CN113410456A - 一类低钠含量的o3型钠离子电池层状正极材料 - Google Patents
一类低钠含量的o3型钠离子电池层状正极材料 Download PDFInfo
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- 239000011734 sodium Substances 0.000 title claims abstract description 64
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 34
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 28
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 12
- 239000010405 anode material Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 11
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 5
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 5
- 229910019020 PtO2 Inorganic materials 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 3
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910000417 bismuth pentoxide Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 238000013461 design Methods 0.000 abstract description 5
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- 238000004146 energy storage Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 239000002033 PVDF binder Substances 0.000 description 2
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- 238000001035 drying Methods 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 201000004569 Blindness Diseases 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于电化学电源领域,具体涉及一类低钠含量的O3型钠离子电池层状正极材料。该层状正极材料化学式为Na0.67AxByCzDrO2,A选自二价金属离子中的两种或三种,B选自三价金属离子中的两种或三种、C选自四价金属离子中的两种或三种、D选自五价金属离子中的一种或两种,过渡金属层元素种类在7~10种之间,且满足x+y+z+r=1,且2.8≤2x+3y+4z+5r≤3.2。本发明基于特定的高熵过渡金属层组分成功获得低钠含量的O3型结构材料,使得材料的结构设计更具有可控性,对高性能的钠离子电池层状正极材料的优化设计提供了新的见解,具有广阔的应用前景。
Description
技术领域
本发明属于电化学电源领域,具体涉及一类低钠含量的O3型钠离子电池层状正极材料。
背景技术
随着人们对环境问题和化石燃料快速消耗的担忧持续增长,现代社会对可再生能源的利用和智能电网的推广的强烈需求推动了先进储能技术的发展,大型电化学储能***的需求在过去的数十年中受到了极大的关注。在各种电能存储***中,充电电池由于其高安全性、高转换效率、低成本和环境友好被认为是先进储能技术最典型的代表之一。碱金属离子电池由于能量密度高、循环寿命长等优点在储能领域占据着极为重要的地位。
近年来,碱金属离子电池中层状氧化物正极材料由于具有可逆脱嵌锂、钠离子等的晶体结构、比容量高、制备方法简单以及价格低廉等一系列优势,使其得到储能领域的科学家们的深入研究,成为备受关注的焦点。
