KR20040082876A - Preparation method for porous silicon and nano-sized silicon powder, and application for anode material in lithium secondary batteries - Google Patents
Preparation method for porous silicon and nano-sized silicon powder, and application for anode material in lithium secondary batteries Download PDFInfo
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
Description
본 발명은 다공성 실리콘 입자 및 나노 크기의 실리콘 미립자를 제조하는 방법에 관한 것으로서, 보다 구체적으로는 실리콘 전구체(산화물)을 환원시키는 단계를 포함하는 다공성 실리콘 입자를 제조하는 방법에 관한 것이다. 또한, 본 발명은 상기 방법에 의해 얻어진 다공성 실리콘 입자를 초음파 처리하는 단계를 더 포함하는 나노 크기의 실리콘 미립자를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing porous silicon particles and nano-sized silicon particles, and more particularly, to a method for producing porous silicon particles including reducing a silicon precursor (oxide). The present invention also relates to a method for producing nano-sized silicon fine particles further comprising the step of sonicating the porous silicon particles obtained by the method.
실리콘은 리튬 이차전지용 음극 재료로서 탄소 재료를 대체할 수 있는 물질이다. 현재 상용화된 흑연질 재료의 경우 이론 용량이 372 mAh/g이나 실리콘은 4000 mAh/g 이상의 이론 용량을 지니고 있다. 그러나, 실리콘의 경우 리튬과의 합금화(alloying) / 비합금화(de-alloying) 과정에서 많은 부피 변화 (310 %)를 겪게되어 전극이 열화되기 때문에, 용량이 급격히 감소하는 문제점이 있다.Silicon is a material that can replace a carbon material as a negative electrode material for a lithium secondary battery. The theoretical capacity of commercially available graphite materials is 372 mAh / g, while silicon has a theoretical capacity of 4000 mAh / g or more. However, in the case of silicon, since the electrode is deteriorated due to undergoing a large volume change (310%) during the alloying (alloy) / de-alloying process with lithium, there is a problem that the capacity is sharply reduced.
이러한 부피변화에 따른 전극의 퇴화를 막을 수 있는 방안으로 실리콘을 다공성을 갖게 하여 부피 변화에 대한 완충 효과를 갖게 하는 방안이 검토되고 있다. 또한 입자의 크기를 나노 크기로 제조함으로서 전극의 절대적인 부피 변화를 최소화하려는 노력이 진행되고 있다.In order to prevent the deterioration of the electrode due to the volume change, a method of providing a buffer effect against the volume change by making the silicon porous has been studied. In addition, efforts are being made to minimize the absolute volume change of the electrode by preparing the size of the particles to a nano size.
다공성 실리콘을 제조하는 방법으로는 화학적 또는 전기 화학적 방법으로 실리콘 웨이퍼를 식각하는 방법이 보고된 바 있다. 상기 방법은 먼저 실리콘 웨이퍼를 식각 용액에 담근 후 전류를 흘려주어 실리콘 웨이퍼의 표면층을 침식 시킴으로써, 서로 아주 약하게 연결된 나노 구조의 정교한 네트워크 구조를 갖는 다공성 실리콘을 제조하는 방법이다. 그러나 상기 방법은 고가인 실리콘 웨이퍼를 출발 물질로 하며 또한 침식 과정에서 매우 유독한 불산 용액을 사용한다는 문제점이 있었다.As a method of manufacturing porous silicon, a method of etching a silicon wafer by a chemical or electrochemical method has been reported. The method is a method of manufacturing porous silicon having an elaborate network structure of nanostructures that are very weakly connected to each other by first immersing the silicon wafer in an etching solution and then flowing current to erode the surface layer of the silicon wafer. However, this method has a problem in that an expensive silicon wafer is used as a starting material and a very toxic hydrofluoric acid solution is used in the erosion process.
나노 크기의 실리콘 입자를 합성하는 방법으로는 유기 - 금속계 전구체를 이용하여 합성하는 방법 또는 액상의 전구체를 환원하는 방법이 알려져 있다. 그러나, 이 경우 유기-금속계 전구체 또는 액상 전구체 들은 반응성이 매우 강하고 독성이 강하여 산소나 수분이 없는 조건에서 합성하여야 한다는 단점이 있다.As a method of synthesizing nano-sized silicon particles, a method of synthesizing using an organo-metallic precursor or a method of reducing a liquid precursor is known. However, in this case, the organo-metallic precursors or the liquid precursors have a disadvantage in that they must be synthesized under conditions that are highly reactive and highly toxic and have no oxygen or moisture.
상기 방법 외에도 실리콘 나노입자는 다공성의 실리콘 입자를 초음파 처리하는 방법이 있고, 콜로이드 합성법, 진공 증착법 등을 이용하여 제조하는 방법이 있다. 최근에는 수용액 상태의 나노 입자를 불활성 기체 내에서 에어로졸로 분사 후 급속 건조하고 기상 환원 반응을 통해 분말화된 나노 입자를 제조하는 방법이 발표된 바 있다. 또한, 액상 전구체를 레이저 삭마(ablation)를 이용하여 나노 크기의 실리콘 입자를 합성하는 방법도 보고된 바 있다. 그러나, 상기 방법 들은 모두 비용이 매우 비싼 공정일 뿐만 아니라 전구체 또는 식각 용액이 매우 유독한 물질이라는 문제가 있었다.In addition to the above method, the silicon nanoparticles may be ultrasonically treated with porous silicon particles, and may be manufactured by using a colloid synthesis method or a vacuum deposition method. Recently, a method of preparing powdered nanoparticles by spraying nanoparticles in an aqueous solution state with an aerosol in an inert gas, followed by rapid drying and vapor phase reduction has been published. In addition, a method of synthesizing nano-sized silicon particles using liquid ablation of laser ablation has been reported. However, all of the above methods have a problem that the precursor or etching solution is a very toxic material as well as a very expensive process.
