CN114628663A - 一种铈掺杂三元正极材料及其制备方法 - Google Patents
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- 239000010406 cathode material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 15
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000007774 positive electrode material Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 7
- 239000006257 cathode slurry Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
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- NIZQEIPBXOYBLV-UHFFFAOYSA-K O.O.O.O.O.O.C(C)(=O)[O-].[Ce+3].C(C)(=O)[O-].C(C)(=O)[O-] Chemical compound O.O.O.O.O.O.C(C)(=O)[O-].[Ce+3].C(C)(=O)[O-].C(C)(=O)[O-] NIZQEIPBXOYBLV-UHFFFAOYSA-K 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 229910003678 NixCoyMnz(OH)2 Inorganic materials 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 230000014759 maintenance of location Effects 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 9
- 239000011259 mixed solution Substances 0.000 abstract description 7
- 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 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 239000006256 anode slurry Substances 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
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- 238000005245 sintering Methods 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
提供了一种锂离子电池用铈掺杂三元正极材料及其制备方法。所述制备方法中,首先将铈源、三元材料前驱体与锂源于溶剂中溶解,制成混合溶液,而后洗涤、过滤、冷冻干燥,经过焙烧得到具有多孔结构的铈掺杂镍钴锰酸锂三元正极材料。通过该制备方法,调控了材料颗粒大小,加强了三元材料的高温稳定性,同时获得的铈掺杂三元正极材料具有多孔结构,由此提高了锂离子电池的高温存储容量保持率和循环性能。
Description
技术领域
本发明属于锂离子电池制造技术领域,具体涉及一种锂离子电池用铈掺杂三元正极材料及其制备方法。
背景技术
近年来,随着工业的发展和化石能源的消耗,环境污染和温室效应已成为日益严重的问题,亟需绿色清洁的能源来解决。相比于其它电池,锂离子电池由于其容量大、工作电压稳定、无环境污染等优势,被广泛应用于笔记本电脑、手机、数码相机、储能和电动汽车等领域。电动汽车具有绿色环保的优势,受到了广泛的关注,同时也对电池的循环寿命、高温存储容量保持率等性能提出更高的要求。
锂离子电池正极材料的性能对锂离子电池的性能会产生决定性的影响。其中,三元正极材料镍钴锰酸锂具备成本低、比容量高等优势,受到广泛的关注和研究。而适量过渡金属阳离子铈的引入可以通过调控材料颗粒大小和加强三元材料的高温稳定性,从而提升锂离子电池的循环稳定性和高温存储容量保持率。
目前铈掺杂三元正极材料的制备工艺主要有高温固相烧结法、水热法和化学沉淀法。
其中;
高温固相烧结法是首先将铈源、镍钴锰氢氧化物前驱体与锂源通过研磨而混合,之后将上述固体粉末在高温下进行煅烧,随炉冷却至室温,最终制得结晶度较高的铈掺杂三元正极材料。其缺点在于:由于粉碎球磨难以控制,且原材料固体粉末的难以混合均匀,高温固相烧结法所得铈掺杂三元正极材料的颗粒大小和表面形貌难以控制。此外,固相法所需能耗大,且制备效率低下,严重限制了其广泛应用。
