TWI737303B - Method of manufacturing silicon oxide particles - Google Patents
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本發明係關於一種製造多顆氧化矽顆粒之方法，並且特別地，關於利用霧化的反應物且無需粉碎塊料、研磨碎料等製程來製造多顆氧化矽顆粒之方法。The present invention relates to a method of manufacturing a plurality of silica particles, and in particular, to a method of manufacturing a plurality of silica particles by using atomized reactants without the need of crushing blocks, grinding scraps and other processes.
關於本發明之相關技術背景，請參考以下所列之技術文獻： [1] Liu N, Lu Z, Zhao J, McDowell MT, Lee H-W, Zhao W, et al. A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes. Nature Nanotechnology. 2014; 9:187-192. [2] Obrovac M, Chevrier V. Alloy negative electrodes for Li-ion batteries. Chemical Reviews. 2014;114:11444-11502. [3] Choi S, Kwon T-W, Coskun A, Choi JW. Highly elastic binders integrating polyrotaxanes for silicon microparticle anodes in lithium ion batteries. Science. 2017;357:279-283. [4] Casimir A, Zhang H, Ogoke O, Amine JC, Lu J, Wu G. Silicon-based anodes for lithium-ion batteries: Effectiveness of materials synthesis and electrode preparation. Nano Energy. 2016;27:359-376. [5] Xing Y, Shen T, Guo T, Wang X, Xia X, Gu C, et al. A novel durable double-conductive core-shell structure applying to the synthesis of silicon anode for lithium ion batteries. Journal of Power Sources. 2018;384:207-213. [6] Shang H, Zuo Z, Yu L, Wang F, He F, Li Y. Low-temperature growth of all-carbon graphdiyne on a silicon anode for high-performance lithium-ion batteries. Advanced Materials. 2018;30:1801459. [7] Li Z, He Q, He L, Hu P, Li W, Yan H, et al. Self-sacrificed synthesis of carbon-coated SiOxnanowires for high capacity lithium ion battery anodes. Journal of Materials Chemistry A. 2017;5:4183-4189. [8] Parimalam BS, Mac Intosh AD, Kadam R, Lucht BL. Decomposition reactions of anode solid electrolyte interphase (SEI) components with LiPF6. The Journal of Physical Chemistry C. 2017;121:22733-22738. [9] Haruta M, Okubo T, Masuo Y, Yoshida S, Tomita A, Takenaka T, et al. Temperature effects on SEI formation and cyclability of Si nanoflake powder anode in the presence of SEI-forming additives. Electrochimica Acta. 2017;224:186-193. [10] Elia GA, Hassoun J. A SiO x-based anode in a high-voltage lithium-ion battery. ChemElectroChem. 2017;4:2164-2168. [11] Park E, Park MS, Lee J, Kim KJ, Jeong G, Kim JH, et al. A highly resilient mesoporous SiOx lithium storage material engineered by oil–water templating. ChemSusChem. 2015;8:688-694. [12] Sun L, Su T, Xu L, Liu M, Du H-B. Two-dimensional ultra-thin SiO x(0 > x > 2) nanosheets with long-term cycling stability as lithium ion battery anodes. Chemical Communications. 2016;52:4341-4344. [13] Guo C, Wang D, Liu T, Zhu J, Lang X. A three dimensional SiO x/C@RGO nanocomposite as a high energy anode material for lithium-ion batteries. Journal of Materials Chemistry A. 2014;2:3521-3527. [14] Zhang J, Zhang C, Liu Z, Zheng J, Zuo Y, Xue C, et al. High-performance ball-milled SiO xanodes for lithium ion batteries. Journal of Power Sources. 2017;339:86-92. [15] Shi L, Wang W, Wang A, Yuan K, Jin Z, Yang Y. Scalable synthesis of core-shell structured SiO x/nitrogen-doped carbon composite as a high-performance anode material for lithium-ion batteries. Journal of Power Sources. 2016;318:184-191. [16] Xu Q, Sun JK, Yin YX, Guo YG. Facile synthesis of blocky SiO x/C with graphite-like structure for high-performance lithium-ion battery anodes. Advanced Functional Materials. 2018;28:1705235. [17] Park E, Yoo H, Lee J, Park M-S, Kim Y-J, Kim H. Dual-size silicon nanocrystal-embedded SiOxnanocomposite as a high-capacity lithium storage material. ACS Nano. 2015;9:7690-7696. [18] Liu Q, Cui Z, Zou R, Zhang J, Xu K, Hu J. Surface coating constraint induced anisotropic swelling of silicon in Si-Void@SiO xnanowire anode for lithium-ion batteries. Small. 2017;13:1603754. [19] Han J, Chen G, Yan T, Liu H, Shi L, An Z, et al. Creating graphene-like carbon layers on SiO anodes via a layer-by-layer strategy for lithium-ion battery. Chemical Engineering Journal. 2018;347:273-279. [20] Dou F, Shi L, Song P, Chen G, An J, Liu H, et al. Design of orderly carbon coatings for SiO anodes promoted by TiO 2toward high performance lithium-ion battery. Chemical Engineering Journal. 2018;338:488-495. For the related technical background of the present invention, please refer to the technical literature listed below: [1] Liu N, Lu Z, Zhao J, McDowell MT, Lee HW, Zhao W, et al. A pomegranate-inspired nanoscale design for large- volume-change lithium battery anodes. Nature Nanotechnology. 2014; 9:187-192. [2] Obrovac M, Chevrier V. Alloy negative electrodes for Li-ion batteries. Chemical Reviews. 