CN114853088A - 铝包覆锂离子电池无钴正极材料的制备方法及正极材料 - Google Patents
铝包覆锂离子电池无钴正极材料的制备方法及正极材料 Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 25
- 239000010405 anode material Substances 0.000 title claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000007774 positive electrode material Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- FXOOEXPVBUPUIL-UHFFFAOYSA-J manganese(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Ni+2] FXOOEXPVBUPUIL-UHFFFAOYSA-J 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011572 manganese Substances 0.000 claims abstract description 6
- 238000007873 sieving Methods 0.000 claims abstract description 5
- 239000010406 cathode material Substances 0.000 claims description 18
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910017119 AlPO Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910003286 Ni-Mn Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229910004761 HSV 900 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- -1 and the like Chemical compound 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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Abstract
本发明涉及H01M10/0525领域，更具体地，本发明涉及铝包覆锂离子电池无钴正极材料的制备方法及正极材料。铝包覆锂离子电池无钴正极材料的制备方法，包括下面步骤：(1)将锂源、镍锰氢氧化物(NixMny(OH)2以及过渡金属氧化物混合后进行一次焙烧，得到一次焙烧正极材料；其中，0.5≤x≤0.7，x+y＝1；(2)一次焙烧正极材料与铝的氧化物混合后，进行二次焙烧，后过筛除磁后得到铝包覆锂离子电池无钴正极材料。本申请制备的铝包覆锂离子电池无钴正极材料经半电池组装测试，在4.35～2.8V电压、0.1C/0.1C充放倍率条件下，首次放电克容量可达到170.5mAh/g以上，常温条件下经50周循环后，容量保持率可达到85％以上，可应用于动力电池领域，具有较大的市场前景。
Description
技术领域
本发明涉及H01M10/0525领域，更具体地，本发明涉及铝包覆锂离子电池无钴正极材料的制备方法及正极材料。
背景技术
随着我国动力电池领域需求量逐渐增多，如二轮电动、电动汽车领域，钴价处于持续增长阶段，因此三元电芯价格高，无钴材料具有一定的成本优势，能量密度和功率密度高是无钴单晶材料的优势之一，受到行业内的广泛关注。然而钴含量降低同时镍含量增加，使得锂镍混排程度增加，导致正极材料的倍率和循环性能降低。
中国专利CN202010330618通过将镍锰氢氧化物、锂源、掺杂物、分散剂混合后压制，然后烧结，继而磁化，磁选，然后再次加入包覆物和分散剂，再次烧结得到正极材料，该方法不仅生产工艺复杂，同时需要多次加入分散剂，增加了用料的复杂性。中国专利CN113517424A公开了一种高电压锂离子电池无钴正极材料，在正极材料基体表面包覆快离子导体层，在降低了材料表面残锂的含量的同时，提升了电池材料的电性能，但该生产工艺复杂，量产要求较高，且可操作性较差，无法发挥无钴材料高功率密度的性能。
