JP2014088292A5 - - Google Patents
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- JP2014088292A5 JP2014088292A5 JP2012239813A JP2012239813A JP2014088292A5 JP 2014088292 A5 JP2014088292 A5 JP 2014088292A5 JP 2012239813 A JP2012239813 A JP 2012239813A JP 2012239813 A JP2012239813 A JP 2012239813A JP 2014088292 A5 JP2014088292 A5 JP 2014088292A5
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 67
- 239000000843 powder Substances 0.000 claims description 42
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 38
- 210000002381 Plasma Anatomy 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000011863 silicon-based powder Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910020230 SIOx Inorganic materials 0.000 claims description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims 3
- 238000001035 drying Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000007790 scraping Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910052904 quartz Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium(0) Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible Effects 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001376 precipitating Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Description
本発明の第１の観点は、無電極型の高周波誘電法により発生した高周波プラズマ中で、二酸化珪素粉末及び金属珪素粉末の混合物を原料として非晶質のＳｉＯｘで表される酸化珪素粉末を製造する方法であって、酸化珪素粉末の酸素含有量Ｘが０．２以上１．０未満の範囲にあり、酸化珪素粉末の不純物濃度が最大で１１．５ｐｐｍであることを特徴とする酸化珪素粉末の製造方法である。 A first aspect of the present invention is to produce amorphous silicon oxide powder represented by SiOx using a mixture of silicon dioxide powder and metal silicon powder as a raw material in high frequency plasma generated by an electrodeless high frequency dielectric method. An oxidation method characterized in that the oxygen content X of the silicon oxide powder is in the range of 0.2 to less than 1.0 and the impurity concentration of the silicon oxide powder is 11.5 pp m at the maximum. This is a method for producing silicon powder.
一方、ステンレス鋼、モリブデン、タングステン等の基板上に析出した酸化珪素を掻き取り等により回収したり、或いはこの回収した酸化珪素をボールミル等により粉砕して粒度を調整している従来の酸化珪素粉末の製造方法等と比較して、本発明では、不純物濃度が最大で１１．５ｐｐｍと低い。上記不純物を含む酸化珪素（珪素低級酸化物）を蒸着材として用いた場合、ガスバリアフィルムに酸化珪素膜を成膜させる際に、異常放電（アークスポット）の原因となり、この異常放電（アークスポット）が発生すると、ガス化していない酸化珪素がガスバリアフィルムに付着するため、ガスフィルムに凸部やピンホール等の酸化珪素の不均一面が生成されてしまい、これによりガスバリア性が低下してしまう問題点があった従来のケイ素低級酸化物粒子の製造方法と比較して、本発明では、酸化珪素粉末の不純物濃度が最大で１１．５ｐｐｍであるので、酸化珪素粉末をガスバリアフィルムとして使用した場合、良好なガスバリア性を有する蒸着膜を形成できる。また上記不純物を含む酸化珪素（珪素低級酸化物）をリチウムイオン二次電池の負極活物質として用いた場合、酸化珪素中の鉄やタングステンにより初回充放電時の不可逆容量が大きくなってしまい、サイクル特性が劣化する問題点があった従来のケイ素低級酸化物粒子の製造方法と比較して、本発明では、酸化珪素粉末の不純物濃度が最大で１１．５ｐｐｍであるので、酸化珪素粉末をリチウムイオン二次電池の負極活性物質として用いた場合、初期充放電時の不可容量を小さくすることができ、これによりサイクル特性を向上できる。 On the other hand, a conventional silicon oxide powder in which the silicon oxide deposited on a substrate such as stainless steel, molybdenum, or tungsten is collected by scraping or the like, or the collected silicon oxide is pulverized by a ball mill or the like to adjust the particle size. In the present invention, the impurity concentration is as low as 11.5 ppm at the maximum, compared with the manufacturing method. When silicon oxide containing the above impurities (silicon lower oxide) is used as a vapor deposition material, it causes abnormal discharge (arc spot) when forming a silicon oxide film on the gas barrier film, and this abnormal discharge (arc spot) When gas is generated, non-gasified silicon oxide adheres to the gas barrier film, so that a non-uniform surface of silicon oxide such as a convex portion or a pinhole is generated on the gas film, thereby reducing gas barrier properties. Compared with the conventional method for producing silicon lower oxide particles, the present invention uses silicon oxide powder as a gas barrier film because the impurity concentration of silicon oxide powder is 11.5 pp m at the maximum. In this case, a deposited film having a good gas barrier property can be formed. Further, when silicon oxide containing the above impurities (silicon lower oxide) is used as the negative electrode active material of a lithium ion secondary battery, the irreversible capacity at the first charge / discharge is increased due to iron or tungsten in the silicon oxide, resulting in a cycle. characteristics as compared to the conventional method of manufacturing a silicon lower oxide particles problem had to be degraded, in the present invention, since the impurity concentration of the silicon oxide powder is at most 11.5 pp m, a silicon oxide powder When used as a negative electrode active material for a lithium ion secondary battery, it is possible to reduce the unacceptable capacity during initial charge / discharge, thereby improving cycle characteristics.
