孔矽粒子中之非線性孔的峰值。 When examining the two enlarged views of the graph in Example 7, the peaks appeared in the average pore size range of 800 nm to 2,000 nm and 50 nm to 600 nm, respectively. Here, the peak in the average pore diameter range of 800 nm to 2,000 nm is a peak corresponding to the peak between the porous tantalum particles and a peak in the average pore diameter range of 50 nm to 600 nm corresponding to the inclusion in the porous tantalum particles. The peak of the nonlinear hole.

可確認：在50nm至600nm的平均孔徑範圍內之總水銀侵入體積係在0.5mL/g至1.2mL/g之範圍。 It was confirmed that the total mercury intrusion volume in the average pore diameter range of 50 nm to 600 nm is in the range of 0.5 mL/g to 1.2 mL/g.

此外，參照圖7，可確認：如實例1至6中孔體積隨著蝕刻時間增加至3小時、6小時、9小時、12小時、18小時、及24小時而增加。特別是，可確認：實例6(其中蝕刻進行24小時)之多孔矽粒子呈現最大孔體積。 Further, referring to Fig. 7, it was confirmed that the pore volume as in Examples 1 to 6 increased as the etching time was increased to 3 hours, 6 hours, 9 hours, 12 hours, 18 hours, and 24 hours. In particular, it was confirmed that the porous ruthenium particles of Example 6 in which etching was performed for 24 hours exhibited the maximum pore volume.

在實例1至6之多孔矽粒子中，可確認：這些孔的平均直徑分佈係於其中中孔(mesopores)具有20nm至100nm的平均直徑之形式，及大孔共存直至蝕刻時間 在3小時至18小時之範圍，及具有50nm或更大的平均直徑之大孔的分佈隨蝕刻時間增加而增加。這被認為是由於所形成的孔隨蝕刻時間增加而彼此連接的事實。 In the porous tantalum particles of Examples 1 to 6, it was confirmed that the average diameter distribution of these pores is in the form in which mesopores have an average diameter of 20 nm to 100 nm, and macropores coexist until etching time The distribution of macropores in the range of 3 hours to 18 hours and having an average diameter of 50 nm or more increases as the etching time increases. This is considered to be due to the fact that the formed holes are connected to each other as the etching time increases.

而且，可確認：實例5(其進行蝕刻18小時)之多孔矽粒子具有其中大多形成具有50nm或更大的平均直徑之大孔的孔分佈。 Moreover, it was confirmed that the porous tantalum particles of Example 5 which was subjected to etching for 18 hours had pore distributions in which macropores having an average diameter of 50 nm or more were mostly formed.

據認為：實例6之多孔矽粒子(其經蝕刻24小時)具有其中孔幾乎合併且彼此連接之孔形狀。 It is believed that the porous tantalum particles of Example 6 (which were etched for 24 hours) have pore shapes in which the pores are nearly joined and connected to each other.

實驗例4：壽命特性及厚度變化率分析 Experimental Example 4: Analysis of life characteristics and thickness change rate

進行以下實驗以便研究實例8至15及比較例5至10中所製備的二次電池之壽命特性及厚度變化率。 The following experiment was conducted to investigate the life characteristics and the thickness change rate of the secondary batteries prepared in Examples 8 to 15 and Comparative Examples 5 to 10.

藉由在第一次循環中在0.1C下進行充電及放電，及在隨後的循環中在0.5C下進行充電及放電來測量各二次電池的壽命特性。該壽命特性係表示為在第49次循環的放電容量對第一循環的放電容量的比率。各二次電池在第50次循環的充電狀態進行拆解及測量電極的厚度。然後，藉由比較上述厚度與第一次循環前電極的厚度來獲得厚度變化率。 The life characteristics of each secondary battery were measured by charging and discharging at 0.1 C in the first cycle, and charging and discharging at 0.5 C in the subsequent cycle. This life characteristic is expressed as the ratio of the discharge capacity at the 49th cycle to the discharge capacity at the first cycle. Each secondary battery was disassembled in the charged state of the 50th cycle and the thickness of the electrode was measured. Then, the thickness change rate is obtained by comparing the above thickness with the thickness of the electrode before the first cycle.

