CN104904047A - Anode active material for sodium secondary battery and method for producing same - Google Patents
Anode active material for sodium secondary battery and method for producing same Download PDFInfo
- Publication number
- CN104904047A CN104904047A CN201380068762.9A CN201380068762A CN104904047A CN 104904047 A CN104904047 A CN 104904047A CN 201380068762 A CN201380068762 A CN 201380068762A CN 104904047 A CN104904047 A CN 104904047A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- electrode active
- rechargeable battery
- active materials
- sodium
- 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.)
- Pending
Links
- 239000011734 sodium Substances 0.000 title claims abstract description 69
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 65
- 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 64
- 239000006183 anode active material Substances 0.000 title abstract 6
- 238000004519 manufacturing process Methods 0.000 title abstract 3
- 239000007774 positive electrode material Substances 0.000 claims description 57
- 238000002360 preparation method Methods 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 9
- 150000003388 sodium compounds Chemical class 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 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000011572 manganese Substances 0.000 description 11
- 239000003002 pH adjusting agent Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 8
- 239000011149 active material Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical group [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- 239000006230 acetylene black Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 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 2
- 150000002696 manganese Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- ZQCQTPBVJCWETB-UHFFFAOYSA-N 4-fluoro-1,3-dioxol-2-one Chemical compound FC1=COC(=O)O1 ZQCQTPBVJCWETB-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 229920006361 Polyflon Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene 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
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
-
- 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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
-
- 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
- H01M4/50—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
- 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
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to an anode active material for a sodium secondary battery and a method for producing same and, more specifically, to an anode active material, having a new O3 structure, for a sodium secondary battery and a method for producing same. The anode active material for a sodium secondary battery according to the present invention has an O3 structure and thus is structurally stable, unlike conventional anode active materials, and accordingly, a sodium battery comprising the anode active material for a sodium secondary battery according to the present invention exhibits excellent lifespan characteristics.
Description
Technical field
The present invention relates to a kind of sodium rechargeable battery positive electrode active materials and preparation method thereof, in more detail, relate to and a kind of novel there is O
3sodium rechargeable battery positive electrode active materials of structure and preparation method thereof.
Background technology
Now, as secondary cell many uses lithium secondary battery of high-energy-density, this lithium secondary battery uses the nonaqueous electrolytic solution that obtained in nonaqueous solvents by dissolving electrolyte salt and lithium ion is moved between a positive electrode and a negative electrode thus carries out discharge and recharge.Use lithium transition-metal oxide as positive electrode, and utilize lithium ion to insert the lithium ion battery of middle reaction just in commercialization.But, because the lithium contained in lithium ion battery is expensive, therefore in fact need price cheaper and there is the battery of high power capacity.
Recently, start to have carried out sodium ion in order to replace the research of the sodium ion secondary battery of lithium ion.Because sodium resource reserves are enriched, if sodium ion therefore can be prepared in order to replace the secondary cell of lithium ion, just secondary cell can be prepared with low cost.
The secondary cell with positive pole and negative pole is specifically recorded in Japanese Unexamined Patent Publication 2007-287661 publication, the composite metal oxide that the raw material that it is 0.7:0.5:0.5 that described positive pole adopts the ratio of components (Na:Mn:Co) of Na, Mn and Co burns till and obtains, described negative pole is made up of sodium metal.Further, in Japanese Unexamined Patent Publication 2005-317511 publication, specifically record the α-NaFeO as composite metal oxide with six side's closest packing (rocksalt-type) crystal structures
2, by by Na
2o
2and Fe
3o
4this composite metal oxide obtained is burnt till at 600 to 700 DEG C in atmosphere after mixing.But for the life characteristic of existing sodium rechargeable battery, namely repeatedly carry out discharge capacity sustainment rate during discharge and recharge, not talkative is sufficient.
Summary of the invention
Technical problem
In order to solve the problem of above-mentioned prior art, the object of the invention is to provide a kind of life characteristic to improve and has sodium rechargeable battery positive electrode active materials of new composition and preparation method thereof.
