CN107342402B - 一种制备LiNi1/3Co1/3Mn1/3O2三元正极材料的方法 - Google Patents
一种制备LiNi1/3Co1/3Mn1/3O2三元正极材料的方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000010406 cathode material Substances 0.000 title claims abstract description 10
- 229910016104 LiNi1 Inorganic materials 0.000 title description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000007774 positive electrode material Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 238000007873 sieving Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 6
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 150000002696 manganese Chemical class 0.000 claims abstract description 6
- 150000002815 nickel Chemical class 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 6
- 229910001437 manganese ion Inorganic materials 0.000 claims description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 2
- 238000000975 co-precipitation Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 18
- 239000002033 PVDF binder Substances 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 229910013716 LiNi Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- -1 and drying Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
本发明提供一种制备LiNi1/3Co1/3Mn1/3O2三元正极材料的方法,具体包括将镍盐、钴盐、锰盐的混合溶液滴加到NaOH溶液中,并加入氨水作为络合剂,搅拌,保温反应10‑12小时,得到黑色悬浊液,静置、过滤、洗涤、干燥得到前驱体;将前驱体和Li2CO3以无水乙醇为介质球磨4‑6小时后,干燥,400‑500℃下烧结3‑6小时,随后在850‑950℃下烧结10‑14小时、过筛,得到LiNi1/3Co1/3Mn1/ 3O2三元正极材料。相比于传统的共沉淀法,本发明中使用的制备方法不需要通入氮气,且大大降低了生产成本;本发明中使用的制备方法在合成前驱体过程中不需严格控制反应体系的pH值,即在合成前驱体的过程中不需通过持续加入氨水来调节pH值。
Description
技术领域
本发明涉及一种简单有效制备高性能LiNi1/3Co1/3Mn1/3O2三元正极材料的方法,属于电化学电源领域。
背景技术
自从2001年Ohzuku和Makimura首次提出LiNi1/3Co1/3Mn1/3O2三元材料可用作锂离子电池正极材料以来,该材料就受到了人们的广泛关注。LiNi1/3Co1/3Mn1/3O2综合了LiCoO2、LiNiO2、LiMnO2三种层状材料的优点,Co可以减少阳离子混排,稳定材料层状结构,Ni可以提高材料容量,Mn不仅可以降低材料成本,还可以提高材料的安全性和稳定性。因此,LiNi1/ 3Co1/3Mn1/3O2三元正极材料具有比容量高、循环性能和热稳定性好、成本低等多种优点,是一种理想的锂离子电池正极材料。大量研究表明,材料的合成方法对电化学性能有重要的影响,因为材料的制备工艺决定着三元材料的阳离子混排,粒径以及形貌等。目前为止,多种多样的合成方法已经成功应用于LiNi1/3Co1/3Mn1/3O2三元材料的合成,包括水热法、固相法、溶胶-凝胶法、喷雾干燥法、共沉淀法等。其中,共沉淀法由于其能控制前驱体的结晶化过程、颗粒的形貌及尺寸而被认为是最佳的合成方法之一。但是合成三元材料所使用的传统共沉淀法对工艺要求比较严格,如:需要不断地通入氮气或氩气、严格控制反应体系的pH值等。这些条件无疑会增加三元材料生产的难度及成本。而本发明在合成前驱体的过程中不需要严格控制反应体系的pH值,在空气气氛中直接合成前驱体,并由该前驱体制备得到了电化学性能优异的LiNi1/3Co1/3Mn1/3O2三元正极材料,大大简化了三元材料的生产工艺。
