CN117410481B - 一种高性能的纳米单晶正极材料及其制备方法 - Google Patents
一种高性能的纳米单晶正极材料及其制备方法 Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 27
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 58
- 238000005245 sintering Methods 0.000 claims abstract description 41
- 238000000498 ball milling Methods 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011164 primary particle Substances 0.000 claims abstract description 15
- 239000010405 anode material Substances 0.000 claims abstract description 13
- 239000000084 colloidal system Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 15
- 229940068041 phytic acid Drugs 0.000 claims description 15
- 235000002949 phytic acid Nutrition 0.000 claims description 15
- 239000000467 phytic acid Substances 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003125 aqueous solvent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 230000009471 action Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract 1
- 239000010419 fine particle Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 238000000678 plasma activation Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 210000002381 plasma Anatomy 0.000 description 9
- 239000010406 cathode material Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000012798 spherical particle Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002490 spark plasma sintering Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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Abstract
本发明公开了一种高性能的纳米单晶正极材料及其制备方法。以二次球形前驱体为基体原料,首先通过液氮球磨法将前驱体进行充分破碎,得到粒度均匀的纳米级一次颗粒前驱体Ⅰ;然后一次颗粒前驱体Ⅰ与锂源混匀,加入植酸溶液与纳米铝粉形成胶体溶液,得到包覆改性后的高强度的前驱体Ⅱ;最后将前驱体Ⅱ在放电等离子体炉中烧结,得到高性能的纳米单晶正极材料。本发明提供的单晶材料前驱体,具有大小均匀,颗粒细小,颗粒强度高,增强了材料的循环稳定性。本发明利用等离子体的活化和快速升温烧结的综合作用,使得最终的产品具有氧空位、致密度高等特点,有利于显著提高材料的容量、倍率性能。
Description
技术领域
本发明属于锂离子电池正极材料制备技术领域,具体涉及一种高性能的纳米单晶正极材料及其制备方法。
背景技术
随着智能手机、平板电脑、电动汽车等行业的快速发展,人们对锂离子电池的能量密度、安全性能和循环寿命等性能的要求不断提升,待机时间和续航里程成为评估锂电池性能的重要因素。