层状过渡金属氧化物NaxMO2(M为过渡金属)是目前研究最广泛的候选材料之一,P2型中钠离子占据三棱柱间隙位,氧层排列规律为ABBA,0.45≤x≤0.8;O3型材料钠离子占据八面***,氧层排列规律为ABCABC,0.8≤x≤1。晶体结构的差异自然对材料电化学性能造成明显的影响。
相结构的差别和材料中所含的钠离子含量息息相关,一般来说,高Na含量(0.8≤x≤1)有助于形成O3型结构,而低Na含量(0.45≤x≤0.8)则形成P2型结构,结构的设计和调控主要还是依靠高通量的尝试性实验,具有明显的盲目性。
发明内容
本发明的目的是提供一类低钠含量的O3型钠离子电池层状正极材料:该层状正极材料化学式Na0.67AxByCzDrO2,A选自二价金属元素中的两种或三种,B选自三价金属元素中的两种或三种,C选自四价金属元素中的两种或三种、D选自五价金属元素中的一种或两种。
层状正极材料Na0.67AxByCzDrO2中过渡金属层元素种类在7~10种之间。
层状正极材料Na0.67AxByCzDrO2中x、y、z、r分别为对应元素所占过渡金属元素组分的摩尔分数,关系满足x+y+z+r=1,且2.8≤2x+3y+4z+5r≤3.2。
所述的A元素为Ni、Cu、Mg或Zn中的两种或三种;
所述的B元素为Fe、Co、Al、Sc或In中的两种或三种;
所述的C元素为Mn、Ti、Sn、V、Cr、Zr或Hf中的两种或三种;
所述的D元素为Sb、Nb、Mo、Pt或Bi中的一种或两种。
上述材料应用传统的固相法即可制得,方法具体如下:
(3)由相应元素的金属氧化物按照比例进行投料研磨混匀,研磨时间24~36h,将研磨混匀后的粉末用压片机在10MPa的压力下压成直径为10mm的圆片;
(4)将圆片放在坩埚中移至马弗炉中进行程序升温煅烧;煅烧温度为800~1000℃;煅烧时间为10~15h,得到本发明所述的一类低钠含量的O3型钠离子电池层状正极材料。
上述程序升温煅烧步骤中,升温速率为3~8℃min-1。
所述的相应氧化物具体为NiO,CuO,MgO,ZnO,Fe2O3,Co3O4,Al2O3,Sc2O3,In2O3,Mn2O3,TiO2,SnO2,VO2,Cr2O3,ZrO2,HfO2,Sb2O3,Nb2O5,MoO3,PtO2,Bi2O5。
本发明中所涉及的试剂和仪器,如无特殊说明,均可从商业途径获得。
通过使用XRD的衍射图谱对比,以上材料均拥有晶面指数为(003)的衍射峰,且符合O3相的标准衍射图谱,故可判断材料是O3型材料。
与现有技术相比,本发明对钠离子层状正极材料的结构设计更有靶向性,为设计高性能正极材料提供了参考,具有一定的规律性和普适性。
上述材料与导电添加剂、粘结剂及溶剂按一定比例混合,经制浆、涂片、干燥等工艺流程制备可得到复合物正极。得到的极片与隔膜、有机电解液、负极金属钠在手套箱中进行组装,可得到钠离子电池进行能量的存储和释放。
本发明利用构筑高熵过渡金属层组分,提升过渡金属层的电荷无序化,弱化过渡金属层和氧层间的相互作用,进而增强了钠层和氧层间的库仑相互作用,所以在低钠含量下钠离子仍然占据层间距更窄的八面***,呈现O3型结构。
附图说明
图1为Na0.67Ni0.12Cu0.12Mg0.12Fe0.15Co0.15Mn0.1Ti0.1Sn0.1Sb0.04O2的XRD图谱
具体实施方式
下面结合附图并通过具体实施例对本发明作进一步说明。
附图中,P2相的三强峰在衍射角度为15.79°、39.45°、48.84°晶面指数分别为(002)、(012)、(104),O3相的三强峰在衍射角度为16.58°、36.89°、41.91°晶面指数分别为(003)、(012)、(104),通过使用XRD的衍射图谱对比,说明以上材料均拥有晶面指数为(003)的衍射峰,且符合O3相的标准衍射图谱,故可判断材料是O3型材料。
实施例1
(一)制备Na0.67Ni0.12Cu0.12Mg0.12Fe0.15Co0.15Mn0.1Ti0.1Sn0.1Sb0.04O2正极材料
按照目标产物中的物质的量称取相应质量的Na2CO3、NiO、CuO、MgO、Fe2O3、Co3O4、Mn2O3、TiO2、Sb2O3、SnO2,球磨24h混合均匀,在10MPa的压力下压成直径10mm的圆片,置于马弗炉中在900℃的高温下程序升温煅烧15h后得到样品粉末,升温速率为8℃min-1。
