TWI699033B - Method for manufacturing anode material containing SiOX - Google Patents

Method for manufacturing anode material containing SiOX Download PDF

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TWI699033B
TWI699033B TW108112235A TW108112235A TWI699033B TW I699033 B TWI699033 B TW I699033B TW 108112235 A TW108112235 A TW 108112235A TW 108112235 A TW108112235 A TW 108112235A TW I699033 B TWI699033 B TW I699033B
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siox
sio
negative electrode
material containing
electrode material
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TW202038497A (en
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李柏翰
翁炳志
葛春明
彭素惠
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國家中山科學研究院
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    • 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
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    • Y02E60/10—Energy storage using batteries

Abstract

本發明係提供一種含SiOx之負極材料的製造方法，步驟包括：(A)提供一矽啟始物、非晶相SiO2與一溶劑於惰性氣氛下進行一混合製程以形成一混合物；(B)將該混合物進行烘乾以得到一矽氧化物前驅物；(C)將該矽氧化物前驅物置入一模具中壓錠並在惰性氣氛或還原性氣氛下進行一鍛燒製程以形成一SiOx固狀物；(D)將該SiOx固狀物進行一粉碎篩分製程以形成一SiOx粉狀物；(E)將該SiOx粉狀物與一有機碳源進行一碳包覆製程以形成一SiOx/C前驅物；(F)將該SiOx/C前驅物進行一碳化製程以形成一SiOx/C複合物；其中，步驟(C)、步驟(D)、步驟(E)及步驟(F)SiOx之x值範圍為0.5<x<1.5。 The present invention provides a method for manufacturing a negative electrode material containing SiOx. The steps include: (A) providing a silicon initiator, amorphous SiO 2 and a solvent under an inert atmosphere to perform a mixing process to form a mixture; (B) ) The mixture is dried to obtain a silicon oxide precursor; (C) the silicon oxide precursor is placed in a mold to press an ingot, and a calcining process is performed in an inert atmosphere or a reducing atmosphere to form a SiOx solid (D) the SiOx solid substance is subjected to a crushing and screening process to form a SiOx powder; (E) the SiOx powder and an organic carbon source are subjected to a carbon coating process to form a SiOx /C precursor; (F) subject the SiOx/C precursor to a carbonization process to form a SiOx/C composite; wherein, step (C), step (D), step (E) and step (F) SiOx The range of x value is 0.5<x<1.5.

Description

一種含SiOX之負極材料的製造方法 Method for manufacturing negative electrode material containing SiOX

本發明係為一種負極材料之製造方法，特別是有關於一種含SiOx之高容量鋰離子電池負極材料之製造方法。 The present invention relates to a method for manufacturing a negative electrode material, and particularly relates to a method for manufacturing a high-capacity lithium ion battery negative electrode material containing SiOx.

鋰離子電池因為具有能量密度高、操作電壓高、使用溫度範為大、無記憶效應、壽命長及可歷經無數次的充放電等優點故被廣泛應用於可攜式電子產品如手機、筆記型電腦、數位相機等，近年來更擴及汽車領域。 Lithium-ion batteries are widely used in portable electronic products such as mobile phones and notebooks because of their high energy density, high operating voltage, large operating temperature range, no memory effect, long life, and countless charging and discharging. Computers, digital cameras, etc. have expanded to the automotive field in recent years.

鋰離子電池負極材料所要求的特性為高能量密度、高安全性、優秀的循環次數以及快速充放電特性，而石墨系碳材因具備高安全性、快速充放電特性且價格相對便宜，故以石墨系碳材為為鋰離子電池負極材料約占整體的98%，但是這一類碳負極材已經過多年材料自身改性如多相包覆、參雜等進行電池工藝化，其實際運用容量已接近材料的理論克電容量，進步空間有限，所以逐漸不易滿足現代電子設備小型化、輕、薄及高能量密度的要求。 The required characteristics of lithium-ion battery anode materials are high energy density, high safety, excellent cycle times, and fast charge and discharge characteristics. Graphite-based carbon materials have high safety, fast charge and discharge characteristics, and are relatively inexpensive. Graphite-based carbon materials account for about 98% of the total anode materials for lithium-ion batteries. However, this type of carbon anode materials have been modified for many years, such as multi-phase coating, doping, etc., for battery technology. The theoretical gram capacity is close to the material, and the room for improvement is limited, so it is gradually difficult to meet the requirements of modern electronic equipment for miniaturization, lightness, thinness and high energy density.

矽元素作為鋰離子電池負極材料時，高於石墨類碳材的理論電容量，可大幅提升負極之單位電容量，未來可應 用於下一世代的鋰離子電池系統中，滿足現代電子設備小型化、輕、薄及高能量密度的要求，但由於矽於充放電過程中產生之體積膨脹達4倍之多，使得矽表面會產生不可逆之缺陷，導致電池電容量下降、庫倫效率低等缺點，因此近年矽負極材料發展轉向SiOx，因其相較於純矽雖然理論電容量只有一半，但在體積改變上亦只有一半。目前SiOx主要是提供作為鋰離子電池用之負極活性物質，以混摻形式添加部分劑量SiOx於鋰離子電池負極中，可大幅提升電池的負極總體能量密度。 When silicon is used as a negative electrode material for lithium-ion batteries, its theoretical capacity is higher than that of graphite-like carbon materials, which can greatly increase the unit capacity of the negative electrode. It is used in the next generation of lithium-ion battery systems to meet the requirements of modern electronic equipment for miniaturization, lightness, thinness and high energy density. However, the volume expansion of silicon during charging and discharging is as much as 4 times, making the silicon surface Irreversible defects will occur, leading to shortcomings such as decreased battery capacity and low Coulomb efficiency. Therefore, in recent years, the development of silicon anode materials has turned to SiOx. Compared with pure silicon, although the theoretical capacity is only half, the volume change is only half. At present, SiOx is mainly used as a negative electrode active material for lithium-ion batteries. Adding a part of SiOx to the negative electrode of lithium-ion batteries in the form of mixing can greatly increase the overall energy density of the negative electrode of the battery.

目前製作鋰離子電池負極材料時，提供作為鋰離子電池用之負極材料SiOx是以高溫氣相法製備，其主要為將Si與SiO2在固定壓力下高溫共燒(1400~1700℃)後產生SiO氣體並進一步凝結製備SiOx，此方式對於量產上較為困難並且十分耗能，且需要精準控制溫度和壓力及在真空環境下才能穩定生產特定氧含量之SiOx，造成製作含SiOx之鋰離子電池負極材料量產之瓶頸。 At present, when making anode materials for lithium-ion batteries, SiOx, the anode material provided for lithium-ion batteries, is prepared by a high-temperature gas phase method, which is mainly produced by co-firing Si and SiO 2 at a high temperature (1400~1700℃) under a fixed pressure SiO gas is further condensed to prepare SiOx. This method is difficult for mass production and consumes energy. It requires precise temperature and pressure control and stable production of SiOx with specific oxygen content in a vacuum environment, resulting in the production of SiOx-containing lithium ion batteries The bottleneck in mass production of anode materials.

