CN116779847B - Positive electrode plate, preparation method thereof, energy storage device and power utilization device - Google Patents
Positive electrode plate, preparation method thereof, energy storage device and power utilization device Download PDFInfo
- Publication number
- CN116779847B CN116779847B CN202311009583.XA CN202311009583A CN116779847B CN 116779847 B CN116779847 B CN 116779847B CN 202311009583 A CN202311009583 A CN 202311009583A CN 116779847 B CN116779847 B CN 116779847B
- Authority
- CN
- China
- Prior art keywords
- sodium
- positive electrode
- mixed
- source
- iron
- 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.)
- Active
Links
- 238000004146 energy storage Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 94
- 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 77
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 77
- XWQGIDJIEPIQBD-UHFFFAOYSA-J sodium;iron(3+);phosphonato phosphate Chemical compound [Na+].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O XWQGIDJIEPIQBD-UHFFFAOYSA-J 0.000 claims abstract description 42
- BYTVRGSKFNKHHE-UHFFFAOYSA-K sodium;[hydroxy(oxido)phosphoryl] phosphate;iron(2+) Chemical compound [Na+].[Fe+2].OP([O-])(=O)OP([O-])([O-])=O BYTVRGSKFNKHHE-UHFFFAOYSA-K 0.000 claims abstract description 35
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 28
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 24
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 24
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 24
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 12
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 11
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 11
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 84
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 32
- 229910052698 phosphorus Inorganic materials 0.000 claims description 32
- 239000011574 phosphorus Substances 0.000 claims description 32
- 229910052742 iron Inorganic materials 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 239000007774 positive electrode material Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 15
- -1 sodium iron pyrophosphate phosphate Chemical compound 0.000 claims description 15
- 239000006258 conductive agent Substances 0.000 claims description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000011267 electrode slurry Substances 0.000 claims description 12
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 9
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 9
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 9
- 235000011008 sodium phosphates Nutrition 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 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 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 235000010288 sodium nitrite Nutrition 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000006184 cosolvent Substances 0.000 claims description 3
- 229960004887 ferric hydroxide Drugs 0.000 claims description 3
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 15
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 description 18
- 239000012535 impurity Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001035 drying Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 238000007600 charging Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 229910000398 iron phosphate Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000006182 cathode active material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229940048084 pyrophosphate Drugs 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 102100020895 Ammonium transporter Rh type A Human genes 0.000 description 1
- 101100301844 Arabidopsis thaliana RH50 gene Proteins 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 101150107345 Rhag gene Proteins 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- OOIOHEBTXPTBBE-UHFFFAOYSA-N [Na].[Fe] Chemical compound [Na].[Fe] OOIOHEBTXPTBBE-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 239000011645 ferric sodium diphosphate Substances 0.000 description 1
- 235000019851 ferric sodium diphosphate Nutrition 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- BRFMYUCUGXFMIO-UHFFFAOYSA-N phosphono dihydrogen phosphate phosphoric acid Chemical compound OP(O)(O)=O.OP(O)(=O)OP(O)(O)=O BRFMYUCUGXFMIO-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a positive pole piece, a preparation method thereof, an energy storage device and an electric device. The positive electrode plate comprises sodium ferric pyrophosphate, and the sodium ferric pyrophosphate comprisesIn the X-ray diffraction pattern of the sodium iron pyrophosphate, the sodium iron pyrophosphate satisfies: the ratio of the components (I) is less than or equal to 1.4:1 1 +I 2 ）/I 3 The ratio of the components is less than or equal to 2.3:1; wherein I is 1 The diffraction peak intensity corresponding to the diffraction angle 2 theta of the sodium ferric pyrophosphate is 33 DEG, I 2 The intensity of the diffraction peak corresponding to the diffraction angle 2 theta of the ferric sodium phosphate is 32.8 DEG, I 3 The diffraction peak intensity of the ferric sodium phosphate corresponding to the diffraction angle 2 theta of 32.1 degrees is obtained. The sodium ferric phosphate provided by the application has higher purity, and is beneficial to improving the capacity and the cycle performance of the battery.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a positive pole piece, a preparation method thereof, an energy storage device and an electric device.
Background
Energy storage batteries are convenient power converters, with the popularization of green energy sources and the continuous improvement of energy safety and urban air quality improvement requirements, the market of the energy storage batteries is rapidly increased in recent years, but the performance of the current energy storage batteries still needs to be improved, wherein the problems of capacity storage and cycle performance are particularly prominent. For energy storage batteries, the positive electrode material is an important factor in determining the capacity and cycle performance of the battery.
Among the current commercialized cathode materials, the sodium iron phosphate pyrophosphate has good structural stability, and is one of the current battery cathode materials with the most industrialization prospect, however, the existing sodium iron phosphate pyrophosphate has high impurity phase content, low gram capacity and poor cycle performance, and the development of sodium iron phosphate pyrophosphate in the battery field is hindered.
Disclosure of Invention
The present invention is mainly based on the following problems and findings:
in order to promote the development of the sodium iron phosphate cathode active material in the field of batteries, various methods are tried to adjust the sodium iron phosphate cathode active material, however, the existing process method generally adopts a single iron source and a single sodium source to prepare the sodium iron phosphate cathode active material, and the impurity phase content in the product prepared by the process is higher, so that the gram capacity of the sodium iron phosphate is lower and the cycle performance is poor.
The present invention aims to solve at least one of the technical problems in the related art to some extent. To this end, an object of the present invention is to provide a positive electrode sheet including sodium iron pyrophosphate including Na, a method of manufacturing the same, an energy storage device, and an electric device 4 Fe 3 (PO 4 ) 2 P 2 O 7 The impurity phase content of the sodium ferric pyrophosphate is low, so that the capacity and the cycle performance of the battery are improved.
In a first aspect of the present invention, the present invention provides a positive electrode sheet comprising sodium iron pyrophosphate including Na according to an embodiment of the present invention 4 Fe 3 (PO 4 ) 2 P 2 O 7 In the X-ray diffraction pattern of the sodium iron pyrophosphate, the sodium iron pyrophosphate satisfies: 1.4:1≤（I 1 +I 2 ）/I 3 Is less than or equal to 2.3:1, wherein I 1 The diffraction peak intensity corresponding to the diffraction angle 2 theta of the sodium ferric pyrophosphate is 33 DEG, I 2 The intensity of the diffraction peak corresponding to the diffraction angle 2 theta of the ferric sodium phosphate is 32.8 DEG, I 3 The diffraction peak intensity of the ferric sodium phosphate corresponding to the diffraction angle 2 theta of 32.1 degrees is obtained.
