WO2023273742A1 - 低硫含量纳米磷酸铁的制备方法 - Google Patents
低硫含量纳米磷酸铁的制备方法 Download PDFInfo
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- WO2023273742A1 WO2023273742A1 PCT/CN2022/095689 CN2022095689W WO2023273742A1 WO 2023273742 A1 WO2023273742 A1 WO 2023273742A1 CN 2022095689 W CN2022095689 W CN 2022095689W WO 2023273742 A1 WO2023273742 A1 WO 2023273742A1
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- ferric phosphate
- slurry
- preparation
- phosphate dihydrate
- water
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 75
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 53
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 53
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 53
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000005864 Sulphur Substances 0.000 title abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000002002 slurry Substances 0.000 claims abstract description 35
- 238000005406 washing Methods 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000004094 surface-active agent Substances 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000007790 solid phase Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 40
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 35
- 239000011593 sulfur Substances 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 3
- 230000002431 foraging effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 25
- 230000032683 aging Effects 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 229910021653 sulphate ion Inorganic materials 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 32
- 239000000047 product Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 14
- 239000012535 impurity Substances 0.000 description 14
- 239000012065 filter cake Substances 0.000 description 12
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000001238 wet grinding Methods 0.000 description 5
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 102220043159 rs587780996 Human genes 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 description 1
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical group [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
- C01P2006/80—Compositional purity
-
- 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
Definitions
- the invention belongs to the technical field of lithium ion batteries, and in particular relates to a method for preparing nano iron phosphate with low sulfur content.
- lithium-ion batteries as a new and green energy supply method, are widely used in automotive power batteries, electrochemical energy storage, 3C product batteries and other fields.
- lithium iron phosphate batteries occupy a large share in the market due to their excellent cycle performance, safety performance, low price, environmental protection and non-pollution, and with the popularization of new energy vehicles, their demand is increasing. quickly growing.
- the main methods for preparing lithium iron phosphate cathode materials include high-temperature solid-phase method, carbothermal reduction method, sol-gel method, co-precipitation method, hydrothermal method, etc.
- the carbothermal reduction method has stable process, low cost and easy control , has become the mainstream industrial preparation method.
- the main method of preparing ferric phosphate is to use ferrous sulfate as raw material and prepare it by controlled crystallization method.
- the product contains a large amount of impurities, which are difficult to remove during subsequent calcination to synthesize lithium iron phosphate, which affects the electrical performance of lithium iron phosphate battery.
- the impact is relatively large, which greatly affects the application of iron phosphate in battery materials.
- impurity sulfur is the most serious. Luo Yanhua et al. found that when the mass fraction of sulfur reaches a certain level, the influence on the particle morphology, discharge capacity and cycle performance of lithium iron phosphate is gradually obvious. When the mass fraction of sulfur is lower than 0.22 %, the shape of lithium iron phosphate particles is spherical, and the first discharge capacity of 1C reaches 152mAh/g.
- the capacity can still be maintained at 140mAh/g, and the electrochemical performance is good; when the mass fraction of sulfur is higher than 0.34%, The lithium iron phosphate particles were agglomerated, and the 1C discharge capacity was lower than 130mAh/g for the first time, and after 150 cycles, the capacity was lower than 107mAh/g.
- the main methods used to control the sulfur content in iron phosphate in the industry include controlling the pH of the synthesis process, multi-stage washing, citric acid washing, and long-term calcination, etc. These methods often affect the tap density, reactivity, and surface shape of the product. appearance and other properties, or use a large amount of washing water and high-cost citric acid, the pollution is relatively large, which puts great pressure on the subsequent wastewater treatment; during the process of calcination and crystallization of ferric phosphate dihydrate Residual sulfate radicals are often released in the form of SO 2 .
- the existing process has low calcination temperature and long calcination time, which has poor effect on the removal of S element, and also causes the melting of ferric phosphate primary particles, and the reactivity decreases. Therefore, it is of great significance to develop a method of reducing sulfur content with good effect, low cost and little impact on the environment to optimize the synthesis process of battery-grade nano-iron phosphate and improve its product performance.
- the present invention aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention proposes a preparation method of nano iron phosphate with low sulfur content.
- a kind of preparation method of nano iron phosphate with low sulfur content comprising the following steps:
- the iron source is ferrous sulfate, and an oxidizing agent is added to the raw material liquid; the molar ratio of iron and phosphorus in the raw material liquid is 1:(0.9-1.1) .
- step S1 the phosphorus source is phosphoric acid.
- the oxidizing agent is H 2 O 2 .
- the oxidizing agent oxidizes Fe 2+ to Fe 3+ .
- the alkali is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, ammonia or ammonium salt; preferably, the Alkali is selected sodium hydroxide for use.