Technical scheme
In order to solve the problems of the technologies described above, the invention provides a kind of sodium rechargeable battery positive electrode active materials, it has O
3crystal structure, and by Na
x[Ni
yfe
zmn
1-y-z] O
2represent, wherein 0.8≤x≤1.2,0.05≤y≤0.9,0.05≤z≤0.9,0.05≤1-y-z≤0.9.
According to sodium rechargeable battery positive electrode active materials of the present invention, it is characterized in that, its to be particle size be spheroidal particle of 5 to 15 μm, particle size distribution is single dispersing type.
According to sodium rechargeable battery positive electrode active materials of the present invention, it is characterized in that, there are 3 peaks within the scope of 30 ° to 40 ° in 2 θ in XRD.
According to sodium rechargeable battery positive electrode active materials of the present invention, it is characterized in that, there is main peak (104) in 2 θ in XRD within the scope of 40 ° to 45 °.
According to sodium rechargeable battery positive electrode active materials of the present invention, it is characterized in that, tap density is 1.0 to 2.4g/cc.
Further, the invention provides a kind of preparation method according to sodium rechargeable battery positive electrode active materials of the present invention, comprise the following steps: sodium rechargeable battery positive electrode active materials presoma is mixed with sodium compound; And heat treatment.
In preparation method according to sodium rechargeable battery positive electrode active materials of the present invention, it is characterized in that, described sodium rechargeable battery positive electrode active materials presoma is represented by the arbitrary formula in following formula 1 to 3:
[formula 1] Ni
xfe
ymn
1-x-y(OH)
2
[formula 2] Ni
xfe
ymn
1-x-yc
2o
4
[formula 3] [Ni
xfe
ymn
1-x-y]
3o
4
In described formula 1 to 3,0.05≤x≤0.9,0.1≤y≤0.9,0.05≤1-x-y≤0.9.
As the present inventor in the application number that on November 19th, 2012 applies for be in the patent of 10-2012-0130824, described sodium rechargeable battery positive electrode active materials presoma is prepared preferably by coprecipitation.
That is, described sodium rechargeable battery positive electrode active materials presoma comprises the following steps:
A distilled water and the first pH adjusting agent are poured in coprecipitation reaction device by (), and air-supplied or nitrogen carries out stirring and keeps the pH value of inside reactor 6.5 to 7.5;
B second pH adjusting agent is fed in described reactor and mixes by () continuously, to adjust pH value in reactor 6.5 to 11; And
C () feeds the transistion metal compound aqueous solution and the complexing agent of nickel salt, molysite and manganese salt containing equivalents ratio, form sodium rechargeable battery positive electrode active materials precursor particle.
In the preparation method of described sodium rechargeable battery positive electrode active materials presoma, it is characterized in that, the group that described second pH adjusting agent is selected from ammonium oxalate, NaOH and KOH is formed in described step (b).
In positive electrode active materials precursor power method of the present invention, it is characterized in that, when feeding KOH or NaOH as described second pH adjusting agent in described step (b), pH value in adjustment reactor is 9 to 11, and when feeding ammonium oxalate as described second pH adjusting agent, the pH value in adjustment reactor is 6.5 to 11.
In the preparation method of sodium rechargeable battery positive electrode active materials presoma of the present invention, it is characterized in that, described nickel salt in described step (c) is selected from the group that nickelous sulfate, nickel nitrate, nickel chloride and nickel fluoride are formed, described molysite is selected from ferric sulfate, ferric nitrate, iron chloride and ferric flouride, and described manganese salt is selected from manganese sulfate, manganese nitrate, manganese chloride and manganous fluoride.
In the preparation method of sodium rechargeable battery positive electrode active materials presoma of the present invention, it is characterized in that, the described complexing agent in described step (c) is selected from ammonia spirit (NH
4oH), ammonium sulfate ((NH
4)
2sO
4), ammonium nitrate (NH
4nO
3) and the first ammonium phosphate ((NH
4)
2hPO
4) group that forms.
