CN105556716A - 锂二次电池用正极活物质 - Google Patents

锂二次电池用正极活物质 Download PDF

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CN105556716A
CN105556716A CN201480037497.2A CN201480037497A CN105556716A CN 105556716 A CN105556716 A CN 105556716A CN 201480037497 A CN201480037497 A CN 201480037497A CN 105556716 A CN105556716 A CN 105556716A
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active material
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manganese
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宣良国
卢享周
尹诚晙
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Hanyang Hak Won Co Ltd
Industry University Cooperation Foundation IUCF HYU
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Abstract

本发明涉及锂二次电池用正极活物质，更详细地涉及一种新结构的锂二次电池用正极活物质，包括从中心向表面方向镍、锰及钴的浓度形成梯度的芯片部，并且，在所述芯片部的镍、锰及钴的浓度梯度至少具有一个顶点。

Description

锂二次电池用正极活物质
技术领域
本发明涉及锂二次电池用正极活物质，更详细地涉及包括从中心向表面方向镍、锰及钴的浓度形成梯度的2个芯片部，并且，所述2个芯片部的镍、锰及钴的浓度梯度的大小被调整的新结构的锂二次电池用正极活物质。
背景技术
锂二次电池的工作电压为3.7V以上，相比镉镍电池或镍氢电池，单位重量的能源密度高，因此，作为便携式电子信息通信设备的驱动动力源，增加了对于锂二次电池的需求。
最近，在美国、日本、欧洲等积极开展为了将内燃机关和锂二次电池进行混合(hybrid)，而作为电动汽车的动力源使用的研究。以美国为中心，正积极开展适用于一日行使少于60英里的汽车的混合动力电动汽车插头(P-HEV)电池开发。所述P-HEV用电池为具有几乎接近电动汽车的特性的电池，有关高容量电池的开发为有待解决的最大问题。尤其，最棘手的问题是开发具有2.0g/cc以上的高振实密度和230mAh/g以上的高容量特性的正极材料。
目前普遍化或正在开发的正极材料为LiCoO2、LiNiO2、LiMnO2、LiMn2O4、Li1+X[Mn2-xMx]O4、LiFePO4等。其中，LiCoO2为具有稳定的充放电特性、优秀的电子导电性、高电池电压、较高稳定性及平坦的放电电压特性的优良物质。但，Co的埋藏量少、价格高，并且，具有对人体有害的毒性，因此，需要开发其他正极材料。并且，因在充电时的脱锂，晶体结构不稳定，使得热特性非常恶劣。
为了改善上述问题，正试图进行将镍的一部分置换为转移金属元素，将发热初始温度向高温侧移动，或为了防止急剧的发热而将放热峰宽大(broad)。但，没有得到满意的结果。即，将镍的一部分置换为钴的LiNi1-xCoxO2(x＝0.1-0.3)物质，虽显示了优秀的充放电特性和寿命特性，但热稳定性问题尚未解决。并且，在欧洲专利第0872450号中，虽然公开了在Ni位置换成Co和Mn及其他金属的LiaCobMncMdNi1-(b+c+d)O2(M＝B、Al、Si、Fe、Cr、Cu、Zn、W、Ti、Ga)型，但仍然未能解决Ni系的热稳定性。
为了解决上述缺点，韩国专利公开第2005-0083869号中，提供了具有金属组成的浓度梯度的锂转移金属氧化物。该方法为先合成一定组成的内部物质后，在外部涂覆具有其他组成的物质，而制作成双重层后，与锂盐混合而进行热处理的方法。所述内部物质可使用在市场中销售的锂转移金属氧化物。
但，该方法在生成的内部物质与外部物质的组成之间，正极活物质的金属组成不连续地变化，并且，非连续、非渐进式地变化。并且，通过该发明合成的粉末，因不使用螯合剂即氨，振实密度低，所以，不适合作为锂二次电池用正极活物质使用。
为了改善上述问题，韩国专利公开第第2007-0097923号，提供了形成内部主体部和外部主体部，并在外部主体部金属成分根据位置形成连续的浓度分布的正极活物质。但，该方法中，在内部主体部形成固定的浓度，而只在外部主体部金属组成发生变化，因此，需开发在稳定性即容量方面更加优秀的新结构的正极活物质。
