CN114597376A - 一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法 - Google Patents
一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法 Download PDFInfo
- Publication number
- CN114597376A CN114597376A CN202210282867.5A CN202210282867A CN114597376A CN 114597376 A CN114597376 A CN 114597376A CN 202210282867 A CN202210282867 A CN 202210282867A CN 114597376 A CN114597376 A CN 114597376A
- Authority
- CN
- China
- Prior art keywords
- carbon
- phosphate
- coated
- ferrous phosphate
- crystal water
- 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.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 95
- 229910000155 iron(II) phosphate Inorganic materials 0.000 title claims abstract description 78
- 229940116007 ferrous phosphate Drugs 0.000 title claims abstract description 76
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 54
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000005245 sintering Methods 0.000 claims abstract description 54
- 239000013078 crystal Substances 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 33
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 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 25
- 239000008103 glucose Substances 0.000 claims description 25
- 239000011268 mixed slurry Substances 0.000 claims description 24
- 238000004321 preservation Methods 0.000 claims description 22
- 238000001694 spray drying Methods 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 14
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 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 5
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 239000006245 Carbon black Super-P Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910009112 xH2O Inorganic materials 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 238000005056 compaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 28
- 239000002245 particle Substances 0.000 description 12
- 238000000227 grinding Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229960004793 sucrose Drugs 0.000 description 3
- 239000005696 Diammonium phosphate Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- 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
