CN114256451A - 一种钠离子电池正极材料及其制备方法和应用 - Google Patents
一种钠离子电池正极材料及其制备方法和应用 Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 39
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 title claims description 27
- 239000011734 sodium Substances 0.000 claims abstract description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021130 PdO2 Inorganic materials 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- 239000012266 salt solution Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- XXSPKSHUSWQAIZ-UHFFFAOYSA-L 36026-88-7 Chemical compound [Ni+2].[O-]P=O.[O-]P=O XXSPKSHUSWQAIZ-UHFFFAOYSA-L 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229960002413 ferric citrate Drugs 0.000 claims description 3
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 2
- MVNQJLFBHVHULX-UHFFFAOYSA-L cobalt(2+);2-hydroxybutanedioate Chemical compound [Co+2].[O-]C(=O)C(O)CC([O-])=O MVNQJLFBHVHULX-UHFFFAOYSA-L 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229940049920 malate Drugs 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 10
- 239000010405 anode material Substances 0.000 abstract description 10
- 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 abstract description 8
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 description 16
- 239000012298 atmosphere Substances 0.000 description 14
- 238000001816 cooling Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 239000001632 sodium acetate Substances 0.000 description 5
- 235000017281 sodium acetate Nutrition 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910019338 NaMnO2 Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910018614 Ni(H2PO2)2 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
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- C01B25/00—Phosphorus; Compounds thereof
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Abstract
本发明属于钠离子电池技术领域,公开了一种钠离子电池正极材料及其制备方法和应用,该钠离子正极材料的通式为NaaMbNicPdO2;M为钴、铁、锰中的至少一种,其中,0<a<1,0<b<1,0<c<1,1‑b‑c<d<1。本发明的钠离子正极材料中部分镍元素和磷元素进入富钠材料晶格内占据钠位;不仅降低了阳离子的混排,也增大了晶体层间距,提高了正极材料的比容量和循环性能;表面还包覆着金属氧化物改善了循环稳定性和安全性,不仅有效的阻止了总阻抗的增加,降低了脱钠状态时充电转移阻抗,而且还阻止了电解液和正极材料的副反应。
Description
技术领域
本发明属于钠离子电池技术领域,具体涉及一种钠离子电池正极材料及其制备方法和应用。
背景技术
钠离子电池已经广泛用于储能领域。钠离子电池具有资源丰富、价格低廉、环境友好等优势,且钠元素不会与铝集流体发生合金化反应,使得负极也可以用便宜的铝替代铜作为集流体,进一步降低了体系成本。但是,钠离子具有较大的离子半径和较慢的动力学速率,成为制约储钠材料发展的主要因素,正极材料的比容量(80~150mAh·g-1)仍远远低于负极材料(碳材料:不低于250mAh·g-1;合金材料:400~600mAh·g-1),因此发展高性能的嵌钠正极材料是提高钠离子电池比能量和推进其应用的关键。