2014;114:11444-11502. [3] Choi S, Kwon TW, Coskun A, Choi JW. Highly elastic binders integrating polyrotaxanes for silicon microparticle anodes in lithium ion batteries. Science. 2017;357:279-283. [4] Casimir A, Zhang H, Ogoke O, Amine JC , Lu J, Wu G. Silicon-based anodes for lithium-ion batteries: Effectiveness of materials synthesis and electrode preparation. Nano Energy. 2016;27:359-376. [5] Xing Y, Shen T, Guo T, Wang X , Xia X, Gu C, et al. A novel durable double-conductive core-shell structure applying to the synthesis of silicon anode for lithium ion batteries. Journal of Power Sources. 2018;384:207-213. [6] Shang H , Zuo Z, Yu L, Wang F, He F, Li Y. Low-temperature growth of a ll-carbon graphdiyne on a silicon anode for high-performance lithium-ion batteries. Advanced Materials. 2018;30:1801459. [7] Li Z, He Q, He L, Hu P, Li W, Yan H, et al. Self-sacrificed synthesis of carbon-coated SiOxnanowires for high capacity lithium ion battery anodes. Journal of Materials Chemistry A. 2017;5:4183-4189. [8] Parimalam BS, Mac Intosh AD, Kadam R, Lucht BL. Decomposition reactions of anode solid electrolyte interphase (SEI) components with LiPF6. The Journal of Physical Chemistry C. 2017;121:22733-22738. [9] Haruta M, Okubo T, Masuo Y, Yoshida S, Tomita A, Takenaka T, et al. Temperature effects on SEI formation and cyclability of Si nanoflake powder anode in the presence of SEI-forming additives. Electrochimica Acta. 2017;224:186-193. [10] Elia GA, Hassoun J. A SiO x -based anode in a high -voltage lithium-ion battery. ChemElectroChem. 2017;4:2164-2168. [11] Park E, Park MS, Lee J, Kim KJ, Jeong G, Kim JH, et al. A highly resilient mesoporous SiOx lithium storage materia l engineered by oil–water templating. ChemSusChem. 2015;8:688-694. [12] Sun L, Su T, Xu L, Liu M, Du HB. Two-dimensional ultra-thin SiO x (0>x> 2 ) nanosheets with long-term cycling stability as lithium ion battery anodes. Chemical Communications. 2016;52:4341-4344. [13] Guo C, Wang D, Liu T, Zhu J, Lang X. A three dimensional SiO x /C @RGO nanocomposite as a high energy anode material for lithium-ion batteries. Journal of Materials Chemistry A. 2014;2:3521-3527. [14] Zhang J, Zhang C, Liu Z, Zheng J, Zuo Y, Xue C, et al. High-performance ball-milled SiO x anodes for lithium ion batteries. Journal of Power Sources. 2017;339:86-92. [15] Shi L, Wang W, Wang A, Yuan K, Jin Z, Yang Y . Scalable synthesis of core-shell structured SiO x /nitrogen-doped carbon composite as a high-performance anode material for lithium-ion batteries. Journal of Power Sources. 2016;318:184-191. [16] Xu Q, Sun JK , Yin YX, Guo YG. Facile synthesis of blocky SiO x /C with graphite-like structure for high-performan ce lithium-ion battery anodes. Advanced Functional Materials. 2018;28:1705235. [17] Park E, Yoo H, Lee J, Park MS, Kim YJ, Kim H. Dual-size silicon nanocrystal-embedded SiOxnanocomposite as a high- capacity lithium storage material. ACS Nano. 2015;9:7690-7696. [18] Liu Q, Cui Z, Zou R, Zhang J, Xu K, Hu J. Surface coating constraint induced anisotropic swelling of silicon in Si-Void@ SiO x nanowire anode for lithium-ion batteries. Small. 2017;13:1603754. [19] Han J, Chen G, Yan T, Liu H, Shi L, An Z, et al. Creating graphene-like carbon layers on SiO anodes via a layer-by-layer strategy for lithium-ion battery. Chemical Engineering Journal. 2018;347:273-279. [20] Dou F, Shi L, Song P, Chen G, An J, Liu H, et al . Design of orderly carbon coatings for SiO anodes promoted by TiO 2 toward high performance lithium-ion battery. Chemical Engineering Journal. 2018;338:488-495.
矽是製造下一代鋰離子電池的關鍵負極材料，其具有更長的循環壽命和更高的能量密度，有助於滿足市場對電動汽車和混合動力汽車不斷增長的需求[1-3]。做為鋰離子電池的主要材料，矽是地球上豐富的元素，並且提供3578mAh/g的高理論電容量(與基於碳的電極的372mAh/g相比)[4-6]。然而，矽負極的體積膨脹率大(~400％)導致矽顆粒的降解和固體電解質界面的破壞[7-9]。這些問題會引起電容的劇烈衰退甚至整體損壞，從而阻礙了矽負極運用在鋰離子電池中的商業應用。Silicon is a key negative electrode material for the manufacture of next-generation lithium-ion batteries. It has a longer cycle life and higher energy density, helping to meet the growing market demand for electric vehicles and hybrid vehicles [1-3]. As the main material of lithium-ion batteries, silicon is an abundant element on the earth and provides a high theoretical capacity of 3578mAh/g (compared to the 372mAh/g of carbon-based electrodes) [4-6]. However, the large volume expansion rate of the silicon anode (~400%) leads to the degradation of silicon particles and the destruction of the solid electrolyte interface [7-9]. These problems can cause severe degradation of the capacitor or even overall damage, which hinders the commercial application of silicon anodes in lithium-ion batteries.
