CN116470028A - 一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料及改性方法 - Google Patents
一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料及改性方法 Download PDFInfo
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- CN116470028A CN116470028A CN202310543151.0A CN202310543151A CN116470028A CN 116470028 A CN116470028 A CN 116470028A CN 202310543151 A CN202310543151 A CN 202310543151A CN 116470028 A CN116470028 A CN 116470028A
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- sodium
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 52
- ZQKXOSJYJMDROL-UHFFFAOYSA-H aluminum;trisodium;diphosphate Chemical compound [Na+].[Na+].[Na+].[Al+3].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZQKXOSJYJMDROL-UHFFFAOYSA-H 0.000 title claims abstract description 42
- WFSRWJJESXWWSH-UHFFFAOYSA-N [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] Chemical compound [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] WFSRWJJESXWWSH-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002715 modification method Methods 0.000 title claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000011734 sodium Substances 0.000 claims abstract description 33
- 239000002105 nanoparticle Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 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 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 15
- 238000000498 ball milling Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- RMZMFASTOVOJPY-UHFFFAOYSA-N [Fe].[Mn].[Ni].[Na] Chemical compound [Fe].[Mn].[Ni].[Na] RMZMFASTOVOJPY-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000000975 co-precipitation Methods 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 239000011572 manganese Substances 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000010405 anode material Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000011164 primary particle Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011163 secondary particle Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims 3
