CN1089193C - 喷雾干燥法制备锂离子电池活性材料超细粉的方法 - Google Patents
喷雾干燥法制备锂离子电池活性材料超细粉的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 239000011149 active material Substances 0.000 title claims abstract description 18
- 238000001694 spray drying Methods 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000011812 mixed powder Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000002562 thickening agent Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 7
- 229920002521 macromolecule Polymers 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229910007943 SnB0.5 P0.5 O3 Inorganic materials 0.000 claims description 3
- 229910014689 LiMnO Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 description 10
- 229910013553 LiNO Inorganic materials 0.000 description 5
- 229910012820 LiCoO Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 3
- 238000001757 thermogravimetry curve Methods 0.000 description 3
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 238000010295 mobile communication Methods 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 238000005469 granulation Methods 0.000 description 1
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- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
本发明涉及一种喷雾干燥法制备锂离子电池活性材料超细粉的方法,该制备方法为首先以化学计量比称取所需产品原料,然后在原料混合物中加入去离子水,再加入增稠剂,将酿成的溶液喷雾干燥,所得混合粉体,在一定温度下烧结,即得锂离子电池活性材料超细粉,本发明制备的产品,具有优良的化学性能,制备方法可直接用于锂离子电池活性材料的大规模工业化生产。
Description
本发明涉及一种喷雾干燥法制备锂离子电池活性材料超细粉的方法,属材料科学技术领域。
在现代信息社会里,伴随着移动通讯和移动计算的飞速发展,GSM(GlobalSystem for Mobile Communication)、DECT(Digital European Cordless)、PHC(Personal Handy Computer)等产品空前活跃,使得人们对于高性能化学电源的要求日益突出。锂离子电池由于具有输出电压高、能量密度大、循环寿命长、无记忆效应等的优点,因此自九十年代以来一直成为研究与开发的热点。
锂-过渡金属复合氧化物,如LiCoO2、LiNiO2、LiMn2O4和LiV3O8等,都是性能优异的锂离子电池正极活性材料。以Sn为主的过渡金属复合氧化物,由于Li+的插入电势较低,是近年来涌现出来的性能优异的锂离子电池负极材料。这类复合氧化物都具备了拓扑化学反应的特征:在充电的过程中,Li+从复合氧化物中脱出嵌入负极材料中;在放电过程则与之相反。当其中Li+的浓度在一定范围变化时,由于过渡金属的多价性,不会影响化合物结构与形貌的变化。
目前,制备锂离子电池活性材料的方法很多,如固相反应法、共沉淀法、溶胶凝胶法等。一般,传统的合成方法均采用固相反应法,其特点是反应物通过多次反复的研磨、粉碎、烧结获得活性材料,有的还需要通过造粒或压片等辅助工艺。烧结的过程也是比较长的,一般需要12~96小时,甚至更长的时间。
本发明的目的是提出一种喷雾干燥法制备锂离子电池活性材料超细粉的方法,通过喷雾干燥法(Spray Drying,简称SD法),在较短的时间内、较低的烧结温度下和较简单的工艺条件下获得均匀无杂相的超细锂离子电池活性材料。