发明内容
发明要解决的问题
本发明为了解决如上述的以往技术的问题，其目的为提供一种包括镍、锰及钴的浓度形成梯度的芯片部，并且，所述芯片部的镍、锰及钴的浓度梯度表现顶点的新结构的的正极活物质。
解决问题的技术方案
本发明为了解决上述的问题，提供一种锂二次电池用正极活物质，其特征在于，包括从中心向表面方向镍、锰及钴的浓度形成梯度的芯片部，
并且，在所述芯片部的所述镍、锰及钴的浓度梯度分别至少具有一个顶点。
根据本发明，所述浓度梯度具有顶点指的是，浓度梯度具有从负值向正值或从正值向负值变化的顶点。例如，所述顶点为镍的浓度从中心向表面方向增加并开始逐渐减少的地点或镍的浓度从中心向表面方向减少并逐渐增加的地点。
或，根据本发明，所述顶点为浓度梯度一开始为(+)，然后开始浓度逐渐固定的地点。例如，镍的浓度从中心向表面方向增加并开始逐渐固定地维持的地点或镍的浓度从中心向表面方向减少并开始固定地维持的地点。
根据本发明的正极活物质，所述芯片部，包括：第1芯片部，所述镍、锰及钴的浓度梯度大小分别为CS1-Ni、CS1-Mn、CS1-Co；及第2芯片部，所述镍、锰及钴的浓度梯度大小分别为CS2-Ni、CS2-Mn、CS2-Co，其中，所述第1芯片部的镍的浓度梯度大小CS1-Ni和所述第2芯片部的镍的浓度梯度大小CS2-Ni满足下列关系式(CS1-Ni)*(CS2-Ni)<0。
即，根据本发明的正极活物质，在所述第1芯片部，如果镍的浓度梯度大小为正值时，所述第2芯片部的镍之间的的浓度梯度大小调节为负值；如果在所述第1芯片部镍的浓度梯度大小为负值时，所述第2芯片部的镍的浓度梯度大小调节为正值。
根据本发明的正极活物质，所述第1芯片部的锰的浓度梯度大小CS1-Mn和所述第2芯片部的锰的浓度梯度大小CS2-Mn满足下列关系式(CS1-Mn)*(CS2-Mn)<0。
即，根据本发明的正极活物质，在所述第1芯片部锰的浓度梯度大小为正值时，所述第2芯片部的锰的浓度梯度大小调节为负值，在所述第1芯片锰的浓度梯度大小为负值时，所述第2芯片部的锰的浓度梯度大小调节为正值。
根据本发明的正极活物质，所述第1芯片部的钴的浓度梯度大小CS1-Co和所述第2芯片部的钴的浓度梯度大小CS2-Co满足下列关系式(CS1-Co)*(CS2-Co)<0。
即，根据本发明的正极活物质，在所述第1芯片部钴的浓度梯度大小为正值时，所述第2芯片部的钴的浓度梯度大小调整为负值，在所述第1芯片部钴的浓度梯度大小为负值时，所述第2芯片部的钴的浓度梯度大小调节为正值。
根据本发明的正极活物质，在所述第1芯片部和所述第2芯片部之间还包括镍、锰及钴的浓度固定的第1浓度维持部。
根据本发明的正极活物质，所述芯片部还包括在所述第1芯片部的中心方向内侧镍、锰及钴的浓度固定的第2浓度维持部。
根据本发明的正极活物质，在所述芯片部的外周面还包括镍、锰及钴的浓度固定的外壳部。
根据本发明的正极活物质，所述外壳部，包括：第1外壳部，镍、锰及钴的浓度以SC1-Ni、SC1-Mn、SC1-Co固定；及第2外壳部，镍、锰及钴的浓度分别以SC2-Ni、SC2-Mn、SC2-Co固定。
根据本发明的正极活物质，所述外壳部的体积为整体体积的30％以下。
本发明提供一种包括根据本发明的正极活物质的锂二次电池。
发明的效果
根据本发明的正极活物质调整镍、锰、钴形成浓度梯度的2个芯片部的浓度梯度，从而，寿命特性和充放电特性优秀，既能够表现高容量，也使得晶体结构稳定化，而在以高电压使用时也能够表现结构稳定性。
附图说明
图1表示有关本发明的一实施例及比较例中制造的活物质的截面的EDX测定结果；
图2及图3表示对于包含本发明的一实施例及比较例中制造的活物质的电池的充放电特性及寿命特性的测定结果。
具体实施方式
以下根据实施例更详细地说明本发明。但，本发明并非限定于以下的实施例。
<实施例>
向共沉淀反应器(容量16L，旋转马达的功率80W以上)投入蒸馏水2.5升后，向反应器以2升/分钟的速度供应N2气体，并使得反应器的温度维持45℃，以400rpm搅拌。
将硫酸镍、硫酸钴及硫酸锰组成以NiX1Coy1Mnz1OH2(x1,y1,z1)混合的第1金属水溶液和以NiX2Coy2Mnz2OH2(x2,y2,z2)混合的第2金属水溶液的混合比率从0至100更换并混合并将其以0.7升/小时，又将25mol浓度的氨溶液以0.07升/小时，向反应器连续性投入，而制造了具有浓度梯度的芯片部。并且，为了调整pH，供应5mol浓度的氢氧化钠溶液，使得pH维持11.5。叶轮速度调整为400rpm。