- H01M10/052—Li-accumulators
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明涉及锂离子电池正极材料制备技术领域,具体公开了一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法,该方法包括:将自制磷酸亚铁与碳源混合,在氮气下低温烧结,去除部分结晶水,得到碳包覆含少量结晶水的磷酸亚铁;再将磷酸亚铁与锂源、磷源、多种碳源混合均匀,调整至合适的铁磷比0.960~0.975和碳含量1.5%~1.8%;再将浆料进行干燥后得到粉料;粉料通过两段升温曲线烧结,自然冷却后粉碎,得到碳包覆的磷酸铁锂材料。该方法制备的纳米级磷酸铁锂材料具有高压实,高容量,长循环性能。
Description
技术领域
本发明属于锂离子电池电极材料制备技术领域,具体涉及一种由磷酸亚铁制备磷酸铁锂材料的方法。
背景技术
橄榄石结构的磷酸铁锂材料具有较高的理论容量170mAh/g和较高的放电电压3.4V,充放电过程中锂离子脱嵌对其固体结构影响很小,循环寿命长,且资源丰富、价格低廉、对环境污染小、化学稳定性好等优点,被认为是最具有应用开发价值的锂离子电池正极材料之一。
通过自制磷酸亚铁材料,可以制备出不同铁磷比的水合磷酸亚铁源材料,再通过包覆有机碳源,在氮气气氛中低温烧结,既可以除去部分结晶水,提高原来中铁和磷的比例,提高原材料利用率,从而提高成品质量;又可以使得有机碳源分解,在磷酸亚铁材料表面包覆一层导电碳,提高材料的导电性。通过添加固相和液相两种磷源,固相为磷酸锂,液相为磷酸二氢铵、磷酸氢二铵和磷酸中的一种或多种,既可以为合成磷酸铁锂提供一定稳定的框架结构,又可以均匀的混合磷源。
结果发现,含较少结晶水碳包覆的磷酸亚铁与传统磷酸铁锂材料相比,具有更高的放电容量,更长的循环寿命。
发明内容
本发明的目的是为了解决磷酸铁锂材料成本高问题,提供一种由磷酸亚铁制备磷酸铁锂材料的方法。本发明方法先对前驱体进行处理,去除部分结晶水,包覆导电性良好的碳层,得到碳包覆磷酸亚铁材料;再通过添加锂源、铁源、磷源和碳源,能够制备出低成本,高容量,长循环的磷酸铁锂材料。
为了实现上述目的,本发明采取如下技术方案:
一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法,包括如下步骤:
(1)将含结晶水的磷酸亚铁与碳源球磨成粉末;
(2)将步骤(1)的粉末在保护气氛下烧结去除部分结晶水,得到碳包覆含结晶水的磷酸亚铁;
(3)将步骤(2)中的碳包覆含结晶水的磷酸亚铁与磷酸锂、固相磷源、液相磷源、碳源、分散剂混合均匀,得混合浆料;
(4)将步骤(3)中的混合浆料干燥后在惰性气氛中烧结,之后自然冷却并粉碎,即得到所述碳包覆的纳米磷酸铁锂材料。
优选的,步骤(1)中,所述含结晶水的磷酸亚铁中,Fe/P为1.46~1.50。
优选的,步骤(1)中,所述碳源为有机碳源,所述有机碳源为选自葡萄糖、PEG、蔗糖、淀粉或柠檬酸中的一种或多种,所述球磨方式为湿法球磨或干法球磨。更有选的,所述有机碳源为PEG。
优选的,步骤(2)中,所述保护气氛采用的气体为选自氮气、氩气或氦气中的至少一种;所述烧结温度为250~400℃,烧结时间为3~6h,更优选烧结温度为300~400℃,烧结时间为3~5h;所述的碳包覆含结晶水的磷酸亚铁中磷酸亚铁化学式为Fe3(PO4)2*xH2O,其中x=2~4。
优选的,步骤(3)中,所述固相磷源为磷酸锂;所述液相磷源为磷酸二氢铵、磷酸氢二铵、磷酸中的一种或多种,所述碳源为有机碳源和无机碳源,所述分散剂为水,所述混合浆料中铁磷比为0.960~0.975。
优选的,步骤(3)中,所述有机碳源为葡萄糖、PEG、蔗糖、淀粉或柠檬酸中的一种或多种,更优选为葡萄糖或PEG中的一种或两种;所述无机碳源为乙炔黑、石墨、Super-P、碳纳米管中的一种或多种,所述混合浆料中铁磷比为0.960-0.975。
优选的,在步骤(4)中,所述干燥的方式为喷雾干燥、鼓风干燥或真空干燥中的一种或多种;所述喷雾干燥的气体为选自氮气、氩气和氦气中的至少一种,所述喷雾干燥的进风温度为130~150℃,出风温度为80~100℃。
优选的,在步骤(4)中,所述惰性气氛采用的气体为选自氮气、氩气和氦气中的至少一种;所述烧结过程分为两段,第一段温度为750~770℃,保温时间为7h,第二段温度为760~780℃,保温时间为1h;所述粉末烧结后粉碎至粒度为0.8-3um。
另外,本发明还要求保护由所述方法制备得到的碳包覆磷酸铁锂材料以及所述碳包覆磷酸铁锂材料作为锂离子电池正极材料的应用。
与现有技术相比,本发明具有如下优点和有益效果:
1、本发明通过将磷酸亚铁与碳源混合,在低温下烧结,可以去除部分结晶水,提高原材料中铁和磷的比例,进一步提高原材料的利用率;进一步在氮气气氛下低温烧结,可以使碳源分解在磷酸亚铁表面形成碳包覆层,既可以抑制二价铁的氧化,将三价铁还原成二价铁;又可以提高材料的导电性;还可以抑制颗粒的过度长大,形成大小颗粒均一的碳包覆磷酸铁锂材料。
2、本发明通过磷酸亚铁、磷酸锂为原材料,能够降低合成成本;再通过添加磷酸二氢铵、磷酸氢二铵、磷酸作为补充液相磷源,调整到合适的铁磷比。