According to the positive electrode sheet of the embodiment of the invention, the positive electrode sheet comprises sodium ferric pyrophosphate, and the sodium ferric pyrophosphate comprises Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 In the X-ray diffraction pattern of the sodium ferric phosphate pyrophosphate, a diffraction peak with a diffraction angle of 2 theta of 33 degrees and a diffraction peak with a diffraction angle of 32.8 degrees are respectively corresponding to an electrochemically inactive sodium ferric phosphate impurity phase peak, the sodium ferric phosphate impurity phase is not electrochemically active, and in the process of charging and discharging a battery, the sodium ferric phosphate impurity is easy to react with electrolyte, the interface between an active material and a current collector can be damaged, so that side reactions between an internal material of a battery and the electrolyte are increased, internal resistance polarization is increased, gas generation of the battery is realized, and the capacity and the cycle performance of the battery are further influenced; the diffraction peak at 32.1℃corresponds to sodium ferric pyrophosphate phosphate Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 And the ratio of the sum of the 33 ° diffraction peak intensity and the 32.8 ° diffraction peak intensity to the 32.1 ° diffraction peak intensity is (1.4-2.3): 1, namely, the content of the impurity phase of the sodium iron phosphate without electrochemical activity in the sodium iron phosphate pyrophosphate is lower, thereby being beneficial to improving the capacity and the cycle performance of the battery.
In addition, the positive electrode sheet according to the above embodiment of the present invention may have the following additional technical features:
in some embodiments of the invention, the sodium ferric pyrophosphate phosphate has a gram capacity of 85mAh/g to 100mAh/g at a 0.1C rate. Thereby, the capacity and cycle performance of the battery are advantageously improved.
In some embodiments of the present invention, the positive electrode tab includes a positive electrode current collector and a positive electrode active material layer provided on at least one side of the positive electrode current collector, the positive electrode active material layer including the sodium iron phosphate pyrophosphate.
In some embodiments of the present invention, the positive electrode active material layer further includes a conductive agent and a binder, and the mass ratio of the sodium iron phosphate pyrophosphate to the conductive agent and the binder is (7-9.5): 0.1-2): 0.1-1. Thereby, the capacity and cycle performance of the battery are advantageously improved.
In some embodiments of the invention, the positive electrode active material layer has a thickness of 50 μm to 90 μm. Thereby, the capacity and cycle performance of the battery are advantageously improved.
In a second aspect of the present invention, the present invention provides a method for preparing the positive electrode sheet described above. According to an embodiment of the invention, the method comprises:
mixing a mixed phosphorus source, a mixed sodium source, a mixed iron source and a carbon source to obtain a mixed material, wherein the mixed phosphorus source comprises at least two compounds containing phosphorus elements, the mixed sodium source at least comprises a first sodium source and a second sodium source containing a cosolvent, the mixed iron source comprises at least two compounds containing iron elements, and the mixed sodium source, the mixed iron source and the mixed phosphorus source are mixed according to the molar ratio of sodium elements, iron elements and phosphorus elements of (3.95-4.05): (2.95-3.05): (3.95-4.05);
calcining the mixture at 400-500 ℃ under protective atmosphere to obtain Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 Sodium iron pyrophosphate (S);
the composition includes Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 The sodium ferric pyrophosphate is prepared into positive electrode slurry, and the positive electrode slurry is applied to at least one side of a positive electrode current collector to obtain the positive electrode plate.
Therefore, the positive pole piece of the sodium ferric pyrophosphate with low impurity phase content can be prepared by adopting the method, so that the capacity and the cycle performance of the battery are improved, and the method is simple in process and is beneficial to industrial production.
In some embodiments of the invention, the mixed phosphorus source comprises at least two of sodium dihydrogen phosphate, iron phosphate, and disodium hydrogen phosphate. Thus, the sodium ferric pyrophosphate with higher purity and gram capacity can be obtained, which is beneficial to improving the capacity and the cycle performance of the battery.
In some embodiments of the invention, the first sodium source comprises at least one of sodium acetate, sodium hydroxide, sodium oxalate, sodium nitrite, sodium dihydrogen phosphate, disodium hydrogen phosphate, anhydrous sodium sulfate, sodium citrate, sodium stearate, sodium alginate, and sodium carboxymethyl cellulose. Thus, the sodium ferric pyrophosphate with higher purity and gram capacity can be obtained, which is beneficial to improving the capacity and the cycle performance of the battery.
In some embodiments of the invention, the second sodium source comprises at least one of sodium carbonate, sodium nitrate, sodium hydroxide, and sodium nitrite. Therefore, the calcining temperature in the preparation process of the sodium ferric phosphate is reduced, the sodium ferric phosphate with higher purity and gram capacity is obtained, and the capacity and the cycle performance of the battery are improved.
In some embodiments of the invention, the second sodium source is present in a mass ratio of 30% to 70% based on the total amount of the mixed sodium source. Therefore, the calcining temperature in the preparation process of the sodium ferric phosphate is reduced, the sodium ferric phosphate with higher purity and gram capacity is obtained, and the capacity and the cycle performance of the battery are improved.
In some embodiments of the invention, the mixed iron source comprises at least two of iron phosphate, ferrous oxalate dihydrate, ferric nitrate, elemental iron powder, iron oxide, ferrous oxide, ferric oxide, ferrous sulfate, ferrous ammonium sulfate, and ferric hydroxide. Thus, the sodium ferric pyrophosphate with higher purity and gram capacity can be obtained, which is beneficial to improving the capacity and the cycle performance of the battery.
In some embodiments of the invention, the carbon source comprises at least one of glucose, sucrose, citric acid, ascorbic acid, polyethylene glycol, carbon nanotubes, and reduced graphene oxide.
In some embodiments of the invention, the mixed phosphorus source, the mixed sodium source, the mixed iron source, the carbon source and the dispersing agent are mixed and ball-milled, wherein the ball-milling speed is 300-600 r/min, and the ball-milling time is 3-12 h. Thus, the sodium ferric pyrophosphate with higher purity and gram capacity can be obtained, which is beneficial to improving the capacity and the cycle performance of the battery.
