JP2015176662A - Positive electrode active material for sodium ion secondary battery - Google Patents
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- JP2015176662A JP2015176662A JP2014050203A JP2014050203A JP2015176662A JP 2015176662 A JP2015176662 A JP 2015176662A JP 2014050203 A JP2014050203 A JP 2014050203A JP 2014050203 A JP2014050203 A JP 2014050203A JP 2015176662 A JP2015176662 A JP 2015176662A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 49
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 40
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000011734 sodium Substances 0.000 claims abstract description 49
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 33
- 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 32
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 49
- 239000002131 composite material Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 16
- 150000002506 iron compounds Chemical class 0.000 claims description 14
- 238000002441 X-ray diffraction Methods 0.000 claims description 11
- 150000003388 sodium compounds Chemical class 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 235000002639 sodium chloride Nutrition 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 9
- 230000002349 favourable effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 238000010304 firing Methods 0.000 description 16
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 12
- -1 iron ion Chemical class 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 150000002505 iron Chemical class 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000011255 nonaqueous electrolyte Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910003321 CoFe Inorganic materials 0.000 description 1
- 229910017086 Fe-M Inorganic materials 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 229910010586 LiFeO 2 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910000528 Na alloy Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical class Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
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Classifications
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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
- Y02E60/10—Energy storage using batteries
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- Compounds Of Iron (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、ナトリウムイオン二次電池用正極活物質、及びこれを用いるナトリウムイオン二次電池に関する。 The present invention relates to a positive electrode active material for a sodium ion secondary battery and a sodium ion secondary battery using the same.
携帯電話、ノート型パーソナルコンピューターPCなどのポータブル電子機器用電源として、コバルト酸リチウムなどのリチウム含有遷移金属酸化物正極、炭素負極および非水系電解液を構成材料とするリチウムイオン二次電池が広く用いられており、近年では、電気自動車や風力・太陽光などの再生可能エネルギー貯蔵用電池としての用途が検討されている。このため、電池の大型化に伴う電荷担体であるリチウム資源確保や正極材料構成金属であるコバルト、ニッケル等の希少遷移金属資源確保の問題が懸念されている。 Lithium ion secondary batteries with lithium-containing transition metal oxide cathodes such as lithium cobaltate, carbon anodes, and non-aqueous electrolytes are widely used as power sources for portable electronic devices such as mobile phones and notebook personal computer PCs. In recent years, use as a battery for storing renewable energy such as an electric vehicle, wind power, and solar light has been studied. For this reason, there are concerns about the problem of securing lithium resources, which are charge carriers, and the securing of rare transition metal resources, such as cobalt and nickel, which are constituent materials of the positive electrode material, as the battery size increases.
これに対して、ナトリウムイオン二次電池は、ナトリウム含有遷移金属酸化物正極、難黒鉛化炭素負極および非水系電解液を主な構成材料とする電池系であり、電荷担体であるナトリウム資源がほぼ無尽蔵にあることから、車載用などの大型電池への適用が期待されている。ナトリウムイオン二次電池では、その構成部材の中で、特に、正極材料の性能（ナトリウム脱離・挿入電圧および脱離・挿入量）が、作動電圧、電池容量等の電池性能に深く関わるために、正極材料開発が最も重要な課題とされている。 In contrast, a sodium ion secondary battery is a battery system mainly composed of a sodium-containing transition metal oxide positive electrode, a non-graphitizable carbon negative electrode, and a non-aqueous electrolyte, and has almost no sodium resources as charge carriers. Since it is inexhaustible, it is expected to be applied to large batteries for in-vehicle use. Among the components of a sodium ion secondary battery, the performance of the positive electrode material (sodium desorption / insertion voltage and desorption / insertion amount) is particularly related to battery performance such as operating voltage and battery capacity. Therefore, positive electrode material development is the most important issue.
しかしながら、ナトリウムイオン二次電池は、ナトリウムの標準電極電位がリチウムに比べて0.3V高いために電池電圧がその分低くなるという欠点がある。さらにナトリウムイオンは、イオン体積、原子量がリチウムに比べて数倍程度大きいために、正極材料の高い放電電圧および充放電容量の確保がリチウムほど簡単ではないという問題がある。 However, the sodium ion secondary battery has a drawback that the standard voltage of sodium is 0.3 V higher than that of lithium, so that the battery voltage is lowered accordingly. Furthermore, since sodium ions have an ion volume and atomic weight several times larger than that of lithium, there is a problem that securing a high discharge voltage and charge / discharge capacity of the positive electrode material is not as easy as lithium.
リチウムイオン二次電池においては、リチウムフェライト(LiFeO2)は電気化学的にLi脱離・挿入が困難な正極材料と認知されているが、ナトリウムフェライト(NaFeO2)については、特定の結晶構造を有するα-NaFeO2相が電気化学的にNa脱離・挿入が可能で、最も動作電圧の高い（3.3V）の正極材料となりうることが報告されている（非特許文献１、特許文献１等参照）。α-NaFeO2相は、資源的に豊富な鉄資源を金属源として用いることから、有望な正極材料の一つと考えられるが、これまでは、充放電特性に優れた高結晶性の試料を得るための工業的製造プロセスの構築が困難と言われてきた。その原因としては、電気化学的なNaイオンの脱離・挿入が困難なβ-NaFeO2相が750℃以上で安定な高温相として生じ、これがいったん生成すると、それ以下の温度に下げても試料中に残留する傾向があることが一因と考えられる。 In lithium ion secondary batteries, lithium ferrite (LiFeO 2 ) is recognized as a positive electrode material that is electrochemically difficult to desorb and insert Li, but sodium ferrite (NaFeO 2 ) has a specific crystal structure. It has been reported that the α-NaFeO 2 phase possessed can electrochemically desorb and insert Na, and can be a positive electrode material having the highest operating voltage (3.3 V) (Non-patent Document 1, Patent Document 1, etc.) reference). The α-NaFeO 2 phase is considered to be one of the promising positive electrode materials because it uses abundant iron resources as a metal source. Until now, a highly crystalline sample with excellent charge / discharge characteristics has been obtained. Therefore, it has been said that it is difficult to construct an industrial manufacturing process. This is because the β-NaFeO 2 phase, which is difficult to desorb and insert electrochemical Na ions, is generated as a stable high-temperature phase at 750 ° C or higher. This is thought to be due to the tendency to remain inside.
