CN115448283A - Phosphate anode material and production process and application thereof - Google Patents
Phosphate anode material and production process and application thereof Download PDFInfo
- Publication number
- CN115448283A CN115448283A CN202211183046.2A CN202211183046A CN115448283A CN 115448283 A CN115448283 A CN 115448283A CN 202211183046 A CN202211183046 A CN 202211183046A CN 115448283 A CN115448283 A CN 115448283A
- Authority
- CN
- China
- Prior art keywords
- phosphate
- lithium
- parts
- positive electrode
- catalyst
- 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
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 57
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 57
- 239000010452 phosphate Substances 0.000 title claims abstract description 57
- 239000010405 anode material Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 30
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 22
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 15
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- 239000002270 dispersing agent Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 42
- 239000002002 slurry Substances 0.000 claims description 29
- 238000005245 sintering Methods 0.000 claims description 25
- 238000000227 grinding Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000011068 loading method Methods 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000004576 sand Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000012716 precipitator Substances 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 238000010902 jet-milling Methods 0.000 claims description 6
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical group [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 5
- 229910001448 ferrous ion Inorganic materials 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 150000002505 iron Chemical class 0.000 abstract description 2
- 159000000014 iron salts Chemical class 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 9
- 229910000398 iron phosphate Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 3
- 229940062993 ferrous oxalate Drugs 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing 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
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/36—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
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a phosphate anode material and a production process and application thereof, wherein the phosphate anode material is prepared from the following raw materials in parts by weight: 55-62 parts of ferrous salt; 7-12 parts of lithium salt; 9-12 parts of a phosphoric acid solution; 1-2 parts of a catalyst; 15-20 parts of a precipitating agent; wherein the catalyst is a complexing agent or a dispersing agent. According to the phosphate anode material and the production process thereof, the raw materials can adopt common iron salts and lithium salts, the raw materials are wide in use source and low in cost, and the risk of the short supply of the raw materials is solved. The catalyst can be gathered around ferrous ions, so that the oxidation of ferrous ions is effectively prevented, the reaction activation energy is reduced, and the effects of a complexing agent and a dispersing agent are achieved, so that the effect of uncontrollable agglomeration in the reaction process can be reduced, the iron salt and the lithium salt can be mixed in an ionic degree, and the reaction of the two raw materials and a phosphoric acid solution to form lithium iron phosphate is facilitated.
Description
Technical Field
The invention relates to the technical field of preparation of a lithium battery anode powder material, in particular to a phosphate anode material and a production process thereof.
Background
In 1997, researchers of John B Goodenough and the like reported that lithium iron phosphate has structural stability and good electrochemical performance, so that the commercialization potential of lithium iron phosphate is unlimited. The iron-based compound has the greatest advantages of no toxicity and good safety except low price and rich raw material reserves, so that the battery has great attention to iron-based positive materials. LiFePO 4 The theoretical capacity of the lithium metal anode is 170mAh/g, compared with a stable discharge platform of a lithium metal anode, the lithium metal anode is 3.4V, has the outstanding advantages of low price, good thermal stability, no environmental pollution and the like, is one of the most potential anode materials at present, and is widely applied to the fields of power batteries and energy storage.
The capacity of the lithium iron phosphate anode material in 2021 years is 45.27 ten thousand tons, the year-round loading capacity of the lithium iron phosphate anode material is increased by 168.9 percent, the year-round loading capacity of the lithium iron phosphate anode material is 80GWH, the percentage is 52 percent, the year-round loading capacity is increased by 227 percent, and in recent years, the year-round power loading capacity of the lithium iron phosphate battery is firstly superior to that of a ternary battery. From the monthly data of 2021, the lithium iron phosphate battery occupancy rate is gradually increased from 38% in the beginning of the year, the machine loading rate is firstly more than three times in 7 months of 2021, the occupancy rate reaches 51%, and the machine loading rate is kept above 55% every month. With the improvement of the technology of the last-year lithium iron CTP, kylin battery and blade battery, the LFP battery has the advantages of increased energy density, better safety, low cost and the like, so that the market demand of the LFP battery in each subdivided field is increased. In addition, along with the large increase of the price of raw materials, the cost expansion space of the battery core is large, and the performance-price ratio of the lithium iron battery is higher than that of a ternary battery, so that the demand of the lithium iron in power, low power and other fields is increased.