In some embodiments of the invention, the Dv50 of the mixture is less than or equal to 0.8 μm. Thus, the sodium ferric pyrophosphate with higher purity and gram capacity can be obtained, which is beneficial to improving the capacity and the cycle performance of the battery.
In some embodiments of the invention, the dispersant comprises at least one of ethanol, acetone, methanol, and isopropanol. Thus, the sodium ferric pyrophosphate with higher purity and gram capacity can be obtained, which is beneficial to improving the capacity and the cycle performance of the battery.
In some embodiments of the invention, calcining the mixture at a temperature of 400 ℃ to 500 ℃ comprises:
heating the mixture to 400-500 ℃ at a heating rate of 2-6 ℃ per minute, preserving the heat for 3-8 hours, and then cooling to room temperature at a cooling rate of 2-6 ℃ per minute.
Thus, the sodium ferric pyrophosphate with higher purity and gram capacity can be obtained, which is beneficial to improving the capacity and the cycle performance of the battery.
In some embodiments of the invention, the composition includes Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 Before the sodium iron pyrophosphate is prepared into the positive electrode slurry, the sodium iron pyrophosphate is crushed in advance. Thereby, the capacity and cycle performance of the battery are advantageously improved.
In some embodiments of the invention, the crushed sodium iron pyrophosphate Dv50 is 3 μm to 6 μm. Thereby, the capacity and cycle performance of the battery are advantageously improved.
In a third aspect of the invention, the invention provides an energy storage device. Therefore, compared with the prior art, the energy storage device has better comprehensive performance and can have higher capacity and better cycle performance.
In a fourth aspect of the invention, the invention provides an electrical device. Therefore, compared with the prior art, the electricity utilization device comprises the energy storage device, the endurance time and the service life of the battery of the electricity utilization device are longer, and the market satisfaction is higher.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 shows a schematic flow chart of preparing a positive electrode sheet according to an embodiment of the present invention;
FIG. 2 shows an X-ray diffraction pattern of sodium ferric pyrophosphate phosphate of example 1 of the present invention;
FIG. 3 shows a scanning electron microscope image of sodium iron pyrophosphate obtained in example 1 of the present invention;
FIG. 4 shows a constant current charge-discharge curve of the positive electrode sheet of example 1 of the present invention at a 1C rate;
fig. 5 shows a cycle chart of the positive electrode sheet of example 1 of the present invention at 1C magnification.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The following examples are illustrative and are intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect, the present invention provides a positive electrode sheet comprising sodium iron pyrophosphate including Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 In an X-ray diffraction pattern (XRD pattern) of the sodium iron pyrophosphate, the sodium iron pyrophosphate satisfies: the ratio of the components (I) is less than or equal to 1.4:1 1 +I 2 ）/I 3 2.3:1, e.g., (I) 1 +I 2 ）/I 3 May be 1.4:1,1.6:1,1.8:1,2:1,2.1:1,2.3:1, etc. I is that 1 The diffraction peak intensity corresponding to the diffraction angle 2 theta of the sodium ferric pyrophosphate is 33 DEG, I 2 The intensity of the diffraction peak corresponding to the diffraction angle 2 theta of the ferric sodium phosphate is 32.8 DEG, I 3 The diffraction peak intensity of the ferric sodium phosphate corresponding to the diffraction angle 2 theta of 32.1 degrees is obtained.
According to the positive electrode sheet of the embodiment of the invention, the positive electrode sheet comprises sodium ferric pyrophosphate, and the sodium ferric pyrophosphate comprises Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 In the XRD pattern of the sodium ferric phosphate pyrophosphate, a diffraction peak with a diffraction angle of 2 theta of 33 degrees and a diffraction peak with a diffraction angle of 32.8 degrees are respectively corresponding to an electrochemical-inactive sodium ferric phosphate impurity phase peak, the sodium ferric phosphate impurity phase is not electrochemical-active, in the charging and discharging process of a battery, the sodium ferric phosphate impurity is easy to react with electrolyte, the interface between an active material and a current collector can be damaged, side reactions between an internal material of the battery and the electrolyte are increased, internal resistance polarization is increased, gas is generated by the battery, and the like, so that the capacity and the cycle performance of the battery are affected; the diffraction peak at 32.1℃corresponds to sodium ferric pyrophosphate phosphate Na 4 Fe 3 (PO4) 2 P 2 O 7 The ratio of the sum of the diffraction peak intensity of 33 degrees and the diffraction peak intensity of 32.8 degrees to the diffraction peak intensity of 32.1 degrees is (1.4-2.3): 1, namely, the content of the impurity phase of the sodium iron phosphate without electrochemical activity in the sodium iron phosphate pyrophosphate is lower, thereby being beneficial to improving the capacity and the cycle performance of the battery.
According to some embodiments of the invention, the sodium ferric pyrophosphate phosphate has a gram capacity of 85mAh/g to 100mAh/g at a 0.1C rate. For example, the sodium ferric pyrophosphate may have a gram capacity of 85mAh/g,87mAh/g,89mAh/g,91mAh/g,93mAh/g,95mAh/g,97mAh/g,99mAh/g,100mAh/g, etc. Thus, the gram capacity of the sodium iron pyrophosphate phosphate of the present application falls within the above range, which is advantageous for improving the capacity of the battery.
According to some embodiments of the invention, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer provided on at least one side of the positive electrode current collector, the positive electrode active material layer including the sodium iron phosphate pyrophosphate. For example, positive electrode active material layers are formed on both upper and lower sides of the positive electrode current collector. Therefore, the positive electrode plate has excellent electrochemical performance, and is beneficial to improving the capacity and cycle performance of the battery.