下表3表示實例8至15及比較例5至10中所製備的二次電池之壽命特性及厚度變化率。 Table 3 below shows the life characteristics and thickness change rates of the secondary batteries prepared in Examples 8 to 15 and Comparative Examples 5 to 10.

-壽命特性：(在第49次循環放電容量/第一次循環放電容量)×100 - Life characteristics: (at the 49th cycle discharge capacity / first cycle discharge capacity) × 100

-厚度變化率：(在第50次循環的充電狀態中之電極厚度-第一次循環前之電極厚度)/第一次循環前之電極厚度×100 - thickness change rate: (electrode thickness in the state of charge of the 50th cycle - electrode thickness before the first cycle) / electrode thickness before the first cycle × 100

如表3中所示，可確認：本發明之實例8至15的二次電池具有比較例5至10之壽命特性及厚度變化 率顯著更好的壽命特性及厚度變化率。 As shown in Table 3, it was confirmed that the secondary batteries of Examples 8 to 15 of the present invention have life characteristics and thickness variations of Comparative Examples 5 to 10. The rate is significantly better for life characteristics and thickness change rate.

具體來說，當特別地比較實例8及比較例6(其中蝕刻進行3小時)時，可確認：相較於使用硝酸銀之比較例6的厚度變化率，使用硫酸銅水溶液作為金屬觸媒之實例8的厚度變化率減少。 Specifically, when Example 8 and Comparative Example 6 were specifically compared (in which etching was performed for 3 hours), it was confirmed that an aqueous copper sulfate solution was used as an example of the metal catalyst as compared with the thickness change rate of Comparative Example 6 using silver nitrate. The thickness change rate of 8 is reduced.

此外，當比較實例14及比較例7(其中蝕刻進行21小時)時，可確認：使用亞磷酸鹽作為弱氧化劑之實例14的壽命特性及厚度變化率二者皆比使用硝酸鐵作為強氧化劑之比較例7的壽命特性及厚度變化率更好。 Further, when Comparative Example 14 and Comparative Example 7 (where etching was carried out for 21 hours), it was confirmed that the life characteristics and the thickness change rate of Example 14 using phosphite as a weak oxidizing agent were both higher than that of using ferric nitrate as a strong oxidizing agent. The life characteristics and the thickness change rate of Comparative Example 7 were better.

在如實例15中之混合石墨及塗佈10wt%碳的多孔矽粒子的情況下，壽命特性為90%及厚度變化率為120%。因此，可理解的是：二次電池之性能被顯著改良。 In the case of the mixed graphite as in Example 15 and the porous tantalum particles coated with 10% by weight of carbon, the life characteristics were 90% and the thickness change rate was 120%. Therefore, it can be understood that the performance of the secondary battery is remarkably improved.

相比之下，關於實例9(其中蝕刻只進行1小時)，厚度變化率為300%，且因此，可確認：體積膨脹並沒有由於孔的形成不足而降低。 In contrast, with respect to Example 9 in which etching was performed only for 1 hour, the thickness change rate was 300%, and therefore, it was confirmed that the volume expansion was not lowered due to insufficient formation of pores.

產業應用性 Industrial applicability

根據本發明之一具體實例的多孔矽基粒子藉由包含具有多個非線性孔之Si或SiOx(0<x<2)粒子可更容易地分散在陽極活性材料漿料中、可將與電解質之副反應減至最少、及可減少在充電及放電期間的體積膨脹。因此，該等多孔矽基粒子可適合於二次電池。 The porous ruthenium-based particles according to an embodiment of the present invention can be more easily dispersed in the anode active material slurry by containing Si or SiO x (0<x<2) particles having a plurality of nonlinear pores, and The side reactions of the electrolyte are minimized and the volume expansion during charging and discharging can be reduced. Therefore, the porous ruthenium-based particles can be suitable for a secondary battery.