水热法是先将铈源、镍源、钴源、锰源与锂源于溶剂中溶解,制成混合溶液,而后于烘箱中加热一定时间,最后将制得的固体颗粒经过多次洗涤、干燥,得到铈掺杂镍钴锰酸锂三元正极材料,其具有颗粒较小,混合均匀的优势。然而,水热法所得的三元材料纯度难以控制,且步骤较为繁琐,产率较低,不能满足工业化大规模生产三元正极材料的实际要求。
由此,亟需一种新的锂离子电池用铈掺杂正极材料制备方法来解决上述技术问题。
发明内容
为此,本发明提供了一种锂离子电池用三元正极材料制备方法及锂离子电池。
本发明提供了一种锂离子电池用铈掺杂三元正极材料制备方法,其为化学沉淀法,具体步骤包括:
(1)将铈源、三元正极材料前驱体加入溶剂中,形成溶液;
(2)向步骤(1)得到的溶液中加入锂源,得到浆料;
(3)对步骤(2)得到的浆料进行抽滤,而后洗涤,得到固体颗粒;
(4)对步骤(3)得到的固体颗粒进行冷冻干燥,得到具有多孔结构的铈掺杂三元正极材料前驱体;
(5)对步骤(4)得到的铈掺杂三元正极材料前驱体进行焙烧,得到具有多孔结构的铈掺杂三元正极材料。
其中,所述铈源包括六水合乙酸铈(Ce(C2H3O2)3·6H2O)。
其中,所述三元正极材料前驱体包括NixCoyMnz(OH)2的二次球或单晶材料前驱体,其中x+y+z=1。
其中,所述锂源包括LiOH·H2O或Li2CO3。
其中,所述溶剂为正丙醇或正丁醇。
其中,铈源的用量为a摩尔,三元正极材料前驱体的用量为b摩尔,锂源的用量为c摩尔,a、b、c满足以下关系式:0.7c≤a+b≤0.8c(优选a+b=0.76c),且a≤0.1b。
其中,所述步骤(1)中,在室温(25℃)的水浴锅中,300~800r/min的转速下,将一定摩尔比的铈源和三元正极材料前驱体依次加入到溶剂中,持续搅拌30~80min使上述材料均匀分散,形成均一溶液。
其中,所述步骤(2)中,向步骤(1)得到的溶液中加入锂源,在室温水浴条件下,以900~1600r/min的转速,搅拌30~90min,获得均匀浆料。
其中,所述步骤(3)中,所述洗涤包括:用去离子水和无水乙醇交替洗涤4-7次(优选5次)。
其中,所述步骤(4)中,所述冷冻干燥包括:将固体颗粒置于冷冻干燥机中,在-90至-70℃(优选-80℃)下冷冻干燥40~60h。
其中,所述步骤(5)中,将步骤(4)得到的铈掺杂三元正极材料前驱体置于管式炉中,在惰性气氛保护下,于450~750℃下焙烧240~480min,随炉冷却至室温,得到具有多孔结构的铈掺杂三元正极材料;其中,所述惰性气氛包括氮气、氦气、氩气中的一种或多种。
本发明还提供了一种锂离子电池用铈掺杂三元正极材料,其由上述锂离子电池用铈掺杂三元正极材料制备方法所制备得到。
本发明还提供了一种锂离子电池正极浆料,其包括上述铈掺杂三元正极材料。
本发明还提供了一种锂离子电池正极浆料的制备方法,包括将上述铈掺杂三元正极材料加入到包括N-甲基吡咯烷酮(NMP)、聚偏氟乙烯(PVDF)、碳纳米管(CNT)、导电剂的混合浆料中,通过搅拌使其均匀分散,得到锂离子电池正极浆料。
本发明还提供了一种锂离子电池,其包括上述锂离子电池正极浆料。
由此,本发明具有以下有益技术效果:
本发明采用化学沉淀法,首先将铈源、三元材料前驱体与锂源于溶剂中溶解,制成混合溶液,而后洗涤,过滤,冷冻干燥,经过焙烧得到具有多孔结构的铈掺杂镍钴锰酸锂三元正极材料。
本发明的方法中,铈的引入增强了三元材料的高温稳定性能,降低了三元材料的结晶度,使得材料颗粒直径减小,提高了锂离子电池的高温存储容量保持率。
本发明通过冷冻干燥法进行干燥,获得的铈掺杂三元正极材料具有多孔结构,促进了电解液的浸润,提供了锂离子传输通道,有利于提升锂离子电池的循环稳定性。
本发明所述方法调控了材料颗粒大小,加强了三元材料的高温稳定性;采用本发明所述铈掺杂三元正极材料所制备的正极浆料具备分散均匀、细度较低的优势,有利于进行后续涂布等工艺步骤;获得的锂离子电池循环性能得到改善,具有稳定的长循环性能和出色的高温存储容量保持率,在常温下循环1300圈后,容量保持率依然高于90%。
附图的简要说明
图1为本发明实施例1的三元正极材料及正极浆料制备流程图。
图2为本发明实施例和对比例的正极浆料细度图。
图3为利用本发明实施例2的三元正极材料所制备的锂离子电池常温循环性能图。
具体实施方式
下面结合具体实施例对本发明作进一步详细的描述。但应理解这些实施例仅用于说明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请权利要求书所限定的范围。
实施例1
实施例1所述三元正极材料及正极浆料制备步骤如图1所示,包括:
步骤(1):在室温(25℃)的水浴锅中,600r/min的转速下,将0.05mol的铈源(六水合乙酸铈,Ce(C2H3O2)3·6H2O)和0.71mol的三元正极材料前驱体Ni0.65Co0.15Mn0.2(OH)2依次加入到500mL正丙醇中,持续搅拌65min使上述材料均匀分散,形成均一溶液;
