TWI723730B - Method of manufacturing porous silicon particles and manufacturing equipment implementing such method - Google Patents
Method of manufacturing porous silicon particles and manufacturing equipment implementing such method Download PDFInfo
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本發明係關於一種製造多顆多孔矽顆粒之方法及執行該方法之製造設備,並且特別地,關於不採用酸洗製程甚至採用從矽泥廢料回收的矽顆粒來製造多顆多孔矽顆粒之方法及執行該方法之製造設備。 The present invention relates to a method for manufacturing multiple porous silicon particles and manufacturing equipment for performing the method, and in particular, to a method for manufacturing multiple porous silicon particles without using a pickling process or even using silicon particles recovered from silicon mud waste And the manufacturing equipment that executes the method.
多孔矽材料具有獨特的光電特性,大的比表面積使其可以應用於各種探測器、生物微感測器、光電納米器械、儲能材料等領域,尤其作為鋰電池的負極材料近年來備受關注。與傳統的負極材料相比,矽具有超高的理論比容量(4200mAh/g)以及較低的脫鋰電位(<0.5V),在充電時難引起表面析鋰,安全性能更佳。目前矽成為鋰離子電池碳基負極升級換代的富有潛力的選擇之一。但矽作為鋰離子電池負極材料缺點是自身的電導率較低,在電化學迴圈過程中體積發生300%以上的膨脹與收縮,將產生的機械作用力會使材料逐漸粉化,造成結構坍塌,導致電池迴圈性能大大降低。所以將矽材料微奈米化、改善微結構、提高導電性都是十分有效的方法,其中微奈米多孔矽的結構能有效緩衝體積膨脹,提高初始效率、迴圈穩定性以及倍率性能。 Porous silicon material has unique photoelectric properties, and its large specific surface area allows it to be used in various detectors, biological micro-sensors, photoelectric nano-devices, energy storage materials and other fields, especially as a negative electrode material for lithium batteries, which has attracted much attention in recent years. . Compared with traditional anode materials, silicon has an ultra-high theoretical specific capacity (4200mAh/g) and a lower delithiation potential (<0.5V). It is difficult to cause surface lithium deposition during charging and has better safety performance. At present, silicon has become one of the promising options for upgrading the carbon-based anode of lithium-ion batteries. However, the disadvantage of silicon as a negative electrode material for lithium-ion batteries is that its own conductivity is low. During the electrochemical loop, the volume expands and contracts by more than 300%. The mechanical force generated will gradually pulverize the material and cause the structure to collapse. , Resulting in greatly reduced battery loop performance. Therefore, micro-nanoization of silicon materials, improvement of microstructure, and conductivity are all very effective methods. Among them, the structure of micro-nanoporous silicon can effectively buffer volume expansion, improve initial efficiency, loop stability, and rate performance.
製造多孔矽顆粒的先前技術係先將多矽顆粒與鎂原料混合加熱反應成鎂矽合金顆粒。先前技術再將鎂矽顆粒在氮氣爐氛中加熱,讓鎂矽合金顆粒中的鎂反應成氮化鎂微粒。先前技術再以酸洗製程去除氮化鎂微粒,進而獲得多 顆多孔矽顆粒。顯見地,製造多孔矽顆粒的先前技術會有將中間產物移出加熱爐造成的費時為題,處理酸洗製程後留下廢酸液處理的環保等問題。 The prior art for manufacturing porous silicon particles is to first mix and heat polysilicon particles with magnesium raw materials to form magnesium-silicon alloy particles. In the prior art, the magnesium-silicon particles are heated in a nitrogen furnace atmosphere to allow the magnesium in the magnesium-silicon alloy particles to react into magnesium nitride particles. In the prior art, the magnesium nitride particles were removed by the pickling process to obtain more Pieces of porous silicon particles. Obviously, the prior art for manufacturing porous silicon particles has the time-consuming problem of moving the intermediate product out of the heating furnace, and the environmental protection problems of leaving the waste acid solution after the pickling process.
此外,光伏產業的主要固體廢棄物之一即是自矽晶錠切割矽晶圓過程中的矽泥廢料。特別是,矽泥廢料的再循環已成為一個迫切的問題,因為每年產生近100,000噸矽泥廢料。 In addition, one of the main solid wastes in the photovoltaic industry is the silicon mud waste in the process of cutting silicon wafers from silicon ingots. In particular, the recycling of silica sludge waste has become an urgent problem because nearly 100,000 tons of silica sludge waste are generated every year.
2018年間,超過100GW矽太陽能電池面板被生產,這些矽太陽能電池面板使用了大約40萬噸矽,這些矽主要由能源密集型的Siemen製程生產。具有諷刺意味的是,在晶圓切片過程中,大約30%到40%的高純度矽以切屑損失的漿料形式被丟棄。如今,填埋是處理矽泥廢料的常見方式。 In 2018, more than 100GW of silicon solar panels were produced. These silicon solar panels used about 400,000 tons of silicon. These silicon are mainly produced by the energy-intensive Siemens process. Ironically, during the wafer slicing process, approximately 30% to 40% of the high-purity silicon is discarded in the form of a slurry loss from chips. Nowadays, landfill is a common way to dispose of silica mud waste.