According to some embodiments of the present invention, the positive electrode active material layer further includes a conductive agent and a binder, and the mass ratio of the sodium iron phosphate to the conductive agent and the binder is (7-9.5): 0.1-2): 0.1-1, for example, the mass ratio of the sodium iron phosphate, the conductive agent, the binder may be 7:0.2:0.1,8:1:0.5,9.5:2:1, or the like. The inventor finds that if the content of the binder is too small, the stripping force of the pole piece is reduced, the pole piece is further subjected to powder and material dropping, the battery preparation yield and the battery cycle performance are deteriorated, and if the content of the binder is too large, the active material ratio is reduced, the resistance of the pole piece is increased, the ion transmission rate is reduced, and the exertion of the battery capacity and the storage of the battery capacity are affected; if the content of the conductive agent is too small, the impedance of the battery is increased, and if the content of the conductive agent is too large, the dispersion of the slurry is difficult; if the content of sodium iron phosphate is too small, the capacity of the battery is too low, and if the content of sodium iron phosphate is too large, the dispersion of the slurry is difficult, resulting in an increase in the processing difficulty. Therefore, the mass ratio of the sodium ferric pyrophosphate, the conductive agent and the adhesive is limited in the range, and the capacity and the cycle performance of the positive electrode plate can be improved, so that the capacity and the cycle performance of the battery are improved.
It should be noted that, in the present invention, the specific types of the binder and the conductive agent are not particularly limited, and those skilled in the art can flexibly select according to practical situations, for example, the binder may include at least one of styrene-butadiene rubber, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, polyacrylate, carboxymethyl cellulose, and sodium alginate; the conductive agent may include at least one of acetylene black, super-P, carbon nanotubes, carbon fibers, graphene.
According to some embodiments of the present invention, the thickness of the positive electrode active material layer is 50 μm to 90 μm, for example, the thickness of the positive electrode active material layer may be 50 μm,60 μm,70 μm,80 μm,90 μm, etc. When the thickness of the positive electrode active material layer is too small, the overall battery energy density is low; when the thickness of the positive electrode active material layer is too large, electrolyte cannot be fully infiltrated, so that the internal resistance and polarization of the battery are increased, meanwhile, the electrode plate is easy to fall off powder during winding, the stripping force of the positive electrode material is reduced, and the cycle performance of the battery is affected. Thus, the thickness of the positive electrode active material layer is limited to the above range, and the capacity and cycle life of the battery can be improved.
The "thickness of the positive electrode active material layer" in the present application refers to the thickness of the positive electrode active material layer on one side of the positive electrode current collector.
In another aspect of the present invention, the present invention provides a method for preparing the positive electrode sheet described above. In accordance with an embodiment of the present invention, and in conjunction with FIG. 1, the method includes:
s100: mixing a mixed phosphorus source, a mixed sodium source, a mixed iron source and a carbon source
In the step, a mixed material is obtained by mixing a mixed phosphorus source, a mixed sodium source, a mixed iron source and a carbon source.
The mixed phosphorus source comprises at least two compounds containing phosphorus elements, the mixed iron source comprises at least two compounds containing iron elements, and the mixed sodium source at least comprises a first sodium source and a second sodium source containing a cosolvent. Specifically, the method adopts the mixed phosphorus source, the mixed iron source and the mixed sodium source at least comprising the first sodium source and the second sodium source, wherein the second sodium source is used as a fluxing agent in the process of preparing the ferric sodium phosphate, so that the overall synthesis temperature of preparing the ferric sodium phosphate can be reduced, the impurity phase generated by decomposition at high temperature is reduced, and the purity of the ferric sodium phosphate can be improved.
According to some specific examples of the invention, the mixed sodium source, the mixed iron source, and the mixed phosphorus source are mixed in a molar ratio of sodium element, iron element, and phosphorus element of (3.95-4.05): 2.95-3.05): 3.95-4.05. Thus, the above-mentioned composition including Na can be obtained 4 Fe 3 (PO 4 ) 2 P 2 O 7 Sodium iron pyrophosphate (S).
According to some specific examples of the invention, the mixed phosphorus source includes at least two of sodium dihydrogen phosphate, iron phosphate, and disodium hydrogen phosphate. Therefore, the compound is selected as a mixed phosphorus source, which is favorable for obtaining sodium ferric pyrophosphate with higher purity and gram capacity.
According to some specific examples of the present invention, the first sodium source comprises at least one of sodium acetate, sodium hydroxide, sodium oxalate, sodium nitrite, sodium dihydrogen phosphate, disodium hydrogen phosphate, anhydrous sodium sulfate, sodium citrate, sodium stearate, sodium alginate, and sodium carboxymethyl cellulose. Therefore, the compound is selected as the first sodium source, which is favorable for obtaining sodium ferric pyrophosphate with higher purity and gram capacity.
According to some specific examples of the invention, the second sodium source comprises at least one of sodium carbonate, sodium nitrate, sodium hydroxide, and sodium nitrite. In the process of preparing the sodium ferric phosphate, the compound is selected as a second sodium source, so that the phase formation temperature point of the sodium ferric phosphate is reduced, the synthesis temperature is lowered, and the purity of the sodium ferric phosphate is improved.
According to some specific examples of the invention, the second sodium source may be present in a mass ratio of 30% -70% based on the total amount of the mixed sodium sources, e.g., the second sodium source may be present in a mass ratio of 30%,35%,40%,45%,50%,60%,70%, etc. Specifically, the mass ratio of the second sodium source is limited in the range, so that the calcining temperature in the preparation process of the sodium ferric pyrophosphate is reduced, and the sodium ferric pyrophosphate with higher purity and gram capacity is obtained.
According to some specific examples of the present invention, the mixed iron source includes at least two of iron phosphate, ferrous oxalate dihydrate, ferric nitrate, elemental iron powder, iron oxide, ferrous oxide, ferric oxide, ferrous sulfate, ferrous ammonium sulfate, ferric hydroxide, and ferric chloride. Thus, sodium ferric pyrophosphate with higher purity and gram capacity is beneficial to be obtained.
In the embodiment of the present invention, the specific kind of the above carbon source is not particularly limited, and may be arbitrarily selected according to actual needs by a person skilled in the art, and the carbon source includes at least one of glucose, sucrose, citric acid, ascorbic acid, polyethylene glycol, carbon nanotubes and reduced graphene oxide as a preferred embodiment. Thus, sodium ferric pyrophosphate with higher purity and gram capacity is beneficial to be obtained.