또한, 다공성 실리콘을 제조하는 방법으로써, 대한민국 공개특허 제2001-35809호(다공질 실리콘의 형성 방법)과 제1998-60790호(다공성 실리콘 발광 소자의 제조 방법) 및 대한민국 특허 제212473호(실리콘 미세결정 제조 방법)등이 있으나,상기 방법은 환경에 매우 유해한 불산을 사용하는 전기화학적 식각 방법을 사용하고 있다는 문제점이 있었다.In addition, as a method of manufacturing porous silicon, Korean Patent Laid-Open Publication No. 2001-35809 (Method of Forming Porous Silicon) and 1998-60790 (Method of Manufacturing Porous Silicon Light Emitting Device) and Korean Patent No. 212473 (Silicone Microcrystals) Manufacturing method), but the above method has a problem in that it uses an electrochemical etching method using hydrofluoric acid which is very harmful to the environment.
상기 종래 기술의 문제점을 해결하기 위하여, 본 발명은 알칼리 또는 알칼리 토금속을 환원제로 사용하여 실리콘 전구체인 실리콘 옥사이드를 환원시킴으로써, 독성이 강한 불산을 사용하지 않고, 원가 부담이 적으며, 부산물의 처리가 용이한 간략화된 다공성 실리콘 입자의 제조 방법을 제공하는 것을 그 목적으로 한다.In order to solve the problems of the prior art, the present invention is to reduce the silicon oxide which is a silicon precursor by using an alkali or alkaline earth metal as a reducing agent, there is no use of toxic hydrofluoric acid, less cost burden, and by-product treatment It is an object of the present invention to provide a method for producing a simplified and simplified porous silicon particle.
상기 방법으로 제조된 다공성 실리콘 입자는 약하게 연결된 네트워크 구조를 가지고 있어, 초음파 처리를 하게 되면 개별적인 입자들로 분리되는 현상에 기초하여, 본 발명은 다공성 실리콘 입자로부터 나노 크기의 실리콘 미립자를 제조하는 방법을 제공한다.The porous silicon particles prepared by the above method have a weakly connected network structure, and based on the phenomenon that the ultrasonic particles are separated into individual particles, the present invention provides a method of preparing nano-sized silicon particles from the porous silicon particles. to provide.
또한, 본 발명은 상기 다공성 실리콘 입자 또는 나노 크기의 실리콘 미립자를 포함하는 리튬 이차 전지를 제공한다.In addition, the present invention provides a lithium secondary battery comprising the porous silicon particles or nano-sized silicon particles.
도 1은 실시예 1의 실리콘 다이옥사이드를 환원하여 합성된 실리콘을 염산으로 세척하기 전과 후의 X선 회절 분석 결과를 나타낸 그래프이다.1 is a graph showing the results of X-ray diffraction analysis before and after washing silicon synthesized by reducing the silicon dioxide of Example 1 with hydrochloric acid.
도 2은 실시예 1의 합성 공정을 도시한 것이다.2 shows the synthesis process of Example 1. FIG.
도 3은 실시예 1의 실리콘 다이옥사드를 환원하여 합성된 실리콘을 염산으로 세척하기 전과 후의 전계 방출 주사 전자 현미경 사진을 나타낸 것이다.Figure 3 shows a field emission scanning electron micrograph before and after washing the silicon synthesized by reducing the silicon dioxad of Example 1 with hydrochloric acid.
도 4는 실시예 2의 실리카겔을 환원하여 합성된 실리콘과 실시예 4의 유리를 환원하여 합성된 실리콘을 염산으로 세착한 후의 전계 방출 주사 전자 현미경 사진을 나타낸 것이다.FIG. 4 shows a field emission scanning electron micrograph after washing silica gel of Example 2 and silicon synthesized by reducing glass of Example 4 with hydrochloric acid.
도 5는 실시예 3의 실리카겔과 마그네슘을 온도에 따라 열처리하고 염산으로 세척한 후의 X선 회절 분석 결과를 나타낸 그래프이다.FIG. 5 is a graph showing the results of X-ray diffraction analysis after silica gel and magnesium of Example 3 were heat-treated according to temperature and washed with hydrochloric acid.
도 6은 실시예 4의 유리를 마그네슘으로 환원하여 합성된 실리콘과 실시예 5의 실리카겔을 리튬으로 환원하여 합성된 실리콘을 염산으로 세척한 후의 X선 회절 분석 결과를 나타낸 그래프이다.FIG. 6 is a graph showing the results of X-ray diffraction analysis after washing the silicon synthesized by reducing the glass of Example 4 with magnesium and silicon synthesized by reducing the silica gel of Example 5 with lithium.
도 7은 실시예 6의 초음파 처리 후의 현탁액에 대한 투과 전자 현미경 사진을나타낸 것이다.7 shows a transmission electron micrograph of the suspension after the ultrasonic treatment in Example 6. FIG.