目前不少研究嘗試將矽泥廢料回收用後許多可行的應用。但是礙於回收矽泥廢料經處理後的純度及金屬雜質尚未達到應用的要求標準,這些矽泥廢料回收後的可行應用仍有很長的路要走。因此,鑒於回收矽泥廢料經處理後的純度及金屬雜質,將回收矽泥廢料淨化後並最終用於製造用於多孔矽顆粒,則除了廢料減少之外,它在經濟上是可行的和有益的。 At present, many studies have tried many feasible applications after recycling silicon mud waste. However, due to the fact that the purity and metal impurities of the recycled silica sludge waste have not yet reached the application requirements, there is still a long way to go for the feasible application of these silica sludge wastes. Therefore, in view of the purity and metal impurities of the recycled silica sludge waste after treatment, it is economically feasible and beneficial to purify the recycled silica sludge waste and finally use it in the manufacture of porous silicon particles. In addition to reducing waste, it is economically feasible and beneficial. of.
因此,本發明所欲解決之一技術問題在於提供一種不採用酸洗製程甚至採用從矽泥廢料回收的矽顆粒來製造多顆多孔矽顆粒之方法及執行該方法之製造設備。 Therefore, one of the technical problems that the present invention intends to solve is to provide a method for manufacturing multiple porous silicon particles without using a pickling process or even using silicon particles recovered from silicon sludge waste, and a manufacturing equipment for implementing the method.
本發明之第一較佳具體實施例之製造多顆多孔矽顆粒之方法,首先係製備多顆矽顆粒以及鎂原料,其中多顆矽顆粒係置於鎂原料之上方。接著,本發明之方法係於鈍態爐氛中,將鎂原料加熱至第一溫度,以產生第一鎂蒸氣,致使多顆矽顆粒與第一鎂蒸氣反應成多顆鎂矽合金顆粒。接 著,本發明之方法係於真空環境中,將多顆鎂矽合金顆粒加熱至第二溫度,致使多顆鎂矽合金顆粒轉變成多顆多孔矽顆粒以及第二鎂蒸氣。最後,本發明之方法係收集多顆多孔矽顆粒。 In the method for manufacturing multiple porous silicon particles in the first preferred embodiment of the present invention, a plurality of silicon particles and a magnesium raw material are prepared first, wherein the multiple silicon particles are placed on top of the magnesium raw material. Next, the method of the present invention is to heat the magnesium raw material to a first temperature in a passive furnace atmosphere to generate a first magnesium vapor, so that a plurality of silicon particles react with the first magnesium vapor to form a plurality of magnesium-silicon alloy particles. Pick up Therefore, the method of the present invention is to heat a plurality of magnesium-silicon alloy particles to a second temperature in a vacuum environment, so that the plurality of magnesium-silicon alloy particles are transformed into a plurality of porous silicon particles and a second magnesium vapor. Finally, the method of the present invention collects multiple porous silicon particles.
本發明之第二較佳具體實施例之製造多顆多孔矽顆粒之方法,首先係製備多顆矽顆粒以及多顆鎂顆粒。接著,本發明之方法係將多顆矽顆粒與多顆鎂顆粒混合。接著,本發明之方法係於鈍態爐氛中,將混合後的多顆矽顆粒與多顆鎂顆粒至第一溫度,以產生第一鎂蒸氣,致使多顆矽顆粒與第一鎂蒸氣反應成多顆鎂矽合金顆粒。接著,本發明之方法係於真空環境中,將多顆鎂矽合金顆粒加熱至第二溫度,致使多顆鎂矽合金顆粒轉變成多顆多孔矽顆粒以及第二鎂蒸氣。最後,本發明之方法係收集多顆多孔矽顆粒。 The method for manufacturing multiple porous silicon particles in the second preferred embodiment of the present invention firstly prepares multiple silicon particles and multiple magnesium particles. Next, the method of the present invention is to mix a plurality of silicon particles with a plurality of magnesium particles. Next, the method of the present invention is to mix the silicon particles and the magnesium particles to a first temperature in a passive furnace atmosphere to generate the first magnesium vapor, causing the silicon particles to react with the first magnesium vapor Into multiple magnesium-silicon alloy particles. Next, the method of the present invention is to heat a plurality of magnesium-silicon alloy particles to a second temperature in a vacuum environment, so that the plurality of magnesium-silicon alloy particles are transformed into a plurality of porous silicon particles and a second magnesium vapor. Finally, the method of the present invention collects multiple porous silicon particles.
於一具體實施例中,第一溫度之範圍為從700℃至850℃。 In a specific embodiment, the first temperature ranges from 700°C to 850°C.
於一具體實施例中,第二溫度之範圍為從800℃至900℃。 In a specific embodiment, the second temperature ranges from 800°C to 900°C.
於一具體實施例中,多顆多孔矽顆粒具有粒徑範圍為0.1μm~5μm。 In a specific embodiment, the plurality of porous silicon particles have a particle size ranging from 0.1 μm to 5 μm.