目前,钠离子电池正极材料的性能还存在许多问题需要改善。正极材料中的钠离子在脱出时,容易造成结构的崩塌和体积的变换。电解液和正极活性材料反应,导致比容量的降低,从而影响电池的性能。正极材料的氧空位不足,导致晶格中氧的脱出,从而影响晶体结构。
因此,急需研究一种新的联合改性正极材料及其制备方法,从而提高正极材料的比容量和循环性能等性能不足。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此,本发明提出一种钠离子电池正极材料及其制备方法和应用,该钠离子正极材料的比容量和循环性能优异。
为实现上述目的,本发明采用以下技术方案:
一种钠离子正极材料,其通式为NaaMbNicPdO2;所述M为钴、铁、锰中的至少一种;其中,0<a<1,0<b<1,0<c<1,1-b-c<d<1。
优选地,所述钠离子正极材料的通式为NaaMbNicPdO2;所述M为钴、铁、锰中的至少一种;其中,0.5<a<1,0<b<0.8,0<c<1,1-b-c<d<1。
优选地,所述钠离子正极材料为Na0.4MnNi0.06P0.04O2、Na0.35CoNi0.09P0.06O2、Na0.6FeNi0.12P0.08O2、Na0.7MnNi0.17P0.13O2中的一种。
一种钠离子正极材料的制备方法,包括以下步骤:
(1)将M盐溶液和钠盐溶液混合,加入螯合剂,反应,进行煅烧,得到NaaMbO2;
(2)将所述NaaMbO2和溶剂混合,加入次磷酸镍,反应,煅烧,得到所述钠离子电池正极材料;所述M盐溶液为锰盐溶液、钴盐溶液、铁盐溶液中的至少一种。
优选地,所述锰盐溶液为苹果酸锰、草酸锰乙酸锰中的至少一种。
优选地,所述钴盐溶液为乙酸钴、苹果酸钴、草酸钴中的至少一种。
优选地,所述铁盐溶液为柠檬酸铁、乙酸铁、草酸铁中的至少一种。
优选地,步骤(1)中,所述加入螯合剂前还包括将M盐溶液和钠盐溶液混合加入分散剂中进行分散,所述分散剂为乙醇、丙醇和甲醛树脂中的至少一种。
优选地,步骤(1)中,所述螯合剂为乙二酸、草酸和柠檬酸中的至少一种。
优选地,步骤(1)中,所述反应的温度为40~60℃,反应的时间为12~24h。
优选地,步骤(1)中,所述煅烧的次数为两次,所述煅烧中的第一次煅烧的温度为300~500℃,第一次煅烧的时间为2~4h;第二次煅烧的温度为800~1000℃,第二次煅烧的时间为12~18h。
优选地,步骤(2)中,所述溶剂为乙醇。
优选地,步骤(2)中,所述反应的温度为40~60℃,反应的时间为4~8h。
优选地,步骤(2)中,所述煅烧的温度为500~600℃,煅烧的时间为6~12h。
步骤(2)中的反应方程式为:
Ni(H2PO2)2=NiHPO4+PH3↑;
2NiHPO4=Ni2P2O7+H2O;
Ni2P2O7+NaaMbO2=Naa-x-yMbNixPyO2+Ni2-xNaxP2-yO7,其中,0<x<1,0<y<1。
一种电池,包括所述的钠离子正极材料。
相对于现有技术,本发明的有益效果如下:
1、本发明的钠离子正极材料NaaMbNicPdO2中部分镍元素和磷元素进入富钠材料晶格内占据钠位;不仅降低了阳离子的混排,也增大了晶体层间距,提高了正极材料的比容量和循环性能,比容量可达174mAh/g;表面还包覆着金属氧化物改善了循环稳定性和安全性,不仅有效的阻止了总阻抗的增加,降低了脱钠状态时充电转移阻抗,而且还阻止了电解液和正极材料的副反应。
2、本发明的制备方法中次磷酸镍在高温条件下会产生PH3,PH3具有强还原性,能够引起电池正极材料的活性氧释放,产生更多的氧空位;氧空位有利于缓冲充放电过程中O2–的迁移,抑制晶格氧的不可逆损失,为下一步生成Ni2P2O7提供有利条件。
附图说明
图1为本发明实施例1的正极材料的SEM图;
图2为本发明实施例1和对比例1的正极材料的XRD图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述,以充分地理解本发明的目的、特征和效果。显然,所描述的实施例只是本发明的一部分实施例,而不是全部实施例,基于本发明的实施例,本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例,均属于本发明保护的范围。
实施例1
本实施例的钠离子正极材料,其式为Na0.4MnNi0.06P0.04O2。
本实施例的钠离子正极材料的制备方法,具体步骤如下:
(1)将0.5mol乙酸钠溶液和1mol乙酸锰溶液溶解在100mL乙醇中,并加入1mol的乙二酸混合,置于40℃的环境下反应12h,再置于300℃空气气氛中煅烧2h,待冷却至室温,合成Na0.5MnO2的中间物,在空气气氛中800℃煅烧12h,待自然冷却至室温后,得到最终产物Na0.5MnO2。
(2)将4mol Na0.5MnO2加入到50mL乙醇中,再加入1mol次磷酸镍,在40℃反应4h至乙醇全部蒸发,研磨,在Ar气氛条件下以500℃煅烧6h,合成钠离子电池正极材料Na0.4MnNi0.06P0.04O2。
实施例2
本实施例的钠离子正极材料,其式为Na0.35CoNi0.09P0.06O2。
本实施例的钠离子正极材料的制备方法,具体步骤如下:
(1)将0.5mol乙酸钠溶液和1mol乙酸钴溶液溶解在100mL乙醇中,并加入1.2mol的乙二酸混合,置于45℃的环境下反应15h,再置于350℃空气气氛中煅烧2.5h,待冷却至室温,合成Na0.5CoO2的中间物,在空气气氛中800℃煅烧12h,待自然冷却至室温后,得到最终产物Na0.5CoO2。
