CN104885265B - 利用共沉淀法的钠二次电池用正极活性材料前驱体的制备方法及由此制备的钠二次电池用正极活性材料前驱体 - Google Patents
利用共沉淀法的钠二次电池用正极活性材料前驱体的制备方法及由此制备的钠二次电池用正极活性材料前驱体 Download PDFInfo
- Publication number
- CN104885265B CN104885265B CN201380068776.0A CN201380068776A CN104885265B CN 104885265 B CN104885265 B CN 104885265B CN 201380068776 A CN201380068776 A CN 201380068776A CN 104885265 B CN104885265 B CN 104885265B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- rechargeable battery
- electrode active
- active materials
- sodium rechargeable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000011734 sodium Substances 0.000 title claims abstract description 62
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 59
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 58
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000000975 co-precipitation Methods 0.000 title claims abstract description 18
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003002 pH adjusting agent Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 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
- -1 ferric flouride Chemical compound 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 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 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 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
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims 1
- 235000019838 diammonium phosphate Nutrition 0.000 claims 1
- 239000011572 manganese Substances 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 238000012360 testing method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000002905 metal composite material Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 238000010671 solid-state reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- ZQCQTPBVJCWETB-UHFFFAOYSA-N 4-fluoro-1,3-dioxol-2-one Chemical compound FC1=COC(=O)O1 ZQCQTPBVJCWETB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229920006361 Polyflon Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- 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