发明内容
针对现有技术中存在的一些问题，本发明第一个方面提供了一种铝包覆锂离子电池无钴正极材料的制备方法，包括下面步骤：
(1)将锂源、镍锰氢氧化物(NixMny(OH)2以及过渡金属氧化物混合后进行一次焙烧，得到一次焙烧正极材料；其中，0.5≤x≤0.7，x+y＝1；
(2)一次焙烧正极材料与铝的氧化物混合后，进行二次焙烧，后过筛除磁后得到铝包覆锂离子电池无钴正极材料。
本申请所述锂源不做特别限定，本领域技术人员可做常规选择，可以列举的有碳酸锂、醋酸锂、氢氧化锂等，优选为碳酸锂。
在一种实施方式中，镍锰氢氧化物为选自金属Mg、Zr、Al、Nb、Sr、La的一种或多种掺杂的镍锰氢氧化物。
在一种实施方式中，所述镍锰氢氧化物和锂源中锂离子的摩尔比为1：(1-1.2)，可以列举的有1.02、1.1、1.15、1.2等。
在一种实施方式中，过渡金属氧化物占一次焙烧正极材料的0.05～0.2wt％，可以列举的有0.05wt％、0.1wt％、0.15wt％、0.2wt％等。
在一种实施方式中，所述过渡金属氧化物为ZrO2和/或Nb2O5。
申请人意外的发现，加入0.05-0.2wt％的过渡金属氧化物，尤其是ZrO2和/或Nb2O5，在一定程度上提高了高温循环性能，申请人认为可能的原因是该特定的过渡金属氧化物有利于金属离子进入材料的晶格内部或包覆在材料表面，可有效抑制材料的高温产气。
在一种实施方式中，步骤(1)中混合的条件为：在高速混料机中混合，转速为500～800r/min，混合时间为30-40min。
在一种实施方式中，步骤(1)中一次焙烧的条件为：800-1000℃焙烧6-10h，升温速率为1-5℃/min。
优选的，一次焙烧正极材料的粒径D50为4-8μm。
在一种实施方式中，所述铝的氧化物选自Al(OH)3、Al2O3、AlPO4、Al(PO3)3中一种或多种，优选为Al(OH)3和/或Al2O3。
优选的，所述铝的氧化物占一次焙烧正极材料与铝的氧化物总量的0.1-0.2wt％。
申请人在实验中意外的发现，在一次焙烧之后添加铝的氧化物，然后再次进行二次焙烧，此时可以显著提高循环稳定性，申请人认为可能的原因是经过该特定的步骤可以有效抑制材料内部应力的增加，降低材料在循环过程中体积膨胀导致的胀气现象。
在一种实施方式中，步骤(2)中二次焙烧的条件为：600～900℃烧结4～6h。
优选的，步骤(2)中过筛的目数为300-400目。
本发明第二个方面提供了一种所述铝包覆锂离子电池无钴正极材料的制备方法制备得到的铝包覆锂离子电池无钴正极材料。
本发明首先通过对前驱体的改进，通过掺杂过渡金属元素提升无钴材料层状的稳定性，随后通过二烧干法包覆的方式实现一次颗粒的表面包覆，从而达到提升正极材料循环性能和倍率性能，为未来产业化生产起到了一定的推动作用。
本发明与现有技术相比具有以下有益效果：
本申请中过渡金属氧化物和铝的氧化物的添加，提升了无钴层状结构的稳定性，减少Ni/Mn偏稀问题，同时提高了常温和高温循环稳定性能，制备的铝包覆锂离子电池无钴正极材料经半电池组装测试，在4.35～2.8V电压、0.1C/0.1C充放倍率条件下，首次放电克容量可达到170.5mAh/g以上，常温条件下经50周循环后，容量保持率可达到85％以上，可应用于动力电池领域，具有较大的市场前景。
附图说明
图1为本申请实施例1得到的正极材料的电镜图；
图2为本申请实施例电极材料组装的半电池的首次充放电曲线；
图3为本申请实施例电极材料组装的半电池的循环测试结果图。
具体实施方式
以下通过具体实施方式说明本发明，但不局限于以下给出的具体实施例。
实施例1
本实施例提供了一种铝包覆锂离子电池无钴正极材料的制备，包括：
一次焙烧：将粉末状镍锰氢氧化物Ni56Mn44(OH)2与碳酸锂混合，按照镍锰氢氧化物和碳酸锂中的锂离子的摩尔比为1:1.02，并加入Nb2O5作为添加剂，加入量为500ppm，在高速混料机中以500r/min混合30min，得到锂源与镍锰氢氧化物的混合物，置于空气气氛辊道窑炉中，焙烧温度为900℃，焙烧时长为8h，升温速率为3℃/min，得到一次焙烧正极材料(D50为4-8μm)；