본 발명은 다공성 실리콘의 제조 방법에 있어서,The present invention provides a method for producing porous silicon,
(a) 분말 상태의 알칼리 금속 또는 알칼리 토금속과 분말 상태의 실리콘 전구체를 혼합하는 단계 ; 및(a) mixing a powdered alkali metal or alkaline earth metal with a powdered silicon precursor; And
(b) 상기 (a)단계에서 생성된 혼합물을 비활성 분위기에서 열처리하는 단계(b) heat-treating the mixture produced in step (a) in an inert atmosphere
를 포함하는 다공성 실리콘 입자의 제조 방법을 제공한다.It provides a method for producing a porous silicon particles comprising a.
또한, 본 발명은 상기 (b) 단계에 이어 산을 첨가하여 부산물을 세척하는 단계를 더 포함하는 다공성 실리콘 입자의 제조방법을 제공한다.In another aspect, the present invention provides a method for producing porous silicon particles further comprising the step of (b) to wash the by-product by adding an acid.
또한, 본 발명은 상기 방법으로 제조된 다공성 실리콘 입자가 분산된 분산액을 제조하는 단계 ; 및 상기 분산액을 초음파 처리하는 단계를 포함하는 나노 크기의 실리콘 미립자의 제조 방법을 제공한다.In addition, the present invention comprises the steps of preparing a dispersion in which the porous silicon particles prepared by the above method is dispersed; And it provides a method for producing nano-sized silicon microparticles comprising the step of sonicating the dispersion.
또한, 본 발명은 양극, 음극 및 분리막을 포함하는 리튬 이차 전지에 있어서, 상기 음극은In addition, the present invention is a lithium secondary battery comprising a positive electrode, a negative electrode and a separator, the negative electrode is
(ⅰ) 금속 재질의 집전체 ; 및(Iii) a current collector made of metal; And
(ⅱ) 상기 집전체에 도포되는 음극 활물질로서 상기 다공성 실리콘 입자 또는 실리콘 미립자를 함유하는 음극활물질 ;(Ii) a negative electrode active material containing the porous silicon particles or silicon fine particles as a negative electrode active material applied to the current collector;
을 포함하는 리튬 이차 전지를 제공한다.It provides a lithium secondary battery comprising a.
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 알칼리 또는 알칼리 토금속을 환원제로 사용하여 실리콘 전구체인 실리콘 옥사이드로부터 다공성 실리콘 입자를 합성하는 방법 및 상기 방법으로 제조된 다공성 실리콘을 초음파 처리하여 나노 크기의 실리콘 입자로 전환하는 방법에 관한 것이다.The present invention relates to a method for synthesizing porous silicon particles from silicon oxide, which is a silicon precursor, using an alkali or alkaline earth metal as a reducing agent, and a method for converting nanoporous silicon particles by sonicating the porous silicon prepared by the above method.
본 발명의 다공성의 실리콘 입자를 합성하는 방법은 다음과 같다.Method for synthesizing porous silicon particles of the present invention is as follows.
먼저 (a) 분말상태의 알칼리 금속 또는 알칼리 토금속과 분말 상태의 실리콘 전구체를 혼합하고 준비하고, (b) 상기 혼합물을 비활성 분위기에서 열처리 함으로써 다공성의 실리콘 입자를 얻을 수 있다. 이때 환원 시 발생하는 급격한 부피 감소로 인하여 다공성 실리콘 입자가 얻어지게 된다.First, (a) a powdered alkali metal or alkaline earth metal and a powdered silicon precursor are mixed and prepared, and (b) the mixture is heat-treated in an inert atmosphere to obtain porous silicon particles. At this time, the porous silicon particles are obtained due to the rapid volume reduction occurring during the reduction.
본 발명에서, 상기 실리콘 전구체인 실리콘 옥사이드로는 실리콘 다이옥사이드 (silicon dioxide), 실리콘 모노옥사이드 (silicon monoxide), 실리카겔 (silica gel), 금속 실리케이트 (metal silicate), 지올라이트 (zeolite), 유리 (glass), 석영 (quartz), 퓸드 실리카 (fumed silica) 등이 바람직하다. 실리콘 산화물의 경우 다양한 형태로의 제조가 용이하고 가격이 저렴한 장점을 지니고 있다.In the present invention, the silicon precursor is a silicon oxide, silicon dioxide, silicon monoxide, silica gel, metal silicate, zeolite, glass , Quartz, fumed silica and the like are preferred. Silicon oxide has advantages in that it is easy to manufacture in various forms and inexpensive.
상기 알칼리 금속으로는 리튬 (Li : lithium), 나트륨 (Na : sodium), 칼륨 (K : potassium), 루비듐 (Rb : rubidium), 세슘 (Cs : cesium), 프란슘 (Fr : francium)이 바람직하며, 알칼리 토금속으로는 베릴륨 (Be : berylium), 마그네슘 (Mg : magnesium), 칼슘 (Ca : calcium), 스트론튬 (Sr : strontium), 바륨 (Ba : barium), 라듐 (Ra : radium)이 바람직하다.As the alkali metal, lithium (Li: lithium), sodium (Na: sodium), potassium (K: potassium), rubidium (Rb: rubidium), cesium (Cs: cesium), francium (Fr: francium) are preferable. As the alkaline earth metal, beryllium (Be: berylium), magnesium (Mg: magnesium), calcium (Ca: calcium), strontium (Sr: strontium), barium (Ba: barium), and radium (Ra: radium) are preferable.