向所述第2金属水溶液供应硫酸镍、硫酸钴及硫酸锰的浓度以NiX3Coy3Mnz3OH2固定的第3金属水溶液，并且，将对于所述第2金属水溶液的第3金属水溶液的混合比率从0至100更换混合而供应，而制造第2芯片部，当形成所需厚度的第2芯片部之后，只供应所述第3金属水溶液，而形成所述第2芯片部的最终浓度和浓度固定的外壳部，制造了金属复合氢氧化物。
实施例1至3中，所述金属水溶液的浓度如下表1。
【表1】
将制造的金属复合氢氧化物进行过滤，用水洗涤后，在110℃暖风干燥机干燥了12小时。将所述金属复合氢氧化物和氢氧化锂(LiOH)以1:1摩尔比混合后，以2℃/min的升温速度加热，之后在450℃下维持10小时，进行了预烧成，然后，在700～900℃下烧成10小时，获得了正极活物质粉末。
<实施例>
如所述实施例制造第1芯片部后，更换第2金属水溶液和所述第3金属水溶液的混合比率进行混合而制造第2芯片部，然后，单独供应硫酸镍、硫酸钴及硫酸锰的浓度以NiX4Coy4Mnz4OH2固定的第4金属水溶液，制造了外壳部。
如上述制造的实施例4及5中，所述金属水溶液的浓度如下表2。
【表2】
将制造的金属复合氢氧化物进行过滤，用水洗涤后，在110℃暖风干燥机干燥了12小时。将所述金属复合氢氧化物和氢氧化锂(LiOH)以1:1摩尔比混合后，以2℃/min的升温速度加热，之后在450℃下维持10小时，进行了预烧成，然后，在700～900℃下烧成10小时，获得了正极活物质粉末。
<比较例>
作为比较例1，供应以相当于所述实施例2的粒子整体平均组成的Ni70Co9Mn21OH2表示的金属水溶液，制造了在粒子整体浓度固定的粒子。
除了在所述实施例2中无第1芯片部之外，与所述实施例2相同地制造了粒子，并作为比较例2。
作为比较例3，供应以相当于所述实施例4的粒子整体平均组成的Ni60Co15Mn25OH2表示的金属水溶液，制造了在粒子整体浓度固定的粒子。
<实验例>EDX照片测定
以EDX测定了从所述实施例21中制造的粒子的中心的距离的Ni、Mn、Co的浓度，并将其结果表示在图1。
图1中，根据本发明的实施例的粒子，第1芯片部的金属的浓度梯度大小和第2芯片部的金属的浓度梯度的大小发生逆转。
<实验例>充放电特性，寿命特性及DSC测定
测定了包括在所述实施例1至5及比较例1至3中制造的活物质的电池的充放电特性、寿命特性及DSC特性，并表示在下表3及图2、图3中。
【表3】
放电容量 寿命特性 DSC
实施例 208.3mAh/g 94.7％ 273.5℃
实施例 199.7mAh/g 95.0％ 280.7℃
实施例 194.8mAh/g 95.6％ 288.9℃
实施例 187.6mAh/g 96.3％ 296.3℃
实施例 205.9mAh/g 95.2％ 281.6℃
比较例 185.3mAh/g 88.8％ 268.2℃
比较例 195.9mAh/g 95.2％ 283.5℃
比较例 178.7mAh/g 91.2％ 267.6℃
图2、图3中可确认根据本发明的实施例制造的活物质相比比较例的活物质的容量得到较大改善，寿命特性大幅改善至100个循环。
工业上的可利用性
根据本发明的正极活物质调整镍、锰、钴形成浓度梯度的2个芯片部的浓度梯度，从而，寿命特性和充放电特性优秀，既能够表现高容量，也使得晶体结构稳定化，而在以高电压使用时也能够表现结构稳定性。

Claims (10)

1.一种锂二次电池用正极活物质，其特征在于，
包括从中心向表面方向镍、锰及钴的浓度形成梯度的芯片部，
并且，在所述芯片部的所述镍、锰及钴的浓度梯度至少具有一个顶点。
2.根据权利要求1所述的锂二次电池用正极活物质，其特征在于，
所述芯片部，包括：
第1芯片部，所述镍、锰及钴的浓度梯度大小分别为CS1-Ni、CS1-Mn、CS1-Co；及
第2芯片部，所述镍、锰及钴的浓度梯度大小分别为CS2-Ni、CS2-Mn、CS2-Co，
其中，所述第1芯片部的镍的浓度梯度大小CS1-Ni和所述第2芯片部的镍的浓度梯度大小CS2-Ni满足下列关系式
(CS1-Ni)*(CS2-Ni)<0。
3.根据权利要求1所述的锂二次电池用正极活物质，其特征在于，
所述第1芯片部的锰的浓度梯度大小CS1-Mn和所述第2芯片部的锰的浓度梯度大小CS2-Mn满足下列关系式
(CS1-Mn)*(CS2-Mn)<0。
4.根据权利要求1所述的锂二次电池用正极活物质，其特征在于，
所述第1芯片部的钴的浓度梯度大小CS1-Co和所述第2芯片部的钴的浓度梯度大小CS2-Co满足下列关系式
(CS1-Co)*(CS2-Co)<0。
5.根据权利要求1所述的锂二次电池用正极活物质，其特征在于，
在所述第1芯片部和所述第2芯片部之间还包括镍、锰及钴的浓度固定的第1浓度维持部。
6.根据权利要求1所述的锂二次电池用正极活物质，其特征在于，
所述芯片部还包括在所述第1芯片部的中心方向内侧镍、锰及钴的浓度固定的第2浓度维持部。