3、本发明通过添加有机碳源和无机碳源两种碳源,有机碳源在氮气气氛中可以提供还原性气体,降低磷酸铁锂中三价铁的含量,还可以提供包覆碳,进一步提高磷酸铁锂材料的导电性。无机碳源混合在浆料中,能够提供多支链状导电网络,从而减少磷酸铁锂材料的物理内阻,提供电子传导性。
4、本发明通过两段烧结温度曲线,第一段烧结过程,能够形成小颗粒的磷酸铁锂材料;第二段烧结温度提温,能够促使磷酸铁锂颗粒的长大,提高磷酸铁锂材料的压实。
5、本发明提供的方法制备的碳包覆磷酸铁锂材料,材料性能优异:1C首次放电容量可达148.39mAh/g,1C充放电循环150圈放电容量可达141.84mAh/g,1C充放电循环150圈后容量保持率可到95.59%。
附图说明
图1是本发明实施例1中自制铁磷比为1.46的磷酸亚铁的SEM图谱;
图2是本发明实施例1中自制铁磷比为1.46的磷酸亚铁的XRD图谱;
图3是本发明实施例1中碳包覆含结晶水的磷酸亚铁的SEM图谱;
图4是本发明实施例1中制备的磷酸铁锂材料的SEM谱图;
图5是本发明实施例1中制备的磷酸铁锂材料的XRD谱图;
图6是本发明实施例1中制备样品的循环曲线图。
具体实施方式
以下结合附图对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。
以下将通过实施例对本发明进行详细描述,但本发明的保护范围并不仅限于此。
实施例1
一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法,包括如下步骤:
(1)将铁磷比为1.46含结晶水的磷酸亚铁与葡萄糖球磨成粉末,葡萄糖与磷酸亚铁的质量比为3%;
(2)将步骤(1)的粉末在氮气氛下400℃保温2小时烧结去除部分结晶水,得到碳包覆含结晶水的磷酸亚铁;
(3)将步骤(2)中的碳包覆含结晶水的磷酸亚铁与磷酸锂1000g、磷酸二氢铵8g、PEG89g、乙炔黑10g、水2500g混合均匀2h,得混合浆料;
(4)将步骤(3)中的混合浆料在氮气气氛下进行喷雾干燥,进风温度为150℃,出风温度为100℃,得到干燥粉末,之后在氮气气氛中烧结,第一段烧结温度为750℃,保温时间7h;第二段烧结温度为760℃,保温时间为1h,最后自然冷却并粉碎,控制粉碎粒径D50=1.6um,即得到所述碳包覆的纳米磷酸铁锂材料。
实施例2
一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法,包括如下步骤:
(1)将铁磷比为1.48含结晶水的磷酸亚铁与葡萄糖球磨成粉末,葡萄糖与磷酸亚铁的质量比为2%;
(2)将步骤(1)的粉末在氮气氛下380℃保温2.5小时烧结去除部分结晶水,得到碳包覆含结晶水的磷酸亚铁;
(3)将步骤(2)中的碳包覆含结晶水的磷酸亚铁1000g与磷酸锂294g、磷酸氢二铵6g、葡萄糖99g、乙炔黑4g、水2500g混合均匀3h,得混合浆料;
(4)将步骤(3)中的混合浆料在氮气气氛下进行喷雾干燥,进风温度为145℃,出风温度为90℃,得到干燥粉末,之后在氮气气氛中烧结,第一段烧结温度为755℃,保温时间7h;第二段烧结温度为765℃,保温时间为1h,最后自然冷却并粉碎,控制粉碎粒径D50=1.3um,即得到所述碳包覆的纳米磷酸铁锂材料。
实施例3
一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法,包括如下步骤:
(1)将铁磷比为1.5含结晶水的磷酸亚铁与葡萄糖球磨成粉末,萄糖与磷酸亚铁的质量比为2.5%;
(2)将步骤(1)的粉末在氮气氛下350℃保温3小时烧结去除部分结晶水,得到碳包覆含结晶水的磷酸亚铁;
(3)将步骤(2)中的碳包覆含结晶水的磷酸亚铁1000g与磷酸锂294g、磷酸4g、葡萄糖84g、石墨4g、水2500g混合均匀4h,得混合浆料;
(4)将步骤(3)中的混合浆料在氮气气氛下进行喷雾干燥,进风温度为130℃,出风温度为95℃,得到干燥粉末,之后在氮气气氛中烧结,第一段烧结温度为760℃,保温时间7h;第二段烧结温度为770℃,保温时间为1h,最后自然冷却并粉碎,控制粉碎粒径D50=1.6um,即得到所述碳包覆的纳米磷酸铁锂材料。
实施例4
一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法,包括如下步骤:
(1)将铁磷比为1.46含结晶水的磷酸亚铁与葡萄糖球磨成粉末,葡萄糖与磷酸亚铁的质量比为2%;
(2)将步骤(1)的粉末在氮气氛下400℃保温2小时烧结去除部分结晶水,得到碳包覆含结晶水的磷酸亚铁;
(3)将步骤(2)中的碳包覆含结晶水的磷酸亚铁1000g与磷酸锂294g、磷酸二氢铵6g、PEG89g、碳纳米管12g、水2500g混合均匀2h,得混合浆料;
(4)将步骤(3)中的混合浆料在氮气气氛下进行喷雾干燥,进风温度为140℃,出风温度为80℃,得到干燥粉末,之后在氮气气氛中烧结,第一段烧结温度为770℃,保温时间7h;第二段烧结温度为780℃,保温时间为1h,最后自然冷却并粉碎,控制粉碎粒径D50=1.2um,即得到所述碳包覆的纳米磷酸铁锂材料。