由於矽的低氧化物(SiO x，0 >x >2)提升的循環穩定性，將其做為矽的潛在替代品引起了相當大的興趣。SiO x不僅表現出相對小的體積膨脹率，而且還形成Li 2O以及鋰矽酸鹽，其在第一次鋰化過程中用做Si的緩衝介質[10-12]。結果，SiO x表現出比Si更好的循環性能。然而，由SiO 2的絕緣性導致的SiO x的低電子傳導性和緩慢的電子傳輸動力學導致差的電化學性能並且阻礙了SiO x作為商業化鋰離子電池的負極材料的應用[13-16]。許多研究人員提出了解決這些問題的策略，從而推動了碳塗層SiO x複合材料的開發。雖然通過碳塗層實現的改善的導電性可以改善SiO x的電化學性能，但是需要複雜的、多步驟以及高溫工藝[17-20]。例如，Liu等人在高溫(1250及1650℃)下使用SiO及ZnS的混合粉末的熱蒸發/化學蝕刻開發了Si-Void@SiO x奈米線複合材料[18]。此外，Han等人以SiO粉末為原料，採用兩步驟製程製備SiO@C複合材料；在3000rpm球磨3小時後，球磨的SiO顆粒在700℃下使用十二烷基苯磺酸鈉煅燒[19]。 Due to the improved cycle stability of silicon suboxide (SiO x , 0>x> 2), it has attracted considerable interest as a potential substitute for silicon. SiO x not only exhibits a relatively small volume expansion rate, but also forms Li 2 O and lithium silicate, which are used as a buffer medium for Si during the first lithiation process [10-12]. As a result, SiO x exhibits better cycle performance than Si. However, the low electronic conductivity and slow electron transport kinetics of SiO x caused by the insulating properties of SiO 2 lead to poor electrochemical performance and hinder the application of SiO x as a negative electrode material for commercial lithium ion batteries [13-16 ]. Many researchers have proposed strategies to solve these problems, which has promoted the development of carbon-coated SiO x composites. Although the improved conductivity achieved by carbon coating can improve the electrochemical performance of SiO x , it requires a complex, multi-step, and high-temperature process [17-20]. For example, Liu et al. developed Si-Void@SiO x nanowire composite materials using thermal evaporation/chemical etching of mixed powders of SiO and ZnS at high temperatures (1250 and 1650°C). In addition, Han et al. used SiO powder as a raw material to prepare SiO@C composites using a two-step process; after ball milling at 3000 rpm for 3 hours, the ball-milled SiO particles were calcined with sodium dodecylbenzene sulfonate at 700°C [19] .
關於氧化矽之製造方法的先前技術，請參閱中國大陸專利公開號1451057A以及美國專利公告號7,431,899B2。這些先前技術揭示將矽粉體與二氧化矽粉體混合，置於高溫下讓矽粉體與二氧化矽粉體反應成氧化矽並昇華為氧化矽蒸氣，再收集氧化矽將其冷卻成氧化矽沉積物。顯見地，製造氧化矽之先前技術所取得的氧化矽為塊料，還需經粉碎塊料、研磨碎料等製程，才能獲得氧化矽顆粒，伴隨著製造上須採用昂貴的防污染、集塵等設備。For the prior art of the manufacturing method of silicon oxide, please refer to Mainland China Patent Publication No. 1451057A and U.S. Patent Publication No. 7,431,899B2. These previous technologies revealed that the silicon powder and the silicon dioxide powder were mixed and placed at a high temperature to allow the silicon powder and the silicon dioxide powder to react to form silicon oxide and sublime into silicon oxide vapor, and then collect the silicon oxide and cool it to oxidize Silicon deposits. Obviously, the silicon oxide obtained by the prior art for the manufacture of silicon oxide is a block material, and the process of crushing the block material and grinding the scrap material is needed to obtain the silicon oxide particles, and along with the production, expensive pollution prevention and dust collection are required. And other equipment.
因此，本發明所欲解決之一技術問題在於提供一種利用霧化的反應物且無需粉碎塊料、研磨碎料等製程來製造多顆被覆碳層的氧化矽顆粒之方法。甚至，本發明之方法在無需複雜碳塗層製程即能製造多顆被覆碳層的氧化矽顆粒。 Therefore, one of the technical problems to be solved by the present invention is to provide a method for manufacturing multiple carbon-coated silicon oxide particles by using atomized reactants without the need of crushing blocks, grinding scraps and other processes. Furthermore, the method of the present invention can produce multiple carbon-coated silicon oxide particles without a complicated carbon coating process.
根據本發明之第一較佳具體實施例之製造多顆氧化矽顆粒之方法，首先，係製備醇類液體、有機溶劑以及矽鹵化物液體。接著，根據本發明之方法係對醇類液體執行氣霧化製程，致使自醇類液體產生多個醇類微液滴。接著，根據本發明之方法係將矽鹵化物液體溶入有機溶劑形成反應溶液。接著，根據本發明之方法係持續攪拌反應溶液，且將多個醇類微液滴導入反應溶液內，致使多個醇類微液滴與反應溶液中之矽鹵化物液體反應成多個矽酸酯微粒。接著，根據本發明之方法係清洗反應溶液，以取得多個矽酸酯微粒。最後，根據本發明之方法係於鈍態爐氛下且於預定溫度下，對多個矽酸酯微粒執行乾燥製程，進而將多個矽酸酯微粒轉變成多顆氧化矽顆粒，其中每一顆氧化矽顆粒係被覆碳層並且其化學式為C-SiOx，1<x<2。在此強調，於下文中，本發明所稱氧化矽即指SiOx，1<x<2。 According to the method of manufacturing a plurality of silicon oxide particles according to the first preferred embodiment of the present invention, firstly, an alcohol liquid, an organic solvent and a silicon halide liquid are prepared. Next, the method according to the present invention is to perform a gas atomization process on the alcohol liquid, so that a plurality of alcohol micro-droplets are generated from the alcohol liquid. Next, according to the method of the present invention, the silicon halide liquid is dissolved in an organic solvent to form a reaction solution. Next, according to the method of the present invention, the reaction solution is continuously stirred, and a plurality of alcohol micro-droplets are introduced into the reaction solution, so that the plurality of alcohol micro-droplets react with the silicon halide liquid in the reaction solution to form a plurality of silicic acid Ester particles. Next, the method according to the present invention is to clean the reaction solution to obtain a plurality of silicate particles. Finally, the method according to the present invention performs a drying process on a plurality of silicate particles under a passive furnace atmosphere and at a predetermined temperature, and then converts the plurality of silicate particles into a plurality of silicon oxide particles, each of which is The silicon oxide particles are coated with a carbon layer and their chemical formula is C-SiO x , 1<x<2. It is emphasized here that in the following, the silicon oxide referred to in the present invention refers to SiO x , 1<x<2.