7.根据权利要求1所述的锂二次电池用正极活物质，其特征在于，
在所述芯片部的外周面还包括镍、锰及钴的浓度固定的外壳部。
8.根据权利要求1所述的锂二次电池用正极活物质，其特征在于，
所述外壳部，包括：
第1外壳部，镍、锰及钴的浓度以SC1-Ni、SC1-Mn、SC1-Co固定；及
第2外壳部，镍、锰及钴的浓度分别以SC2-Ni、SC2-Mn、SC2-Co固定。
9.根据权利要求1所述的锂二次电池用正极活物质，其特征在于，
所述外壳部的体积为整体体积的30％以下。
10.一种包括权利要求1至9中某一项的锂二次电池用正极活物质的锂二次电池。
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Families Citing this family (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160049648A1 (en) * 2013-04-29 2016-02-18 Iucf-Hyu (Industry-University Cooperation Foundation Hanyang University) Positive electrode active material and secondary battery comprising the same
KR101611251B1 (ko) * 2014-10-29 2016-04-12 한양대학교 산학협력단 양극활물질, 및 이를 포함하는 이차 전지
CN107004851A (zh) * 2014-12-31 2017-08-01 北京当升材料科技股份有限公司 锂离子电池用梯度结构的多元材料、其制备方法、锂离子电池正极以及锂离子电池
KR20160081545A (ko) * 2014-12-31 2016-07-08 주식회사 에코프로 양극활물질 및 이의 제조 방법
KR101953155B1 (ko) * 2014-12-31 2019-02-28 주식회사 에코프로비엠 농도 구배를 나타내는 리튬 이차전지용 양극활물질 전구체 및 양극활물질을 제조하는 방법, 및 이에 의하여 제조된 농도 구배를 나타내는 리튬 이차전지용 양극활물질 전구체 및 양극활물질
KR102355196B1 (ko) * 2015-01-26 2022-01-24 에스케이온 주식회사 리튬 이차 전지용 양극 활물질, 이를 포함하는 양극 및 리튬 이차 전지
KR102460961B1 (ko) * 2015-11-06 2022-10-31 삼성에스디아이 주식회사 리튬이차전지용 양극 활물질, 그 제조방법 및 이를 포함한 양극을 구비한 리튬이차전지
KR102521323B1 (ko) 2015-12-09 2023-04-13 에스케이온 주식회사 리튬이차전지
KR102580002B1 (ko) 2016-01-13 2023-09-19 에스케이온 주식회사 리튬 이차 전지
KR102516459B1 (ko) * 2016-04-08 2023-04-04 한양대학교 산학협력단 양극활물질, 그 제조 방법, 및 이를 포함하는 리튬이차전지
WO2017188802A1 (ko) * 2016-04-29 2017-11-02 한양대학교 산학협력단 양극활물질, 그 제조 방법, 및 이를 포함하는 리튬이차전지
US10522828B2 (en) * 2016-05-26 2019-12-31 Iucf-Hyu (Industry-University Cooperation Foundation Hanyang University) Positive active material for rechargeable sodium battery, and method of fabricating the same
PL3279979T3 (pl) * 2016-08-02 2021-12-20 Ecopro Bm Co., Ltd. Złożony tlenek litu dla dodatniego materiału aktywnego baterii wtórnej i sposób jego wytwarzania
US10199650B2 (en) * 2016-11-18 2019-02-05 Sk Innovation Co., Ltd. Lithium secondary battery and method of fabricating the same
KR102025190B1 (ko) 2016-12-22 2019-09-25 주식회사 포스코 양극 활물질, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지
