CN1288777C - 阴极活性物质及使用它的锂二次电池 - Google Patents
阴极活性物质及使用它的锂二次电池 Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 66
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000006182 cathode active material Substances 0.000 title claims abstract description 56
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052745 lead Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 239000011244 liquid electrolyte Substances 0.000 claims description 4
- 229920000867 polyelectrolyte Polymers 0.000 claims description 4
- 239000002075 main ingredient Substances 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 abstract description 7
- 239000011029 spinel Substances 0.000 abstract description 7
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 238000001237 Raman spectrum Methods 0.000 description 14
- 239000011149 active material Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 8
- 239000006183 anode active material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- -1 cobalt oxides compound Chemical class 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000006229 carbon black Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 238000007789 sealing Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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Abstract
提供了一种下面通式(1)的阴极活性物质和使用这种阴极活性物质的锂二次电池,它具有更长的循环寿命及有效的充电/放电特性:LixCoyM1-yA2...(1),式中0.95≤x≤1.0;0≤y≤1;M是选自Ni,Fe,Pb,Mg,Al,K,Na,Ca,Si,Ti,Sn,V,Ge,Ga,B,As,Zr,Mn及Cr中的至少一个;而A是选自O,F,S和P中的一个。所述阴极活性物质如拉曼光谱法所测定的,其尖晶石与六方晶系A1g振动模式之间的峰强度比值在1∶0.1至1∶0.4的范围,六方晶系A1g与Eg振动模式之间的峰强度比值在1∶0.9至1∶3.5的范围。而尖晶石A1g与F2g振动模式之间的峰强度比值在1∶0.2至1∶0.4的范围。
Description
技术领域
本发明涉及用于锂二次电池的氧化锂阴极活性物质以及使用此阴极活性物质的锂二次电池,更具体地说,本发明涉及在其拉曼光谱中具有特别相对峰强度的氧化锂阴极活性物质及使用它的锂二次电池。
背景技术
随着制造手提无绳设备的近来迅速发展,锂二次电池已变成小电子设备例如便携式计算机、移动电话、摄像录像机等的适用电源。自从Mizusima在1980年公开了锂钴氧化物(LiCoO2)作为有效的阴极活性物质以来,已对锂的复杂氧化物进行了深入研究。