实施例5
一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法,包括如下步骤:
(1)将铁磷比为1.47含结晶水的磷酸亚铁与葡萄糖球磨成粉末,萄糖与磷酸亚铁的质量比为3.5%;
(2)将步骤(1)的粉末在氮气氛下360℃保温3小时烧结去除部分结晶水,得到碳包覆含结晶水的磷酸亚铁;
(3)将步骤(2)中的碳包覆含结晶水的磷酸亚铁1000g与磷酸锂294g、磷酸氢二铵6g、蔗糖44g、Super-P10g、水2500g混合均匀3h,得混合浆料;
(4)将步骤(3)中的混合浆料在氮气气氛下进行喷雾干燥,进风温度为135℃,出风温度为85℃,得到干燥粉末,之后在氮气气氛中烧结,第一段烧结温度为760℃,保温时间7h;第二段烧结温度为770℃,保温时间为1h,最后自然冷却并粉碎,控制粉碎粒径D50=1.5um,即得到所述碳包覆的纳米磷酸铁锂材料。
实施例6
一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法,包括如下步骤:
(1)将铁磷比为1.49含结晶水的磷酸亚铁与葡萄糖球磨成粉末,葡萄糖与磷酸亚铁的质量比为3%;
(2)将步骤(1)的粉末在氮气氛下280℃保温4小时烧结去除部分结晶水,得到碳包覆含结晶水的磷酸亚铁;
(3)将步骤(2)中的碳包覆含结晶水的磷酸亚铁1000g与磷酸锂294g、磷酸8g、柠檬酸88g、石墨烯12g、水2500g混合均匀3h,得混合浆料;
(4)将步骤(3)中的混合浆料在氮气气氛下进行喷雾干燥,进风温度为140℃,出风温度为85℃,得到干燥粉末,之后在氮气气氛中烧结,第一段烧结温度为755℃,保温时间7h;第二段烧结温度为765℃,保温时间为1h,最后自然冷却并粉碎,控制粉碎粒径D50=1.8um,即得到所述碳包覆的纳米磷酸铁锂材料。
对比例1
与实施例不同的是,在步骤(1)中,自制磷酸亚铁的铁磷比为1.4,为制备铁磷比合适的磷酸铁锂材料,需要补充的不是磷源,而是铁源。
一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法,包括如下步骤:
(1)将铁磷比为1.4含结晶水的磷酸亚铁与葡萄糖球磨成粉末,葡萄糖与磷酸亚铁的质量比为2%;
(2)将步骤(1)的粉末在氮气氛下400℃保温2小时烧结去除部分结晶水,得到碳包覆含结晶水的磷酸亚铁;
(3)将步骤(2)中的碳包覆含结晶水的磷酸亚铁1000g与磷酸锂312g、氧化铁30g、PEG93g、乙炔黑10g、水2500g混合均匀2h,得混合浆料;
(4)将步骤(3)中的混合浆料在氮气气氛下进行喷雾干燥,进风温度为150℃,出风温度为100℃,得到干燥粉末,之后在氮气气氛中烧结,第一段烧结温度为750℃,保温时间7h;第二段烧结温度为760℃,保温时间为1h,最后自然冷却并粉碎,控制粉碎粒径D50=1.6um,即得到所述碳包覆的纳米磷酸铁锂材料。
对比例2
与实施例的方法不同的是,将步骤(1)的粉末在氮气氛下30℃保温2小时。
一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法,包括如下步骤:
(1)将铁磷比为1.46含结晶水的磷酸亚铁与葡萄糖球磨成粉末,葡萄糖与磷酸亚铁的质量比为2%;
(2)将步骤(1)的粉末在氮气氛下30℃保温2小时,未能烧结去除结晶水,只是磷酸亚铁与葡萄糖的混合物;
(3)将步骤(2)中的磷酸亚铁与葡萄糖的混合物1000g与磷酸锂245g、磷酸二氢铵8g、PEG74g、乙炔黑10g和水2500g混合均匀2h,得混合浆料,调整成品磷酸铁锂的铁磷比0.965和碳含量1.5%;
(4)将步骤(3)中的混合浆料在氮气气氛下进行喷雾干燥,进风温度为150℃,出风温度为100℃,得到干燥粉末,之后在氮气气氛中烧结,第一段烧结温度为750℃,保温时间7h;第二段烧结温度为760℃,保温时间为1h,最后自然冷却并粉碎,控制粉碎粒径D50=1.6um,即得到所述碳包覆的纳米磷酸铁锂材料。
测试例
将实施例1-6和对比例1-2制备的磷酸铁锂正极材料与Super-P以及PVDF按照质量比80:10:10分散在NMP中,球磨分散均匀后,涂覆在铝箔上,真空烘干,制得正极极片,电解液为1mol/L的LiPF6,其中溶剂体积比为EC:DMC:EMC=1:1:1(体积比),隔膜为Celgard聚丙烯膜,金属锂片为负极,共同组装成为扣电半电池。测试电压范围为2.5V~3.9V,以恒流恒压充电方式充电至3.9V,以恒流放电方式进行放电至2.5V,充放电电流为0.2C循环3cycle;再以1C充放电电流,循环150cycle,截止条件同0.2C。测试结果如表1所示。
表1
通过表1的结果可以看出,采用本发明所述的方法制备的碳包覆磷酸铁锂材料制备成锂离子电池后,1C首次放电比容量、1C充放电循环150周放电比容量和1C充放电循环150周容量保持率均有所提高。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的内容,均属于本发明的保护范围。
Claims (10)