WO2018135253A1 (ja) * 2017-01-20 2018-07-26 Ｎｅｃエナジーデバイス株式会社 正極活物質、正極およびリチウムイオン二次電池
CN111052458A (zh) * 2017-08-30 2020-04-21 微宏动力系统（湖州）有限公司 锂离子阴极颗粒的制备方法以及由此形成的阴极活性材料
KR102448292B1 (ko) 2017-09-21 2022-09-28 삼성에스디아이 주식회사 배터리 팩 진단 장치
KR102306545B1 (ko) * 2017-10-19 2021-09-30 주식회사 엘지에너지솔루션 리튬 이차전지용 양극재, 이의 제조방법, 이를 포함하는 리튬 이차전지용 양극 및 리튬 이차전지
KR102268079B1 (ko) 2017-11-21 2021-06-23 주식회사 엘지화학 이차전지용 양극 활물질, 그 제조방법 및 이를 포함하는 리튬 이차전지
KR102041578B1 (ko) 2017-12-08 2019-11-06 주식회사 포스코 리튬 이차 전지용 양극 활물질 및 이를 포함하는 리튬 이차 전지
KR102016156B1 (ko) * 2017-12-13 2019-08-29 성균관대학교 산학협력단 이차전지 양극 활물질용 전구체, 이의 제조 방법 및 이를 이용한 이차전지용 양극 활물질의 제조 방법
KR102429236B1 (ko) 2018-01-05 2022-08-05 주식회사 엘지에너지솔루션 이차전지용 양극 활물질, 그 제조방법 및 이를 포함하는 리튬 이차전지
KR102313091B1 (ko) 2018-01-19 2021-10-18 주식회사 엘지화학 리튬 이차전지용 양극 활물질, 이의 제조방법, 이를 포함하는 리튬 이차전지용 양극 및 리튬 이차전지
JP7021366B2 (ja) * 2018-03-28 2022-02-16 ユミコア 充電式リチウム二次電池用正極活物質としてのリチウム遷移金属複合酸化物
US11349118B2 (en) 2018-09-24 2022-05-31 Uchicago Argonne, Llc Tangent gradient concentration material for battery, digital gradient concentration material for battery
CN109411718B (zh) * 2018-09-28 2021-07-20 佛山市德方纳米科技有限公司 掺杂改性的三元正极材料的制备方法
US10978741B2 (en) 2019-02-04 2021-04-13 Uchicago Argonne, Llc Non-aqueous electrolytes for electrochemical cells
KR20210141785A (ko) * 2019-04-12 2021-11-23 캠엑스 파워 엘엘씨 대용량의, 온도 범위 확장 가능하고, 과충전 및 방전 오용 관용성이 높은 재충전식 배터리 전지 및 팩
US11165065B2 (en) 2019-04-12 2021-11-02 Camx Power Llc High power, extended temperature range-capable, highly abuse overcharge and discharge tolerant rechargeable battery cell and pack
US11309544B2 (en) 2019-04-12 2022-04-19 Camx Power Llc High power, extended temperature range-capable, highly abuse overcharge and discharge tolerant rechargeable battery cell and pack
CN111224093B (zh) * 2019-10-12 2022-05-27 南方科技大学 具有锰浓度梯度的电极材料及其制备方法和钠离子电池
KR102213787B1 (ko) * 2019-10-18 2021-02-08 주식회사 에코프로비엠 양극 활물질 및 이를 포함하는 리튬 이차전지
KR20220036072A (ko) * 2020-09-15 2022-03-22 에스케이온 주식회사 리튬 이차 전지용 양극 활물질 및 이를 포함하는 리튬 이차 전지