Claims (39)

一種包含矽(Si)或SiOx(0<x<2)粒子之多孔矽基粒子，其中該粒子包含多個非線性孔，及該等非線性孔係在粒子的表面中形成為開孔。 A porous ruthenium-based particle comprising cerium (Si) or SiO x (0 < x < 2) particles, wherein the particle comprises a plurality of nonlinear pores, and the nonlinear pores are formed as open pores in the surface of the particle. 如申請專利範圍第1項之多孔矽基粒子，其中該等非線性孔之至少二或多者彼此連接。 The porous ruthenium-based particles of claim 1, wherein at least two or more of the nonlinear pores are connected to each other. 如申請專利範圍第1項之多孔矽基粒子，其中該等非線性孔的平均直徑以粒子的中心之方向逐漸減小。 The porous ruthenium-based particles of claim 1, wherein the average diameter of the nonlinear pores gradually decreases in the direction of the center of the particles. 如申請專利範圍第1項之多孔矽基粒子，其中該等在表面處的開孔之平均直徑係在約30nm至約500nm之範圍。 The porous ruthenium-based particles of claim 1, wherein the average diameter of the openings at the surface is in the range of from about 30 nm to about 500 nm. 如申請專利範圍第1項之多孔矽基粒子，其中侵入孔中之水銀體積的變化率，其係藉由多孔矽基粒子之水銀孔隙度測定法(mercury porosimetry)測定，具有在30nm至2,500nm的平均孔徑範圍之峰值。 The porous sulfhydryl particle according to claim 1, wherein the rate of change of the volume of mercury in the intrusion hole is determined by mercury porosimetry of the porous sulfhydryl particle, and has a ratio of 30 nm to 2,500 nm. The peak of the average pore size range. 如申請專利範圍第5項之多孔矽基粒子，其中該水銀體積之變化率具有在50nm至600nm的平均孔徑範圍之峰值。 The porous ruthenium-based particles of claim 5, wherein the change rate of the mercury volume has a peak of an average pore diameter range of 50 nm to 600 nm. 如申請專利範圍第5項之多孔矽基粒子，其中於峰值處的總水銀侵入體積係在0.5mL/g至1.2mL/g之範圍。 The porous sulfhydryl particle of claim 5, wherein the total mercury intrusion volume at the peak is in the range of 0.5 mL/g to 1.2 mL/g. 如申請專利範圍第1項之多孔矽基粒子，其中多孔矽基粒子的比表面積(Brunauer-Emmett-Teller(BET)-SSA) 係在5m2/g至50m2/g之範圍。 The porous ruthenium-based particles of claim 1, wherein the specific surface area (Brunauer-Emmett-Teller (BET)-SSA) of the porous ruthenium-based particles is in the range of 5 m 2 /g to 50 m 2 /g. 如申請專利範圍第1項之多孔矽基粒子，其中該非線性孔的深度係在0.1μm至5μm之範圍。 The porous ruthenium-based particles of claim 1, wherein the nonlinear pores have a depth in the range of 0.1 μm to 5 μm. 如申請專利範圍第1項之多孔矽基粒子，其中多孔矽基粒子的平均粒徑(D50)係在1μm至20μm之範圍。 The porous ruthenium-based particles of the first aspect of the invention, wherein the average particle diameter (D 50 ) of the porous ruthenium-based particles is in the range of from 1 μm to 20 μm. 一種多孔矽基粒子，其包含：包含矽(Si)或SiOx(0<x<2)之核心部分；及在該核心部分上的包含多個非線性孔之Si或SiOx外殼部分，其中外殼部分之表面具有開孔。 A porous germanium-based particle comprising: a core portion comprising germanium (Si) or SiO x (0 < x <2); and a Si or SiO x outer shell portion comprising a plurality of nonlinear pores on the core portion, wherein The surface of the outer casing portion has an opening. 如申請專利範圍第11項之多孔矽基粒子，其中該核心部分的長度對外殼部分的長度之比率係在1：9至9：1之範圍。 