1.一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法,其特征在于,包括如下步骤:
(1)将含结晶水的磷酸亚铁与碳源球磨成粉末;
(2)将步骤(1)的粉末在保护气氛下烧结去除部分结晶水,得到碳包覆含结晶水的磷酸亚铁;
(3)将步骤(2)中的碳包覆含结晶水的磷酸亚铁与磷酸锂、固相磷源、液相磷源、碳源、分散剂混合均匀,得混合浆料;
(4)将步骤(3)中的混合浆料干燥后在惰性气氛中烧结,之后自然冷却并粉碎,即得到所述碳包覆的纳米磷酸铁锂材料。
2.根据权利要求1所述的方法,其特征在于,步骤(1)中,所述含结晶水的磷酸亚铁中,Fe/P摩尔比为1.46~1.50;碳源与磷酸亚铁的质量比为2%~3.5%。
3.根据权利要求1所述的方法,其特征在于,在步骤(1)中,所述碳源为有机碳源,所述有机碳源为选自葡萄糖、PEG、蔗糖、淀粉或柠檬酸中的一种或多种,所述球磨方式为湿法球磨或干法球磨。
4.根据权利要求1所述的方法,其特征在于,在步骤(2)中,所述保护气氛采用的气体为选自氮气、氩气或氦气中的至少一种;所述烧结温度为250~400℃,烧结时间为3~6h;所述的碳包覆含结晶水的磷酸亚铁中磷酸亚铁化学式为Fe3(PO4)2*xH2O,其中x=2~4。
5.根据权利要求1所述的方法,其特征在于,在步骤(3)中,所述固相磷源为磷酸锂;所述液相磷源为磷酸二氢铵、磷酸氢二铵、磷酸中的一种或多种,所述碳源为有机碳源和无机碳源,所述分散剂为水,所述混合浆料中铁磷比为0.960~0.975。
6.根据权利要求5所述的方法,其特征在于,所述有机碳源为葡萄糖、PEG、蔗糖、淀粉或柠檬酸中的一种或多种;所述无机碳源为乙炔黑、石墨、Super-P、碳纳米管中的一种或多种,所述混合浆料中铁磷比为0.960-0.975。
7.根据权利要求1所述的方法,其特征在于,在步骤(4)中,所述干燥的方式为喷雾干燥、鼓风干燥或真空干燥中的一种或多种;所述喷雾干燥的气体为选自氮气、氩气和氦气中的至少一种,所述喷雾干燥的进风温度为130~150℃,出风温度为80~100℃。
8.根据权利要求1所述的方法,其特征在于,在步骤(4)中,所述惰性气氛采用的气体为选自氮气、氩气和氦气中的至少一种;所述烧结过程分为两段,第一段温度为750~770℃,保温时间为7h,第二段温度为760~780℃,保温时间为1h;所述粉末烧结后粉碎至粒度为0.8-3um。
9.一种由权利要求1-8任一项所述方法制备得到的碳包覆磷酸铁锂材料。
10.一种权利要求9所述碳包覆磷酸铁锂材料作为锂离子电池正极材料的应用。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210282867.5A CN114597376B (zh) | 2022-03-22 | 2022-03-22 | 一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法 |
KR1020220136032A KR20230137807A (ko) | 2022-03-22 | 2022-10-20 | 인산제1철로 탄소 코팅 인산철리튬 재료를 제조하는 방법 |
EP22202974.6A EP4250385A1 (en) | 2022-03-22 | 2022-10-21 | Method for preparing carbon-coated lithium iron phosphate material from ferrous phosphate |
JP2022172514A JP7473769B2 (ja) | 2022-03-22 | 2022-10-27 | リン酸第一鉄から炭素被覆リン酸鉄リチウム材料を製造する方法 |
US17/978,241 US20230080632A1 (en) | 2022-03-22 | 2022-11-01 | Method for preparing carbon-coated lithium iron phosphate material from ferrous phosphate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210282867.5A CN114597376B (zh) | 2022-03-22 | 2022-03-22 | 一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114597376A true CN114597376A (zh) | 2022-06-07 |
CN114597376B CN114597376B (zh) | 2023-08-22 |
Family
ID=81810853
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210282867.5A Active CN114597376B (zh) | 2022-03-22 | 2022-03-22 | 一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20230080632A1 (zh) |