In the preparation method of sodium rechargeable battery positive electrode active materials presoma of the present invention, it is characterized in that, the concentration of the described complexing agent in described step (c) is 0.8 to 1.2 with the ratio of the concentration of the described transistion metal compound aqueous solution.
In preparation method according to sodium rechargeable battery positive electrode active materials of the present invention, it is characterized in that, described sodium compound is the one in sodium carbonate, sodium nitrate, sodium acetate, NaOH, NaOH hydrate, sodium oxide molybdena or its combination.
In preparation method according to sodium rechargeable battery positive electrode active materials of the present invention, it is characterized in that, in the step that sodium rechargeable battery is mixed with sodium compound with positive electrode active materials presoma, relative to every 1 mole of described sodium rechargeable battery positive electrode active materials presoma, mix described sodium compound with the ratio of 1.0 to 1.5 moles.
In preparation method according to sodium rechargeable battery positive electrode active materials of the present invention, it is characterized in that, in described heat treatment step, heat-treat at 1000 DEG C at 800 DEG C.
Technique effect
Sodium rechargeable battery positive electrode active materials according to the present invention is different from tradition, is have O
3structure and Stability Analysis of Structures, comprise thus and provide excellent life characteristic according to the sode cell of sodium rechargeable battery positive electrode active materials of the present invention.
Accompanying drawing explanation
Fig. 1 to Fig. 4 represents the SME figure of the presoma prepared in embodiments of the invention;
Fig. 5 to Fig. 8 represents the result of the presoma prepared in embodiments of the invention being carried out to particle size distribution;
Fig. 9 represents the result of the presoma prepared in embodiments of the invention being carried out to XRD determining;
Figure 10 represents the result of the presoma prepared in embodiments of the invention being carried out to particle size distribution;
Figure 11 and Figure 12 represents the SME figure of the presoma prepared in embodiments of the invention;
Figure 13 and Figure 14 represents the result of the presoma prepared in embodiments of the invention being carried out to particle size distribution;
Figure 15 to Figure 22 represents the result of the positive electrode active materials prepared in embodiments of the invention being carried out to XRD determining;
Figure 23 to Figure 33 represents the result measured life characteristic or the charge-discharge characteristic of the sodium rechargeable battery comprising the positive electrode active materials prepared in embodiments of the invention.
Embodiment
Below, more elaborate the present invention according to embodiment, but the present invention is not limited in following examples.
< embodiment 1 to 4 >
4L distilled water is poured in reactor, stirs under 1000rpm while adding ammonia, and keep inside reactor pH value 7, internal temperature is at 50 DEG C.Feed the NaOH solution of 4M as the second pH adjusting agent, keep 30 minutes to adjust inside reactor pH value 10.2.
By NiSO
46H
2o, FeSO
47H
2o, MnSO
45H
2o press equivalents ratio mixing as the transistion metal compound aqueous solution, and with the NH as complexing agent
4oH is fed in reactor together, to be prepared as follows the presoma shown in table 1.
Repeat the operation of embodiment 1, difference is, regulates the mixed proportion of the transistion metal compound aqueous solution in described embodiment 1, to prepare the presoma of embodiment 2 to 4, as shown in table 1 below they respectively by Ni
0.25fe
0.35mn
0.4(OH)
2, Ni
0.25fe
0.5mn
0.25(OH)
2and Ni
0.15fe
0.35mn
0.5(OH)
2represent.