The porous ruthenium-based particles of claim 11, wherein the ratio of the length of the core portion to the length of the outer shell portion is in the range of 1:9 to 9:1. 如申請專利範圍第11項之多孔矽基粒子，其中該等非線性孔之至少二或多者彼此連接。 The porous ruthenium-based particles of claim 11, wherein at least two or more of the nonlinear pores are connected to each other. 如申請專利範圍第11項之多孔矽基粒子，其中該孔的直徑以粒子的中心之方向逐漸減小。 The porous ruthenium-based particle of claim 11, wherein the diameter of the pore gradually decreases in the direction of the center of the particle. 如申請專利範圍第11項之多孔矽基粒子，其中該等開孔的平均直徑係在約30nm至約500nm之範圍。 The porous ruthenium-based particles of claim 11, wherein the average diameter of the openings is in the range of from about 30 nm to about 500 nm. 如申請專利範圍第1或11項之多孔矽基粒子，其進一步包含在該多孔矽基粒子上之碳塗層。 The porous ruthenium-based particles of claim 1 or 11, further comprising a carbon coating on the porous ruthenium-based particles. 如申請專利範圍第1或11項之多孔矽基粒子，其中該多孔矽基粒子的孔隙度以多孔矽基粒子的總體積為基準計係在5%至90%之範圍。 The porous ruthenium-based particles of claim 1 or 11, wherein the porosity of the porous ruthenium-based particles is in the range of 5% to 90% based on the total volume of the porous ruthenium-based particles. 如申請專利範圍第1或11項之多孔矽基粒子，其中該多孔矽基粒子的孔隙度以多孔矽基粒子的總體積為基準計係在10%至70%之範圍。 The porous ruthenium-based particles of claim 1 or 11, wherein the porosity of the porous ruthenium-based particles is in the range of 10% to 70% based on the total volume of the porous ruthenium-based particles. 一種陽極活性材料，其包含如申請專利範圍第1或11項之多孔矽基粒子。 An anode active material comprising the porous ruthenium-based particles of item 1 or 11 of the patent application. 如申請專利範圍第19項之陽極活性材料，其進一步包含碳基材料。 The anode active material of claim 19, which further comprises a carbon-based material. 如申請專利範圍第20項之陽極活性材料，其中該碳基材料包含選自由下列所組成群組中之至少一者：天然石墨、人造石墨、中間相碳微球(MCMB)、碳纖維、及碳黑。 The anode active material of claim 20, wherein the carbon-based material comprises at least one selected from the group consisting of natural graphite, artificial graphite, mesocarbon microbeads (MCMB), carbon fibers, and carbon. black. 如申請專利範圍第20項之陽極活性材料，其中該碳基材料之包含量以100重量份的多孔矽基粒子為基準計為0重量份至90重量份。 The anode active material according to claim 20, wherein the carbon-based material is contained in an amount of from 0 part by weight to 90 parts by weight based on 100 parts by weight of the porous sulfonium group. 一種製備如申請專利範圍第1項之多孔矽基粒子之方法，該方法包括下列步驟：(i)使用蝕刻溶液移除存在於矽(Si)或SiOx(0<x<2)粒子之表面上的氧化物層；及(ii)藉由以混合及攪拌包括Si或SiOx(0<x<2)粒子之蝕刻溶液與金屬觸媒來蝕刻Si或SiOx(0<x<2)粒子而在Si或SiOx(0<x<2)粒子中形成非線性孔。 A method of preparing porous ruthenium-based particles according to claim 1 of the patent application, the method comprising the steps of: (i) removing an existing surface of yttrium (Si) or SiO x (0 < x < 2) particles using an etching solution And (ii) etching Si or SiO x (0<x<2) particles by mixing and stirring an etching solution comprising Si or SiO x (0<x<2) particles with a metal catalyst A nonlinear hole is formed in the Si or SiO x (0 < x < 2) particles. 如申請專利範圍第23項之方法，其中該金屬觸媒包含選自由下列所組成群組中任一者：銅(Cu)、鉑(Pt)、及鎳(Ni)、或彼等的二或多個元素。 