상기 (a)단계를 통하여 생성된 혼합물의 열처리는 600oC 내지 1400oC 범위에서 1분 내지 100시간 동안 열처리하는 것이 바람직하다. 상기 열처리 온도가 600oC 미만인 경우에는 상기 반응이 이루어지지 않는 문제가 있고, 1400oC를 초과할 경우에는 합성된 실리콘이 용융되어 입자가 뭉치는 문제가 있으며 또한, 열처리 시간이 1 분 미만인 경우에는 상기 반응이 일어나지 않으며, 상기 반응시간이 100 시간을 초과할 경우에는 입자들의 소결 현상이 발생하여 입도가 커지는 문제가 있다.Heat treatment of the mixture produced through the step (a) is preferably heat treatment for 1 minute to 100 hours in the range of 600 o C to 1400 o C. When the heat treatment temperature is less than 600 o C there is a problem that the reaction is not made, when the heat treatment temperature exceeds 1400 o C there is a problem that the synthesized silicon is melted and the particles are agglomerated, and the heat treatment time is less than 1 minute The reaction does not occur, and when the reaction time exceeds 100 hours, the sintering phenomenon of the particles occurs, there is a problem that the particle size increases.
또한, 상기 (b) 단계를 통하여 제조된 다공성 실리콘 입자와 함께 생성된 부산물인 금속산화물을 제거하기 위하여, 산처리하는 (c) 단계를 더 포함하는 것이 바람직하다. 산으로는 염산 (HCl : hydrochloric acid), 황산 (H2SO4: sulfuric acid), 인산 (H3PO4: phosphoric acid), 초산 (CH3COOH : acetic acid), 질산 (HNO3: nitric acid) 등이 바람직하다.In addition, in order to remove the metal oxide which is a by-product generated with the porous silicon particles prepared through the step (b), it is preferable to further include the step (c) of the acid treatment. Acids include hydrochloric acid (HCl: hydrochloric acid), sulfuric acid (H 2 SO 4 : sulfuric acid), phosphoric acid (H 3 PO 4 : phosphoric acid), acetic acid (CH 3 COOH: acetic acid), nitric acid (HNO 3 : nitric acid ) Is preferred.
또한, 상기 (c) 단계는 산과 함께 물 (H2O)과 알코올 (alcohol)을 첨가하여 세척하는 단계를 더 포함시키는 것이 바람직하며, 상기 알코올의 종류에는 특별한 제한이 없으나, 메탄올 (CH3OH : methanol), 에탄올 (C2H5OH : ethanol), 프로판올 (C3H7OH : propanol), 부탄올 (C4H9OH : butanol)등이 바람직하다.In addition, the step (c) preferably further comprises the step of washing by adding water (H 2 O) and alcohol (alcohol) with the acid, there is no particular limitation on the type of alcohol, methanol (CH 3 OH : methanol), ethanol (C 2 H 5 OH: ethanol), propanol (C 3 H 7 OH: propanol), butanol (C 4 H 9 OH: butanol), and the like.
상기 방법으로 제조된 다공성 실리콘 입자로부터 나노 크기의 실리콘 미립자를 제조하는 방법은, 우선, 상기 방법으로 제조된 다공성의 실리콘 입자를 용매 특히 아세톤과 증류수에 분산시키고, 초음파 처리를 하는 단계를 포함하여 이루어 진다.The method for producing nano-sized silicon particles from the porous silicon particles prepared by the above method comprises, first, dispersing the porous silicon particles prepared by the above method in a solvent, particularly acetone and distilled water, and performing ultrasonication. Lose.
상기 초음파의 진동수는 뭉쳐 있는 작은 입자들을 분쇄하기 위하여 20 kHz 이상이 바람직하며, 특히 진동수가 40 kHz 일때 분쇄가 용이하다. 또한, 초음파 처리는 입자들을 충분히 분쇄하기 위하여 24 시간 이상 수행하여야 바람직하다. 이때 약하게 연결된 실리콘 네트워크 구조는 쉽게 부스러지면서 여러 가지 크기의 개별적인 입자들로 분리된다. 그 중에 좀 크고 무거운 입자들은 석출되어 나오며, 이보다 작은 입자들은 현탁액 안에 존재하게 되는데, 이 현탁액을 회수한 후, 용매를 증발시켜 실리콘 나노 입자들을 회수할 수 있다.The frequency of the ultrasonic wave is preferably 20 kHz or more in order to pulverize the small particles that are agglomerated, particularly when the frequency is 40 kHz. In addition, the sonication is preferably performed for at least 24 hours in order to sufficiently grind the particles. The weakly connected silicon network structure is easily broken and separated into individual particles of various sizes. The larger and heavier particles are precipitated out, and the smaller particles are present in the suspension. After the suspension is recovered, the silicon nanoparticles can be recovered by evaporating the solvent.
상기 방법으로 제조된 다공성 실리콘 또는 나노 크기 실리콘 미립자를 리튬 이차전지 음극 활물질로 사용될 수 있다.Porous silicon or nano-sized silicon fine particles prepared by the above method may be used as a lithium secondary battery negative electrode active material.