- 150000002505 iron Chemical class 0.000 claims 2
- 150000002696 manganese Chemical class 0.000 claims 2
- 150000002815 nickel Chemical class 0.000 claims 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims 1
- 239000004280 Sodium formate Substances 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000001632 sodium acetate Substances 0.000 claims 1
- 235000017281 sodium acetate Nutrition 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims 1
- 235000019254 sodium formate Nutrition 0.000 claims 1
- 235000009518 sodium iodide Nutrition 0.000 claims 1
- 239000004317 sodium nitrate Substances 0.000 claims 1
- 235000010344 sodium nitrate Nutrition 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 30
- -1 nickel iron sodium manganate Chemical compound 0.000 abstract description 13
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 241000080590 Niso Species 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910000863 Ferronickel Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- XLCPLIJTRIGVDU-UHFFFAOYSA-N [O-2].[Mn+2].[Ni+2].[Na+] Chemical compound [O-2].[Mn+2].[Ni+2].[Na+] XLCPLIJTRIGVDU-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- 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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Abstract
本发明公开一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料及改性方法,涉及电池材料领域,包括以下步骤:(1)将镍铁锰金属盐溶液、氢氧化钠沉淀剂溶液和络合剂溶液加入装有底液的反应釜中进行共沉淀反应得到镍铁锰酸钠三元氢氧化物前驱体。(2)将步骤(1)中得到的镍铁锰酸钠三元氢氧化物前驱体与钠源、铝源、磷源按照一定比例进行球磨混合,混合均匀后,在氧化性气氛下进行高温烧结,即得到纳米尺寸磷酸铝钠包覆的镍铁锰酸钠正极材料,磷酸铝钠层包覆在正极材料表面可以在一定程度上减轻相变应力,从而减少正极材料在循环过程中的破碎,稳定其结构。
Description
技术领域
本发明属于电池材料领域,尤其涉及一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料及改性方法。
背景技术
锂离子电池(LIBs)凭借其能量密度高、循环寿命长以及环境友好等优点广泛应用于新能源汽车及储能系统。然而,金属资源不断减少、分布不均以及价格不断上涨等问题又限制了其进一步发展。再加上电动汽车对锂离子电池的需求不断增加,限制了其在大规模储能系统中的应用。因此,钠离子电池(NIBs)凭借资源丰度高、成本低、安全性能好等优势脱颖而出,受到广泛关注,被认为是一种很有前景的替代品。其中,层状过渡金属氧化物材料(NaxTMO2,TM通常代表Ti、V、Cr、Mn、Ni、Zn、Cu等一种或多种元素)因其具有较高的理论比容量、结构简单、易于合成等优势,在目前的研究中占主导地位。