(二)对Na0.67Ni0.12Cu0.12Mg0.12Fe0.15Co0.15Mn0.1Ti0.1Sn0.1Sb0.04O2正极材料样品粉末进行XRD测试
使用X射线衍射仪,利用X射线在晶体物质中的衍射效应获得Na0.67Ni0.12Cu0.12Mg0.12Fe0.15Co0.15Mn0.1Ti0.1Sn0.1Sb0.04O2样品粉末的XRD图谱,参照标准的PDF卡片对材料的结构进行分析,如附图所示。
(三)应用:
Na0.67Ni0.12Cu0.12Mg0.12Fe0.15Co0.15Mn0.1Ti0.1Sn0.1Sb0.04O2制备复合物正极
将制备的本实施例制备的正极材料与导电添加剂Super-P、粘结剂聚偏二氟乙烯(PVDF)按质量比为8∶1∶1均匀混合,并加入溶剂N-甲基吡咯烷酮经过制浆、涂片、干燥等工艺得到复合物正极。
将上述制备的复合物正极同钠负极在手套箱中组装成钠离子电池,电解液选择碳酸酯电解液(1M NaClO4的EC/PC(体积比为1:1)溶液),使用蓝电充放电测试仪对上述钠离子电池进行恒定倍率0.2C下的充放电测试,结果良好。
实施例2
(一)制备Na0.67Ni0.12Cu0.12Zn0.12Fe0.1Co0.1Al0.1Mn0.1V0.1Sb0.14O2正极材料。(原材料为Na2CO3、NiO、CuO、ZnO、Fe2O3、Co3O4、Al2O3、Mn2O3、VO2、Sb2O3,其余步骤同实施例1)
(二)对Na0.67Ni0.12Cu0.12Zn0.12Fe0.1Co0.1Al0.1Mn0.1V0.1 Sb0.14O2样品粉末进行XRD测试(具体步骤同实施例1)
(三)应用(具体步骤同实施例1)
实施例3
(一)制备Na0.67Ni0.18Zn0.18Fe0.1Sc0.1Al0.1Mn0.1V0.1Ti0.1Nb0.04O2正极材料。(原材料为Na2CO3、NiO、ZnO、Fe2O3、Sc2O3、Al2O3、Mn2O3、VO2、TiO2、Nb2O5,其余步骤同
实施例1)
(二)对Na0.67Ni0.18Zn0.18Fe0.1Sc0.1Al0.1Mn0.1V0.1Ti0.1Nb0.04O2样品粉末进行XRD测试(具体步骤同实施例1)
(三)应用(具体步骤同实施例1)
实施例4
(一)制备Na0.67Mg0.18Zn0.18Fe0.1Sc0.1In0.1Mn0.16Ti0.16Pt0.02O2正极材料。(原材料为Na2CO3、MgO、ZnO、Fe2O3、Sc2O3、In2O3、Mn2O3、TiO2、PtO2,其余步骤同实施例1)
(二)对Na0.67Mg0.18Zn0.18Fe0.1Sc0.1In0.1Mn0.16Ti0.16Pt0.02O2样品粉末进行XRD测试(具体步骤同实施例1)
(三)应用(具体步骤同实施例1)
实施例5
(一)制备Na0.67Ni0.12Zn0.12Mg0.12Sc0.15Al0.15Sn0.11V0.11Hf0.11Pt0.01O2正极材料。(原材料为Na2CO3、NiO、ZnO、MgO、Sc2O3、Al2O3、SnO2、VO2、HfO2、PtO2,其余步骤同实施例1)
(二)对Na0.67Ni0.12Zn0.12Mg0.12Sc0.15Al0.15Sn0.11V0.11Hf0.11Pt0.01O2样品粉末进行XRD测试(具体步骤同实施例1)
(三)应用(具体步骤同实施例1)
对比例1
(一)制备Na0.67Ni0.18Mg0.18Co0.3Mn0.23Sn0.2O2正极材料。(原材料为Na2CO3、NiO、MgO、Co3O4、Mn2O3、SnO2,其余步骤同实施例1)
(二)对Na0.67Ni0.18Mg0.18Co0.3Mn0.23Sn0.2O2样品粉末进行XRD测试(具体步骤同实施例1)
(三)应用(具体步骤同实施例1)
对比例2
(一)制备Na0.67Ni0.12Cu0.12Mg0.12Al0.15Co0.15Mn0.43O2正极材料。(原材料为Na2CO3、NiO、CuO、MgO、Al2O3、Co3O4、Mn2O3,其余步骤同实施例1)
(二)对Na0.67Ni0.12Cu0.12Mg0.12Al0.15Co0.15Mn0.43O2样品粉末进行XRD测试(具体步骤同实施例1)
(三)应用(具体步骤同实施例1)
对比例3
(一)制备Na0.67Ni0.18Mg0.18Co0.3Sn0.2Mn0.14O2正极材料。(原材料为Na2CO3、NiO、MgO、Co3O4、SnO2、Mn2O3,其余步骤同实施例1)