本発明の第３の観点の酸化珪素粉末の製造方法では、酸化珪素粉末の平均粒径が体積基準で０．００２〜１μｍの範囲にあるため、ステンレス鋼等の基板上に析出した酸化珪素を掻き取り等によって回収する必要がなく、また回収した酸化珪素をボールミル等により粉砕して粒度を調整する必要がなく、酸化珪素粉末への不純物の混入が少なくなる。この結果、酸化珪素粉末中の不純物濃度が最大で１１．５ｐｐｍと低くなる。 In the method for producing silicon oxide powder according to the third aspect of the present invention, since the average particle size of the silicon oxide powder is in the range of 0.002 to 1 μm on a volume basis, silicon oxide deposited on a substrate such as stainless steel is used. There is no need to collect by scraping or the like, and there is no need to adjust the particle size by pulverizing the collected silicon oxide with a ball mill or the like, so that impurities are not mixed into the silicon oxide powder. As a result, the impurity concentration in the silicon oxide powder is as low as 11.5 ppm at maximum.
上記高周波プラズマ装置１０では、ガス導入管１８から石英管１３ａ内にアルゴンガス、ヘリウムガス、水素ガス、窒素ガス及び酸素ガスからなる群より選ばれた１種又は２種以上の混合ガスを導入して、高周波誘導コイル１３ｂに所定の高周波電力を供給すると、石英管１３ａ内からチャンバ１４内にかけて高周波プラズマ１２を発生し、原料粉末である二酸化珪素粉末及び金属珪素粉末の混合物は原料供給管１７を通って高周波プラズマ４０中に供給されるようになっている。また上記高周波プラズマ１２の高周波出力をＡ(Ｗ)とし、二酸化珪素粉末及び金属珪素粉末の混合物の供給速度をＢ(ｋｇ／時)とするとき、Ａ／Ｂが１．０×１０4(Ｗ・時／ｋｇ)以上になるように調整して、高周波プラズマ１２を発生させる。ここで、Ａ／Ｂを１．０×１０4(Ｗ・時／ｋｇ)以上に限定したのは、１．０×１０4（Ｗ・時／ｋｇ）より小さいと、二酸化珪素粉末と金属珪素粉末に与える高周波プラズマのエネルギが少ないため、二酸化珪素粉末及び金属珪素粉末の反応速度が遅くなるという理由に基づく。また高周波プラズマ１２の発生雰囲気の圧力は、全圧（混合ガス全体の圧力）で０．０５〜０．１２ＭＰａの範囲、好ましくは０．０７〜０．１０ＭＰａの範囲に調整される。ここで、高周波プラズマ１２の発生雰囲気の圧力の下限値を全圧で０．０５ＭＰａに限定したのは、電子だけではなく、イオンや原子等の重粒子も高温になるため、高周波プラズマ１２のエネルギ密度が大きくなり、二酸化珪素粉末及び金属珪素粉末を短時間で効率良く加熱でき、また高温領域における二酸化珪素粉末及び金属珪素粉末の反応速度の指数関数的な増大が期待できるからである。また、高周波プラズマ１２の発生雰囲気の圧力の上限値を全圧で０．１２ＭＰａに限定したのは、０．１２ＭＰａより大きくなると、高周波プラズマにより加熱される混合ガスの温度が高くなり過ぎ、チャンバ１４の表面を融解させてしまうからである。 In the high-frequency plasma apparatus 10, one or more mixed gases selected from the group consisting of argon gas, helium gas, hydrogen gas, nitrogen gas and oxygen gas are introduced from the gas introduction tube 18 into the quartz tube 13a. When a predetermined high-frequency power is supplied to the high-frequency induction coil 13b, a high-frequency plasma 12 is generated from the quartz tube 13a to the chamber 14, and a mixture of silicon dioxide powder and metal silicon powder, which are raw material powder, is supplied to the raw material supply tube 17. It is supplied to the high frequency plasma 40 through. When the high-frequency output of the high-frequency plasma 12 is A (W) and the supply rate of the mixture of silicon dioxide powder and metal silicon powder is B (kg / hour), A / B is 1.0 × 10 4 (W Adjust the frequency so that it becomes more than hour / kg) to generate the high-frequency plasma 12. Here, when A / B is limited to 1.0 × 10 4 (W · hour / kg) or more, if it is smaller than 1.0 × 10 4 (W · hour / kg), silicon dioxide powder and metallic silicon This is based on the reason that the reaction rate of the silicon dioxide powder and the metal silicon powder is slow because the energy of the high frequency plasma applied to the powder is small. The pressure of the atmosphere in which the high-frequency plasma 12 is generated is adjusted to a range of 0.05 to 0.12 MPa, preferably 0.07 to 0.10 MPa, in terms of total pressure (pressure of the entire mixed gas). Here, the reason why the lower limit value of the pressure of the atmosphere in which the high-frequency plasma 12 is generated is limited to 0.05 MPa in terms of the total pressure is that not only electrons but also heavy particles such as ions and atoms become high temperature. This is because the density increases, the silicon dioxide powder and the metal silicon powder can be efficiently heated in a short time, and an exponential increase in the reaction rate of the silicon dioxide powder and the metal silicon powder in a high temperature region can be expected. The upper limit of the pressure of the atmosphere in which the high-frequency plasma 12 is generated is limited to 0.12 MPa as the total pressure. If the pressure exceeds 0.12 MPa, the temperature of the mixed gas heated by the high-frequency plasma becomes too high, and the chamber 14 This is because the surface of the material is melted.