特許文献１は、α相を有するNaFeO2系材料の製造方法として、主にナトリウム化合物と鉄化合物とを含有する混合物を、特定の雰囲気に制御して加熱する方法を開示している。この方法で得られる複合酸化物は、非水電解質二次電池用正極材料として有用であるとされているが、本発明者の研究によれば、非水系二次電池の正極活物質として用いた場合に、放電容量が十分ではないことが明らかとなった。 Patent Document 1 discloses a method for heating a mixture containing mainly a sodium compound and an iron compound in a specific atmosphere as a method for producing a NaFeO 2 -based material having an α phase. The composite oxide obtained by this method is said to be useful as a positive electrode material for non-aqueous electrolyte secondary batteries, but according to the study of the present inventors, it was used as a positive electrode active material for non-aqueous secondary batteries. In some cases, it became clear that the discharge capacity was not sufficient.
本発明は、上記した従来技術の現状に鑑みてなされたものであり、その主な目的は、資源として豊富な物質である鉄化合物、ナトリウム化合物等を原料として、工業的な製造方法として適した方法で得られるナトリウムフェライト系材料であって、ナトリウムイオン二次電池用正極活物質として用いた場合に、従来の材料として比較して優れた充放電性能を発揮し得る材料を提供することである。 The present invention has been made in view of the current state of the prior art described above, and its main purpose is suitable as an industrial production method using iron compounds, sodium compounds, etc., which are abundant as resources, as raw materials. It is a sodium ferrite material obtained by the method, and provides a material capable of exhibiting excellent charge / discharge performance as compared with conventional materials when used as a positive electrode active material for sodium ion secondary batteries. .
本発明者は、上記した目的を達成すべく鋭意研究を重ねてきた。その結果、原料として鉄化合物と特定の金属化合物を用い、これらの原料を水熱合成反応に供することによって、鉄の一部が他の金属元素で置換されたFe3O4を得ることができ、更に、これをナトリウム化合物と混合して焼成する方法によれば、鉄の一部が平均価数２．５〜３．５の範囲にある元素によって置換された高い結晶性を有するナトリウムフェライト(NaFeO2)系複合酸化物を得ることができることを見出した。この方法で得られる生成物は、高い結晶性を有し、ナトリウムイオン二次電池の正極活物質として用いた場合に、充放電容量、初回充放電効率等の充放電性能やサイクル特性が良好で、高い体積エネルギー密度を有するものとなり、特に、無置換のナトリウムフェライト(NaFeO2)系複合酸化物と比較した場合に、充放電容量が高く、サイクル特性も良好な正極活物質となることを見出した。 The present inventor has intensively studied to achieve the above-described object. As a result, by using an iron compound and a specific metal compound as raw materials and subjecting these raw materials to a hydrothermal synthesis reaction, Fe 3 O 4 in which a part of iron is substituted with other metal elements can be obtained. Furthermore, according to the method in which this is mixed with a sodium compound and fired, sodium ferrite having high crystallinity in which a part of iron is substituted by an element having an average valence of 2.5 to 3.5 ( It has been found that a NaFeO 2 ) -based composite oxide can be obtained. The product obtained by this method has high crystallinity, and when used as a positive electrode active material of a sodium ion secondary battery, charge / discharge performance such as charge / discharge capacity and initial charge / discharge efficiency and cycle characteristics are good. It has been found that it has a high volumetric energy density, and in particular, when compared with an unsubstituted sodium ferrite (NaFeO 2 ) -based composite oxide, it has a high charge / discharge capacity and good cycle characteristics. It was.
本発明は、これらの知見に基づいて更に研究を重ねた結果、完成されたものである。 The present invention has been completed as a result of further research based on these findings.
即ち、本発明は、下記のナトリウム二次電池用正極活物質、該正極活物質の製造方法及びナトリウムイオン二次電池を提供するものである。
項１． 組成式：Na（Fe1-xMx）O2（式中、Mは、平均価数が２．５〜３．５の範囲にある一種又は二種以上の元素を示し、０＜ｘ≦０．４である）で表され、六方晶層状岩塩型構造の結晶構造を有するナトリウムフェライト系複合酸化物からなる、ナトリウムイオン二次電池用正極活物質。
項２． ｘ値が０．０５≦ｘ≦０．４である上記項１に記載のナトリウムイオン二次電池用正極活物質。
項３． Cu-Kα線を用いたＸ線回折法により得られる回折角度2θ= 16.3°付近の（003）面の回折ピークにおける半値幅が0.13°以下であるナトリウムフェライト系複合酸化物からなる、上記項１又は２に記載のナトリウムイオン二次電池用正極活物質。
項４． （ｉ）水溶性鉄化合物、及び元素Mを含む化合物を含有する水溶液を加熱して水熱合成反応によって元素Mを含むFe3O4を得る工程、並びに
（ii）工程(i)で得られた元素Mを含むFe3O4と水溶性ナトリウム化合物を混合して焼成する工程、
を含む上記項１〜３のいずれかに記載されたナトリウムイオン二次電池用正極活物質の製造方法。
項５． 上記項１〜３のいずれかに記載のナトリウムイオン二次電池用正極活物質を構成要素として含むナトリウムイオン二次電池。
That is, this invention provides the following positive electrode active material for sodium secondary batteries, the manufacturing method of this positive electrode active material, and a sodium ion secondary battery.
Item 1. Composition formula: Na (Fe 1-x M x ) O 2 (wherein M represents one or more elements having an average valence of 2.5 to 3.5, and 0 <x ≦ 0.4) and a positive electrode active material for a sodium ion secondary battery comprising a sodium ferrite composite oxide having a hexagonal layered rock salt type crystal structure.
The manufacturing method of the positive electrode active material for sodium ion secondary batteries as described in any one of said claim | item 1-3 containing this.
Item 5. The sodium ion secondary battery which contains the positive electrode active material for sodium ion secondary batteries in any one of said claim | item 1-3 as a component.
以下、本発明のナトリウムイオン二次電池用正極活物質について具体的に説明する。 Hereinafter, the positive electrode active material for sodium ion secondary batteries of the present invention will be described in detail.
