CN102870257A - 二次电池用正极活性材料 - Google Patents
二次电池用正极活性材料 Download PDFInfo
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- CN102870257A CN102870257A CN201180021842XA CN201180021842A CN102870257A CN 102870257 A CN102870257 A CN 102870257A CN 201180021842X A CN201180021842X A CN 201180021842XA CN 201180021842 A CN201180021842 A CN 201180021842A CN 102870257 A CN102870257 A CN 102870257A
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- China
- Prior art keywords
- positive electrode
- electrode active
- active materials
- battery
- lithium
- Prior art date
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Links
- 239000006182 cathode active material Substances 0.000 title abstract 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- 150000003624 transition metals Chemical class 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 17
- 239000011149 active material Substances 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- -1 halogens such as F Chemical class 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 230000004087 circulation Effects 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000011572 manganese Substances 0.000 description 9
- 239000011255 nonaqueous electrolyte Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004020 conductor Substances 0.000 description 7
- 239000005696 Diammonium phosphate Substances 0.000 description 6
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- 230000004888 barrier function Effects 0.000 description 6
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 6
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 150000004862 dioxolanes Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
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- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- HLXZNVUGXRDIFK-UHFFFAOYSA-N nickel titanium Chemical compound [Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni] HLXZNVUGXRDIFK-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