於一具體實施例中，醇類液體可以是乙二醇、丙二醇或甘油等醇類液體。 In a specific embodiment, the alcohol liquid may be an alcohol liquid such as ethylene glycol, propylene glycol, or glycerin.
於一具體實施例中，有機溶劑可以是己烷、苯、***或石油醚等有機溶劑。 In a specific embodiment, the organic solvent may be an organic solvent such as hexane, benzene, diethyl ether, or petroleum ether.
於一具體實施例中，矽鹵化物液體可以是SiCl4 或SiBr4等矽鹵化物液體。 In a specific embodiment, the silicon halide liquid may be a silicon halide liquid such as SiCl 4 or SiBr 4 .
於一具體實施例中，反應溶液中矽鹵化物液體之體積：有機溶劑之體積=1：5。 In a specific embodiment, the volume of the silicon halide liquid in the reaction solution: the volume of the organic solvent=1:5.
於一具體實施例中，預定溫度的範圍為700~1000℃。 In a specific embodiment, the predetermined temperature ranges from 700°C to 1000°C.
於一具體實施例中，多顆被覆碳層的一氧化矽顆粒具有粒徑範圍為0.1μm~10μm。 In a specific embodiment, the silicon monoxide particles covered with the carbon layer have a particle size in the range of 0.1 μm-10 μm.
根據本發明之第二較佳具體實施例之製造多顆氧化矽顆粒之方法，首先，係製備醇類液體以及矽鹵化物液體。接著，根據本發明之方法係對醇類液體執行第一氣霧化製程，致使自醇類液體產生多個醇類微液滴。接著，根據本發明之方法係對矽鹵化物液體執行第二氣霧化製程，致使自矽鹵化物液體產生多個矽鹵化物微液滴。接著，根據本發明之方法係將多個醇類微液滴以及多個矽鹵化物微液滴導入反應室內，致使多個醇類微液滴與多個矽鹵化物微液滴反應成多個矽酸酯微粒。接著，根據本發明之方法係取得多個矽酸酯微粒。最後，根據本發明之方法係於鈍態爐氛下且於預定溫度下，對多個矽酸酯微粒執行乾燥製程，進而將多個矽酸酯微粒轉變成多顆氧化矽顆粒，其中每一顆氧化矽顆粒之化學式為SiOx，1<x<2。 According to the method of manufacturing a plurality of silicon oxide particles according to the second preferred embodiment of the present invention, first, an alcohol liquid and a silicon halide liquid are prepared. Next, according to the method of the present invention, the first gas atomization process is performed on the alcohol liquid, so that a plurality of alcohol micro-droplets are generated from the alcohol liquid. Next, according to the method of the present invention, a second gas atomization process is performed on the silicon halide liquid, so that a plurality of silicon halide microdroplets are generated from the silicon halide liquid. Next, according to the method of the present invention, a plurality of alcohol micro-droplets and a plurality of silicon halide micro-droplets are introduced into the reaction chamber, so that the plurality of alcohol micro-droplets and a plurality of silicon halide micro-droplets react into a plurality of micro-droplets. Silicate particles. Next, according to the method of the present invention, a plurality of silicate particles are obtained. Finally, the method according to the present invention performs a drying process on a plurality of silicate particles under a passive furnace atmosphere and at a predetermined temperature, and then converts the plurality of silicate particles into a plurality of silicon oxide particles, each of which is The chemical formula of silicon oxide particles is SiO x , 1<x<2.
於一具體實施例中，醇類液體可以是乙二醇、丙二醇或甘油等醇類液體。 In a specific embodiment, the alcohol liquid may be an alcohol liquid such as ethylene glycol, propylene glycol, or glycerin.
於一具體實施例中，矽鹵化物液體可以是SiCl4或SiBr4等矽鹵化物液體。 In a specific embodiment, the silicon halide liquid may be a silicon halide liquid such as SiCl 4 or SiBr 4 .
於一具體實施例中，預定溫度的範圍為700~1000℃。 In a specific embodiment, the predetermined temperature ranges from 700°C to 1000°C.
於一具體實施例中，多顆氧化矽顆粒具有粒徑範圍為0.1μm~10μm。 In a specific embodiment, the plurality of silicon oxide particles have a particle size ranging from 0.1 μm to 10 μm.
與先前技術不同，根據本發明之方法係採用霧化的反應物反應成多個矽酸酯微粒，最終在高溫乾燥下，多個矽酸酯微粒轉變成多顆氧化矽顆粒，甚至變成多顆被覆碳層的氧化矽顆粒。根據本發明之方法無需先前技術所採用粉碎塊料、研磨碎料、複雜碳塗層等製程。 Different from the prior art, the method according to the present invention uses the atomized reactant to react into a plurality of silicate particles, and finally, under high temperature drying, the plurality of silicate particles are transformed into a plurality of silica particles, or even into a plurality of silica particles. Silicon oxide particles coated with a carbon layer. The method according to the present invention does not require the processes of crushing blocks, grinding scraps, and complex carbon coatings used in the prior art.
關於本發明之優點與精神可以藉由以下的發明詳述及所附圖式得到進一步的瞭解。 The advantages and spirit of the present invention can be further understood from the following detailed description of the invention and the accompanying drawings.
請參閱圖1，為根據本發明之第一較佳具體實施例之方法1之流程圖。根據本發明之較佳具體實施例之方法1無需粉碎塊料、研磨碎料等製程，即可以製造多顆氧化矽顆粒。甚至，根據本發明之第一較佳具體實施例之方法1無須複雜碳塗層製程即可以製造多顆被覆碳層的氧化矽顆粒。Please refer to FIG. 1, which is a flowchart of method 1 according to the first preferred embodiment of the present invention. According to the method 1 of the preferred embodiment of the present invention, a plurality of silicon oxide particles can be produced without the need of pulverizing block materials, grinding scraps and other processes. Furthermore, according to the method 1 of the first preferred embodiment of the present invention, a plurality of carbon-coated silicon oxide particles can be produced without a complicated carbon coating process.