Just because of the demand of lithium battery anode materials in the market, in 2021, the lithium iron phosphate anode materials have a spread of production, and according to incomplete statistics, the capacity of the lithium iron phosphate anode materials in the market reaches 145 million tons/year by the end of 2022.
However, with the drastic expansion of material production energy, product homogenization and manufacturing cost cannot be ignored. How to improve the product quality and the cost competitiveness of the manufacturing process is also pushed to the product upgrading demand schedule. The process of lithium iron phosphate can be divided into three types according to main raw materials: the iron oxide is used as a raw material in the iron oxide red route, the ferrous oxalate route and the iron phosphate route, and the iron oxide red route has poor performance and low cost. The ferrous oxalate route is the ferrous oxalate used as raw material, and has the environmental problem of ammonium salt treatment and large processing difficulty. Iron phosphate route; namely, the iron phosphate is used as the raw material to synthesize the lithium iron phosphate, the process is mature, the expansion production is easy, and the performance is more stable. At present, lithium iron phosphate manufactured by an iron phosphate route is the mainstream. In the last years, due to the lack of product material performance, other routes are replaced by iron phosphate routes, but the iron phosphate raw materials are not easy to obtain and have higher cost, and the iron phosphate routes are not necessarily suitable for pursuing high quality and low cost in the future from the aspects of cost, performance and the like.
Therefore, the development of a production process with easily available raw materials and complete production chain can promote the healthy development of the lithium iron phosphate industry and increase the product competitiveness of enterprises. Based on the above-mentioned problems faced by the market environment and production of lithium iron phosphate, i have proposed an important research and development subject to solve the current dilemma.
Disclosure of Invention
In order to solve the technical problems of high processing difficulty or high raw material cost of the production process of the phosphate cathode material in the prior art, the invention provides a phosphate cathode material and a production process thereof to solve the problems.
The invention provides a phosphate anode material which is prepared from the following raw materials in parts by weight: 55-62 parts of ferrous salt; 7-12 parts of a lithium salt; 9-12 parts of a phosphoric acid solution; 1-2 parts of a catalyst; 15-20 parts of a precipitating agent; wherein the catalyst is a complexing agent or a dispersing agent.
Further, the ferrous salt is ferrous sulfate, ferrous chloride or ferrous nitrate.
Further, the lithium salt is lithium phosphate or lithium hydroxide.
Further, the precipitator is sodium hydroxide or ammonia water.
Further, the catalyst is citric acid, EDTA or PEG4000-6000.
The invention also provides a production process of the phosphate anode material, which comprises the following steps:
s1: preparing a phosphate solution: dissolving ferrous salt and lithium salt into a phosphoric acid solution, adding a catalyst, uniformly stirring, adding the catalyst into a reaction kettle, adding a precipitator into the reaction kettle while stirring until the reaction is finished, and forming the initial phosphate slurry.
S2: fine grinding: and (3) grinding the phosphate initial slurry obtained in the step (S1) by a sand mill and a refiner for one time in sequence to form refined slurry.
S3: and (3) drying: and (3) conveying the fine grinding slurry obtained in the step (S2) to a filter press for filter pressing, transferring to a vacuum vibration dryer, loading the dried material into a graphite crucible, and then entering an inert gas protection kiln for sintering.
S4: material molding: and S3, performing jet milling and demagnetizing screening on the sintered material to form the lithium iron phosphate anode material.
Further, in step S1, continuously testing the pH value in the reaction kettle after adding the precipitant, and ending the reaction until the pH value reaches 6.5 to 7.0, thereby generating the initial phosphate slurry.
Further, in the step S3, the dried material is transferred to a high-speed mixer, and 3% -5% of carbon source is added for high-speed mixing; mixing for 15-20 min, and sintering in a graphite crucible.