目前商业化的锂离子电池正极材料大多是由纳米级的一次颗粒组成的微米级二次球形颗粒团聚体。在团聚体中,存在大量晶界,如果一次颗粒之间空隙较多时,材料的比表面积增大,与电解液的接触面积增加,导致循环容量的衰减;其次,球形二次颗粒团聚体的机械强度不高,在较高压力下,造成二次颗粒破碎,从而导致电化学性能下降;另外,团聚体材料的热稳定性不佳,对电池安全性产生隐患。
然而,单晶材料内部不存在晶界以及界面应力等不稳定影响因素,具备较高的机械强度和结构稳定性的特点,可以解决电池长久以来面对的产气、长循环和热稳定性等问题,可以在高电压电解液体系中应用,大幅度地提升了电池的循环稳定性和安全性。
但是单晶正极材料也存在很多不足:(1)前驱体破碎时,会存在破碎时间长、能耗高、破碎不完全、一次颗粒大小不均等现象,严重影响单晶材料的形貌,导致在充放电过程中锂离子脱嵌程度不同,影响其循环稳定性;(2)单晶材料较大的粒径会导致在充放电过程中,锂离子扩散和迁移的通道较长,同时颗粒本身较差的电子电导,会导致单晶正极材料的倍率性能较差;(3)单晶材料在合成过程中周期长、能耗高。因此,针对这些问题,目前单晶正极材料的制备工艺需要进一步改进,
发明内容
本发明解决的技术问题在于提供一种高性能的纳米单晶正极材料及其制备方法,本发明利用液氮球磨法-放电等离子体烧结技术,制备具有低能耗、生产周期短、容量高、循环稳定性强和倍率性能好的纳米级锂离子电池的正极材料。
本发明提供一种高性能的纳米单晶正极材料的制备方法,包括以下步骤:
步骤1:将二次球形前驱体进行低温球磨,得到粒度均匀的纳米级一次颗粒前驱体Ⅰ;
步骤2:将植酸分散于非水性溶剂中形成溶液A;加入适量的纳米铝粉于A溶液中,搅拌均匀,形成胶体溶液B;
步骤3:将一次颗粒前驱体Ⅰ与锂源,在高混机中混合均匀,再加入胶体溶液B,混匀后,干燥,得到包覆改性后颗粒强度高的前驱体Ⅱ;
步骤4:将前驱体Ⅱ置于石墨模具中,放入放电等离子体烧结炉的炉腔内,在真空、惰性气氛下进行烧结,并粉碎、过筛制备成高性能的纳米单晶正极材料。
进一步,所述二次球形前驱体为锂离子电池正极材料前驱体:NixCoyMn1-x-yCO3或NixCoyMn1-x-y(OH)2,其中0≤x≤1.0,0≤y≤ 1.0,x+y≤ 1.0。
进一步,所述球磨是在液氮行星式球磨机中进行,球料比为17~20:1,液氮占球磨罐体积的50%~65%,球磨速度200~400rpm,球磨时间0.5~2h。
进一步,所述植酸为质量分数为60~70%的植酸溶液;所述植酸的摩尔量与前驱体Ⅰ中的过渡金属总摩尔量的比为1:(3~7);所述非水性溶剂均为乙醇、甲醇、异丙醇、乙二醇中的任意一种。
进一步,所述纳米铝粉用量为前驱体Ⅰ质量分数的0.5~1.5%,所述锂源为碳酸锂、氢氧化锂、硝酸锂、醋酸锂、氯化锂等,其中锂元素与前驱体Ⅰ中的过渡金属总摩尔数的摩尔比为(1.05~1.2):1。
进一步,所述高混机转速为20~50HZ,混合时间为4~12min;所述放电等离子体烧结炉的条件为:烧结压力40~60MPa、烧结温度800~900℃、烧结时间6~8min。
本发明还提供一种高性能的纳米单晶正极材料,使用上述的方法制备得到。
有益效果
利用液氮球磨法对二次球形前驱体进行破碎,液氮可使球形颗粒在低温下脆化,在外力作用下易破碎,提高球形颗粒的破碎效率,减少球磨时间,且得到的颗粒更均匀。
(2)植酸溶液与纳米铝粉形成胶体溶液,不仅有助于提高前驱体Ⅰ颗粒的强度和缓解团聚问题,还可以作为包覆液对前驱体进行改性,在材料表面形成磷酸锂、偏铝酸锂包覆层作为快离子导体,有助于促进锂离子扩散,同时植酸自身发生碳化,也可作为保护层,都可抑制电解液与活性材料之间有害的副反应;同时,植酸呈酸性,与过渡金属有较强的螯合能力,可以有效抑制在电池充放电过程中过渡金属离子的溶出,酸性溶液还能降低材料的pH值,降低纳米单晶材料表面残锂量。
(3)利用放电等离子体烧结技术的等离子体的活化和快速升温烧结的综合作用处理前驱体,等离子体对过渡金属氧化物进行活化,引入氧空位,提高纳米单晶正极材料表面的导电性;具有快速升温烧结、加热均匀、生产周期短、节能等优点,抑制晶粒的长大,有助于实现单晶材料的纳米化、颗粒均匀、振实密度高、电化学性能好的特点。
(4)制备得到的纳米级单晶正极材料的振实密度大幅度地提升,显著提升了材料的体积能量密度。