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- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种二次电池用正极活性材料，其包含具有含锂的过渡金属层的至少一种化合物，所述化合物选自下式1的化合物：Li(Li3x±yM1-yPx)O2+z (1)，其中M是对六配位结构稳定的元素，其为选自属于第一周期元素和第二周期元素的过渡金属中的至少一种元素；0<x<0.1；0<y<0.3；-4x<z≤4x；且在3x-y的情况下满足3x>y。
Description
技术领域
本发明涉及二次电池用正极活性材料。更具体地，本发明涉及具有长寿命和优异存储性能并基于特定的元素组成而发挥优异安全性的二次电池用正极活性材料。
背景技术
移动装置的技术开发和需求的增加，导致对作为能源的二次电池的需求快速增加。在这些二次电池中，具有高能量密度和电压、长寿命和低自放电的锂二次电池可商购获得并被广泛使用。
另外，对环境问题的关注的增加引起了与电动车辆(EV)和混合电动车辆(HEV)相关的大量研究，所述电动车辆(EV)和混合电动车辆(HEV)作为使用化石燃料的车辆如汽油车辆和柴油车辆的替代品，所述使用化石燃料的车辆是空气污染的主要因素。这些电动车辆通常将镍-金属氢化物(Ni-MH)二次电池用作电动车辆(EV)、混合电动车辆(HEV)等的电源。然而，目前正在进行与使用具有高能量密度和放电电压的锂二次电池相关的大量研究且其一部分可商购获得。
特别地，用于电动车辆的锂二次电池应具有高能量密度，在短时间内展示大功率并在苛刻条件下可使用10年以上，由此与常规小锂二次电池相比，需要上述二次电池具有显著优越的稳定性和长寿命。
常规锂二次电池通常将具有层状结构的锂钴复合氧化物用于正极并将石墨基材料用于负极。然而，考虑到存在极昂贵的钴作为主要元素和低安全性，不利地，这种锂钴复合氧化物不适用于电动车辆。因此，具有尖晶石结构并含有廉价且具有优异安全性的锰的锂锰复合氧化物适合用作电动车辆用锂离子二次电池的正极。
然而，由于在高温下存储时因电解质的影响而将锰释放入电解质中，所以锂锰复合氧化物造成电池性能劣化。因此，需要解决该现象的方案。另外，与常规锂钴复合氧化物或锂镍复合氧化物相比，锂锰复合氧化物具有单位重量的容量低的劣势，由此单位电池重量的容量的增加受到限制。为了使得锂锰复合氧化物在实际上可用作电动车辆的电源，应将所述锂锰复合氧化物与能够解决该现象的电池设计组合使用。
为了解决这些劣势，使用层状混合金属氧化物LiNixMnyCozO2(x+y+z=1)等，但它们尚不能确保良好的稳定性。为了解决该劣势，尝试进行表面处理，但由于需要其他加工而导致产生诸如价格提高的问题，所述问题是在电池市场如电动车辆中最重要的问题之一。
发明内容
技术问题
因此，为了解决上述问题和尚未解决的其他技术问题而完成了本发明。
作为为了解决上述问题而进行的各种广泛且细致的研究和实验的结果，本发明的发明人已经发现，当使用具有式1的化合物中所示的特定元素组成并包含含锂的过渡金属层的正极活性材料制造正极并基于所述正极制造二次电池时，能够在不使用其他工艺的条件下大大提高寿命。基于该发现，完成了本发明。
技术方案
根据本发明的一个方面，提供一种二次电池用正极活性材料，其包含具有含锂的过渡金属层的化合物作为选自下式1中的至少一种化合物：
Li(Li3x±yM1-yPx)O2+z (1)
其中M是对六配位结构稳定的元素，其为选自属于第一周期元素和第二周期元素的过渡金属中的至少一种元素；
0<x<0.1；
0<y<0.3；
-4x<z≤4x；且
在3x-y的情况下满足3x>y的方程式。
根据本发明的正极活性材料，基于在元素组成中含有的P的强结合力和由存在于过渡金属层中的Li(锂)导致的氧化数的变化，通过稳定晶体结构而展示了活性材料的改进的循环性能和存储性能。
当P的含量过高时，其抑制正极活性材料的结晶且可能难以提高活性材料的性能。如上文所限定的，所述含量优选低于0.1，更优选0<x≤0.05。
另外，当Li在过渡金属层中的含量过高时，会造成容量劣化。因此，限定的含量范围是优选的，且0.015≤3x≤y≤0.3是更优选的。
通过在元素组成中含有P，氧(O)的含量可在所述范围内变化，即-4x<z≤4x。