Further, the sintering temperature in the kiln is 780-800 ℃; the sintering time is 10-10.5 h.
Further, in the step S3, the pressure filtration pressure is not more than 0.4Mpa; the drying time is 20-30 min.
The invention also provides the application of the phosphate anode material prepared by the production process in the lithium battery anode material.
The beneficial effects of the invention are:
(1) According to the phosphate anode material and the production process thereof, the raw materials can adopt common iron salts and lithium salts, the raw materials are wide in use source and low in cost, and the risk of the short supply of the raw materials is solved. The catalyst can be gathered around ferrous ions, so that the oxidation of ferrous iron is effectively prevented, the reaction activation energy is reduced, and the effects of a complexing agent and a dispersing agent are achieved, so that the effect of uncontrollable agglomeration in the reaction process can be reduced, the iron salt and the lithium salt can be mixed in an ionic degree, and the reaction of two raw materials and a phosphoric acid solution is facilitated to form lithium iron phosphate.
(2) According to the phosphate anode material and the production process thereof, the catalyst only consists of C, H, O, and can be removed through the subsequent sintering or carbonization process after the reaction is finished.
(3) The phosphate anode material and the production process thereof simplify the process, improve the yield of the sintering process and reduce the equipment investment for material production.
(4) The phosphate anode material and the production process thereof have the advantages that the specific surface area of the produced material is small, the later-stage battery core manufacturing is facilitated, and the consumption of the binder is reduced. Under the normal pressure preparation environment, the primary particle size reaches the nanometer size, the transmission resistance of lithium ions in the application of the battery cell is reduced, the conductivity is increased, and the ion conduction resistance is reduced.
Drawings
The invention is further illustrated with reference to the following figures and examples.
Fig. 1 is a flow chart of a process for producing a phosphate positive electrode material according to the present invention;
fig. 2 is an SEM image of a phosphate positive electrode material according to example 1 of the present invention;
fig. 3 is an SEM image of a phosphate positive electrode material according to example 2 of the present invention;
fig. 4 is an SEM image of a phosphate positive electrode material of example 3 according to the present invention;
fig. 5 is an XRD pattern of the phosphate cathode material of examples 1-3 according to the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
The phosphate cathode material is prepared from the following raw materials in parts by weight: 55-62 parts of ferrous salt; 7-12 parts of lithium salt; 9-12 parts of a phosphoric acid solution; 1-2 parts of a catalyst; 15-20 parts of a precipitating agent; wherein the catalyst is a complexing agent or a dispersing agent.
The ferrous salt and the lithium salt can be common materials with lower cost, for example, the ferrous salt can be ferrous sulfate, ferrous chloride or ferrous nitrate, the lithium salt can be lithium phosphate or lithium hydroxide, the components can be directly purchased, and can also be extracted from waste materials or prepared by the user, for example, the lithium phosphate has low price, can be directly purchased, and can also be prepared from lithium and phosphoric acid, and the ferrous chloride can be extracted from waste iron. The precipitant reacts with acid radical in the solution to regulate pH value of the solution, and sodium hydroxide, ammonia water, etc. are selected.
In the prior art, ferric phosphate is used as a raw material, ferric iron is reduced into ferrous iron by adopting a carbon reduction mode, a solid material can be directly formed after carbon reduction, and unstable ferrous ions cannot exist. When the lithium iron phosphate is prepared by reacting ferrous salt with phosphoric acid, the ferrous salt is unstable in state and is easily oxidized into ferric salt in a liquid state, so that the ferrous salt, the lithium salt and the phosphoric acid cannot react to generate the lithium iron phosphate.
The catalyst only consists of C, H, O elements, and can be removed through subsequent sintering or carbonization processes after the reaction is finished. For example, the catalyst may be citric acid, EDTA, PEG4000-6000, or the like.
The phosphate cathode material uses various additives which are safe and easy to remove, for example, sodium salt in the precipitator can be extracted through filtration or high-temperature sintering, the processing is simple, and the extracted sodium salt is safe and recyclable.