鑒於上述習知技術之缺點，本發明之主要目的在於提供一種簡單且成本較低的固相反應法製備SiOx，用以製作出一種含SiOx之高容量負極材料。 In view of the shortcomings of the above-mentioned conventional technology, the main purpose of the present invention is to provide a simple and low-cost solid-phase reaction method for preparing SiOx to produce a high-capacity negative electrode material containing SiOx.

為了達到上述目的，根據本發明所提出之一種含SiOx之負極材料之製備方法，步驟包括：(A)提供一矽啟始物、非晶相SiO2與一溶劑於惰性氣氛下進行一混合製程以形成一 混合物；(B)將該混合物進行烘乾以得到一矽氧化物前驅物；(C)將該矽氧化物前驅物置入一模具中壓錠並在惰性氣氛或還原性氣氛下進行一鍛燒製程以形成一SiOx固狀物；(D)將該SiOx固狀物進行一粉碎篩分製程以形成一SiOx粉狀物；(E)將該SiOx粉狀物與一有機碳源進行一碳包覆製程以形成一SiOx/C前驅物；(F)將該SiOx/C前驅物進行一碳化製程以形成一SiOx/C複合物；其中，步驟(C)、步驟(D)、步驟(E)及步驟(F)SiOx之x值範圍為0.5<x<1.5。 In order to achieve the above objective, according to the method for preparing a SiOx-containing negative electrode material proposed in the present invention, the steps include: (A) providing a silicon initiator, amorphous SiO 2 and a solvent in an inert atmosphere for a mixing process To form a mixture; (B) drying the mixture to obtain a silicon oxide precursor; (C) placing the silicon oxide precursor in a mold and pressing an ingot and performing a forging in an inert atmosphere or a reducing atmosphere Firing process to form a SiOx solid; (D) the SiOx solid is subjected to a crushing and screening process to form a SiOx powder; (E) the SiOx powder and an organic carbon source are subjected to a carbon The coating process is used to form a SiOx/C precursor; (F) the SiOx/C precursor is subjected to a carbonization process to form a SiOx/C composite; wherein, step (C), step (D), step (E) ) And step (F) The range of x value of SiOx is 0.5<x<1.5.

上述中矽啟始物係選自Si、SiOx其中之一或其混合，其中SiOx之X為0.1<X<0.5，步驟(A)之混合製程為在惰性氣體下以濕式球磨混合，球磨珠大小可為0.1~5mm，溶劑係選自酒精、異丙醇、丙酮之其一或其混合。 The above-mentioned medium silicon starting material is selected from one of Si, SiOx or a mixture thereof, wherein X of SiOx is 0.1<X<0.5, and the mixing process of step (A) is mixing by wet ball milling under inert gas, ball milling beads The size can be 0.1~5mm, and the solvent is selected from one of alcohol, isopropanol, acetone or a mixture thereof.

步驟(A)流程中，其中該惰性氣體係為氬氣或氮氣。 In the process of step (A), the inert gas system is argon or nitrogen.

步驟(B)流程中，烘乾溫度為100℃~150℃之間。 In the process of step (B), the drying temperature is between 100°C and 150°C.

上述步驟(C)流程中，該鍛燒製程之鍛燒溫度係為600℃~950℃之間，經鍛燒製程後，使矽氧化物前驅物中的Si或SiOx(0.1<X<0.5)與SiO2反應形成一SiOx固狀物，SiOx固狀物之X為0.5<x<1.5；上述步驟(D)流程中，該粉碎過篩製程中的粉碎方法可以選自切削、球磨、研磨其中之一或其混合(但不以此為限)，另在粉碎過篩製程中包含使用一篩網，該篩網之網目數量範圍可以是80-600mesh。 In the above step (C) process, the calcination temperature of the calcination process is between 600°C and 950°C. After the calcination process, Si or SiOx in the silicon oxide precursor (0.1<X<0.5) It reacts with SiO 2 to form a solid SiOx, the X of the solid SiOx is 0.5<x<1.5; in the above step (D), the crushing method in the crushing and sieving process can be selected from cutting, ball milling, and grinding. One or a mixture thereof (but not limited to this), and the other includes using a screen in the crushing and sieving process, and the number of meshes of the screen may range from 80 to 600 mesh.

上述步驟(E)流程中，該有機碳源包括檸檬酸。 In the above step (E) process, the organic carbon source includes citric acid.

上述步驟(F)流程中，該碳化製程為在氮氣下進行，製程溫度係為在600℃~800℃之間。 In the above step (F), the carbonization process is performed under nitrogen, and the process temperature is between 600°C and 800°C.

以上之概述與接下來的詳細說明及附圖，皆是為了能進一步說明本創作達到預定目的所採取的方式、手段及功效。而有關本創作的其他目的及優點，將在後續的說明及圖式中加以闡述。 The above summary and the following detailed description and drawings are for the purpose of further explaining the methods, means and effects of this creation to achieve the intended purpose. The other purposes and advantages of this creation will be elaborated in the subsequent description and diagrams.

S101-106‧‧‧步驟 S101-106‧‧‧Step

第一圖係為本發明一種含有SiOx之負極材料之製作方法流程圖；第二圖係為本發明SiOx(Si：SiO2=1：1)、SiOx/C(commercial)、Si及SiO2樣品之同步輻射X光繞射(synchrotron X-ray diffraction,SXRD)圖譜；第三圖係為本發明SiOx(Si：SiO2=1：1)/C複合物之SEM(scan electron microscope)影像與其EDS mapping；第四圖係為本發明SiOx/C(commercial)樣品之SEM(scan electron microscope)影像與其EDS mapping；第五圖係為本發明SiOx(Si：SiO2=1：1)/C複合物與SiOx/C(commercial)樣品之SEM圖；第六圖係為本發明SiOx(Si：SiO2=1：1)/C複合物與SiOx(commercial)樣品之XPS Si2p之頻譜分析圖 第七圖係為本發明實施例1之半電池測試圖；第八圖係為本發明實施例2之半電池測試圖；第九圖係為本發明實施例1及實施例2半電池長循環充放電測試圖。第一圖係為本發明之矽碳負極材料示意圖。 The first figure is a flow chart of the method for preparing a negative electrode material containing SiOx in the present invention; the second figure is the synchronization of SiOx (Si: SiO2=1:1), SiOx/C (commercial), Si and SiO2 samples of the present invention The radiation X-ray diffraction (synchrotron X-ray diffraction, SXRD) spectrum; the third image is the SEM (scan electron microscope) image of the SiOx(Si:SiO2=1:1)/C composite of the present invention and its EDS mapping; The fourth figure is the SEM (scan electron microscope) image of the SiOx/C (commercial) sample of the present invention and its EDS mapping; the fifth figure is the SiOx(Si:SiO2=1:1)/C composite and SiOx/C of the present invention (commercial) SEM image of the sample; the sixth image is the spectrum analysis diagram of XPS Si2p of the SiOx(Si:SiO2=1:1)/C composite and SiOx(commercial) samples of the present invention The seventh figure is the half-cell test diagram of the first embodiment of the present invention; the eighth diagram is the half-cell test diagram of the second embodiment of the present invention; the ninth diagram is the half-cell long cycle of the first embodiment and the second embodiment of the present invention Charge and discharge test chart. The first figure is a schematic diagram of the silicon-carbon anode material of the present invention.