본 발명의 다공성 실리콘의 경우 리튬 이차 전지의 음극 재료로 사용시 입자내에 존재하는 기공으로 인하여 부피팽창을 억제할 수 있어서 장기적인 성능의 안정성을 가져오게 되며, 또한 표면적의 증가로 인하여 리튬 이온과 반응할 수 있는 장소의 증가로 전극의 저항을 줄일 수 있는 장점을 지니고 있다. 마찬가지로 나노 크기의 실리콘은 입도의 감소로 인해 부피 팽창을 억제하여 전극의 퇴화를 방지하고, 반응의 일어날 수 있는 장소가 증가시키는 작용을 한다.In the case of the porous silicon of the present invention, when used as a negative electrode material of a lithium secondary battery, it is possible to suppress volume expansion due to the pores present in particles, resulting in long-term stability of performance, and also reacting with lithium ions due to an increase in surface area. Increasing the number of places, has the advantage of reducing the resistance of the electrode. Similarly, nano-sized silicon inhibits volume expansion due to a decrease in particle size, preventing the degradation of electrodes and increasing the place where reactions can occur.
이차 전지의 음극은 금속재질의 집전체와 상기 집전체에 도포되는 음극 활물질을 포함하며, 상기 음극활물질은 결합제와 본 발명의 방법으로 제조된 상기 실리콘 입자를 포함한다.The negative electrode of the secondary battery includes a metal current collector and a negative electrode active material applied to the current collector, and the negative electrode active material includes a binder and the silicon particles produced by the method of the present invention.
우선, 전극의 성형 방법의 예로는 본 발명의 방법으로 제조된 상기 실리콘과 결합제를 전체 분산액의 1 ~ 30 중량 %의 함량으로 첨가 및 교반하여 페이스트를 제조한 후 이를 집전체용 금속 재료에 도포하고 압축한 뒤 건조하여 라미네이트 형상의 전극을 제조하는 방법이 바람직하다.First, as an example of the method of forming the electrode, the silicone and the binder prepared by the method of the present invention are added and stirred in an amount of 1 to 30% by weight of the total dispersion to prepare a paste, and then applied to the current collector metal material. It is preferable to compress and dry to prepare a laminate electrode.
상기 결합제의 예로는 폴리테트라플루오로에틸렌(PTFE), 폴리비닐리덴 플루오라이드(PVdF), 셀룰로오즈(cellulose) 등이 있으며, 분산재의 대표적인 예로는 이소프로필 알코올, N-메틸피롤리돈(NMP), 아세톤 등이 있다.Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), cellulose, and the like, and representative examples of the dispersant are isopropyl alcohol, N-methylpyrrolidone (NMP), Acetone and the like.
또한, 집전체용 금속 재료는 전도성이 높은 금속으로서 상기 재료의 페이스트가 용이하게 접착될 수 있는 금속이면 어느 것이라도 사용될 수 있으며, 대표적인 예로는 구리 또는 니켈로 된 메쉬(mesh), 호일(foil) 등이 있다.In addition, the metal material for the current collector may be any metal as long as it is a metal having high conductivity and to which the paste of the material can be easily adhered. A representative example is a mesh or a foil made of copper or nickel. Etc.
전극 재료의 페이스트를 금속 재료에 고르게 도포하는 방법은 재료의 특성 등을 감안하여 공지 방법 중에서 선택하거나 새로운 적절한 방법으로 행할 수 있다. 예를 들면, 페이스트를 집전체 위에 분배시킨 후 닥터 블레이드(doctor blade) 등을 사용하여 균일하게 분산시키는 것이 바람직하다. 경우에 따라서는 분배와 분산 과정을 하나의 공정으로 실행하는 방법을 사용할 수도 있다. 이밖에도 다이캐스팅(die casting), 콤마코팅(comma coating), 스크린 프린팅(screen printing) 등의 방법을 택할 수도 있으며, 또는 별도의 기재(substrate) 위에 성형한 후 프레싱 또는 라미네이션 방법에 의해 집전체와 접합시킬 수도 있다.The method of evenly applying the paste of the electrode material to the metal material can be selected from known methods or performed by a new suitable method in consideration of the properties of the material. For example, it is preferable to disperse the paste onto the current collector and then to uniformly disperse it using a doctor blade or the like. In some cases, a method of distributing and dispersing in one process may be used. In addition, die casting, comma coating, screen printing, or the like may be used. Alternatively, a separate substrate may be formed and bonded to the current collector by pressing or lamination. It may be.
금속 재료 위에 도포된 페이스트의 건조는 50 내지 200℃의 진공오븐에서 1 내지 3일 동안 건조시키는 것이 바람직하다. 경우에 따라서는, 전극의 저항을 더 줄이기 위하여 도전재로서 카본 블랙을 음극 활물질과 결합재로 이루어진 전극 100중량부에 대하여 중량 대비 5 내지 30 중량%로 첨가할 수 있다. 시판되고 있는 도전재의 예로는 아세틸렌 블랙 계열 (쉐브론 케미칼 컴퍼니(Chevron Chemical Company) 또는 걸프 오일 컴퍼니(Gulf Oil Company) 제품 등), 케트젠블랙(Ketjenblack), EC 계열(아르막 컴퍼니(Armak Company) 제품), 불칸(Vulcan) XC-72(캐보트 컴퍼니(Cabot Company) 제품) 및 수퍼(Super) P(엠엠엠(MMM)사 제품) 등이 있다.Drying of the paste applied on the metal material is preferably dried for 1 to 3 days in a vacuum oven at 50 to 200 ℃. In some cases, in order to further reduce the resistance of the electrode, carbon black as the conductive material may be added in an amount of 5 to 30% by weight based on 100 parts by weight of the electrode made of the negative electrode active material and the binder. Examples of commercially available conductive materials include acetylene black series (Chevron Chemical Company or Gulf Oil Company), Ketjenblack, EC series (Armak Company). ), Vulcan XC-72 (manufactured by Cabot Company), and Super P (manufactured by MMM).