本発明のナトリウムイオン二次電池用正極活物質は、組成式：Na（Fe1-xMx）O2（式中、Mは、平均価数が２．５〜３．５の範囲にある一種又は二種以上の元素を示し、０＜ｘ≦０．４である）で表され、空間群 The positive electrode active material for a sodium ion secondary battery of the present invention has a composition formula: Na (Fe 1-x M x ) O 2 (wherein M has an average valence in the range of 2.5 to 3.5). 1 or 2 or more elements, 0 <x ≦ 0.4)
で表される六方晶層状岩塩型構造の結晶構造（以下、「α相」ということがある）を有する複合酸化物である。特に、後述する焼成工程における反応を充分に進行させることによって、Cu-Kα線を用いたＸ線回折法により得られる回折角度2θ= 16.3°付近の（003）面の回折ピークの半値幅が0.13°以下という非常に結晶性の高い複合酸化物とすることができる。 Is a complex oxide having a crystal structure of a hexagonal layered rock salt type structure (hereinafter, also referred to as “α phase”). In particular, by fully advancing the reaction in the firing step described later, the half-value width of the diffraction peak on the (003) plane near the diffraction angle 2θ = 16.3 ° obtained by the X-ray diffraction method using Cu—Kα rays is 0.13. A complex oxide having a very high crystallinity of less than or equal to 0 ° can be obtained.
この様な特徴を有するナトリウムフェライト系複合酸化物は、従来知られているナトリウムフェライト系複合酸化物と比較して結晶性が高く、ナトリウムイオン二次電池用正極活物質として用いた場合に、高い放電容量、高い初回充放電効率等の優れた性能を発揮でき、サイクル特性も良好となる。 The sodium ferrite composite oxide having such characteristics has higher crystallinity than a conventionally known sodium ferrite composite oxide, and is high when used as a positive electrode active material for a sodium ion secondary battery. Excellent performance such as discharge capacity and high initial charge / discharge efficiency can be exhibited, and cycle characteristics are also good.
上記組成式において、Mは、平均価数が２．５〜３．５の範囲の一種又は二種以上の元素を示す。具体的には、価数が２．５〜３．５の範囲にある元素であれば、一種単独で用いることができ、価数がこの範囲外の元素については、二種以上の元素の価数の平均値が２．５〜３．５の範囲となるように組み合わせて用いればよい。Mの平均価数は、好ましくは、２．８〜３．２であり、より好ましくは２．９〜３．１であり、特に好ましくは３である。Mの具体例としては、Al、Ti、V、Cr、Mn、Co、Ni、Cu等を挙げることができ、Al、Ti、Mn、Co、Ni等が好ましい。 In the above composition formula, M represents one or more elements having an average valence of 2.5 to 3.5. Specifically, any element having a valence in the range of 2.5 to 3.5 can be used alone, and for elements having a valence outside this range, the valence of two or more elements can be used. What is necessary is just to use it combining so that the average value of a number may become the range of 2.5-3.5. The average valence of M is preferably 2.8 to 3.2, more preferably 2.9 to 3.1, and particularly preferably 3. Specific examples of M include Al, Ti, V, Cr, Mn, Co, Ni, Cu and the like, and Al, Ti, Mn, Co, Ni and the like are preferable.
上記組成式におけるM元素導入量を表すｘの値は、０＜ｘ≦０．４の範囲であり、好ましくは０．０５≦ｘ≦０．４の範囲であり、より好ましくは０．１≦ｘ≦０．３５の範囲である。 The value of x representing the amount of introduced M element in the composition formula is in the range of 0 <x ≦ 0.4, preferably in the range of 0.05 ≦ x ≦ 0.4, more preferably in the range of 0.1 ≦ x. The range is x ≦ 0.35.
本発明のナトリウムイオン二次電池用正極活物質は、平均価数が２．５〜３．５の範囲にある元素MをFeの一部の置換元素として含有することによって、元素Mを含まないナトリウムフェライト系複合酸化物と比較して、放電容量が高く、サイクル特性も良好となる。 The positive electrode active material for a sodium ion secondary battery of the present invention does not contain the element M by containing the element M having an average valence in the range of 2.5 to 3.5 as a partial substitution element of Fe. Compared with sodium ferrite complex oxide, the discharge capacity is high and the cycle characteristics are also good.
本発明のナトリウムイオン二次電池用正極活物質では、上記した条件を満足するα相の単相であることが好ましいが、これ以外の結晶相、例えば、斜方晶構造を有するβ-NaFeO2相（以下、単に「β相」ということがある）や炭酸ナトリウム等が含まれていてもよい。これらのα相以外の相については、複合酸化物全体を基準として、１０重量％程度以下であることが好ましい。 In the positive electrode active material for a sodium ion secondary battery of the present invention, it is preferable that it is an α-phase single phase that satisfies the above-mentioned conditions, but other crystal phases, for example, β-NaFeO 2 having an orthorhombic structure. A phase (hereinafter sometimes simply referred to as “β phase”), sodium carbonate, or the like may be contained. About phases other than these alpha phases, it is preferable that it is about 10 weight% or less on the basis of the composite oxide whole.
ナトリウムフェライト系複合酸化物の製造方法
上記した本願発明のナトリウム二次電池用正極活物資の有効成分である特定の条件を満足するナトリウムフェライト系複合酸化物は、例えば、下記の方法に従って、水熱合成反応によって、元素Mを含むFe3O4を得た後、ナトリウム化合物と混合して焼成する方法によって得ることができる。以下、この方法について具体的に説明する。
Method for Producing Sodium Ferrite Complex Oxide Sodium ferrite complex oxide satisfying specific conditions that are the active ingredients of the positive electrode active material for sodium secondary battery of the present invention described above is, for example, hydrothermal After obtaining Fe 3 O 4 containing the element M by a synthesis reaction, it can be obtained by a method of mixing with a sodium compound and baking. Hereinafter, this method will be specifically described.
（ｉ）水熱合成反応工程：
まず、水熱合成反応工程では、原料としては、鉄化合物、及び元素Mを含む化合物を用いる。更に、必要に応じて、鉄イオン価数を3価に安定化するための酸化剤を用いることができる。これらの化合物を含有する水溶液を加熱して水熱合成反応を行うことによって、目的とする、元素Mを含むFe3O4を得ることができる。加熱は、通常、密閉容器中で行えばよい。
(I) Hydrothermal synthesis reaction step:
First, in the hydrothermal synthesis reaction step, an iron compound and a compound containing element M are used as raw materials. Furthermore, if necessary, an oxidizing agent for stabilizing the iron ion valence to trivalent can be used. By subjecting an aqueous solution containing these compounds to a hydrothermal synthesis reaction, the target Fe 3 O 4 containing the element M can be obtained. Heating is usually performed in a sealed container.