以下係藉由特定的具體實例說明本發明之實施方式，熟悉此技藝之人士可由本說明書所揭示之內容輕易地了解本發明之優點及功效。 The following is a specific example to illustrate the implementation of the present invention. Those familiar with the art can easily understand the advantages and effects of the present invention from the content disclosed in this specification.

以高溫氣相法製備SiOx，主要為將Si與SiO2在固定壓力下高溫共燒(1400~1700℃)後產生SiO氣體並進一步凝結製備SiOx，此方式對於量產上較為困難並且十分耗能，以及需要精準控制溫度和壓力才能穩定生產特定氧含量之SiOx，造成製作含SiOx之鋰離子電池負極材料量產之瓶頸；本發明的目的在於提供一種簡單且成本較低的固相反應法製備SiOx以製作出含SiOx之高容量負極材料來解決上述問題。 SiOx is prepared by high-temperature gas phase method, mainly by co-firing Si and SiO 2 at high temperature (1400~1700℃) under a fixed pressure to produce SiO gas and further condense to prepare SiOx. This method is difficult and energy-consuming for mass production. , And the need for precise control of temperature and pressure to stably produce SiOx with a specific oxygen content, causing a bottleneck in the mass production of SiOx-containing lithium ion battery anode materials; the purpose of the present invention is to provide a simple and low-cost solid-phase reaction method for preparation SiOx can solve the above-mentioned problems by producing high-capacity anode materials containing SiOx.

請參閱第一圖所示，為本發明一種含有SiOx之負極材料之製作方法流程圖。如圖所示，本發明提供一種含有SiOx的負極材料之製作方法，步驟包括：(A)提供一矽啟始物、非晶相SiO2與一溶劑於惰性氣氛下進行一混合製程以形成一混合物S101；(B)將該混合物進行烘乾以得到一矽氧化物前驅物S102；(C)將該矽氧化物前驅物置入一模具中壓錠並在惰性 氣氛或還原性氣氛下進行一鍛燒製程以形成一SiOx固狀物S103；(D)將該SiOx固狀物進行一粉碎篩分製程以形成一SiOx粉狀物S104；(E)將該SiOx粉狀物與一有機碳源進行一碳包覆製程以形成一SiOx/C前驅物S105；(F)將該SiOx/C前驅物進行一碳化製程以形成一SiOx/C複合物S106；其中，步驟(C)、步驟(D)、步驟(E)及步驟(F)SiOx之x值範圍為0.5<x<1.5。 Please refer to the first figure, which is a flow chart of a method for manufacturing a negative electrode material containing SiOx in the present invention. As shown in the figure, the present invention provides a method for manufacturing a negative electrode material containing SiOx. The steps include: (A) providing a silicon initiator, amorphous SiO 2 and a solvent in an inert atmosphere for a mixing process to form a Mixture S101; (B) Dry the mixture to obtain a silicon oxide precursor S102; (C) Place the silicon oxide precursor in a mold and press an ingot and perform a calcining in an inert atmosphere or a reducing atmosphere Process to form a SiOx solid material S103; (D) the SiOx solid material is subjected to a crushing and screening process to form a SiOx powder material S104; (E) the SiOx powder material is combined with an organic carbon source Carbon coating process to form a SiOx/C precursor S105; (F) the SiOx/C precursor is subjected to a carbonization process to form a SiOx/C composite S106; wherein, step (C), step (D), The range of x value of SiOx in step (E) and step (F) is 0.5<x<1.5.

實施例1：以Si粉與非晶相SiO2依比例1：1(wt.%)加入球磨罐中，氧化鋯球(2mm)：Si+SiO2：酒精=2：1：10(wt.%)，置入含氧化鋯內襯之球磨罐，於每分鐘300轉之轉速球磨6小時使Si與SiO2混合均勻。球磨6小時後，將溶液(混合物)過濾取出Si+SiO2粉體，經過110℃烘乾，取得矽氧化物前驅物。將矽氧化物前驅物以模具壓錠，置入模具得厚度約5mm之錠片。所得錠片於900℃氮氣中燒結(鍛燒)8小時，得到SiOx固狀物。取出並以粉碎機粉碎後得到SiOx粉狀物，之後將其過350mesh之篩網，再將粉體置入球磨罐中，並添加檸檬酸、少量去離子水及氧化鋯球進行球磨3小時(碳包覆製程)，藉由有機碳源進行碳包覆。而後取出SiOx漿料，以110℃將此漿料乾燥使去離子水揮發，取得SiOx/C之前驅物。SiOx/C前驅物再以700℃氮氣中碳化5小時(碳化製程)，即可取得SiOx(Si：SiO2=1：1)/C複合物。而後將SiOx(Si：SiO2=1：1)/C(15%)混合95%的商業化石墨材料中間相碳微球進行混漿(活性材：導電助劑：PAA：SBR：CMC=93：3：0.67：1.5：1.83)、極板製備及電池組裝，此樣品稱為15wt.% SiOx(Si：SiO2=1：1)/C+85wt.%介相碳微球(mesocarbon microbead,MCMB)。 Example 1: Si powder and amorphous phase SiO 2 were added to the ball milling tank in a ratio of 1:1 (wt.%), zirconia balls (2mm): Si+SiO 2 : alcohol = 2: 1: 10 (wt. %), placed in a ball mill tank with zirconia lining, ball milled at 300 rpm for 6 hours to mix Si and SiO 2 uniformly. After 6 hours of ball milling, the solution (mixture) was filtered to take out the Si+SiO 2 powder and dried at 110°C to obtain the silicon oxide precursor. The silicon oxide precursor is pressed into an ingot with a mold and placed in the mold to obtain an ingot with a thickness of about 5 mm. The obtained ingot was sintered (calcined) in nitrogen at 900°C for 8 hours to obtain a solid SiOx. Take out and pulverize with a pulverizer to obtain SiOx powder, then pass it through a 350 mesh screen, then put the powder into a ball milling tank, and add citric acid, a small amount of deionized water and zirconia balls for ball milling for 3 hours ( Carbon coating process), carbon coating is carried out by organic carbon source. Then, the SiOx slurry was taken out, and the slurry was dried at 110° C. to volatilize the deionized water to obtain the SiOx/C precursor. The SiOx/C precursor is then carbonized in nitrogen at 700°C for 5 hours (carbonization process) to obtain a SiOx (Si: SiO 2 =1:1)/C composite. Then mix SiOx (Si: SiO 2 =1:1)/C (15%) with 95% of commercial graphite material mesophase carbon microspheres for mixing (active material: conductive aid: PAA: SBR: CMC=93 ：3：0.67：1.5：1.83), plate preparation and battery assembly, this sample is called 15wt.% SiOx (Si: SiO 2 =1:1)/C+85wt.% mesocarbon microbead, MCMB).