According to some specific examples of the present invention, mixing a mixed phosphorus source, a mixed sodium source, a mixed iron source, and a carbon source to obtain a mixed material includes: mixing the mixed phosphorus source, the mixed sodium source, the mixed iron source, the carbon source and the dispersing agent, and performing ball milling, wherein the ball milling speed is 300r/min-600r/min, for example, the ball milling speed can be 300r/min,320r/min,360r/min,400r/min,450r/min,550r/min,600r/min and the like, and the ball milling time can be 3h-12h, for example, the ball milling time can be 3h,3.5h,4h,5h,7h,9h,11h,12h and the like. Further, the ground product is dried in a blast oven at a drying temperature of 30-100 ℃, for example, the drying temperature may be 30 ℃,40 ℃,50 ℃,70 ℃,90 ℃,100 ℃, etc., and the drying time may be 3-12 hours, for example, the drying time may be 3 hours, 5 hours, 9 hours, 10 hours, 11 hours, 12 hours, etc.
According to some specific examples of the invention, the Dv50 of the mixture is less than or equal to 0.8 μm, e.g., the Dv50 of the mixture may be 0.8 μm,0.7 μm,0.6 μm,0.5 μm, etc. The Dv50 refers to the particle size corresponding to the cumulative volume distribution percentage of the sample reaching 50%.
In the embodiment of the present invention, the specific kind of the above-mentioned dispersing agent is not particularly limited, and may be arbitrarily selected according to actual needs by those skilled in the art, so long as the effect of dispersing the mixed phosphorus source, the mixed sodium source, the mixed iron source and the carbon source can be achieved and can be easily removed in the subsequent drying step, for example, at least one of ethanol, acetone, methanol and isopropyl alcohol is included.
S200: calcining the mixture at 400-500 deg.c in protective atmosphere
In the step, the mixed materials are calcined under the protective atmosphere, so that chemical reaction between the mixed materials is carried out to obtain sodium ferric pyrophosphate. According to some specific examples of the present invention, the mixture is heated at a heating rate of 2 ℃/min-4 ℃/min, for example, the heating rate may be 2 ℃/min,3 ℃/min,4 ℃/min, etc., the temperature is raised to a temperature of 400 ℃ to 500 ℃ under a protective atmosphere, for example, the temperature may be 400 ℃,420 ℃,440 ℃,460 ℃,480 ℃,500 ℃ etc., and the temperature is kept for 3h-8h, for example, the temperature keeping time may be 3h,4h,5h,6h,7h,8h, etc., and then cooled to room temperature at a cooling rate of 2 ℃/min-5 ℃/min, for example, the cooling rate may be 2 ℃/min,3 ℃/min,4 ℃/min,5 ℃/min, etc., when the calcining temperature is too high, na may be caused 4 Fe 3 (PO 4 ) 2 P 2 O 7 Partial decomposition into the hetero-phase NaFePO 4 The impurity phase is not electrochemically active, so that the capacity of the whole material is low; when the temperature of calcination is too low, the yield of sodium iron phosphate pyrophosphate is too low. Thus, the condition parameters of calcination are limited to the above ranges, which is advantageous in obtaining sodium iron pyrophosphate having a higher purity and gram capacity.
The specific type of the protective atmosphere in the present invention is not particularly limited, and those skilled in the art can flexibly select the protective atmosphere according to practical situations, for example, calcination may be performed under a nitrogen atmosphere.
S300: will include Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 The sodium ferric pyrophosphate is prepared into positive electrode slurry, and the positive electrode slurry is applied to at least one side of a positive electrode current collector
In this step, the above obtained material including Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 Phosphoric acid pyrophosphate of (2)And mixing the iron sodium, the conductive agent and the binder to obtain positive electrode slurry, and then applying the positive electrode slurry to at least one side of a positive electrode current collector, for example, applying the obtained positive electrode slurry to two sides of the positive electrode current collector, and drying to obtain the positive electrode plate.
According to some specific examples of the invention, the composition includes Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 Before the sodium iron pyrophosphate is prepared into the positive electrode slurry, the sodium iron pyrophosphate is crushed in advance. The specific surface area of the sodium ferric phosphate particles can be increased by crushing the prepared sodium ferric phosphate in advance, which is beneficial to improving the capacity and the cycle performance of the battery. The crushing method is not particularly limited, and may be freely selected as required by those skilled in the art.
According to some specific examples of the invention, the crushed sodium iron pyrophosphate Dv50 is 3 μm-6 μm, for example, the crushed sodium iron pyrophosphate Dv50 may be 3 μm,4 μm,4.5 μm,5 μm,5.5 μm,6 μm, etc. The Dv50 of the crushed sodium iron pyrophosphate is limited to the above range, and the specific surface area of the sodium iron pyrophosphate can be further increased, which is advantageous for improving the capacity and cycle performance of the battery.
It should be noted that the features described above for the positive electrode sheet are also applicable to the method for preparing the positive electrode sheet, and are not described herein.
In a third aspect of the invention, the invention provides an energy storage device. According to the embodiment of the invention, the energy storage device comprises the positive electrode plate or the positive electrode plate prepared by the method, and compared with the prior art, the energy storage device has better comprehensive performance and can have higher capacity and cycle performance.
It should be noted that the energy storage device may include, but is not limited to, a single battery, a battery module, a battery pack, a battery system, and the like. The practical application form of the energy storage device provided in the embodiment of the present application may be, but is not limited to, the listed products, and may also be other application forms, and the embodiment of the present application does not strictly limit the application form of the energy storage device. In the embodiment of the application, the energy storage device is only taken as a multi-core battery for illustration. When the energy storage device is a single battery, the energy storage device may be at least one of a cylindrical battery, a prismatic battery, and the like.
In a fourth aspect of the invention, the invention provides an electrical device. According to the embodiment of the invention, the power utilization device comprises the energy storage device, and compared with the prior art, the power utilization device has longer endurance time and longer service life of a battery, and has higher market satisfaction. For example, the electrical devices may include, but are not limited to, electric only vehicles, hybrid electric vehicles, and the like.