O3型镍铁锰酸钠作为一种经典的钠电正极材料,因其比容量高、工作电压高且原料低廉易得而受到了广大储能研究者的青睐。在对O3型镍铁锰酸钠正极材料的研究中,其存在的缺点主要有充放电过程会产生复杂的相变、空气稳定性差、离子扩散缓慢以及首次库伦效率低等。为了提高O3型镍铁锰酸钠正极材料的电化学性能,目前的研究中采取的主要方法有掺杂取代、控制微观形貌、包覆改性、制作混相等,以从不同的角度改善材料的性能。目前包覆改性主要利用非原位包覆手段,获得的正极材料需要二次热处理促使包覆涂层与原始基础材料之间进行良好的结合,本发明通过简单的一步法实现纳米尺寸磷酸铝钠在正极表面构建原位包覆层,不仅过程简单,且还可以显著提升材料的表面及本体的结构稳定性,同时表现出较高水平的离子传输性能。
发明内容
本发明所要解决的技术问题是克服以上背景技术中提到的不足和缺陷,提供一种高稳定性、大倍率的磷酸铝钠包覆的镍铁锰酸钠三元正极材料的改性方法。为解决上述技术问题,本发明提出的技术方案为:
一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料的改性方法,包括以下步骤:
(1)将镍铁锰金属盐溶液、氢氧化钠沉淀剂溶液和络合剂溶液加入装有底液的反应釜中进行共沉淀反应得到镍铁锰酸钠三元氢氧化物前驱体。
(2)将步骤(1)中得到的镍铁锰酸钠三元氢氧化物前驱体与钠源、铝源、磷源按照一定比例进行球磨混合,混合均匀后,在氧化性气氛下进行高温烧结,即得到纳米尺寸磷酸铝钠包覆的镍铁锰酸钠正极材料。
上述制备方法中,优选的,步骤(1)中共沉淀反应时的具体过程如下:将镍铁锰金属盐溶液、氢氧化钠沉淀剂溶液和络合剂溶液逐滴加入到底液中,控制反应条件进行共沉淀反应,反应完全后经陈化、过滤、洗涤、干燥后得到实心结构的镍铁锰三元氢氧化物前驱体。
优选的,步骤(1)中所述镍、铁、锰的金属盐类型为可溶性硝酸盐、乙酸盐、硫酸盐、草酸盐中的一种或几种;所述NaOH沉淀剂的浓度为2-6molL-1;所述NH3·H2O络合剂的浓度为10-40wt%;所述溶液pH值为10-12,所述共沉淀反应时间为10-30h。
优选的,步骤(2)中所述球磨过程中所需球磨转速为100~700r/min,球磨时间2~10h。
优选的,步骤(2)中所述高温烧结过程中所用的钠源为碳酸钠、氢氧化钠、碳酸氢钠中的一种或几种,所述氢氧化物前驱体:钠源:铝源:磷源的摩尔比为1:(0.9-1.05):(0.01-0.1)。
优选的,步骤(2)中所述高温烧结过程中预烧温度为300-600℃,预烧时间为3-9h;所述再煅烧为温度为800-950℃,煅烧时间为6-15h。
优选的,步骤(2)中所述烧结过程中气氛中氧气含量超过50%,水和CO2含量低于0.1%。
本发明的发明原理是采用一步烧结法制备了纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料,通过将前驱体、钠源、铝源、磷源充分混合,在高温烧结过程中,在Na+进入前驱体生成镍铁锰酸钠正极材料的同时,在正极材料表面形成磷酸铝钠包覆层;此外,Al3+在高温烧结过程中也能够掺杂进入材料中,最终得到磷酸铝钠包覆、Al3+掺杂共改性的镍铁锰酸钠正极材料,本发明所得的改性材料颗粒均匀,提升了镍铁锰酸钠材料的大倍率充放电能力及其稳定性。
本发明与现有技术相比的有益效果在于:
(1)本发明的纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料,其纳米尺寸的磷酸铝钠具有高离子电导率和稳定的结构,包覆在正极材料最外层的磷酸铝钠形成了一层屏障,在保护正极材料不受水分影响的情况下还可以阻挡隔绝电解液,抑制界面副反应。同时,磷酸铝钠层包覆在正极材料表面可以在一定程度上减轻相变应力,从而减少正极材料在循环过程中的破碎,稳定其结构。此外,将磷酸铝钠包覆于正极材料上能够加速Na+的迁移,提升材料的倍率性能。
(2)本发明使用纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料,高温驱动下Al3+也掺杂进入材料,进而增强结构稳定性,使得材料的循环性能得到显著的提升。
(3)本发明使用纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料,电压区间在2.0~4.0V,1C倍率下循环100圈后容量保持率为87.5%。
(4)本发明制备的纳米尺寸磷酸铝钠包覆层采用一步法合成,在材料表面实现原位包覆。制备方法简单、流程短、易于操作、成本低、电池安全有效,适用于大规模生产。
附图说明
图1为实施例1制备的纳米尺寸磷酸铝钠包覆的镍铁锰酸钠正极材料及对比例1中纯相镍铁锰酸钠正极材料的XRD图。
图2为实施例1制备的纳米尺寸磷酸铝钠包覆的镍铁锰酸钠正极材料的SEM图。
图3为实施例1制备的纳米尺寸磷酸铝钠包覆的镍铁锰酸钠正极材料的EDS能谱图。