實施例2：以Si粉與非晶相SiO2依比例1：0.5(wt.%)加入球磨罐中，氧化鋯球(2mm)：Si+SiO2：酒精=2：1：10(wt.%)，置入含氧化鋯內襯之球磨罐，於每分鐘300轉之轉速球磨6小時使Si與SiO2混合均勻。球磨6小時後，將溶液過濾取出Si+SiO2粉體，經過110℃烘乾，取得矽氧化物前驅物。將矽氧化物前驅物以模具壓錠，置入模具得厚度約5mm之錠片。所得錠片於900℃氮氣中燒結(鍛燒)8小時，得到SiOx固狀物。取出並以粉碎機粉碎後SiOx粉狀物，之後將其過350mesh之篩網，再將粉體置入球磨罐中，並添加檸檬酸、少量去離子水及氧化鋯球進行球磨3小時(碳包覆製程)，藉由有機碳源進行碳包覆。而後取出SiOx漿料，以110℃將此漿料乾燥使去離子水揮發，取得SiOx/C之前驅物。SiOx/C前驅物再以700℃氮氣中碳化5小時(碳化製程)，即可取得SiOx(Si：SiO2=1：0.5)/C複合物。而後將SiOx(Si：SiO2=1：0.5)/C(15%)混合95%的商業化石墨材料中間相碳微球進行混漿(活性材：導電助劑：PAA：SBR：CMC=93：3：0.67：1.5：1.83)、極板製備及電池組裝，此樣品稱為15wt.% SiOx(Si：SiO2=1：0.5)/C+85wt.%介相碳微球(mesocarbon microbead,MCMB)。 Example 2: Add Si powder and amorphous SiO 2 into a ball milling tank in a ratio of 1:0.5 (wt.%), zirconia balls (2mm): Si+SiO 2 : Alcohol = 2: 1: 10 (wt. %), placed in a ball mill tank with zirconia lining, ball milled at 300 rpm for 6 hours to mix Si and SiO 2 uniformly. After 6 hours of ball milling, the solution was filtered to take out the Si+SiO 2 powder and dried at 110°C to obtain the silicon oxide precursor. The silicon oxide precursor is pressed into an ingot with a mold and placed in the mold to obtain an ingot with a thickness of about 5 mm. The obtained ingot was sintered (calcined) in nitrogen at 900°C for 8 hours to obtain a solid SiOx. Take out and pulverize the SiOx powder with a pulverizer, then pass it through a 350 mesh screen, then place the powder in a ball milling tank, and add citric acid, a small amount of deionized water and zirconia balls for ball milling for 3 hours (carbon Coating process), carbon coating is carried out by organic carbon source. Then, the SiOx slurry was taken out, and the slurry was dried at 110° C. to volatilize the deionized water to obtain the SiOx/C precursor. The SiOx/C precursor is then carbonized in nitrogen at 700°C for 5 hours (carbonization process) to obtain a SiOx (Si: SiO 2 =1: 0.5)/C composite. Then mix SiOx (Si: SiO 2 =1: 0.5)/C (15%) with 95% commercial graphite material mesophase carbon microspheres for mixing (active material: conductive aid: PAA: SBR: CMC=93 ：3：0.67：1.5：1.83), plate preparation and battery assembly, this sample is called 15wt.% SiOx (Si: SiO 2 =1: 0.5)/C+85wt.% mesocarbon microbead, MCMB).

比較例1：購買商業化之碳包覆SiOx/C複合物(0.8<x<0.95)，以商業化之SiOx/C混合95%的商業化石墨材料中 間相碳微球進行混漿(活性材：導電助劑：PAA：SBR：CMC=93：3：0.67：1.5：1.83)、極板製備及電池組裝，此樣品稱為5wt% SiOx(commercial)+95wt% MCMB。若以相同之電容量來進行比較其可與實施例1比較。 Comparative Example 1: Purchase commercialized carbon-coated SiOx/C composite (0.8<x<0.95), and mix 95% commercialized graphite material with commercialized SiOx/C Interphase carbon microspheres are mixed (active material: conductive aid: PAA: SBR: CMC=93: 3: 0.67: 1.5: 1.83), plate preparation and battery assembly, this sample is called 5wt% SiOx (commercial) +95wt% MCMB. If the same capacitance is used for comparison, it can be compared with Example 1.

比較例2：購買商業化之碳包覆SiOx/C複合物(0.8<x<0.95)，以商業化之SiOx/C混合85%的商業化石墨材料中間相碳微球進行混漿(活性材：導電助劑：PAA：SBR：CMC=93：3：0.67：1.5：1.83)、極板製備及電池組裝，此樣品稱為15wt% SiOx(commercial)+85wt% MCMB。若以相同之電容量來進行比較其可與實施例2比較。 Comparative Example 2: Commercialized carbon-coated SiOx/C composite (0.8<x<0.95) was purchased, and commercialized SiOx/C was mixed with 85% of the commercial graphite material mesophase carbon microspheres for mixing (active material : Conductive aid: PAA: SBR: CMC=93:3:0.67:1.5:1.83), plate preparation and battery assembly, this sample is called 15wt% SiOx(commercial)+85wt% MCMB. If the same capacitance is used for comparison, it can be compared with Example 2.

本發明所製備之SiOx/C複合物與黏結劑、導電助劑依一定比例混成漿料後，將其塗佈於10μm銅箔上，先於80℃下將溶劑烘乾，而後進真空烘箱以110℃烘烤24h，去除溶劑。完成之極板，以直徑12mm之圓(12Φ)切下，製作成CR2032鈕扣型鋰離子二次電池，並進行半電池(對極為鋰金屬(直徑1.5mm之圓，15Φ))之電容量試驗，電解液使用1.0M LiPF6在EC(ethylene carbonate)：FEC(floroethylene carbonate)：DMC(dimethyl carbonate)：EMC(ethylene methyl carbonate)=28：7：10：55溶劑中並額外添加添加劑1% VC(vinylene carbonate)與1.5% PS(1,3-propane sultone)，使用的電容量測定機台廠牌型號為BAT-750B。 After the SiOx/C composite prepared by the present invention is mixed with a binder and a conductive assistant in a certain proportion to form a slurry, it is coated on a 10μm copper foil, the solvent is dried at 80°C, and then it is put into a vacuum oven to Bake at 110°C for 24 hours and remove the solvent. The completed electrode plate was cut with a circle (12Φ) with a diameter of 12mm to produce a CR2032 button-type lithium-ion secondary battery, and a half-cell (for lithium metal (circle with a diameter of 1.5mm, 15Φ)) was tested for the capacitance , The electrolyte uses 1.0M LiPF 6 in EC (ethylene carbonate): FEC (floroethylene carbonate): DMC (dimethyl carbonate): EMC (ethylene methyl carbonate) = 28: 7: 10: 55 solvent and an additional additive 1% VC (vinylene carbonate) and 1.5% PS (1,3-propane sultone), the model of the capacitance measuring machine used is BAT-750B.