二次焙烧：将Al2O3加入到一次焙烧正极材料中混合，Al2O3的加入量为1000ppm，并置于空气气氛炉中，二次焙烧，焙烧温度为600℃，时长6h，后经过筛(300-400目)、除磁、包装得到正极材料。
将实施例1提供的正极材料进行电池组装：称取活性物质(实施例1制备得到的正极材料)9.5g，同时加入0.3g乙炔黑(SP)作导电剂和0.2g PVDF(HSV-900)作粘结剂，充分混合后加入N-甲基-吡咯烷酮(NMP)溶剂至固含量为70wt％进行分散，匀浆均匀后于16μm厚的铝箔上拉浆制成正极极片，在厌氧手套箱中以金属锂片为负极，隔膜为12+4μm的陶瓷隔膜，电解液选用1mol/L LiPF6的碳酸乙酯(EC)、碳酸二甲酯(DMC)和碳酸二乙酯(EMC)混合液(体积比为1:1:1)，采用标准半电池构型，电池壳采用(CR2032)纽扣式电池，组装成半电池进行后期电池测试。
实施例1提供的正极材料组装成的半电池，其正极材料的形貌电镜如图1所示，半电池的首次充放电曲线和循环测试如图2和图3所示，电池在4.35-2.8V电压范围内，0.1C/0.1C充放倍率下，测其首次放电克容量为170.5mAh/g，常温和高温循环容量保持率均在85％以上。
实施例2
本实施例提供一种锂离子电池正极材料的制备方法，包括：
一次焙烧：将粉末状镍锰氢氧化物Ni60Mn40(OH)2与碳酸锂混合，按照镍锰氢氧化物和碳酸锂中的锂离子的摩尔比为1:1.10，并加入ZrO2作为添加剂，加入量为1000ppm，在高速混料机中以700r/min混合30min，得到锂源与镍锰氢氧化物的混合物，置于空气气氛辊道窑炉中，焙烧温度为1000℃，焙烧时长为10h，升温速率为3℃/min，得到一次焙烧正极材料(D50为4-8μm)；
二次焙烧：将Al(OH)3加入到一次焙烧正极材料中混合，Al(OH)3的加入量为2000ppm，并置于空气气氛炉中，二次焙烧，焙烧温度为800℃，时长6h，后经过筛(300-400目)、除磁、包装得到正极材料。
将实施例2提供的正极材料按照实施例1的方法进行电池组装，组装成半电池进行后期电池测试。
实施例2提供的正极材料组装成半电池后的首次充放电曲线如图2所示，电池在4.35-2.8V电压范围内，0.1C/0.1C充放倍率下，测其首次放电克容量为172.4mAh/g。
Claims (10)
1.一种铝包覆锂离子电池无钴正极材料的制备方法，其特征在于，包括下面步骤：
(1)将锂源、镍锰氢氧化物(NixMny(OH)2以及过渡金属氧化物混合后进行一次焙烧，得到一次焙烧正极材料；其中，0.5≤x≤0.7，x+y＝1；
(2)一次焙烧正极材料与铝的氧化物混合后，进行二次焙烧，后过筛除磁后得到铝包覆锂离子电池无钴正极材料。
2.根据权利要求1所述铝包覆锂离子电池无钴正极材料的制备方法，其特征在于，所述镍锰氢氧化物和锂源中锂离子的摩尔比为1：(1-1.2)。
3.根据权利要求2所述铝包覆锂离子电池无钴正极材料的制备方法，其特征在于，所述过渡金属氧化物占一次焙烧正极材料的0.05～0.2wt％。
4.根据权利要求3所述铝包覆锂离子电池无钴正极材料的制备方法，其特征在于，所述过渡金属氧化物为ZrO2和/或Nb2O5。
5.根据权利要求1-4任一项所述包覆锂离子电池无钴正极材料的制备方法，其特征在于，述铝的氧化物选自Al(OH)3、Al2O3、AlPO4、Al(PO3)3中一种或多种。
6.根据权利要求5所述包覆锂离子电池无钴正极材料的制备方法，其特征在于，所述铝的氧化物占一次焙烧正极材料与铝的氧化物总量的0.1-0.2wt％。
7.根据权利要求6所述包覆锂离子电池无钴正极材料的制备方法，其特征在于，所述镍锰氢氧化物为选自金属Mg、Zr、Al、Nb、Sr、La的一种或多种掺杂的镍锰氢氧化物。
8.根据权利要求6或7所述包覆锂离子电池无钴正极材料的制备方法，其特征在于，步骤(1)中一次焙烧的条件为：800-1000℃焙烧6-10h，升温速率为1-5℃/min。
9.根据权利要求8所述包覆锂离子电池无钴正极材料的制备方法，其特征在于，步骤(2)中二次焙烧的条件为：600-900℃烧结4-6h。
10.一种根据权利要求1-9任一项所述包覆锂离子电池无钴正极材料的制备方法制备得到的铝包覆锂离子电池无钴正极材料。
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