(5)制备得到的纳米级单晶正极材料,颗粒粒径小且均匀,大大缩短了锂离子在电池充放电过程中嵌入和脱出的扩散通道,从而有效改善了材料的倍率性能。
附图说明
图1为实施例1制备的纳米单晶正极材料的SEM示意图;
图2为对比例1制备的纳米单晶正极材料的SEM示意图;
图3为对比例3制备的纳米单晶正极材料的SEM示意图;
图4为对比例2制备的纳米单晶正极材料的SEM示意图。
具体实施例
下面结合具体例子对本发明进行详细的分析,实施例和对比例选用的二次球形前驱体均为Ni0.5Co0.2Mn0.3(OH)2 。
实施例1
步骤1:10.0g二次球形前驱体在占球磨罐体积60%的液氮中,进行低温球磨,球磨速度300rpm,球磨时间1h,得到粒度均匀的纳米级一次颗粒前驱体Ⅰ;
步骤2:将2.0g(含量为60%)植酸分散于50m L乙二醇中形成溶液A;加入1.0g的纳米铝粉于A溶液中,搅拌均匀,形成胶体溶液B;
步骤3:将碳酸锂与前驱体Ⅰ在高混机中转速为30HZ,混合时间为8min,混合均匀,其中nLi/n(Ni+Co+Mn)=1.10,再加入胶体溶液B,混合时间为4min后,于烘箱中100℃干燥,得到包覆改性后颗粒强度高的前驱体Ⅱ;
步骤4:将前驱体Ⅱ置于石墨模具中,放电等离子体烧结炉的炉腔内,在烧结压力50MPa、烧结温度900℃、烧结时间5min 的真空气氛下进行烧结,将烧结后的物料自然冷却至室温,经粉碎、过筛制备成高性能的纳米单晶正极材料。
实施例2
与实施例1的区别在于,步骤1中10.0g二次球形前驱体在占球磨罐体积50%的液氮中,进行低温球磨,球磨速度300rpm,球磨时间0.5h,得到粒度均匀的纳米级一次颗粒前驱体Ⅰ;
实施例3
与实施例1的区别在于,步骤1中10.0g二次球形前驱体在占球磨罐体积65%的液氮中,进行低温球磨,球磨速度300rpm,球磨时间0.5h,得到粒度均匀的纳米级一次颗粒前驱体Ⅰ;
实施例4
与实施例1的区别在于,步骤2中将1.5g(含量为60%)植酸分散于50m L乙二醇中形成溶液A;加入1.0g的纳米铝粉于A溶液中,搅拌均匀,形成胶体溶液B;
实施例5
与实施例1的区别在于,步骤2中将3.0g(含量为60%)植酸分散于50m L乙二醇中形成溶液A;加入1.5g的纳米铝粉于A溶液中,搅拌均匀,形成胶体溶液B;
实施例6
与实施例1的区别在于,步骤3中nLi/n(Ni+Co+Mn)=1.05。
实施例7
与实施例1的区别在于,步骤3中nLi/n(Ni+Co+Mn)=1.15。
实施例8
与实施例1的区别在于,步骤3中nLi/n(Ni+Co+Mn)=1.20。
实施例9
与实施例1的区别在于,步骤4中烧结压力50MPa、烧结温度800℃、烧结时间7min 。
实施例10
与实施例1的区别在于,步骤4中烧结压力40MPa、烧结温度800℃、烧结时间8min 。
对比例1
步骤1:10.0g二次球形前驱体在占球磨罐体积60%的液氮中,进行低温球磨,球磨速度300rpm,球磨时间1h,得到粒度均匀的纳米级一次颗粒前驱体Ⅰ;
步骤2:将2.5g(含量为60%)植酸分散于50m L乙二醇中形成溶液A;加入1.0g的纳米铝粉于A溶液中,搅拌均匀,形成胶体溶液B;
步骤3:nLi/n(Ni+Co+Mn)=1.10,将90%的碳酸锂与前驱体Ⅰ在高混机中转速为30HZ,混合时间为8min,混合均匀,再加入胶体溶液B,混合时间为4min后,于烘箱中100℃干燥,得到包覆改性后颗粒强度高的的前驱体Ⅱ,进行970℃*8h高温烧结,研磨后;再加入剩余10%的碳酸锂,进行900℃*10h烧结,得到微米级单晶正极材料。
对比例2
步骤1:10.0g二次球形前驱体进行球磨,球磨速度300rpm,球磨时间1h,得到一次颗粒前驱体Ⅰ;
步骤2:将2.5g(含量为60%)植酸分散于50m L乙二醇中形成溶液A;加入1.0g的纳米铝粉于A溶液中,搅拌均匀,形成胶体溶液B;
步骤3:将碳酸锂与前驱体Ⅰ在高混机中转速为30HZ,混合时间为8min,混合均匀,其中nLi/n(Ni+Co+Mn)=1.05,再加入胶体溶液B,混合时间为4min后,于烘箱中100℃干燥,得到包覆改性后颗粒强度高的前驱体Ⅱ;
步骤4:将前驱体Ⅱ置于石墨模具中,放电等离子体烧结炉的炉腔内,在烧结压力50MPa、烧结温度900℃、烧结时间5min 的真空气氛下进行烧结,将烧结后的物料自然冷却至室温,经粉碎、过筛制备成高性能的纳米单晶正极材料。