EP (1) | EP4250385A1 (zh) |
JP (1) | JP7473769B2 (zh) |
KR (1) | KR20230137807A (zh) |
CN (1) | CN114597376B (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115490266A (zh) * | 2022-09-27 | 2022-12-20 | 安徽博石高科新材料股份有限公司 | 一种碳包覆锰酸锂复合材料的制备方法 |
CN115594160A (zh) * | 2022-10-19 | 2023-01-13 | 雅安天蓝新材料科技有限公司(Cn) | 一种磷酸铁锂及其制备方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116409773B (zh) * | 2023-04-17 | 2023-11-07 | 郑州大学 | 一种长循环电池级磷酸铁锂的制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003292309A (ja) * | 2002-01-31 | 2003-10-15 | Nippon Chem Ind Co Ltd | リチウム鉄リン系複合酸化物炭素複合体、その製造方法、リチウム二次電池正極活物質及びリチウム二次電池 |
CN102674291A (zh) * | 2012-05-25 | 2012-09-19 | 广西诺方储能科技有限公司 | 超细纳米磷酸铁锂电极材料的制备方法及应用 |
CN106252620A (zh) * | 2016-08-17 | 2016-12-21 | 浙江美思锂电科技有限公司 | 一种采用cvd低温制备碳包覆磷酸铁锂正极材料的方法 |
CN110970605A (zh) * | 2018-09-30 | 2020-04-07 | 深圳市贝特瑞纳米科技有限公司 | 一种碳包覆磷酸亚铁、制备方法,利用其制备的碳包覆磷酸亚铁锂和应用 |
CN113054174A (zh) * | 2021-03-12 | 2021-06-29 | 湖北融通高科先进材料有限公司 | 一种复合磷源制备磷酸铁锂材料的方法以及由该方法制备的磷酸铁锂材料 |
-
2022
- 2022-03-22 CN CN202210282867.5A patent/CN114597376B/zh active Active
- 2022-10-20 KR KR1020220136032A patent/KR20230137807A/ko unknown
- 2022-10-21 EP EP22202974.6A patent/EP4250385A1/en active Pending
- 2022-10-27 JP JP2022172514A patent/JP7473769B2/ja active Active
- 2022-11-01 US US17/978,241 patent/US20230080632A1/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003292309A (ja) * | 2002-01-31 | 2003-10-15 | Nippon Chem Ind Co Ltd | リチウム鉄リン系複合酸化物炭素複合体、その製造方法、リチウム二次電池正極活物質及びリチウム二次電池 |
CN102674291A (zh) * | 2012-05-25 | 2012-09-19 | 广西诺方储能科技有限公司 | 超细纳米磷酸铁锂电极材料的制备方法及应用 |
CN106252620A (zh) * | 2016-08-17 | 2016-12-21 | 浙江美思锂电科技有限公司 | 一种采用cvd低温制备碳包覆磷酸铁锂正极材料的方法 |
CN110970605A (zh) * | 2018-09-30 | 2020-04-07 | 深圳市贝特瑞纳米科技有限公司 | 一种碳包覆磷酸亚铁、制备方法,利用其制备的碳包覆磷酸亚铁锂和应用 |
CN113054174A (zh) * | 2021-03-12 | 2021-06-29 | 湖北融通高科先进材料有限公司 | 一种复合磷源制备磷酸铁锂材料的方法以及由该方法制备的磷酸铁锂材料 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115490266A (zh) * | 2022-09-27 | 2022-12-20 | 安徽博石高科新材料股份有限公司 | 一种碳包覆锰酸锂复合材料的制备方法 |
CN115594160A (zh) * | 2022-10-19 | 2023-01-13 | 雅安天蓝新材料科技有限公司(Cn) | 一种磷酸铁锂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN114597376B (zh) | 2023-08-22 |
KR20230137807A (ko) | 2023-10-05 |