The invention also provides a production process of the phosphate cathode material, which comprises the following steps as shown in figure 1:
s1: preparing a phosphate solution: dissolving ferrous salt and lithium salt into a phosphoric acid solution, adding a catalyst, uniformly stirring, adding the catalyst into a reaction kettle, adding a precipitator into the reaction kettle while stirring until the reaction is finished to form phosphate initial slurry, wherein the phosphate initial slurry is a mixture of various solutions, for example, sodium salt exists when the precipitator is sodium hydroxide. Regarding the observation of the reaction progress, a rough method can be calculated according to the reaction time, a more precise method can be determined according to the pH value in the reaction kettle, the pH value in the reaction kettle is continuously tested after the precipitator is added, and the reaction is finished when the pH value reaches 6.5-7.0, so that the initial phosphate slurry is generated.
S2: fine grinding: and (2) grinding the phosphate initial slurry obtained in the step (S1) by a sand mill and a refiner in sequence for one time to form refined slurry, wherein the step (S1) only needs one-time refining because the mixing and the reaction processes are fully stirred, and the prior art needs about four times of circular refining when the iron phosphate is prepared.
S3: and (3) drying: conveying the fine grinding slurry obtained in the step S2 to a filter press for filter pressing, transferring the fine grinding slurry to a vacuum vibration dryer, wherein the drying time is preferably 20-30 min, putting the dried material into a graphite crucible, and then, putting the graphite crucible into an inert gas protection kiln for sintering, wherein the sintering temperature is preferably 780-800 ℃; the sintering time is preferably 10 to 10.5 hours. Most of the solution except the lithium iron phosphate can be removed in the filter press, the lithium iron phosphate is pressed into a filter cake, and the drying process is to remove water vapor and redundant salt solution on the surface of the material. The sintering function is to ensure that the crystallinity of the material is higher, improve the performance of the material, and simultaneously ensure that the carbon source added at the earlier stage is carbonized and coated on the surface of the material to improve the conductivity. In order to increase the conductive effect of the materials, preferably, the dried materials are transferred into a high-speed mixer, and 3 to 5 percent of carbon source is added for high-speed mixing; mixing for 15-20 min and sintering in kiln. In addition, the small amount of catalyst added as described above may also carbonize or decompose during sintering.
S4: material molding: and S3, performing jet milling and demagnetizing screening on the sintered material to form the lithium iron phosphate anode material.
The method combines a filter press and a vacuum vibration dryer, effectively shortens the process time, reduces the occupied area and the operation cost of equipment, gradually dries and sinters the materials under the multi-stage temperature gradient, and finally forms the finished product with small specific surface area and uniform size after crushing and screening, which can basically ensure the primary particle size of about 100nm-200nm and has high product quality.
The following analysis is carried out in conjunction with the specific examples:
example one
S1: preparing a phosphate solution: weighing 1mol (278.01 g) of ferrous sulfate and 1mol (42 g) of lithium hydroxide, dissolving the ferrous sulfate and the lithium hydroxide into 500ml of 1mol/L phosphoric acid solution, adding a catalyst citric acid after the solid is completely dissolved, and adding 4 g of citric acid at a time. And adding the mixture into a reactor after uniformly stirring, adding ammonia water while performing sand grinding circulation, continuously testing the pH value of the reaction solution in the reactor on line in the process, and finishing the reaction when the pH value reaches 6.8 to generate the initial phosphate slurry.
S2: fine grinding: and (3) grinding the phosphate initial slurry obtained in the step (S1) by a sand mill and a refiner for one time in sequence to form refined slurry.
S3: and (3) drying: and (3) conveying the fine grinding slurry obtained in the step (S2) to a filter press for filter pressing, wherein the pressure of the filter pressing is less than or equal to 0.4Mpa, transferring the filter pressing filter cake to a vacuum vibration dryer, transferring the material after drying for 30 minutes to a high-speed mixer, and simultaneously adding 3% of carbon source for high-speed mixing. Mixing for 15min, loading the materials into a specific graphite crucible, and sintering at 800 ℃ under the protection of nitrogen. The sintering time is 10h.