原料とする鉄化合物としては、特に限定されないが、酸化水酸化鉄（FeOOH）、酸化鉄(III)(Fe2O3)、マグネタイト（Fe3O4）、ウスタイト（FeO）、金属鉄、塩化鉄(IIまたはIII)、硝酸鉄(IIまたはIII)、硫酸鉄(IIまたはIII)などの鉄塩等を用いることができる。 The iron compound used as a raw material is not particularly limited, but iron oxide hydroxide (FeOOH), iron oxide (III) (Fe 2 O 3 ), magnetite (Fe 3 O 4 ), wustite (FeO), metallic iron, chloride Iron salts such as iron (II or III), iron nitrate (II or III), and iron sulfate (II or III) can be used.
鉄塩を原料とする場合には、水熱合成反応前の原料混合時にアルカリとの急激な中和反応を抑制するために、あらかじめ鉄塩を水酸化ナトリウム、水酸化カリウムなどのアルカリ溶液に徐々に添加し、形成された沈殿物を必要に応じて空気酸化など方法で熟成処理した後、濾過し、得られた沈殿物を原料として用いることが好ましい。 When iron salt is used as a raw material, the iron salt is gradually added to an alkali solution such as sodium hydroxide or potassium hydroxide in advance in order to suppress a rapid neutralization reaction with alkali during mixing of the raw material before the hydrothermal synthesis reaction. Preferably, the precipitate formed is aged by a method such as air oxidation, if necessary, and then filtered, and the resulting precipitate is used as a raw material.
また、金属鉄、マグネタイト、ウスタイトなどの鉄イオン価数が0価〜2価の鉄化合物が原料に含まれる場合には、水熱合成反応時に鉄イオンの価数を３価に上げるために酸化剤（塩素酸ナトリウム、塩素酸カリウム、過酸化水素等）を適量水熱反応時に加えることが好ましい。酸化剤の使用量については特に限定はないが、通常、鉄化合物１モルに対して、１〜3モル程度とすることが好ましい。 In addition, when iron compounds such as metallic iron, magnetite, and wustite with an iron ion valence of 0 to 2 are included in the raw material, oxidation is performed to increase the iron ion valence to 3 during the hydrothermal synthesis reaction. It is preferable to add an appropriate amount of an agent (sodium chlorate, potassium chlorate, hydrogen peroxide, etc.) during the hydrothermal reaction. Although there is no limitation in particular about the usage-amount of an oxidizing agent, Usually, it is preferable to set it as about 1-3 mol with respect to 1 mol of iron compounds.
また、二価の鉄塩を用いる場合には、NH4Cl,NaOH等を含む水溶液中で水熱処理してFe3O4を形成し、これを原料として用いてもよい。 When a divalent iron salt is used, Fe 3 O 4 may be formed by hydrothermal treatment in an aqueous solution containing NH 4 Cl, NaOH, etc., and used as a raw material.
元素Mを含む化合物としては、鉄源と同様に特に限定されず、金属、酸化水酸化物（MOOH）、水酸化物、酸化物などを用いることができ、その他に、硝酸塩、硫酸塩、塩化物等の水溶性塩を用いることができる。水溶性塩を用いる場合には、鉄塩の場合と同様に、水熱合成反応前の原料混合時にアルカリとの急激な中和反応を抑制するため、鉄塩と共に水に溶解し、水酸化ナトリウム、水酸化カリウムなどのアルカリ溶液に徐々に添加して中和処理を行い、形成された殿物を必要に応じて空気酸化などの方法で熟成処理した後、濾過し、得られたFe-M沈殿物を水熱合成反応の原料として用いることが望ましい。 The compound containing the element M is not particularly limited as in the case of the iron source, and metal, oxide hydroxide (MOOH), hydroxide, oxide, etc. can be used. In addition, nitrate, sulfate, chloride Water-soluble salts such as products can be used. In the case of using a water-soluble salt, as in the case of iron salt, in order to suppress a rapid neutralization reaction with alkali when mixing the raw material before the hydrothermal synthesis reaction, it is dissolved in water together with the iron salt and sodium hydroxide. Fe-M obtained by gradually adding to an alkaline solution such as potassium hydroxide and neutralizing, and aging the formed residue by a method such as air oxidation as necessary, followed by filtration. It is desirable to use the precipitate as a raw material for the hydrothermal synthesis reaction.
原料として用いる水溶性鉄化合物、及び元素Mを含む化合物としては、無水物及び水和物のいずれを用いてもよく、それぞれの化合物は一種単独又は二種以上混合して用いることもできる。 As the water-soluble iron compound used as a raw material and the compound containing element M, either an anhydride or a hydrate may be used, and each compound may be used alone or in combination of two or more.
水熱合成反応に用いる水溶液中における水溶性鉄化合物と元素Mを含む化合物の濃度は、特に限定的ではないが、水溶性鉄化合物と元素Mを含む化合物の合計濃度として、10〜100 mol/L程度であることが好ましく、20〜60mol/L程度であることがより好ましい。 The concentration of the compound containing the water-soluble iron compound and the element M in the aqueous solution used for the hydrothermal synthesis reaction is not particularly limited, but the total concentration of the compound containing the water-soluble iron compound and the element M is 10 to 100 mol / It is preferably about L, and more preferably about 20 to 60 mol / L.
水溶性鉄化合物と元素Mを含む化合物の比率については、目的とする複合酸化物におけるFeとMの元素比と同様の比率とすればよい。 The ratio of the water-soluble iron compound and the compound containing the element M may be the same ratio as the element ratio of Fe and M in the target composite oxide.
水熱合成反応を行う際の水溶液のｐＨについては、通常、ｐＨ10程度以上とすることが好ましく、ｐＨ11程度以上とすることがより好ましい。上記したｐＨ範囲に調製するためには、例えば、水酸化ナトリウム、水酸化カリウム、水酸化リチウムなどのアルカリ金属水酸化物を用いればよい。
About pH of the aqueous solution at the time of performing a hydrothermal synthesis reaction, it is usually preferably about
水溶性鉄化合物、及び元素Mを含む化合物を含有する水溶液を加熱することによって、水熱合成反応を進行させることができる。水熱合成反応は、通常の水熱反応装置（例えば、市販のオートクレーブ）を用いて行うことができる。 By heating the aqueous solution containing the water-soluble iron compound and the compound containing the element M, the hydrothermal synthesis reaction can proceed. The hydrothermal synthesis reaction can be performed using a normal hydrothermal reaction apparatus (for example, a commercially available autoclave).
