CN105453313B - 正极活性材料和包含其的锂二次电池以及制备正极活性材料的方法 - Google Patents
正极活性材料和包含其的锂二次电池以及制备正极活性材料的方法 Download PDFInfo
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- CN105453313B CN105453313B CN201480044433.5A CN201480044433A CN105453313B CN 105453313 B CN105453313 B CN 105453313B CN 201480044433 A CN201480044433 A CN 201480044433A CN 105453313 B CN105453313 B CN 105453313B
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- lithium
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 45
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims abstract description 13
- 229910005565 NiaMnb Inorganic materials 0.000 claims abstract description 5
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- -1 lithium transition-metal Chemical class 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000010316 high energy milling Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910007998 ZrF4 Inorganic materials 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910011543 Li1Ni1/3Mn1/3Co1/3O2 Inorganic materials 0.000 claims description 2
- 229910012748 LiNi0.5Mn0.3Co0.2O2 Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 239000006182 cathode active material Substances 0.000 claims 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 12
- 239000011737 fluorine Substances 0.000 abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002243 precursor Substances 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
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- 159000000002 lithium salts Chemical class 0.000 description 5
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- 229910045601 alloy Inorganic materials 0.000 description 2
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- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000004862 dioxolanes Chemical class 0.000 description 2
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- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
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- 229910052736 halogen Inorganic materials 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
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