JP2023140266A (ja) | 2023-10-04 |
EP4250385A1 (en) | 2023-09-27 |
US20230080632A1 (en) | 2023-03-16 |
JP7473769B2 (ja) | 2024-04-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN114597376B (zh) | 一种由磷酸亚铁制备碳包覆磷酸铁锂材料的方法 | |
TW201335067A (zh) | 電極材料、電極板、鋰離子電池、電極材料之製造方法及電極板之製造方法 | |
CN113054171A (zh) | 一种磷酸铁锂材料以及以混合铁源与混合磷源制备磷酸铁锂材料的方法 | |
KR20230164547A (ko) | 다중 탄소 코팅 고압축 인산망간철리튬의 제조 방법 | |
CN114665058A (zh) | 一种锂离子电池正极材料磷酸锰铁锂的制备方法 | |
CN115231543A (zh) | 一种多重碳包覆高压实磷酸锰铁锂的制备方法 | |
CN113651303A (zh) | 一种纳米片状磷酸铁的制备方法及应用其制得的LiFePO4/C正极活性材料 | |
CN112421040A (zh) | 一种磷酸盐正极材料及其制备方法和应用 | |
CN115101738A (zh) | 一种碳包覆的铁钒双金属磷酸焦磷酸钠复合材料及其制备方法和应用 | |
CN114649530A (zh) | 钒钛掺杂复合碳纳米管的纳米磷酸锰铁锂材料的制备方法及该纳米磷酸锰铁锂材料 | |
JP5381115B2 (ja) | リン酸リチウム粉体とリン酸リチウム含有スラリー及び電極活物質の製造方法並びにリチウムイオン電池 | |
CN114551880A (zh) | 一种碳覆多孔Cr-Cu合金/磷酸铁锂正极及其制备方法 | |
CN114171729A (zh) | 一种石墨烯基磷酸铁锂正极材料的制备方法 | |
EP3799159B1 (en) | Positive electrode material for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and lithium ion secondary battery | |
CN111099569B (zh) | 一种还原氧化石墨烯/碳材料包覆的磷酸铁锂材料的制备方法 | |
CN116730310A (zh) | 一种制备锂离子电池正极材料磷酸铁锰锂的方法 | |
EP4283713A1 (en) | High-rate lithium iron phosphate positive electrode material and preparation method therefor, positive electrode thereof, and battery | |
CN114050250A (zh) | 一种碳包覆的磷酸铁钠钠离子电池正极材料、其制备方法及应用 | |
CN112186144A (zh) | 掺杂钴金属的铁酸锂正极材料及其制备方法以及正极片 | |
CN114436234B (zh) | 一种使用FePO4/C复合材料制备的磷酸铁锂材料及其制备方法 | |
CN114583137B (zh) | 一种在碳表面进行硫掺杂磷修饰的方法及其应用 | |
CN111816851B (zh) | 一种分级多孔LiMnxFe1-xPO4/C复合微球正极材料的无模板水热制备方法 | |
CN115360354B (zh) | 一种钠离子电池正极材料制备方法及应用 | |
CN115259128B (zh) | 一种高压实高容量低成本磷酸铁锂的制备方法 | |
CN111082010B (zh) | 一种正极材料及其制备方法和应用 |
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 | ||
CB02 | Change of applicant information |
Address after: 435100 No. 66 Changle Avenue, Luojiaqiao Street, Daye City, Huangshi City, Hubei Province Applicant after: Hubei Rongtong High tech Advanced Materials Group Co.,Ltd. Address before: 435100 No. 66 Changle Avenue, Luojiaqiao Street, Daye City, Huangshi City, Hubei Province Applicant before: HUBEI RT ADVANCED MATERIALS Co.,Ltd. |
|
CB02 | Change of applicant information | ||
GR01 | Patent grant | ||
GR01 | Patent grant |