CN115448283B - Phosphate positive electrode material and production process and application thereof - Google Patents
Phosphate positive electrode material and production process and application thereof Download PDFInfo
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- CN115448283B CN115448283B CN202211183046.2A CN202211183046A CN115448283B CN 115448283 B CN115448283 B CN 115448283B CN 202211183046 A CN202211183046 A CN 202211183046A CN 115448283 B CN115448283 B CN 115448283B
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 52
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 52
- 239000010452 phosphate Substances 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims description 48
- 239000002002 slurry Substances 0.000 claims description 31
- 238000000227 grinding Methods 0.000 claims description 26
- 238000005245 sintering Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000003825 pressing Methods 0.000 claims description 18
- 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
- 238000002156 mixing Methods 0.000 claims description 15
- 239000010405 anode material Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000010406 cathode material Substances 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011164 primary particle Substances 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000010902 jet-milling Methods 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 6
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 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 4
- 239000002994 raw material Substances 0.000 abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 13
- 159000000002 lithium salts Chemical class 0.000 abstract description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 10
- 239000008139 complexing agent Substances 0.000 abstract description 5
- 239000002270 dispersing agent Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 229910001448 ferrous ion Inorganic materials 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 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
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000005955 Ferric phosphate Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229940032958 ferric phosphate Drugs 0.000 description 6
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder 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
- 238000012545 processing Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 230000009467 reduction Effects 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
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 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
- 238000001914 filtration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 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
- 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
- 239000011343 solid material Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
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- 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
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- 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
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- 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
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- 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
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- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- 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
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- 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
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Abstract
The invention discloses a phosphate positive electrode material, a production process and application thereof, wherein the phosphate positive electrode 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 phosphoric acid solution; 1-2 parts of a catalyst; 15-20 parts of precipitant; wherein the catalyst is a complexing agent or a dispersing agent. According to the phosphate positive electrode material and the production process thereof, common ferric salt and lithium salt can be adopted as raw materials, and raw materials with wide sources and low cost are used, so that the risk of raw material outage 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, the functions of a complexing agent and a dispersing agent are achieved, the uncontrollable agglomeration effect in the reaction process can be reduced, the iron salt and the lithium salt can be mixed to the extent of ions, and the two raw materials can be reacted with a phosphoric acid solution to form lithium iron phosphate.
Description
Technical Field
The invention relates to the technical field of preparation of lithium battery anode powder materials, in particular to a phosphate anode material and a production process thereof.
Background
In 1997, lithium iron phosphate was reported by researchers such as John B Goodenough to possess structural stability and good electrochemical properties, thereby making lithium iron phosphate potentially limitless for commercialization. The iron-based compound has the advantages of low price, rich raw material reserves, no toxicity and good safety, so that the battery world is very concerned with the iron-based positive electrode material. LiFePO 4 The theoretical capacity of the lithium metal anode is 170mAh/g, the stable discharge platform is 3.4V relative to the lithium metal anode, and the lithium metal anode has the outstanding advantages of low price, good thermal stability, no environmental pollution and the like, and isOne of the most potential positive electrode materials at present has been widely used in the fields of power batteries and energy storage.
The capacity of the 2021 lithium iron phosphate positive electrode material is 45.27 ten thousand tons, the same ratio is increased by 168.9%, the annual installed capacity of the battery is 80GWh, the occupied ratio is 52%, the same ratio is increased by 227%, and in recent years, the annual installed capacity of the lithium iron phosphate battery exceeds that of a ternary battery for the first time. From 2021 monthly data, the lithium iron phosphate battery was gradually increased in rate from 38% at the beginning of year to 2021, where the installed amount was first exceeded three-way, up to 51%, after which the installed amount per month was kept above 55%. With the improvement of technologies of lithium iron CTP, kylin batteries and blade batteries in the last year, the energy density of the LFP battery is increased, the safety is better, the cost performance advantage of low cost and the like is that the market demand of the LFP battery in various subdivision fields is increased. In addition, as the price of raw materials increases greatly, the cost expansion space of the battery core is larger, and compared with a ternary battery, the cost performance of the iron lithium battery is higher, so that the demand ratio of the iron lithium in the power, the small power and other fields increases.
The lithium iron phosphate anode material has expanded production tide in 2021 due to the demand of the lithium ion battery anode material in the market burst, and the capacity of the lithium iron phosphate anode material in the market at the end of 2022 reaches 145 ten thousand tons/year according to incomplete statistics.
However, with the rapid expansion of material productivity, the product homogeneity and manufacturing cost are not negligible. How to improve the quality of products and the cost competitiveness of manufacturing processes is also being pushed to the product's new and new demand schedule. The process of lithium iron phosphate can be divided into three types according to the main raw materials: the iron oxide is used as raw material, and the iron oxide route, the ferrous oxalate route and the iron phosphate route are poor in performance and low in cost. The ferrous oxalate route is that ferrous oxalate is used as raw material, and has the environmental problem of ammonium salt treatment, and the processing difficulty is great. A railway line of phosphoric acid; namely, the lithium iron phosphate is synthesized by taking the ferric phosphate as the raw material, the process is mature, the production expansion is easy, and the performance is stable. Currently, lithium iron phosphate manufactured by a railway line is the main stream. In the last few years, due to the lack of material performance of products, other routes are replaced by a ferric phosphate route, but the ferric phosphate route is not easy to obtain raw materials of the ferric phosphate and has higher cost, and the ferric phosphate route is 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 market environment and the problems faced by the production of lithium iron phosphate, I propose an important research and development topic for solving the current dilemma.
Disclosure of Invention
In order to solve the technical problems of high processing difficulty or high raw material cost in 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 positive electrode material which 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 phosphoric acid solution; 1-2 parts of a catalyst; 15-20 parts of precipitant; 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 precipitant 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 positive electrode material, which comprises the following steps:
s1: phosphate solution preparation: and dissolving ferrous salt and lithium salt into a phosphoric acid solution, adding a catalyst, stirring uniformly, adding a reaction kettle, adding a precipitant into the reaction kettle while stirring until the reaction is completed, and forming a phosphate initial slurry.
S2: and (3) fine grinding: and (3) grinding the phosphate initial slurry in the step (S1) sequentially through a sand mill and a fine grinder for one time to form fine grinding 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, feeding into an inert gas protection kiln for sintering.
S4: and (3) material forming: and S3, carrying out jet milling and demagnetizing screening on the sintered material to form the lithium iron phosphate anode material.
Further, in step S1, after adding the precipitant, continuously testing the pH value in the reaction kettle, and ending the reaction when the pH value reaches 6.5-7.0, thereby generating the initial phosphate slurry.
Further, in the step S3, the dried material is transferred into 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 of the filter pressing is not more than 0.4Mpa; the drying time is 20-30 min.
The invention also provides application of the phosphate positive electrode material prepared by the production process in a positive electrode material of a lithium battery.
The beneficial effects of the invention are as follows:
(1) According to the phosphate positive electrode material and the production process thereof, common ferric salt and lithium salt can be adopted as raw materials, and raw materials with wide sources and low cost are used, so that the risk of raw material outage 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, the functions of a complexing agent and a dispersing agent are achieved, the uncontrollable agglomeration effect in the reaction process can be reduced, the iron salt and the lithium salt can be mixed to the extent of ions, and the two raw materials can be reacted with a phosphoric acid solution to form lithium iron phosphate.
(2) The phosphate anode material and the production process thereof provided by the invention have the advantages that the catalyst only consists of C, H, O elements, and the catalyst can be removed through subsequent sintering or carbonization after the reaction is completed.
(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 of material production.
(4) The phosphate positive electrode material and the production process thereof have small specific surface area, are beneficial to the later-stage cell manufacturing and reduce the consumption of the binder. Under normal pressure preparation environment, the primary particle size reaches nano-size, so that the transmission resistance of lithium ions in the application of the battery core is reduced, the conductivity is increased, and the ion conduction resistance is reduced.
Drawings
The invention will be further described with reference to the drawings 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 cathode material of example 1 according to the invention;
FIG. 3 is an SEM image of a phosphate cathode material of example 2 according to the invention;
FIG. 4 is an SEM image of a phosphate cathode material of example 3 according to the invention;
fig. 5 is an XRD pattern of the phosphate cathode materials of examples 1 to 3 according to the present invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
A phosphate positive electrode material, which 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 phosphoric acid solution; 1-2 parts of a catalyst; 15-20 parts of precipitant; wherein the catalyst is a complexing agent or a dispersing agent.
Ferrous salts and lithium salts can be common materials with lower cost, for example, ferrous salts can be ferrous sulfate, ferrous chloride or ferrous nitrate, lithium salts can be lithium phosphate or lithium hydroxide, the components can be directly purchased, or can be extracted from waste materials or prepared by themselves, for example, lithium phosphate has low price, can be directly purchased, can be prepared by using lithium and phosphoric acid, and 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 or ammonia water is selected.
In the prior art, ferric phosphate is used as a raw material, ferric iron is reduced into ferrous iron in a carbon reduction mode, and solid materials can be directly formed after carbon reduction, so that unstable ferrous ions can not exist. When ferrous salt and phosphoric acid are used for reaction preparation, the ferrous salt is unstable in a liquid state and is easily oxidized into ferric salt, so that ferrous salt, lithium salt and phosphoric acid cannot react to generate lithium iron phosphate.