(2)将3mol Na0.5CoO2加入到50mL乙醇中,再加入1mol次磷酸镍,在40℃反应4h至乙醇全部蒸发,研磨,在Ar气氛条件下以500℃煅烧6h,合成钠离子电池正极材料Na0.35CoNi0.09P0.06O2。
实施例3
本实施例的钠离子正极材料,其式为Na0.6FeNi0.12P0.08O2。
本实施例的钠离子正极材料的制备方法,具体步骤如下:
(1)将0.8mol乙酸钠溶液和1mol柠檬酸铁溶液溶解在100mL乙醇中,并加入1.5mol的乙二酸混合,置于50℃的环境下反应18h,再置于300℃空气气氛中煅烧2h,待冷却至室温,合成Na0.8FeO2的中间物,在空气气氛中800℃煅烧16h,待自然冷却至室温后,得到最终产物Na0.8FeO2。
(2)将2mol Na0.8FeO2加入到50mL乙醇中,再加入1mol次磷酸镍,在50℃反应6h至乙醇全部蒸发,研磨,在Ar气氛条件下以560℃煅烧10h,合成钠离子电池正极材料Na0.6FeNi0.12P0.08O2。
实施例4
本实施例的钠离子正极材料,其式为Na0.7MnNi0.17P0.13O2。
本实施例的钠离子正极材料的制备方法,具体步骤如下:
(1)将1mol乙酸钠溶液和1mol乙酸锰溶液溶解在100mL乙醇中,并加入2mol的乙二酸混合,置于50℃的环境下反应18h,再置于300℃空气气氛中煅烧2h,待冷却至室温,合成NaMnO2的中间物,在空气气氛中1000℃煅烧18h,待自然冷却至室温后,得到最终产物NaMnO2。
(2)将1mol NaMnO2加入到50mL乙醇中,再加入1mol次磷酸镍,在60℃反应8h至乙醇全部蒸发,研磨,在Ar气氛条件下以600℃煅烧12h,合成钠离子电池正极材料Na0.7MnNi0.17P0.13O2。
对比例1
本对比例的钠离子正极材料,其式为Na0.5MnO2。
本对比例的钠离子正极材料的制备方法,具体步骤如下:
(1)将0.5mol乙酸钠溶液和1mol乙酸锰溶液溶解在100mL乙醇中,并加入1mol的乙二酸混合,置于40℃的环境下反应12h,再置于300℃空气气氛中煅烧2h,待冷却至室温,合成Na0.5MnO2的中间物,在空气气氛中800℃煅烧12h,待自然冷却至室温后,得到最终产物Na0.5MnO2。
实施例1-4与对比例1分析:
将钠离子正极材料、碳黑导电剂、聚四氟乙烯以质量比为80:10:10混合溶于去离子水中配成浆料,然后涂布在铝箔上,形成极片,将极片放于干燥箱中在80℃下干燥12h,模具冲压制成圆片;将圆片剪成直径为10mm的对电极极片;向碳酸酯中加入1.0mol/L NaClO4为电解液,Celgard2400为隔膜,在氩气氛围下的真空手套箱中进行电池组装。循环性能用电化学工作站进行测试,测试的电流密度为150mA·g-1,2C倍率下测试。
表1:实施例1-4与对比例1效果数据
从图1-图2可得,图1为本发明实施例1的正极材料的SEM图,从图1可知,制备的电池正极材料呈块状;图2为本发明实施例1和对比例1制备得到正极材料的XRD图,从图2可知,镍元素和磷元素掺杂到了电池正极材料中。
上面结合附图对本发明实施例作了详细说明,但是本发明不限于上述实施例,在所属技术领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。此外,在不冲突的情况下,本发明的实施例及实施例中的特征可以相互组合。
Claims (10)
1.一种钠离子正极材料,其特征在于,所述钠离子正极材料的通式为NaaMbNicPdO2;所述M为钴、铁、锰中的至少一种;其中,0<a<1,0<b<1,0<c<1,1-b-c<d<1。
2.根据权利要求1所述的钠离子正极材料,其特征在于,所述钠离子正极材料为Na0.4MnNi0.06P0.04O2、Na0.35CoNi0.09P0.06O2、Na0.6FeNi0.12P0.08O2、Na0.7MnNi0.17P0.13O2中的一种。
3.权利要求1-2任一项所述的钠离子正极材料的制备方法,其特征在于,包括以下步骤:
(1)将M盐溶液和钠盐溶液混合,加入螯合剂,反应,进行煅烧,得到NaaMbO2;
(2)将所述NaaMbO2和溶剂混合,加入次磷酸镍,反应,煅烧,得到所述钠离子电池正极材料;所述M盐溶液为锰盐溶液、钴盐溶液、铁盐溶液中的至少一种。
4.根据权利要求3所述的制备方法,其特征在于,所述锰盐溶液为苹果酸锰、草酸锰乙酸锰中的至少一种;所述钴盐溶液为乙酸钴、苹果酸钴、草酸钴中的至少一种。
5.根据权利要求3所述的制备方法,其特征在于,所述铁盐溶液为柠檬酸铁、乙酸铁、草酸铁中的至少一种。
6.根据权利要求3所述的制备方法,其特征在于,步骤(1)中,所述加入螯合剂前还包括将M盐溶液和钠盐溶液混合加入分散剂中进行分散,所述分散剂为乙醇、丙醇和甲醛树脂中的至少一种。
7.根据权利要求3所述的制备方法,其特征在于,步骤(1)中,所述螯合剂为乙二酸、草酸和柠檬酸中的至少一种。
8.根据权利要求3所述的制备方法,其特征在于,步骤(1)中,所述煅烧的次数为两次,所述煅烧中的第一次煅烧的温度为300~500℃,第一次煅烧的时间为2~4h;第二次煅烧的温度为800~1000℃,第二次煅烧的时间为12~18h。
9.根据权利要求3所述的制备方法,其特征在于,步骤(2)中,所述NaaMbO2和次磷酸镍的摩尔比为(1-4):1。
10.一种电池,其特征在于,包括权利要求1-2任一项所述的钠离子正极材料。
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