关于二次电池的发展,循环寿命、充电/放电特性及容量特性是应考虑的重要性能度量。构成二次电池的阴极和阳极活性物质、电解质、粘结剂等等的组成及结构是影响二次电池特性的主要因素。
可以通过评估影响电池功能的这类因素而制造具有所希望性能的电池。如美国专利5344726,6335121等所公开的,评估取决于电池制造中所用阳极活性物质的电池特性的方法,包括X-射线技术及拉曼光谱,利用它们可以读到含碳阳极活性物质的各个峰。
但是,用基于拉曼光谱而评估取决于所用阴极活性物质的电池特性的方法,却几乎没有报导。这是因为在制造阴极中,阴极活性物质通常以与粘结剂、导电碳等的混合物使用,难于从其他物质中将它分离出来供分析用。
因此,通常直接使用完全电池对例如循环寿命、充电/放电特性及容量特性等进行性能评估。很明显,在开发活性物质阶段,常使用X-射线衍射分析法来预测电池性能。但是,用这种分析方法不能观察到阴极活性物质的微小结构变化。当在电池中使用具体阴极活性物质时,没有替代的办法,只有使用完全电池去评估使用期限和安全措施,这因而增加了制造时间和增加了开发阴极活性物质电池的成本。
发明内容
本发明提供了一种阴极活性物质,它使得能采用电池组件而不是采用完全电池,通过用拉曼光谱法分析阴极活性物质的结构变化,以预测循环寿命和充电/放电特性,以便能制造可靠电池。本发明也提供了采用此阴极活性物质的锂二次电池。
在一个方面,本发明提供了一种下面通式(1)的阴极活性物质:
LixCoyM1-yA2 …(1)
式中0.95≤x≤1.0;0≤y≤1;M是选自Ni,Fe,Pb,Mg,Al,K,Na,Ca,Si,Ti,Sn,V,Ge,Ga,B,As,Zr,Mn及Cr中的至少一个;而A是选自O,F,S和P中的一个;其中通式(1)的阴极活性物质如拉曼光谱法所测定的,其尖晶石与六方晶系A1g振动模式之间的峰强度比值在1∶0.1至1∶0.4的范围,六方晶系A1g与Eg振动模式之间的峰强度比值在1∶0.9至1∶3.5的范围,而尖晶石A1g与F2g振动模式之间的峰强度比值在1∶0.2至1∶0.4的范围。
在另一方面,本发明提供了一种锂二次电池,它包括:含有作为主要组份的含碳物质的阳极;含有作为阴极活性物质的上述通式(1)锂基化合物的阴极;安置在阳极与阴极之间的隔板;及液态电解液和聚合物电解液中的一种。如上所述,用作阴极活性物质的通式(1)锂基化合物如拉曼光谱所测出的,其尖晶石与六方晶系A1g振动模式之间的峰强度比值在1∶0.1至1∶0.4的范围,六方晶系A1g与Eg振动模式之间的峰强度比值在1∶0.9至1∶3.5的范围,而尖晶石A1g与F2g振动模式之间的峰强度比值在1∶0.2至1∶0.4的范围。
当上述锂化合物用作阴极活性物质时,在电池的制造结束之前,可以预测电池的循环寿命、充电/放电特性和容量特性。因此,使用本发明的锂基阴极活性物质能更有效制造具有所希望特性的电池。
附图说明
通过参考所附附图详细描述其示范性实施方案,则本发明的上述或其他特征将变得更清晰,在附图中:
图1是锂钴氧化物本身被用作电池的阴极活性物质之前的拉曼光谱;
图2说明锂钴氧化物被用作根据本发明的电池中的阴极活性物质之前的六方晶系A1g和Eg分子振动模式;
图3是锂钴氧化物样品在制造电池中在被用作阴极活性物质之后的拉曼光谱;
图4是电池的容量~充电/放电循环次数图,而这种电池是在本发明实施例中用锂钴氧化物作为阴极活性物质而制造的。
具体实施方式
下面参考附图将对根据本发明的阴极活性物质和使用它的非水锂二次电池作详细描述。
锂二次电池如此制造:用阴极和阳极制成电极组件,而阴极和阳极由能可逆地嵌入或脱出锂离子的物质制成,又制成置于阴极和阳极之间的隔板;往电极组件中加入液态电解液或聚合物电解液。原则上说,锂二次电池经氧化反应和还原反应产生电能,而当锂离子嵌入阴极和阳极以及从阴极和阳极脱出时发生氧化反应和还原反应。锂二次电池的循环寿命、充电/放电特性及容量特性依据所用阴极活性物质的微结构变化而改变。
根据本发明,使用下列通式(1)的锂基化合物作为阴极活性物质:
LixCoyM1-yA2 …(1)
式中0.95≤x≤1.0;0≤y≤1;M是选自Ni,Fe,Pb,Mg,Al,K,Na,Ca,Si,Ti,Sn,V,Ge,Ga,B,As,Zr,Mn及Cr中的至少一个;而A是选自O,F,S和P中的一个。