Table 1
[Table1]
| Distinguish | Presoma forms |
| Embodiment 1 | Ni 0.25Fe 0.25Mn 0.5(OH) 2 |
| Embodiment 2 | Ni 0.25Fe 0.35Mn 0.4(OH) 2 |
| Embodiment 3 | Ni 0.25Fe 0.5Mn 0.25(OH) 2 |
| Embodiment 4 | Ni 0.15Fe 0.35Mn 0.5(OH) 2 |
| Embodiment 5 | Ni 0.25Fe 0.5Mn 0.25C 2O 4 |
| Embodiment 6 | Ni 0.2Fe 0.6Mn 0.2C 2O 4 |
| Embodiment 7 | Ni 0.17Fe 0.66Mn 0.17C 2O 4 |
| Embodiment 8 | Ni 0.2Fe 0.55Mn 0.25C 2O 4 |
| Embodiment 9 | Ni 0.3Fe 0.45Mn 0.25C 2O 4 |
| Embodiment 10 | Ni 0.35Fe 0.4Mn 0.25C 2O 4 |
| Embodiment 11 | (Ni 0.25Fe 0.5Mn 0.25) 3O 4 |
| Embodiment 12 | (Ni 0.25Fe 0.25Mn 0.5) 3O 4 |
The mensuration of < test case 1 > SEM figure
Measure the SEM figure of the presoma of preparation in described embodiment 1 to 4, and be shown in Fig. 1 to Fig. 4.
The mensuration of < test case 2 > particle size distribution
Particle size distribution is carried out to the presoma of preparation in described embodiment 1 to 4, and is shown in Fig. 5 to Fig. 8.From Fig. 5 to Fig. 8, the granularity of precursor particle is single dispersing type.
< embodiment 5 to 10 > Ni
xfe
ymn
1-x-yc
2o
4the preparation of presoma
Repeat the operation of embodiment 1, difference is, ammonia is used to adjust inside reactor pH value 7 as the first pH adjusting agent, and use the 0.5M ammonium oxalate aqueous solution as the second pH adjusting agent to adjust inside reactor pH value 7, to prepare the presoma of embodiment 5 to 10, composition as shown in Table 1.
The mensuration of < test case 3 > XRD
XRD determining is carried out to the presoma of preparation in described embodiment 5 to 7, and is shown in Fig. 9.
The mensuration of < test case 4 > particle size distribution
Particle size distribution is carried out to the presoma of preparation in described embodiment 5 to 7, and is shown in Figure 10.
< embodiment 11 and embodiment 12 >
Repeat the operation of embodiment 1, difference is, ammonia is used to adjust inside reactor pH value 7 as the first pH adjusting agent, and the NaOH adding 4M as the second pH adjusting agent to adjust inside reactor pH value 9.2, to prepare the presoma of embodiment 11 and embodiment 12, they are respectively by (Ni
0.25fe
0.5mn
0.25)
3o
4(Ni
0.25fe
0.25mn
0.5)
3o
4represent.
The mensuration of < test case 5 > SEM figure
Measure the SEM figure of the presoma of preparation in described embodiment 11 and embodiment 12, and be shown in Figure 11 and Figure 12.
The mensuration of < test case 6 > particle size distribution
Particle size distribution is carried out to the presoma of preparation in described embodiment 11 and embodiment 12, and is shown in Figure 13 and Figure 14.From Figure 13 and Figure 14, particle size distribution is single dispersing type.
The preparation of < embodiment 13 to 24 > positive electrode active materials
The presoma of preparation in the embodiment 1 to 12 in upper table 1 is mixed with the sodium carbonate as sodium compound and stirs, heat-treats afterwards, to prepare the positive electrode active materials of embodiment 13 to 24.
The mensuration of < test case > XRD
The result of the positive electrode active materials of described embodiment 13 to 16 being carried out to XRD determining is shown in Figure 15 to Figure 18, the result of the positive electrode active materials of described embodiment 17 to 19 being carried out to XRD determining is shown in Figure 19, the result of the positive electrode active materials of described embodiment 20 to 22 being carried out to XRD determining is shown in Figure 20, and is shown in Figure 21 and Figure 22 to the result that the positive electrode active materials of described embodiment 23 and embodiment 24 carries out XRD determining.