The aspects of the present disclosure will be explained below with reference to examples. Those skilled in the art will appreciate that the following examples are illustrative of the present disclosure and should not be construed as limiting the scope of the present disclosure. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
(1) Sodium dihydrogen phosphate and ferric phosphate are selected as mixed phosphorus sources, sodium carbonate and sodium dihydrogen phosphate are selected as mixed sodium sources, ferrous oxalate dihydrate and ferric phosphate are selected as mixed iron sources, glucose is selected as a carbon source, wherein the first sodium source is sodium dihydrogen phosphate, the second sodium source is sodium carbonate, and the sodium carbonate accounts for 50% of the total mass of the mixed sodium sources. Mixing the mixed sodium source, the mixed iron source, the mixed phosphorus source and the carbon source according to the molar ratio of sodium element, iron element, phosphorus element and carbon element of 4:3:4:3, placing the mixture in a ball mill, adding dispersant ethanol, setting the ball mill revolution number to be 500r/min, placing the ground product in a blast oven for drying after the mixing time is 5 hours, wherein the drying temperature is 60 ℃, and the drying time is 6 hours, so as to obtain a mixed material with Dv50 of 0.8 mu m;
(2) The dried mixture was placed in a nitrogen tube furnace, heated to 420 ℃ at a heating rate of 4 ℃/min and kept for 5 hours, and then cooled to room temperature at a cooling rate of 5 ℃/min, to obtain sodium iron phosphate (XRD pattern of which is shown in FIG. 2). Crushing the obtained sodium ferric pyrophosphate to obtain a crushed sodium ferric pyrophosphate product with the Dv50 of 5 mu m;
(3) Mixing crushed ferric sodium pyrophosphate, a conductive agent Super-P and a binder PVDF according to a mass ratio of 7:2:1, placing the mixed powder into a vacuum stirrer, adding N-methylpyrrolidone, and uniformly stirring to obtain positive electrode active slurry (the solid content is 38%); uniformly coating positive electrode active slurry on the surfaces of two opposite sides of an aluminum foil of a positive electrode current collector, transferring the positive electrode current collector coated with the positive electrode slurry into an oven for drying, and rolling and cutting to obtain a positive electrode plate (the thickness of a positive electrode active material layer on one side of the positive electrode current collector is 70 mu m);
(3) Preparation of button cell: pressing the prepared positive electrode plate to prepare a round electrode plate, then taking the round small sodium plate as a counter electrode, adopting a glass carbon fiber diaphragm isolating membrane, injecting electrolyte (mixing Ethylene Carbonate (EC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) according to a volume ratio of 1:1:1 to obtain a mixed solution, and adding dried sodium salt NaPF into the mixed solution 6 Preparing electrolyte with the concentration of 1mol/L, and assembling to obtain the button cell.
The positive electrode sheets of examples 2 to 22 and comparative example 1 were the same as example 1 except for the experimental parameters (see table 1).
Experimental parameters of the positive electrode sheets of examples 1 to 22 and comparative example 1 of the present application are shown in table 1.
Table 1 experimental parameters of examples 1-22 and comparative example 1
/>
Testing and analysis
Under the same conditions, the sodium iron pyrophosphate produced in examples 1 to 22 and comparative example 1 was subjected to XDR characterization, the sum of the diffraction peak intensities of 33 ° and 32.8 ° in the XRD patterns was calculated, and the diffraction peak intensities of 32.1 ° were counted, and FIG. 2 is an XRD pattern of sodium iron pyrophosphate produced in example 1 and comparative example 1, and as can be seen from FIG. 2, the diffraction peak intensities of 33 ° and 32.8 ° in the XRD pattern of sodium iron pyrophosphate produced in example 1 are significantly lower than those of comparative example 1, indicating that sodium iron pyrophosphate of example 1 has a lower impurity phase. In addition, the gram capacity of sodium iron pyrophosphate phosphate and the button cell prepared in examples 1 to 22 and comparative example 1 above were subjected to the battery capacity and cycle performance test under the same conditions, and the specific test methods were as follows:
battery capacity: and standing the packaged button cell for 12h under the conditions of 25 ℃ and RH50%, and then carrying out constant current charging and discharging for 5 times under the small current of 0.1C, and taking the average discharge capacity of 3-5 circles as the cell capacity of the button cell under the temperature of 0.1C.
Gram capacity of sodium iron pyrophosphate = battery capacity/mass of sodium iron pyrophosphate of the pole piece active material.
Cycle performance: charging the button cell to 4.0V at 25deg.C constant current, and discharging to 1.7V at 1C constant current to obtain discharge specific capacity C of the button cell 0 Then charging and discharging for 250 circles with a constant current of 1C, taking the discharge specific capacity C of the 250 th circle 1 . Battery cycle 250 cycles capacity retention = C 1 /C 0 ×100%。
The test results are shown in Table 2.
Table 2 test results of examples 1-22 and comparative example 1
FIG. 3 is a scanning electron microscope image (SEM image) of sodium iron pyrophosphate obtained in example 1; FIG. 4 is a constant current charge-discharge curve (GCD curve) of the positive electrode sheet of example 1 at a 1C rate, from which the battery obtained in example 1 can be obtained, and the gram capacity obtained by calculation is 98.3mAh/g under the condition that the voltage window is 4.0V-1.7V at a 0.1C charge-discharge rate, so that the negative electrode material provided by the application has a higher gram capacity; fig. 5 is a cycle chart of the positive electrode sheet of example 1 at a 1C rate, from which the battery obtained in example 1 can be obtained, and after 250 cycles of charge and discharge at the 1C rate, the capacity retention rate of the battery is 99.98%, so that the negative electrode material provided by the present application has a better cycle performance.
By combining table 2, the sodium ferric pyrophosphate obtained in examples 1-23 has higher purity and gram capacity, and the battery negative electrode plate prepared by adopting the sodium ferric pyrophosphate provided by the application can improve the capacity and cycle performance of the battery. However, the sodium iron phosphate obtained in comparative example 1 contains a relatively high content of sodium iron phosphate impurities, and compared with examples 1 to 23, the sodium iron phosphate obtained in comparative example 1 has relatively low purity and gram capacity, and the corresponding battery capacity and cycle performance are reduced, because the impurity content in the sodium iron phosphate greatly reduces the stability of sodium iron phosphate, and further influences the cycle performance of the battery, and therefore, the use of the mixed sodium and the mixed iron source provided by the application can greatly improve the cycle performance of sodium iron phosphate, and after 250 cycles at 1C, the battery capacity is close to 100%, which indicates that the sodium iron phosphate prepared by the method provided by the application has relatively good stability and has relatively great potential in commercial application as a high-cycle product.