상기의 방법으로 제작된 전극을 음극으로 사용하고 LiCoO2, LiNiO2,LiMn2O4등을 양극으로 사용하고 그 사이에 분리막을 삽입 시킴으로써, 리튬 이차 전지를구성할 수 있다.The lithium secondary battery can be configured by using the electrode produced by the above method as a cathode, using LiCoO 2 , LiNiO 2, LiMn 2 O 4, etc. as an anode, and inserting a separator therebetween.
상기 분리막은 두 개 전극의 내부 단락을 차단하고 전해액을 함침하는 역할을 하며, 분리막의 재료로는 고분자, 그라스화이버 매트, 크라프트지 등이 있으며, 현재 시판중인 대표적인 예로는 셀가드 계열(CelgardR2400, 2300(Hoechest Celanese Corp. 제품), 폴리프로필렌 분리막(polypropylene membrane; Ube Industries Ltd. 제품 또는 Pall RAI사 제품) 등이 있다. 상기의 전해질은 유기 용매에 리튬 염을 용해시킨 계로써, 리튬 염으로는 LiClO4, LiCF3SO3, LiAsF6, LiBF4, LiN(CF3SO2)2, LiPF6,LiSCN 및LiC(CF3SO2)3등이 발람직하고, 유기용매로는 에틸렌카보네이트(ethylene carbonate), 프로필렌카보네이트(propylene carbonate), 디에틸카보네이트(diethyl carbonate), 디메틸카보네이트(dimethylcarbonate), 1,2-디메톡시에탄(1,2-dimethoxyethane), 1,2-디에톡시에탄(1,2-diethoxyethane), 감마-부티로락톤(gamma-butyrolactone), 테트라히드로퓨란(tetrahydrofuran), 2-메틸테트라히드로푸란(2-methyltetrahydrofurna), 1,3 -디옥센(1,3-dioxolane), 4-메틸-1,3-디옥센(4-methyl-1,3-dioxolane), 디에틸에테르(diethy ether), 술포란 (sulfolane)등을 단독 또는 서로 혼합하여 사용할 수 있다.The separator is in serves, the membrane material to block the internal short circuit of the two electrodes and impregnated with an electrolytic solution is a polymer, a glass fiber mat, kraft paper or the like, representative examples on the market is the cell guard sequence (Celgard R 2400 , 2300 (manufactured by Hoechest Celanese Corp.), polypropylene membrane (manufactured by Ube Industries Ltd. or Pall RAI), etc. The electrolyte is a system in which lithium salt is dissolved in an organic solvent. LiClO 4 , LiCF 3 SO 3 , LiAsF 6 , LiBF 4 , LiN (CF 3 SO 2 ) 2 , LiPF 6 , LiSCN and LiC (CF 3 SO 2 ) 3 are preferred, and the organic solvent is ethylene carbonate ( ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane (1, 2-diethoxyethane), gamma-butyrolacto ne), tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxene (1,3-dioxolane), 4-methyl-1,3-dioxene (4-methyl -1,3-dioxolane), diethyl ether (diethy ether), sulfolane (sulfolane) and the like can be used alone or in combination with each other.
이하의 실시 예를 통하여 본 발명을 더욱 자세하게 설명한다. 단, 실시예는 본 발명을 예시하기 위한 것이지 이들 만으로 한정하는 것은 아니다.The present invention will be described in more detail with reference to the following examples. However, an Example is for illustrating this invention and is not limited only to these.
[실시예 1]Example 1
실리콘 다이옥사이드 (SiO2,silicon dioxide, Sigma Chem. Co., 평균 입자 크기= 3 마이크로미터) 1 g을 마그네슘 (Mg : magnesium, Junsei Chem. Co., 평균 입자 크기 = 500 마이크로미터) 0.8 g과 혼합한 후 비활성 분위기인 아르곤 분위기에서 1000oC에서 2시간 동안 열처리 하였다. 열처리된 시료를 마노유발에서 분쇄하였으며, 이 물질의 X선 회절 분석결과를 도 1의 (가)에 나타내었다.1 g of silicon dioxide (SiO 2, silicon dioxide, Sigma Chem. Co., average particle size = 3 micrometers) is mixed with 0.8 g of magnesium (Mg: magnesium, Junsei Chem. Co., average particle size = 500 micrometers) After heat treatment at 1000 o C for 2 hours in an inert argon atmosphere. The heat-treated sample was ground in agate induction, and the X-ray diffraction analysis of this material is shown in FIG.