发明内容
本发明的目的在于提供一种利用简单方法制备的LiNi1/3Co1/3Mn1/3O2三元正极材料,所涉及的LiNi1/3Co1/3Mn1/3O2三元正极材料其合成原料为锂盐(Li2CO3)、Ni盐(NiSO4·6H2O)、Co盐(CoSO4·7H2O)、Mn盐(MnSO4·H2O)。
所述的锂盐、镍盐、钴盐、锰盐的摩尔比为1.03-1.12:0.333:0.333:0.333。
所述的锂盐、镍盐、钴盐、锰盐的纯度均大于98 %。
本发明所述的简单合成LiNi1/3Co1/3Mn1/3O2三元正极材料的方法有以下优势:(1)相比于传统的共沉淀法,本发明中使用的制备方法不需要通入氮气,生产操作更容易,且大大降低了生产成本;(2)本发明中使用的制备方法在合成前驱体过程中不需严格控制反应体系的pH值,即在合成前驱体的过程中不需通过持续加入氨水来调节pH值,使合成工艺更简单。
本发明的另一目的在于提供一种简单有效的制备高性能LiNi1/3Co1/3Mn1/3O2三元正极材料的方法。将在空气中合成的前驱体干燥后与过量的锂盐混合,进行高温烧结得到电化学性能优异的LiNi1/3Co1/3Mn1/3O2三元正极材料。
具体的制备方法为:
将混合均匀的含镍离子、钴离子、锰离子的溶液滴加到NaOH溶液中,(均匀搅拌并保温12小时)得到黑色的悬浊液。将悬浊液静置6-8小时后,过滤、洗涤、干燥,得到前驱体。将前驱体与Li2CO3在无水乙醇介质中球磨4-6小时,干燥,在空气气氛中400-500 ℃下烧结3-6小时,随后在850-950 ℃下烧结10-14小时,冷却后,研磨过筛,得到LiNi1/3Co1/3Mn1/3O2三元正极材料。
附图说明
图1为样品的X射线衍射图谱:(a)对比例,(b)实施例1,(c)实施例2,(d)实施例3。
图2为实施例2与比较例1样品的电化学性能图:(a)充放电曲线,(b)循环性能曲线。
具体实施方式
下面通过实施例的描述,进一步阐述本发明的实质性特点和优势。为描述方便,首先对比较例加以叙述,然后再描述实施例,与之比较,显示出本发明的效果。
比较例1
将1.7515 g NiSO4·6H2O、1.8731 g CoSO4·7H2O、1.1266 g MnSO4·H2O以摩尔比1:1:1依次溶解在80 mL去离子水中,搅拌30分钟使其完全溶解,同时将1.6109 g NaOH加入到80 mL去离子水中。然后,将含镍离子、钴离子、锰离子的混合溶液滴加到NaOH溶液中,并加入15 mL浓度为3.35 mol L-1的氨水作为络合剂,以400 r min-1的转速进行搅拌,在反应体系中充入氮气作为保护气体,在50-55 ℃下保温反应12小时,得到粉红色悬浊液,静置6-8小时后过滤,洗涤数次,在90 ℃烘箱中干燥9小时,得到前驱体。在前驱体(1.8 g)中加入0.7265 g Li2CO3,以无水乙醇为介质球磨6小时后,干燥,并在450 ℃下烧结5小时后再在900 ℃下烧结12小时,冷却、过筛,得到LiNi1/3Co1/3Mn1/3O2三元正极材料。将LiNi1/3Co1/ 3Mn1/3O2三元正极材料与乙炔黑、聚偏氟乙烯(PVdF)按质量比为75:15:10混合成浆料,涂布于铝箔上,经过干燥、冲膜和压膜制成LiNi1/3Co1/3Mn1/3O2三元正极材料电极片。以金属锂箔为对电极,Celgard 2400为隔膜,1M LiPF6/(EC+DMC) (1:1)为电解液,组装成R2025扣式电池进行恒流充放电测试,电压范围在2.8-4.5 V之间。材料在0.5 C时的首次放电比容量为182.7 mAh g-1,经过50次循环后其放电比容量为146.3 mAh g-1。
实施例1
将1.7515 g NiSO4·6H2O、1.8731 g CoSO4·7H2O、1.1266 g MnSO4·H2O以摩尔比1:1:1依次溶解在40 mL去离子水中,搅拌30分钟使其完全溶解,同时将1.6109 g NaOH加入到80 mL去离子水中。然后,将含镍离子、钴离子、锰离子的混合溶液滴加到NaOH溶液中,并加入15 mL浓度为3.35 mol L-1的氨水作为络合剂,以400 r min-1的转速进行搅拌,在50-55 ℃下保温反应12小时,得到黑色悬浊液,静置6-8小时后过滤,洗涤数次,在90 ℃烘箱中干燥9小时,得到前驱体。在前驱体(1.8 g)中加入0.7265 g Li2CO3,以无水乙醇为介质球磨6小时后,干燥,并在450 ℃下烧结5小时后再在900 ℃下烧结12小时,冷却、过筛,得到LiNi1/3Co1/3Mn1/3O2三元正极材料。将LiNi1/3Co1/3Mn1/3O2三元正极材料与乙炔黑、聚偏氟乙烯(PVdF)按质量比为75:15:10混合成浆料,涂布于铝箔上,经过干燥、冲膜和压膜制成LiNi1/ 3Co1/3Mn1/3O2三元正极材料电极片。以金属锂箔为对电极,Celgard 2400为隔膜,1M LiPF6/(EC+DMC) (1:1)为电解液,组装成R2025扣式电池进行恒流充放电测试,电压范围在2.8-4.5 V之间。该三元材料在0.5 C时的首次放电比容量为189.2 mAh g-1,经过50次循环后其放电比容量为150.8 mAh g-1。