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- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- HSFDLPWPRRSVSM-UHFFFAOYSA-M lithium;2,2,2-trifluoroacetate Chemical compound [Li+].[O-]C(=O)C(F)(F)F HSFDLPWPRRSVSM-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 239000011787 zinc oxide Substances 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
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Abstract
本发明提供正极活性材料、包含其的锂二次电池及其制备方法，且提供制备涂布有ZrO2和F的正极活性材料的方法，以及通过使用所述方法制备的正极活性材料，所述方法包括以下步骤：(a)制备以下化学式1的锂金属氧化物，Li1+ zNiaMnbCo1‑(a+b)O2(1)(在所述式中，0≤z≤0.1，0.1≤a≤0.8，0.1≤b≤0.8，且a+b<1)；(b)将锂金属氧化物和锆与含氟的前体进行干混；以及(c)在步骤(b)的干混之后进行热处理以将包含锆和氟的前体转变成ZrO2，并利用F取代部分氧(O)阴离子。
Description
技术领域
本发明涉及正极活性材料和包含其的锂二次电池以及制备正极活性材料的方法。更具体地，本发明涉及制备涂布有ZrO2和F的正极活性材料的方法，所述方法包括：制备预定的锂金属氧化物，将包含锂金属氧化物、锆和氟的前体进行干混，以及在干混之后通过热处理将包含锆和氟的前体变成ZrO2并且利用F取代一些氧(O)阴离子。
背景技术
显示高能量密度和工作电位的锂二次电池具有长循环寿命和低自放电率。由于这样的特性，锂二次电池被广泛用于移动装置和诸如电动车辆(EV)、混合动力电动车辆(HEV)、电力存储装置等的中型和大型装置。
作为锂二次电池的正极活性材料，主要使用含锂的钴氧化物诸如LiCoMO2。除了含锂的钴氧化物以外，还在考虑使用诸如LiNiMO2的含锂的镍氧化物、诸如具有层状结构的LiMnMO2的锂锰氧化物和诸如具有尖晶石结构的LiMn2MO4的锂锰氧化物。近来，正在使用其中M为Co、Ni和Mn的LiMO2。
在合成过程中，在其中M为Co、Ni和Mn的LiMO2的表面上生成大量的Li副产物。大多数Li副产物由Li2CO3和LiOH组成，因此在正极糊料制备过程期间正极糊料可能会胶化，并且在制备电极后，可能会通过充放电而生成气体。
同时，在锂二次电池中，电解质是作为用于离子传输的媒介的必需元素。电解质通常由溶剂和锂盐组成。因此考虑到溶解度、化学稳定性等，主要使用作为锂盐的LiBF4、6LiPF6等。然而，通过溶解如上所述的包含氟(F)的锂盐而制备的电解质与电解质中的少量水反应，因此生成氢氟酸(HF)，且生成的氢氟酸可能会使电极分解。
另外，碳酸锂(Li2CO3)在水不溶性的纯溶剂中不被洗脱(elute)并且稳定存在。然而，当碳酸锂(Li2CO3)与氢氟酸(HF)反应时，碳酸锂(Li2CO3)在电解质中被洗脱，从而生成二氧化碳(CO2)。因此，在存储和循环期间生成大量气体。结果，可能会引起电池膨胀，且可能使高温稳定性劣化。
发明内容
技术问题
因此，已经完成了本发明以解决以上和其它尚未解决的技术问题。
特别地，本发明的目的在于提供制备正极活性材料的方法，所述正极活性材料通过经由ZrO2和F涂层防止存在于正极活性材料的表面上的杂质(Li2CO3和LiOH)和电解质中的氢氟酸(HF)接触并且通过ZrO2与电解质中的氢氟酸(HF)反应生成稳定的材料而具有优异的稳定性和循环特性。
本发明的另一个目的是提供根据所述方法制备的具有新结构的正极活性材料。
技术方案
根据本发明的一方面，提供制备正极活性材料的方法，所述方法包括：
(a)制备如下式1的锂金属氧化物：
Li1+zNiaMnbCo1-(a+b)O2 (1)
其中0≤z≤0.1，0.1≤a≤0.8，0.1≤b≤0.8，且a+b<1；
(b)将所述锂金属氧化物和包含锆及氟的前体进行干混；以及
(c)在步骤(b)的干混之后通过热处理将包含锆和氟的前体变成ZrO2，并且利用F取代一些氧(O)阴离子。因此，本发明提供涂布有ZrO2和F的正极活性材料。
根据本发明的制备方法形成的ZrO2和F膜可以防止存在于正极活性材料的表面上的杂质(Li2CO3和LiOH)和电解质中的氢氟酸(HF)接触。另外，ZrO2膜可能与电解质中的氢氟酸(HF)反应，从而可以形成稳定的ZrO2·5HF·H2O。因此，可以使正极活性材料的表面稳定。
因此，根据本发明制备的正极活性材料可以防止正极活性材料的结构因与电解质的接触而坍塌。另外，所述正极活性材料可以抑制由于副反应而导致的二氧化碳的生成。因此，由于膨胀最小化，所以可以提高包含所述正极活性材料的锂二次电池的稳定性。另外，可以提高包含所述正极活性材料的锂二次电池的循环特性。
在式1的锂金属氧化物中，镍的量(a)和锰的量(b)分别可以特别地为0.1以上且0.8以下。更具体地，式1的锂金属氧化物可以为Li1Ni1/3Mn1/3Co1/3O2或LiNi0.5Mn0.3Co0.2O2。
可以根据本领域中公知的方法诸如固态反应、共沉淀等制备这种锂过渡金属氧化物粒子。省略了这些方法的详细说明。