本發明之第三較佳具體實施例之製造設備包含爐體、冷卻夾套、至少一沉積基板、真空抽氣裝置以及鈍態氣體供應裝置。兩者擇一地,鎂原料與多顆矽顆粒係置於爐體內,並且多顆矽顆粒係置於鎂原料之上方,或者多顆矽顆粒與多顆鎂顆粒混合後置於爐體內。冷卻夾套係安置於爐體之第一頂部上,並且與爐體之第一頂部連通。冷卻夾套具有儲液腔、液體入口以及液體出口。至少一沉積基板係放置於冷卻夾套內,並且與冷卻夾套之內壁熱耦合。真空抽氣裝置係與冷卻夾套的第二頂部連通。鈍態氣體供應裝置係與冷卻 夾套的第二頂部連通。鈍態氣體供應裝置持續運作供應鈍態氣體將爐體內以及冷卻夾套內形成鈍態爐氛。爐體接著升溫至第一溫度,以將鎂原料或多顆鎂顆粒產生第一鎂蒸氣,致使多顆矽顆粒與第一鎂蒸氣反應成多顆鎂矽合金顆粒。於多顆鎂矽合金顆粒冷卻後,真空抽氣裝置接著持續運作將爐體內以及冷卻夾套內形成真空環境。爐體接著升溫至第二溫度,致使多顆鎂矽合金顆粒轉變成多顆多孔矽顆粒以及第二鎂蒸氣。冷卻液體從冷卻夾套的液體入口流入儲液腔從冷卻夾套的液體出口流出,讓至少一沉積基板的溫度低於第三溫度,致使流經冷卻夾套內之第二鎂蒸氣沉積於至少一沉積基板上形成鎂沉積物。 The manufacturing equipment of the third preferred embodiment of the present invention includes a furnace body, a cooling jacket, at least one deposition substrate, a vacuum exhaust device, and a passive gas supply device. Alternatively, the magnesium raw material and multiple silicon particles are placed in the furnace body, and the multiple silicon particles are placed on the magnesium raw material, or multiple silicon particles and multiple magnesium particles are mixed and placed in the furnace body. The cooling jacket is arranged on the first top of the furnace body and communicates with the first top of the furnace body. The cooling jacket has a liquid storage cavity, a liquid inlet and a liquid outlet. At least one deposition substrate is placed in the cooling jacket and thermally coupled with the inner wall of the cooling jacket. The vacuum pumping device is in communication with the second top of the cooling jacket. Passive gas supply system and cooling The second top of the jacket communicates. The passive gas supply device continuously operates to supply the passive gas to form a passive furnace atmosphere in the furnace body and the cooling jacket. The furnace body is then heated to the first temperature to generate the first magnesium vapor from the magnesium raw material or the plurality of magnesium particles, so that the plurality of silicon particles react with the first magnesium vapor to form a plurality of magnesium-silicon alloy particles. After the plurality of magnesium-silicon alloy particles are cooled, the vacuum exhaust device continues to operate to form a vacuum environment in the furnace body and the cooling jacket. The furnace body is then heated to a second temperature, so that the plurality of magnesium-silicon alloy particles are transformed into a plurality of porous silicon particles and a second magnesium vapor. The cooling liquid flows from the liquid inlet of the cooling jacket into the liquid storage chamber and flows out from the liquid outlet of the cooling jacket, so that the temperature of at least one deposition substrate is lower than the third temperature, so that the second magnesium vapor flowing through the cooling jacket is deposited on at least A magnesium deposit is formed on a deposition substrate.
進一步,根據本發明之製造設備還包含第一檔板。第一檔板係安置於至少一沉積基板所圍成之空間的上方。第二鎂蒸氣也沉積於第一檔板上。 Further, the manufacturing equipment according to the present invention further includes a first baffle plate. The first baffle is arranged above the space enclosed by at least one deposition substrate. The second magnesium vapor is also deposited on the first barrier.
進一步,根據本發明之製造設備還包含第二檔板。真空抽氣裝置係以導管與冷卻夾套之第二頂部連通。第二檔板係安置於冷卻夾套內靠近導管,以阻擋該第二鎂蒸氣被抽出冷卻夾套。 Furthermore, the manufacturing equipment according to the present invention further includes a second baffle plate. The vacuum pumping device is communicated with the second top of the cooling jacket through a pipe. The second baffle plate is arranged in the cooling jacket close to the duct to prevent the second magnesium vapor from being drawn out of the cooling jacket.
與先前技術不同,本發明之方法不採用酸洗製程甚至採用從矽泥廢料回收的矽顆粒來製造多顆多孔矽顆粒。執行本發明之方法的製造設備,在製造過程中無須將中間產物冷卻後取出,甚至能回收鎂蒸氣再利用。 Unlike the prior art, the method of the present invention does not use a pickling process or even uses silicon particles recovered from silicon mud waste to produce multiple porous silicon particles. The manufacturing equipment implementing the method of the present invention does not need to cool the intermediate product and then take it out during the manufacturing process, and can even recover the magnesium vapor for reuse.