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
本发明涉及一种利用共沉淀法的钠二次电池用正极活性材料前驱体的制备方法及由此制备的钠二次电池用正极活性材料前驱体。根据本发明的利用共沉淀法的钠二次电池用正极活性材料的制备方法,是在利用共沉淀法的同时适当地调节络合剂的种类和pH值,从而能够提供一种寿命特性改善且具有新组成的钠二次电池用正极活性材料前驱体。
Description
技术领域
本发明涉及一种利用共沉淀法的钠二次电池用正极活性材料前驱体的制备方法及由此制备的钠二次电池用正极活性材料前驱体。
背景技术
现在,作为高能量密度的二次电池多使用锂二次电池,这种锂二次电池使用将电解质盐溶解于非水溶剂而得的非水电解液、并使锂离子在正极和负极之间移动从而进行充放电。使用锂过渡金属氧化物作为正极材料,并且利用锂离子插入中间的反应的锂离子电池正在商用化。但是,由于锂离子电池中含有的锂价格昂贵,因此实际上需要价格更低廉且具有高容量的电池。
最近,开始进行了钠离子用以代替锂离子的钠离子二次电池的研究。由于钠资源储藏量丰富,因此若能够制备钠离子用以代替锂离子的二次电池,就可以以低成本制备二次电池。
日本特开2007-287661号公报中具体记载有具有正极和负极的二次电池,所述正极采用对Na、Mn和Co的组成比(Na:Mn:Co)为0.7:0.5:0.5的原料进行烧成而得的复合金属氧化物,所述负极由金属钠构成。并且,在日本特开2005-317511号公报中具体记载有作为复合金属氧化物具有六方最密堆积(层状岩盐型)晶体结构的α-NaFeO2,通过将Na2O2和Fe3O4混合后在空气中600至700℃下烧成制得该复合金属氧化物。但是,对于现有的钠二次电池的寿命特性,即反复进行充放电时的放电容量维持率来说,不能说是充分的。
并且,在现有的制备用于锂二次电池或钠二次电池的正极活性材料方法中,最常规的制法是固态反应法,是指如下方法,其中将每种组成元素的碳酸盐或氢氧化物作为原料,将该些粉末混合,然后烧成,并重复几次此过程。但是,固态反应法具有以下缺点:固态之间很难形成固溶体(solid solution),并且当混合时引入杂质量大;很难控制一定的粒子大小;以及需要高生产温度和长生产时间。
相反地,在湿法中,共沉淀法具有能够将组成元素控制在原子范围内,并且能够制备球形复合金属碳酸化物等优点。然而,为了制备用于钠二次电池的正极活性材料,在现有方法中主要采用了固态反应法,还没有进行对于采用共沉淀法制备用于钠二次电池的正极活性材料方法的研究。
发明内容
技术问题
为了解决上述现有技术的问题,本发明目的在于提供一种利用共沉淀法的钠二次电池用正极活性材料前驱体的制备方法。
进一步地,本发明目的在于提供一种由本发明的制备方法制备的寿命特性改善且具有新组成的钠二次电池用正极活性材料前驱体。
技术方案
为了解决上述技术问题,本发明提供一种利用共沉淀法的钠二次电池用正极活性材料前驱体的制备方法,包括以下步骤:
(a)将蒸馏水和第一pH调节剂倒入共沉淀反应器中,并且供入空气或氮气进行搅拌并保持反应器内部的pH值在6.5至7.5;
(b)将第二pH调节剂连续供入到所述反应器中进行混合,以调整反应器内的pH值在6.5至11;以及
(c)供入含有当量比例的镍盐、铁盐和锰盐的过渡金属化合物水溶液和络合剂,形成钠二次电池用正极活性材料前驱体粒子。
根据本发明的钠二次电池用正极活性材料前驱体的制备方法中,其特征在于,所述步骤(a)中的所述第一pH调节剂为氨水溶液或硫酸铵水溶液。
根据本发明的钠二次电池用正极活性材料前驱体的制备方法中,其特征在于,所述步骤(b)中的所述第二pH调节剂选自草酸铵、KOH和NaOH所构成的群组。
根据本发明的钠二次电池用正极活性材料前驱体的制备方法中,其特征在于,在所述步骤(b)中供入KOH或NaOH作为所述第二pH调节剂时,调整反应器内的pH值在9至11。
根据本发明的钠二次电池用正极活性材料前驱体的制备方法中,其特征在于,在所述步骤(b)中供入草酸铵作为所述第二pH调节剂时,调整反应器内的pH值在6.5至11。
根据本发明的钠二次电池用正极活性材料前驱体的制备方法中,其特征在于,所述步骤(c)中的所述镍盐选自硫酸镍、硝酸镍、氯化镍、氟化镍、乙酸镍和氢氧化镍所构成的群组,所述铁盐选自硫酸铁、硝酸铁、氯化铁、氟化铁、乙酸铁和氢氧化铁所构成的群组,所述锰盐选自硫酸锰、硝酸锰、氯化锰、氟化锰、乙酸锰和氢氧化锰所构成的群组。