式1的M是满足上述条件的过渡金属，且可以是选自Ni、Mn、Co、Cr、Fe、V、Zr等中的一种或多种元素，所述正极活性材料优选含有Ni和Mn作为必要元素，并含有Co作为任选元素。在此情况下，Ni、Mn和Co的含量满足下式2的方程式。
M=NiaMnbCoc (2)
其中0.10<a<0.85，0.10<b<0.85，0≤c<0.5。
在某些情况下，少量过渡金属(M)可以被具有六配位结构的金属或非金属元素如Al、Mg或B置换。在此情况下，基于过渡金属(M)的总量，置换量优选为0.2摩尔以下。
另外，可以通过其他阴离子如卤素元素如F、Cl、Br和I；硫；硫属元素；氮等对氧(O)进行置换。在此情况下，基于氧(O)的总量，置换量优选为0.1摩尔以下。
基于式子的组成，可通过本领域中熟知的方法制备根据本发明的正极活性材料。
例如，通过利用诸如共沉淀的各种方法制备混合过渡金属前体，向其中添加锂化合物如氢氧化锂和碳酸锂以及磷化合物如磷酸二铵并对制得的化合物进行焙烧，可制备正极活性材料。
或者，例如，通过在制备混合过渡金属前体的过程中添加磷化合物如磷酸二铵以制备含有磷(P)成分的混合过渡金属前体，并将所述前体与锂化合物一起进行焙烧，可制备正极活性材料。
本发明还提供包含所述正极活性材料的二次电池用正极。
除了式1的化合物之外，所述正极可还含有普通锂过渡金属氧化物作为正极活性材料。所述普通锂过渡金属氧化物包括含有Ni、Co和Mn中的一种元素的氧化物以及含有其两种以上元素的氧化物，且其实例包括本领域中已知的锂过渡金属氧化物。在此情况下，基于所述活性材料的总量，式1的化合物可以以至少30重量%以上的量、优选50重量%以上的量存在。
通过将正极混合物与溶剂如水或NMP进行混合以制备浆料，并将浆料涂布在正极集电体上，随后进行干燥和压制，可制备根据本发明的正极。
所述正极混合物可任选地含有选自粘度控制剂和填料中的至少一种物质。
通常将正极集电体制成具有3～500μm的厚度。所述正极集电体没有特别限制，只要其具有合适的导电性而不会在制造的电池中造成不利的化学变化即可。正极集电体的实例包括不锈钢；铝；镍；钛；烧结碳；和利用碳、镍、钛或银表面处理过的铝或不锈钢。如果需要，还可对这些集电体进行加工而在其表面上形成细小的不规则，从而提高对正极活性材料的粘合强度。另外，可以以包括膜、片、箔、网、多孔结构、泡沫和无纺布的各种形式使用所述集电体。
基于包含正极活性材料的混合物的总重量，通常以0.01～30重量%的量添加所述导电材料。可以使用任意导电材料而没有特别限制，只要其具有合适的导电性而不会在电池中造成不利的化学变化即可。导电材料的实例包括导电材料，包括：石墨；碳黑如碳黑、乙炔黑、科琴黑、槽法碳黑、炉黑、灯黑和热裂法碳黑；导电纤维如碳纤维和金属纤维；金属粉末如氟化碳粉末、铝粉末和镍粉末；导电晶须如氧化锌和钛酸钾；导电金属氧化物如二氧化钛；和聚亚苯基衍生物。
粘合剂为提高电极活性材料对导电材料和集电体的粘合的成分。基于包含正极活性材料的混合物的总重量，通常以1～30重量%的量添加所述粘合剂。粘合剂的实例包括聚乙二烯、聚乙烯醇、羧甲基纤维素(CMC)、淀粉、羟丙基纤维素、再生纤维素、聚乙烯基吡咯烷酮、四氟乙烯、聚乙烯、聚丙烯、乙烯丙烯二烯三元共聚物(EPDM)、磺化的EPDM、丁苯橡胶、氟橡胶和各种共聚物。
粘度控制剂对电极混合物的粘度进行控制，从而促进电极混合物的混合并将其涂布到集电体上且基于电极混合物的总重量，可以以30重量%的量添加其。粘度控制剂的实例包括但不限于，羧甲基纤维素、聚丙烯酸和聚偏二氟乙烯。如果需要，所述溶剂也可以充当粘度控制剂。
填料为用于抑制电极膨胀而任选使用的成分。可使用任何填料而没有特别限制，只要其不会在制造的电池中造成不利的化学变化且为纤维状材料即可。填料的实例包括烯烃聚合物如聚乙烯和聚丙烯；以及纤维状材料如玻璃纤维和碳纤维。
本发明还提供一种包含正极、负极、隔膜和含锂盐的非水电解质的锂二次电池。
例如，通过将包含负极活性材料的负极混合物涂布到负极集电体上，随后进行干燥，可制备负极。如果需要，所述负极混合物可包含上述成分即导电材料、粘合剂和填料。
通常将负极集电体制成具有3～500μm的厚度。所述负极集电体没有特别限制，只要其具有合适的导电性而不会在制造的电池中造成不利的化学变化即可。负极集电体的实例包括铜；不锈钢；铝；镍；钛；烧结碳；和利用碳、镍、钛或银表面处理过的铜或不锈钢；以及铝-镉合金。与正极集电体类似，如果需要，还可对这些集电体进行加工而在其表面上形成细小的不规则，从而提高对负极活性材料的粘合强度。另外，可以以包括膜、片、箔、网、多孔结构、泡沫和无纺布的各种形式使用所述集电体。
