CN106629648B - Na3.64Fe2.18(P2O7)2正极材料及制备方法和应用 - Google Patents
Na3.64Fe2.18(P2O7)2正极材料及制备方法和应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000011734 sodium Substances 0.000 claims abstract description 61
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 20
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 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 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 239000002738 chelating agent Substances 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- -1 iron ion Chemical class 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 241000040710 Chela Species 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical group 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 229920000447 polyanionic polymer Polymers 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HEAFLBOWLRRIHV-UHFFFAOYSA-N [Na].[P] Chemical compound [Na].[P] HEAFLBOWLRRIHV-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011645 ferric sodium diphosphate Substances 0.000 description 1
- 235000019851 ferric sodium diphosphate Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- XWQGIDJIEPIQBD-UHFFFAOYSA-J sodium;iron(3+);phosphonato phosphate Chemical compound [Na+].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O XWQGIDJIEPIQBD-UHFFFAOYSA-J 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
本发明公开了一种Na3.64Fe2.18(P2O7)2正极材料及制备方法和应用，正极材料是将钠源，铁源，磷源，还原剂和螯合剂通过溶胶凝胶法制得前驱体后在惰性气氛下烧结而成。本发明利用溶胶凝胶法合成了新型的Na3.64Fe2.18(P2O7)2正极材料，该制备方法简便、快捷、成本低；Na3.64Fe2.18(P2O7)2作为钠离子电池正极材料具有优良的容量以及良好的循环性能。
Description
本发明属于材料领域，具体涉及焦磷酸铁钠[Na3.64Fe2.18(P2O7)2]正极材料及其制备方法和在电池领域的应用。
背景技术