对比例3
步骤1:10.0g二次球形前驱体在占球磨罐体积60%的液氮中,进行低温球磨,球磨速度300rpm,球磨时间1h,得到粒度均匀的纳米级一次颗粒前驱体Ⅰ;
步骤2:将1.0g的纳米铝粉分散于50m L乙二醇中,搅拌均匀,形成胶体溶液B;
步骤3:将碳酸锂与前驱体Ⅰ在高混机中转速为30HZ,混合时间为8min,混合均匀,其中nLi/n(Ni+Co+Mn)=1.05,再加入胶体溶液B,混合时间为4min后,于烘箱中100℃干燥,得到包覆改性后颗粒强度高的前驱体Ⅱ;
步骤4:将前驱体Ⅱ置于石墨模具中,放电等离子体烧结炉的炉腔内,在烧结压力50MPa、烧结温度900℃、烧结时间5min 的真空气氛下进行烧结,将烧结后的物料自然冷却至室温,经粉碎、过筛制备成高性能的纳米单晶正极材料。
扣式电池制作:分别用上述实施例和对比例制作的正极材料,按照正极材料、导电剂SP、粘结剂PVDF的质量比8:1:1称量,与NMP混合均匀后,制备成浆料;再涂布在集流体铝箔上,真空干燥、辊压成正极片, 裁成Φ14mm的圆片,以锂片为负极,采用玻璃纤维隔膜,高压电解液,组装成扣式电池。
材料的性能测试采用蓝电电池测试系统,在25℃下进行测试,测试电压范围为2.75-4.3V,电流密度为1C的条件下,测试材料的倍率性能和循环性能、放电比容量。另外,采用电位滴定法测试材料的残余碱量,测试结果如表1。
从表中数据和SEM图可知,通过实施例1、2、3 与对比例2相比,利用液氮球磨法对二次球形前驱体进行破碎,提高球形颗粒的破碎效率,减少球磨时间,且得到的颗粒更均匀,物料的振实密度增大。
通过实施例1、4、5 与对比例3相比,植酸溶液与纳米铝粉形成的胶体溶液,可缓解纳米单晶颗粒的团聚问题,同时植酸呈酸性,与过渡金属有较强的螯合能力,可以有效抑制在电池充放电过程中过渡金属离子的溶出,显著地提高了材料的放电比容量、循环稳定性,植酸特有的酸性,还能降低材料的pH值,使材料表面残锂量降低。
通过实施例1、9、10与对比例1相比,利用放电等离子体烧结技术的等离子体的活化和快速升温烧结的综合作用处理前驱体,引入氧空位,提高纳米单晶正极材料电性能,快速升温烧结、加热均匀、生产周期短、节能等优点,抑制晶粒的长大,有助于实现单晶材料的纳米化、颗粒均匀、振实密度高的特点。
Claims (5)
1.一种纳米单晶正极材料的制备方法,其特征在于,包括以下步骤:
步骤1:将二次球形前驱体进行低温球磨,得到粒度均匀的纳米级一次颗粒前驱体Ⅰ;所述二次球形前驱体为锂离子电池正极材料前驱体:NixCoyMn1-x-yCO3或NixCoyMn1-x-y(OH)2,其中0≤x≤1.0,0≤y≤ 1.0,x+y≤ 1.0;所述球磨是在液氮行星式球磨机中进行,球料比为17~20:1,液氮占球磨罐体积的50%~65%,球磨速度200~400rpm,球磨时间0.5~2h;
步骤2:将植酸分散于非水性溶剂中形成溶液A;加入适量的纳米铝粉于A溶液中,搅拌均匀,形成胶体溶液B;
步骤3:将一次颗粒前驱体Ⅰ与锂源,在高混机中混合均匀,再加入胶体溶液B,混匀后,干燥,得到包覆改性后颗粒强度高的前驱体Ⅱ;
步骤4:将前驱体Ⅱ置于石墨模具中,放入放电等离子体烧结炉的炉腔内,在真空、惰性气氛下进行烧结,并粉碎、过筛制备成高性能的纳米单晶正极材料;所述放电等离子体烧结炉的条件为:烧结压力40~60MPa、烧结温度800~900℃、烧结时间6~8min。
2.如权利要求1所述的一种纳米单晶正极材料的制备方法,其特征在于,
所述植酸为质量分数为60~70%的植酸溶液;所述植酸的摩尔量与前驱体Ⅰ中的过渡金属总摩尔量的比为1:(3~7);所述非水性溶剂为乙醇、甲醇、异丙醇、乙二醇中的任意一种。
3.如权利要求1所述的一种纳米单晶正极材料的制备方法,其特征在于,
所述纳米铝粉用量为前驱体Ⅰ质量分数的0.5~1.5%,所述锂源为碳酸锂、氢氧化锂、硝酸锂、醋酸锂、氯化锂,其中锂元素与前驱体Ⅰ中的过渡金属总摩尔数的摩尔比为(1.05~1.2):1。
4.如权利要求1所述的一种纳米单晶正极材料的制备方法,其特征在于,
所述高混机转速为20~50HZ,混合时间为4~12min。
5.一种纳米单晶正极材料,使用权利要求1-4任一所述的方法制备得到。
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