- the surfactant is sodium stearate, polyvinylpyrrolidone, sodium dodecylsulfonate, dodecylphenol polyoxyethylene ether, cetyl At least one of trimethylammonium bromide or cetyltrimethylammonium chloride.
- the surfactant in step S1, is compounded with polyvinylpyrrolidone and sodium dodecylsulfonate at a mass ratio of about 1:1.
- polyvinylpyrrolidone and sodium dodecylsulfonate at a mass ratio of about 1:1.
- step S1 the pH is 1.0-2.5.
- step S1 the mass ratio of the raw material liquid to the lye is 1: (0.1-0.3).
- step S1 the stirring speed is 100-800 rpm; the reaction temperature is 20-60° C., and the reaction time is 0.5-5 h.
- step S1 the surfactant and water are formulated into a surfactant mixed solution with a mass concentration of 10-40%, and the mass ratio of the raw material solution to the surfactant mixed solution is 1: (0.004-0.04).
- step S2 the mass concentration of the phosphoric acid solution is 60-80%; the pH is 1.0-2.0.
- step S2 the stirring speed of aging is 50-300 rpm, the aging temperature is 60-100° C., and the aging time is 1-5 h.
- the obtained ferric phosphate dihydrate has a particle size of 8-20 ⁇ m.
- the particle size of the dispersed phase of the ground slurry is 2.5-10 ⁇ m.
- the particle size of wet grinding needs to be adjusted according to the requirements of the later lithium iron phosphate synthesis process.
- step S3 the mass ratio of ferric phosphate dihydrate to water is 1:(1-4).
- step S4 the number of washings is twice.
- the washing solution is one of water or 0.5-2% sodium carbonate solution; preferably, the water is hot water at 60-90°C.
- the present invention in addition to conventional deionized water, the present invention also innovatively selects hot pure water, which can reduce the viscosity of the slurry and improve the washing effect.
- Sodium carbonate solution is also innovatively selected. Sodium carbonate and sulfate have a good reaction effect and are easy to remove. At the same time, waste water is easy to treat, which can further reduce the content of impurity sulfur in iron phosphate.
- the choice of washing liquid can be selected according to production cost control and product performance requirements.
- step S4 the mass ratio of washing liquid to ferric phosphate dihydrate is (5-20):1.
- step S4 the water content of the filter residue is 15-30%.
- step S4 the calcination temperature is 450-800° C., the calcination time is 0.5-5 h; the heating rate is 2-10° C./min.
- the calcination temperature is 600-800°C, and the calcination time is 0.5-3h.
- the calcination temperature is increased to above 600°C, and the calcination time is controlled within 3 hours, which can effectively remove the residual sulfate radicals in the iron phosphate particles and ensure the chemical properties of the product. .
- step S4 compressed air needs to be introduced into the calcination. Introducing pure compressed air can speed up the extraction of S elements.
- the present invention innovatively advances the grinding process in the lithium iron phosphate synthesis process, adopts wet grinding to reduce the particle size of iron phosphate dihydrate, and opens up the agglomeration of its secondary particles, so that the sulfate radicals wrapped in it can be better Dissolved in the washing water, and then come out, greatly reducing the amount of washing water.
- the present invention directly calcines without drying. In the process of losing free water and crystal water in the ferric phosphate dihydrate filter residue, pores are left in the particles, which provides favorable conditions for the diffusion and removal of SO 2 .
- the S content in the obtained finished product is less than 0.01%, reaching the national standard for battery-grade nano-iron phosphate finished products.
- the process of the present invention is simple, low in cost, stable in control, and easy for large-scale industrialization; when the traditional carbothermal reduction method is used to prepare lithium iron phosphate, it is necessary to reduce the particle size of the raw materials through wet grinding, improve the dispersion uniformity of each raw material, and then carry out Spray dry.
- the present invention advances the subsequent wet grinding process to the iron phosphate preparation process, combines the front and rear processes, and optimizes and combines the process steps.
- the preparation process of the product has certain reference function.
- Fig. 1 is the process flow chart of the embodiment of the present invention 1;
- Fig. 2 is the SEM figure of the nano iron phosphate that the embodiment of the present invention 1 makes;
- Fig. 3 is an XRD comparison chart of nanometer iron phosphate prepared in Example 1 and Comparative Example 1 of the present invention.
- the present embodiment has prepared a kind of nano iron phosphate of low sulfur content, with reference to the process flow chart of Fig. 1, concrete process is:
- the ICP test result is: the S content in the ferric phosphate dihydrate filter residue obtained in this embodiment is 0.3564%.