請參閱第二圖，第二圖為本發明SiOx(Si： SiO2=1：1)、SiOx/C(commercial)、Si及SiO2樣品之同步輻射X光繞射(synchrotron X-ray diffraction,SXRD)圖譜，其中Si與SiO2為標準品，波長為0.826567Å。如圖所示，SiOx(Si：SiO2=1：1)樣品與標準品Si在矽Si的峰值位置上十分接近。差異在於~12o的地方為SiOx的繞射峰值，由圖可以清楚的看到，Si之標準品在此處仍有些許峰值的SiO2，此部分可由SiO2的標準品比對得知。而在Si的標準品上仍可以看到SiO2的訊號是因為奈米矽在大氣下本身就容易氧化而導致形成一SiO2薄層。而在SiOx的樣品中可以看到SiO2之訊號較Si標準品強度高出許多，因此可以確認此合成方式確實為Si/SiOx之複合樣品，但由於X光對於氧的敏感度較差，因此要判斷其為SiO2或SiOx將需以光電子能譜儀(XPS)來進行判定。在商業化SiOx的部分，是一種非晶相之材料由Si與SiO2組成，目前在此材料之結構研究上認為Si原子周圍能同時與四個Si原子鍵結(Si相)或與四個O原子鍵結(SiO2相)為一種兩相材料，但也有研究指出SiOx是一種單相材料，其中Si-Si鍵及Si-O鍵是隨機分布在整個結構中的。在SXRD之結果，可以得知此材料SiOx(Si：SiO2=1：1)確實是有非晶相SiOx與晶相的Si所組成之材料。 Please refer to the second figure. The second figure is the synchrotron X-ray diffraction (synchrotron X-ray diffraction, SiOx (Si: SiO 2 =1:1), SiOx/C (commercial), Si and SiO 2 samples of the present invention). SXRD) spectrum, where Si and SiO 2 are standard products, and the wavelength is 0.826567Å. As shown in the figure, the SiOx (Si:SiO 2 =1:1) sample and the standard Si are very close to the peak position of silicon Si. The difference is that ~12o is the diffraction peak of SiOx. It can be clearly seen from the figure that there is still a little SiO 2 in the standard product of Si. This part can be learned by comparing the standard product of SiO 2 . The SiO 2 signal can still be seen on the Si standard product because the nanosilicon itself is easily oxidized in the atmosphere, which leads to the formation of a thin SiO 2 layer. In the SiOx sample, it can be seen that the SiO 2 signal is much stronger than the Si standard product. Therefore, it can be confirmed that the synthesis method is indeed a Si/SiOx composite sample. However, due to the poor sensitivity of X-ray to oxygen, it is necessary Determining whether it is SiO 2 or SiOx will need to be determined by a photoelectron spectrometer (XPS). In the commercial portion of SiOx, the amorphous phase is a material made of SiO 2 and Si, in the present study of the structure of this material that can simultaneously around the Si atom bonded to four Si atoms (Si) or a four O atom bonding (SiO 2 phase) is a two-phase material, but some studies have pointed out that SiOx is a single-phase material, in which Si-Si bonds and Si-O bonds are randomly distributed throughout the structure. From the results of SXRD, it can be known that the material SiOx (Si:SiO 2 =1:1) is indeed a material composed of amorphous SiOx and crystalline Si.

請參閱第三圖、第四圖及第五圖，第三圖為本發明SiOx(Si：SiO2=1：1)/C樣品之SEM(scan electron microscope)影像與其EDS mapping、第四圖為本發明SiOx/C(commercial)樣品之SEM(scan electron microscope)影像與其EDS mapping、第五圖 為本發明SiOx(Si：SiO2=1：1)/C與SiOx/C(commercial)樣品之SEM圖，圖三SiOx(Si：SiO2=1：1)/C樣品之SEM(scan electron microscope)影像與其EDS mapping之結果與圖四SiOx/C(commercial)樣品相似，其EDS mapping結果顯示C,Si,O是均勻分布在顆粒上面的，並且C的含量之較低的。此商業化產品是由高溫氣相法製備而成，因此整個塊材的組成是一致的，最後才進行粉碎而後再進行碳包覆。而本製程是由固相反應法先製備SiOx並且粉碎過篩後再用液相的球磨進行碳包覆，所得到之結果與商業品相似。圖五為SiOx(Si：SiO2=1：1)/C與SiOx/C(commercial)樣品之SEM影像(倍率為10000倍)，由尺寸大小可以觀察到SiOx(Si：SiO2=1：1)/C大約為2μm而SiOx/C(commercial)大約為5μm，但基本表面形貌是相似的。 Please refer to the third, fourth and fifth figures. The third figure is the SEM (scan electron microscope) image of the SiOx (Si: SiO 2 =1:1)/C sample of the present invention and its EDS mapping. The fourth figure is The SEM (scan electron microscope) image of the SiOx/C (commercial) sample of the present invention and its EDS mapping, the fifth figure is the SEM of the SiOx (Si: SiO 2 =1:1)/C and SiOx/C (commercial) samples of the present invention Fig. 3 The SEM (scan electron microscope) image of the SiOx (Si: SiO 2 =1:1)/C sample and its EDS mapping result are similar to those of the SiOx/C (commercial) sample in Fig. 4, and the EDS mapping result shows C, Si and O are evenly distributed on the particles, and the content of C is relatively low. This commercial product is prepared by a high-temperature gas phase method, so the composition of the entire block is consistent, and it is finally crushed and then coated with carbon. In this process, SiOx is prepared by a solid-phase reaction method, crushed and sieved, and then coated with carbon by a liquid-phase ball mill. The results obtained are similar to commercial products. Figure 5 shows SEM images of SiOx (Si: SiO 2 =1:1)/C and SiOx/C (commercial) samples (magnification 10000 times). SiOx (Si: SiO 2 =1:1) can be observed from the size )/C is about 2μm and SiOx/C (commercial) is about 5μm, but the basic surface morphology is similar.

請參閱第六圖，第六圖為本發明SiOx(Si：SiO2=1：1)/C與SiOx/C(commercial)樣品之XPS Si2p之頻譜分析圖，由第六圖XPS分析之結果可以得知，SiOx(Si：SiO2=1：1)之價數之分峰Si0為99.6eV,Si+1為100.1eV,Si+2為101.5eV,Si+3為102.9eV,Si+4為103.9eV，樣品表面Si的價數由Si0至Si4+都有，其原始材料Si為0價而SiO2為4價，藉由壓錠鍛燒使部分0價矽去還原4價的SiO2產生+1~+3的價態，可由計算得知此樣品為SiOx,x=1.3。此一結果證實Si與SiO2確實可藉由此製程生產出SiOx，而並非是Si與SiO2之混合物，若最終樣品為Si與SiO2之混合物，XPS之結果應該清楚顯示僅有0價的 Si與4價的SiO2。反觀SiOx/C(commercial)之樣品，Si之價數主要為2+，經價數分析計算可知x=0.94，此與該廠商之專利所註明的氧含量(x=0.95)相近。儘管SiOx之價態組成有所不同，但若電化學性能是與之相當的，那本發明之樣品在量產難易度與成本上都將有優勢。 Please refer to the sixth figure. The sixth figure is the XPS Si2p spectrum analysis diagram of the SiOx (Si: SiO 2 =1:1)/C and SiOx/C (commercial) samples of the present invention. The result of the XPS analysis in the sixth figure can be It is known that the valence peak of SiOx (Si: SiO 2 =1:1) Si0 is 99.6eV, Si+1 is 100.1eV, Si+2 is 101.5eV, Si+3 is 102.9eV, Si+4 is 103.9eV, the valence of Si on the sample surface ranges from Si0 to Si4+. The original material Si is 0 valence and SiO 2 is 4 valence. By ingot calcining, part of 0 valence silicon is reduced to 4 valence SiO 2 to produce +1 The valence state of ~+3 can be calculated to know that this sample is SiOx, x=1.3. This result confirms that Si and SiO 2 can indeed produce SiOx by this process, and not a mixture of Si and SiO 2. If the final sample is a mixture of Si and SiO 2 , the XPS result should clearly show that there is only zero valence Si and tetravalent SiO 2 . In contrast to the SiOx/C (commercial) sample, the valence of Si is mainly 2+. The valence analysis and calculation show that x=0.94, which is similar to the oxygen content (x=0.95) specified in the manufacturer’s patent. Although the valence composition of SiOx is different, if the electrochemical performance is comparable, the sample of the present invention will have advantages in terms of ease of mass production and cost.