S4: material molding: and S3, performing jet milling, demagnetizing and screening on the sintered material to form the lithium iron phosphate anode material with the primary particle size of about 100 nm.
Example two
S1: preparing a phosphate solution: 3mol of ferrous chloride (596.43 g) and 1mol of lithium phosphate (115.79 g) are dissolved in 2000ml of 1mol/L phosphoric acid solution, and after the solid is completely dissolved, the catalyst EDTA is added, and 20 g of EDTA is added at a time. And adding the mixture into a reactor after uniformly stirring, adding ammonia water while performing sand grinding circulation, continuously testing the pH value of the reaction solution in the reactor on line in the process, and finishing the reaction when the pH value reaches 7.0 to generate the initial phosphate slurry.
S2: fine grinding: and (3) grinding the phosphate initial slurry obtained in the step (S1) by a sand mill and a refiner for one time in sequence to form refined slurry.
S3: and (3) drying: and (3) conveying the fine grinding slurry obtained in the step (S2) to a filter press for filter pressing, transferring the filter pressing filter cake to a vacuum vibration dryer, transferring the material after drying for 30 minutes to a high-speed mixer, and simultaneously adding 5% of a carbon source for high-speed mixing, wherein the pressure of the filter pressing is less than or equal to 0.4 Mpa. Mixing for 20min, loading the materials into a specific graphite crucible, and sintering at 780 ℃ under the protection of nitrogen. The sintering time is 10h.
S4: material molding: and S3, performing jet milling, demagnetizing and screening on the sintered material to form the lithium iron phosphate anode material with the primary particle size of about 200 nm.
EXAMPLE III
S1: preparing a phosphate solution: 1587Kg of ferrous sulfate and 222Kg of lithium phosphate are weighed and dissolved in 4000L of 1mol/L phosphoric acid solution, and after the solid is completely dissolved, the catalyst citric acid is added, and 30 Kg of citric acid is added at one time. And adding the mixture into a reactor after uniformly stirring, adding ammonia water while performing sand grinding circulation, continuously testing the pH value of the reaction solution in the reactor on line in the process, and finishing the reaction when the pH value reaches 7.0 to generate the initial phosphate slurry.
S2: fine grinding: and (3) grinding the phosphate initial slurry obtained in the step (S1) by a sand mill and a refiner for one time in sequence to form refined slurry.
S3: and (3) drying: and (3) conveying the fine grinding slurry obtained in the step (S2) to a filter press for filter pressing, wherein the pressure of the filter pressing is less than or equal to 0.4Mpa, transferring the filter pressing filter cake to a vacuum vibration dryer, transferring the dried material for 7.0 minutes to a high-speed mixer, and simultaneously adding 5% of carbon source for high-speed mixing. Mixing for 20min, loading the materials into a graphite crucible for sintering under nitrogen protection, wherein the sintering temperature is 790 ℃. The sintering time is 10.5h.
S4: material molding: and S3, performing jet milling, demagnetizing and screening on the sintered material to form the lithium iron phosphate anode material with the primary particle size of about 200 nm.
Table 1 below shows the electrical performance test results of the lithium iron phosphate positive electrode materials prepared in the examples, and table 2 shows the cost per ton converted by the conventional method and the method of the present invention under the condition of capacity of 7 tons/day.
Table 1:
table 2:
as can be seen from Table 1, the capacity and first-pass of the synthesized material of the present invention are both at a high level. As can be seen from Table 2, the cost of each ton of the method of the invention is reduced by about 17000 yuan, and the method has great economic benefit.
Fig. 1 shows the process flow of the present invention, and it can be seen from SEM images of various embodiments of fig. 2 to 4 that the particle size of the primary particle of the lithium iron phosphate material prepared by the present invention is relatively uniform, and is generally about 100nm to 200 nm. Fig. 5 shows XRD characterization of the materials of the three embodiments, which is consistent with standard PDF cards, and indicates that the lithium iron phosphate prepared by the method of the present invention is a pure phase material.
The invention also provides the application of the phosphate anode material prepared by the production process in the lithium battery anode material, and the high-quality phosphate anode material can be prepared at lower cost, so that the production cost of the lithium battery anode material is greatly reduced, and the enterprise competitiveness is improved.