所述负极活性材料的实例包括碳和石墨材料如天然石墨、人造石墨、膨胀石墨、碳纤维、硬碳、碳黑、碳纳米管、二萘嵌苯、活性炭；可与锂形成合金的金属如Al、Si、Sn、Ag、Bi、Mg、Zn、In、Ge、Pb、Pd、Pt和Ti以及含有这些元素的化合物；碳和石墨材料与金属及其化合物的复合材料；和含锂的氮化物。其中，更优选碳基活性材料、硅基活性材料、锡基活性材料或硅-碳基活性材料。所述材料可单独或以其两种以上组合的方式使用。
隔膜插入在所述正极与所述负极之间。作为隔膜，使用具有高离子渗透率和机械强度的绝缘薄膜。所述隔膜典型地具有0.01～10μm的孔径和5～300μm的厚度。作为隔膜，使用由烯烃聚合物如聚丙烯和/或玻璃纤维或聚乙烯制成的片或无纺布，其具有耐化学性和疏水性。当使用诸如聚合物的固体电解质作为电解质时，所述固体电解质还可以充当隔膜和电解质两者。
所述含锂盐的非水电解质由非水电解质和锂盐构成。作为所述非水电解质，可利用非水电解质溶液、有机固体电解质和无机固体电解质。
能够用于本发明中的非水电解质的实例包括非质子有机溶剂如N-甲基-2-吡咯烷酮、碳酸亚丙酯、碳酸亚乙酯、碳酸亚丁酯、碳酸二甲酯、碳酸二乙酯、γ-丁内酯、1,2-二甲氧基乙烷、四羟基Franc、2-甲基四氢呋喃、二甲亚砜、1,3-二氧戊环、甲酰胺、二甲基甲酰胺、二氧戊环、乙腈、硝基甲烷、甲酸甲酯、乙酸甲酯、磷酸三酯、三甲氧基甲烷、二氧戊环衍生物、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑烷酮、碳酸亚丙酯衍生物、四氢呋喃衍生物、醚、丙酸甲酯和丙酸乙酯。
用于本发明中的有机固体电解质的实例包括聚乙烯衍生物、聚环氧乙烷衍生物、聚环氧丙烷衍生物、磷酸酯聚合物、poly agitation lysine、聚酯硫化物、聚乙烯醇、聚偏二氟乙烯和含有离子离解基团的聚合物。
所述无机固体电解质的实例包括锂的氮化物、卤化物和硫酸盐如Li3N、LiI、Li5NI2、Li3N-LiI-LiOH、LiSiO4、LiSiO4-LiI-LiOH、Li2SiS3、Li4SiO4、Li4SiO4-LiI-LiOH和Li3PO4-Li2S-SiS2。
所述锂盐是易溶于上述非水电解质中的材料且其实例包括LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi、氯硼烷锂、低级脂族羧酸锂、四苯基硼酸锂和酰亚胺。
另外，为了提高充/放电特性和阻燃性，例如，可以向非水电解质中添加吡啶、亚磷酸三乙酯、三乙醇胺、环醚、乙二胺、正甘醇二甲醚、六磷酰三胺(hexaphosphoric triamide)、硝基苯衍生物、硫、醌亚胺染料、N-取代的
唑烷酮、N,N-取代的咪唑烷、乙二醇二烷基醚、铵盐、吡咯、2-甲氧基乙醇、三氯化铝等。如果需要，为了赋予不燃性，所述非水电解质可还包含含卤素的溶剂如四氯化碳和三氟乙烯。此外，为了提高高温储存特性，所述非水电解质可还包含二氧化碳气体等且可还包含氟代碳酸亚乙酯(FEC)、丙烯磺酸内酯(PRS)、氟代碳酸亚丙酯(FPC)等。
根据本发明的锂二次电池可以用作电池模块的单元电池，所述电池模块为需要高温稳定性和长循环的中型和大型装置的电源。
优选地，中型和大型装置的实例包括：由电池驱动的电动机提供动力的电动工具；包括电动车辆(EV)、混合电动车辆(HEV)和插电式混合电动车辆(PHEV)的电动车辆；包括电动自行车(E-自行车)、电动踏板车(E-踏板车)的电动双轮车辆；电动高尔夫球车等。
因此，本发明提供包含所述二次电池作为单元电池的中型或大型电池组。所述中型或大型电池组的普通结构及制造方法在本领域内是已知的且本文中省略其详细说明。
附图说明
从结合附图进行的下列详细说明，将更清楚地理解本发明的上述和其他目的、特征和其他优势，其中：
图1是显示实验例2中实施例1的电池和比较例1的电池在第5和第25个循环时的放电曲线的图。
具体实施方式
现在参考下列实施例对本发明进行更详细的说明。提供这些实施例仅用于说明本发明且不应将其解释为限制本发明的范围和主旨。
<实施例1>
通过本领域中已知的共沉淀法制备了具有组成Ni:Mn:Co=0.53:0.27:0.2(摩尔比)的混合过渡金属前体，并向所述混合过渡金属前体中添加氢氧化锂和磷酸二铵，使得满足式1中的条件x=0.01、y=0.02和z=0.04，随后在炉子中在900℃下进行焙烧以合成正极活性材料。