随着便携式电子设备的发展以及电动汽车的兴起，当今世界对锂离子电池的需求正在不断增大。但锂资源在地球上的储量非常的少，在地壳中的含量仅0.0065％，全球锂储量仅为 3978万吨，其中具有开采价值的仅为1350万吨。然而根据美国地质调查局2015年发布的数据，2014年全球锂产量约为36000吨，随着电动汽车的兴起这个数字任然会不断地增加，按照这种开发速度，锂资源将远远满足不了将来人们对储能方面的需求，锂将会成为一种枯竭速度更快的资源。钠在地壳中的含量为2.64％，为锂的400倍，相比之下，钠资源比锂资源丰富的多，这也就意味着钠离子电池的成本将会比锂离子电池低的多。在当前的市场形势下，开发低成本的钠离子电池具有重大的意义。
目前钠离子电池正极材料主要有两大类，一种是金属氧化物型，一种是聚阴离子型。人们对钠离子电池的研究最开始集中在金属氧化物上，这类材料拥有很高的理论容量，但是由于金属氧化物的晶体结构本身就不是很稳定，再加上钠离子的半径比锂离子的大，在充放电过程中更容易破坏金属氧化物的晶体结构，导致钠离子电池在金属氧化物中循环性能普遍不是很理想。另一方面来说，由于钠离子的氧化还原电位比锂离子的要高，也导致了金属氧化物材料的操作电压较低。为了解决以上的问题，科学家尝试在晶体中引入磷酸根，焦磷酸根，硫酸根等聚阴离子，借助聚阴离子四面体的形状来稳定晶体结构。在聚阴离子的体系中，钠离子嵌入脱出的通道有了明显的增加，充放电过程中的晶体结构也更加稳定，另外由于聚阴离子强烈的诱导效应的影响，导致聚阴离子材料拥有比金属氧化物材料更高的操作电压，因此聚阴离子钠离子电池材料成了当今钠离子电池研究的热门，有望成为新一代的电池材料。
作为一种新型钠离子电池正极材料，Na3.64Fe2.18(P2O7)2其理论容量为105mAh/g，具有较大的钠离子迁移通道，具有3V的工作电压，以及稳定的循环性能，具有研究和开发的价值。
发明内容
有鉴于此，本发明的目的之一在于提供Na3.64Fe2.18(P2O7)2正极材料的制备方法，该制备方法操作简便、周期短、成本低；目的之二在于提供采用所述方法制得的Na3.64Fe2.18(P2O7)2正极材料，所得Na3.64Fe2.18(P2O7)2具有独特的多孔结构、形貌均一、孔隙率高、碳复合性好、电化学性能好等优点；目的之三在于提供Na3.64Fe2.18(P2O7)2正极材料在钠离子电池方面的应用。为实现上述目的，本发明具体提供了如下的技术方案：
1.Na3.64Fe2.18(P2O7)2正极材料的制备方法，通过溶胶凝胶法依次将铁源、还原剂、钠源、磷源和螯合剂在水中溶解搅拌制得Na3.64Fe2.18(P2O7)2前驱体凝胶，将所述Na3.64Fe2.18(P2O7)2前驱体凝胶在惰性气氛下烧结得到Na3.64Fe2.18(P2O7)2正极材料；所述钠源、铁源、磷源中的钠离子：铁离子：磷离子的摩尔比为3.64:2.18:4。
进一步，该方法包括以下步骤：
1)溶胶凝胶法制备Na3.64Fe2.18(P2O7)2前驱体：将铁源溶于水中，得I液；将还原剂溶于I液中得II液；将钠源和磷源溶于II液中，搅拌至溶液澄清，得Ⅲ液；将螯合剂溶于Ⅲ液中， 60-70℃水浴搅拌直到溶液蒸干,得到粘稠的溶胶；将溶胶在100-120℃温度下真空干燥或冷冻干燥，得到Na3.64Fe2.18(P2O7)2前驱体凝胶；
2)高温煅烧Na3.64Fe2.18(P2O7)2前驱体凝胶：将步骤1)制得的Na3.64Fe2.18(P2O7)2前驱体凝胶在
500-600℃惰性气氛下煅烧，获得Na3.64Fe2.18(P2O7)2正极材料。。
进一步，所述还原剂的用量为铁离子摩尔用量的0.5～1倍；所述螯合剂的用量为铁离子摩尔用量的0.5～1倍。
进一步，所述钠源为碳酸钠、碳酸氢钠、磷酸二氢钠、磷酸氢二钠或氢氧化钠中的一种或多种。
进一步，所述铁源为九水硝酸铁、乙酰丙酮铁、硫酸亚铁或硫酸铁中的一种或多种。
进一步所述磷源为磷酸二氢铵、磷酸氢二铵、磷酸铵、磷酸或磷酸二氢钠中的一种或多种。