The catalyst is composed of only C, H, O elements, and can be removed by subsequent sintering or carbonization after the reaction is completed. For example, the catalyst may be citric acid, EDTA or PEG4000-6000, etc.
The phosphate anode material is made of safe and easily-removed materials, for example, sodium salt in the precipitant 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 positive electrode material, as shown in figure 1, comprising the following steps:
s1: phosphate solution preparation: the ferrous salt and the lithium salt are dissolved into a phosphoric acid solution, then a catalyst is added, the mixture is stirred uniformly, then the mixture is added into a reaction kettle, a precipitator is added into the reaction kettle while stirring until the reaction is completed, and a phosphate initial slurry is formed, 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 progress of the reaction, the rough method can be calculated according to the reaction time, the more accurate 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 precipitant is added, and the reaction is finished when the pH value reaches 6.5-7.0, and the phosphate initial slurry is generated at the moment.
S2: and (3) fine grinding: the phosphate initial slurry in the step S1 is sequentially ground by a sand mill and a refiner for one time to form refined slurry, and the step S1 is only required to be refined by one time due to the sufficient stirring in the mixing and reacting processes, and four times or so are required to be circularly refined when the iron phosphate is adopted for preparation in the prior art.
S3: and (3) drying: conveying the fine grinding slurry obtained in the step S2 to a filter press for filter pressing, transferring into a vacuum vibration dryer, wherein the drying time is preferably 20-30 min, and placing the dried material into a graphite crucible and then sintering in an inert gas protection kiln, 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 used for removing water vapor and redundant salt solution on the surface of the material. The sintering effect is to make the crystallinity of the material higher, promote the performance of the material, and simultaneously make the carbon source added earlier carbonize and coat the surface of the material, promote the conductivity. In order to increase the conductive effect of the materials, preferably, the dried materials are transferred into a high-speed mixer and simultaneously added with 3 to 5 percent of carbon source 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: and (3) material forming: and S3, carrying out jet milling and demagnetizing screening on the sintered material to form the lithium iron phosphate anode material.
In the prior art, the material is directly dried into powder in a spray drying mode, the specific surface area of the material powder formed by the method is larger, the size of the powder is different, the quality of the product is low, the method combines a filter press and a vacuum vibration dryer, the process time is effectively shortened, the occupied area and the operation cost of equipment are reduced, the material is gradually dried and sintered under a multi-stage temperature gradient, and finally, the finished product of the material formed by crushing and screening has small specific surface area and uniform size, the primary particle size of about 100nm-200nm can be basically ensured, and the product quality is high.
The following analysis was performed in connection with specific examples:
example 1
S1: phosphate solution preparation: 1mol (278.01 g) of ferrous sulfate was weighed out, 1mol (42 g) of lithium hydroxide was dissolved in 500ml of a 1mol/L phosphoric acid solution, and after the solid was completely dissolved, 4 g of citric acid as a catalyst was added at a time. Adding the mixture into a reactor after stirring uniformly, adding ammonia water while performing sanding circulation, continuously testing the pH value of the reaction solution in the reactor on line in the process, and after the pH value reaches 6.8, ending the reaction to generate the initial phosphate slurry.
S2: and (3) fine grinding: and (3) grinding the phosphate initial slurry in the step (S1) sequentially through a sand mill and a fine grinder for one time to form fine grinding 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 a filter cake of the filter pressing into a vacuum vibration dryer, transferring the dried material into a high-speed mixer, and simultaneously adding 3% of carbon source for high-speed mixing. Mixing for 15min, and loading the materials into a specific graphite crucible for nitrogen protection sintering at 800 ℃. Sintering time is 10h.
S4: and (3) material forming: and S3, carrying out 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: phosphate solution preparation: ferrous chloride 3mol (596.43 g), lithium phosphate 1mol (115.79 g) were dissolved in 2000ml of a 1mol/L phosphoric acid solution, and after the solid was completely dissolved, catalyst EDTA was added, and 20 g was added at a time. Adding the mixture into a reactor after stirring uniformly, adding ammonia water while performing sanding circulation, continuously testing the pH value of the reaction solution in the reactor on line in the process, and ending the reaction when the pH value reaches 7.0 to generate phosphate initial slurry.
S2: and (3) fine grinding: and (3) grinding the phosphate initial slurry in the step (S1) sequentially through a sand mill and a fine grinder for one time to form fine grinding 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 a filter cake of the filter pressing into a vacuum vibration dryer, transferring the dried material into a high-speed mixer, and simultaneously adding 5% of carbon source for high-speed mixing. Mixing for 20min, and loading the materials into a specific graphite crucible for nitrogen protection sintering at 780 ℃. Sintering time is 10h.