通式(1)的锂基阴极活性物质原本仅具有六方晶系结构,但在制造电池中被加工后则具有六方晶系和尖晶石结构。电池的充电/放电特性和循环寿命依据上述两种结构的比例而大大变化。用X-射线衍射法不能检测出这一微小结构变化,但仅使用拉曼光谱法就可以检测出。
拉曼光谱由分子振动模式而提供物质分子结构的情报,并提供分子结构的微小和局部变化的精确测量。当样品用具体波长的光照射时,发生非弹性拉曼散射和产生依据分子结构变化的信号。这种拉曼光谱法可用于分析阴极活性物质的分子结构。各种拉曼光谱峰的出现取决于阴极活性物质的分子结构,因此可能区别适于产生所希望电池特性的锂基阴极活性物质。
具体地说,锂基化合物半高宽度(FWHM)、相对峰强度及A1g、Eg和F2g振动模式的峰位置随着阴极活性物质的分子结构而变化。基于这些变化,可以筛选出所希望的阴极活性物质。
根据本发明的锂基阴极活性物质的拉曼光谱,在被加工例如制造电池之前,具有相应于两种振动模式的两个峰,如图1所示。换句话说,出现了如图2所说明的相应于两种振动模式即A1g和Eg模式的两个明显的峰。
但是,在制造电池中被加工之后,根据本发明的锂基阴极活性物质具有六方晶系及尖晶石结构。为将在制造电池中被加工后的锂基阴极活性物质进行拉曼光谱分析,将阴极板从电池中分离出来,在400-650℃加热1-10分钟以留下阴极活性物质和含碳物质。这些留下的阴极活性物质及含碳物质被用作拉曼光谱法的样品。电池的特性由所加入的阴极活性物质的结构来决定,而不是由使用之前未加工的阴极活性物质的起始结构来决定。因此,在制造电池之后从阴极板将锂基阴极活性物质分离出来也是重要的。通过分析电池中所用化合物的两种结构的相对峰强度和FWHM,能够制造具有有效充电/放电特性和循环寿命的电池。
在拉曼光谱中,可以使用514nm激光束作为激发源。锂基化合物的拉曼光谱含有相应于A1g(六方晶系及尖晶石结构)、Eg(六方晶系结构)及F2g(尖晶石结构)振动模式的峰,并适用Lorentzian函数进行分析。
在通式(1)的锂基阴极活性物质的拉曼结构中,尖晶石与六方晶系A1g振动模式之间峰强度的比值在1∶0.1至1∶0.4的范围,六方晶系A1g与Eg振动模式之间峰强度的比值在1∶0.9至1∶3.5的范围,而尖晶石A1g与F2g振动模式之间峰强度的比值在1∶0.2至1∶0.4的范围。
另一方面,通过(1)的锂基阴极活性物质可含有10-1000ppm的镍,镍可以改进电池的特性。
锂基化合物的六方晶系A1g和Eg振动模式当具有上述峰强度的比值时,其FWHM值可分别为12.8-13.6cm-1及9.3-11.3cm-1。锂基化合物的尖晶石A1g和F2g振动模式当具有上述峰强度的比值时,其FWHM值可分别为12.2-13.0cm-1及14.1-16.6cm-1。
本发明也提供一种锂二次电池,它包括:含有作为主要成份的含碳物质的阳极;含有作为阴极活性物质的通式(1)锂基化合物的阴极;安置在阳极与阴极之间的隔板;及液态电解液和聚合物电解液中的一种。关于用作阴极活性物质的通式(1)锂基化合物,如拉曼光谱法所测定的,其尖晶石与六方晶系A1g振动模式之间的峰强度比值在1∶0.1至1∶0.4的范围,六方晶系A1g与Eg振动模式之间的峰强度比值在1∶0.9至1∶3.5的范围,而尖晶石A1g与F2g振动模式之间的峰强度比值在1∶0.2至1∶0.4的范围。此锂二次电池具有有效的充电/放电特性和循环寿命特性。
将参考下列实施例对本发明作更详细的描述。下列实施例是为了解释的目的,而且不是对本发明范围的限制。
制备实施例1:制备锂阴极活性物质
将48gCo3O4和23g含有镍杂质的Li2CO3称重和混合到一起。把此混合物在800℃煅烧。将已煅烧的产物研磨并分级以提供锂钴氧化物复合物(样品1)。此锂钴氧化物含159ppm的Ni。
制备实施例2和3
以与制备实施例1相同的方式合成分别含24ppm(样品2)和623ppm(样品3)Ni的锂钴氧化物复合物。
实施例1至3:制造锂二次电池
分别将在制备实施例100g 1至3中制备的锂钴氧化物与5g作为粘结剂的聚偏氟乙烯、10g作为导电剂的碳黑及100g N-甲基-2-吡咯烷酮混合,制成三种混合物。用球磨机分别地将这些混合物研磨约10小时,得到阴极物质。将这些阴极物质用距离为250μm的刮涂器分别地涂在厚度为15μm、宽度为30cm的铝箔上。把此涂了阴极物质的铝箔干燥、辊压并切成预定的大小以制造阴极板。