步骤(2):向上述混合溶液中加入1mol的锂源(LiOH·H2O),在25℃水浴条件下,以1600r/min的转速,搅拌80min,获得均匀浆料;
步骤(3):将上一步所得浆料进行抽滤,并采用去离子水和无水乙醇交替洗涤5次;
步骤(4):将步骤(3)所得固体颗粒置于冷冻干燥机中,在-80℃下冷冻干燥50h,得到具有多孔结构的掺杂比例为7.04%的铈掺杂三元正极材料前驱体;
步骤(5):将步骤(4)所得铈掺杂三元正极材料前驱体置于管式炉中,在氮气气氛保护下,于720℃下焙烧240min,随炉冷却至室温,得到具有多孔结构的掺杂比例为7.04%的铈掺杂三元正极材料;
步骤(6):使用步骤(5)所得的铈掺杂三元正极材料,加入到N-甲基吡咯烷酮(NMP)、聚偏氟乙烯(PVDF)、碳纳米管(CNT)、导电剂的混合浆料中,通过搅拌使其均匀分散,得到锂离子电池正极浆料。
实施例1所得三元正极材料对应正极浆料细度如图2(a)所示,细度约为30μm;
实施例1所得三元正极材料对应锂离子电池高温(45℃)存储(7天)容量保持率如表1所示,为96.7%。
表1实施例和对比例的高温存储容量保持率
实施例1 | 实施例2 | 对比例1 | |
容量保持率 | 96.7% | 97.5% | 95.8% |
实施例2
具体步骤和反应条件与实施例1一致,区别在于,步骤(1)中Ce(C2H3O2)3·6H2O和三元正极材料前驱体Ni0.65Co0.15Mn0.2(OH)2的添加量分别为0.01mol和0.75mol,最终获得具有多孔结构的掺杂比例为1.33%的铈掺杂三元正极材料。
实施例2所得铈掺杂三元正极材料对应正极浆料细度如图2(b)所示,细度低于30μm;
实施例2所得铈掺杂三元正极材料制备的锂离子电池常温循环性能如图3所示,常温下循环1300圈后,容量保持率依然高于90%。
实施例2所得三元正极材料对应锂离子电池高温存储(7天)容量保持率如表1所示,为97.5%;
对比例1
具体步骤和反应条件与实施例1一致,区别在于,步骤(1)中Ce(C2H3O2)3·6H2O和三元正极材料前驱体Ni0.65Co0.15Mn0.2(OH)2的添加量分别为0mol和0.76mol,最终获得未掺杂的三元正极材料。
对比例1制得正极浆料细度如图2(c)所示,细度高于30μm。
对比例1所得三元正极材料对应锂离子电池高温存储(7天)容量保持率如表1所示,为95.8%。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (10)
1.一种锂离子电池用铈掺杂三元正极材料制备方法,包括:
(1)将铈源、三元正极材料前驱体加入溶剂中,形成溶液;
(2)向步骤(1)得到的溶液中加入锂源,得到浆料;
(3)对步骤(2)得到的浆料进行抽滤,而后洗涤,得到固体颗粒;
(4)对步骤(3)得到的固体颗粒进行冷冻干燥,得到具有多孔结构的铈掺杂三元正极材料前驱体;
(5)对步骤(4)得到的铈掺杂三元正极材料前驱体进行焙烧,得到具有多孔结构的铈掺杂三元正极材料。
2.如权利要求1所述的铈掺杂三元正极材料制备方法,其中,所述铈源包括六水合乙酸铈(Ce(C2H3O2)3·6H2O);所述三元正极材料前驱体包括NixCoyMnz(OH)2的二次球或单晶材料前驱体,其中x+y+z=1;所述锂源包括LiOH·H2O或Li2CO3;所述溶剂为正丙醇或正丁醇。
3.如权利要求1所述的铈掺杂三元正极材料制备方法,其中,铈源的用量为a摩尔,三元正极材料前驱体的用量为b摩尔,锂源的用量为c摩尔,a、b、c满足以下关系式:0.7c≤a+b≤0.8c,且a≤0.1b。
4.如权利要求1所述的铈掺杂三元正极材料制备方法,其中,所述步骤(1)中,在室温的水浴锅中,将一定摩尔比的铈源和三元正极材料前驱体依次加入到溶剂中,持续搅拌使其均匀分散,形成均一溶液。
5.如权利要求1所述的铈掺杂三元正极材料制备方法,其中,所述步骤(2)中,向步骤(1)得到的溶液中加入锂源,在室温水浴条件下,搅拌获得均匀浆料。
6.如权利要求1所述的铈掺杂三元正极材料制备方法,其中,所述步骤(4)中,所述冷冻干燥包括:将固体颗粒置于冷冻干燥机中,在-90至-70℃下冷冻干燥40~60h。
7.如权利要求1所述的铈掺杂三元正极材料制备方法,其中,所述步骤(5)中,将步骤(4)得到的铈掺杂三元正极材料前驱体在惰性气氛保护下,于450~750℃下焙烧240~480min,然后冷却。
8.一种锂离子电池用铈掺杂三元正极材料,其由权利要求1-7任一所述锂离子电池用铈掺杂三元正极材料制备方法所制备得到。
9.一种锂离子电池正极浆料,其包括如权利要求8所述的铈掺杂三元正极材料。
10.一种锂离子电池,其包括如权利要求9所述的锂离子电池正极浆料。
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