In this specification, the schematic representations of the terms are not necessarily referring to the same embodiment. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The phosphate cathode material is characterized by being prepared from the following raw materials in parts by weight: 55-62 parts of ferrous salt; 7-12 parts of lithium salt; 9-12 parts of a phosphoric acid solution; 1-2 parts of a catalyst; 15-20 parts of a precipitating agent; wherein the catalyst is a complexing agent or a dispersing agent.
2. The phosphate positive electrode material according to claim 1, characterized in that: the ferrous salt is ferrous sulfate, ferrous chloride or ferrous nitrate.
3. The phosphate positive electrode material according to claim 1, characterized in that: the lithium salt is lithium phosphate or lithium hydroxide.
4. The phosphate positive electrode material according to claim 1, characterized in that: the precipitant is sodium hydroxide or ammonia water.
5. The phosphate positive electrode material according to claim 1, characterized in that: the catalyst is citric acid, EDTA or PEG4000-6000.
6. A production process of a phosphate positive electrode material is characterized by comprising the following steps:
s1: preparing a phosphate solution: dissolving ferrous salt and lithium salt into a phosphoric acid solution, adding a catalyst, uniformly stirring, adding the catalyst into a reaction kettle, adding a precipitator into the reaction kettle while stirring until the reaction is finished to form phosphate initial slurry;
s2: fine grinding: grinding the phosphate initial slurry obtained in the step S1 by a sand mill and a refiner in sequence for one time to form refined slurry;
s3: and (3) drying: conveying the fine grinding slurry obtained in the step S2 to a filter press for filter pressing, transferring to a vacuum vibration dryer, loading the dried material into a graphite crucible, and then entering an inert gas protection kiln for sintering;
s4: material molding: and S3, performing jet milling and demagnetizing screening on the sintered material to form the lithium iron phosphate anode material.
7. The process for producing a phosphate positive electrode material according to claim 6, characterized in that: in the step S1, continuously testing the pH value in the reaction kettle after adding the precipitator, and finishing the reaction when the pH value reaches 6.5-7.0, thus generating the initial phosphate slurry.
8. The process for producing a phosphate positive electrode material according to claim 6, characterized in that: in the step S3, transferring the dried material into a high-speed mixer, and simultaneously adding 3-5% of carbon source for high-speed mixing; mixing for 15-20 min, and sintering in a graphite crucible.
9. The process for producing a phosphate positive electrode material according to claim 6, characterized in that: the sintering temperature in the kiln is 780-800 ℃; the sintering time is 10-10.5 h.
10. Use of the phosphate positive electrode material prepared by the production process according to any one of claims 6 to 9 in a positive electrode material for a lithium battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211183046.2A CN115448283B (en) | 2022-09-27 | 2022-09-27 | Phosphate positive electrode material and production process and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211183046.2A CN115448283B (en) | 2022-09-27 | 2022-09-27 | Phosphate positive electrode material and production process and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115448283A true CN115448283A (en) | 2022-12-09 |
| CN115448283B CN115448283B (en) | 2024-04-12 |
Family
ID=84306532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211183046.2A Active CN115448283B (en) | 2022-09-27 | 2022-09-27 | Phosphate positive electrode material and production process and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115448283B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101752564A (en) * | 2010-01-20 | 2010-06-23 | 河北工业大学 | Hydrothermal synthesis method of LiFePO4 of anode material of lithium ion battery with one-dimensional nanometer structure |
| CN102637853A (en) * | 2011-02-12 | 2012-08-15 | 同济大学 | Preparation method of lithium ion battery anode composite material |
| CN106169567A (en) * | 2016-08-08 | 2016-11-30 | 郑州百成新能源科技有限公司 | A kind of lithium iron phosphate positive material of carbon cladding and preparation method thereof |