将100g用作阳极活性物质的结晶人造石墨(MIMB2528,得自OSAKAGAS,日本),15g用作粘结剂的聚偏氟乙烯及200g N-甲基-2-吡咯烷酮混合到一起并球磨约10小时,生成阳极活性物质组合物。
把此阳极活性物质组合物用距离为300μm的刮涂器涂到厚度为12μm、宽度为30cm的铜箔上,将此涂了阳极活性物质组合物的铜箔干燥、辊压并切成预定的大小以形成阴极板。
将厚度为20μm的聚乙烯隔板(得自CELGARD,美国)分别置于阴极板与阳极板之间,密封制成电池组件。把含有1.1M LiPF6的由体积比为35∶55∶5∶10的碳酸亚乙酯(EC)、碳酸乙甲酯(EMC)、碳酸亚丙酯(PC)、氟代苯(FB)的混合物,注射入每个电池组件中,以生成完全的锂二次电池。
比较实施例
以与实施例1相同的方式制造一种锂二次电池,不同的是所用的阴极活性物质含有少于10ppm的Ni。
实验实施例1:拉曼光谱的测定
在将实施例1至3制备的锂二次电池充电和放电一次之后,从锂二次电池把阴极板分离开并在650℃加热10分钟以便把阴极活性物质和含碳物质留下。来自锂二次电池的阴极活性物质和含碳物质被用作拉曼光谱测定用的样品。
用拉曼光谱仪(System 3000,得自RENISHAW)进行拉曼光谱测定。在测定拉曼光谱中使用514nm激光器作为激发源。用Lorentzian函数对拉曼光谱中相应于锂钴氧化物的A1g、Eg和F2g的振动模式的峰进行分析。
分析结果示于表1及图3之中。
表1
实施例 | 结构 | 振动模式 | 峰位置 | I(六方晶系)(Eg/A1g) | I(尖晶石)(F2g/A1g) | I(六方晶系)(A1g)/尖晶石(A1g) | FWHM |
实施例1 | 六方晶系 | Eg | 482 | 0.93-1.02 | 0.27-0.29 | 0.34-0.38 | 9.6-10.7 |
A1g | 592 | 12.8-13.6 | |||||
尖晶石 | F2g | 522 | 14.1-16.6 | ||||
A1g | 690 | 12.2-13.0 | |||||
实施例2 | 六方晶系 | Eg | 482 | 2.07-3.49 | 0.23-0.37 | 0.06-0.14 | 11.4-13.3 |
A1g | 593 | 18.3-19.4 | |||||
尖晶石 | F2g | 523 | 14.4-23.4 | ||||
A1g | 690 | 13.8-14.4 | |||||
实施例3 | 六方晶系 | Eg | 481 | 1.48-1.57 | 0.24 | 0.18-0.21 | 9.3-11.3 |
A1g | 592 | 13.0-13.1 | |||||
尖晶石 | F2g | 521 | 13.3-16.4 | ||||
A1g | 689 | 11.5-11.8 | |||||
比较实施例 | 六方晶系 | Eg | 483 | 0.45-0.61 | N/A | 2.5-2.6 | 9.4-10.0 |
A1g | 592 | N/A | |||||
尖晶 | F2g | N/A | 13.2-14.3 |
石 | A1g | 690 | 13.3-15.1 |
从表1和图3可以明显看到,用作阴极活性物质的根据本发明的锂钴氧化物复合物具有尖晶石结构及六方晶系结构,并显示具有具体宽度和强度比值的拉曼峰。
实验实施例2:循环寿命检验
将实施例1至3及比较实施例中制得的额定容量为1800mAh的圆筒形锂二次电池,在恒定的1800mA电流下充电至4.2V电压,放置30分钟,再在1800mA电流下放电至2.75V电压。重复此充电和放电循环以测定充电/放电循环寿命特性。结果示于图4中。
正如从图4中所明显看到的,使用根据本发明的阴极活性物质制得的锂二次电池甚至在300次循环之后其充电/放电容量也不显示大的变化,在比较实施例中制的锂二次电池则在300次循环后其充电/放电容量发生大的降低。
如上所述,根据本发明的上面通式(1)的阴极活性物质和使用此阴极活性物质的锂二次电池具有改进的循环寿命及充电/放电特性,并具有更大的放电容量。锂二次电池的性能可以在制造完全电池之前使用含在锂二次电池之中的阴极活性物质来测定,因此能够大大节省用于开发电极活性物质和电池所需的时间和成本。
尽管本发明通过参考其说明性实施例已作了具体展示和描述,但是本技术领域技术熟练人员应该明白,在不违背权利要求书所限定的本发明的精神实质和范围的前提下,可以对形式和细节作出各种改变。
Claims (8)
1.一种下面通式(1)的阴极活性物质:
LixCoyM1-yA2 ...(1)
式中0.95≤x≤1.0;0≤y≤1;M是选自Ni,Fe,Pb,Mg,Al,K,Na,Ca,Si,Ti,Sn,V,Ge,Ga,B,As,Zr,Mn及Cr中的至少一个;而A是选自O,F,S和P中的一个,
该通式(1)的阴极活性物质利用拉曼光谱法测出,其尖晶石与六方晶系A1g振动模式之间的峰强度比值在1∶0.1至1∶0.4的范围,六方晶系A1g与Eg振动模式之间的峰强度比值在1∶0.9至1∶3.5的范围,而尖晶石A1g与F2g振动模式之间的峰强度比值在1∶0.2至1∶0.4的范围。
2.权利要求1的阴极活性物质,含有数量为10-1000ppm的镍。
3.权利要求1的阴极活性物质,其中利用拉曼光谱法测出,该通式(1)的阴极活性物质的六方晶系A1g和Eg振动模式的半高宽度分别为12.8-13.6cm-1和9.3-11.3cm-1。
4.权利要求1的阴极活性物质,其中利用拉曼光谱法测出,该通式(1)的阴极活性物质的尖晶石A1g和F2g振动模式的半高宽度分别为12.2-13.0cm-1和14.1-16.6cm-1。
5.一种锂二次电池,它包括:
含有作为主要成份的含碳物质的阳极;
含有作为阴极活性物质的通式(1)锂基化合物的阴极;
安置在阳极与阴极之间的隔板;及
液态电解液和聚合物电解液中的一种;
LixCoyM1-yA2 ...(1)
式中0.95≤x≤1.0;0≤y≤1;M是选自Ni,Fe,Pb,Mg,Al,K,Na,Ca,Si,Ti,Sn,V,Ge,Ga,B,As,Zr,Mn及Cr中的至少一个;而A是选自O,F,S和P中的一个,其中通式(1)的锂基化合物利用拉曼光谱法测出,其尖晶石与六方晶系A1g振动模式之间的峰强度比值在1∶0.1至1∶0.4的范围,六方晶系A1g与Eg振动模式之间的峰强度比值在1∶0.9至1∶3.5的范围,而尖晶石A1g与F2g振动模式之间的峰强度比值在1∶0.2至1∶0.4的范围。
6.权利要求5的锂二次电池,其中该阴极活性物质含10-1000ppm的镍。
7.权利要求5的锂二次电池,其中利用拉曼光谱法测出,该通式(1)的锂基化合物的六方晶系A1g和Eg振动模式的半高宽度分别为12.8-13.6cm-1和9.3-11.3cm-1。
8.权利要求5的锂二次电池,其中利用拉曼光谱法测出,该通式(1)的锂基化合物的尖晶石A1g和F2g振动模式的半高宽度分别为12.2-13.0cm-1和14.1-16.6cm-1。
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JP6326396B2 (ja) * | 2015-11-10 | 2018-05-16 | 株式会社神戸製鋼所 | LiCoO2含有スパッタリングターゲットおよびLiCoO2含有焼結体 |
EP3333128A1 (en) | 2016-12-07 | 2018-06-13 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Novel chargeable crystalline materials, in particular for use as electrode materials in electrochemical storage devices |
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JP6907805B2 (ja) * | 2017-08-17 | 2021-07-21 | セイコーエプソン株式会社 | 複合体、リチウム電池、複合体の製造方法、リチウム電池の製造方法、電子機器 |