The test data of the positive electrode plates obtained in comparative examples 1-8 can be obtained, and the mixed phosphorus source, the mixed sodium source and the mixed iron source provided in the embodiment of the application are selected to obtain the positive electrode plate with higher purity and gram capacity, wherein the mixed sodium source can reduce the phase formation temperature point of sodium ferric phosphate, lower the synthesis temperature and improve the purity of sodium ferric phosphate.
Test data of the positive electrode sheets obtained in comparative example 1 and examples 9 to 11 are available, and the molar ratio of sodium element, iron element, phosphorus element and carbon element in the mixed sodium source, the mixed iron source, the mixed phosphorus source and the carbon source is limited to be within the range of the examples of the present application, which is favorable for obtaining the positive electrode sheet with higher purity and gram capacity.
Test data of the negative electrode materials obtained in comparative example 1, example 12 and examples 14 to 16 were available, and the Dv50 of the mixture was limited to a range of not more than 0.8 μm, which was advantageous for improving the purity of sodium iron pyrophosphate.
Test data of the positive electrode sheet obtained in comparative example 1 and examples 17 to 22 are available, and calcination parameters and Dv50 of crushed materials are limited within the range of examples of the present application, which is favorable for obtaining sodium ferric pyrophosphate with higher purity and gram capacity, and further can improve the capacity and cycle performance of the battery.
In the description of the present specification, the descriptions of the terms "one embodiment," "some embodiments," "examples," "particular examples," "some embodiments," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (11)
1. The preparation method of the positive electrode plate is characterized by comprising the following steps:
mixing a mixed phosphorus source, a mixed sodium source, a mixed iron source and a carbon source to obtain a mixed material, wherein the mixed phosphorus source comprises at least two compounds containing phosphorus elements, the mixed sodium source at least comprises a first sodium source and a second sodium source containing a cosolvent, the mixed iron source comprises at least two compounds containing iron elements, and the mixed sodium source, the mixed iron source and the mixed phosphorus source are mixed according to the molar ratio of sodium elements, iron elements and phosphorus elements of (3.95-4.05): (2.95-3.05): (3.95-4.05);
calcining the mixture at 400-500 ℃ under protective atmosphere to obtain Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 Sodium iron pyrophosphate (S);
the composition includes Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 Preparing positive electrode slurry from sodium ferric pyrophosphate, and applying the positive electrode slurry to at least one side of a positive electrode current collector to obtain the positive electrode plate;
the mixed phosphorus source comprises at least two of sodium dihydrogen phosphate, ferric phosphate and disodium hydrogen phosphate;
the first sodium source comprises at least one of sodium acetate, sodium hydroxide, sodium oxalate, sodium nitrite, sodium dihydrogen phosphate, disodium hydrogen phosphate, anhydrous sodium sulfate, sodium citrate, sodium stearate, sodium alginate and sodium carboxymethylcellulose;
the second sodium source comprises at least one of sodium carbonate, sodium nitrate, sodium hydroxide, and sodium nitrite;
the mass ratio of the second sodium source is 30-70% based on the total amount of the mixed sodium sources;
the mixed iron source comprises at least two of ferric phosphate, ferrous oxalate dihydrate, ferric nitrate, elemental iron powder, ferric oxide, ferrous oxide, ferric oxide, ferrous sulfate, ferrous ammonium sulfate, ferric hydroxide and ferric chloride.
2. The method of claim 1, wherein the carbon source comprises at least one of glucose, sucrose, citric acid, ascorbic acid, polyethylene glycol, carbon nanotubes, and reduced graphene oxide.
3. The method according to claim 1, wherein the mixed phosphorus source, the mixed sodium source, the mixed iron source, the carbon source and the dispersing agent are mixed and ball-milled, the ball-milling speed is 300-600 r/min, and the ball-milling time is 3-12 h.
4. The method of claim 1, wherein calcining the mixture at a temperature of 400 ℃ to 500 ℃ comprises:
heating the mixture to 400-500 ℃ at a heating rate of 2-4 ℃ per minute, preserving the heat for 3-8 hours, and then cooling to room temperature at a cooling rate of 2-5 ℃ per minute.
5. A positive electrode sheet, characterized in that the positive electrode sheet is produced by the method of any one of claims 1 to 4, the positive electrode sheet comprises sodium iron pyrophosphate, and the sodium iron pyrophosphate comprises Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 In the X-ray diffraction pattern of the sodium iron pyrophosphate, the sodium iron pyrophosphate satisfies: the ratio of the components (I) is less than or equal to 1.4:1 1 +I 2 ）/I 3 ≤2.3:1；
Wherein I is 1 The diffraction peak intensity corresponding to the diffraction angle 2 theta of the sodium ferric pyrophosphate is 33 DEG, I 2 The intensity of the diffraction peak corresponding to the diffraction angle 2 theta of the ferric sodium phosphate is 32.8 DEG, I 3 The diffraction peak intensity of the ferric sodium phosphate corresponding to the diffraction angle 2 theta of 32.1 degrees is obtained.
6. The positive electrode sheet according to claim 5, wherein the sodium iron pyrophosphate phosphate has a gram capacity of 85mAh/g to 100mAh/g at a 0.1C rate.
7. The positive electrode sheet according to claim 5 or 6, characterized in that the positive electrode sheet comprises a positive electrode current collector and a positive electrode active material layer provided on at least one side of the positive electrode current collector, the positive electrode active material layer comprising the sodium iron pyrophosphate phosphate.
8. The positive electrode sheet according to claim 7, wherein the positive electrode active material layer further comprises a conductive agent and a binder, and a mass ratio of the sodium iron phosphate pyrophosphate to the conductive agent and the binder is (7-9.5): (0.1-2): (0.1-1).
9. The positive electrode sheet according to claim 7, wherein the positive electrode active material layer has a thickness of 50 μm to 90 μm.
10. An energy storage device comprising a positive electrode sheet obtained by the method of any one of claims 1 to 4 or a positive electrode sheet according to any one of claims 5 to 9.