水熱合成反応の条件は、特に限定されるものではないが、通常105〜300℃程度、好ましくは150〜250℃程度に加熱すればよい。加熱時間は、通常、0.5〜150時間程度とすればよく、10〜100時間程度とすることが好ましい。 The conditions for the hydrothermal synthesis reaction are not particularly limited, but are usually about 105 to 300 ° C, preferably about 150 to 250 ° C. The heating time is usually about 0.5 to 150 hours, preferably about 10 to 100 hours.
上記した方法で水熱合成反応を行った後、通常、原料化合物などの残存物を除去するために、反応生成物を洗浄する。洗浄には、例えば、水、水-アルコール、アセトンなどを用いることができる。次いで、生成物を濾過し、例えば、80℃以上の温度(通常は100℃程度)で乾燥することにより、Feの置換元素として元素Mを含むFe3O4を得ることができる。 After the hydrothermal synthesis reaction is carried out by the above-described method, the reaction product is usually washed in order to remove residues such as raw material compounds. For example, water, water-alcohol, acetone or the like can be used for washing. Next, the product is filtered and, for example, dried at a temperature of 80 ° C. or higher (usually about 100 ° C.), whereby Fe 3 O 4 containing the element M as a substitution element for Fe can be obtained.
（ii）焼成工程：
上記した方法で元素Mを含むFe3O4を得た後、ナトリウム化合物と混合して焼成することによって、目的とする組成式：Na（Fe1-xMx）O2（式中、Mは、平均価数が２．５〜３．５の範囲にある一種又は二種以上の元素を示し、０＜ｘ≦０．４である）で表される六方晶層状岩塩型構造の結晶構造を有する複合酸化物を得ることができる。
(Ii) Firing step:
After obtaining Fe 3 O 4 containing the element M by the above-described method, mixing with a sodium compound and firing, the desired composition formula: Na (Fe 1-x M x ) O 2 (where M Is a hexagonal layered rock salt structure crystal structure represented by one or more elements having an average valence of 2.5 to 3.5 and 0 <x ≦ 0.4) A composite oxide having the following can be obtained.
ナトリウム化合物としては、特に限定されず、酸化ナトリウム、塩化ナトリウム、硝酸ナトリウム、硫酸ナトリウム、酢酸ナトリウム等の水溶性ナトリウム塩、水酸化ナトリウム等を用いることができる。特に、反応性が良好であることから、Na2O2が好ましい。 The sodium compound is not particularly limited, and water-soluble sodium salts such as sodium oxide, sodium chloride, sodium nitrate, sodium sulfate, and sodium acetate, sodium hydroxide, and the like can be used. In particular, Na 2 O 2 is preferable because of good reactivity.
混合方法については特に限定はないが、焼成反応を効率良く進行させるためには、例えば、乳鉢などを用いて充分に混合することが好ましい。 Although there is no limitation in particular about the mixing method, in order to advance a baking reaction efficiently, it is preferable to fully mix using a mortar etc., for example.
ナトリウム化合物の使用量については、未反応物や不純物の生成を抑制して、目的とする組成式：Na（Fe1-xMx）O2で表される複合酸化物の収率を向上させるためには、Mを含むFe3O4における鉄と元素Mの合計モル数に対するナトリウム元素のモル比率であるNa/（Fe + M）を０．９〜１．１程度とすることが好ましく、０．９５〜１．０５程度とすることがより好ましく、Na/（Fe + M）を約１とすることが特に好ましい。 Regarding the amount of sodium compound used, the yield of the composite oxide represented by the target composition formula: Na (Fe 1-x M x ) O 2 is improved by suppressing the formation of unreacted substances and impurities. Therefore, it is preferable that Na / (Fe + M), which is the molar ratio of sodium element to the total number of moles of iron and element M in Fe 3 O 4 containing M, is about 0.9 to 1.1, More preferably, the ratio is about 0.95 to 1.05, and Na / (Fe + M) is particularly preferably about 1.
焼成温度については、特に限定的はないが、700℃程度以上とすることが好ましい。但し、元素Mの導入量を示すｘの値が0.2未満の場合には、充放電に寄与しないβ相（斜方晶）の生成を避けるために、730℃程度以下とすることが好ましい。M元素導入量を表すｘの値が0.2以上の場合には、焼成時にβ相が生じ難いので、焼成温度を730℃以上とすることができ、900℃以上の焼成温度とすることも可能である。焼成温度を高くすることによって、該複合酸化物の結晶性がより良好となり、更に、タップ密度が向上して、高い体積エネルギー密度を有する複合酸化物とすることができる。 The firing temperature is not particularly limited, but is preferably about 700 ° C. or higher. However, when the value of x indicating the introduction amount of the element M is less than 0.2, it is preferable to set the temperature to about 730 ° C. or less in order to avoid the formation of a β phase (orthorhombic crystal) that does not contribute to charge / discharge. When the value of x representing the amount of introduced M element is 0.2 or more, the β phase is unlikely to occur during firing, so the firing temperature can be set to 730 ° C or higher, and can be set to 900 ° C or higher. is there. By increasing the firing temperature, the crystallinity of the composite oxide becomes better, the tap density is further improved, and a composite oxide having a high volumetric energy density can be obtained.
焼成雰囲気については特に限定はなく、大気中、還元雰囲気中、酸化雰囲気中などの任意の雰囲気とすることができる。焼成時間についても特に限定はなく、例えば1〜100時間程度とすることが好ましい。 There is no particular limitation on the firing atmosphere, and any atmosphere such as the air, a reducing atmosphere, or an oxidizing atmosphere can be used. There are no particular limitations on the firing time, and it is preferably about 1 to 100 hours, for example.
上記した条件の範囲内において、焼成温度を高くし、焼成時間を長くすることによって、目的とする組成式：Na（Fe1-xMx）O2で表される複合酸化物の結晶性を向上させることができる。 Within the range of the above conditions, by increasing the firing temperature and lengthening the firing time, the crystallinity of the composite oxide represented by the target composition formula: Na (Fe 1-x M x ) O 2 is improved. Can be improved.