如圖1所示，根據本發明之方法1，首先係執行步驟S10，製備醇類液體、有機溶劑以及矽鹵化物液體。As shown in FIG. 1, according to method 1 of the present invention, step S10 is first performed to prepare alcohol liquid, organic solvent and silicon halide liquid.
於一具體實施例中，醇類液體可以是乙二醇、丙二醇或甘油等醇類液體。In a specific embodiment, the alcohol liquid may be an alcohol liquid such as ethylene glycol, propylene glycol, or glycerin.
於一具體實施例中，有機溶劑可以是己烷、苯、***或石油醚等有機溶劑。In a specific embodiment, the organic solvent may be an organic solvent such as hexane, benzene, diethyl ether, or petroleum ether.
於一具體實施例中，矽鹵化物液體可以是SiCl 4或SiBr 4等矽鹵化物液體。 In a specific embodiment, the silicon halide liquid may be a silicon halide liquid such as SiCl 4 or SiBr 4 .
接著，根據本發明之方法1係執行步驟S12，對醇類液體執行氣霧化製程，致使自醇類液體產生多個醇類微液滴。Next, according to the method 1 of the present invention, step S12 is performed to perform a gas atomization process on the alcohol liquid, so that a plurality of alcohol micro-droplets are generated from the alcohol liquid.
於一具體實施例中，氣霧化製程可以藉由加熱方式或超音波震盪方式進行。In a specific embodiment, the gas atomization process can be performed by heating or ultrasonic vibration.
接著，根據本發明之方法1係執行步驟S14，將矽鹵化物液體溶入有機溶劑形成反應溶液。Next, according to the method 1 of the present invention, step S14 is performed to dissolve the silicon halide liquid into an organic solvent to form a reaction solution.
於一具體實施例中，反應溶液中矽鹵化物液體之體積：有機溶劑之體積=1：5。In a specific embodiment, the volume of the silicon halide liquid in the reaction solution: the volume of the organic solvent=1:5.
接著，根據本發明之方法1係執行步驟S16，持續攪拌反應溶液，且將多個醇類微液滴導入反應溶液內，致使多個醇類微液滴與反應溶液中之矽鹵化物液體反應成多個矽酸酯微粒。Then, according to the method 1 of the present invention, step S16 is performed, the reaction solution is continuously stirred, and a plurality of alcohol micro-droplets are introduced into the reaction solution, so that a plurality of alcohol micro-droplets react with the silicon halide liquid in the reaction solution Into multiple silicate particles.
於一具體實施例中，攪拌反應溶液之攪拌轉速範圍為400~1000rpm下執行。In a specific embodiment, the stirring speed range for stirring the reaction solution is 400~1000 rpm.
於一具體實施例中，多個醇類微液滴可以藉由氮氣等鈍態氣體帶至盛裝反應溶液的容器內，進而將多個醇類微液滴導入反應溶液內。In a specific embodiment, a plurality of alcohol micro-droplets can be brought into the container containing the reaction solution by a passive gas such as nitrogen, and then a plurality of alcohol micro-droplets are introduced into the reaction solution.
接著，根據本發明之方法1係執行步驟S18，清洗反應溶液，以取得多個矽酸酯微粒。Next, according to the method 1 of the present invention, step S18 is executed to clean the reaction solution to obtain a plurality of silicate particles.
最後，根據本發明之方法1係執行步驟S19，於鈍態爐氛下且於預定溫度下，對多個矽酸酯微粒執行乾燥製程，進而將多個矽酸酯微粒轉變成多顆氧化矽顆粒，其中每一顆氧化矽顆粒係被覆碳層並且其化學式為C-SiO x，1>x>2。 Finally, according to the method 1 of the present invention, step S19 is performed, in a passive furnace atmosphere and at a predetermined temperature, a drying process is performed on a plurality of silicate particles, and then the plurality of silicate particles are converted into a plurality of silica particles. Particles, each of the silicon oxide particles is coated with a carbon layer and its chemical formula is C-SiO x , 1>x>2.
於一具體實施例中，預定溫度的範圍為700~1000℃。In a specific embodiment, the predetermined temperature ranges from 700°C to 1000°C.
於一具體實施例中，多顆被覆碳層的氧化矽顆粒具有粒徑範圍為0.1μm~10μm。In a specific embodiment, the silicon oxide particles coated with the carbon layer have a particle size in the range of 0.1 μm-10 μm.
請參閱圖2，為根據本發明之第二較佳具體實施例之方法2之流程圖。根據本發明之較佳具體實施例之方法2無需粉碎塊料、研磨碎料等製程，即可以製造多顆氧化矽顆粒。Please refer to FIG. 2, which is a flowchart of method 2 according to a second preferred embodiment of the present invention. According to the method 2 of the preferred embodiment of the present invention, a plurality of silicon oxide particles can be manufactured without the need of crushing blocks, grinding scraps and other processes.
如圖所示，根據本發明之方法2，首先係執行步驟S20，製備醇類液體以及矽鹵化物液體。As shown in the figure, according to method 2 of the present invention, step S20 is first performed to prepare alcohol liquid and silicon halide liquid.
於一具體實施例中，醇類液體可以是乙二醇、丙二醇或甘油等醇類液體。In a specific embodiment, the alcohol liquid may be an alcohol liquid such as ethylene glycol, propylene glycol, or glycerin.
於一具體實施例中，矽鹵化物液體可以是SiCl 4或SiBr 4等矽鹵化物液體。 In a specific embodiment, the silicon halide liquid may be a silicon halide liquid such as SiCl 4 or SiBr 4 .
接著，根據本發明之方法2係執行步驟S22，對醇類液體執行第一氣霧化製程，致使自醇類液體產生多個醇類微液滴。Next, according to the method 2 of the present invention, step S22 is performed to perform a first gas atomization process on the alcohol liquid, so that a plurality of alcohol micro-droplets are generated from the alcohol liquid.