进一步，所述还原剂为抗坏血酸、葡萄糖、果糖、麦芽糖或柠檬酸中的一种或多种。
进一步，所述螯合剂为柠檬酸、酒石酸、乙二胺四乙酸或葡萄糖酸中的一种或多种。
2.采用该方法制得的Na3.64Fe2.18(P2O7)2正极材料。
3.Na3.64Fe2.18(P2O7)2正极材料在钠离子电池方面的应用。
本发明的有益效果在于：本发明利用溶胶凝胶法合成了新型的Na3.64Fe2.18(P2O7)2正极材料，将钠源，铁源，磷源，还原剂和螯合剂通过溶胶凝胶法制得前驱体后在氢氩混合气下烧结而成。该制备方法简便、快捷、成本低，Na3.64Fe2.18(P2O7)2作为钠离子电池正极材料，具有优良的容量以及良好的循环性能。
附图说明
为了使本发明的目的、技术方案和有益效果更加清楚，本发明提供如下附图：
图1为实施例1所得产品的扫描电镜图。
图2为实施例1所得产品的物相XRD图。
图3为实施例2所得产品的扫描电镜图
图4为实施例3所述产品的恒流充放电曲线。
图5为实施例3所述产品的循环曲线图。
图6为实施例3所述产品的倍率性能图。
具体实施方式
下面将结合附图，对本发明的优选实施例进行详细的描述。实施例中未注明具体条件的实验方法，通常按照常规条件或按照制造厂商所建议的条件。
实施例1、Na3.64Fe2.18(P2O7)2正极材料的合成
称取1.7614g九水硝酸铁溶于40ml去离子水中,得I液；称取0.357g抗坏血酸溶于I液中，得II液；称取0.3858g碳酸钠和0.9202g磷酸二氢铵溶于II液中，搅拌至溶液澄清得Ⅲ液；称取2.236g柠檬酸溶于Ⅲ液中，60-70℃水浴搅拌至溶液蒸干，得到粘稠状的溶胶；将溶胶 100-120℃真空干燥12h，得Na3.64Fe2.18(P2O7)2前驱体凝胶；将所得凝胶在氢氩混合气氛(10％H2+90％Ar)下500-600℃煅烧24h，得到Na3.64Fe2.18(P2O7)2正极材料。所得产物形貌如图1所示，样品形貌均一碳包覆均匀，呈现疏松海绵状，伴有纳米级别的孔洞。产品的物相XRD图如图2所示。由图2可知，所制得的样品和标准卡片峰位置一致并且无杂峰，说明通过此种方法可以成功制备出Na3.64Fe2.18(P2O7)2正极材料，并且通过此种方法合成的该材料纯净无杂质。
实施例2、Na3.64Fe2.18(P2O7)2正极材料的合成
称取1.7614g九水硝酸铁溶于40ml去离子水中,得I液；称取0.357g抗坏血酸溶于I液中，得II液；称取0.3858g碳酸钠和0.9202g磷酸二氢铵溶于II液中，搅拌至溶液澄清得Ⅲ液；称取4.472g柠檬酸溶于Ⅲ液中，60-70℃水浴搅拌至溶液蒸干，得到粘稠状的溶胶；将溶胶 100-120℃真空干燥12h，得Na3.64Fe2.18(P2O7)2前驱体凝胶；将所得凝胶在氢氩混合气氛(10％H2+90％Ar)下500-600℃煅烧24h，得到Na3.64Fe2.18(P2O7)2正极材料。所得产物形貌如图3示，由图3可知，2倍螯合剂制备出的Na3.64Fe2.18(P2O7)2正极材料没有实施例1制备出的材料蓬松。
实施例3、电池的制备及电化学性能测试
取实施例1制得的Na3.64Fe2.18(P2O7)2与乙炔黑和PVDF粘结剂按照8:2:1的比例混合，取适量的1-甲基-2-吡咯烷酮(NMP)作为溶剂，在玛瑙研钵里研磨20分钟，得到黑色粘稠的正极浆料。取正极浆料均匀的涂在铝箔上，120℃真空干燥12h，然后用压片机将铝箔裁剪成直径为19mm的圆形，即得正极片；将制好的正极片转移到手套箱里进行纽扣电池的组装，使用的纽扣电池型号为CR2032，隔膜型号为Celgard 2400，电解液为1mol/L的NaClO4溶液(溶剂为碳酸乙烯酯与碳酸二甲酯按体积比1:1组成的混合液)，负极为金属钠片。组装完毕后，将电池移出手套箱，常温下静置6h后在Land测试系统上进行电化学性能的测试，测试电压范围为1.6～4V。所得恒流充放电曲线如图4示，所得循环曲线如图5示，所得倍率性能如图6示。