实施例2
将1.7515 g NiSO4·6H2O、1.8731 g CoSO4·7H2O、1.1266 g MnSO4·H2O以摩尔比1:1:1依次溶解在80 mL去离子水中,搅拌30分钟使其完全溶解,同时将1.6109 g NaOH加入到80 mL去离子水中。然后,将含镍离子、钴离子、锰离子的混合溶液缓慢滴加到NaOH溶液中,并加入15 mL浓度为3.35 mol L-1的氨水作为络合剂,以400 r min-1的转速进行搅拌,在50-55 ℃下保温反应12小时,得到黑色悬浊液,静置6-8小时后过滤,洗涤数次,在90 ℃烘箱中干燥9小时,得到前驱体。在前驱体(1.8 g)中加入0.7265 g Li2CO3,以无水乙醇为介质球磨6小时后,干燥,并在450 ℃下烧结5小时后再在900 ℃下烧结12小时,冷却、过筛,得到LiNi1/3Co1/3Mn1/3O2三元正极材料。将LiNi1/3Co1/3Mn1/3O2三元正极材料与乙炔黑、聚偏氟乙烯(PVdF)按质量比为75:15:10混合成浆料,涂布于铝箔上,经过干燥、冲膜和压膜制成LiNi1/3Co1/3Mn1/3O2三元正极材料电极片。以金属锂箔为对电极,Celgard 2400为隔膜,1MLiPF6/(EC+DMC) (1:1)为电解液,组装成R2025扣式电池进行恒流充放电测试,电压范围在2.8-4.5 V之间。该三元材料在0.5 C时的首次放电比容量为187.8 mAh g-1,经过50次循环后其放电比容量为160.2 mAh g-1。
实施例3
将1.7515 g NiSO4·6H2O、1.8731 g CoSO4·7H2O、1.1266 g MnSO4·H2O以摩尔比1:1:1依次溶解在200 mL去离子水中,搅拌30分钟使其完全溶解,同时将1.6109 g NaOH加入到80 mL去离子水中。然后,将含镍离子、钴离子、锰离子的混合溶液缓慢滴加到NaOH溶液中,并加入15 mL浓度为3.35 mol L-1的氨水作为络合剂,以400 r min-1的转速进行搅拌,在50-55 ℃下保温反应12小时,得到黑色悬浊液,静置6-8小时后过滤,洗涤数次,在90 ℃烘箱中干燥9小时,得到前驱体。在前驱体(1.8 g)中加入0.7265 g Li2CO3,以无水乙醇为介质球磨6小时后,干燥,并在450 ℃下烧结5小时后再在900 ℃下烧结12小时,冷却、过筛,得到LiNi1/3Co1/3Mn1/3O2三元正极材料。将LiNi1/3Co1/3Mn1/3O2三元正极材料与乙炔黑、聚偏氟乙烯(PVdF)按质量比为75:15:10混合成浆料,涂布于铝箔上,经过干燥、冲膜和压膜制成LiNi1/3Co1/3Mn1/3O2三元正极材料电极片。以金属锂箔为对电极,Celgard 2400为隔膜,1MLiPF6/(EC+DMC) (1:1)为电解液,组装成R2025扣式电池进行恒流充放电测试,电压范围在2.8-4.5 V之间。该三元材料在0.5 C时的首次放电比容量为195.3mAh g-1,经过50次循环后其放电比容量为160.1 mAh g-1。
Claims (3)
1.一种制备LiNi1/3Co1/3Mn1/3O2三元正极材料的方法,其特征在于,包括如下步骤:
(1)将镍盐、钴盐、锰盐加入到去离子水中,搅拌0.5-1小时,使其完全溶解,得到浓度为0.1-0.5 mol L-1的混合溶液,同时将NaOH溶解在去离子水中,得到浓度为0.1-0.3 mol L-1的NaOH溶液,锂盐为Li2CO3或LiOH;Ni盐为NiSO4·6H2O;Co盐为CoSO4·7H2O;Mn盐为MnSO4·H2O;
(2)将含有镍离子、钴离子、锰离子的混合溶液滴加到浓度为0.1-0.3 mol L-1的NaOH溶液中,并加入浓度为3.30-3.70 mol L-1的氨水作为络合剂,以300-500r min-1的转速进行搅拌,在50-55℃下保温反应10-12小时,得到黑色悬浊液,静置6-8小时后过滤、洗涤,并在90℃下干燥7-10小时,得到前驱体,在合成前驱体过程中不需严格控制反应体系的pH值,即在合成前驱体的过程中不需通过持续加入氨水来调节pH值;
(3)将前驱体和Li2CO3以无水乙醇为介质球磨4-6小时后,干燥,并在空气气氛中400-500℃下烧结3-6小时,随后在850-950℃下烧结10-14小时、过筛,得到LiNi1/3Co1/3Mn1/3O2三元正极材料;
上述的制备方法中不需要通入氮气。
2.权利要求1所述的制备LiNi1/3Co1/3Mn1/3O2三元正极材料的方法,其特征在于,锂盐、镍盐、钴盐、锰盐的摩尔比为1.01-1.15:0.333:0.333:0.333。
3.权利要求1所述的制备LiNi1/3Co1/3Mn1/3O2三元正极材料的方法,其特征在于,锂盐、镍盐、钴盐、锰盐的纯度均大于98 %。
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