The method of claim 23, wherein the metal catalyst comprises one selected from the group consisting of copper (Cu), platinum (Pt), and nickel (Ni), or two of them or Multiple elements. 如申請專利範圍第23項之方法，其中該氧化物層的移除係在20℃至90℃的溫度範圍進行30分鐘至3小時。 The method of claim 23, wherein the removing of the oxide layer is carried out at a temperature ranging from 20 ° C to 90 ° C for from 30 minutes to 3 hours. 如申請專利範圍第23項之方法，其中該蝕刻溶液包含至少一種選自由下列所組成群組之溶液：氟化氫(HF)、氟矽酸(H2SiF6)、及氟化銨(NH4F)。 The method of claim 23, wherein the etching solution comprises at least one selected from the group consisting of hydrogen fluoride (HF), fluoroantimonic acid (H 2 SiF 6 ), and ammonium fluoride (NH 4 F) ). 如申請專利範圍第23項之方法，其中該蝕刻溶液的濃度係在5M至20M之範圍。 The method of claim 23, wherein the concentration of the etching solution is in the range of 5M to 20M. 如申請專利範圍第23項之方法，其中該金屬觸媒的濃度係在5mM至100mM之範圍。 The method of claim 23, wherein the concentration of the metal catalyst is in the range of 5 mM to 100 mM. 如申請專利範圍第28項之方法，其中該金屬觸媒的沈積係進行1小時至12小時。 The method of claim 28, wherein the deposition of the metal catalyst is carried out for 1 hour to 12 hours. 如申請專利範圍第23項之方法，其進一步包含在步驟(ii)中添加弱氧化劑。 The method of claim 23, further comprising adding a weak oxidizing agent in step (ii). 如申請專利範圍第30項之方法，其中該弱氧化劑包含選自由下列所組成群組中任一者：亞磷酸鹽、亞硫酸鹽、及磷酸鹽、或彼等的二或多個之混合物。 The method of claim 30, wherein the weak oxidizing agent comprises a mixture selected from the group consisting of phosphite, sulfite, and phosphate, or a mixture of two or more thereof. 如申請專利範圍第30項之方法，其中該弱氧化劑的濃度係在0.25M至1.0M之範圍。 The method of claim 30, wherein the concentration of the weak oxidant is in the range of 0.25 M to 1.0 M. 如申請專利範圍第23項之方法，其中該蝕刻係進行3小時至24小時。 The method of claim 23, wherein the etching is performed for 3 hours to 24 hours. 如申請專利範圍第23項之方法，其進一步包含蝕刻之後藉由混合多孔矽基粒子與碳前驅物而用碳塗佈多孔矽基粒子的外表面及進行熱處理。 The method of claim 23, further comprising, after etching, coating the outer surface of the porous ruthenium-based particles with carbon by mixing the porous ruthenium-based particles with the carbon precursor and performing heat treatment. 如申請專利範圍第34項之方法，其中該碳前驅物包含瀝青或烴基材料。 The method of claim 34, wherein the carbon precursor comprises a bitumen or a hydrocarbon based material. 如申請專利範圍第34項之方法，其中該碳前驅物之使用量以多孔矽基粒子的總體積為基準計為10wt%至40wt%。 The method of claim 34, wherein the carbon precursor is used in an amount of 10% by weight to 40% by weight based on the total volume of the porous cerium-based particles. 如申請專利範圍第34項之方法，其中該熱處理係在300℃至1,400℃的溫度範圍中進行。 The method of claim 34, wherein the heat treatment is carried out at a temperature ranging from 300 ° C to 1,400 ° C. 一種陽極，其包含如申請專利範圍第19項之陽極活性材料。 An anode comprising an anode active material as in claim 19 of the patent application. 一種鋰二次電池，其包含如申請專利範圍第38項之陽極。 A lithium secondary battery comprising the anode of claim 38 of the patent application.
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