以使得活性材料:导电材料:粘合剂的比例为95:2.5:2.5(重量比)的方式将合成的正极活性材料与NMP混合，并将所述混合物涂布在20μm厚的Al箔上以制造正极。对所述正极进行压制，使得内孔比为25%，从而制造硬币型电池。将Li金属箔用作负极并将1M LiPF6在碳酸酯混合溶剂(EC:DMC:DEC=1:2:1，体积比)中的溶液用作电解质。
<实施例2>
除了合成具有组成x=0.03的正极活性材料之外，以与实施例1中相同的方式制造了电池。
<比较例1>
除了合成具有组成x=0的正极活性材料之外，以与实施例1中相同的方式制造了电池。
<实施例3>
除了合成具有组成x=0.05的正极活性材料之外，以与实施例1中相同的方式制造了电池。
<实施例4>
除了合成具有组成x=0.005的正极活性材料之外，以与实施例1中相同的方式制造了电池。
<实验例1>
在0.1C下对实施例1～4以及比较例1和2中制造的电池进行充放电，测量了其容量，并在0.5C充放电条件下测量容量随循环的劣化。将由此得到的结果示于下表1中。
[表1]
从上表1能够看出，尽管实施例1～4的电池含有P作为过渡金属以外的不同元素，但是它们在容量方面未展示大的差别。随着P含量的增大，其容量稍微下降，但不明显。
另一方面，与使用不含P的正极活性材料的电池(比较例1)相比，使用含有P的正极活性材料的电池(实施例1～4)展示了明显低的随循环增加的容量劣化。具体地，关于第30个循环的容量/第1个循环的容量，与比较例1的电池相比，实施例1～4的电池展示至少4%以上的容量。在300个循环以上时，这种差别达到百分之几十，并且如上所述，将车辆用电池充电1000个循环以上，且在这些条件下，所述差别增大。
<实验例2>
在0.5C下对实施例1和比较例1中制造的电池充放电5和25个循环，并将在这些循环下的放电曲线示于图1中。
从图1中能够看出，与比较例1的电池相比，实施例1的电池展示了放电末期的劣化，特别是压降的显著下降。这意味着，劣化因正极的结构变化而下降。放电末期的这种劣化是使得电动车辆或混合电动车辆用电池的电力快速劣化的最重要因素且所述因素是比在普通电池中能够测量的下降容量更重要的因素。
在这点上，本发明的正极活性材料能够显著降低放电末期的劣化。从图1中能够看出，随着循环次数的增加，这种现象变得严重。即，在第25个循环时放电末期的劣化差比第5个循环时的劣化差更大。
车辆用电池要求充放电3600个循环以上，但其在10年以上的产品保证条件下每天仅充放电一次，由此使得这种差别显著大。因此，在小型常规电池中的小差别在车辆用电池中进一步增大，且循环性能的差别、充放电曲线的变化等比容量差小更重要。
尽管出于例示性目的而公开了本发明的优选实施方案，但是本领域技术人员应理解，在不背离附属权利要求书中所公开的本发明的范围和主旨的条件下，各种变化、添加和替代是可能的。
工业实用性
根据上述可清楚，根据本发明的正极活性材料可以基于特定的元素组成而提高寿命性能，且特别地，由此因优异的循环性能而优选可用于需要长期使用的装置中。
Claims (9)
1.一种二次电池用正极活性材料，其包含具有含锂的过渡金属层的化合物作为选自下式1中的至少一种化合物：
Li(Li3x±yM1-yPx)O2+z (1)
其中M是对六配位结构稳定的元素，其为选自属于第一周期元素和第二周期元素的过渡金属中的至少一种元素；
0<x<0.1；
0<y<0.3；
-4x<z≤4x；且
在3x-y的情况下满足3x>y。
2.如权利要求1所述的正极活性材料，其中P的含量满足条件0<x≤0.05。
3.如权利要求1所述的正极活性材料，其中在所述过渡金属层中Li的含量满足条件0.015≤3x≤y≤0.3。
4.如权利要求1所述的正极活性材料，其中所述M是选自Ni、Mn、Co、Cr、Fe、V和Zr中的至少一种元素。
5.如权利要求4所述的正极活性材料，其中所述M含有Ni和Mn作为必要元素，并含有Co作为任选元素。
6.如权利要求5所述的正极活性材料，其中所述M具有下式2的组成：
M=NiaMnbCoc (2)
其中0.10<a<0.85，0.10<b<0.85，0≤c<0.5。
7.一种二次电池用正极，其包含权利要求1～6中任一项的正极活性材料。
8.一种锂二次电池，其包含权利要求7的正极。
9.一种电池组，其包含权利要求8的锂二次电池作为单元电池。
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