請參閱第七圖及第八圖，第七圖為本發明實施例1之半電池測試圖、第八圖為本發明實施例21之半電池測試圖，圖七前2圈之充放電曲線，操作電壓範圍為0.01~0.8V，速率為0.2C(1C=450mA g-1)，圖八前2圈之充放電曲線，操作電壓範圍為0.01~0.8V，速率為0.2C(1C=500mA g-1)，由圖七及圖八可以看到雖然只混摻了15%的SiOx(Si：SiO2=1：1)/C或SiOx(Si：SiO2=1：0.5)/C，但以電容量來看Si所佔之電容量仍較高，因此在充放電曲線上仍是以SiOx材料為主。但由於有85%的石墨負極，因此可以有較好的首圈庫倫效率以及循環壽命，初始之庫倫效率皆可達91%，與商業品石墨材料通常庫倫效率可達92~94%已相近，但電容量可達~420與~520mAh g-1。其結果也顯示，此一材料可藉由控制Si與SiO2之比例達到控制其SiOx之電容量。 Please refer to the seventh and eighth figures. The seventh figure is the half-cell test diagram of Embodiment 1 of the present invention, the eighth figure is the half-cell test diagram of Embodiment 21 of the present invention, and the charge and discharge curves of the first two circles in Figure 7. The operating voltage range is 0.01~0.8V, and the rate is 0.2C (1C=450mA g-1). The charging and discharging curve of the first two circles in Figure 8 is the operating voltage range of 0.01~0.8V and the rate is 0.2C (1C=500mA g-1). -1). It can be seen from Figure 7 and Figure 8 that although only 15% SiOx (Si: SiO 2 =1:1)/C or SiOx (Si: SiO 2 =1: 0.5)/C is mixed, In terms of capacitance, Si still accounts for a relatively high capacitance, so SiOx is still the main material in the charge and discharge curve. However, due to the 85% graphite negative electrode, it can have better first-lap Coulomb efficiency and cycle life. The initial Coulomb efficiency can reach 91%, which is similar to that of commercial graphite materials, which usually can reach 92~94%. But the electric capacity can reach ~420 and ~520mAh g-1. The results also show that this material can control the capacitance of SiOx by controlling the ratio of Si to SiO 2 .

請參閱第九圖及表一，第九圖為本發明實施例1及實施例2半電池長循環充放電測試圖，表一為實施例1、2與比較例1、2之半電池電性測試表。圖九操作電壓範圍為0.01~0.8V，前5圈充放電循環速率為0.2C，長圈數壽命測試(後續100 圈)，電流大小為0.5C。SiOx(Si：SiO2=1：1)/C其電容量相較於SiOx(Si：SiO2=1：0.5)/C低，但以0.5C速率進行長循環測試100圈後，電容量仍可維持於90%以上。相較於容量較高之樣品SiOx(Si：SiO2=1：0.5)/C，電容量100圈充放電以後為87%。對比表一比較例1及比較例2商品化SiOx之結果，電容量雖然相近，但充放電循環壽命以本發明實施例1及實施例2所製備之樣品較高。 Please refer to the ninth figure and Table 1. The ninth figure is the long-cycle charge and discharge test diagram of the half-cell of Example 1 and Example 2 of the present invention. Table 1 is the electrical properties of the half-cell of Examples 1 and 2 and Comparative Examples 1 and 2 Test table. Figure 9 The operating voltage range is 0.01~0.8V, the first 5 cycles of charge and discharge cycle rate is 0.2C, and the long cycle life test (the subsequent 100 cycles), the current is 0.5C. SiOx (Si: SiO 2 = 1 : 1) / C compared to its capacity after SiOx (Si:: SiO 2 = 1 0.5) / C is low, but the rate of 0.5C 100 turns long cycle test, the capacity is still Can be maintained above 90%. Compared with the sample SiOx (Si: SiO 2 =1: 0.5)/C with a higher capacity, the capacitance is 87% after 100 cycles of charge and discharge. Comparing the results of the commercial SiOx of Comparative Example 1 and Comparative Example 2 in Table 1, although the capacitance is similar, the charge-discharge cycle life is higher for the samples prepared in Example 1 and Example 2 of the present invention.

Figure 108112235-A0101-12-0012-1
Figure 108112235-A0101-12-0012-1

本發明含SiOx之負極材料較商業化含SiOx產品之首圈庫倫效率較高，且充放電循環壽命本發明樣品相較於商業化產品較佳，此外，固相反應法在工業製程上相較於氣相法是相對容易量產與控制的，製程所需熱處理溫度(950℃以 下)也較高溫氣相法(1450~1700℃)低許多，且高溫氣相法還需控制其反應器中之壓力較固相反應法製程繁複許多。 The SiOx-containing negative electrode material of the present invention has higher first-cycle coulombic efficiency than commercial SiOx-containing products, and the charge-discharge cycle life of the sample of the present invention is better than that of commercial products. In addition, the solid-phase reaction method is relatively better in industrial processes The gas phase method is relatively easy to mass produce and control, and the heat treatment temperature required for the process (950 ℃ or less The lower) is also much lower in the higher temperature gas phase method (1450~1700°C), and the high temperature gas phase method also needs to control the pressure in the reactor than the solid phase reaction method.