根据本发明的钠二次电池用正极活性材料前驱体的制备方法中,其特征在于,所述步骤(c)中的所述络合剂选自氨水溶液(NH4OH)、硫酸铵((NH4)2SO4)、硝酸铵(NH4NO3)和第一磷酸铵((NH4)2HPO4)所构成的群组。
根据本发明的钠二次电池用正极活性材料前驱体的制备方法中,其特征在于,所述步骤(c)中的所述络合剂的浓度与所述过渡金属化合物水溶液的浓度之比为0.8至1.2。
进一步地,本发明提供一种由本发明的制备方法制备的钠二次电池用正极活性材料前驱体,其特征在于,其是粒子大小为5至15μm的球形,粒度分布呈单分散型。
根据本发明的钠二次电池用正极活性材料前驱体,其特征在于,其由NixFeyMn1-x-y(OH)2表示,其中0.1≤x≤0.3,0.2≤y≤0.7,0.1≤1-x-y≤0.5。
根据本发明的钠二次电池用正极活性材料前驱体,其特征在于,其由NixFeyMn1-x- yC2O4表示,其中0.1≤x≤0.3,0.2≤y≤0.7,0.1≤1-x-y≤0.5。
根据本发明的钠二次电池用正极活性材料前驱体,其特征在于,其由[NixFeyMn1-x-y]3O4表示,其中0.1≤x≤0.3,0.2≤y≤0.7,0.1≤1-x-y≤0.5。
进一步地,本发明提供一种利用根据本发明的钠二次电池用正极活性材料前驱体制备的钠二次电池用正极活性材料及包含其的钠二次电池。
技术效果
根据本发明利用共沉淀法的钠二次电池用正极活性材料的制备方法,是在利用共沉淀法的同时适当地调节络合剂的种类和pH值,从而能够提供一种寿命特性改善且具有新组成的钠二次电池用正极活性材料前驱体。
附图说明
图1至图4表示本发明一实施例中制备的前驱体的SME图;
图5至图8表示对本发明一实施例中制备的前驱体进行粒度分布测定的结果;
图9和图10表示对本发明一实施例中制备的前驱体进行XRD测定的结果;
图11表示对本发明一实施例中制备的前驱体进行粒度分布测定的结果;
图12和图13表示本发明一实施例中制备的前驱体的SME图;
图14和图15表示对本发明一实施例中制备的前驱体进行粒度分布测定的结果;
图16至图21表示对本发明一实施例中制备的正极活性材料进行XRD测定的结果;
图22表示对本发明一实施例中制备的正极活性材料进行XRD测定的结果;
图23和图24表示本发明一实施例中制备的正极活性材料的SME图。
具体实施方式
以下,根据实施例更详细阐述本发明。但是,本发明并不仅限于以下实施例。
<实施例1>
将4L蒸馏水倒入反应器中,在加入氨的同时在1000rpm下搅拌,并保持反应器内部pH值在7、内部温度在50℃。供入4M的NaOH溶液作为第二pH调节剂,以调整反应器内部pH值在10.2并保持30分钟。
将NiSO4·6H2O、FeSO4·7H2O、MnSO4·5H2O按当量比例混合作为过渡金属化合物水溶液,并且与作为络合剂的NH4OH一起供入到反应器中,以制备如下表1所示的前驱体。
重复实施例1的操作,不同在于,调节所述实施例1中过渡金属化合物水溶液的混合比例,以制备实施例2至4的前驱体,它们分别由Ni0.25Fe0.35Mn0.4(OH)2、Ni0.25Fe0.5Mn0.25(OH)2和Ni0.15Fe0.35Mn0.5(OH)2表示。
表1
[Table1]
区分 | 前驱体组成 |
实施例1 | Ni0.25Fe0.25Mn0.5(OH)2 |
实施例2 | Ni0.25Fe0.35Mn0.4(OH)2 |
实施例3 | Ni0.25Fe0.5Mn0.25(OH)2 |
实施例4 | Ni0.15Fe0.35Mn0.5(OH)2 |
实施例5 | Ni0.25Fe0.5Mn0.25C2O4 |
实施例6 | Ni0.2Fe0.6Mn0.2C2O4 |
实施例7 | Ni0.17Fe0.66Mn0.17C2O4 |
实施例8 | Ni0.2Fe0.55Mn0.25C2O4 |
实施例9 | Ni0.3Fe0.45Mn0.25C2O4 |
实施例10 | Ni0.35Fe0.4Mn0.25C2O4 |
实施例11 | Ni0.4Fe0.35Mn0.25C2O4 |
实施例12 | Ni0.45Fe0.3Mn0.25C2O4 |
实施例13 | (Ni0.25Fe0.5Mn0.25)3O4 |
实施例14 | (Ni0.25Fe0.25Mn0.5)3O4 |
<测试例1>SEM图的测定
测定所述实施例1至4中制备的前驱体的SEM图,并示于图1至图4。
<测试例2>粒度分布的测定
对所述实施例1至4中制备的前驱体进行粒度分布测定,并示于图5至图8。从图5至图8可知,根据本发明的实施例制备的前驱体粒子的粒度分布呈单分散型。
<实施例5至12>
