公开(公告)号：EP2492995A1

公开(公告)日：2012-08-29

申请号：EP10824610.9

申请日：2010-10-04

Applicant: OSAKA Titanium Technologies Co., Ltd.

Inventor： KANNO, Hideaki ,  KIZAKI, Shingo

IPC: H01M4/48 ,  H01M4/36 ,  C01B33/113

CPC classification number: H01M4/485 ,  C01P2002/82 ,  H01M4/134 ,  H01M4/386 ,  H01M10/0525 ,  H01M2004/021

Abstract: Provided is a negative electrode active material for a lithium-ion secondary battery, comprising SiO x that has an intensity ratio A 1 /A 2 of 0.1 or less in spectra measured by a Fourier transform infrared spectrometer after subjecting the SiO x to evacuation treatment at 200°C, given that A 1 designates an intensity of a silanol group-derived peak which appears around 3400 to 3800 cm -1 , and A 2 designates an intensity of a siloxane bond-derived peak which appears around 1000 to 1200 cm -1 . It is preferred that x in the SiO x satisfies x 3 that may normally exhibit around 2100 cm -1 in spectra of the SiO x measured by a laser Raman spectrometer; and a ratio Y/X is 0.98 or less, given that X is a mole ratio of O to Si in the whole body of the SiO x , and Y is a mole ratio of O to Si in a surface vicinity of the SiO x . A lithium-ion secondary battery having high initial efficiency and charge/discharge capacity can be obtained by using this active material.

Abstract translation: 本发明提供一种锂离子二次电池用负极活性物质，其特征在于，在通过傅立叶变换红外光谱仪测定的光谱的强度比A 1 / A 2为0.1以下的SiO x，使SiO x进行排气处理后， 假定A 1表示出现在3400至3800cm -1附近的硅烷醇基衍生峰的强度，A 2表示出现在约1000至1200cm -1附近的硅氧烷键衍生峰的强度 。 优选SiO x中的x满足x <1; 在激光拉曼光谱仪测量的SiO x的光谱中，通常不会出现约2100cm -1的Si-H键衍生峰A 3的迹象。 并且Y / X为0.98以下，X为SiO x的全体中的O与Si的摩尔比，Y为SiO x表面附近的O与Si的摩尔比。 通过使用该活性物质，可以得到初期效率和充放电容量高的锂离子二次电池。

公开(公告)号：EP2477260A1

公开(公告)日：2012-07-18

申请号：EP10815089.7

申请日：2010-06-17

Applicant: OSAKA Titanium Technologies Co., Ltd.

Inventor： KIZAKI, Shingo ,  KANNO, Hideaki

IPC: H01M4/48 ,  H01M4/13

CPC classification number: H01M4/485 ,  C01B33/113 ,  H01M4/131 ,  H01M4/134 ,  H01M10/0525

Abstract: Provided is a silicon oxide in the form of powder, which is used for a negative electrode active material of a lithium-ion secondary battery and is represented by SiO x , wherein, when the silicon oxide is measured by use of an X-ray diffractometer comprising a sealed tube light source as a light source and a high speed detector as a detector, a halo is detected at 20°≤2θ≤40°, and a peak is detected at the highest quartz line position therein, and the height P1 of the halo and the height P2 of the peak at the highest quartz line position satisfy P2/P1≤0.05. This silicon oxide is used as the negative electrode active material, whereby a lithium-ion secondary battery having stable initial efficiency and cycle characteristic can be obtained. The x of the SiO x is preferably 0.7

Abstract translation: 本发明提供一种粉末形式的氧化硅，其用于锂离子二次电池的负极活性物质，由SiO x表示，其中，当使用X射线衍射仪 包括作为光源的密封管光源和作为检测器的高速检测器，在20°¤2¸‰º40°检测到光晕，并且在其中最高的石英线位置处检测到峰值，并且 卤素的高度P1和最高石英线位置处的峰的高度P2满足P2 / P1‰¤0.05。 使用该氧化硅作为负极活性物质，可以得到稳定的初期效率和循环特性的锂离子二次电池。 SiO x的x优选为0.7

公开(公告)号：EP3236521A1

公开(公告)日：2017-10-25

申请号：EP15869515.5

申请日：2015-12-07

Applicant: OSAKA Titanium Technologies Co., Ltd.