图4为实施例1制备的纳米尺寸磷酸铝钠包覆的镍铁锰酸钠正极材料及纯相镍铁锰酸钠正极材料在2-4V电压区间、1C电流倍率下的循环性能图。
图5为实施例1制备的纳米尺寸磷酸铝钠包覆的镍铁锰酸钠正极材料在2-4V电压区间0.1C电流倍率下的首圈充放电曲线。
图6为对比例1制备的未包覆的镍铁锰酸钠正极材料的SEM图。
图7为对比例1制备的纯相镍铁锰酸钠正极材料在2-4V电压区间0.1C电流倍率下的首圈充放电曲线。
实施方式
为了便于理解本发明,下文将结合说明书附图和较佳的实施例对本发明作更全面、细致地描述,但本发明的保护范围并不限于以下具体的实施例。
除非另有定义,下文中所使用的所有专业术语与本领域技术人员通常理解的含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的,并不是旨在限制本发明的保护范围。
除非另有特别说明,本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。
实施例1
一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料的制备方法,包括以下步骤:
将NiSO4·7H2O,FeSO4·7H2O,MnSO4·H2O按摩尔比1:1:1溶于去离子水中,配置成2molL-1的金属离子溶液,然后在氮气气氛保护下将其加入到连续搅拌釜式反应器中,加入4molL-1NaOH沉淀剂和20wt%NH3·H2O络合剂后,使溶液的pH保持在10-11范围内,经过充分的反应后抽滤,反复洗涤,除去杂质,干燥后得到Ni1/3Fe1/3Mn1/3(OH)2前驱体。取1mol的Ni1/ 3Fe1/3Mn1/3(OH)2前驱体与0.505mol的Na2CO3、0.01的molAl(NO3)3·9H2O和0.01mol的NH4H2PO4进行充分球磨混合,在气氛炉中以5℃/min升温至500℃,预烧4h,再升温至890℃烧结12h后,即得Na3-3xAlxPO4@NaNi1/3Fe1/3Mn1/3O2活性材料。
图1为实施例1制备的纳米尺寸Na3-3xAlxPO4包覆NaNi1/3Fe1/3Mn1/3O2正极材料的X射线衍射图,所有峰形都与标准卡片对应,20.5°和34°左右出现的衍射峰为Na3-3xAlxPO4材料的衍射峰,证明成功合成Na3-3xAlxPO4@NaNi1/3Fe1/3Mn1/3O2正极材料。同时,相比于纯相的NaNi1/3Fe1/3Mn1/3O2材料,磷酸铝钠包覆材料的(003)峰明显偏移,表明Al3+成功掺杂进入材料晶格中。图2为实施例1制备的Na3-3xAlxPO4@NaNi1/3Fe1/3Mn1/3O2材料的SEM,材料一次颗粒为纳米粒状,二次球粒径约5微米,包覆物颗粒尺寸约10nm。图3为实施例1制备的Na3- 3xAlxPO4@NaNi1/3Fe1/3Mn1/3O2材料的EDS能谱图,从图中可以看到Al元素和P元素在材料中均匀分布,表明成功合成Na3-3xAlxPO4材料包覆NaNi1/3Fe1/3Mn1/3O2表面。
电池的组装:称取0.0800g本实施例所得a3-3xAlxPO4@NaNi1/3Fe1/3Mn1/3O2正极材料,加入0.0100g导电碳黑作导电剂和0.0100gPVDF(聚偏氟乙烯)作粘结剂,混合均匀后涂在铝箔上制成正极片,在真空手套箱中以金属钠片为负极,电池隔膜为WhatmanGF/D的玻璃纤维隔膜,电解液为1mol/LNaClO4(EC:DMC=1:1(体积比)+5%FEC),组装成CR2032的扣式电池。
材料组装成半电池之后,在2-4.0V区间内进行电化学性能测试,如图5所示,在0.1C电流倍率下,首次库伦效率为94.87%,放电比容量可达129.64mAh/g,循环100次后容量保持率如图4所示,为87.50%。
实施例2
一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料的制备方法,包括以下步骤:
将NiSO4·7H2O,FeSO4·7H2O,MnSO4·H2O按摩尔比2:4:4溶于去离子水中,配置成2molL-1的金属离子溶液,然后在氮气气氛保护下将其加入到连续搅拌釜式反应器中,加入4molL-1NaOH沉淀剂和20wt%NH3·H2O络合剂后,使溶液的pH保持在10-11范围内,经过充分的反应后抽滤,反复洗涤,除去杂质,干燥后得到Ni1/3Fe1/3Mn1/3(OH)2前驱体。取1molNi1/ 5Fe2/5Mn2/5(OH)2前驱体与0.505molNa2CO3、0.01molAl(NO3)3·9H2O和0.01molNH4H2PO4进行充分球磨混合,在气氛炉中以5℃/min升温至500℃,预烧4h,再升温至890℃烧结12h后,即得Na3-3xAlxPO4@NaNi1/5Fe2/5Mn2/5O2活性材料。
