CN113611838A - 一种新型双掺杂混合无钴体系正极片,锂离子电池 - Google Patents
一种新型双掺杂混合无钴体系正极片,锂离子电池 Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- 239000011572 manganese Substances 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007774 positive electrode material Substances 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000011883 electrode binding agent Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910014985 LiMnxFe1-xPO4 Inorganic materials 0.000 claims description 2
- 229910014982 LiMnxFe1−xPO4 Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010450 olivine Substances 0.000 claims description 2
- 229910052609 olivine Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- 229910001170 xLi2MnO3-(1−x)LiMO2 Inorganic materials 0.000 claims description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229910015645 LiMn Inorganic materials 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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Abstract
本发明属于锂离子电池技术领域,具体涉及一种新型双掺杂混合无钴体系正极片及包含该正极片的锂离子电池,所述正极片包括正极集流体和涂覆在正极集流体上的正极涂层,正极涂层的组分包括正极活性物质,所述正极活性物质为锰酸锂、磷酸锰铁锂和富锂锰基正极材料组成的混合物。本发明将磷酸锰铁锂、锰酸锂、富锂锰基正极材料混合搭配使用,锰酸锂低成本、高安全,磷酸锰铁锂提供高容量,长循环,富锂锰基正极材料改善锰酸锂的高温性能和高温循环性能。使用本发明正极片的电池的能量密度、高温和循环、安全性能均明显优于纯锰酸锂材料的电池,并且由于极片中没有三元材料,因此也显著降低了电池的制造成本。
Description
技术领域
本发明属于锂离子电池技术领域,具体涉及一种新型双掺杂混合无钴体系正极片,锂离子电池。
背景技术
电动汽车、电动自行车和电动工具等领域对锂离子电池的需求量逐年增加。在不久的将来锂离子电池的产量必将迎来一段时间的爆发式增长。
现有锂离子电池正极材料有钴酸锂、锰酸锂、磷酸铁锂、三元材料等,其中钴酸锂能量密度高,压实密度高,但是循环性能一般、且含有稀缺元素钴,价格昂贵;锰酸锂具有价格便宜、锰资源丰富、安全性好的特点,但是克容量偏低,且循环性能、高温性能差;磷酸铁锂具有安全、循环性能好、价格低等优势,但压实密度低、电子电导率差、电压平台低,仅为3.2V,难以搭配与锰酸锂或镍钴锰酸锂等材料混搭使用;镍钴锰酸锂材料具有克容量高,循环性能好等优势,但同样含有钴,且安全性很差。
与磷酸铁锂相比,磷酸锰铁锂具有4.0V左右的高电位,以及与磷酸铁锂相同的理论容量,在同等容量的前提下,磷酸锰铁锂电池比磷酸铁锂电池能量密度高近20%。且与磷酸铁锂相比,磷酸锰铁锂与其具有同样地循环和安全性能。
发明内容
本发明的第一个目的是针对现有电池材料体系技术中所存在的问题,提供新型双掺杂混合无钴体系正极片,发挥各材料的优势取长补短;本发明的第二个目的提供一种包含上述正极片的锂离子电池。
为达到上述目的,本发明采用的技术方案如下:
一种新型双掺杂混合无钴体系正极片,包括正极集流体和涂覆在所述正极集流体上的正极涂层,所述正极涂层的组分包括正极活性物质、正极导电剂、正极粘结剂,所述正极活性物质为锰酸锂、磷酸锰铁锂和富锂锰基正极材料组成的混合物;
本发明中作为基体材料的锰酸锂具有较大的粒径,而作为掺混材料的磷酸锰铁锂分别具有中等的粒径和较小的粒径;在混合过程中,小颗粒粒径的磷酸锰铁锂接力可以填入大粒径的锰酸锂颗粒的空隙中,从而提升作为复合材料的正极活性材料的压实密度与体积能量密度,进而提高容量性能,基体材料中加入富锂锰基正极材料,有助于改善纯锰酸锂材料电芯的高温性能。
优选地,所述锰酸锂具有尖晶石型晶体结构,化学式为LiMn2O4;所述磷酸锰铁锂具有斜方晶的橄榄石型晶体结构,化学式为LiMnxFe1-xPO4,其中0.5≤x<1.0;所述富锂锰基正极材料具有层状结构,化学式为xLi2MnO3(1-x)LiMO2,其中,M=Ni、Mn。
优选地,所述正极涂层以百分比计包括以下组分:10~90%wt锰酸锂,3~25%wt磷酸锰铁锂,3~25%wt富锂锰基正极材料,0.3~4%wt正极导电剂,0.3~4%wt正极粘结剂。
优选地,所述正极导电剂为炭黑、碳纳米管、导电石墨、碳纤维中的一种或两种以上的混合物。