Inventor： KIZAKI, Shingo ,  KASHITANI, Yusuke ,  TAKESHITA, Kohki

IPC: H01M4/485 ,  H01M4/36

CPC classification number: H01M4/36 ,  C01B33/20 ,  C01P2002/74 ,  C01P2004/51 ,  C01P2004/64 ,  C01P2006/12 ,  H01M4/485

Abstract: This invention provides a powder for a negative electrode of a lithium ion secondary battery, which is a powder that includes a silicon oxide powder containing Li. When a molar ratio between Li, Si and O is taken as y:1:x, the average composition of the powder overall satisfies the relation 0.5 α ray, a relation P2/P1 ≤ 1.0 and a relation P3/P1 ≤ 1.0 are satisfied, where P1 represents a height of a peak attributed to Li 2 SiO 3 , P2 represents a height of a peak attributed to crystalline Si, and P3 represents a height of a peak attributed to Li 4 SiO 4 . When this powder is used for a negative electrode of a lithium ion secondary battery, the initial efficiency and the capacity retention rate over a long-term cycle can be increased.

Abstract translation: 本发明提供一种锂离子二次电池的负极用粉末，其是包含含有Li的氧化硅粉末的粉末。 当Li，Si和O之间的摩尔比为y:1:x时，粉末的平均组成满足关系0.5

公开(公告)号：EP2597708A1

公开(公告)日：2013-05-29

申请号：EP11809423.4

申请日：2011-07-08

Applicant: OSAKA Titanium Technologies Co., Ltd.

Inventor： YASUDA, Kouji ,  KIZAKI, Shingo ,  SHIMOSAKI, Shinji

IPC: H01M4/48 ,  H01G9/058 ,  H01M4/36

CPC classification number: H01M4/134 ,  H01G9/0425 ,  H01G11/06 ,  H01G11/30 ,  H01M4/131 ,  H01M4/366 ,  H01M4/485 ,  H01M4/625 ,  Y02E60/122 ,  Y02E60/13

Abstract: A negative electrode material powder for a lithium ion secondary battery having a conductive carbon film on the surface of a lower-silicon-oxide powder; wherein a specific surface area in BET measurement ranges from more than 0.3 m 2 /g to 40 m 2 /g, and no SiC peak appears at 2θ= 35.6°±0.01° or the half-value width of the appeared peak is 2° or more in XRD measurement using CuK α rays. The proportion of said carbon film preferably ranges from 0.2% to 2.5% by mass. Said powder preferably has 100000 Ωcm or less of specific resistance. In XRD, P2/P1 x and a value P2 of the strongest linear peak of Si (111) above the halo.
Accordingly, said powder can be used in the secondary battery with a large discharge capacity and a preferable cycle characteristics for practical use.

Abstract translation: 的负极材料粉末的较低氧化硅粉末的表面上形成具有导电性碳皮膜的锂离子二次电池; worin在BET测量范围从大于0.3米2 /克至40m 2 / g的比表面积，和没有的SiC峰2 = 35.6°±0.01°显示或该峰的半值宽度为2出现了 °或使用CuK更多在XRD测定±射线。 膜所述碳优选为0.2％至2.5质量％的比例。 所述粉末优选地具有100000©cm或更小的电阻率的。 在XRD，P2 / P1 <0.01是卤素以上的SiO x的卤素的最高值P1和Si（111）的最强峰线性的值P2之间优选地满足。 因此，所述粉末可以在二次电池中可使用具有大的放电容量和实际使用一个周期优选的特性。

公开(公告)号：EP2487135A1

公开(公告)日：2012-08-15

申请号：EP10821726.6

申请日：2010-10-04

Applicant: OSAKA Titanium Technologies Co., Ltd.

Inventor： KANNO, Hideaki ,  KIZAKI, Shingo

IPC: C01B33/113 ,  B65D81/24 ,  H01M4/48

CPC classification number: H01M4/62 ,  C01B33/113 ,  H01M4/131 ,  H01M4/485 ,  H01M10/0525

Abstract: Provided is SiO x , wherein the amount of generated H 2 O gas detected in a temperature range of 200 to 800°C in a temperature-programmed desorption gas analysis is 680 ppm or less. The amount of the generated H 2 O is desirably 420 ppm or less. In addition, in a graph obtained by X-ray diffraction, the peak intensity P1 at a Si peak point exhibited near 2θ = 28° and the base intensity P2 at a peak point interpolated from the gradient of average intensities in the fore and aft positions near the peak point desirably satisfy (P1-P2)/P2≤0.2. This SiO x is used as a vapor deposition material, whereby the generation of splashing is suppressed in forming a film, and a vapor-deposited film having excellent gas barrier properties can be formed. In addition, this SiO x is used as a negative electrode active material, whereby high initial efficiency of a lithium-ion secondary battery can be maintained.