重复实施例1的操作,不同在于,使用氨水溶液作为第一pH调节剂来调整反应器内部pH值在7,并且使用0.5M草酸铵水溶液作为第二pH调节剂来调整反应器内部pH值在7,以制备实施例5至12的前驱体,组成如上表1所示。
<测试例3>XRD的测定
对所述实施例5至7中制备的前驱体进行XRD测定,并示于图9。对所述实施例5和实施例8至12中制备的前驱体进行XRD测定,并示于图10。
<测试例4>粒度分布的测定
对所述实施例5至7中制备的前驱体进行粒度分布测定,并示于图11。
<实施例13和实施例14>
重复实施例1的操作,不同在于,使用氨水溶液作为第一pH调节剂来调整反应器内部pH值在7,并且加入4M的NaOH作为第二pH调节剂来调整反应器内部pH值在9.2,以制备实施例13和实施例14的前驱体,它们分别由(Ni0.25Fe0.5Mn0.25)3O4和(Ni0.25Fe0.25Mn0.5)3O4表示。
<测试例5>SEM图的测定
测定所述实施例13和实施例14中制备的前驱体的SEM图,并示于图12和图13。
<测试例6>粒度分布的测定
对所述实施例8和实施例9中制备的前驱体进行粒度分布测定,并示于图14和图15。从图14和图15可知,粒度分布呈单分散型。
<实施例>正极活性材料的制备
将上表1中的实施例1至14中制备的前驱体与作为钠化合物的碳酸钠混合并搅拌,之后进行热处理,以制备实施例15至28的正极活性材料。
<测试例>XRD的测定
对所述实施例15至实施例28中制备的正极活性材料进行XRD测定的结果示于图16至图21。
对所述实施例19和实施例22至实施例26中制备的正极活性材料进行XRD测定的结果示于图22。
<测试例>SEM图的测定
测定所述实施例19中制备且由Na[Ni0.25Fe0.5Mn0.25]O2表示的正极活性材料和所述实施例28中制备且由Na[Ni0.25Fe0.25Mn0.5]O2表示的正极活性材料的SEM图,并示于图23和图24。
<制备例>电池的制备
分别称量复合金属氧化物、作为导电材料的乙炔黑(电气化学工业株式会社制)及作为粘合剂的PVDF(株式会社吴羽制、聚偏氟乙烯聚四氟乙烯(PolyVinylideneDiFluoride Polyflon)),以使其成为复合金属氧化物:导电材料:粘合剂=85:10:5(重量比)的组成。
其后,首先将复合金属氧化物和乙炔黑用玛瑙乳钵(agate mortar)充分地混合,在该混合物中适量加入N-甲基-2-吡咯烷酮(NMP:东京化成工业株式会社制),进一步加入PVDF继续混合,以使其为均匀,进行浆料化。将所得到的浆料在作为集电体的厚度40μm的铝箔上使用涂抹器以100μm的厚度涂敷,将其放入干燥机,一边除去NMP,一边充分地进行干燥,由此得到正极片。将该正极片用电极冲孔机冲孔为直径1.5cm后,用手动按压机充分地压接,得到正极。
在纽扣电池(宝泉株式会社制)的下侧部分的凹处将铝箔向下放置所得到的正极,而且将作为非水电解液的1M的NaClO4/碳酸丙烯酯+2vol%氟代碳酸乙烯酯(FEC,FluoroEthylene Carbonate)、作为间隔件的聚丙烯多孔质膜(厚度20μm)及作为负极的金属钠组合在一起,制作钠二次电池。
<测试例>充放电特性的测定
对包含由所述实施例1至8的前驱体而成的实施例15至22的活性材料的钠二次电池的充放电特性进行测定,其结果示于下表2。
表2
[Table2]
从上表2可知,包含利用根据本发明制备的钠电池正极活性材料前驱体制备的活性材料的电池,其初始充放电效率显示为90%以上。
<测试例>寿命特性的测定
对包含由所述实施例1至4和实施例8中制备的前驱体制备的实施例15至18和实施例22的活性材料的钠二次电池的充放电特性进行测定,其结果示于下表3。
表3
[Table3]
从上表3可知,包含根据本发明制备的前驱体的钠二次电池,其重复20循环充放电的效率为90%左右,体现出极佳的寿命特性。
工业应用性
根据本发明利用共沉淀法的钠二次电池用正极活性材料的制备方法,是在利用共沉淀法的同时适当地调节络合剂的种类和pH值,从而能够提供一种寿命特性改善且具有新组成的钠二次电池用正极活性材料前驱体。
Claims (10)
1.一种利用共沉淀法的钠二次电池用正极活性材料前驱体的制备方法,包括以下步骤:
(a)将蒸馏水和第一pH调节剂倒入共沉淀反应器中,并且供入空气或氮气进行搅拌并保持反应器内部的pH值在6.5至7.5;
(b)在通过步骤(a)调节所述反应器内部的pH值后,将第二pH调节剂连续供入到所述反应器中进行混合,以调整反应器内的pH值在6.5至11;以及
(c)在通过步骤(b)调节所述反应器内部的pH值后,供入含有当量比例的镍盐、铁盐和锰盐的过渡金属化合物水溶液和络合剂,形成钠二次电池用正极活性材料前驱体粒子;