本发明提出的喷雾干燥法制备锂离子电池活性材料超细粉的方法中所制备的锂离子电池活性材料为正极材料和负极材料,正极材料的分子式为:LiCoO2、LiNiO2和LiMnO4中的任何一种,负极材料的分子式为:SnMnO2或SnB0.5P0.5O3,其制备方法包括下列各步骤:
(1)原料准备:以化学计量比称量所需制备产品的原料,并将其混合;
(2)溶液配置:上述的混合物加入去离子水,配成0.05~1.0mol/l的溶液,并加入一定量的高分子化合物作为增稠剂,质量百分比为5~30%,增稠剂为聚乙二醇、聚丙烯酸或聚乙烯醇中的任何一种;
(3)喷雾干燥:将配成的溶液经喷雾干燥得到混合粉体,用气流式喷雾干燥器干燥,采用并流干燥方式,雾化装置采用二流式喷嘴,进料溶液用蠕动泵进样,速度为12~20ml/min;喷嘴气体流量由压缩空气的压力控制,在约0.1MPa下产生雾化;控制空气进口温度为300~400℃,出口为100~200℃;出口空气经一级旋涡分离放空;
(4)混合粉体的烧结:混合粉体在500~1200℃烧结4~20小时即可获得具有优良电化学性能的锂离子电池活性材料超细粉。
本技术不但适用于制备锂离子电池正极材料,如LixCoO2、LixNiO2、LixMn2O4、LixMnO2、LixV3O8,以及多元体系,如LixCoaNi1-aO2、LixCobV1-bO2、LixCocB1-cO2、LixNiaCo1-aO2、LixNibMn1-bO2、LixMnbV2-bO4、LixMnbCu2-bO4、LixMnbAl2-bO4、LixVcCo3-cO8(0.5≤x≤1.5,0.5≤a≤1.0,0.5≤b≤0.98,0.85≤c≤0.99)等;还适合于制备氧化物为主的锂离子电池负极材料,如SnMnO2、SnTiOz、SnCoOz、SnVOz、SnNiOz、SnCuOz、SnWOz等,以及多元体系,如SnBePtOz、SnAldBeOz、SnAldBeMfOz、SnAldSieOz、SnAldSieMfOz(M=P、Mg、F、K、Ba等,0.1≤d≤1.0,0≤e≤0.65,0≤f≤0.5,2≤z≤5)等。
对于锂离子电池正极材料,原料主要为A+B+C三类:A类为可溶于水的锂盐(如硝酸锂、乙酸锂等);B类为可溶于水的钴盐、镍盐、锰盐、钒盐等;C类为增稠剂,其为可溶于水的高分子化合物(如聚乙二醇(PEG)、聚丙烯酸(PAA)、聚乙烯醇(PVA)、甲基纤维素等),或在水中能发生聚合反应的有机酸(如己二酸、顺丁烯二酸等)。
对于锂离子电池负极材料,原料主要为A+B+C三类:A类为可溶于水锡化合物;B类为可溶于水的钴盐、镍盐、锰盐、钒盐等;C类为可溶于水的高分子化合物(如聚乙二醇(PEG)、聚丙烯酸(PAA)、聚乙烯醇(PVA)、甲基纤维素等)。
利用本发明制备的锂离子电池活性材料超细粉,具有优良的化学性能,制备方法可直接用于锂离子电池活性材料的大规模工业化生产。
附图说明:
图1是利用本发明的方法制备的超细粉的差热热重分析曲线。
图2是锂钴氧化合物的X光衍射谱图。
图3是LiCoO2超细粉扫描电镜照片。
图4是LiCoO2粉末首次充电曲线。
图5是LiCoO2粉末首次放电曲线。
下面介绍本发明的实施例。
实施例1:
以Li∶Co摩尔比1∶1的配比称量乙酸锂和乙酸钴,并称取5%的高分子化合物聚乙二醇(PEG),加入去离子水配成0.1mol/l的溶液。所得到的溶液用气流式喷雾干燥器干燥,进料溶液用蠕动泵进样,速度为12ml/min;喷嘴气体流量由压缩空气的压力控制,在约0.1MPa下产生雾化;控制空气进口温度为300℃,出口为100℃;出口空气经一级旋涡分离放空。喷雾干燥所得的聚乙二醇与乙酸锂、乙酸钴的混合粉体在800℃经过4小时的烧结即获得LiCoO2超细粉。
通过对图1的差热热重分析曲线的数据进行分析,可以看出喷雾干燥获得的混合粉体在300℃以下便基本反应完全,在180℃之前基本表现为水份的得失情况,同时伴随者吸放热;在180℃~300℃之间,TGA曲线表现出三个明显的失重:分别在187℃,231℃,241℃,同时在DTA曲线中有三个明显的放热峰;在300℃以后,几乎无重量损失,表明在此温度以上为晶相的形成和完善。
图2是所制得的锂钴氧化合物的X光衍射谱图,由图可见,800℃烧结4小时后,即可得具有α-NaFeO2层状结构的HT-LiCoO2,表现为2θ值为18.90°、37.40°、45.24°出现的对应于(003)、(101)、(104)的三强峰,并且基本未出现其他杂相峰。
图3是制得的LiCoO2超细粉末扫描电镜的照片,从图可得到LiCoO2粉末的一些信息。(a)为LiCoO23K的SEM图,可见制得的为粒径较均一、表面光滑、无明显团聚的细粉;(b)为LiCoO220K的SEM图,由扫描电镜标尺可见其颗粒大的约有700nm,小的为200nm左右。