- Figure 2 is the SEM image of the nano-iron phosphate prepared in this example. It can be clearly seen from the SEM image that the synthesized battery-grade nano-iron phosphate has changed from conventional secondary particle agglomerates to relatively loose primary particle disorder The distribution is closer to the state of iron phosphate in the wet grinding and rough grinding process in the later stage, and the secondary particle aggregates are opened to help the detachment of the impurity sulfur element attached to the inside.
- Fig. 3 is the XRD pattern of the nano iron phosphate that the embodiment of the present invention 1 and comparative example 1 make, can find out obviously by XRD pattern, the iron phosphate that comparative example 1 adopts conventional low-temperature long-period calcining dehydration method to obtain is amorphous state, However, the ferric phosphate obtained by the rapid high-temperature short-cycle calcination method used in Example 1 has good crystallinity, sharp characteristic peaks, and a pure crystal phase structure without impurities.
- Table 1 shows the particle size distribution of the ferric phosphate product obtained in this example.
- This embodiment has prepared a kind of nano iron phosphate of low sulfur content, and specific process is:
- This embodiment has prepared a kind of nano iron phosphate of low sulfur content, and specific process is:
- This comparative example has prepared a kind of nano iron phosphate, and concrete process is:
- the ferric phosphate dihydrate filter residue was prepared, and the ferric phosphate dihydrate filter residue was directly washed 3 times with 50 times of deionized water, each time for 30 minutes, and dried at 120 ° C after pressure filtration 10h, then put into a bowl, carry out high-temperature calcination at 300°C for 5h, the heating rate is 5°C/min, and 10Nm 3 /h of pure compressed air is introduced, and the calcined material can be prepared by grinding, pulverizing, and sieving to obtain battery-grade nano phosphoric acid Iron products.
- This embodiment has prepared a kind of ferric phosphate dihydrate, and the difference with embodiment 1 is that the proportioning of surfactant solution is different, and concrete process is:
- the ICP test result is: the S content in the ferric phosphate dihydrate filter residue obtained in this comparative example is 0.8129%.
- Table 1 shows the content of impurity elements in the battery-grade nano-iron phosphate finished products prepared in Examples 1-3 and Comparative Example 1, and the specific data are obtained by testing with ICP-AES equipment.
- Table 2 shows the main differences between the preparation process of Examples 1-3 and Comparative Example 1.
Abstract
Description
D10 | D50 | D90 | D99 | |
粒径(μm) | 0.66 | 2.47 | 12.72 | 25.90 |
杂质元素含量(%) | 实施例1 | 实施例2 | 实施例3 | 对比例1 |
S | 0.0093 | 0.0086 | 0.0097 | 0.0649 |
Mn | 0.0012 | 0.0011 | 0.0004 | 0.0026 |
Na | 0.0092 | 0.0065 | 0.0133 | 0.0064 |
Co | 0.0003 | 0.0002 | 0.0008 | 0.0089 |
Al | 0.0052 | 0.0049 | 0.0076 | 0.0213 |
Cr | 0.0143 | 0.0074 | 0.0097 | 0.0155 |
实验组 | 总用水量 | 脱S耗时 |
实施例1 | 40:1 | 7h |
实施例2 | 30:1 | 6.5h |
实施例3 | 30:1 | 6h |
对比例1 | 150:1 | 20h |
Claims (10)