电池的组装:称取0.2000g本实施例所得镍锰酸钠正极材料,加入0.0250g导电碳黑作导电剂和0.0250gPVDF(聚偏氟乙烯)作粘结剂,混合均匀后涂在铝箔上制成正极片,在真空手套箱中以金属钠片为负极,电池隔膜为WhatmanGF/D的玻璃纤维隔膜,电解液为1mol/LNaClO4(EC:DMC=1:1(体积比)+5%FEC),组装成CR2032的扣式电池。
材料组装成半电池之后,在2-4.0V区间内进行电化学性能测试,如图3所示,在1C电流倍率下,首次库伦效率为93.37%,放电比容量可达122.7mAh/g,循环100次后容量保持率如图4所示,为86.68%。
实施例3
一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料的制备方法,包括以下步骤:
将NiSO4·7H2O,FeSO4·7H2O,MnSO4·H2O按摩尔比1:1:1溶于去离子水中,配置成2molL-1的金属离子溶液,然后在氮气气氛保护下将其加入到连续搅拌釜式反应器中,加入4molL-1NaOH沉淀剂和20wt%NH3·H2O络合剂后,使溶液的pH保持在10-11范围内,经过充分的反应后抽滤,反复洗涤,除去杂质,干燥后得到Ni1/3Fe1/3Mn1/3(OH)2前驱体。取1molNi1/ 3Fe1/3Mn1/3(OH)2前驱体与0.51molNa2CO3、0.02molAl(NO3)3·9H2O和0.02molNH4H2PO4进行充分球磨混合,在气氛炉中以5℃/min升温至500℃,预烧4h,再升温至890℃烧结12h后,即得Na3-3xAlxPO4@NaNi1/3Fe1/3Mn1/3O2活性材料。
电池的组装:称取0.2000g本实施例所得镍锰酸钠正极材料,加入0.0250g导电碳黑作导电剂和0.0250gPVDF(聚偏氟乙烯)作粘结剂,混合均匀后涂在铝箔上制成正极片,在真空手套箱中以金属钠片为负极,电池隔膜为WhatmanGF/D的玻璃纤维隔膜,电解液为1mol/LNaClO4(EC:DMC=1:1(体积比)+5%FEC),组装成CR2032的扣式电池。
材料组装成半电池之后,在2-4.0V区间内进行电化学性能测试,如图3所示,在1C电流倍率下,首次库伦效率为93.1%,放电比容量可达121.6mAh/g,循环100次后容量保持率如图4所示,为89.68%。
实施例4
一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料的制备方法,包括以下步骤:
将NiSO4·7H2O,FeSO4·7H2O,MnSO4·H2O按摩尔比1:1:1溶于去离子水中,配置成2molL-1的金属离子溶液,然后在氮气气氛保护下将其加入到连续搅拌釜式反应器中,加入4molL-1NaOH沉淀剂和20wt%NH3·H2O络合剂后,使溶液的pH保持在10-11范围内,经过充分的反应后抽滤,反复洗涤,除去杂质,干燥后得到Ni1/3Fe1/3Mn1/3(OH)2前驱体。取1molNi1/ 3Fe1/3Mn1/3(OH)2前驱体与0.505molNa2CO3、0.01molAl(NO3)3·9H2O和0.01molNH4H2PO4进行充分球磨混合,在气氛炉中以5℃/min升温至500℃,预烧4h,再升温至910℃烧结12h后,即得Na3-3xAlxPO4@NaNi1/3Fe1/3Mn1/3O2活性材料。
电池的组装:称取0.2000g本实施例所得镍锰酸钠正极材料,加入0.0250g导电碳黑作导电剂和0.0250gPVDF(聚偏氟乙烯)作粘结剂,混合均匀后涂在铝箔上制成正极片,在真空手套箱中以金属钠片为负极,电池隔膜为WhatmanGF/D的玻璃纤维隔膜,电解液为1mol/LNaClO4(EC:DMC=1:1(体积比)+5%FEC),组装成CR2025的扣式电池。
材料组装成半电池之后,在2-4.0V区间内进行电化学性能测试,如图3所示,在1C电流倍率下,首次库伦效率为94.19%,放电比容量可达126.7mAh/g,循环100次后容量保持率如图4所示,为86.93%。
对比例1
一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料的制备方法,包括以下步骤:
将NiSO4·7H2O,FeSO4·7H2O,MnSO4·H2O按摩尔比1:1:1溶于去离子水中,配置成2molL-1的金属离子溶液,然后在氮气气氛保护下将其加入到连续搅拌釜式反应器中,加入4molL-1NaOH沉淀剂和20wt%NH3·H2O络合剂后,使溶液的pH保持在10-11范围内,经过充分的反应后抽滤,反复洗涤,除去杂质,干燥后得到Ni1/3Fe1/3Mn1/3(OH)2前驱体。取1molNi1/ 3Fe1/3Mn1/3(OH)2前驱体与0.5molNa2CO3进行充分球磨混合,在气氛炉中以5℃/min升温至500℃,预烧4h,再升温至890℃烧结12h后,即得NaNi1/3Fe1/3Mn1/3O2活性材料。