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.
1‧‧‧方法 1‧‧‧Method
S10~S16‧‧‧流程步驟 S10~S16‧‧‧Process steps
2‧‧‧方法 2‧‧‧Method
S20~S28‧‧‧流程步驟 S20~S28‧‧‧Process steps
3‧‧‧製造設備 3‧‧‧Manufacturing equipment
30‧‧‧爐體 30‧‧‧Furnace body
300‧‧‧第二通孔 300‧‧‧Second through hole
301‧‧‧上加熱空間 301‧‧‧Upper heating space
302‧‧‧第一頂部 302‧‧‧First top
303‧‧‧下加熱空間 303‧‧‧Lower heating space
304‧‧‧座體 304‧‧‧Seat body
306‧‧‧加熱器 306‧‧‧Heater
31‧‧‧隔板 31‧‧‧Partition
312‧‧‧第一通孔 312‧‧‧First through hole
32‧‧‧冷卻夾套 32‧‧‧Cooling Jacket
322‧‧‧第二頂部 322‧‧‧Second top
324‧‧‧儲液腔 324‧‧‧Liquid reservoir
326‧‧‧液體入口 326‧‧‧Liquid inlet
328‧‧‧液體出口 328‧‧‧Liquid outlet
33‧‧‧沉積基板 33‧‧‧Deposition substrate
332‧‧‧空間 332‧‧‧Space
34‧‧‧真空抽氣裝置 34‧‧‧Vacuum pumping device
342‧‧‧導管 342‧‧‧Conduit
35‧‧‧鈍態氣體供應裝置 35‧‧‧Passive gas supply device
36‧‧‧第一檔板 36‧‧‧First stop
37‧‧‧第二檔板 37‧‧‧Second stop
40‧‧‧矽顆粒 40‧‧‧Silicon particles
42‧‧‧鎂原料 42‧‧‧Magnesium raw material
43‧‧‧第一鎂蒸氣 43‧‧‧First magnesium vapor
44‧‧‧鎂矽合金顆粒 44‧‧‧Magnesium-silicon alloy particles
45‧‧‧第二鎂蒸氣 45‧‧‧Second Magnesium Vapor
46‧‧‧多孔矽顆粒 46‧‧‧Porous silicon particles
47‧‧‧鎂沉積物 47‧‧‧Magnesium deposits
5‧‧‧坩堝 5‧‧‧Crucible
L‧‧‧冷卻液體 L‧‧‧Cooling liquid
圖1係本發明之第一較佳具體實施例之方法的各個程序步驟流程 圖。 Fig. 1 is the flow of each program step of the method of the first preferred embodiment of the present invention Figure.
圖2係本發明之第二較佳具體實施例之方法的各個程序步驟流程圖。 Fig. 2 is a flowchart of various program steps of the method of the second preferred embodiment of the present invention.
圖3係本發明之第三較佳具體實施例之製造設備的架構之示意圖。 FIG. 3 is a schematic diagram of the structure of the manufacturing equipment of the third preferred embodiment of the present invention.
圖4及圖5係圖3所示製造設備處於製造多顆多孔矽顆粒不同階段的示意圖。 4 and 5 are schematic diagrams of the manufacturing equipment shown in FIG. 3 in different stages of manufacturing multiple porous silicon particles.
圖6係本發明之第一範例所採用回收自矽泥之高純度矽粉體的掃描式電子顯微鏡(SEM)照片。 6 is a scanning electron microscope (SEM) photograph of the high-purity silicon powder recovered from the silicon mud used in the first example of the present invention.
圖7係本發明之一範例所獲得多顆鎂矽合金顆粒的SEM照片及經X射線能量散佈分析儀(EDS)分析成份結果。 FIG. 7 is an SEM photograph of a plurality of magnesium-silicon alloy particles obtained by an example of the present invention and the composition result of an X-ray energy dispersive analyzer (EDS).
圖8係本發明之第一範例於真空環境下加熱至800℃並持溫30min所獲得多顆多孔矽顆粒的SEM照片及EDS分析成份結果。 FIG. 8 is the SEM photograph and EDS analysis result of multiple porous silicon particles obtained by heating to 800° C. under a vacuum environment and holding the temperature for 30 minutes in the first example of the present invention.
圖9係本發明之第一範例於真空環境下加熱至850℃並持溫60min所獲得多顆多孔矽顆粒的SEM照片及EDS分析成份結果。 FIG. 9 is the SEM photograph and EDS analysis result of multiple porous silicon particles obtained by heating to 850° C. under a vacuum environment and holding the temperature for 60 minutes in the first example of the present invention.
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。根據本發明之第一較佳具體實施例之方法1不採用先前技術所採用的酸洗製程來製造多顆多孔矽顆粒。
Please refer to FIG. 1, which is a flowchart of
如圖1所示,本發明之方法1,首先係執行步驟S10,製備多顆矽顆粒以及鎂原料,其中多顆矽顆粒係置於鎂原料之上方。
As shown in FIG. 1, the
於實際應用中,多顆矽粉體可以採用回收自矽泥 之高純度矽粉體。矽泥即為運用線切割技術切削矽晶棒、矽晶鑄錠而得,矽泥的成份包含有機質、金屬物質、多個矽粉末以及多個碳化矽粉末。已有先前技術可以從矽泥中回收純度甚高的矽,在此不做贅述。鎂原料可以是顆粒狀或塊狀。 In practical applications, multiple silicon powders can be recycled from silicon mud The high-purity silica powder. Silicon mud is obtained by cutting silicon crystal rods and silicon crystal ingots using wire cutting technology. The components of silicon mud include organic matter, metal substances, multiple silicon powders, and multiple silicon carbide powders. The prior art can recover silicon with very high purity from the silicon sludge, so I will not repeat it here. The magnesium raw material may be granular or lumpy.
接著,本發明之方法1係執行步驟S12,於鈍態爐氛中,將鎂原料加熱至第一溫度,以產生第一鎂蒸氣,致使多顆矽顆粒與第一鎂蒸氣反應成多顆鎂矽合金顆粒。
Next, the
於一具體實施例中,第一溫度之範圍為從700℃至850℃。 In a specific embodiment, the first temperature ranges from 700°C to 850°C.
於一具體實施例中,鈍態爐氛為氬氣,通入氬氣的體積流率範圍為0.1L/min至2L/min。 In a specific embodiment, the passive atmosphere of the furnace is argon, and the volume flow rate of argon is in the range of 0.1L/min to 2L/min.
接著,本發明之方法1係執行步驟S14,於真空環境中,將多顆鎂矽合金顆粒加熱至第二溫度,致使多顆鎂矽合金顆粒轉變成多顆多孔矽顆粒以及第二鎂蒸氣。
Next, the
於一具體實施例中,第二溫度之範圍為從800℃至900℃。 In a specific embodiment, the second temperature ranges from 800°C to 900°C.
於一具體實施例中,真空環境的真空度為小於1torr。 In a specific embodiment, the vacuum degree of the vacuum environment is less than 1 torr.
最後,本發明之方法1係執行步驟S16,收集多顆多孔矽顆粒。
Finally, the
於一具體實施例中,多顆多孔矽顆粒具有粒徑範圍為0.1μm~5μm。 In a specific embodiment, the plurality of porous silicon particles have a particle size ranging from 0.1 μm to 5 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。同樣地,根據本發明之第二較佳具體實施例之方法2不採用先前技術所採用的酸洗製程來製造多顆多孔矽顆粒。
Please refer to FIG. 2, which is a flowchart of
如圖2所示,本發明之方法2,首先係執行步驟S20,製備多顆矽顆粒以及多顆鎂顆粒。
As shown in FIG. 2, the
於實際應用中,多顆矽粉體可以採用回收自矽泥之高純度矽粉體。矽泥即為運用線切割技術切削矽晶棒、矽晶鑄錠而得,矽泥的成份包含有機質、金屬物質、多個矽粉末以及多個碳化矽粉末。已有先前技術可以從矽泥中回收純度甚高的矽,在此不做贅述。鎂原料可以是顆粒狀或塊狀。 In practical applications, high-purity silica powder recovered from silica mud can be used for multiple silicon powders. Silicon mud is obtained by cutting silicon crystal rods and silicon crystal ingots using wire cutting technology. The components of silicon mud include organic matter, metal substances, multiple silicon powders, and multiple silicon carbide powders. The prior art can recover silicon with very high purity from the silicon sludge, so I will not repeat it here. The magnesium raw material may be granular or lumpy.
接著,本發明之方法2係執行步驟S22,將多顆矽顆粒與多顆鎂顆粒混合。
Next, the
接著,本發明之方法2係執行步驟S24,於鈍態爐氛中,將混合後的多顆矽顆粒與多顆鎂顆粒加熱至第一溫度,以產生第一鎂蒸氣,致使多顆矽顆粒與第一鎂蒸氣反應成多顆鎂矽合金顆粒。
Next, the
於一具體實施例中,第一溫度之範圍為從700℃至850℃。 In a specific embodiment, the first temperature ranges from 700°C to 850°C.
接著,本發明之方法2係執行步驟S26,於真空環境中,將多顆鎂矽合金顆粒加熱至第二溫度,致使多顆鎂矽合金顆粒轉變成多顆多孔矽顆粒以及第二鎂蒸氣。
Next, the
於一具體實施例中,第二溫度之範圍為從800℃至900℃。 In a specific embodiment, the second temperature ranges from 800°C to 900°C.
於一具體實施例中,真空環境的真空度為小於1torr。 In a specific embodiment, the vacuum degree of the vacuum environment is less than 1 torr.
最後,本發明之方法2係執行步驟S28,收集多顆多孔矽顆粒。
Finally, the
於一具體實施例中,多顆多孔矽顆粒具有粒徑範圍為0.1μm~5μm。 In a specific embodiment, the plurality of porous silicon particles have a particle size ranging from 0.1 μm to 5 μm.
請參閱圖3、圖4及圖5,圖3、圖4及圖5係示意地繪示本發明之第三較佳具體實施例之製造設備3的架構。於圖3、圖4及圖5中,部分元件及裝置係以剖面視圖顯示。
Please refer to FIG. 3, FIG. 4, and FIG. 5. FIG. 3, FIG. 4, and FIG. 5 schematically illustrate the structure of the
如圖3、圖4及圖5所示,根據本發明之第三較佳具體實施例之製造設備3包含爐體30、冷卻夾套32、至少一沉積基板33、真空抽氣裝置34以及鈍態氣體供應裝置35。
As shown in FIGS. 3, 4, and 5, the
爐體30包含熱絕緣的座體304以及至少一加熱器306。於一具體實施例中,座體304可以由碳纖維所製成,但並不以此為限。兩者擇一地,鎂原料42與多顆矽顆粒40係置於爐體30內,並且多顆矽顆粒40係置於鎂原料42之上方,或者多顆矽顆粒40與多顆鎂顆粒(未繪示於圖中)混合後置於爐體30內。
The
同樣如圖3所示,根據本發明之第三較佳具體實施例之製造設備3還包含隔板31。隔板31係置於爐體30內,以將爐體30隔成上加熱空間301以及下加熱空間303。隔板31具有多個第一通孔312。圖3所示案例是將多顆矽顆粒40置於爐體30之上加熱空間301內。鎂原料42係置於爐體之下加熱空間303內。多個第一通孔312讓上加熱空間301與下加熱空間303連通。
Also as shown in FIG. 3, the
圖3所示案例是將多顆矽顆粒40以及鎂原料42可以置於坩堝5內。鎂原料42可以置於坩堝5的底部。隔板31可以安裝於坩堝5的中間部位。多顆矽顆粒40可以置於於隔板31上。再將盛裝多顆第一矽顆粒40以及鎂原料42的坩堝5置於爐體30內,至少一加熱器306圍繞在坩堝5的外壁。於一具體實施例中,坩堝5可以由石墨所製成,但並不以此為限。於一具體實施例中,隔板31的每一個第一通孔312之孔徑係小於每一顆矽顆粒40之粒徑。
The case shown in FIG. 3 is that a plurality of
兩者擇一地,利用根據本發明之第三較佳具體實施例之製造設備3,可以將多顆矽顆粒40與多顆鎂顆粒(未繪示於圖中)混合後置於坩堝5內,再將坩堝5置於爐體30內。
Alternatively, by using the
冷卻夾套32係安置於爐體30之第一頂部302上,並且與爐體30之第一頂部302連通。例如,如圖3所示,爐體30之第一頂部302上具有多個第二通孔300。多個第二通孔300讓冷卻夾套32與爐體30之第一頂部302連通。
The cooling
冷卻夾套32具有儲液腔324、液體入口326以及液體出口328。冷卻液體L從冷卻夾套32之液體入口326流入冷卻夾套32之儲液腔324從冷卻夾套32之液體出口328流出。
The cooling
至少一沉積基板33係放置於冷卻夾套32內,並且與冷卻夾套32之內壁熱耦合。真空抽氣裝置34係與冷卻夾套32之第二頂部322連通。鈍態氣體供應裝置35係與冷卻夾套32的第二頂部322連通。
At least one
請再參閱圖3及圖4、圖5,利用根據本發明之第三較佳具體實施例之製造設備3製造多顆多孔矽顆粒46如下文所述。
Please refer to FIGS. 3, 4, and 5 again, using the
如圖4所示,接著,鈍態氣體供應裝置35持續運作供應鈍態氣體(例如,氬氣)將爐體30內以及冷卻夾套32內形成鈍態爐氛。接著,爐體30升溫至第一溫度且維持第一加熱時間,讓鎂原料42(或者多顆鎂顆粒)蒸發成第一鎂蒸氣43。第一鎂蒸氣43通過多個第一通孔312流至上加熱空間301,致使多顆矽顆粒40與第一鎂蒸氣43反應成多顆鎂矽合金顆粒44。第一溫度之範圍如上文所述,在此不再贅述。第一加熱時間可以是2hr至8hr。
As shown in FIG. 4, then, the passive
如圖5所示,接著,於多顆鎂矽合金顆粒44冷卻後,真空抽氣裝置34接著持續運作將爐體30內以及冷卻
夾套32內形成真空環境。爐體30接著升溫至第二溫度且維持第二加熱時間,致使多顆鎂矽合金顆粒44轉變成多顆多孔矽顆粒46以及第二鎂蒸氣45。
As shown in FIG. 5, after the plurality of magnesium-
第二鎂蒸氣45經過第二通孔300,流入冷卻夾套32內。第二通孔300還可以避免多顆矽顆粒40、多顆鎂矽合金顆粒44或多顆多孔矽顆粒46飛濺進入冷卻夾套32內。
The
冷卻液體L持續從冷卻夾套32之液體入口326流入冷卻夾套32之儲液腔324從冷卻夾套32之液體出口328流出,讓至少一沉積基板33之溫度低於第三溫度,致使流經冷卻夾套32內之第二鎂蒸氣45沉積於至少一沉積基板33上形成鎂沉積物47。最後,爐體30冷卻後,取出多顆多孔矽顆粒46以及鎂沉積物47。第二溫度之範圍以及真空環境的真空度如上文所述,在此不再贅述。第二加熱時間可以是20min至2hr。
The cooling liquid L continues to flow from the
於一具體實施例中,冷卻液體L可以是水,但並不以此為限。 In a specific embodiment, the cooling liquid L may be water, but it is not limited to this.