S4: and (3) material forming: and S3, carrying out 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: phosphate solution preparation: 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 is added at a time. Adding the mixture into a reactor after stirring uniformly, adding ammonia water while performing sanding circulation, continuously testing the pH value of the reaction solution in the reactor on line in the process, and ending the reaction when the pH value reaches 7.0 to generate phosphate initial slurry.
S2: and (3) fine grinding: and (3) grinding the phosphate initial slurry in the step (S1) sequentially through a sand mill and a fine grinder for one time to form fine grinding 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 a filter cake of the filter pressing into a vacuum vibration dryer, transferring the dried material for 7.0 minutes into a high-speed mixer, and simultaneously adding 5% of carbon source for high-speed mixing. Mixing for 20min, and loading the materials into a graphite crucible for nitrogen protection sintering at 790 ℃. Sintering time is 10.5h.
S4: and (3) material forming: and S3, carrying out 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 results of electrical performance testing of the lithium iron phosphate cathode materials prepared in the examples, and table 2 shows the costs per ton for 7 tons per day of capacity, as compared to conventional methods and methods of the present invention.
Table 1:
table 2:
from table 1, it can be seen that the capacity and the first effect of the materials synthesized according to the invention are at a high level. As can be seen from Table 2, the cost per 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 the SEM images of the embodiments of fig. 2 to 4 show that the primary particles of the lithium iron phosphate material prepared by the present invention have a relatively uniform particle size, and are generally about 100nm to 200 nm. Figure 5 shows XRD characterization of the materials of three examples, which demonstrates that lithium iron phosphate prepared by the method of the present invention belongs to a pure phase material by conforming to standard PDF cards.
The invention also provides application of the phosphate positive electrode material prepared by the production process in the positive electrode material of the lithium battery, and the high-quality phosphate positive electrode material can be prepared by lower cost, so that the production cost of the positive electrode material of the lithium battery is greatly reduced, and the competitiveness of enterprises is improved.
In this specification, a schematic representation of the terms does not necessarily refer to the same embodiment. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (3)
1. The production process of the phosphate positive electrode material is characterized by comprising the following steps of:
s1: phosphate solution preparation: 1mol of ferrous sulfate and 1mol of lithium hydroxide are weighed and dissolved into 500ml of 1mol/L phosphoric acid solution, and after the solid is completely dissolved, 4 g of catalyst citric acid is added at a time; adding the mixture into a reactor after stirring uniformly, adding ammonia water while performing sanding circulation, and continuously testing the pH value of the reaction solution in the reactor on line in the process, and after the pH value reaches 6.8, ending the reaction to generate phosphate initial slurry;
s2: and (3) fine grinding: grinding the phosphate initial slurry in the step S1 sequentially through a sand mill and a fine grinder for one time to form fine grinding slurry;
s3: and (3) drying: 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 a filter cake of the filter pressing into a vacuum vibration dryer, transferring the dried material into a high-speed mixer, and simultaneously adding 3% of carbon source for high-speed mixing; mixing for 15min, loading the materials into a graphite crucible, and sintering at 800 ℃ under nitrogen protection; sintering time is 10h;
s4: and (3) material forming: and S3, carrying out jet milling, demagnetizing and screening on the sintered material to form the lithium iron phosphate anode material with the primary particle size of 100 nm.
2. The production process of the phosphate positive electrode material is characterized by comprising the following steps of:
s1: phosphate solution preparation: 3mol of ferrous chloride and 1mol of lithium phosphate are dissolved in 2000ml of 1mol/L phosphoric acid solution, and after the solid is completely dissolved, 20 g of catalyst EDTA is added at a time; adding the mixture into a reactor after stirring uniformly, adding ammonia water while performing sanding circulation, and continuously testing the pH value of the reaction solution in the reactor on line in the process, and ending the reaction when the pH value reaches 7.0 to generate phosphate initial slurry;
s2: and (3) fine grinding: grinding the phosphate initial slurry in the step S1 sequentially through a sand mill and a fine grinder for one time to form fine grinding slurry;
s3: and (3) drying: 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 a filter cake of the filter pressing into a vacuum vibration dryer, transferring the dried materials into a high-speed mixer, and simultaneously adding 5% of carbon source for high-speed mixing; mixing for 20min, and loading the materials into a graphite crucible for nitrogen protection sintering at 780 ℃; sintering time is 10h;
s4: and (3) material forming: and S3, carrying out jet milling, demagnetizing and screening on the sintered material to form the lithium iron phosphate anode material with the primary particle size of 200 nm.
3. The use of the phosphate cathode material prepared by the production process of claim 1 or 2 in a cathode material of a lithium battery.
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| CN110048120A (en) * | 2019-04-23 | 2019-07-23 | 王柯娜 | A kind of preparation method of nanometer of ferrous acid lithium |
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| 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 |
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| 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 |
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