ナトリウムイオン二次電池用正極活物質
以上の方法によって、組成式：Na（Fe1-xMx）O2（式中、Mは、平均価数が２．５〜３．５の範囲にある一種又は二種以上の元素を示し、０＜ｘ≦０．４である）で表される六方晶層状岩塩型構造の結晶構造を有するナトリウムフェライト系複合酸化物を得ることができる。
The composition formula: Na (Fe 1-x M x ) O 2 (wherein M has an average valence in the range of 2.5 to 3.5) by the method more than the positive electrode active material for sodium ion secondary battery A sodium ferrite composite oxide having a crystal structure of a hexagonal layered rock salt structure represented by one or two or more elements and represented by 0 <x ≦ 0.4 can be obtained.
上記した水熱合成反応によって元素Mを含むFe3O4を得た後、ナトリウム化合物と混合し焼成して得られるナトリウムフェライト系複合酸化物は、結晶性が良好な複合酸化物であり、焼成工程において、焼成反応を充分に進行させることによって、Ｘ線回折法によって得られる（003）面からの回折ピークにおける半値幅が0.13°以下という結晶性の高い複合酸化物とすることができ、焼成反応を更に進行させた場合には半値幅が0.12°以下という非常に結晶性に優れた複合酸化物とすることもできる。 After obtaining Fe 3 O 4 containing element M by the hydrothermal synthesis reaction described above, the sodium ferrite complex oxide obtained by mixing and firing with a sodium compound is a complex oxide with good crystallinity and firing. By sufficiently advancing the firing reaction in the process, a complex oxide with high crystallinity having a half-value width of 0.13 ° or less at the diffraction peak from the (003) plane obtained by the X-ray diffraction method can be obtained. When the reaction is further advanced, a complex oxide having a very high crystallinity with a half width of 0.12 ° or less can be obtained.
該複合酸化物は、ナトリウムイオン二次電池用正極活物質として用いた場合に、放電容量を100mAh/g程度、又はこれを上回る高い値とすることが可能であり、優れた充放電性能を有するものである。 The composite oxide, when used as a positive electrode active material for a sodium ion secondary battery, can have a discharge capacity of about 100 mAh / g or higher, and has excellent charge / discharge performance. Is.
これに対して、原料化合物を直接焼成して得られる、ナトリウムフェライト系複合酸化物は、Ｘ線回折法によって得られる（003）面からの回折ピークにおける半値幅が0.13°を上回る値となり、ナトリウムイオン二次電池の正極活物質として用いる場合に、十分な放電容量を得ることができず、充放電性能が劣るものとなる。 On the other hand, the sodium ferrite composite oxide obtained by directly firing the raw material compound has a half-value width exceeding 0.13 ° at the diffraction peak from the (003) plane obtained by the X-ray diffraction method. When used as a positive electrode active material of an ion secondary battery, a sufficient discharge capacity cannot be obtained, and charge / discharge performance is inferior.
上記したナトリウムフェライト系複合酸化物からなる正極活物質を用いるナトリウムイオン二次電池の構造については特に限定はなく、上記した複合酸化物を正極活物質として使用する他は、基本的な構造は、公知の非水系ナトリウムイオン二次電池と同様でよい。 There is no particular limitation on the structure of the sodium ion secondary battery using the positive electrode active material composed of the above-described sodium ferrite composite oxide, and the basic structure is as follows except that the above-described composite oxide is used as the positive electrode active material. It may be the same as a known non-aqueous sodium ion secondary battery.
例えば、正極については、上記した複合酸化物を正極活物質として用い、更に、導電剤、バインダーなどを含む正極合剤をＡｌ、Ｎｉ、ステンレスなどの正極集電体に担持させればよい。導電剤としては、例えば、黒鉛、コークス類、カーボンブラックなどの炭素材料を用いることができる。 For example, for the positive electrode, the composite oxide described above may be used as a positive electrode active material, and a positive electrode mixture containing a conductive agent, a binder, and the like may be supported on a positive electrode current collector such as Al, Ni, and stainless steel. As the conductive agent, for example, carbon materials such as graphite, cokes, and carbon black can be used.
負極としては、例えば、ナトリウム金属、ナトリウム合金、ナトリウムイオンをドープ・脱ドープ可能な材料などを活物質として用いることができる。これらの負極活物質についても、必要に応じて、導電剤、バインダーなどを用いて、Ａｌ、Ｃｕ、Ｎｉ、ステンレスなどからなる負極集電体に担持させればよい。 As the negative electrode, for example, sodium metal, a sodium alloy, a material that can be doped / undoped with sodium ions, and the like can be used as the active material. These negative electrode active materials may be supported on a negative electrode current collector made of Al, Cu, Ni, stainless steel or the like using a conductive agent, a binder, or the like, if necessary.
セパレータとしては、例えば、ポリエチレン、ポリプロピレンなどのポリオレフィン樹脂、フッ素樹脂、ナイロン、芳香族アラミドなどの材質からなり、多孔質膜、不織布、織布などの形態の材料を用いることができる。 The separator is made of, for example, a polyolefin resin such as polyethylene or polypropylene, a fluororesin, nylon, or an aromatic aramid, and a material such as a porous film, a nonwoven fabric, or a woven fabric can be used.
非水電解質の溶媒としては、カーボネート類、エーテル類、ニトリル類、含硫黄化合物等の非水系二次電池の溶媒として公知の溶媒を用いることができる。非水電解質として固体電解質を用いてもよく、固体電解質としては、例えばポリエチレンオキサイド系の高分子化合物、ポリオルガノシロキサン鎖もしくはポリオキシアルキレン鎖の少なくとも一種以上を含む高分子化合物などを例示できる。 As the solvent for the nonaqueous electrolyte, known solvents can be used as solvents for nonaqueous secondary batteries such as carbonates, ethers, nitriles, and sulfur-containing compounds. A solid electrolyte may be used as the non-aqueous electrolyte. Examples of the solid electrolyte include polyethylene oxide polymer compounds, polymer compounds containing at least one polyorganosiloxane chain or polyoxyalkylene chain.
ナトリウムイオン二次電池の形状についても特に限定はなく、円筒型、角型などのいずれであってもよい。 The shape of the sodium ion secondary battery is not particularly limited, and may be any of a cylindrical shape and a rectangular shape.