图1为对比例1制备的纯相NaNi1/3Fe1/3Mn1/3O2材料的X射线衍射图,所有峰形都与标准卡片对应,证明成功合成NaNi1/3Fe1/3Mn1/3O2正极材料。材料图6为对比例1制备的未包覆的镍铁锰酸钠正极材料的SEM图,材料表面光滑,无明显包覆物。
电池的组装:称取0.2000g本实施例所得纯相NaNi1/3Fe1/3Mn1/3O2正极材料,加入0.0250g导电碳黑作导电剂和0.0250gPVDF(聚偏氟乙烯)作粘结剂,混合均匀后涂在铝箔上制成正极片,在真空手套箱中以金属钠片为负极,电池隔膜为WhatmanGF/D的玻璃纤维隔膜,电解液为1mol/LNaClO4(EC:DMC=1:1(体积比)+5%FEC),组装成CR2025的扣式电池。
材料组装成半电池之后,在2-4.0V区间内进行电化学性能测试,如图7所示,在1C电流倍率下,首次库伦效率为94.52%,放电比容量可达122.4mAh/g,循环100次后容量保持率如图4所示,为84.39%。
Claims (9)
1.一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料,其特征在于,经包覆后的镍铁锰酸钠三元正极材料的化学式为:Na3-3xAlxPO4@NaNiyFezMn1-y-zO2,其中0≤x≤0.1,0≤y≤1/3,0≤z≤1/3。
2.根据权利要求1所述的一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料,其特征在于,所述包覆层为一步原位包覆。
3.根据权利要求1-2中所述的一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料,其特征在于,所述正极材料一次颗粒为100~200nm粒状,二次颗粒为4~10μm球,包覆物尺寸为1~20nm。
4.一种根据权利要求1-2中任一项所述的一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料的改性方法,其特征在于,包括以下步骤:
(1)将化学计量比的镍盐、铁盐和锰盐溶于去离子水中,配制成金属盐溶液,然后在氮气气氛保护下将其加入到连续搅拌釜式反应器中,加入NaOH沉淀剂和NH3·H2O络合剂,调整溶液的pH,共沉淀反应一定时间后,经过水洗、醇洗、干燥后制得氢氧化物前驱体;
(2)将氢氧化物前驱体与钠源、铝源、磷源球磨混合,混合均匀后在氧化性气氛下进行高温烧结,得到磷酸铝钠包覆的镍铁锰酸钠正极材料。
5.根据权利要求4所述的一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料的改性方法,其特征在于,步骤(1)中所述的锰盐、镍盐和铁盐为可溶性的硫酸盐、硝酸盐、甲酸盐、乙酸盐中的一种或多种;所述NaOH沉淀剂的浓度为2~6molL-1;所述NH3·H2O络合剂的浓度为10-40wt%;所述溶液pH值为10~12,所述共沉淀反应时间为10~30h。
6.根据权利要求4所述的一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料的改性方法,其特征在于,步骤(2)所述高温烧结过程中的钠源为碳酸钠、氢氧化钠、醋酸钠、硝酸钠、甲酸钠和碘化钠中的一种或多种。
7.根据权利要求4所述的一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料的改性方法,其特征在于,步骤(2)所述球磨过程中的球磨转速为100~700r/min,球磨时间2~10h。
8.根据权利要求4中所述的一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料的改性方法,其特征在于,所述步骤(2)中,高温烧结过程包括预煅烧和再煅烧,所述预煅烧为以1-10℃/min的升温速率从室温升至300-600℃,预烧4-10h;所述再煅烧为以1-10℃/min的升温速率升温至800-950℃,煅烧6-15h。
9.根据权要求4中所述的一种纳米尺寸磷酸铝钠包覆的镍铁锰酸钠三元正极材料的改性方法,其特征在于,所述步骤(2)中氧化性气氛中氧气含量超过50%,水和CO2含量低于0.1%。
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