从图4可以看出：所制得的Na3.64Fe2.18(P2O7)2正极材料有两个充放电平台，一个是在3V 左右，一个是在2.5V左右。对于钠离子电池来说该材料电压平台很高，平台明显且平缓，有商业化的价值。
从图5可以看出：该材料在1C的倍率下容量接近90mAh g-1，并且经过200圈的循环之后材料性能依旧没有衰减，说明通过该方法合成的Na3.64Fe2.18(P2O7)2正极材料循环性能良好。
从图6可以看出：即使在充放电电流发生变化时该材料循环性能依旧平稳，说明该材料的倍率性能良好，而且在5C的电流密度下依旧拥有50mAh g-1的容量，即使当电流密度达到 10C后，该材料依旧拥有很好的可逆性。
最后说明的是，以上优选实施例仅用以说明本发明的技术方案而非限制，尽管通过上述优选实施例已经对本发明进行了详细的描述，但本领域技术人员应当理解，可以在形式上和细节上对其作出各种各样的改变，而不偏离本发明权利要求书所限定的范围。
Claims (10)
1.Na3.64Fe2.18(P2O7)2正极材料的制备方法，其特征在于，通过溶胶凝胶法依次将铁源、还原剂、钠源、磷源和螯合剂在水中溶解搅拌制得Na3.64Fe2.18(P2O7)2前驱体凝胶，将所述Na3.64Fe2.18(P2O7)2前驱体凝胶在惰性气氛下烧结得到Na3.64Fe2.18(P2O7)2正极材料；所述钠源、铁源、磷源中的钠离子：铁离子：磷离子的摩尔比为3.64:2.18:4。
2.根据权利要求1所述的Na3.64Fe2.18(P2O7)2正极材料的制备方法，其特征在于，包括以下步骤：
1)溶胶凝胶法制备Na3.64Fe2.18(P2O7)2前驱体：将铁源溶于水中，得I液；将还原剂溶于I液中得II液；将钠源和磷源溶于II液中，搅拌至溶液澄清，得Ⅲ液；将螯合剂溶于Ⅲ液中，60-70℃水浴搅拌直到溶液蒸干，得到粘稠的溶胶；将溶胶在100-120℃温度下真空干燥或冷冻干燥，得到Na3.64Fe2.18(P2O7)2前驱体凝胶；
2)高温煅烧Na3.64Fe2.18(P2O7)2前驱体凝胶：将步骤1)制得的Na3.64Fe2.18(P2O7)2前驱体凝胶在500-600℃惰性气氛下煅烧，获得Na3.64Fe2.18(P2O7)2正极材料。
3.根据权利要求1所述的Na3.64Fe2.18(P2O7)2正极材料的制备方法，其特征在于，所述还原剂的用量为铁离子摩尔用量的0.5～1倍；所述螯合剂的用量为铁离子摩尔用量的0.5～1倍。
4.根据权利要求1所述的Na3.64Fe2.18(P2O7)2正极材料的制备方法，其特征在于：所述钠源为碳酸钠、碳酸氢钠、磷酸二氢钠、磷酸氢二钠或氢氧化钠中的一种或多种。
5.根据权利要求1所述的Na3.64Fe2.18(P2O7)2正极材料的制备方法，其特征在于：所述铁源为九水硝酸铁、乙酰丙酮铁、硫酸亚铁或硫酸铁中的一种或多种。
6.根据权利要求1所述的Na3.64Fe2.18(P2O7)2正极材料的制备方法，其特征在于：所述磷源为磷酸二氢铵、磷酸氢二铵、磷酸铵、磷酸或磷酸二氢钠中的一种或多种。
7.根据权利要求1所述的Na3.64Fe2.18(P2O7)2正极材料的制备方法，其特征在于：所述还原剂为抗坏血酸、葡萄糖、果糖、麦芽糖或柠檬酸中的一种或多种。
8.根据权利要求1所述的Na3.64Fe2.18(P2O7)2正极材料的制备方法，其特征在于：所述螯合剂为柠檬酸、酒石酸、乙二胺四乙酸或葡萄糖酸中的一种或多种。
9.采用权利要求1至8任一项所述方法制得的Na3.64Fe2.18(P2O7)2正极材料。
10.权利要求9所述的Na3.64Fe2.18(P2O7)2正极材料在钠离子电池方面的应用。
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