在本发明的制备方法中，对包含锆和氟的前体没有特别限制，只要可以提供Zr和F即可。特别地，包含锆和氟的前体可以为ZrF4。
在一个具体实施方案中，可以控制混合的锂过渡金属氧化物的量，使得基于正极活性材料的总重量，在步骤(b)的锂过渡金属氧化物上涂布的ZrO2和F的量为0.001重量％至0.100重量％。特别地，基于正极活性材料的总重量，ZrO2和F的量可以为0.001重量％至0.010重量％。
当ZrO2和F的量太小时，难以获得期望的效果。相反，当ZrO2和F的量太大时，比容量可能会降低。
可以通过例如简单的混合或高能研磨(high-energy milling)进行步骤(b)的干混。尤其是，可以使用例如机械熔合(Mechanofusion)装置或Nobilta装置实现高能研磨。通过使用机械熔合装置，通过干燥状态下的强的物理旋转力形成混合物，且在构成材料间形成静电结合强度。
可以例如在大气下、在400℃至1000℃的温度下进行4小时至10小时的热处理。通过热处理，将包含锆和氟的前体变成ZrO2且利用F取代一些氧(O)阴离子。结果，可以制备涂布有ZrO2和F的锂过渡金属氧化物。
热处理的温度范围为获得本发明期望的正极活性材料的最佳范围。当热处理温度太低或太高时，可能会出现诸如杂质、晶体粘结、样品破裂等的问题。
本发明还提供根据所述制备方法制备的涂布有ZrO2和F的二次电池用正极活性材料。
涂层的厚度可以特别地为0.01μm至0.1μm，更特别地为0.01μm至0.05μm。当涂层的厚度太薄时，在电池工作步骤期间可能不能防止与电解质的接触或者可能会使电池损坏。相反，当涂层的厚度太厚时，比容量可能会降低。
基于正极活性材料的表面积，ZrO2和F的涂布面积可以为例如60％至100％，特别是80％至100％。当涂层的面积太小时，正极活性材料和电解质的接触面积可能会扩大。
本发明还提供包含上述正极活性材料的二次电池用正极混合物和涂布有正极混合物的二次电池用正极。
除了正极活性材料以外，正极混合物还可以选择性地包含导电材料、粘合剂、填料等。
基于包含正极活性材料的混合物的总重量，通常以1重量％至30重量％的量添加导电材料。对于导电材料没有特别限制，只要其不在制备的电池中造成化学变化且具有导电性即可。导电材料的实例包括但不限于石墨如天然或人造石墨；炭黑类材料如炭黑、乙炔黑、科琴黑、槽法炭黑、炉黑、灯黑和热裂法炭黑；导电纤维如碳纤维和金属纤维；金属粉末如氟化碳粉末、铝粉和镍粉；导电晶须如氧化锌和钛酸钾；导电金属氧化物如氧化钛；以及聚亚苯基衍生物。
粘合剂是帮助活性材料和导电材料之间的粘合以及活性材料对集电器的粘合的成分。基于包含正极活性材料的混合物的总重量，通常以1重量％至30重量％的量添加粘合剂。粘合剂的实例包括但不限于聚偏二氟乙烯、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EPDM、丁苯橡胶、氟橡胶和各种共聚物。
任选地使用填料作为用于抑制正极膨胀的成分。填料没有特别限制，只要其为不在制备的二次电池中造成化学变化的纤维材料即可。填料的实例包括烯烃基聚合物如聚乙烯和聚丙烯；以及纤维材料如玻璃纤维和碳纤维。
通过如下可以制备根据本发明的正极：在正极集电器上涂布通过混合包含上述化合物的正极混合物和诸如NMP等的溶剂而制备的浆料之后，对涂布的集电器进行干燥和压制。
正极集电器通常制备成3μm至500μm的厚度。正极集电器没有特别限制，只要其不在制备的锂二次电池中造成化学变化且具有导电性即可。例如，正极集电器可以由不锈钢，铝，镍，钛，烧结碳，用碳、镍、钛或银表面处理过的铝或不锈钢等制成。正极集电器可以在其表面具有微小的不规则处以增加正极活性材料和正极集电器之间的附着力。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中的任一种使用正极集电器。
本发明还提供包含正极、负极、隔膜和含锂盐的非水电解质的锂二次电池。
例如通过在负极集电器上涂布包含负极活性材料的负极混合物之后进行干燥来制备负极。在这种情况下，根据需要，负极混合物可以包含上述元素。
负极活性材料的实例包括例如碳如硬碳和石墨基碳；金属复合氧化物如LixFe2O3(其中0≤x≤1)，LixWO2(其中0≤x≤1)，SnxMe1-xMe’yOz(其中Me：Mn，Fe，Pb或Ge；Me’：Al，B，P，Si，I、II和III族元素，或者卤素；0<x≤1；1≤y≤3；且1≤z≤8)；锂金属；锂合金；硅基合金；锡基合金；金属氧化物如SnO、SnO2、PbO、PbO2、Pb2O3、Pb3O4、Sb2O3、Sb2O4、Sb2O5、GeO、GeO2、Bi2O3、Bi2O4和Bi2O5；导电聚合物如聚乙炔；和Li-Co-Ni基材料。
负极集电器通常制备成3μm至500μm的厚度。负极集电器没有特别限制，只要其不在制备的二次电池中造成化学变化且具有导电性即可。例如，负极集电器可以由铜，不锈钢，铝，镍，钛，烧结碳，用碳、镍、钛、银等表面处理过的铜或不锈钢，或铝-镉合金制成。另外，与正极集电器类似，负极集电器可以在其表面具有微小的不规则处以增加负极活性材料和负极集电器之间的附着力。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中的任一种使用负极集电器。