於一具體實施例中，第一氣霧化製程可以藉由加熱方式或超音波震盪方式進行。In a specific embodiment, the first gas atomization process can be performed by heating or ultrasonic vibration.
接著，根據本發明之方法2係執行步驟S24，對矽鹵化物液體執行第二氣霧化製程，致使自矽鹵化物液體產生多個矽鹵化物微液滴。Next, according to the method 2 of the present invention, step S24 is performed to perform a second gas atomization process on the silicon halide liquid, so that a plurality of silicon halide micro droplets are generated from the silicon halide liquid.
於一具體實施例中，第二氣霧化製程可以藉由加熱方式或超音波震盪方式進行。或在室溫下，矽鹵化物液體本身沸點低易蒸發產生氣霧。以SiCl 4為例，SiCl 4的沸點為57.65℃，所以SiCl 4在室溫下易蒸發產生氣霧。 In a specific embodiment, the second gas atomization process can be performed by heating or ultrasonic vibration. Or at room temperature, the silicon halide liquid itself has a low boiling point and easily evaporates to produce aerosol. Taking SiCl 4 as an example, the boiling point of SiCl 4 is 57.65°C, so SiCl 4 is easy to evaporate at room temperature to produce aerosol.
接著，根據本發明之方法2係執行步驟S26，將多個醇類微液滴以及多個矽鹵化物微液滴導入反應室內，致使多個醇類微液滴與多個矽鹵化物微液滴反應成多個矽酸酯微粒。Next, according to the method 2 of the present invention, step S26 is performed to introduce a plurality of alcohol micro-droplets and a plurality of silicon halide micro-droplets into the reaction chamber, resulting in a plurality of alcohol micro-droplets and a plurality of silicon halide micro-liquids The droplet reacts into a plurality of silicate particles.
於一具體實施例中，多個醇類微液滴以及多個矽鹵化物微液滴可以分別藉由氮氣等鈍態氣體帶至反應室內。In a specific embodiment, a plurality of alcohol micro-droplets and a plurality of silicon halide micro-droplets can be respectively carried into the reaction chamber by a passive gas such as nitrogen.
接著，根據本發明之方法2係執行步驟S28，取得多個矽酸酯微粒。Next, according to the method 2 of the present invention, step S28 is executed to obtain a plurality of silicate particles.
最後，根據本發明之方法2係執行步驟S29，於鈍態爐氛下且於預定溫度下，對多個矽酸酯微粒執行乾燥製程，進而將多個矽酸酯微粒轉變成多顆氧化矽顆粒，其中每一顆氧化矽顆粒之化學式為C-SiO x，1>x>2。 Finally, according to the method 2 of the present invention, step S29 is performed, in a passive furnace atmosphere and at a predetermined temperature, a drying process is performed on a plurality of silicate particles, and then the plurality of silicate particles are converted into a plurality of silica particles. Particles, the chemical formula of each silicon oxide particle is C-SiO x , 1>x>2.
於一具體實施例中，預定溫度的範圍為700~1000℃。In a specific embodiment, the predetermined temperature ranges from 700°C to 1000°C.
於一具體實施例中，多顆被覆碳層的氧化矽顆粒具有粒徑範圍為0.1μm~10μm。In a specific embodiment, the silicon oxide particles coated with the carbon layer have a particle size in the range of 0.1 μm-10 μm.
於第一範例中，根據本發明之第一較佳具體實施例之方法製備乙二醇液體、10ml SiCl 4以及50ml 己烷。根據本發明之第一較佳具體實施例之方法藉由加熱方式將乙二醇液體氣霧化，以產生多個乙二醇微液滴。根據本發明之第一較佳具體實施例之方法將SiCl 4溶入己烷形成反應溶液。根據本發明之第一較佳具體實施例之方法將多個乙二醇微液滴導入持續攪拌的反應溶液內。攪拌反應溶液之攪拌轉速為600rpm。多個乙二醇微液滴與SiCl 4反應成多個矽酸酯微粒。根據本發明之第一較佳具體實施例之方法清洗反應溶液，以取得多個矽酸酯微粒。根據本發明之第一較佳具體實施例之方法於鈍態爐氛下且於預定溫度下，對多個矽酸酯微粒執行乾燥製程，進而將多個矽酸酯微粒轉變成多顆氧化矽顆粒，其中每一顆氧化矽顆粒係被覆碳層。本發明之第一範例所獲得多顆被覆碳層的氧化矽顆粒的SEM照片請見圖3所示。由圖3之SEM照片證實，本發明之第一範例可獲得多顆被覆碳層的氧化矽顆粒之粒徑。本發明之第一範例所獲得多顆被覆碳層的氧化矽顆粒的XRD結果請見圖4所示。圖4所示的波峰證實本發明之第一範例所獲得多顆被覆碳層的氧化矽顆粒含有碳元素。 In the first example, ethylene glycol liquid, 10 ml of SiCl 4 and 50 ml of hexane were prepared according to the method of the first preferred embodiment of the present invention. According to the method of the first preferred embodiment of the present invention, the ethylene glycol liquid gas is atomized by heating to generate a plurality of ethylene glycol micro-droplets. According to the method of the first preferred embodiment of the present invention, SiCl 4 is dissolved in hexane to form a reaction solution. According to the method of the first preferred embodiment of the present invention, a plurality of ethylene glycol micro-droplets are introduced into the continuously stirred reaction solution. The stirring speed for stirring the reaction solution was 600 rpm. A plurality of ethylene glycol micro-droplets react with SiCl 4 to form a plurality of silicate particles. According to the method of the first preferred embodiment of the present invention, the reaction solution is cleaned to obtain a plurality of silicate particles. The method according to the first preferred embodiment of the present invention performs a drying process on a plurality of silicate particles at a predetermined temperature in a passive furnace atmosphere, and then converts the plurality of silicate particles into a plurality of silica particles Particles, each of which is a silicon oxide particle is coated with a carbon layer. The SEM picture of the silicon oxide particles covered with the carbon layer obtained in the first example of the present invention is shown in FIG. 3. It is confirmed by the SEM photograph of FIG. 3 that the first example of the present invention can obtain the particle size of a plurality of silicon oxide particles coated with a carbon layer. The XRD results of a plurality of silicon oxide particles coated with a carbon layer obtained in the first example of the present invention are shown in FIG. 4. The wave peak shown in FIG. 4 confirms that the silicon oxide particles coated with the carbon layer obtained in the first example of the present invention contain carbon element.