KR102502591B1 (ko) * 2020-12-21 2023-02-23 포스코홀딩스 주식회사 양극 활물질 및 이를 포함하는 리튬 이차 전지
KR20230166448A (ko) 2022-05-31 2023-12-07 서울대학교산학협력단 리튬이차전지용 양극 활물질, 이의 제조방법, 이를 포함하는 리튬이차전지용 양극 및 리튬이차전지

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102368548A (zh) * 2011-10-31 2012-03-07 上海中兴派能能源科技有限公司 改性三元材料、其前驱体及该材料和前驱体的制备方法
KR20120079802A (ko) * 2011-01-05 2012-07-13 한양대학교 산학협력단 입자 전체 농도 구배 리튬이차전지 양극활물질, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지
KR20130001703A (ko) * 2011-06-27 2013-01-04 주식회사 에코프로 양극활물질, 상기 양극활물질을 포함하는 리튬 이차 전지 및 상기 리튬 이차 전지를 전기화학적으로 활성화시키는 방법
CN102891309A (zh) * 2012-09-22 2013-01-23 湘潭大学 一种浓度渐变的球形富锂正极材料及其制备方法

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1055802A (ja) * 1996-06-06 1998-02-24 Furukawa Battery Co Ltd:The アルカリ二次電池の電極およびその製造方法
US6040090A (en) 1997-04-15 2000-03-21 Sanyo Electric Co., Ltd. Positive electrode material for use in non-aqueous electrolyte battery, process for preparing the same, and non-aqueous electrolyte battery
KR100326460B1 (ko) * 2000-02-10 2002-02-28 김순택 리튬 이차 전지용 양극 활물질 및 그의 제조 방법
KR100399642B1 (ko) * 2001-10-24 2003-09-29 삼성에스디아이 주식회사 리튬 이차 전지용 양극 활물질 및 그 제조방법
KR100809847B1 (ko) 2002-10-31 2008-03-04 주식회사 엘지화학 금속성분의 조성에 구배를 갖는 리튬 전이금속 산화물
US20060057019A1 (en) * 2004-09-16 2006-03-16 Kwo Young Hydrogen storage alloys having reduced PCT hysteresis
KR100822012B1 (ko) 2006-03-30 2008-04-14 한양대학교 산학협력단 리튬 전지용 양극 활물질, 그 제조 방법 및 그를 포함하는리튬 이차 전지
KR100752703B1 (ko) * 2006-06-29 2007-08-29 한양대학교 산학협력단 리튬 이차 전지용 양극 활물질, 그 제조 방법 및 그를사용한 리튬 이차 전지
JP5589536B2 (ja) * 2009-09-09 2014-09-17 ソニー株式会社 正極活物質、正極、非水電解質電池および正極活物質の製造方法
KR101206651B1 (ko) * 2009-09-10 2012-11-29 주식회사 엘앤에프신소재 성능이 우수한 리튬 이차 전지용 양극활물질, 그 제조방법 및 이를 포함하는 리튬 이차 전지
CN102612775B (zh) * 2009-11-05 2015-03-11 尤米科尔公司 双壳芯型锂镍锰钴氧化物
KR101185366B1 (ko) * 2010-01-14 2012-09-24 주식회사 에코프로 회분식 반응기(batch reactor)를 사용하여 농도구배층을 가지는 리튬 이차 전지용 양극활물질 전구체 및 양극활물질을 제조하는 방법
KR101215829B1 (ko) * 2010-07-22 2012-12-27 주식회사 에코프로 리튬 이차전지용 양극활물질의 제조방법, 그에 의하여 제조된 리튬 이차전지용 양극활물질 및 그를 이용한 리튬 이차전지