JP6966308B2 (ja) * | 2017-12-11 | 2021-11-10 | トヨタ自動車株式会社 | リチウムイオン電池用正極活物質及びその製造方法、リチウムイオン電池、並びに、リチウムイオン電池システム |
WO2019244955A1 (ja) | 2018-06-21 | 2019-12-26 | 株式会社Gsユアサ | 非水電解質二次電池用正極活物質、非水電解質二次電池用正極活物質の製造方法、非水電解質二次電池用正極、非水電解質二次電池、非水電解質二次電池の製造方法、及び非水電解質二次電池の使用方法 |
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CN111785927A (zh) * | 2019-04-03 | 2020-10-16 | 中国科学院物理研究所 | 钠离子电池钛基复合相负极活性材料及其制备方法和应用 |
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JP2643035B2 (ja) * | 1991-06-17 | 1997-08-20 | シャープ株式会社 | 非水系二次電池用炭素負極およびその製造方法 |
JPH076753A (ja) | 1993-06-15 | 1995-01-10 | Toray Ind Inc | 電極およびその製造方法、およびその電極を用いた二次電池 |
JPH07320785A (ja) | 1994-05-26 | 1995-12-08 | Sony Corp | 非水電解液二次電池 |
WO1998024134A1 (en) * | 1996-11-26 | 1998-06-04 | Kao Corporation | Negative electrode material for nonaqueous secondary battery |
JP2000294240A (ja) * | 1999-04-08 | 2000-10-20 | Toyota Central Res & Dev Lab Inc | リチウム二次電池正極活物質用リチウム複合酸化物およびこれを用いたリチウム二次電池 |
JP4246342B2 (ja) | 1999-12-15 | 2009-04-02 | 日立マクセル株式会社 | リチウム二次電池とリチウム二次電池用正極活物質 |
JP4020565B2 (ja) * | 2000-03-31 | 2007-12-12 | 三洋電機株式会社 | 非水電解質二次電池 |
JP4986098B2 (ja) | 2001-03-15 | 2012-07-25 | 日立金属株式会社 | 非水系リチウム二次電池用正極およびそれを用いた非水系リチウム二次電池 |
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Cited By (2)
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US8048564B2 (en) | 2007-06-25 | 2011-11-01 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery and method of forming positive electrode |
CN101689631B (zh) * | 2007-06-25 | 2013-03-06 | 三洋电机株式会社 | 非水电解质二次电池和正极的制造方法 |
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US20050019661A1 (en) | 2005-01-27 |
KR100563047B1 (ko) | 2006-03-24 |
US7563540B2 (en) | 2009-07-21 |
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JP2005044785A (ja) | 2005-02-17 |
CN1577924A (zh) | 2005-02-09 |
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