其中,所述步骤(a)中的所述第一pH调节剂为氨水溶液或硫酸铵水溶液;
所述步骤(b)中的所述第二pH调节剂选自草酸铵、KOH和NaOH所构成的群组;并且在所述步骤(b)中供入KOH或NaOH作为所述第二pH调节剂时,调整反应器内的pH值在9至11;在所述步骤(b)中供入草酸铵作为所述第二pH调节剂时,调整反应器内的pH值在6.5至11。
2.根据权利要求1所述的利用共沉淀法的钠二次电池用正极活性材料前驱体的制备方法,其特征在于,所述步骤(c)中的所述镍盐选自硫酸镍、硝酸镍、氯化镍、氟化镍、乙酸镍和氢氧化镍所构成的群组,所述铁盐选自硫酸铁、硝酸铁、氯化铁、氟化铁、乙酸铁和氢氧化铁所构成的群组,所述锰盐选自硫酸锰、硝酸锰、氯化锰、氟化锰、乙酸锰和氢氧化锰所构成的群组。
3.根据权利要求1所述的利用共沉淀法的钠二次电池用正极活性材料前驱体的制备方法,其特征在于,所述步骤(c)中的所述络合剂选自氨水溶液(NH4OH)、硫酸铵((NH4)2SO4)、硝酸铵(NH4NO3)和磷酸氢二铵((NH4)2HPO4)所构成的群组。
4.根据权利要求1所述的利用共沉淀法的钠二次电池用正极活性材料前驱体的制备方法,其特征在于,所述步骤(c)中的所述络合剂的浓度与所述过渡金属化合物水溶液的浓度之比为0.8至1.2。
5.一种由根据权利要求1至4中任一项所述的制备方法制备的钠二次电池用正极活性材料前驱体,其特征在于,其是粒子大小为5至15μm的球形,粒度分布呈单分散型。
6.根据权利要求5所述的钠二次电池用正极活性材料前驱体,其特征在于,所述钠二次电池用正极活性材料前驱体由NixFeyMn1-x-y(OH)2表示,其中0.1≤x≤0.3,0.2≤y≤0.7,0.1≤1-x-y≤0.5。
7.根据权利要求5所述的钠二次电池用正极活性材料前驱体,其特征在于,所述钠二次电池用正极活性材料前驱体由NixFeyMn1-x-yC2O4表示,其中0.1≤x≤0.3,0.2≤y≤0.7,0.1≤1-x-y≤0.5。
8.根据权利要求5所述的钠二次电池用正极活性材料前驱体,其特征在于,所述钠二次电池用正极活性材料前驱体由[NixFeyMn1-x-y]3O4表示,其中0.1≤x≤0.3,0.2≤y≤0.7,0.1≤1-x-y≤0.5。
9.一种钠二次电池用正极活性材料,利用根据权利要求5所述的钠二次电池用正极活性材料前驱体来制备。
10.一种钠二次电池,包含根据权利要求9所述的钠二次电池用正极活性材料。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2012-0130824 | 2012-11-19 | ||
KR20120130824 | 2012-11-19 | ||
KR10-2013-0140907 | 2013-11-19 | ||
PCT/KR2013/010520 WO2014077662A1 (ko) | 2012-11-19 | 2013-11-19 | 공침법을 이용한 나트륨 이차전지용 양극활물질 전구체의 제조 방법 및 이에 의하여 제조된 나트륨 이차전지용 양극활물질 전구체 |
KR1020130140907A KR101570125B1 (ko) | 2012-11-19 | 2013-11-19 | 공침법을 이용한 나트륨 이차전지용 양극활물질 전구체의 제조 방법 및 이에 의하여 제조된 나트륨 이차전지용 양극활물질 전구체 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104885265A CN104885265A (zh) | 2015-09-02 |
CN104885265B true CN104885265B (zh) | 2018-02-13 |
Family
ID=50892001
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201380068776.0A Expired - Fee Related CN104885265B (zh) | 2012-11-19 | 2013-11-19 | 利用共沉淀法的钠二次电池用正极活性材料前驱体的制备方法及由此制备的钠二次电池用正极活性材料前驱体 |
Country Status (2)
Country | Link |
---|---|
KR (1) | KR101570125B1 (zh) |