电化学性能的测试主要通过组装成试验电池测试其充放电容量。电池正极由80%的LiCoO2粉末和20%的TAB(聚四氟乙烯+乙炔黑)构成,电解液为IMLiPF6+EC∶DMC(1∶1),参考负极为金属锂片。充放电电流密度为0.5mA/cm2,电压为3.0~4.3V。图4为LiCoO2粉末的首次充电曲线,由图可见,其在充电过程中在4.0v左右存在一明显的充电平台,其充电容量为148mAh/g;图5为LiCoO2粉末的首次放电曲线,对应于充电曲线,在3.9v左右存在一明显的放电平台,放电容量为135mAh/g,充放电效率为91.22%。
其它实施例见表1,表中AC为醋酸根的缩写。
表1
编号 | 所制得的活性物资 | 原料 | 喷雾进口温度(℃) | 喷雾出口温度(℃) | 烧结温度(℃) | 烧结时间(小时) | 可利用容量(mAh/g) |
2 | LiCoO2 | LiNO3+Co(NO3)2+PEG(5%) | 300 | 100 | 700 | 4 | 135 |
LiAC+Co(NO3)2+PEG(5%) | 300 | 130 | 800 | 4 | 144 | ||
LiNO3+Co(AC)2+PEG(5%) | 300 | 120 | 800 | 4 | 146 | ||
3 | LiNiO2 | LiNO3+Ni(NO3)2+PAA(5%) | 300 | 130 | 750(通氧) | 8 | 160 |
4 | LiMn2O4 | LiAC+Mn(NO3)2+PAA(5%) | 300 | 130 | 800 | 4 | 130 |
LiNO3+Mn(NO3)2+PAA(5%) | 300 | 130 | 750 | 4 | 128 | ||
LiNO3+Mn(AC)2+PVA(5%) | 300 | 130 | 800 | 4 | 133 | ||
LiAC+Mn(AC)2+PEG(5%) | 300 | 130 | 750 | 4 | 128 | ||
5 | SnMnO2 | Sn(AC)2+Mn(AC)2+PVA(5%) | 300 | 130 | 1000 | 6 | 498 |
6 | SnB0.5P0.5O3 | Sn(AC)2+HBO3+H3PO4+PVA(5%) | 300 | 130 | 1000 | 6 | 520 |
Claims (1)
1、一种喷雾干燥法制备锂离子电池活性材料超细粉的方法,其特征在于,所制备的锂离子电池活性材料为正极材料或负极材料,正极材料的分子式为:LiCoO2、LiNiO2和LiMnO4中的任何一种,负极材料的分子式为:SnMnO2或SnB0.5P0.5O3,其制备方法包括下列各步骤:
(1)原料准备:以化学计量比称量所需制备产品的原料,并将其混合;
(2)溶液配置:上述的混合物加入去离子水,配成0.05~1.0mol/l的溶液,并加入一定量的高分子化合物作为增稠剂,质量百分比为5~30%,增稠剂为聚乙二醇、聚丙烯酸或聚乙烯醇中的任何一种;
(3)喷雾干燥:将配成的溶液经喷雾干燥得到混合粉体;
(4)混合粉体的烧结:混合粉体在500~1200℃烧结4~20小时即为锂离子电池活性材料超细粉。
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JP4106644B2 (ja) * | 2000-04-04 | 2008-06-25 | ソニー株式会社 | 電池およびその製造方法 |
CN102484241A (zh) * | 2009-03-03 | 2012-05-30 | 尤米科尔公司 | 制备用于锂离子电池的合金复合负电极材料的方法 |
JP2012519360A (ja) * | 2009-03-03 | 2012-08-23 | ユミコア ソシエテ アノニム | リチウムイオン電池のための合金複合材の陰極材料の製造方法 |
CN103985855A (zh) * | 2013-12-16 | 2014-08-13 | 青岛乾运高科新材料股份有限公司 | 一种锂电池正极材料固溶体超细粉的制备方法 |
CN104064754B (zh) * | 2014-06-27 | 2016-05-11 | 胡莹 | 一种锂锰氧化物的制备方法 |
CN104332623A (zh) * | 2014-09-09 | 2015-02-04 | 上海纳米技术及应用国家工程研究中心有限公司 | 用于锂离子二次电池负极材料锰钴氧的制备方法 |
CN106564940B (zh) * | 2016-10-28 | 2017-12-22 | 昆明理工大学 | 一种纳米级二氧化锡微粒的制备方法 |
CN109809497B (zh) * | 2019-01-17 | 2021-10-01 | 合肥国轩高科动力能源有限公司 | 一种超声喷雾煅烧合成LiCoO2粉体的方法及其应用 |
CN110311128A (zh) * | 2019-07-10 | 2019-10-08 | 深圳市本征方程石墨烯技术股份有限公司 | 一种石墨烯掺杂的钴酸锂正极材料及其制备方法 |
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