상기 시료를 0.5 몰농도의 염산 (HCl : hydrochloric acid )에 넣고 6시간 동안 교반한 후 여과하여 합성 과정 중에 부산물로 생성되는 마그네슘 산화물 (MgO)을 제거하였다. 염산에 의하여 세척된 시료를 건조하여 X선 회절분석을 하였고 이 결과를 도 1의 (나)에 나타내었다.The sample was placed in 0.5 molar hydrochloric acid (HCl: hydrochloric acid), stirred for 6 hours, and filtered to remove magnesium oxide (MgO) produced as a by-product during the synthesis. The sample washed with hydrochloric acid was dried and subjected to X-ray diffraction analysis. The results are shown in FIG.
상기에서 마그네슘과 실리콘 옥사이드를 열처리하였을 때, 실리콘 옥사이드가 환원되어 금속상태의 실리콘으로 전환되고, 마그네슘이 산화되어 부산물인 마그네슘 옥사이드 (MgO)가 생성되는데, 상기 부산물인 마그네슘 옥사이드는 묽은 염산으로 세척하여 제거하였다.When the magnesium and silicon oxide are heat treated in the above, silicon oxide is reduced to be converted to silicon in the metal state, and magnesium is oxidized to produce magnesium oxide (MgO) as a byproduct, which is washed with dilute hydrochloric acid. Removed.
상기 세척 전 후의 전계 방출 주사전자 현미경 (FE-SEM : Field Emission Scanning Electron Microscope) 사진을 도 3의 (가)와 (나)에 각각 도시하였다. 이 결과를 통하여 나노미터 크기의 실리콘 입자가 뭉쳐져 있는 형상의 다공성의 실리콘이 합성 되었음을 확인할 수 있다.Field emission scanning electron microscope (FE-SEM) photographs before and after the washing are shown in FIGS. 3A and 3B, respectively. Through this result, it can be confirmed that porous silicon having a shape in which nanometer-sized silicon particles are aggregated is synthesized.
[실시예 2]Example 2
실리콘 다이옥사이드 대신 실리카겔 (silica gel, Aldrich Chem. Co., 평균 입자 크기 = 40 마이크로미터 )을 사용한 것을 제외하고는 실시예 1과 같은 방법으로 다공성의 실리콘 입자 및 나노 크기의 실리콘 미립자를 제조하였다. 합성된 다공성의 실리콘 입자의 전계 방출 주사전자 현미경 사진을 도 4의 (가)에 도시하였다.Porous silicon particles and nano-sized silicon particles were prepared in the same manner as in Example 1 except that silica gel (silica gel, Aldrich Chem. Co., average particle size = 40 micrometers) was used instead of silicon dioxide. A field emission scanning electron micrograph of the synthesized porous silicon particles is shown in FIG.
[실시예 3]Example 3
실시예 2에서, 열처리 온도를 700oC, 800oC, 900oC로 달리하여 열처리한 것을 제외하고는 실시예 2와 같은 방법으로 합성하였다. 그 결과 800oC 이상의 온도에서 실리콘이 합성됨을 확인 할 수 있었다. 각 시료는 모두 염산으로 세척하였으며 세척 후의 X선 회절 분석결과를 도 5에 도시하였다.In Example 2, it was synthesized in the same manner as in Example 2, except that the heat treatment by different heat treatment temperature to 700 ° C, 800 ° C, 900 ° C. As a result, it was confirmed that the silicon is synthesized at a temperature of 800 o C or more. Each sample was washed with hydrochloric acid and the result of X-ray diffraction analysis after washing is shown in FIG. 5.
[실시예 4]Example 4
실리콘 다이옥사이드 대신 유리 (glass), 수정 (quartz), 실리콘 모노옥사이드 (silicon monoxide), 지올라이트 (zeolite), 메탈 실리케이트 (metal silicate), 퓸드 실리카 (fumed silica)를 사용한 것을 제외하고는 실시예 1과 같은 방법으로 다공성의 실리콘 입자를 제조할 수 있었다. 유리를 이용하여 사용하여 합성된 다공성의 실리콘 입자의 전계 방출 주사전자 현미경 사진을 도 4의 (나)에 도시하였고 또한 X선 회절분석 결과를 도 6의 (가)에 도시하였다.Example 1 except that glass, quartz, silicon monoxide, zeolite, metal silicate and fumed silica were used instead of silicon dioxide. In the same manner, porous silicon particles could be prepared. Field emission scanning electron micrographs of porous silicon particles synthesized using glass are shown in FIG. 4B and X-ray diffraction results are shown in FIG. 6A.
[실시예 5]Example 5
마그네슘 대신 리튬을 사용한 것을 제외하고는 실시예 2와 같은 방법으로, 다공성의 실리콘 입자를 제조할 수 있었다. 본 방법으로 합성된 실리콘 입자의 X선 회절분석 결과를 도 6의 (나)에 도시하였다.Except for using lithium instead of magnesium in the same manner as in Example 2, it was possible to produce a porous silicon particles. X-ray diffraction analysis results of the silicon particles synthesized by the present method are shown in FIG.