CN (1) | CN104885265B (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20160083616A (ko) * | 2014-12-31 | 2016-07-12 | 삼성에스디아이 주식회사 | 리튬이차전지용 양극 활물질의 전구체, 그 제조방법, 리튬이차전지용 양극 활물질, 그 제조방법, 및 상기 양극 활물질을 포함하는 리튬이차전지 |
CN105692721B (zh) * | 2016-01-29 | 2017-08-25 | 太原理工大学 | 一种钠离子电池正极材料及其制备方法和使用方法 |
CN109830679B (zh) * | 2019-02-01 | 2021-04-06 | 中国科学院过程工程研究所 | 一种正极材料前驱体、及其制备方法和用途 |
WO2020235909A1 (ko) * | 2019-05-17 | 2020-11-26 | 한양대학교 산학협력단 | 칼슘 도핑된 나트륨 이차전지용 양극활물질 및 이를 포함하는 나트륨 이차전지 |
KR102466222B1 (ko) * | 2019-05-17 | 2022-11-11 | 한양대학교 산학협력단 | 칼슘 도핑된 나트륨 이차전지용 양극활물질 및 이를 포함하는 나트륨 이차전지 |
CN113415830B (zh) * | 2021-08-24 | 2021-11-05 | 金驰能源材料有限公司 | 锂离子电池正极材料前驱体的制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1665053A (zh) * | 2004-03-03 | 2005-09-07 | 王岩 | 一种锂离子电池正极活性材料及其制备方法 |
CN1893151A (zh) * | 2005-07-01 | 2007-01-10 | 深圳市比克电池有限公司 | 锂复合金属氧化物的制备方法 |
CN102088080A (zh) * | 2011-01-07 | 2011-06-08 | 中南大学 | 一种制备磷酸盐系列锂离子电池正极材料的方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4475941B2 (ja) * | 2003-12-12 | 2010-06-09 | 日本化学工業株式会社 | リチウムマンガンニッケル複合酸化物の製造方法 |
CN103348511B (zh) | 2011-02-15 | 2016-08-31 | 住友化学株式会社 | 钠二次电池电极及钠二次电池 |
-
2013
- 2013-11-19 CN CN201380068776.0A patent/CN104885265B/zh not_active Expired - Fee Related
- 2013-11-19 KR KR1020130140907A patent/KR101570125B1/ko active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1665053A (zh) * | 2004-03-03 | 2005-09-07 | 王岩 | 一种锂离子电池正极活性材料及其制备方法 |
CN1893151A (zh) * | 2005-07-01 | 2007-01-10 | 深圳市比克电池有限公司 | 锂复合金属氧化物的制备方法 |
CN102088080A (zh) * | 2011-01-07 | 2011-06-08 | 中南大学 | 一种制备磷酸盐系列锂离子电池正极材料的方法 |
Also Published As
Publication number | Publication date |
---|---|
KR101570125B1 (ko) | 2015-11-18 |
CN104885265A (zh) | 2015-09-02 |
KR20140064680A (ko) | 2014-05-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107210441B (zh) | 非水系电解质二次电池用正极活性物质和其制造方法,以及使用了该正极活性物质的非水系电解质二次电池 | |
CN104885265B (zh) | 利用共沉淀法的钠二次电池用正极活性材料前驱体的制备方法及由此制备的钠二次电池用正极活性材料前驱体 | |
CN107251285B (zh) | 非水系电解质二次电池用正极活性物质和其制造方法,以及非水系电解质二次电池 | |
CN104904047A (zh) | 钠二次电池用正极活性材料及其制备方法 | |