Can determine from Figure 15 to Figure 22, there are 3 peaks within the scope of 30 ° to 40 ° in the sodium rechargeable battery positive electrode active materials prepared in embodiments of the invention 2 θ in XRD, is occur having O within the scope of 40 ° to 45 ° at 2 θ
3(104) main peak of crystal structure characteristic.
The preparation of < preparation example > battery
Weigh composite metal oxide E1, the acetylene black (Deuki Kagaku Kogyo Co., Ltd's system) as electric conducting material and the PVDF as adhesive (Kureha Corp.'s system, Kynoar polytetrafluoroethylene (PolyVinylidene DiFluoride Polyflon)) respectively, to become composite metal oxide E1: electric conducting material: the composition of adhesive=85:10:5 (weight ratio).
Thereafter, first composite metal oxide and acetylene black agate mortar (agate mortar) are mixed fully, add METHYLPYRROLIDONE (NMP: Tokyo HuaCheng Industry Co., Ltd's system) in the mixture in right amount, add PVDF further and continue mixing, to be even, carry out slurried.On the aluminium foil of the thickness 40 μm as collector body, used by obtained slurry applicator with the thickness of 100 μm coating, put it into drying machine, remove NMP, carry out drying fully on one side, obtain positive plate thus.Be, after diameter 1.5cm, crimp this positive plate electrode punching machine punch fully with Manual press machine, obtain positive pole.
At the recess of the lower portion of button cell (precious Izumi Ltd. system), aluminium foil is placed obtained positive pole downwards, and using the NaClO of the 1M as nonaqueous electrolytic solution
4/ propene carbonate+2vol% fluorinated ethylene carbonate (FEC, Fluoro Ethylene Carbonate), as distance piece polypropylene multiple aperture plasma membrane (thickness 20 μm) and combine as the sodium metal of negative pole, make sodium rechargeable battery.
The mensuration of < test case > charge-discharge characteristic
The charge-discharge characteristic comprised by described embodiment 1 to 7 and the embodiment 13 to 19 of presoma of embodiment 11 and the sodium rechargeable battery of the active material of embodiment 23 is measured, the results are shown in following table 2.
Table 2
[Table2]
From described table 2, comprise and prepared in accordance with the present invention there is O
3the battery of the sode cell positive electrode active materials of crystal structure, its initial charge/discharge efficiency is shown as more than 90%.
The mensuration of < test case > life characteristic
By the embodiment 13 to 16 of the presoma of described embodiment 1 to 4 and embodiment 11 and embodiment 23, there is O to comprising
3the charge-discharge characteristic of the sodium rechargeable battery of the active material of crystal structure measures, and the results are shown in following table 3, and has O to comprising by the embodiment 17 to 19 of the presoma of described embodiment 5 to 7
3the charge-discharge characteristic of the sodium rechargeable battery of the active material of crystal structure measures, and the results are shown in lower Figure 27.
Table 3
[Table3]
From described table 2 and Figure 27, comprise, according to of the present invention, there is O
3the sodium rechargeable battery of the active material of crystal structure, its efficiency repeating 20 cycle charge-discharges is about 90%, embodies splendid life characteristic.
The mensuration of < test case > charge-discharge characteristic and life characteristic
The charge-discharge characteristic of the sodium rechargeable battery comprising the active material prepared in described embodiment 13 to 16 is measured, the results are shown in Figure 23 to 26, the charge-discharge characteristic of the sodium rechargeable battery of described embodiment 17 to 19 is measured, the results are shown in Figure 27 and Figure 28, the charge-discharge characteristic of the sodium rechargeable battery comprising the active material prepared in described embodiment 17 and embodiment 20 to 22 is measured, the results are shown in Figure 29 to 31, and to what to comprise in described embodiment 23 and embodiment 24 preparation, there is O
3charge-discharge characteristic and the life characteristic of the sodium rechargeable battery of the active material of crystal structure measure, and the results are shown in Figure 32 and Figure 33.
Industrial applicability
Sodium rechargeable battery positive electrode active materials according to the present invention is different from tradition, is have O
3structure and Stability Analysis of Structures, comprise thus and provide excellent life characteristic according to the sode cell of sodium rechargeable battery positive electrode active materials of the present invention.