於第二範例中，根據本發明之第一較佳具體實施例之方法製備乙二醇液體、10ml SiCl4以及50ml己烷。根據本發明之第一較佳具體實施例之方法藉由超音波震盪方式將乙二醇液體氣霧化，以產生多個乙二醇微液滴。根據本發明之第一較佳具體實施例之方法將SiCl4溶入己烷形成反應溶液。根據本發明之第一較佳具體實施例之方法將多個乙二醇微液滴導入持續攪拌的反應溶液內。攪拌反應溶液之攪拌轉速為600rpm。多個乙二醇微液滴與SiCl4反應成多個矽酸酯微粒。根據本發明之第一較佳具體實施例之方法清洗反應溶液，以取得多個矽酸酯微粒。根據本發明之第一較佳具體實施例之方法於鈍態爐氛下且於預定溫度下，對多個矽酸酯微粒執行乾燥製程，進而將多個矽酸酯微粒轉變成多顆氧化矽顆粒，其中每一顆氧化矽顆粒係被覆碳層。本發明之第二範例所獲得多顆被覆碳層的氧化矽顆粒的SEM照片請見圖5所示。由圖5之SEM照片證實，本發明之第二範例所獲得多顆被覆碳層的氧化矽顆粒之粒徑相當均一。本發明之第二範例所獲得多顆被覆碳層的氧化矽顆粒的XRD結果請見圖6所示。圖6所示的波峰證實本發明之第二範例所獲得多顆被覆碳層的氧化矽顆粒含有碳元素。 In the second example, ethylene glycol liquid, 10 ml of SiCl 4 and 50 ml of hexane are prepared according to the method of the first preferred embodiment of the present invention. According to the method of the first preferred embodiment of the present invention, the ethylene glycol liquid gas is atomized by ultrasonic vibration to generate a plurality of ethylene glycol micro-droplets. According to the method of the first preferred embodiment of the present invention, SiCl 4 is dissolved in hexane to form a reaction solution. According to the method of the first preferred embodiment of the present invention, a plurality of ethylene glycol micro-droplets are introduced into the continuously stirred reaction solution. The stirring speed for stirring the reaction solution was 600 rpm. A plurality of ethylene glycol micro-droplets react with SiCl 4 to form a plurality of silicate particles. According to the method of the first preferred embodiment of the present invention, the reaction solution is cleaned to obtain a plurality of silicate particles. The method according to the first preferred embodiment of the present invention performs a drying process on a plurality of silicate particles at a predetermined temperature in a passive furnace atmosphere, and then converts the plurality of silicate particles into a plurality of silica particles Particles, each of which is a silicon oxide particle is coated with a carbon layer. The SEM photograph of the silicon oxide particles covered with the carbon layer obtained in the second example of the present invention is shown in FIG. 5. It is confirmed by the SEM photograph of FIG. 5 that the particle size of the silicon oxide particles coated with the carbon layer obtained in the second example of the present invention is quite uniform. The XRD results of the silicon oxide particles covered with the carbon layer obtained in the second example of the present invention are shown in FIG. 6. The peak shown in FIG. 6 confirms that the silicon oxide particles coated with the carbon layer obtained in the second example of the present invention contain carbon element.
於第三範例中，根據本發明之第一較佳具體實施例之方法製備乙二醇液體以及SiCl4。根據本發明之第二較佳具體實施例之方法藉由加熱方式將乙二醇液體氣霧化，以產生多個乙二醇微液滴。根據本發明之第二較佳具體實施例之方法將SiCl4置於室溫下即蒸發產生產生多個矽鹵化物微液滴。根據本發明之第二較佳具體實施例之方法將多個醇類微 液滴以及多個矽鹵化物微液滴導入反應室內，致使多個醇類微液滴與多個矽鹵化物微液滴反應成多個矽酸酯微粒。於第三範例中，多個矽鹵化物微液滴藉由流速為50ml/min的氮氣導入反應室內，多個醇類微液滴藉由流速為100ml/min的氮氣導入反應室內。 In the third example, the ethylene glycol liquid and SiCl 4 are prepared according to the method of the first preferred embodiment of the present invention. The method according to the second preferred embodiment of the present invention atomizes the ethylene glycol liquid gas by heating to generate a plurality of ethylene glycol micro-droplets. According to the method of the second preferred embodiment of the present invention, SiCl 4 is placed at room temperature and evaporated to generate a plurality of micro droplets of silicon halide. According to the method of the second preferred embodiment of the present invention, a plurality of alcohol micro-droplets and a plurality of silicon halide micro-droplets are introduced into the reaction chamber, resulting in a plurality of alcohol micro-droplets and a plurality of silicon halide micro-liquids The droplet reacts into a plurality of silicate particles. In the third example, a plurality of silicon halide micro-droplets are introduced into the reaction chamber by nitrogen at a flow rate of 50 ml/min, and a plurality of alcohol micro-droplets are introduced into the reaction chamber by nitrogen with a flow rate of 100 ml/min.