本発明のナトリウムイオン二次電池用正極活物質を用いるナトリウムイオン二次電池は、従来の結晶性の低い複合酸化物を正極活物質として用いるナトリウムイオン二次電池と比較して、高い放電容量を有し、初回充放電効率が高く、サイクル特性も良好である。特に、元素Mを含有することによって、放電容量、サイクル特性などについて非常に優れた性能を発揮できる。 The sodium ion secondary battery using the positive electrode active material for the sodium ion secondary battery of the present invention has a higher discharge capacity than the sodium ion secondary battery using a composite oxide having low crystallinity as the positive electrode active material. It has a high initial charge / discharge efficiency and good cycle characteristics. In particular, by including the element M, it is possible to exhibit extremely excellent performance in terms of discharge capacity, cycle characteristics, and the like.
従って、本発明のナトリウムイオン二次電池用正極活物質は、低コストの原料を用いて得ることができ、しかも優れた性能を有するナトリウム二次電池用正極活物質として有用性の高いものである。 Therefore, the positive electrode active material for sodium ion secondary batteries of the present invention can be obtained by using a low-cost raw material, and is highly useful as a positive electrode active material for sodium secondary batteries having excellent performance. .
以下、実施例を挙げて本発明を更に詳細に説明するが、本発明は下記実施例のみには限定されない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited only to the following Example.
実施例１
ガラスビーカーに44.48gのFeSO4・7H2O(0.16mol)と11.24gのCoSO4・7H2O(0.04mol)を秤量し、蒸留水300mlを加え攪拌することにより完全に溶解させた。別のガラスビーカーに水酸化ナトリウム30gと塩化アンモニウム34.77gを秤量し、蒸留水300mlを加えて攪拌し完全に溶解させた。両者を混合し１時間攪拌した後に、混合物をポリテトラフルオロエチレン（PTFE）製ビーカーに入れ、これを水熱処理炉内に静置し、密閉後、220℃で20時間水熱処理を行った。水熱処理後、室温まで反応炉を冷却させてからPTFEビーカーを取り出し、蒸留水で洗浄し、濾過することによって過剰の水酸化ナトリウム等を除去し、100℃で乾燥させ、水熱処理物を得た。X線回折による定性分析により水熱処理物はFeの20モル%がCoで置換されたFe3O4が主成分であり少量のCoFe合金を含むことがわかった。
Example 1
In a glass beaker, 44.48 g of FeSO 4 .7H 2 O (0.16 mol) and 11.24 g of CoSO 4 .7H 2 O (0.04 mol) were weighed, and 300 ml of distilled water was added and stirred to completely dissolve. In another glass beaker, 30 g of sodium hydroxide and 34.77 g of ammonium chloride were weighed, 300 ml of distilled water was added and stirred to completely dissolve. After mixing both and stirring for 1 hour, the mixture was put into a polytetrafluoroethylene (PTFE) beaker, which was left in a hydrothermal treatment furnace, sealed, and then hydrothermally treated at 220 ° C. for 20 hours. After hydrothermal treatment, the reactor was cooled to room temperature, then the PTFE beaker was taken out, washed with distilled water, filtered to remove excess sodium hydroxide, etc., and dried at 100 ° C. to obtain a hydrothermal treatment product . Qualitative analysis by X-ray diffraction showed that the hydrothermally treated product was mainly composed of Fe 3 O 4 in which 20 mol% of Fe was replaced by Co and contained a small amount of CoFe alloy.
上記20％Co置換Fe3O4（0.386g）と和光純薬工業製のNa2O2（0.195g）を、めのう乳鉢を用いてアルゴン雰囲気下のグローブボックス中で10分間撹拌混合した。得られた混合物を金ルツボへ投入し、800℃で10時間、大気雰囲気下で焼成した。焼成後、粉砕処理を施し目的の複合酸化物を得た。 The 20% Co-substituted Fe 3 O 4 (0.386 g) and Na 2 O 2 (0.195 g) manufactured by Wako Pure Chemical Industries, Ltd. were stirred and mixed for 10 minutes in a glove box under an argon atmosphere using an agate mortar. The obtained mixture was put into a gold crucible and baked at 800 ° C. for 10 hours in an air atmosphere. After firing, pulverization was performed to obtain the target composite oxide.
得られた試料のX線パターン（図１）から、試料が六方晶層状岩塩型構造を有するα- Na(Fe0.8Co0.2)O2のみからなり、（003）面からの回折ピークの半値幅が0.124°であることが確認できた。 From the X-ray pattern of the obtained sample (Fig. 1), the sample consists only of α-Na (Fe 0.8 Co 0.2 ) O 2 having a hexagonal layered rock salt structure, and the half-width of the diffraction peak from the (003) plane Was found to be 0.124 °.
比較例１
蒸留水500mlに硝酸鉄(III)9水和物0.2mol（80.80g）を加えて良く攪拌して完全に溶解させた。別のビーカーに水酸化ナトリウム60gを蒸留水１リットルに溶解させた水酸化ナトリウム水溶液を調製した。その水酸化ナトリウム溶液に、数時間かけて徐々に硝酸鉄水溶液を滴下して沈殿物を作製した。得られた沈殿物を空気バブリング処理により一晩熟成後、濾過して溶媒を除去した。
Comparative Example 1
To 500 ml of distilled water, 0.2 mol (80.80 g) of iron (III) nitrate nonahydrate was added and stirred well to dissolve completely. In another beaker, an aqueous sodium hydroxide solution in which 60 g of sodium hydroxide was dissolved in 1 liter of distilled water was prepared. An aqueous iron nitrate solution was gradually added dropwise to the sodium hydroxide solution over several hours to produce a precipitate. The resulting precipitate was aged overnight by air bubbling and then filtered to remove the solvent.
次いで、得られた熟成沈殿物をPTFE製ビーカーに採取し、水酸化ナトリウム270gと蒸留水100mlを加えて良く攪拌した。これを水熱反応炉内に静置し、密閉後、220℃で20時間水熱合成反応を行った。水熱合成反応後、室温まで反応炉を冷却させてからPTFEビーカーを取り出し、１リットルのエタノールで洗浄および濾過することによって過剰の水酸化ナトリウムを除去し、100℃で乾燥させることによって、目的とするナトリウムフェライト系複合酸化物を得た。 Next, the resulting mature precipitate was collected in a PTFE beaker, and 270 g of sodium hydroxide and 100 ml of distilled water were added and stirred well. This was left standing in a hydrothermal reactor, sealed and then subjected to a hydrothermal synthesis reaction at 220 ° C. for 20 hours. After the hydrothermal synthesis reaction, the reactor is cooled to room temperature, and then the PTFE beaker is taken out, washed with 1 liter of ethanol and filtered to remove excess sodium hydroxide and dried at 100 ° C. A sodium ferrite composite oxide was obtained.