Abstract translation: 提供为SiO X，worin生成量H 2中在升温脱附气体分析的温度范围200〜800℃的检测O气体为680 ppm以下。 所生成的H 2 O量优选为420 ppm以下。 另外，在通过X射线衍射，在接近2 = 28°呈现出Si峰点的峰强度P 1和在前后从平均强度的梯度内插的峰值点的碱强度P2获得的图 峰值点附近的位置希望满足（P1-P2）/P2‰¤0.2。 此的SiO x被用作蒸镀材料，由此飞溅的产生在形成膜被抑制，和气相沉积具有膜优异的气体阻挡性，可以形成。 另外，这种的SiO x被用作负电极活性材料，从而可以保持一个锂离子二次电池的高初始效率。

公开(公告)号：EP2618407A1

公开(公告)日：2013-07-24

申请号：EP11832271.8

申请日：2011-10-07

Applicant: OSAKA Titanium Technologies Co., Ltd.

Inventor： YASUDA, Kouji ,  FUJITA, Takehisa ,  KIZAKI, Shingo ,  SHIMOSAKI, Shinji

IPC: H01M4/48 ,  H01G9/058 ,  H01M4/36

CPC classification number: H01M4/386 ,  H01G11/24 ,  H01G11/50 ,  H01M4/366 ,  H01M4/483 ,  H01M4/5825 ,  H01M4/625 ,  H01M10/0525 ,  H01M2004/021 ,  Y02E60/13

Abstract: In a lithium ion secondary battery using a negative electrode material powder including a lower silicon oxide powder as a negative electrode material, a charge electric potential at 0.45-1.0 V relative to a Li reference upon initial charging results in a lithium ion secondary battery having a large discharge capacity with excellent cycle characteristics, which can be durable in practical use. On this occasion, the charge electric potential being 0.45-1.0 V relative to the Li reference upon initial charging means that an electric potential plateau caused by the generation of Li-silicate is observed, and the Li-silicate is uniformly generated in the negative electrode material. The negative electrode material powder according to the present invention having the charge electric potential of 0.45-1.0 V relative to the Li reference upon initial charging prevents the negative electrode material from being finely torn apart upon charging/discharging which results in cycle characteristic degradation, and excellent cycle characteristics are obtained. It is preferable for the negative electrode material powder according to the present invention to have an electrically conductive carbon film on the surface, and for the ratio of the electrically conductive carbon film to the surface of the powder to be 0.2-10 mass %.

Abstract translation: 在使用负极材料粉末包括下部的氧化硅粉末作为负极材料，在0.45-1.0 V相的电荷电位在锂离子具有二次电池在初始充电的结果的锂基准的锂离子二次电池 放电容量大，具有优异的循环特性，可在实际使用耐用。 在这种情况下，充电电势是相对于在初始充电bedeutet锂参考0.45-1.0 V，DASS在由硅酸锂的生成引起的电位高原-观察到的，和硅酸锂在负电极均匀地产生 材料。 的负极材料粉末gemäß到本发明的具有相对于在初始充电时的锂参考0.45-1.0 V的电荷电位被精细地撕开时的充电/放电，这导致劣化的循环特性，防止负电极材料，以及 优异的循环特性得到。 优选的是，负极材料粉末gemäß到本发明的具有在导电的碳薄膜的表面，并为导电性碳电影到粉末的表面的比例为0.2〜10质量％。

公开(公告)号：EP2581970A1

公开(公告)日：2013-04-17

申请号：EP11795367.9

申请日：2011-06-03

Applicant: OSAKA Titanium Technologies Co., Ltd.

Inventor： YASUDA, Kouji ,  KIZAKI, Shingo ,  SHIMOSAKI, Shinji

IPC: H01M4/48 ,  H01G9/058 ,  H01M4/36

CPC classification number: H01M4/134 ,  H01G11/06 ,  H01G11/42 ,  H01G11/50 ,  H01M4/131 ,  H01M4/1391 ,  H01M4/1395 ,  H01M4/36 ,  H01M4/38 ,  H01M10/052 ,  Y02E60/13