於一具體實施例中,第三溫度之範圍為從400℃至600℃。 In a specific embodiment, the third temperature ranges from 400°C to 600°C.
進一步,同樣如圖3、圖4及圖5所示,根據本發明之第三較佳具體之實施例之製造設備3還包含第一檔板36。第一檔板36係安置於至少一沉積基板33所圍成之空間332的上方。第二鎂蒸氣45也沉積於第一檔板36上。
Furthermore, as shown in FIG. 3, FIG. 4, and FIG. 5, the
進一步,同樣如圖3、圖4及圖5所示,根據本發明之第三較佳具體實施例之製造設備3還包含第二檔板37。真空抽氣裝置34係以導管342與冷卻夾套32之第二頂部322連通。第二檔板37係安置於冷卻夾套32內靠近導管342以阻擋第二鎂蒸氣45被抽出冷卻夾套32。
Furthermore, as also shown in FIGS. 3, 4 and 5, the
於第一範例中,根據本發明之第一較佳具體實施例之方法採用回收自矽泥之高純度矽粉體來製造多顆多孔矽顆粒。回收自矽泥之高純度矽粉體的SEM照片請見圖6所示。接著,本發明之第一範例於氬氣鈍態爐氛中,將鎂原料加熱至800℃並持溫5hr,以產生第一鎂蒸氣,致使多顆矽顆粒與第一鎂蒸氣反應成多顆鎂矽合金顆粒。本發明之第一範例所得多顆鎂矽合金顆粒的SEM照片及EDS分析成份結果請見圖7所示。圖7的EDS分析成份結果證實,本發明之第一範例所獲得多顆鎂矽合金顆粒的鎂/矽比為1.9,且會有尺寸約為100μm顆粒聚集物。殘存的鎂原料會產生MgO顆粒,經成份檢測發現MgO顆粒中含有碳、鎳。本發明之第一範例將所得多顆鎂矽合金顆粒於真空環境下,將多顆鎂矽合金顆粒加熱至800℃並持溫30min,致使多顆鎂矽合金顆粒轉變成多顆多孔矽顆粒以及第二鎂蒸氣。本發明之第一範例加熱至800℃並持溫30min獲得的多顆多孔矽顆粒的SEM照片及EDS分析成份結果請見圖8所示。圖8的EDS分析成份結果證實,多顆多孔矽顆粒的鎂/矽比為0.12,圖8的SEM照片證實顆粒聚集已減少。本發明之第一範例另將所得多顆鎂矽合金顆粒於真空環境下,將多顆鎂矽合金顆粒加熱至850℃並持溫60min,致使多顆鎂矽合金顆粒轉變成多顆多孔矽顆粒以及第二鎂蒸氣。本發明之第一範例加熱至850℃並持溫60min獲得的多顆多孔矽顆粒的SEM照片及EDS分析成份結果請見圖9所示。圖9的EDS分析成份結果證實,多顆多孔矽顆粒的鎂/矽比為0.19,圖9的SEM照片證實顆粒聚集已減少。 In the first example, the method according to the first preferred embodiment of the present invention uses high-purity silicon powder recovered from silicon mud to produce a plurality of porous silicon particles. The SEM photo of the high-purity silica powder recovered from the silica mud is shown in Figure 6. Next, in the first example of the present invention, in an argon passive atmosphere, the magnesium raw material is heated to 800°C and held at the temperature for 5 hours to generate the first magnesium vapor, so that multiple silicon particles react with the first magnesium vapor to form multiple particles Magnesium-silicon alloy particles. The SEM photos and EDS analysis results of the multiple magnesium-silicon alloy particles obtained in the first example of the present invention are shown in FIG. 7. The EDS analysis result of FIG. 7 confirms that the magnesium/silicon ratio of the magnesium-silicon alloy particles obtained in the first example of the present invention is 1.9, and there are particle aggregates with a size of about 100 μm. The remaining magnesium raw materials will produce MgO particles, and the MgO particles are found to contain carbon and nickel through composition testing. The first example of the present invention heats the obtained magnesium-silicon alloy particles to 800°C and holds the temperature for 30 minutes in a vacuum environment, so that the magnesium-silicon alloy particles are transformed into porous silicon particles and The second magnesium vapor. In the first example of the present invention, the SEM photographs and EDS analysis results of multiple porous silicon particles obtained by heating to 800° C. and holding the temperature for 30 minutes are shown in FIG. 8. The EDS analysis result of Figure 8 confirms that the Mg/Si ratio of multiple porous silicon particles is 0.12, and the SEM photo of Figure 8 confirms that particle aggregation has been reduced. The first example of the present invention further heats the obtained magnesium-silicon alloy particles to 850°C and holds the temperature for 60 minutes in a vacuum environment, so that the magnesium-silicon alloy particles are transformed into porous silicon particles. And the second magnesium vapor. In the first example of the present invention, the SEM pictures and EDS analysis results of multiple porous silicon particles obtained by heating to 850° C. and holding the temperature for 60 minutes are shown in FIG. 9. The EDS analysis result of Fig. 9 confirms that the Mg/Si ratio of multiple porous silicon particles is 0.19, and the SEM photograph of Fig. 9 confirms that particle aggregation has been reduced.