因為SiOx商業化之產品電容量約1600~1800mAh g-1，但其循環壽命較佳，主要是因SiO或SiOx在第一次充電時鋰離子會與SiO或SiOx反應生成Li2O、Li4SiO4與Li15Si4，其中Li2O與Li4SiO4是不具活性之材料，功能為吸收Si之體積改變，而生成之Li15Si4之尺寸會因原始SiO或SiOx之尺寸而形成更小的奈米矽，因此SiOx之體積改變大約為160%。但由於在首圈充電時需要多餘的鋰去生成Li2O與Li4SiO4，因此首圈庫倫效率SiOx為65.1~82.1%相較於矽材(77.5~84%)較低。純SiO在第一次充放電過程後會產生Si、Li2O、Li4SiO4、Li2SiO3，而其中只有Si是具有電容量之活性物質。而本發明Si與SiO2共燒(鍛燒)，可以藉由改變Si與SiO2之含量，使第一次充放電過程後產生Si、Li2O、少量Li2SiO3、SiO2，可減少Li的消耗，使其首圈庫倫效率會較高。 Because the capacity of SiOx commercial products is about 1600~1800mAh g-1, but its cycle life is better, mainly because SiO or SiOx will react with SiO or SiOx during the first charge to form Li 2 O, Li 4 SiO 4 and Li 15 Si 4 , among which Li 2 O and Li 4 SiO 4 are inactive materials, whose function is to absorb the volume change of Si, and the size of the resulting Li 15 Si 4 will be formed by the size of the original SiO or SiOx Smaller nano-silicon, so the volume change of SiOx is about 160%. However, since excess lithium is needed to generate Li 2 O and Li 4 SiO 4 during the first cycle of charging, the first cycle of coulombic efficiency SiOx is 65.1-82.1%, which is lower than that of silicon (77.5-84%). Pure SiO will produce Si, Li 2 O, Li 4 SiO 4 , and Li 2 SiO 3 after the first charge and discharge process, and among them, only Si is an active material with electric capacity. And Si to SiO 2 of the present invention is co-fired (calcined), can be changed by the content of Si and SiO 2, so that after the first charge and discharge process to produce Si, Li 2 O, a small amount of Li 2 SiO 3, SiO 2, can be Reduce the consumption of Li, so that the first lap Coulomb efficiency will be higher.

請參閱表二，表二為本發明及市面上生產SiOx之材料成本比較表，表二為本發明實施例2(以Si：SiO2=1：0.5wt.%為例)及比較例2之負極材料材料成本評估，以實施例2為例：電費以1度電3塊錢計算，目前生產粉體為每批次1kg實驗室級。高溫爐900℃，使用功率4000W，時間8小時，耗用電費144元/公斤-SiOx。純度99.99%之氮氣使用成本~16元/公斤-SiOx。機械球磨，使用功率400W，時間6小時，耗用電費7.2元/公斤- SiOx。1μm-Si粉成本200元/公斤-SiOx，3-5μm非晶SiO

Figure 108112235-A0101-12-0014-11
2粉成本50元/公斤-SiOx。以Si：SiO2=1：0.5wt.%計算，生產SiOx每公斤材料成本為417元；購買市場上較好的商業品SiOx樣品成本為4500元/公斤(比較例2)，但若是經由電芯廠購買實際生產用，其價格約在3000元/公斤。而本發明實施例2所提出之生產方式，材料成本為417元/公斤。使用之高溫爐僅需900℃，相較於1450℃之真空爐設備建置成本也較低。使用之機械球磨，而非高能球磨在成本及量產上也較無問題，主要是使Si與非晶SiO2混合均勻使其容易反應。在產品物化特性上，商業品之SiOx為Si2+為主之材料，在首圈充放電過程中會形成Li2O與Li4SiO4兩者非活性之物質，使其首圈庫倫效率較低，數據請參閱表一(比較例2：89%)。而本產品由於可保留部分Si0+使其首圈庫倫效率較高，數據請參閱表一(實施例2,91%)。目前電芯廠對高容量之負極材料要求，至少首圈庫倫效率要在90%以上。在電池特性上，500mAh/g之負極為下世代之高容量負極材料規格，在半電池測試0.5C速率下進行100圈充放電長循環測試後，本發明SiOx有87%之電容量保持率，相較於商業品之SiOx有更好的壽命。 Please refer to Table 2. Table 2 is a comparison table of the material cost of the present invention and SiOx produced on the market. Table 2 is the comparison of Example 2 of the present invention (taking Si:SiO 2 =1:0.5wt.% as an example) and Comparative Example 2 For the evaluation of the material cost of the negative electrode material, take Example 2 as an example: the electricity fee is calculated at 3 yuan per kilowatt-hour, and the current production of powder is 1kg laboratory-grade per batch. The high temperature furnace is 900 ℃, the use power is 4000W, the time is 8 hours, and the electricity consumption is 144 yuan/kg-SiOx. The cost of using nitrogen with a purity of 99.99% is ~16 yuan/kg-SiOx. Mechanical ball mill, using power 400W, time 6 hours, electricity consumption 7.2 yuan/kg-SiOx. 1μm-Si powder cost 200 yuan/kg-SiOx, 3-5μm amorphous SiO
Figure 108112235-A0101-12-0014-11
2 Powder cost 50 yuan/kg-SiOx. Calculated on the basis of Si:SiO 2 =1:0.5wt.%, the cost of producing SiOx is 417 yuan per kilogram of material; the cost of buying a good commercial SiOx sample on the market is 4500 yuan/kg (comparative example 2), but if it is through electricity The core factory purchases actual production use, and the price is about 3000 yuan/kg. In the production method proposed in Embodiment 2 of the present invention, the material cost is 417 yuan/kg. The high-temperature furnace used only requires 900°C, which is also lower in cost than the vacuum furnace at 1450°C. The mechanical ball mill used, instead of high-energy ball milling, is also less problematic in terms of cost and mass production. The main reason is to mix Si and amorphous SiO 2 uniformly to make it easy to react. In terms of the physical and chemical properties of the product, the commercial SiOx is a Si 2+ -based material, and Li 2 O and Li 4 SiO 4 are formed during the first cycle of charging and discharging, making the first cycle of coulombic efficiency better. Low, please refer to Table 1 (Comparative Example 2: 89%). However, this product can retain a part of Si 0+ to make the first lap coulombic efficiency higher. Please refer to Table 1 (Example 2, 91%) for the data. At present, battery cell factories require high-capacity anode materials that at least the first lap coulombic efficiency should be above 90%. In terms of battery characteristics, the 500mAh/g negative electrode is the next-generation high-capacity negative electrode material specification. After 100 cycles of charging and discharging at a half-cell test rate of 0.5C, the SiOx of the present invention has a capacity retention rate of 87%. Compared with commercial products, SiOx has a better life.

本發明之負極材料以Si與非晶相SiO2依比例混合為原料進行固相反應法，並且最後再以有機裂解碳層進行碳包覆及碳化製程。因為SiOx與SiO2能有效減緩Si因充放電造成的體積膨脹效應與破裂情形。將此SiOx複合材料15%與商業化之石墨負極材料經物理混摻、製漿、製成極板，而後製作成CR2032電池，實測所得可逆電容量約~430與~520mAh g-1，較純石墨負極材料的電容量(~350mAh g-1)有所提升，且首圈庫倫效率可達91%，並能穩定維持100圈能有90%(SiOx(Si：SiO2=1：1)/C)或87%(SiOx(Si：SiO2=1：0.5)/C)電容量保持率，相較於商業化SiOx有更好的電容量保持率以及製程成本優勢，適合作為高能量密度之鋰離子電池負極材料。 The negative electrode material of the present invention uses Si and amorphous SiO 2 as raw materials to be mixed in a solid phase reaction method, and finally an organic cracked carbon layer is used for carbon coating and carbonization processes. Because SiOx and SiO 2 can effectively slow down the volume expansion effect and cracking of Si caused by charge and discharge. The 15% SiOx composite material and commercial graphite anode material are physically mixed, pulped, and made into electrode plates, and then made into CR2032 batteries. The measured reversible capacitance is about ~430 and ~520mAh g-1, which is relatively pure The capacitance (~350mAh g-1) of the graphite anode material has been improved, and the first lap coulombic efficiency can reach 91%, and it can stably maintain 100 cycles with 90% (SiOx(Si: SiO 2 =1:1)/ C) or 87% (SiOx (Si: SiO 2 =1: 0.5)/C) capacity retention rate. Compared with commercial SiOx, it has better capacity retention rate and process cost advantages, and is suitable for high energy density Lithium-ion battery anode material.