Claims (10)
1. a sodium rechargeable battery positive electrode active materials, has O
3crystal structure, and by Na
x[Ni
yfe
zmn
1-y-z] O
2represent, wherein 0.8≤x≤1.2,0.05≤y≤0.9,0.05≤z≤0.9,0.05≤1-y-z≤0.9.
2. sodium rechargeable battery positive electrode active materials according to claim 1, is characterized in that, described sodium rechargeable battery positive electrode active materials to be particle size the be spheroidal particle of 5 to 15 μm, particle size distribution is single dispersing type.
3. sodium rechargeable battery positive electrode active materials according to claim 1, is characterized in that, described sodium rechargeable battery positive electrode active materials 2 θ in XRD occur 3 peaks within the scope of 30 ° to 40 °.
4. sodium rechargeable battery positive electrode active materials according to claim 3, is characterized in that, described sodium rechargeable battery positive electrode active materials 2 θ in XRD occur main peak 104 within the scope of 40 ° to 45 °.
5. sodium rechargeable battery positive electrode active materials according to claim 1, is characterized in that, the tap density of described sodium rechargeable battery positive electrode active materials is 1.0 to 2.4g/cc.
6. a preparation method for sodium rechargeable battery positive electrode active materials according to claim 1, comprises the following steps:
Sodium rechargeable battery positive electrode active materials presoma is mixed with sodium compound; And
Heat-treat.
7. the preparation method of sodium rechargeable battery positive electrode active materials according to claim 6, is characterized in that, described sodium rechargeable battery positive electrode active materials presoma is represented by the arbitrary formula in following formula 1 to 3:
[formula 1] Ni
xfe
ymn
1-x-y(OH)
2
[formula 2] Ni
xfe
ymn
1-x-yc
2o
4
[formula 3] [Ni
xfe
ymn
1-x-y]
3o
4
In described formula 1 to 3,0.05≤x≤0.9,0.1≤y≤0.9,0.05≤1-x-y≤0.9.
8. the preparation method of sodium rechargeable battery positive electrode active materials according to claim 6, is characterized in that, described sodium compound is the one in sodium carbonate, sodium nitrate, sodium acetate, NaOH, NaOH hydrate, sodium oxide molybdena or its combination.
9. the preparation method of sodium rechargeable battery positive electrode active materials according to claim 6, is characterized in that, relative to every 1 mole of described sodium rechargeable battery positive electrode active materials presoma, mixes described sodium compound with the ratio of 1.0 to 1.5 moles.
10. the preparation method of sodium rechargeable battery positive electrode active materials according to claim 6, is characterized in that, in described heat treatment step, heat-treats at 1000 DEG C at 800 DEG C.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20120131027 | 2012-11-19 | ||
| KR10-2012-0131027 | 2012-11-19 | ||
| KR10-2013-0140911 | 2013-11-19 | ||
| PCT/KR2013/010521 WO2014077663A1 (en) | 2012-11-19 | 2013-11-19 | Anode active material for sodium secondary battery and method for producing same |
| KR1020130140911A KR20140064681A (en) | 2012-11-19 | 2013-11-19 | Positive active material for sodium rechargeable batteries and method of manufacturing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104904047A true CN104904047A (en) | 2015-09-09 |
Family
ID=50892002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380068762.9A Pending CN104904047A (en) | 2012-11-19 | 2013-11-19 | Anode active material for sodium secondary battery and method for producing same |
Country Status (2)
| Country | Link |
|---|---|
| KR (2) | KR20140064681A (en) |
| CN (1) | CN104904047A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711440A (en) * | 2017-01-20 | 2017-05-24 | 东莞市迈科新能源有限公司 | Nano flaky sodium-ion battery anode material and preparation method thereof |