於第二範例中,根據本發明之第二較佳具體實施例之方法採用回收自矽泥之高純度矽粉體來製造多顆多孔矽顆粒。接著,本發明之第二範例於氬氣鈍態爐氛中,將多顆矽顆粒與多顆鎂顆粒混合後加熱至800℃並持溫5hr,以產生第一鎂蒸氣,致使多顆矽顆粒與第一鎂蒸氣反應成多顆鎂矽合金顆粒。本發明之第二範例所得多顆鎂矽合金顆粒的EDS 分析成份結果證實,本發明之第二範例所獲得多顆鎂矽合金顆粒的鎂/矽比為2.4。本發明之第二範例將所得多顆鎂矽合金顆粒於真空環境下,將多顆鎂矽合金顆粒加熱至800℃並持溫30min,致使多顆鎂矽合金顆粒轉變成多顆多孔矽顆粒以及第二鎂蒸氣。本發明之第二範例加熱至800℃並持溫30min獲得的多顆多孔矽顆粒的表面上的孔洞較為明顯。 In the second example, the method according to the second preferred embodiment of the present invention uses high-purity silicon powder recovered from silicon mud to produce a plurality of porous silicon particles. Next, in the second example of the present invention, a plurality of silicon particles and a plurality of magnesium particles are mixed in an argon passive atmosphere, and then heated to 800°C and held at the temperature for 5 hours to generate the first magnesium vapor, resulting in a plurality of silicon particles It reacts with the first magnesium vapor to form a plurality of magnesium-silicon alloy particles. EDS of multiple magnesium-silicon alloy particles obtained in the second example of the present invention The analysis of the composition results confirms that the magnesium/silicon ratio of the magnesium-silicon alloy particles obtained in the second example of the present invention is 2.4. The second example of the present invention heats the obtained multiple magnesium-silicon alloy particles to 800°C and holds the temperature for 30 minutes under a vacuum environment, so that the multiple magnesium-silicon alloy particles are transformed into multiple porous silicon particles and The second magnesium vapor. In the second example of the present invention, the holes on the surface of multiple porous silicon particles obtained by heating to 800° C. and holding the temperature for 30 minutes are more obvious.
與先前技術相比較,本發明之方法不採用酸洗製程甚至採用從矽泥廢料回收的矽顆粒來製造多顆多孔矽顆粒,沒有廢酸液處理的環保問題,還能減少矽泥廢料將其轉化為經濟上是可行的和有益的產物。執行本發明之方法的製造設備,在製造過程中無須將中間產物冷卻後取出,甚至能回收鎂蒸氣再利用。 Compared with the prior art, the method of the present invention does not use the pickling process or even uses the silicon particles recovered from the silicon mud waste to produce multiple porous silicon particles. There is no environmental protection problem of the waste acid liquid treatment, and it can also reduce the waste of the silicon mud. It is transformed into an economically feasible and beneficial product. The manufacturing equipment implementing the method of the present invention does not need to cool the intermediate product and then take it out during the manufacturing process, and can even recover the magnesium vapor for reuse.
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, the 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 1‧‧‧Method
S10~S16‧‧‧流程步驟 S10~S16‧‧‧Process steps
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CN102237519A (en) * | 2011-07-11 | 2011-11-09 | 三峡大学 | Fluorine-free preparation method for three-dimensional porous silica powder anode material of lithium ion battery |
CN104051714A (en) * | 2013-03-14 | 2014-09-17 | 通用汽车环球科技运作有限责任公司 | Anodes including mesoporous hollow silicon particles and a method for synthesizing mesoporous hollow silicon particles |
CN107848809A (en) * | 2016-06-15 | 2018-03-27 | 罗伯特·博世有限公司 | Porous silicon grain and the method for producing silicon grain |
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CN102237519A (en) * | 2011-07-11 | 2011-11-09 | 三峡大学 | Fluorine-free preparation method for three-dimensional porous silica powder anode material of lithium ion battery |
CN104051714A (en) * | 2013-03-14 | 2014-09-17 | 通用汽车环球科技运作有限责任公司 | Anodes including mesoporous hollow silicon particles and a method for synthesizing mesoporous hollow silicon particles |
CN107848809A (en) * | 2016-06-15 | 2018-03-27 | 罗伯特·博世有限公司 | Porous silicon grain and the method for producing silicon grain |
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