[실시예 6]Example 6
실시예 2에서 합성된 다공성의 실리콘을 아세톤과 증류수에 넣은 후 24 시간동안 40 kHz의 초음파(ultrasonic)로 처리하였다. 초음파 처리 후에 침천물과 현탁액을 분리하였다. 현탁액 (suspension)을 건조하여 나노크기의 실리콘을 얻었다. 이와 같이 얻어진 물질의 투과전자 현미경 (TEM : transmission electron microscope) 사진을 도 7에 도시하였다. 입자크기가 20 나노미터인 실리콘 입자가 합성 되었음을 확인할 수 있다.The porous silicon synthesized in Example 2 was added to acetone and distilled water and treated with ultrasonic at 40 kHz for 24 hours. After sonication, the precipitate and suspension were separated. The suspension was dried to obtain nanosize silicon. A transmission electron microscope (TEM) photograph of the material thus obtained is shown in FIG. 7. It can be seen that the silicon particles having a particle size of 20 nanometers were synthesized.
[실시예 7]Example 7
실시예 1 내지 5의 방법으로 합성된 시료, 도전재인 탄소 및 바인더인 폴리테트라플루오로에틸렌 (PTFE) 를 중량비 65 : 25 : 10 으로 혼합하여 구리 집전체에 압착한 후 120 ℃ 진공오븐에서 12시간 이상 건조시켰다. 반대전극은 리튬 금속 호일 또는 리튬 코발트 산화물 (LiCoO2)를 사용하였고 기준 전극으로는 리튬 금속 호일을 사용하였다.Samples synthesized by the methods of Examples 1 to 5, carbon as a conductive material and polytetrafluoroethylene (PTFE) as a binder were mixed at a weight ratio of 65:25:10, and pressed onto a copper current collector, followed by 12 hours in a vacuum oven at 120 ° C. It was dried over. The counter electrode used lithium metal foil or lithium cobalt oxide (LiCoO 2 ) and a lithium metal foil as reference electrode.
그리고, 전해질로서 1 몰 농도 LiClO4/ 에틸렌카보네이트 (EC): 디에틸카보네이트 (DEC) (부피비 1:1) 을 사용하여 비이커 형태의 3극 셀을 제조하고 상온에서 정전류로 충방전 실험을 수행하였다.In addition, a beaker-type tripolar cell was prepared using 1 mol concentration of LiClO 4 / ethylene carbonate (EC): diethyl carbonate (DEC) (volume ratio 1: 1) as an electrolyte, and a charge / discharge experiment was performed under constant current at room temperature. .
그 결과 전류 밀도는 0.5 mA/cm2이었으며, 충방전 영역은 2.0 에서 0.01 V(vs. Li/Li+)로 실험을 수행하였다. 첫 충전 용량은 2800 mAh/g 이었으며 방전용량은 800 mAh/g 이었다.As a result, the current density was 0.5 mA / cm 2 , and the charge / discharge region was experimented at 2.0 to 0.01 V ( vs. Li / Li + ). The first charge capacity was 2800 mAh / g and the discharge capacity was 800 mAh / g.
[실시예 8]Example 8
실시예 6에서 만들어진 나노크기 실리콘을 활물질로 사용한 것을 제외하고는 실시예 7과 동일한 방법으로 충방전 실험을 진행하였다. 그 결과 첫 충전 용량은 2400 mAh/g 이었으며 방전용량은 800 mAh/g 이었다.Charge and discharge experiments were conducted in the same manner as in Example 7, except that the nano-sized silicon made in Example 6 was used as the active material. As a result, the first charge capacity was 2400 mAh / g and the discharge capacity was 800 mAh / g.
상기에서 살펴본 바와 같이, 본 발명은 알칼리 또는 알칼리 토금속을 환원제로 사용하여 실리콘 전구체인 실리콘 옥사이드를 환원하여 다공성의 실리콘 입자를 합성하는 단계를 채택함으로써, 독성이 강한 불산을 사용하지 않고, 원가 부담이 적으며, 부산물의 제거도 용이하며, 다공성 실리콘 입자의 제조 방법을 간략화하는 효과가 있다.As described above, the present invention adopts a step of reducing the silicon oxide which is a silicon precursor by using an alkali or alkaline earth metal as a reducing agent to synthesize porous silicon particles, thereby avoiding the use of highly toxic hydrofluoric acid and reducing the cost burden. It is less, it is easy to remove the by-products, there is an effect to simplify the manufacturing method of the porous silicon particles.
또한, 본 발명은 상기 방법으로 제조된 다공성의 실리콘 입자를 분산 처리 및 초음파 처리를 통하여 나노 크기의 실리콘 미립자를 간략하게 얻을 수 있는 우수한 제조 방법이다.In addition, the present invention is an excellent manufacturing method that can simply obtain the nano-sized silicon fine particles through the dispersion and ultrasonic treatment of the porous silicon particles produced by the above method.
또한, 본 발명의 방법으로 제조된 다공성 실리콘 또는 나노 크기의 실리콘 미립자는 리튬 이차 전지의 음극재료로 사용할 경우, 입자 내에 존재하는 기공으로 인하여 부피팽창을 억제할 수 있어서 전극의 퇴화를 방지하는 등 장기적인 성능의 안정성을 가져오게 되며, 또한 표면적의 증가로 인하여 리튬 이온과 반응할 수 있는 장소의 증가로 전극의 저항을 감소시키는 우수한 효과가 있다.In addition, when the porous silicon or nano-sized silicon fine particles prepared by the method of the present invention is used as a negative electrode material of a lithium secondary battery, it is possible to suppress volume expansion due to the pores present in the particles, thereby preventing deterioration of the electrode. It brings about stability of performance, and also has an excellent effect of reducing the resistance of the electrode due to the increase of the place where it can react with lithium ions due to the increase of the surface area.
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