| CN110048120A (en) * | 2019-04-23 | 2019-07-23 | 王柯娜 | A kind of preparation method of nanometer of ferrous acid lithium |
| CN111422852A (en) * | 2020-04-18 | 2020-07-17 | 蒋央芳 | Preparation method of iron vanadium phosphate |
-
2022
- 2022-09-27 CN CN202211183046.2A patent/CN115448283B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101752564A (en) * | 2010-01-20 | 2010-06-23 | 河北工业大学 | Hydrothermal synthesis method of LiFePO4 of anode material of lithium ion battery with one-dimensional nanometer structure |
| CN102637853A (en) * | 2011-02-12 | 2012-08-15 | 同济大学 | Preparation method of lithium ion battery anode composite material |
| CN106169567A (en) * | 2016-08-08 | 2016-11-30 | 郑州百成新能源科技有限公司 | A kind of lithium iron phosphate positive material of carbon cladding and preparation method thereof |
| CN110048120A (en) * | 2019-04-23 | 2019-07-23 | 王柯娜 | A kind of preparation method of nanometer of ferrous acid lithium |
| CN111422852A (en) * | 2020-04-18 | 2020-07-17 | 蒋央芳 | Preparation method of iron vanadium phosphate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115448283B (en) | 2024-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108183234B (en) | Preparation method of lithium iron phosphate/carbon composite material | |
| AU2010265710B2 (en) | Method for producing composite lithium iron phosphate material and composite lithium iron phosphate material produced thereby | |
| EP2509143A2 (en) | Anode active material precursor and active material for a rechargeable lithium battery comprising hollow nanofibrous carbon, and a production method therefor | |
| CN101417794B (en) | Production manufacturing method of high rate lithium ionic cell cathode F series material | |
| CN115367725B (en) | Doped lithium iron phosphate and preparation method and application thereof | |
| CN115448278B (en) | Method for continuously preparing ferric phosphate and application | |
| CN115611258B (en) | Sodium-ion battery positive electrode material Na 3 Fe 2 (PO 4 )P 2 O 7 Preparation method of (1) | |
| CN114804056A (en) | Carbon-coated high-capacity lithium manganese iron phosphate material and preparation method and application thereof | |
| CN113353909A (en) | Method for preparing lithium iron phosphate cathode material by utilizing recovered lithium | |
| CN113772650A (en) | Preparation method and application of lithium iron phosphate | |
| CN114516626B (en) | Preparation method of phosphate positive electrode material | |
| CN113735196A (en) | Recycling method of waste ternary precursor and ternary cathode material obtained by recycling | |
| CN115448283B (en) | Phosphate positive electrode material and production process and application thereof | |
| CN102556998B (en) | Preparation method of lithium iron phosphate material | |
| CN115490227B (en) | Desulfurization-modification method for medium-high sulfur petroleum coke and preparation method and application of desulfurization-modification method for medium-high sulfur petroleum coke to graphite negative electrode | |
| CN116002648A (en) | High-compaction low-temperature lithium iron phosphate positive electrode material, and preparation method and application thereof | |
| CN113716542B (en) | High-capacity high-compaction-density high-iron-phosphorus-ratio nano lithium iron phosphate and preparation method thereof | |
| CN102556999B (en) | Reduction processing method for synthesizing lithium iron phosphate materials | |
| CN114899392A (en) | Preparation method of lithium iron phosphate or lithium ferromanganese anode material of lithium ion battery | |
| CN117246990B (en) | Lithium iron manganese phosphate, preparation method thereof and lithium ion battery | |
| CN114572955B (en) | Battery-grade aluminum-containing ferric phosphate and preparation method thereof, lithium iron phosphate positive electrode material and preparation method thereof, and battery | |
| CN115838162B (en) | Sodium vanadium iron phosphate anode material and preparation method thereof | |
| CN117902560A (en) | Spherical ferric pyrophosphate sodium carbon composite positive electrode material, precursor, preparation method of spherical ferric pyrophosphate sodium carbon composite positive electrode material and precursor, and sodium ion battery | |
| CN117682490A (en) | Preparation method of high-compaction small-particle modified sodium ferric pyrophosphate cathode material | |
| CN117566718A (en) | Method for synthesizing lithium iron phosphate with lithium phosphate as lithium source at low cost |
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 |