根據本發明之第二較佳具體實施例之方法取得多個矽酸酯微粒。根據本發明之第二較佳具體實施例之方法於鈍態爐氛下且於預定溫度下，對多個矽酸酯微粒執行乾燥製程，進而將多個矽酸酯微粒轉變成多顆氧化矽顆粒。本發明之第三範例所獲得多顆氧化矽顆粒的SEM照片及EDS分析成份結果請見圖7所示。由圖7之SEM照片證實，本發明之第三範例可獲得多顆氧化矽顆粒。由圖7之EDS分析成份結果證實，本發明之第三範例所獲得多顆氧化矽顆粒的氧/矽比為1.4。 According to the method of the second preferred embodiment of the present invention, a plurality of silicate particles are obtained. The method according to the second preferred embodiment of the present invention performs a drying process on a plurality of silicate particles at a predetermined temperature in a passive furnace atmosphere, and then converts the plurality of silicate particles into a plurality of silica particles Particles. The SEM photos and EDS analysis results of the multiple silicon oxide particles obtained in the third example of the present invention are shown in FIG. 7. It is confirmed by the SEM photograph of FIG. 7 that the third example of the present invention can obtain a plurality of silicon oxide particles. It is confirmed by the EDS analysis result of FIG. 7 that the oxygen/silicon ratio of the silicon oxide particles obtained in the third example of the present invention is 1.4.
藉由以上較佳具體實施例之詳述，相信能清楚了解，根據本發明之方法係採用霧化的反應物反應成多個矽酸酯微粒，最終在高溫乾燥下，多個矽酸酯微粒轉變成多顆氧化矽顆粒。根據本發明之方法可以製造粒徑相當均一多顆氧化矽顆粒，並且無需先前技術所採用粉碎塊料、研磨碎料、複雜碳塗層等製程。 From the detailed description of the above preferred embodiments, it is believed that it can be clearly understood that the method according to the present invention uses atomized reactants to react into a plurality of silicate particles, and finally, under high temperature drying, the plurality of silicate particles Transformed into multiple silicon oxide particles. According to the method of the present invention, a plurality of silicon oxide particles with a fairly uniform particle size can be produced, and there is no need for manufacturing processes such as crushing blocks, grinding scraps, and complex carbon coatings used in the prior art.
藉由以上較佳具體實施例之詳述，係希望能更加清楚描述本發明之特徵與精神，而並非以上述所揭露的較佳具體實施例來對本發明之面向加以限制。相反地，其目的是希望能涵蓋各種改變及具相等性的安排於本發明所欲申請之專利範圍的面向內。因此，本發明所申請之專利範圍的面向應該根據上述的說明作最寬廣的解釋，以致使其涵蓋所有可能的改變以及具相等性的安排。Based on the above detailed description of the preferred embodiments, it is hoped that the characteristics and spirit of the present invention can be described more clearly, rather than limiting the aspect of the present invention by the preferred embodiments disclosed above. On the contrary, its purpose is to cover various changes and equivalent arrangements within the scope of the patent for which the present invention is intended. Therefore, the aspect of the patent scope applied for by the present invention should be interpreted in the broadest way based on the above description, so as to cover all possible changes and equivalent arrangements.
1:方法 S10~S19:流程步驟 2:方法 S20~S29:流程步驟 1: method S10~S19: Process steps 2: method S20~S29: Process steps
圖1係根據本發明之第一較佳具體實施例之製造方法的各個製程步驟流程圖。 FIG. 1 is a flowchart of various process steps of the manufacturing method according to the first preferred embodiment of the present invention.
圖2係根據本發明之第二較佳具體實施例之製造方法的各個製程步驟流程圖。 FIG. 2 is a flowchart of each process step of the manufacturing method according to the second preferred embodiment of the present invention.
圖3係本發明之第一範例所獲得多顆被覆碳層的氧化矽顆粒的掃描式電子顯微鏡(SEM)照片。 3 is a scanning electron microscope (SEM) photograph of a plurality of silicon oxide particles coated with a carbon layer obtained in the first example of the present invention.
圖4係本發明之第一範例所獲得多顆被覆碳層的氧化矽顆粒的之X射線繞射圖案分析(XRD)結果圖。 圖5係本發明之第二範例所獲得多顆被覆碳層的氧化矽顆粒的SEM照片。 圖6係本發明之第二範例所獲得多顆被覆碳層的氧化矽顆粒的之X射線繞射圖案分析結果圖。 圖7係本發明之第三範例所獲得多顆氧化矽顆粒的SEM照片及經X射線能量散佈分析儀(EDS)分析成份結果。 4 is a diagram showing the X-ray diffraction pattern analysis (XRD) results of a plurality of silicon oxide particles coated with a carbon layer obtained in the first example of the present invention. FIG. 5 is an SEM photograph of a plurality of silicon oxide particles coated with a carbon layer obtained in the second example of the present invention. 6 is a diagram showing the X-ray diffraction pattern analysis result of a plurality of silicon oxide particles coated with a carbon layer obtained in the second example of the present invention. FIG. 7 is an SEM photograph of a plurality of silicon oxide particles obtained in the third example of the present invention and the composition result of the X-ray energy dispersive analyzer (EDS).
1:方法 1: method
S10~S19:流程步驟 S10~S19: Process steps
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| TW200642785A (en) * | 2005-01-14 | 2006-12-16 | Cabot Corp | Metal nanoparticle compositions |
| CN101242814A (en) * | 2005-06-17 | 2008-08-13 | 澳大利亚核科学技术组织 | Particles comprising a releasable dopant therein |
| US9985279B2 (en) * | 2014-02-10 | 2018-05-29 | Industry-Academia Cooperation Group Of Sejong Univ | Silicon oxide-carbon composite, method of manufacturing the composite, and energy storage device having the composite |
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| TW200642785A (en) * | 2005-01-14 | 2006-12-16 | Cabot Corp | Metal nanoparticle compositions |
| CN101242814A (en) * | 2005-06-17 | 2008-08-13 | 澳大利亚核科学技术组织 | Particles comprising a releasable dopant therein |
| US9985279B2 (en) * | 2014-02-10 | 2018-05-29 | Industry-Academia Cooperation Group Of Sejong Univ | Silicon oxide-carbon composite, method of manufacturing the composite, and energy storage device having the composite |
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