隔膜设置在正极和负极之间，且将具有高离子渗透性和机械强度的绝缘薄膜用作隔膜。隔膜通常具有0.01μm至10μm的孔径和5μm至300μm的厚度。作为隔膜，使用由具有耐化学性和疏水性的烯烃聚合物如聚丙烯、玻璃纤维或聚乙烯制成的片或无纺布。当采用固体电解质如聚合物作为电解质时，固体电解质还可以作为隔膜和电解质两者。
含锂盐的非水电解质由电解质和锂盐组成。电解质可以为非水有机溶剂、有机固体电解质、无机固体电解质等。
例如，非水有机溶剂可以为非质子有机溶剂如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、四氢呋喃、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等。
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、聚海藻酸盐-赖氨酸、聚酯硫醚、聚乙烯基醇、聚偏二氟乙烯和含有离子离解基团的聚合物。
无机固体电解质的实例包括锂(Li)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。
锂盐是易溶于非水电解质的材料。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锂。
另外，为了改善充放电特性和阻燃性，例如，可以向电解质中添加吡啶、亚磷酸三乙酯、三乙醇胺、环醚、乙二胺、正甘醇二甲醚、六甲基磷酰三胺、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。在某些情况下，为了赋予不燃性，电解质还可以包含含卤素的溶剂如四氯化碳和三氟乙烯。另外，为了改善高温存储特性，电解质还可以包含二氧化碳气体、氟代碳酸亚乙酯(FEC)、丙烯磺酸内酯(PRS)、氟代碳酸亚丙酯(FPC)等。
根据本发明的二次电池可以用于用作小型装置的电源的电池单元，且还可以用作包含多个电池单元的中型和大型电池模块的单元电池。
本发明还提供作为中型和大型装置的电源的包含所述电池模块的电池组。中型和大型装置的实例包括但不限于电动车辆(EV)、混合动力电动车辆(HEV)和插电式混合动力电动车辆(PHEV)；以及储电装置。
附图说明
图1为根据本发明的一个实施例获得的过渡金属氧化物的电子显微镜照片；且
图2为显示根据实验例1的寿命特性的图。
具体实施方式
现在将参考以下实施例对本发明进行更详细地说明。提供这些实施例仅用于说明本发明且不应被解释为限制本发明的范围和主旨。
<实施例1>
作为三元体系锂过渡金属氧化物，使用了Li1+zNiaMnbCo1-(a+b)O2，其中0≤z≤0.1，0.1≤a≤0.8，0.1≤b≤0.8且a+b<1。在将Li1+zNiaMnbCo1-(a+b)O2与0.01重量％至0.20重量％的ZrF4混合后，在300℃至700℃的温度下对混合物进行3小时至10小时的热处理。如图1中所示，合成了涂布在正极活性材料的表面上的ZrF。
以95:2.5:2.5的比率使用正极活性材料、导电剂和粘合剂以制备浆料，且将浆料涂布在厚度为20μm的Al箔上以制备硬币型电池。使用Li金属作为负极。使用包含1:2:1的EC:EMC:DEC的混合物的1M LiPF6作为电解质。
<比较例1>
以与实施例1中相同的方式制备了正极和硬币型电池，不同之处在于使用了由LiNi3/5Mn1/5Co1/5O2表示的锂金属氧化物作为锂过渡金属氧化物，使得未将ZrF涂布在正极活性材料的表面上。
<实验例1>
通过在45℃下进行200次循环对根据实施例1和比较例1制备的电池的寿命特性进行了分析。结果示于图2中。
作为实验的结果，如图2中所示，当与比较例1的电池相比时，根据本发明的实施例1的电池显示了大幅改善的寿命特性。也就是说，确认了由于电池表面的涂层而显著改善了电池的寿命和容量特性。
本领域技术人员可以以上述内容为基础，在本发明的范围内进行各种应用和变化。
工业应用性
如上所述，根据本发明的制备正极活性材料的方法包括在对包含锆和氟的前体以及锂过渡金属氧化物进行干混之后进行热处理。将ZrO2和F涂布在根据所述方法制备的正极活性材料的表面上，因此ZrO2和F与电解质中的氢氟酸(HF)反应，导致生成稳定的材料。
因此，可以抑制由于与电解质的接触而导致的正极活性材料结构的坍塌和作为副反应产物的二氧化碳的生成。另外，包含本发明的正极活性材料的锂二次电池由于最小化的膨胀情形而具有升高的稳定性和改善的循环特性。
Claims (14)
1.一种制备二次电池用正极活性材料的方法，所述方法包括：
制备下式1的锂金属氧化物：
Li1+zNiaMnbCo1-(a+b)O2 (1)
其中0≤z≤0.1，0.1≤a≤0.8，0.1≤b≤0.8，且a+b<1；
将所述锂金属氧化物和ZrF4进行干混；以及
在干混之后通过热处理将ZrF4变成ZrO2，并利用F取代一些氧(O)阴离子，
其中所述正极活性材料涂布有ZrO2和F。
2.根据权利要求1所述的方法，其中所述式1的锂金属氧化物为Li1Ni1/3Mn1/3Co1/3O2或LiNi0.5Mn0.3Co0.2O2。
3.根据权利要求1所述的方法，其中，在干混中，控制混合的锂过渡金属氧化物的量，使得基于所述正极活性材料的总重量，涂布在锂过渡金属氧化物上的ZrO2和F的总量为0.001重量％至0.100重量％。