优选地,所述正极粘结剂为聚偏氟乙烯。
优选地,所述正极片的制备包含以下步骤:
S1.按比例分别称量锰酸锂、磷酸锰铁锂、富锂锰基正极材料、正极导电剂、正极导电剂,加入N-甲基吡咯烷酮作为溶剂搅拌均匀,得到浆料;
S2.将上述浆料均匀地涂布在铝箔上,烘干、辊压。
基于一个总的发明构思,本发明的另一个目的在于保护一种锂离子电池,包含上述任意一项所述的新型双掺杂混合无钴体系正极片。
与现有技术相比,本发明的优点和积极效果如下:
1、本发明采用的正极片将磷酸锰铁锂、锰酸锂、富锂锰基正极材料混合搭配使用,锰酸锂低成本、高安全,磷酸锰铁锂提供高容量,长循环,富锂锰基正极材料改善锰酸锂的高温性能和高温循环性能。
2、使用本发明正极片的锂离子电池,能量密度、高温性能和循环性能明显优于纯锰酸锂材料的电池。
3、使用本发明正极片的锂离子电池,安全性能明显高于纯镍钴锰酸锂材料电池,并且由于极片中没有三元材料,因此也显著降低了电池的制造成本。
附图说明
图1为本发明实施例1循环容量保持率对比图。
具体实施方式
为使本发明的目的、技术方案和优点更加明白清楚,结合具体实施方式,对本发明做进一步描述,但是本发明并不限于这些实施例。需要说明的是,在不相冲突的前提下,以下描述的各实施例之间或各技术特征之间可以任意组合形成新的实施例。在本发明中,若非特指,所有的份、百分比均为质量单位,所采用的设备和原料等均可从市场购得或是本领域常用的。下述实施例中的方法,如没有特别说明,均为本领域的常规方法。
下面结合附图对本发明的具体实施例做详细说明。
实施例1
按质量比为4%∶13%∶79%∶1%∶0.7%∶2.3%称取对应的LiMn7Fe3PO4、6Li2MnO34LiMO2、LiMn2O4、炭黑、碳纳米管、聚偏氟乙烯,加入适量的N-甲基吡咯烷酮,搅拌均匀得到常规粘度的浆料;将浆料涂敷在铝箔上,烘干、辊压、裁切成合适大小的正极片;用此极片组成锂离子电池,并测试其电性能。
同时,在其他条件相同的情况下,制作正极仅用锰酸锂材料制作的电池,作为对比样1。如图1所示为循环容量保持率对比图,实施例1:1C充放循环360周容量保持率91.08%,对比样1:1C充放循环360周容量保持率73.88%。
实施例2
按质量比为8%∶19%∶99%∶1%∶0.7%∶2.3%称取对应的LiMn6Fe4PO4、6Li2MnO34LiMO2、LiMn2O4、炭黑、碳纳米管、聚偏氟乙烯,加入适量的N-甲基吡咯烷酮,搅拌均匀得到常规粘度的浆料;将浆料涂敷在铝箔上,烘干、辊压、裁切成合适大小的正极片;用此极片组成锂离子电池,并测试其电性能。
同时,在其他条件相同的情况下,制作正极仅用锰酸锂材料制作的电池,作为对比样2;如下表1所示为100%SOC针刺试验对比结果:
由图1和表1可知,采用本发明新型双掺杂混合无钴体系正极片制成的锂离子电池的电性能和安全性能均优于单独使用镍钴锰酸锂材料和锰酸锂材料制成的锂离子电池。
上述实施例仅仅是本发明的较优实施方式,凡是依据本发明的技术实质对以上实施例所做的任何简单修饰、修改及替代变化,均属于本发明技术方案的范围内。
Claims (7)
1.一种新型双掺杂混合无钴体系正极片,其特征在于,包括正极集流体和涂覆在所述正极集流体上的正极涂层,所述正极涂层的组分包括正极活性物质、正极导电剂、正极粘结剂,所述正极活性物质为锰酸锂、磷酸锰铁锂和富锂锰基正极材料组成的混合物。
2.根据权利要求1所述的一种新型双掺杂混合无钴体系正极片,其特征在于,所述锰酸锂具有尖晶石型晶体结构,化学式为LiMn2O4;所述磷酸锰铁锂具有斜方晶的橄榄石型晶体结构,化学式为LiMnxFe1-xPO4,其中0.5≤x<1.0;所述富锂锰基正极材料具有层状结构,化学式为xLi2MnO3(1-x)LiMO2,其中,M=Ni、Mn。
3.根据权利要求1所述的一种新型双掺杂混合无钴体系正极片,其特征在于,所述正极涂层以百分比计包括以下组分:10~90%wt锰酸锂,3~25%wt磷酸锰铁锂,3~25%wt富锂锰基正极材料,0.3~4%wt正极导电剂,0.3~4%wt正极粘结剂。
4.根据权利要求1所述的一种新型双掺杂混合无钴体系正极片,其特征在于,所述正极导电剂为炭黑、碳纳米管、导电石墨、碳纤维中的一种或两种以上的混合物。
5.根据权利要求1所述的一种新型双掺杂混合无钴体系正极片,其特征在于,所述正极粘结剂为聚偏氟乙烯。
6.根据权利要求1所述的一种新型双掺杂混合无钴体系正极片,其特征在于,所述正极片的制备包含以下步骤:
S1.按比例分别称量锰酸锂、磷酸锰铁锂、富锂锰基正极材料、正极导电剂、正极导电剂,加入N-甲基吡咯烷酮作为溶剂搅拌均匀,得到浆料;
S2.将上述浆料均匀地涂布在铝箔上,烘干、辊压。
7.一种锂离子电池,其特征在于,包含权利要求1~6中任意一项所述的新型双掺杂混合无钴体系正极片。
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CN115939305A (zh) * | 2022-08-12 | 2023-04-07 | 宁德时代新能源科技股份有限公司 | 正极片及其制备方法、电极组件、电池单体、电池和用电设备 |
WO2023159385A1 (zh) * | 2022-02-23 | 2023-08-31 | 宁德时代新能源科技股份有限公司 | 正极极片及二次电池、电池模块、电池包和用电装置,及平衡电池内部电压差的方法 |
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