上述之實施例僅為例示性說明本創作之特點及功效，非用以限制本創作之實質技術內容的範圍。任何熟悉此技藝之人士均可在不違背創作之精神及範疇下，對上述實施例進行修飾與變化。因此，本創作之權利保護範圍，應如後述之申請專利範圍所列。 The above-mentioned embodiments are merely illustrative to illustrate the characteristics and effects of this creation, and are not intended to limit the scope of the essential technical content of this creation. Anyone familiar with this technique can modify and change the above-mentioned embodiments without violating the spirit and scope of creation. Therefore, the scope of protection of the rights of this creation should be listed in the scope of patent application described later.

S101-106‧‧‧步驟 S101-106‧‧‧Step

Claims (10)

一種含SiOx之負極材料的製造方法，步驟包括：(A)提供一矽啟始物、非晶相SiO2與一溶劑於惰性氣氛下進行一混合製程以形成一混合物，其中該矽啟始物係為矽粉；(B)將該混合物進行烘乾以得到一矽氧化物前驅物；(C)將該矽氧化物前驅物置入一模具中壓錠並在惰性氣氛或還原性氣氛下進行一鍛燒製程以形成一SiOx固狀物；(D)將該SiOx固狀物進行一粉碎篩分製程以形成一SiOx粉狀物；(E)將該SiOx粉狀物與一有機碳源進行一碳包覆製程以形成一SiOx/C前驅物；及(F)將該SiOx/C前驅物進行一碳化製程以形成一SiOx/C複合物；其中，步驟(C)、步驟(D)、步驟(E)及步驟(F)SiOx之x值範圍為0.5<x<1.5。 A method for manufacturing a negative electrode material containing SiO x , the steps include: (A) providing a silicon initiator, amorphous SiO 2 and a solvent under an inert atmosphere to perform a mixing process to form a mixture, wherein the silicon starts The material is silicon powder; (B) the mixture is dried to obtain a silicon oxide precursor; (C) the silicon oxide precursor is placed in a mold and pressed into an ingot and subjected to an inert atmosphere or a reducing atmosphere Calcining process to form a SiO x solid; (D) subject the SiO x solid to a crushing and screening process to form a SiO x powder; (E) the SiO x powder and an organic The carbon source is subjected to a carbon coating process to form a SiOx/C precursor; and (F) the SiO x /C precursor is subjected to a carbonization process to form a SiO x /C composite; wherein, step (C), The range of x value of SiO x in step (D), step (E) and step (F) is 0.5<x<1.5. 如申請專利範圍第1項所述之含SiOx之負極材料的製造方法，其中該矽啟始物係選自Si、SiOx(0.1<x<0.5)其中之一或其混合。 According to the method for manufacturing a negative electrode material containing SiO x as described in item 1 of the scope of patent application, the silicon starting material is selected from one of Si, SiO x (0.1<x<0.5) or a mixture thereof. 如申請專利範圍第1項所述之含SiOx之負極材料的製造方法，其中該步驟(A)之混合製程為以濕式球磨混合，球磨珠粒徑範圍係為0.1~5mm之間。 According to the method for manufacturing a negative electrode material containing SiO x as described in item 1 of the scope of patent application, the mixing process of step (A) is wet ball milling and the ball milling bead size ranges between 0.1 and 5 mm. 如申請專利範圍第1項所述之含SiOx之負極材料的製造方法，其中步驟(A)之惰性氣氛係為氬氣或氮氣。 According to the method for manufacturing a negative electrode material containing SiO x as described in item 1 of the scope of patent application, the inert atmosphere in step (A) is argon or nitrogen. 如申請專利範圍第1項所述之含SiOx之負極材料的製造方法，其中，該步驟(A)之該溶劑係選自酒精、異丙醇、丙酮之其一或其混合。 The method for manufacturing a negative electrode material containing SiO x as described in the first item of the scope of patent application, wherein the solvent in step (A) is selected from one of alcohol, isopropanol, acetone or a mixture thereof. 如申請專利範圍第1項所述之含SiOx之負極材料的製造方法，其中該步驟(B)之烘乾溫度係介於100℃~150℃之間。 The method for manufacturing a negative electrode material containing SiO x as described in the first item of the scope of patent application, wherein the drying temperature of step (B) is between 100°C and 150°C. 如申請專利範圍第1項所述之含SiOx之負極材料的製造方法，其中該鍛燒製程之鍛燒溫度範圍係為600℃~950℃之間。 According to the method for manufacturing a negative electrode material containing SiO x as described in item 1 of the scope of patent application, the calcining temperature range of the calcining process is between 600°C and 950°C. 如申請專利範圍第1項所述之含SiOx之負極材料的製造方法，其中該步驟(C)之惰性氣氛係為氬氣或氮氣，該還原性氣氛係為氬氣、氮氣、氫氬其中之一或其混合。 The method for manufacturing a negative electrode material containing SiO x as described in the scope of the patent application, wherein the inert atmosphere of step (C) is argon or nitrogen, and the reducing atmosphere is argon, nitrogen, hydrogen argon One or a mixture of them. 如申請專利範圍第1項所述之含SiOx之負極材料的製造方法，其中該步驟(D)之該粉碎篩分製程係包含一篩網，該篩網之網目數量範圍係為80-600mesh之間。 The method for manufacturing a negative electrode material containing SiO x as described in the first item of the scope of patent application, wherein the crushing and sieving process of step (D) includes a screen, and the number of meshes of the screen is 80-600 mesh between. 如申請專利範圍第1項所述之含SiOx之負極材料的製造方法，其中該步驟(D)之該粉碎過篩製程中的粉碎方法係選自切削、球磨、研磨其中之一或其混合。 The method for manufacturing a negative electrode material containing SiO x as described in the scope of the patent application, wherein the crushing method in the crushing and sieving process of the step (D) is selected from one of cutting, ball milling, grinding, or a mixture thereof .
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TWI392133B (en) * 2006-03-27 2013-04-01 Shinetsu Chemical Co Silicon-silicon oxide-lithium composite and its preparation method and non-electrolyte battery anode material
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CN105409035A (en) * 2013-04-27 2016-03-16 罗伯特·博世有限公司 SiOx/Si/c composite material and process of producing thereof, and anode for lithium ion battery comprising said composite material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI392133B (en) * 2006-03-27 2013-04-01 Shinetsu Chemical Co Silicon-silicon oxide-lithium composite and its preparation method and non-electrolyte battery anode material
CN102593426A (en) * 2011-05-07 2012-07-18 天津锦美碳材科技发展有限公司 Method for preparing silicon oxide (SiOx) / carbon (C) composite materials and prepared silicon carbon cathode materials for lithium ion battery
CN103917491A (en) * 2011-09-19 2014-07-09 魁北克电力公司 Particulate anode materials and methods for their preparation
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