- 一种低硫含量纳米磷酸铁的制备方法,其特征在于,包括以下步骤:S1:将磷源和铁源混合得到原料液,再加入碱和表面活性剂,调节pH,搅拌反应,得到二水磷酸铁浆料;S2:向二水磷酸铁浆料中加入磷酸溶液,调节pH,加热搅拌进行陈化,过滤得到二水磷酸铁;S3:将二水磷酸铁加水制浆,进行研磨,得到研磨后浆料;S4:将所述研磨后浆料加入洗涤液进行洗涤,固液分离,取固相进行煅烧,得到低硫含量纳米磷酸铁。
- 根据权利要求1所述的制备方法,其特征在于,步骤S1中,所述铁源为硫酸亚铁,所述原料液中还添加有氧化剂;所述原料液中铁和磷的摩尔比为1:(0.9-1.1)。
- 根据权利要求1所述的制备方法,其特征在于,步骤S1中,所述表面活性剂采用质量比约为1:1的聚乙烯吡咯烷酮和十二烷基磺酸钠复配。
- 根据权利要求1所述的制备方法,其特征在于,步骤S1中,所述pH为1.0-2.5。
- 根据权利要求3所述的制备方法,其特征在于,步骤S1中,所述表面活性剂与水配制成质量浓度为10-40%的表面活性剂混合液,所述原料液与表面活性剂混合液的质量比为1:(0.004-0.04)。
- 根据权利要求1所述的制备方法,其特征在于,步骤S2中,所得到的二水磷酸铁的粒径为8-20μm。
- 根据权利要求1所述的制备方法,其特征在于,步骤S3中,所述研磨后浆料的分散相的粒径D50为2.5-10μm。
- 根据权利要求1所述的制备方法,其特征在于,步骤S4中,所述洗涤液为水或0.5-2%的碳酸钠溶液中的一种;优选的,所述水为60-90℃的热水。
- 根据权利要求1所述的制备方法,其特征在于,步骤S4中,所述煅烧的温度为450-800℃,煅烧的时间为0.5-5h。
- 根据权利要求1所述的制备方法,其特征在于,步骤S4中,所述煅烧需通入压缩空气。
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GB2309433.7A GB2616230A (en) | 2021-07-01 | 2022-05-27 | Preparation method for nano ferric phosphate with low sulphur content |
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CN113479861B (zh) * | 2021-07-01 | 2023-02-14 | 广东邦普循环科技有限公司 | 低硫含量纳米磷酸铁的制备方法 |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120237425A1 (en) * | 2009-09-09 | 2012-09-20 | Takahisa Nishio | Ferric phosphate hydrate particles and process for producing the same, olivine type lithium iron phosphate particles and process for producing the same, and non-aqueous electrolyte secondary battery |
CN104628020A (zh) * | 2015-01-27 | 2015-05-20 | 北方联合电力有限责任公司 | 一种以粉煤灰和可循环铵盐为原料生产冶金级氧化铝的方法 |
CN108117055A (zh) * | 2017-12-30 | 2018-06-05 | 彩客化学(东光)有限公司 | 一种电池级磷酸铁的制备方法和生产装置 |
CN111153391A (zh) * | 2020-01-09 | 2020-05-15 | 湖南雅城新材料有限公司 | 一种低硫含量电池级磷酸铁的制备方法 |
CN112645299A (zh) * | 2020-12-03 | 2021-04-13 | 广东邦普循环科技有限公司 | 一种磷酸铁的制备方法和应用 |
CN113479861A (zh) * | 2021-07-01 | 2021-10-08 | 广东邦普循环科技有限公司 | 低硫含量纳米磷酸铁的制备方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100588611C (zh) * | 2007-10-11 | 2010-02-10 | 河北工业大学 | 用于制备磷酸铁锂材料的磷酸铁的制备方法 |
CN105118995A (zh) * | 2015-10-14 | 2015-12-02 | 湖南省正源储能材料与器件研究所 | 一种电池级磷酸铁的生产方法 |
CN106882780A (zh) * | 2017-04-05 | 2017-06-23 | 河南省净寰新能源科技有限公司 | 一种电池级磷酸铁微粉的制备方法 |
CN109850862B (zh) * | 2019-04-23 | 2021-01-29 | 王柯娜 | 一种电池级无水磷酸铁的制备方法 |
CN110857216B (zh) * | 2019-09-29 | 2021-11-12 | 湖南雅城新材料有限公司 | 一种电池级磷酸铁前驱体、磷酸铁锂及其制备方法与应用 |
CN110510593B (zh) * | 2019-10-24 | 2020-04-10 | 湖南雅城新材料有限公司 | 一种磷酸铁前驱体及磷酸铁锂的制备方法 |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120237425A1 (en) * | 2009-09-09 | 2012-09-20 | Takahisa Nishio | Ferric phosphate hydrate particles and process for producing the same, olivine type lithium iron phosphate particles and process for producing the same, and non-aqueous electrolyte secondary battery |
CN104628020A (zh) * | 2015-01-27 | 2015-05-20 | 北方联合电力有限责任公司 | 一种以粉煤灰和可循环铵盐为原料生产冶金级氧化铝的方法 |
CN108117055A (zh) * | 2017-12-30 | 2018-06-05 | 彩客化学(东光)有限公司 | 一种电池级磷酸铁的制备方法和生产装置 |
CN111153391A (zh) * | 2020-01-09 | 2020-05-15 | 湖南雅城新材料有限公司 | 一种低硫含量电池级磷酸铁的制备方法 |
CN112645299A (zh) * | 2020-12-03 | 2021-04-13 | 广东邦普循环科技有限公司 | 一种磷酸铁的制备方法和应用 |
CN113479861A (zh) * | 2021-07-01 | 2021-10-08 | 广东邦普循环科技有限公司 | 低硫含量纳米磷酸铁的制备方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116621141A (zh) * | 2023-04-25 | 2023-08-22 | 浙江友山新材料有限公司 | 低锰、镁磷酸铁的制备方法 |
CN116621141B (zh) * | 2023-04-25 | 2023-12-26 | 浙江友山新材料科技有限公司 | 低锰、镁磷酸铁的制备方法 |
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