(二)对Na0.67Ni0.18Mg0.18Co0.3Sn0.2Mn0.14O2样品粉末进行XRD测试(具体步骤同实施例1)
(三)应用(具体步骤同实施例1)
对比例4
(一)制备Na0.67Ni0.12Cu0.12Mg0.12Co0.3Mn0.34O2正极材料。(原材料为Na2CO3、NiO、CuO、MgO、Co3O4、Mn2O3,其余步骤同实施例1)
(二)对Na0.67Ni0.12Cu0.12Mg0.12Co0.3Mn0.34O2样品粉末进行XRD测试(具体步骤同实施例1)
(三)应用(具体步骤同实施例1)
对比例5
(一)制备Na0.67Ni0.36Al0.1Fe0.1Co0.1Ti0.1Mn0.24O2正极材料。(原材料为Na2CO3、NiO、Al2O3、Co3O4、Fe2O3、TiO2、Mn2O3,其余步骤同实施例1)
(二)对Na0.67Ni0.36Al0.1Fe0.1Co0.1Ti0.1Mn0.24O2样品粉末进行XRD测试(具体步骤同实施例1)
(三)应用(具体步骤同实施例1)
通过上述实施例与对比例的对比可以看出,通过高温固相法,在相同的温度和反应时间的条件下,实施例1、2、3、4、5在过渡金属层元素种类不小于7种不大于10种的情况下获得了O3相,而对比例1、2、3、4、5的过渡金属层组分不满足这已要求均未获得O3相,故基于高熵过渡金属层组分设计低钠含量的O3型层状正极材料的方法有效可行。
综上所述,本发明基于构筑高熵过渡金属层组分得到的低钠含量O3型钠离子电池层状正极材料,相应的制备方法简单,原料易得,价格低廉,因此本发明可以对高性能的钠离子电池正极层状材料结构的优化设计提供新的见解,具有广阔的应用前景。
上述内容仅为本发明的优选实施例,并非用于限制本发明的实施方案,本领域普通技术人员根据本发明的主要构思和精神,可以十分方便地进行相应的变通或修改,因此本发明的保护范围应以权利要求书所要求的保护范围为准。
Claims (8)
1.一类低钠含量O3型钠离子层状正极材料,其特征在于:该层状正极材料化学式Na0.67AxByCzDrO2,A选自二价金属元素中的两种或三种,B选自三价金属元素中的两种或三种,C选自四价金属元素中的两种或三种、D选自五价金属元素中的一种或两种;
层状正极材料Na0.67AxByCzDrO2中过渡金属层元素种类在7~10种之间;
层状正极材料Na0.67AxByCzDrO2中x、y、z、r分别为对应元素所占过渡金属元素组分的摩尔分数,关系满足x+y+z+r=1,且2.8≤2x+3y+4z+5r≤3.2。
2.根据权利要求1所述的一类低钠含量的O3型钠离子层状正极材料,其特征在于所述的A元素为Ni、Cu、Mg或Zn中的两种或三种。
3.根据权利要求1所述的一类低钠含量的O3型钠离子层状正极材料,其特征在于所述的B元素为Fe、Co、Al、Sc或In中的两种或三种。
4.根据权利要求1所述的一类低钠含量的O3型钠离子层状正极材料,其特征在于所述的所述的C元素为Mn、Ti、Sn、V、Cr、Zr或Hf中的两种或三种。
5.根据权利要求1所述的一类低钠含量的O3型钠离子层状正极材料,其特征在于所述的所述的D元素为Sb、Nb、Mo、Pt或Bi中的一种或两种。
6.根据权利要求1所述的一类低钠含量的O3型钠离子层状正极材料,其特征在于所述的一类低钠含量的O3型钠离子层状正极材料,具体制备方法如下:
(1)由相应元素的金属氧化物按照比例进行投料研磨混匀,研磨时间24~36h,将研磨混匀后的粉末用压片机在10MPa的压力下压成直径为10mm的圆片;
(2)将圆片放在坩埚中移至马弗炉中进行程序升温煅烧;煅烧温度为800~1000℃;煅烧时间为10~15h,得到所述的一类低钠含量的O3型钠离子电池层状正极材料。
7.根据权利要求6所述的一类低钠含量的O3型钠离子层状正极材料,其特征在于所述的程序升温煅烧步骤中,升温速率为3~8℃ min-1。
8.根据权利要求6所述的一类低钠含量的O3型钠离子层状正极材料,其特征在于所述的所述的相应氧化物具体为NiO,CuO,MgO,ZnO,Fe2O3,Co3O4,Al2O3,Sc2O3,In2O3,Mn2O3,TiO2,SnO2,VO2,Cr2O3,ZrO2,HfO2,Sb2O3,Nb2O5,MoO3,PtO2,Bi2O5。
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