| CN109830679A (en) * | 2019-02-01 | 2019-05-31 | 中国科学院过程工程研究所 | A kind of positive electrode material precursor, and its preparation method and application |
| CN109873153A (en) * | 2019-04-04 | 2019-06-11 | 中南大学 | A kind of O3 type sodium-ion battery positive material and preparation method thereof |
| CN110350187A (en) * | 2019-06-25 | 2019-10-18 | 浙江工业大学 | A kind of stratiform ternary sodium-ion battery method for preparing anode material |
| CN117012949A (en) * | 2023-10-07 | 2023-11-07 | 有研(广东)新材料技术研究院 | Low-nickel high-energy-density layered sodium-ion battery positive electrode material and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019039639A1 (en) * | 2017-08-23 | 2019-02-28 | 전자부품연구원 | Positive electrode active material for sodium ion battery and manufacturing method therefor |
| WO2020059902A1 (en) * | 2018-09-19 | 2020-03-26 | 전자부품연구원 | Cathode material having silicon oxide coating layer formed thereon, cathode comprising same, sodium ion battery, and manufacturing method therefor |
| TR2021003028A2 (en) * | 2021-02-24 | 2022-09-21 | Erci̇yes Üni̇versi̇tesi̇ Strateji̇ Geli̇şti̇rme Dai̇re Başkanliği | DEVELOPMENT OF NEW O3-NAXMO2 TYPE LAYERED METAL OXIDES FOR SODIUM ION BATTERIES STABLE IN AIR |
| CN115498154A (en) * | 2022-09-22 | 2022-12-20 | 深圳市贝特瑞新能源技术研究院有限公司 | Positive electrode material, preparation method thereof and sodium ion battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101908615A (en) * | 2010-07-27 | 2010-12-08 | 中信国安盟固利电源技术有限公司 | Ferro-manganese nickel anode material and preparation method thereof |
| CN101933179A (en) * | 2008-02-04 | 2010-12-29 | 住友化学株式会社 | Composite metal oxide and sodium rechargeable battery |
| CN101933180A (en) * | 2008-02-04 | 2010-12-29 | 住友化学株式会社 | Composite metal oxide and sodium rechargeable battery |
| WO2012111681A1 (en) * | 2011-02-15 | 2012-08-23 | 住友化学株式会社 | Sodium secondary battery electrode and sodium secondary battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9203088B2 (en) | 2010-11-05 | 2015-12-01 | Tokyo University Of Science Educational Foundation Administrative Organization | Composite metal oxide, process for producing the composite metal oxide, positive active material for sodium secondary battery, positive electrode for sodium secondary battery, and sodium secondary battery |
-
2013
- 2013-11-19 CN CN201380068762.9A patent/CN104904047A/en active Pending
- 2013-11-19 KR KR1020130140911A patent/KR20140064681A/en active Application Filing
-
2016
- 2016-05-04 KR KR1020160055651A patent/KR101762540B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101933179A (en) * | 2008-02-04 | 2010-12-29 | 住友化学株式会社 | Composite metal oxide and sodium rechargeable battery |
| CN101933180A (en) * | 2008-02-04 | 2010-12-29 | 住友化学株式会社 | Composite metal oxide and sodium rechargeable battery |
| CN101908615A (en) * | 2010-07-27 | 2010-12-08 | 中信国安盟固利电源技术有限公司 | Ferro-manganese nickel anode material and preparation method thereof |
| WO2012111681A1 (en) * | 2011-02-15 | 2012-08-23 | 住友化学株式会社 | Sodium secondary battery electrode and sodium secondary battery |
Non-Patent Citations (1)
| Title |
|---|
| DONGHAN KIM ET.AL: "Layered Na(Ni1/3Fe1/3Mn1/3)O2 cathodes for Na-ion battery application,", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711440A (en) * | 2017-01-20 | 2017-05-24 | 东莞市迈科新能源有限公司 | Nano flaky sodium-ion battery anode material and preparation method thereof |
| CN109830679A (en) * | 2019-02-01 | 2019-05-31 | 中国科学院过程工程研究所 | A kind of positive electrode material precursor, and its preparation method and application |
| CN109830679B (en) * | 2019-02-01 | 2021-04-06 | 中国科学院过程工程研究所 | Positive electrode material precursor, preparation method and application thereof |
| CN109873153A (en) * | 2019-04-04 | 2019-06-11 | 中南大学 | A kind of O3 type sodium-ion battery positive material and preparation method thereof |