KR101350811B1 (ko) * 2010-11-17 2014-01-14 한양대학교 산학협력단 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지
WO2014178624A1 (ko) * 2013-04-29 2014-11-06 한양대학교 산학협력단 리튬 이차 전지용 양극활물질
CA2831756A1 (en) * 2011-03-31 2012-10-04 Toda Kogyo Corporation Positive electrode active substance particles for non-aqueous electrolyte secondary batteries and process of production thereof
ES2661935T3 (es) * 2011-04-14 2018-04-04 Toda Kogyo Corp. Polvo de partículas de óxido de un compuesto de li-ni y proceso para la producción del mismo y batería secundaria de electrolito no acuoso
KR101316053B1 (ko) * 2011-04-26 2013-10-11 국립대학법인 울산과학기술대학교 산학협력단 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지
JP2012238581A (ja) * 2011-04-28 2012-12-06 Nichia Chem Ind Ltd 非水電解液二次電池用正極活物質
WO2013002559A2 (ko) * 2011-06-27 2013-01-03 주식회사 에코프로 양극활물질, 상기 양극활물질을 포함하는 리튬 이차 전지 및 상기 리튬 이차 전지를 전기화학적으로 활성화시키는 방법
KR101452029B1 (ko) * 2011-09-20 2014-10-23 주식회사 엘지화학 고용량 양극활물질 및 이를 포함하는 리튬이차전지
EP2833446B1 (en) * 2012-03-31 2017-08-23 IUCF-HYU (Industry-University Cooperation Foundation Hanyang University) Method for preparing cathode active material precursor for lithium secondary battery and cathode active material precursor for lithium secondary battery prepared thereby
CN105378985B (zh) * 2013-05-31 2019-03-01 汉阳大学校产学协力团 锂电池用正极活性物质及其制造方法
CN103441293B (zh) * 2013-08-30 2015-04-22 哈尔滨工业大学 一种利用固体氧化物燃料电池中元素高温扩散的方法制备阳极/电解质半电池的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120079802A (ko) * 2011-01-05 2012-07-13 한양대학교 산학협력단 입자 전체 농도 구배 리튬이차전지 양극활물질, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지
KR20130001703A (ko) * 2011-06-27 2013-01-04 주식회사 에코프로 양극활물질, 상기 양극활물질을 포함하는 리튬 이차 전지 및 상기 리튬 이차 전지를 전기화학적으로 활성화시키는 방법
CN102368548A (zh) * 2011-10-31 2012-03-07 上海中兴派能能源科技有限公司 改性三元材料、其前驱体及该材料和前驱体的制备方法
CN102891309A (zh) * 2012-09-22 2013-01-23 湘潭大学 一种浓度渐变的球形富锂正极材料及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZONGHAI CHEN ET.AL.: ""Advanced cathode materials for lithium-ion batteries"", 《MRS BULLETIN》 *

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