Abstract: Provided is a negative-electrode material powder used for a lithium-ion secondary battery having a large discharge capacity and sufficient cycle characteristics as being durable in use. The powder for the battery includes a conductive carbon film on a lower silicon oxide powder, surface and satisfies requirements that: Si in SiC is 15.1 wt% or less in content, or A3 (=A2-A1) is 15.1 or less, given A1 (wt%): Si content measured by acid solution process, and A2 (wt%): Si content measured by alkali solution process; and a specific resistance is 30,000 Ωcm or less. In the lower silicon oxide powder, a maximum value P1 of SiO x -derived halos appearing at 2θ=10° to 30° and a value P2 of the strongest line peak of Si (111) appearing at 2θ=28.4±0.3°, in XRD using CuKα beam, preferably satisfy P2/P1

Abstract translation: 提供的是用于具有大放电容量和足够的循环特性为在使用耐用的锂离子二次电池的负极材料粉末。 对于电池内的粉末包括在下部的氧化硅粉末，表面和SATIS外资企业要求的导电性碳电影的是：硅在SiC中是15.1％（重量）或更少的内容，或A3（= A2-A1）为1.15或更小，给出A1 （重量％）：Si含量由酸溶液处理测量，并且A2（重量％）：Si含量通过碱溶液处理的测量; 和比电阻为30,000©cm以下。 在较低的氧化硅粉末的SiO的极大值P1 X衍生的晕圈在2 = 10°露面至30°和Si中的2 = 28.4±0.3°亮相的最强线的峰（111）的值P2 在使用CuK±光束XRD，优选满足P2 / P1 <0.01。 焦油成分的含量优选为1ppm以上且4000 ppm以下。

公开(公告)号：EP2445038A1

公开(公告)日：2012-04-25

申请号：EP10789144.2

申请日：2010-04-21

Applicant: OSAKA Titanium Technologies Co., Ltd.

Inventor： KIZAKI, Shingo

IPC: H01M4/48 ,  C01B33/113 ,  H01M4/13

CPC classification number: H01M4/485 ,  C01B33/113 ,  H01M4/134 ,  H01M10/0525 ,  Y02E60/122

Abstract: Provided is a silicon oxide to be used for a negative electrode active material of a lithium-ion secondary battery, characterized in that : a g-value measured by an ESR spectrometer is in the range of not less than 2.0020 to not more than 2.0050; and given that A, B, and C are the area intensities of peaks near 420 cm -1 , 490 cm -1 and 520 cm -1 respectively in a Raman spectrum measured by a Raman spectroscopy, A/B is not less than 0.5 and C/B is not more than 2. The silicon oxide is used as a negative electrode active material, whereby a lithium-ion secondary battery having excellent cycle characteristic and initial efficiency in addition to high capacity can be obtained. The silicon oxide preferably has a spin density in the range of not less than 1×10 17 spins/g to not more than 5×10 19 spins/g. A negative electrode material for lithium-ion secondary battery contains not less than 20% by mass of this silicon oxide as a negative electrode active material.

Abstract translation: 提供一种用于锂离子二次电池的负极活性物质的氧化硅，其特征在于：由ESR光谱仪测定的g值在不小于2.0020〜2.0050的范围内; 并且A，B和C分别是通过拉曼光谱测量的拉曼光谱中分别在420cm -1，490cm -1和520cm -1附近的峰的面积强度，A / B不小于0.5， C / B为2以下。作为负极活性物质使用氧化硅，可以得到除了高容量以外，具有优异的循环特性和初期效率的锂离子二次电池。 氧化硅优选具有在不小于1×10 17自旋/ g至不大于5×10 19自旋/ g的范围内的自旋密度。 作为负极活性物质，作为锂离子二次电池用负极材料含有20质量％以上的氧化硅。

公开(公告)号：EP1795624B1

公开(公告)日：2012-04-25

申请号：EP05770381.1

申请日：2005-08-09

Applicant: OSAKA Titanium Technologies Co., Ltd.

Inventor： NISHIOKA, Kazuo ,  KIZAKI, Shingo

IPC: C23C14/24 ,  C01B33/037 ,  C01B33/113

CPC classification number: C01B33/113 ,  C23C14/10

Abstract: Disclosed is an SiO deposition material characterized by having a hydrogen gas content of not more than 50 ppm. By using such an SiO deposition material, occurrence of splash can be suppressed when SiO is deposited on a base, and there can be formed an SiO deposited film which is excellent in transparency and barrier properties. By carrying out degasification so that the hydrogen gas content of a raw material Si powder for the deposition material is not more than 10 ppm, the SiO deposition material having a hydrogen gas content of not more than 50 ppm can be produced highly efficiently at low cost. Consequently, this method for producing SiO can be widely applied to methods for producing deposition materials for packaging materials which have transparency and barrier properties and are used for foods, medical products, medicinal products and the like.