4.根据权利要求3所述的方法，其中控制混合的锂过渡金属氧化物的量，使得基于正极活性材料的总重量，ZrO2和F的总量为0.001重量％至0.010重量％。
5.根据权利要求1所述的方法，其中通过高能研磨进行所述干混。
6.根据权利要求1所述的方法，其中在400℃至1000℃下进行4小时至7小时的热处理。
7.一种涂布有ZrO2和F的二次电池用正极活性材料，其通过使用根据权利要求1所述的方法制得，所述正极活性材料包含：
式1的锂金属氧化物，其中含有Li2CO3和/或LiOH作为杂质；和
在所述锂金属氧化物上的含有ZrO2和F的涂层。
8.根据权利要求7所述的正极活性材料，其中ZrO2和F涂布至0.01μm至0.10μm的厚度。
9.根据权利要求7所述的正极活性材料，其中基于所述正极活性材料的表面积，涂布有ZrO2和F的面积为60％至100％。
10.一种正极混合物，其包含根据权利要求7所述的正极活性材料。
11.一种二次电池用正极，其包含涂布在集电器上的根据权利要求10所述的正极混合物。
12.一种锂二次电池，其包含根据权利要求11所述的二次电池用正极。
13.根据权利要求12所述的锂二次电池，其中所述锂二次电池为作为中型和大型装置的电源的电池模块的单元电池。
14.根据权利要求13所述的锂二次电池，其中所述中型和大型装置为电动车辆、混合动力电动车辆、插电式混合动力电动车辆或电力存储系统。
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| KR100989901B1 (ko) * | 2007-05-07 | 2010-10-26 | 한양대학교 산학협력단 | 리튬 이차 전지용 양극 활물질의 제조방법, 이 방법으로제조된 리튬 이차 전지용 양극 활물질 및 이를 포함하는리튬 이차 전지 |
| JP5434278B2 (ja) * | 2009-05-29 | 2014-03-05 | Ｔｄｋ株式会社 | 活物質及び電極の製造方法、活物質及び電極 |
| US8535832B2 (en) * | 2009-08-27 | 2013-09-17 | Envia Systems, Inc. | Metal oxide coated positive electrode materials for lithium-based batteries |
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| JPWO2013018692A1 (ja) * | 2011-07-29 | 2015-03-05 | 三洋電機株式会社 | 非水電解質二次電池用正極活物質、その製造方法、当該正極活物質を用いた非水電解質二次電池用正極、及び、当該正極を用いた非水電解質二次電池 |
| KR20130030660A (ko) * | 2011-09-19 | 2013-03-27 | 삼성전자주식회사 | 전극활물질, 그 제조방법 및 이를 채용한 전극 및 리튬전지 |
| KR20130033154A (ko) | 2011-09-26 | 2013-04-03 | 전자부품연구원 | 리튬 이차전지용 양극 활물질, 그의 제조방법 및 그를 포함하는 리튬이차전지 |
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| CN102598371A (zh) * | 2009-10-29 | 2012-07-18 | Agc清美化学股份有限公司 | 锂离子二次电池用正极材料的制造方法 |
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| Publication number | Publication date |
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| EP3012890A1 (en) | 2016-04-27 |
| KR20150022090A (ko) | 2015-03-04 |
| TWI559603B (zh) | 2016-11-21 |
| EP3012890A4 (en) | 2017-03-08 |
| US9905841B2 (en) | 2018-02-27 |
| JP6135000B2 (ja) | 2017-05-31 |
| PL3012890T3 (pl) | 2019-11-29 |
| CN105453313A (zh) | 2016-03-30 |
| JP2016528686A (ja) | 2016-09-15 |
| US20160181593A1 (en) | 2016-06-23 |
| TW201523988A (zh) | 2015-06-16 |
| WO2015026080A1 (ko) | 2015-02-26 |
| EP3012890B1 (en) | 2019-05-15 |
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