11. An electrical device comprising the energy storage device of claim 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311009583.XA CN116779847B (en) | 2023-08-11 | 2023-08-11 | Positive electrode plate, preparation method thereof, energy storage device and power utilization device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311009583.XA CN116779847B (en) | 2023-08-11 | 2023-08-11 | Positive electrode plate, preparation method thereof, energy storage device and power utilization device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116779847A CN116779847A (en) | 2023-09-19 |
| CN116779847B true CN116779847B (en) | 2024-01-23 |
Family
ID=87993310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311009583.XA Active CN116779847B (en) | 2023-08-11 | 2023-08-11 | Positive electrode plate, preparation method thereof, energy storage device and power utilization device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116779847B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115064695A (en) * | 2022-07-15 | 2022-09-16 | 湖北万润新能源科技股份有限公司 | Full-iron-based sodium ion battery and preparation method thereof |
| CN116002650A (en) * | 2022-12-28 | 2023-04-25 | 浙江钠创新能源有限公司 | Preparation method of composite ferric sodium pyrophosphate polyanion type positive electrode material and application of composite ferric sodium pyrophosphate polyanion type positive electrode material in sodium ion battery |
| CN116230923A (en) * | 2021-12-03 | 2023-06-06 | 中国科学院过程工程研究所 | Carbon-coated sodium ferric pyrophosphate cathode material and preparation method and application thereof |
| CN116487545A (en) * | 2022-09-28 | 2023-07-25 | 中南大学 | Carbon composite ferric sodium pyrophosphate composite material, preparation method thereof and application thereof in sodium ion battery |
| CN116534830A (en) * | 2023-05-29 | 2023-08-04 | 浙江鑫钠新材料科技有限公司 | Sodium ion battery positive electrode material and preparation method and application thereof |
| CN116553505A (en) * | 2022-01-29 | 2023-08-08 | 中国科学院大连化学物理研究所 | Iron phosphate-based polyanion positive electrode material, preparation and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2623459A4 (en) * | 2010-09-29 | 2015-10-14 | Oceans King Lighting Science | Lithium iron phosphate composite material, production method and use thereof |
| CN106030888A (en) * | 2014-02-21 | 2016-10-12 | 住友化学株式会社 | Sodium secondary battery |
-
2023
- 2023-08-11 CN CN202311009583.XA patent/CN116779847B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116230923A (en) * | 2021-12-03 | 2023-06-06 | 中国科学院过程工程研究所 | Carbon-coated sodium ferric pyrophosphate cathode material and preparation method and application thereof |
| CN116553505A (en) * | 2022-01-29 | 2023-08-08 | 中国科学院大连化学物理研究所 | Iron phosphate-based polyanion positive electrode material, preparation and application |
| CN115064695A (en) * | 2022-07-15 | 2022-09-16 | 湖北万润新能源科技股份有限公司 | Full-iron-based sodium ion battery and preparation method thereof |
| CN116487545A (en) * | 2022-09-28 | 2023-07-25 | 中南大学 | Carbon composite ferric sodium pyrophosphate composite material, preparation method thereof and application thereof in sodium ion battery |
| CN116002650A (en) * | 2022-12-28 | 2023-04-25 | 浙江钠创新能源有限公司 | Preparation method of composite ferric sodium pyrophosphate polyanion type positive electrode material and application of composite ferric sodium pyrophosphate polyanion type positive electrode material in sodium ion battery |
| CN116534830A (en) * | 2023-05-29 | 2023-08-04 | 浙江鑫钠新材料科技有限公司 | Sodium ion battery positive electrode material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 钠离子电池用铁基正极材料的研究进展;张洪霞;李少芳;赵博;侯宪坤;吴兴隆;;无机化学学报(07);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116779847A (en) | 2023-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109192953B (en) | High-rate spherical lithium iron phosphate carbon composite cathode material and preparation method thereof | |
| US8865349B2 (en) | Method of producing positive electrode active material and nonaqueous electrolyte battery using the same | |
| CN103456936A (en) | Sodium ion secondary battery, and layered titanate active substance, electrode material, anode and cathode adopted by the sodium ion secondary battery, and preparation method of the layered titanate active substance | |
| Yuan et al. | Surfactant-assisted hydrothermal synthesis of V2O5 coated LiNi1/3Co1/3Mn1/3O2 with ideal electrochemical performance | |
| CN110589791B (en) | Preparation method of tin-doped titanium pyrophosphate | |
| CN110931781A (en) | Preparation method and application of biomass carbon/sodium iron fluorophosphate composite material | |
| CN114665058A (en) | Preparation method of lithium ion battery anode material lithium iron manganese phosphate | |
| CN113479860B (en) | SbPO (styrene-ethylene-propylene-diene monomer) 4 Preparation method of nitrogen-doped carbon composite material | |
| CN110875473A (en) | Positive electrode active material, preparation method thereof and sodium ion battery | |
| CN111029560A (en) | Spinel structure positive active material doped with sodium ions in gradient manner and preparation method thereof | |
| CN111009659A (en) | Preparation method and application of biomass carbon/poly-sodium manganese fluorophosphate composite material | |
| CN103618065B (en) | LiFePO 4 material and preparation method thereof | |
| CN112701281A (en) | Composite olivine structure positive electrode material and preparation method and application thereof | |
| CN103378355A (en) | Alkali metal secondary battery as well as negative active substance, negative material and negative electrode thereof, and preparation method of negative active substance | |
| CN109980221A (en) | A kind of anode material for high-voltage lithium ion and its preparation method and application | |
| CN116477661A (en) | Lithium supplementing material and preparation method and application thereof | |
| CN102364728B (en) | Positive electrode material for lithium ion cells and preparation method thereof | |
| CN116779847B (en) | Positive electrode plate, preparation method thereof, energy storage device and power utilization device | |
| CN114620702A (en) | Preparation method of positive electrode material, positive plate and sodium ion battery | |
| CN109461897B (en) | Preparation method of spindle-shaped carbon-coated vanadium-based positive electrode material | |
| CN112018364A (en) | Equimolar hydrothermal method for preparing LiMnPO4Method for preparing composite material and application of composite material in lithium battery | |
| CN116779778B (en) | Positive electrode plate, preparation method thereof, energy storage device and power utilization device | |
| CN111162253A (en) | Preparation method of metal oxide coated long-cycle lithium nickel manganese oxide electrode material | |
| CN114583137B (en) | Method for modifying carbon surface by sulfur doped phosphorus and application thereof | |
| CN116741944A (en) | Positive electrode plate, preparation method thereof, energy storage device and power utilization device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |