CN107925062B - 负极活性材料和包含其的二次电池 - Google Patents
负极活性材料和包含其的二次电池 Download PDFInfo
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- CN107925062B CN107925062B CN201680046820.1A CN201680046820A CN107925062B CN 107925062 B CN107925062 B CN 107925062B CN 201680046820 A CN201680046820 A CN 201680046820A CN 107925062 B CN107925062 B CN 107925062B
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- 239000007773 negative electrode material Substances 0.000 title claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000002388 carbon-based active material Substances 0.000 claims abstract description 47
- 239000006183 anode active material Substances 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 33
- 239000002409 silicon-based active material Substances 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 150000001721 carbon Chemical group 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
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- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 125000001165 hydrophobic group Chemical group 0.000 claims description 5
- 229910021382 natural graphite Inorganic materials 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
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- 238000003860 storage Methods 0.000 claims description 3
- 239000005046 Chlorosilane Substances 0.000 claims description 2
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 2
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- 229910003002 lithium salt Inorganic materials 0.000 description 3
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- 238000006243 chemical reaction Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- 229910001558 CF3SO3Li Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 229910007966 Li-Co Inorganic materials 0.000 description 1
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- 229910008080 Li-Ni-Co-Mn Inorganic materials 0.000 description 1
- 229910003253 LiB10Cl10 Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910008295 Li—Co Inorganic materials 0.000 description 1
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- 229910006461 Li—Ni—Co—Mn Inorganic materials 0.000 description 1
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910006145 SO3Li Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- BEKPOUATRPPTLV-UHFFFAOYSA-N [Li].BCl Chemical compound [Li].BCl BEKPOUATRPPTLV-UHFFFAOYSA-N 0.000 description 1
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- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 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
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种负极活性材料和包含其的二次电池,且具体地,提供一种负极活性材料粒子,所述负极活性材料粒子包含:核,所述核包含碳基活性材料和氧官能团;以及壳,所述壳包围所述核并且包含硅基活性材料。根据本发明的负极活性材料粒子包含氧官能团,使得硅基活性材料可以粘附到碳基活性材料的表面。由于高电负性的氧而带负电的所述氧官能团通过静电引力吸引所述硅基活性材料的带正电的硅原子,并因此所述硅基活性材料可以强烈粘附至所述碳基活性材料。另外,由于氧官能团与所述碳基活性材料表面上的最外面的碳原子上可共价结合的位点的总数的2.0%~4.0%键合,所以可以使所述负极活性材料粒子的导电性能不因所述氧官能团而劣化。
Description
技术领域
相关申请的交叉参考
本申请要求于2015年10月15日和2016年10月14日提交的韩国专利申请2015-0143861号和2016-0133663号的优先权和权益,通过参考将其公开内容以其完整形式并入本文中。
本发明涉及负极活性材料及包含其的二次电池。
背景技术
由于化石燃料的使用迅速增加,所以对替代能源或清洁能源的使用的需求正在增加,并且使用电化学反应的发电和蓄电领域作为其一部分是当前最活跃的研究领域。
二次电池是使用电化学能的电化学装置的当前代表性实例。而且,其应用领域也一直在逐渐增加。近来,随着便携式装置如便携式计算机、移动电话、照相机等的技术发展和需求的不断增加,对作为能源的二次电池的需求正在迅速增加。对二次电池中提供高能量密度和工作电位并且具有长循环寿命和低自放电率的锂二次电池已经进行了大量研究,使得二次电池已经商业化并被广泛使用。
通常,二次电池包含正极、负极和电解质。此处,由于来自于正极活性材料的锂离子用于在通过在第一次充电中嵌入诸如碳粒子的负极活性材料中并在放电的情况下从其脱嵌而在两电极之间穿梭的同时传递能量,所以二次电池可以充电和放电。
例如,锂二次电池具有其中锂电解质浸渍在电极组件中的结构,所述电极组件含有包含锂过渡金属氧化物作为电极活性材料的正极、包含碳基活性材料的负极和多孔隔膜。通过以包含锂过渡金属氧化物的正极混合物涂布铝箔来制造正极,且通过以包含碳基活性材料的负极混合物涂布铜箔来制造负极。
在近年来作为高容量材料而进行研究的硅基材料中,硅-碳复合活性材料是通过将硅基材料设置在碳基负极活性材料的表面上而形成的活性材料,并在比碳基负极活性材料的理论容量(372mAh/g)更高的容量下具有优异的放电效率(80%),使其预期会作为高容量二次电池材料而得到普及。
然而,由于碳与硅的界面之间的结合力弱,所以在电极制造过程期间出现其中最外面的硅层从碳上脱落的现象。由于所述现象降低了硅的导电性并增加了其不可逆容量,因此其容量和效率降低。
因此,需要开发能够在提高碳与硅之间的结合力的同时提供优异导电性的负极活性材料。
现有技术文献
[专利文献]
(专利文献1)韩国专利公布10-2011-0100209号
发明内容
[技术问题]
本发明的第一个技术方面是提供一种负极活性材料粒子,所述负极活性材料粒子通过用氧官能团改性碳基活性材料的表面并且通过利用氧官能团与硅基活性材料之间的静电引力将碳基活性材料附着至硅基活性材料而具有高导电性和低不可逆容量。
本发明的第二个技术方面是提供包含所述负极活性材料粒子的二次电池、电池模块和电池组。
[技术方案]
根据本发明的一个方面,提供一种负极活性材料粒子,所述负极活性材料粒子包含:核,所述核包含碳基活性材料和氧官能团;以及壳,所述壳包围所述核并包含硅基活性材料。
根据本发明的另一个实施方式,提供一种二次电池、电池模块和电池组,所述二次电池包含负极、正极和电解质,其中向所述负极施涂了包含所述负极活性材料粒子的负极混合物。
有益效果
根据本发明的实施方式,负极活性材料粒子包含氧官能团,使得硅基活性材料附着至碳基活性材料的表面。由于氧官能团因具有高电负性的氧而带负电,所以氧官能团通过利用静电引力吸引带正电的硅基活性材料的硅原子,使得硅基活性材料和碳基活性材料彼此牢固结合。此外,相对于所述氧官能团可以共价结合的、在所述碳基活性材料的表面上的最外面碳原子的所有位点,当氧官能团结合至所述所有位点的2.0%~4.0%时,可以防止由于氧官能团而导致的负极活性材料粒子导电性的下降。
附图说明
图1是显示本说明书的实施例1~3和比较例1的循环效率的图。
具体实施方式
下文中,为了理解本发明将对本发明进行详细描述。
说明书和权利要求书中使用的术语不限于一般的或词汇的含义,并且应在发明人能够适当定义术语的含义而以最佳方式描述发明人的本发明的原则的基础上理解为具有适用于本发明的技术概念的含义和概念。
本文中使用的术语仅用于描述示例性实施方式,且并不旨在限制本发明。除非上下文另外定义,否则单数形式包括复数形式。
在整个说明书中,应当理解,术语“包含”、“具有”等在本文中用于指定所应用的特征、数字、步骤、要素或其组合的存在,但不排除存在或添加一个或多个其他特征、数字、步骤、要素或其组合。
根据本发明的一个实施方式,提供一种负极活性材料粒子,所述负极活性材料粒子包含:核,所述核包含碳基活性材料和氧官能团;以及壳,所述壳包围所述核并包含硅基活性材料。
碳基活性材料可以具有球形形状和5.0μm~20.0μm的平均直径D50。作为碳基活性材料,可以使用选自由如下构成的组中的一种或多种:天然石墨、人造石墨、硬碳和软碳。详细地,当使用球形天然石墨作为碳基活性材料时,可以提供将硅容易地分布到石墨表面的效果。
氧官能团可以共价结合至碳基活性材料的最外面碳原子。由于氧官能团因具有高电负性的氧而具有负电荷并且与具有正电荷的硅基活性材料的硅原子具有静电引力,所以碳基活性材料和硅基活性材料可以由于氧官能团而具有优异的结合力。
此处,相对于氧官能团可以共价结合的碳基活性材料的最外面碳原子的所有位点,氧官能团可以结合至所述所有位点的约2.0%~4.0%。当氧官能团以小于2.0%的比率结合时,由于对硅基活性材料提供静电引力的氧官能团的量较小,所以存在的问题是,碳基活性材料与硅基活性材料之间的结合力不足。当氧官能团以大于4.0%的比率结合时,活性材料的导电性降低。
指示氧官能团与碳基活性材料表面之间的连接程度的比率可通过使用X射线光电子能谱法或元素分析仪来定量测量。详细地,碳基活性材料的表面的氧含量可以通过X射线光电子能谱法导出。在本说明书中,相对于氧官能团可共价结合的碳基活性材料的最外面碳原子的所有位点,氧官能团对所述所有位点的结合率对应于通过X射线光电子能谱法测量的氧含量。以上述比率将氧官能团结合至碳基活性材料的表面可以通过在常压臭氧条件下在距碳基活性材料表面5~130mm的距离下发射具有184.9~253.7nm波长和0.02~0.05W/cm2强度的紫外线2~7小时来执行。此处,常压是指与大气压力相似的1个大气压的压力。
氧官能团可以是亲水基团和疏水基团中的一种或多种。特别地,当包含亲水基团和疏水基团两者时,提供了减少由于与电解质的反应而引起的产生HF的效果。
亲水基团可以是羟基和羧基中的一种或多种,且疏水基团可以是醚基和羰基中的一种或多种。然而,氧官能团不限于此。
包含硅基活性材料的壳可以具有包围核的至少一部分的形状,具体地包围核的整个表面的形状,并且可以具有均匀的厚度。壳的厚度可以是0.02μm~0.1μm。当壳的厚度小于0.02μm时,可能发生负极活性材料的容量不充分增加的问题。当壳的厚度大于0.1μm时,可能发生与硅基活性材料的粘附性降低的问题。
作为硅基活性材料,可以使用选自由如下构成的组中的一种或多种:结晶硅基活性材料、无定形硅基活性材料、硅氧化物(SiOx,0<x<2)和涂布有氧化物层的硅基活性材料。详细地,当使用无定形硅时,可以提供与碳基活性材料的氧官能团更高的静电引力。然而,硅基活性材料不限于此。
负极活性材料粒子可以进一步包含包围所述壳并包含碳基材料和聚合物中的一种或多种的涂层。所述碳基材料和聚合物可以使负极活性材料的导电性进一步提高,抑制负极活性材料的体积膨胀,并且减少其与电解质的反应。
此处,无定形碳可以用作所述碳基材料,导电聚合物可以用作所述聚合物,并且所述涂层可以具有0.02μm~0.1μm的厚度。另外,可以以负极活性材料粒子的总重量的1重量%~50重量%的量包含所述涂层。当所述涂层的含量小于所述总重量的1重量%时,存在抑制体积膨胀和导电性改善效果不足的问题。当所述涂层的含量超过所述总重量的50重量%时,存在锂离子难以脱嵌的问题。
根据本发明的一个实施方式,提供一种制造负极活性材料粒子的方法,所述方法包括对碳基活性材料进行紫外线-臭氧处理的操作(操作1)和在紫外线-臭氧处理的碳基活性材料上形成硅基活性材料壳的操作(操作2)。
在操作1中,碳基活性材料经紫外线-臭氧处理以将碳基活性材料的表面氧化,使得碳基活性材料的表面被改性成氧官能团。
此处,所述紫外线-臭氧处理可以在其中在常压臭氧条件下在距离碳基活性材料1~150mm处发射具有150~270nm波长和0.01~0.08W/cm2强度的紫外线的条件下进行。当在上述条件下进行紫外线-臭氧处理时,可以提供与硅基活性材料的优异的粘附性,并且可以保持活性材料的导电性。此处,常压是指与大气压力相似的1个大气压的压力。
详细地,在紫外线-臭氧处理条件下,在常压臭氧条件下在距离碳基活性材料5~130mm处发射具有184.9~253.7nm波长和0.02~0.05W/cm2强度的紫外线2~7小时。相对于氧官能团可共价结合的在碳基活性材料的最外面碳原子处的所有位点,氧官能团可以结合至所述所有位点的约2.0%~4.0%。
在操作2中,在紫外线-臭氧处理的碳基活性材料上形成硅基活性材料壳。操作2中的硅基活性材料涂层可以使用选自由如下构成的组中的一种或多种蒸汽通过化学气相沉积方法来形成:硅烷、三氯硅烷和氯硅烷。
根据本发明的一个实施方式,提供了一种二次电池,所述二次电池包含负极、正极和电解质,其中向所述负极施涂了包含所述负极活性材料粒子的负极混合物。
根据本发明实施方式的二次电池包含所述负极活性材料粒子。由于所述负极活性材料粒子因连接到碳基活性材料的氧官能团与硅基活性材料之间的静电引力而在碳基活性材料与硅基活性材料之间具有优异的粘附性,所以可以制造具有高容量和高密度的负极,并且包含所述负极的二次电池可以提供高循环特性。
例如通过将正极活性材料粒子、导电材料、粘合剂、填料和诸如N-甲基-2-吡咯烷酮(NMP)的溶剂等混合而成的正极混合物施涂到正极集电器,并对正极集电器进行干燥和辊压,可以制造根据本发明实施方式的正极。通过将包含根据本发明实施方式的负极活性材料粒子的负极混合物与有机溶剂混合而形成的浆料施涂到负极集电器,并对负极集电器进行干燥和辊压,可以制造负极。
正极活性材料没有特别限制,且详细地,可以是锂过渡金属氧化物。作为锂过渡金属氧化物,例如存在Li-Co类复合氧化物如LiCoO2等;Li-Ni-Co-Mn类复合氧化物如LiNixCoyMnzO2等;Li-Ni类复合氧化物如LiNiO2等;Li-Mn类复合氧化物如LiMn2O4等。可以将所述复合氧化物中的一种或多种用作正极材料。
导电材料没有特别限制,只要导电材料具有导电性而不会引起相应电池的化学变化即可。例如,可以使用:导电材料如石墨;炭黑如乙炔黑、科琴黑、槽法炭黑、炉黑、灯黑、热裂法炭黑等;导电纤维如碳纤维、金属纤维等;碳氟化合物;铝;金属粉末如镍粉等;导电晶须如钛酸等;聚亚苯基衍生物等。
正极或负极可以具有其中将正极混合物或负极混合物施涂到集电器的形式。集电器没有特别限制,只要集电器具有导电性而不引起相应电池的化学变化即可。例如,可以使用:铜,不锈钢,铝,镍,钛,烧制碳,其表面用碳、镍、钛、银等处理过的铝或不锈钢。
电解质可以包含非水有机溶剂和金属盐。
作为非水有机溶剂,例如可以使用非质子有机溶剂,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、丙酸乙酯等。
金属盐可以是锂盐。锂盐是在非水电解质中良好溶解的材料。例如,可以将如下物质用作锂盐: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、4-苯基硼酸锂、亚氨基锂等。
根据本发明的另一实施方式,提供了一种包含二次电池作为单元电池的电池模块以及包含电池模块的电池组。由于所述电池模块和电池组包含具有高循环特性的二次电池,所以电池模块和电池组可以用作诸如如下的一种或多种中-大型装置的电源:电动工具;电动车,包括电动车辆(EV)、混合动力车辆(HEV)和插电式HEV(PHEV);以及电力存储系统。
下文中,将详细描述本发明的实施例以使得本领域的普通技术人员能够实现本发明。然而,本发明可以以几种不同的形式来实现,而不限于本文中所描述的实施方式。
<实施例1>
操作1:将氧官能团引入到碳基活性材料的表面
通过将5.0g具有15μm平均直径D50的球形天然石墨放入紫外线-臭氧清洗器中,并在1个大气压的压力和25℃的温度下发射具有185nm波长和0.02W/cm2强度的紫外线,在常压下在阻断水的臭氧条件下在130mm的距离下持续3小时,从而制造了具有与其结合的-COOH或-OH的氧官能团的碳基活性材料。
操作2:制造硅基活性材料壳
通过将操作1中制造的具有与其结合的氧官能团的球形天然石墨放入化学气相沉积(CVD)室中,向其中供应硅烷气体,并在460℃下对所述室进行加热,制造了涂布有具有30nm厚度的无定形硅的壳。
操作3:制造碳涂层
最后,通过使用乙炔气体在900℃下用无定形碳对涂布有无定形硅的球形天然石墨进行涂布,制造了负极活性材料。此处,通过热重分析(TGA)设备检查其碳含量,并且碳含量为负极活性材料总重量的5重量%。
操作4:制造二次电池
通过将负极活性材料粒子、作为导电材料的炭黑、作为粘合剂的羧甲基纤维素(CMC)和丁苯橡胶(SBR)以95.8:1.7:1.5的重量比混合,制造了负极混合物。通过将该负极混合物施涂在铜集电器上,在130℃的温度下在真空烘箱中对具有负极混合物的铜集电器进行干燥,并对干燥的铜集电器进行辊压,制造了负极。通过在该负极与使用Li金属的对电极之间插入多孔聚乙烯隔膜,将碳酸甲乙酯(EMC)和碳酸亚乙酯(EC)以7:3的体积混合比混合而得到混合溶液、并将0.5重量%的碳酸亚乙烯基酯溶于该混合溶液中,并注入其中以1M的浓度溶解有LiPF6的电解质,制造了锂硬币型半电池。
<实施例2>
除了在紫外线-臭氧清洗器中发射的臭氧发射1小时以代替实施例1的操作1中的3小时之外,以与实施例1类似的方式制造了二次电池。
<实施例3>
除了在紫外线-臭氧清洗器中发射的臭氧发射8小时以代替实施例1的操作1中的3小时之外,以与实施例1类似的方式制造了二次电池。
<比较例1>制造不具有氧官能团的负极活性材料粒子
除了在实施例1的操作1中未引入氧官能团的事实之外,通过实施与实施例1类似的操作制造了二次电池。
<实验例1>
通过X射线光电子能谱法测定实施例1~3和比较例1的操作1中制造的碳基活性材料的氧含量,并将其结果示于表1。
[表1]
氧含量(%) | |
实施例1 | 2.32 |
实施例2 | 1.04 |
实施例3 | 5.30 |
比较例1 | 0.05 |
如表1所示,由于实施例1中的氧含量比比较例1高约45倍,因此能够确认,通过实施例1的操作1的紫外线-臭氧处理在碳基活性材料的表面上形成了包含氧的氧官能团,另外,在臭氧发射时间为3小时(满足2~7小时的条件)的实施例1中,氧含量为2.32%。另一方面,可以看出,不满足2~7小时的臭氧发射时间的实施例2和3的氧含量分别是小于实施例1的1.04%和大于实施例1的5.30%。
<实验例2>容量特性
按如下对实施例1和比较例1中制造的二次电池进行了评价,并将其结果示于下表2中。
充放电评价方法
充电恒定电流(CC)/恒定电压(CV)(5mV/0.005C电流截止(cut-off))条件
放电CC条件1.5V
电池的充电和放电在前两个循环中以0.1C实施,并且第3到第49个循环以0.5C实施。在50个循环的充电(其中锂在负极中)之后完成充电和放电,拆卸电池以测量其厚度,并计算电极厚度变化率。另外,使用每个循环的放电容量相对于充电容量之比率来测量循环效率,并且示于图1中。
[表2]
如表2所示,能够看出,与比较例1相比,实施例1~3中容量保持率和电极厚度变化率得到改善。
详细地,实施例1~3的初始效率比比较例1的更高。另外,氧含量为2.32%(满足2~4%)的实施例1具有比实施例2~3(不满足所述范围)更高的初始效率。
由此可以看出,与比较例1的二次电池相比,由于实施例1的二次电池通过使氧官能团存在于硅-石墨复合材料的界面上而增加了硅-石墨复合材料的结合力,因此其寿命特性提高且其电极厚度变化率也可以降低。
当参考图1对循环效率进行比较时,可以看出,比较例1的循环特性比实施例1~3的循环特性更差。另外,氧含量小于2%的实施例2的循环特性比实施例1的稍差。此外,可以看出,氧含量高于4%的实施例3在大多数循环中比实施例1具有更低的效率。
尽管以上已经对本发明的示例性实施方式进行了描述,但是本发明的范围不限于此,并且还包括本领域技术人员使用如下权利要求书中定义的本发明的基本概念而可想象到的各种变化和改进形式。
Claims (17)
1.一种负极活性材料粒子,所述负极活性材料粒子包含:核,所述核包含碳基活性材料和氧官能团;以及壳,所述壳包围所述核并包含硅基活性材料,
其中相对于所述氧官能团可以共价结合的所述碳基活性材料的最外面碳原子的所有位点,所述氧官能团结合至所述所有位点的2.0%~4.0%。
2.根据权利要求1所述的负极活性材料粒子,其中所述氧官能团包含亲水基团和疏水基团中的一种或多种。
3.根据权利要求2所述的负极活性材料粒子,其中所述亲水基团包含羟基和羧基中的一种或多种,且所述疏水基团包含醚基和羰基中的一种或多种。
4.根据权利要求1所述的负极活性材料粒子,其中所述氧官能团共价结合至所述碳基活性材料的最外面碳原子。
5.根据权利要求1所述的负极活性材料粒子,还包含涂层,所述涂层包围所述壳并包含碳基材料和聚合物中的一种或多种。
6.根据权利要求5所述的负极活性材料粒子,其中所述碳基材料包含无定形碳,且所述聚合物包含导电聚合物。
7.根据权利要求5所述的负极活性材料粒子,其中所述涂层为所述负极活性材料粒子的总重量的1~50重量%。
8.根据权利要求1所述的负极活性材料粒子,其中所述碳基活性材料包含选自由如下构成的组中的一种或多种:天然石墨、合成石墨、硬碳和软碳。
9.根据权利要求1所述的负极活性材料粒子,其中所述壳的厚度为0.02μm~0.1μm。
10.一种制造根据权利要求1所述的负极活性材料粒子的方法,包括:
操作1:对碳基活性材料进行紫外线-臭氧处理;和
操作2:在紫外线-臭氧处理的碳基活性材料上形成硅基活性材料壳。
11.根据权利要求10所述的方法,其中所述紫外线-臭氧处理通过在臭氧条件下在1~150mm距离下发射具有150~270nm波长和0.01~0.08W/cm2强度的紫外线来执行。
12.根据权利要求10所述的方法,其中所述紫外线-臭氧处理的条件通过在臭氧条件下在5~130mm距离下发射具有184.9~253.7nm波长和0.02~0.05W/cm2强度的紫外线2~7小时来执行。
13.根据权利要求10所述的方法,其中操作2中的所述硅基活性材料壳是使用选自由如下构成的组中的一种或多种蒸汽通过化学气相沉积(CVD)法来形成:硅烷、三氯硅烷和氯硅烷。
14.一种二次电池,所述二次电池包含负极、正极和电解质,其中向所述负极施涂了包含权利要求1的负极活性材料粒子的负极混合物。
15.一种电池模块,所述电池模块包含权利要求14的二次电池作为其单元电池。
16.一种电池组,所述电池组包含权利要求15的电池模块并用作中-大型装置的电源。
17.根据权利要求16所述的电池组,其中所述中-大型装置是选自由如下构成的组中的一种:电动车辆、混合动力车辆以及电力存储系统。
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