このようにして製造された酸化珪素粉末では、平均粒径が体積基準で０．００２〜１μｍの範囲にあるため、ステンレス鋼等の基板上に析出した酸化珪素を掻き取り等によって回収する必要がなく、また回収した酸化珪素をボールミル等により粉砕して粒度を調整する必要がなく、酸化珪素粉末への不純物の混入が少ない。この結果、酸化珪素粉末中の不純物濃度が最大で１１．５ｐｐｍと低くなる。なお、酸化珪素粉末の平均粒径は体積基準で０．０５〜０．５μｍの範囲にあることが好ましく、酸化珪素粉末中の不純物濃度は最大で１ｐｐｍ未満であることが好ましい。 In the silicon oxide powder produced in this way, the average particle size is in the range of 0.002 to 1 μm on a volume basis, so it is necessary to collect silicon oxide deposited on a stainless steel substrate by scraping or the like. In addition, there is no need to adjust the particle size by pulverizing the recovered silicon oxide with a ball mill or the like, and there is little mixing of impurities into the silicon oxide powder. As a result, the impurity concentration in the silicon oxide powder is as low as 11.5 ppm at maximum. In addition, it is preferable that the average particle diameter of silicon oxide powder exists in the range of 0.05-0.5 micrometer on a volume basis, and it is preferable that the impurity concentration in silicon oxide powder is less than 1 ppm at maximum.
Claims (5)
前記酸化珪素粉末の酸素含有量Ｘが０．２以上１．０未満の範囲にあり、
前記酸化珪素粉末の不純物濃度が最大で１１．５ｐｐｍである
ことを特徴とする酸化珪素粉末の製造方法。 In a high-frequency plasma generated by an electrodeless high-frequency dielectric method, a method for producing an amorphous silicon oxide powder represented by SiOx using a mixture of silicon dioxide powder and metal silicon powder as a raw material,
The oxygen content X of the silicon oxide powder is in the range of 0.2 or more and less than 1.0,
Method for producing a silicon oxide powder in which the impurity concentration of the silicon oxide powder is characterized in that it is a 11.5 pp m at maximum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012239813A JP5994573B2 (en) | 2012-10-31 | 2012-10-31 | Method for producing silicon oxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012239813A JP5994573B2 (en) | 2012-10-31 | 2012-10-31 | Method for producing silicon oxide powder |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2014088292A JP2014088292A (en) | 2014-05-15 |
| JP2014088292A5 true JP2014088292A5 (en) | 2016-04-28 |
| JP5994573B2 JP5994573B2 (en) | 2016-09-21 |
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| JP2012239813A Expired - Fee Related JP5994573B2 (en) | 2012-10-31 | 2012-10-31 | Method for producing silicon oxide powder |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015015795A1 (en) * | 2013-07-30 | 2015-02-05 | 東京印刷機材トレーディング株式会社 | Siox powder manufacturing process and siox powder manufacturing apparatus |
| JP2017061411A (en) * | 2016-12-01 | 2017-03-30 | 株式会社日清製粉グループ本社 | Manufacturing method of nonstoichiometric oxide particle |
| SG11202006013VA (en) * | 2018-01-26 | 2020-07-29 | Denka Company Ltd | Amorphous silica powder, production method therefor, and use thereof |
| WO2023074217A1 (en) * | 2021-10-27 | 2023-05-04 | 三菱ケミカル株式会社 | Silicon oxide particles and method for producing same, particles and method for producing same, and secondary battery and method for producing same |
| CN114349011B (en) * | 2022-01-14 | 2023-04-11 | 宁波广新纳米材料有限公司 | Preparation method of nano-sized silicon monoxide powder |
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| JP4900573B2 (en) * | 2006-04-24 | 2012-03-21 | 信越化学工業株式会社 | Method for producing silicon oxide powder |
| JP2011079724A (en) * | 2009-10-09 | 2011-04-21 | Osaka Titanium Technologies Co Ltd | METHOD FOR PRODUCING SiOx (x<1) |
| JP5362614B2 (en) * | 2010-02-16 | 2013-12-11 | 日清エンジニアリング株式会社 | Method for producing silicon monoxide fine particles and silicon monoxide fine particles |
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