| CN110350187A (en) * | 2019-06-25 | 2019-10-18 | 浙江工业大学 | A kind of stratiform ternary sodium-ion battery method for preparing anode material |
| CN117012949A (en) * | 2023-10-07 | 2023-11-07 | 有研(广东)新材料技术研究院 | Low-nickel high-energy-density layered sodium-ion battery positive electrode material and preparation method thereof |
| CN117012949B (en) * | 2023-10-07 | 2024-01-26 | 有研(广东)新材料技术研究院 | Low-nickel layered sodium ion battery positive electrode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20160056319A (en) | 2016-05-19 |
| KR20140064681A (en) | 2014-05-28 |
| KR101762540B1 (en) | 2017-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104904047A (en) | Anode active material for sodium secondary battery and method for producing same | |
| KR101577180B1 (en) | Positive electrode active material with improved energy density | |
| EP2741349B1 (en) | Method for preparing a cathode active material for lithium secondary batteries. | |
| Huang et al. | Structural and electrochemical properties of Mg-doped nickel based cathode materials LiNi 0.6 Co 0.2 Mn 0.2− x Mg x O 2 for lithium ion batteries | |
| 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 | |
| KR101689457B1 (en) | Cathode active material for sodium rechargeable batteries and manufacturing method thereof | |
| KR20130063868A (en) | Positive active material for lithium secondary, method for preparing thereof, and lithium secondary battery containing the same | |
| CN104885265B (en) | Using the sodium rechargeable battery of coprecipitation with the preparation method of positive electrode active materials presoma and the sodium rechargeable battery positive electrode active materials presoma thus prepared | |
| JP5733912B2 (en) | Positive electrode for lithium air secondary battery, method for producing the same, and lithium air secondary battery | |
| JP5541670B2 (en) | Lithium air secondary battery and method for producing lithium air secondary battery | |
| KR101970201B1 (en) | Manufacturing method of cathod active material for lithium rechargeable battery and cathod active material made by the same | |
| KR20140119621A (en) | Precusor for lithium rich active material and lithium rich active material made by the same | |
| KR20190113607A (en) | Cathode active material precursor and lithium secondary battery utilizing the same | |
| KR101497190B1 (en) | Lithium metal oxide composite for lithium secondary battery, method for preparing thereof, and lithium secondary battery including the same | |
| CN103956456A (en) | Halogen anion doped lithium-rich positive electrode material as well as preparation method and application of positive electrode material | |
| KR101219395B1 (en) | Anode Material for Lithium Secondary Battery and Manufacturing Method of the Same | |
| JP5700696B2 (en) | Lithium air secondary battery | |
| CN117136443A (en) | Preparation method of double-layer coated lithium-sodium composite lithium-rich manganese-based positive electrode material | |
| CN116741984A (en) | Positive electrode material of sodium ion battery, preparation method of positive electrode material, positive electrode and sodium ion battery | |
| KR20140066051A (en) | Cathode active material, method for preparing the same, and lithium secondary batteries comprising the same | |
| JP5562204B2 (en) | Positive electrode for lithium air secondary battery, method for producing the same, and lithium air secondary battery | |
| KR20160123406A (en) | Positive active material for lithium secondary battery and manufacturing method thereof | |
| CN114933292A (en) | Preparation method and application of lithium iron phosphate | |
| JP5643182B2 (en) | Lithium-air secondary battery and method for producing air electrode thereof | |
| KR100276965B1 (en) | Zinc sulfate (II) aqueous solution secondary battery containing manganese salt (II) and carbon powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150909 |