CN108292749B (zh) | 非水系电解质二次电池用正极材料及其制造方法、正极复合材料膏、非水系电解质二次电池 | |
US10781110B2 (en) | Manufacturing method of positive active material precursor for sodium rechargeable batteries, positive active material precursor for sodium rechargeable batteries made by the same, and manufacturing method of positive active material for sodium rechargeable batteries, positive active material for sodium rechargeable batteries made by the same | |
CN107534143B (zh) | 正极活性物质和其制造方法、以及非水系电解质二次电池 | |
TW201424100A (zh) | Li-Ni複合氧化物粒子粉末以及非水電解質蓄電池 | |
CN108134064B (zh) | 一种正极材料前驱体及其制备方法和正极材料 | |
KR20140119621A (ko) | 리튬 과량 양극활물질 제조용 전구체 및 이에 의하여 제조된 리튬 과량 양극활물질 | |
US20170187039A1 (en) | Positive electrode active material for sodium secondary battery, and method for preparing same | |
KR20140049868A (ko) | 리튬이차전지용 리튬금속산화물 복합체, 그 제조방법 및 이것을 포함하는 리튬이차전지 | |
JP5596726B2 (ja) | マグネシウム電池 | |
CN103956456A (zh) | 卤素阴离子掺杂的富锂正极材料及其制备方法和应用 | |
KR101219395B1 (ko) | 리튬이차전지용 양극재료 및 그의 제조방법 | |
KR101449421B1 (ko) | 고체초강산으로 표면 처리된 비수계 리튬이차전지용 양극활물질 및 그 제조방법 | |
CN111211320A (zh) | 一种锂镍钴氧化物正极材料及其制备方法、锂离子电池 | |
CN106058221B (zh) | 一种磷酸根聚阴离子复合锰盐包覆富锂锰基正极材料的制备方法 | |
JP5819786B2 (ja) | 銅酸リチウム正極材料、同正極材料の製造方法、および同正極材料を正極活物質として含むリチウム二次電池 | |
CN116741984A (zh) | 一种钠离子电池正极材料及制备方法、正极及钠离子电池 | |
CN114864894B (zh) | 一种耐高压包覆层修饰的富锂锰基正极材料及其制备方法和应用 | |
CN109817968B (zh) | 经表面包覆的镍锰酸锂颗粒及其制造方法 | |
US20230135908A1 (en) | Metal composite hydroxide, method for producing same, positive electrode active material for nonaqueous electrolyte secondary batteries, method for producing said positive electrode active material, and nonaqueous electrolyte secondary battery using said positive electrode active material | |
CN113113588B (zh) | 一种利用共价界面工程策略制备锂快离子导体类材料包覆高镍三元层状氧化物的方法 | |
CN113206241B (zh) | 一种单晶镍钴锰酸锂三元材料的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
EXSB | Decision made by sipo to initiate substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180213 |
|
CF01 | Termination of patent right due to non-payment of annual fee |