得られた試料のXRD回折図を図２に示す。図２のXRDパターンから、試料が六方晶層状岩塩型構造を有するα- NaFeO2 98重量％と炭酸ナトリウム２重量％からなり、（003）面からの回折ピークの半値幅が0.119°であることが確認できた。 The XRD diffractogram of the obtained sample is shown in FIG. From the XRD pattern of FIG. 2, the sample is composed of 98% by weight of α-NaFeO 2 having a hexagonal layered rock salt structure and 2% by weight of sodium carbonate, and the half-value width of the diffraction peak from the (003) plane is 0.119 °. Was confirmed.
充放電試験
実施例１で得られたCoを含有するナトリウムフェライト系複合酸化物と比較例１で得られたCoを含まないナトリウムフェライト系複合酸化物をそれぞれ正極活物質として用いて二極式セルを作製し、規制充電電位を４．５V、規制充電容量を100mAh/gという高い値として下記の条件で充放電試験を行った。
Charge / Discharge Test Bipolar cell using the Co-containing sodium ferrite composite oxide obtained in Example 1 and the Co-free sodium ferrite composite oxide obtained in Comparative Example 1 as positive electrode active materials, respectively. A charge / discharge test was conducted under the following conditions with a regulated charge potential of 4.5 V and a regulated charge capacity of 100 mAh / g.
容量規制充放電試験条件
正極：活物質：ケッチェンブラック（KB）：ポリテトラフルオロエチレン（PTFE）（重量比）＝84:8:8を混合して、Alメッシュ上に圧着。
負極：金属ナトリウム。
電解液：NaPF6をエチレンカーボネート（EC）とジエチルカーボネート（DEC）の混合溶媒中に１．０mol/Lの濃度で溶解させたもの。
試験温度：３０℃。
電流密度（活物質あたり）：２０mA/g
規制充電容量：１００mAh/g
規制充電電位：４．５V
放電電位：１．０V
Capacity-regulated charge / discharge test conditions <br/> Positive electrode: Active material: Ketjen black (KB): Polytetrafluoroethylene (PTFE) (weight ratio) = 84: 8: 8 mixed and pressed onto an Al mesh.
Negative electrode: metallic sodium.
Electrolytic solution: NaPF 6 dissolved in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) at a concentration of 1.0 mol / L.
Test temperature: 30 ° C.
Current density (per active material): 20 mA / g
Regulated charging capacity: 100mAh / g
Regulated charging potential: 4.5V
Discharge potential: 1.0V
上記充放電試験の結果の内で、実施例１で得られたCoを含有するナトリウムフェライト系複合酸化物（α-Na(Fe0.8Co0.2)O2）を正極活物質とした場合の結果を図３に示し、比較例１で得られたCoを含まないナトリウムフェライト系複合酸化物（α- NaFeO2）を正極活物質とした場合の結果を図４に示す。 Among the results of the charge / discharge test, the results obtained when the sodium ferrite composite oxide (α-Na (Fe 0.8 Co 0.2 ) O 2 ) containing Co obtained in Example 1 was used as the positive electrode active material were as follows. FIG. 4 shows the results when the sodium ferrite composite oxide (α-NaFeO 2 ) containing no Co and obtained in Comparative Example 1 is used as the positive electrode active material.
図３に示す通り、実施例１で得られたCoを含有するナトリウムフェライト系複合酸化物用いた場合には、放電容量は90mAh/g以上であり、１０サイクル後もほとんど容量が低下しておらず、放電曲線もほとんど変化していないことが確認できた。 As shown in FIG. 3, when the sodium ferrite composite oxide containing Co obtained in Example 1 was used, the discharge capacity was 90 mAh / g or more, and the capacity was hardly decreased after 10 cycles. In addition, it was confirmed that the discharge curve hardly changed.
これに対して、比較例１で得られたCoで置換していないNaFeO2を用いた場合には、図４に示す通り、１０サイクル後に約６０mAh/gまで低下し、充放電曲線が大きく変化した。 On the other hand, when NaFeO 2 not substituted with Co obtained in Comparative Example 1 was used, it decreased to about 60 mAh / g after 10 cycles as shown in FIG. did.
これらの結果から、20%Co置換したNa(Fe0.8Co0.2)O2を正極活物質とした場合には、無置換のNaFeO2と比較して、規制充電電位が４．５V、規制充電容量が100mAh/gという高い値の場合であっても良好なサイクル特性を示し、優れたサイクル特性を有することが確認できた。 From these results, when 20% Co-substituted Na (Fe 0.8 Co 0.2 ) O 2 is used as the positive electrode active material, the regulated charging potential is 4.5 V and the regulated charging capacity compared to unsubstituted NaFeO 2. Even in the case of a high value of 100 mAh / g, good cycle characteristics were exhibited, and it was confirmed that it had excellent cycle characteristics.
Claims (5)
（ii）工程(i)で得られた元素Mを含むFe3O4と水溶性ナトリウム化合物を混合して焼成する工程、
を含む請求項１〜３のいずれかに記載されたナトリウムイオン二次電池用正極活物質の製造方法。 (I) a step of heating an aqueous solution containing a water-soluble iron compound and a compound containing element M to obtain Fe 3 O 4 containing element M by a hydrothermal synthesis reaction; and (ii) obtained in step (i). A step of mixing and baking Fe 3 O 4 containing the element M and a water-soluble sodium compound,
The manufacturing method of the positive electrode active material for sodium ion secondary batteries described in any one of Claims 1-3 containing this.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110249457A (en) * | 2017-02-13 | 2019-09-17 | 日本碍子株式会社 | Sintered lithium complex oxide plate and lithium secondary battery |
| CN110249458A (en) * | 2017-02-13 | 2019-09-17 | 日本碍子株式会社 | Sintered lithium complex oxide plate |
| CN116154287A (en) * | 2022-12-26 | 2023-05-23 | 三一红象电池有限公司 | High-concentration electrolyte and sodium ion battery |
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| CN116154287A (en) * | 2022-12-26 | 2023-05-23 | 三一红象电池有限公司 | High-concentration electrolyte and sodium ion battery |
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