CN114497479A - High-compaction high-performance lithium iron phosphate cathode material and preparation method thereof - Google Patents
High-compaction high-performance lithium iron phosphate cathode material and preparation method thereof Download PDFInfo
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- CN114497479A CN114497479A CN202111668249.6A CN202111668249A CN114497479A CN 114497479 A CN114497479 A CN 114497479A CN 202111668249 A CN202111668249 A CN 202111668249A CN 114497479 A CN114497479 A CN 114497479A
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 155
- 238000005056 compaction Methods 0.000 title claims abstract description 39
- 239000010406 cathode material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 102
- 238000005245 sintering Methods 0.000 claims abstract description 49
- 239000002002 slurry Substances 0.000 claims abstract description 48
- 239000002245 particle Substances 0.000 claims abstract description 44
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 39
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000012875 nonionic emulsifier Substances 0.000 claims abstract description 14
- 239000007774 positive electrode material Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 239000010405 anode material Substances 0.000 claims description 13
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 238000010902 jet-milling Methods 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 239000005955 Ferric phosphate Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 229940032958 ferric phosphate Drugs 0.000 claims description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims 1
- 239000012466 permeate Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000843 powder Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 9
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000004576 sand Substances 0.000 description 7
- 238000001694 spray drying Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- -1 titanium ions Chemical class 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
-
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
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- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention discloses a high-compaction high-performance lithium iron phosphate cathode material and a preparation method thereof, wherein large-particle-size iron phosphate and small-particle-size iron phosphate are selected, a nonionic emulsifier is added to optimize slurry preparation, a titanium-containing compound and carbon are added to carry out primary sintering at different temperatures to modify the materials to obtain two lithium iron phosphate materials, the two materials are mixed according to a certain proportion to mutually fill particles with different sizes, different shapes, looseness and compactness, and secondary sintering is carried out to mutually permeate the carbon net and the titanium-containing compound of the two materials to obtain the high-compaction high-performance lithium iron phosphate cathode material, and the compaction density is 2.66g/cm3Above, it is used to make buttonsThe charge-discharge gram capacity of the battery at 0.1C reaches above 163.9 mAh/g.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a high-compaction high-performance lithium iron phosphate cathode material and a preparation method thereof.
Background
The lithium ion battery has the characteristics of portability, high efficiency, long cycle life, good safety performance and the like, so that the application field of the lithium ion battery is continuously expanded and the lithium ion battery is gradually applied to the field of electric automobiles. The anode material is an important component of the lithium ion battery, and the lithium iron phosphate anode material is widely researched and applied due to the advantages of high charging and discharging efficiency, good cycling stability, more durability, high safety, low price, abundant resources and high importance. But the energy density of a battery system formed by the composite material is low, so that the application of the composite material in a power battery is limited; the capacity of lithium iron phosphate on the market at present is close to the theoretical value, and the lifting space is small, so that the energy density of the lithium iron phosphate can be improved by improving the compaction density of the lithium iron phosphate.
For example, CN 103618083B discloses a production method of a high-capacity high-compaction lithium iron phosphate positive electrode material, which prepares the high-capacity high-compaction lithium iron phosphate positive electrode material by adopting a multiple-compaction and sintering method, thereby effectively realizing improvement of compaction density, electrochemical gram-volume and cycle performance of lithium iron phosphate; the method has the disadvantages that after primary sintering, secondary doping sintering and three-time coating sintering are carried out, a primary crystal phase is formed after the primary sintering, so that the deep penetration of the dopant and the coating to the material is not facilitated, the improvement effect of the dopant and the coating to the material performance is poor, multiple compaction and multiple sintering are required, the process is complicated, the manufacturing difficulty is high, and the batch implementation is not facilitated.
CN 108011104 a discloses a high compaction density lithium iron phosphate positive electrode material and a preparation method thereof, wherein two kinds of particle slurry are selected, and in the grinding stage, the large particle slurry and the small particle slurry are mixed according to a certain proportion, and then are respectively subjected to drying treatment and heat treatment to prepare the high compaction density lithium iron phosphate. The real density of the lithium iron phosphate is 3.60g/cm3The method can improve the compaction density to a certain extent, but the compaction density still can not break through 2.60g/cm3。
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a high-compaction high-performance lithium iron phosphate positive electrode material, and the compaction density of the lithium iron phosphate positive electrode material is 2.66g/cm3The gram capacity of charge and discharge of 0.1C detected by a button battery made of the lithium iron phosphate anode material reaches above 163.9 mAh/g.
The invention also aims to provide a preparation method of the high-compaction high-performance lithium iron phosphate positive electrode material.
A preparation method of a high-compaction high-performance lithium iron phosphate positive electrode material comprises the following steps:
s1, preparing a first lithium iron phosphate material: mixing and emulsifying pure water, a lithium source, iron phosphate, a non-ionic emulsifier and a carbon source to obtain slurry, grinding until the particle size D50 of particles in the slurry is 0.50-0.60 mu m, drying, sintering at 790-840 ℃, and carrying out jet milling to obtain a first lithium iron phosphate material;
s2, preparing a second lithium iron phosphate material: mixing pure water, a lithium source, iron phosphate and a titanium-containing compound to obtain slurry, grinding until the particle size D50 of particles in the slurry is 0.50-0.60 mu m, drying, sintering at 730-780 ℃, and carrying out jet milling to obtain a second lithium iron phosphate material; the titanium-containing compound accounts for 0.4-0.8% of the mass of the ferric phosphate;
s3, preparing a lithium iron phosphate mixed material: mixing the first lithium iron phosphate material in the step S1 and the second lithium iron phosphate material in the step S2 according to a mass ratio of 1: 1-1: 4 to obtain a lithium iron phosphate mixed material;
s4, preparing a lithium iron phosphate anode material: and S3, carrying out secondary sintering on the lithium iron phosphate mixed material in the step S3 to obtain the lithium iron phosphate anode material.
In the scheme, a non-ionic emulsifier and a carbon source are added in the preparation of the first lithium iron phosphate material, the slurry is formed into an emulsified state under the action of the non-ionic emulsifier, so that particles are mutually agglomerated, and the first lithium iron phosphate material which is large in particles coated by a carbon net, irregular in appearance, loose and porous is obtained by sintering at a higher temperature (790-840 ℃); adding a titanium-containing compound in the preparation of the second lithium iron phosphate material, mixing and grinding the titanium-containing compound and the slurry, uniformly fusing the titanium-containing compound and the slurry in material particles of the slurry, and sintering at 730-780 ℃ for one time to obtain a second lithium iron phosphate material which is smaller in particles coated with metal titanium ions, regular in appearance and dense in particles; by mixing two lithium iron phosphate materials, the two lithium iron phosphate materials can be mutually filled and mutually permeate in secondary sintering to improve the compaction density and the overall performance.
In step s1. or s2. the milled particles produce spheroidal secondary particles composed of primary particles during sintering, and the agglomerated secondary particles are opened by the jet milling described in step s1. or s2. and exist independently in a state of separate primary particles. The jet milling mode is adopted, and primary particles with smaller volume cannot be damaged.
Preferably, in step s1 or/and step s2, the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium nitrate or lithium acetate.
The carbon source can form a carbon network among particles of the material, so that the conductivity among the particles can be obviously improved, and the finishing performance of the lithium iron phosphate material can be improved. The carbon source may be selected from carbon sources for conventionally preparing lithium iron phosphate particles, and preferably, in step s1, the carbon source is one or more of glucose, starch, phenolic resin, polyvinyl alcohol, and polyethylene glycol.
Preferably, in step s1, the nonionic emulsifier is a polyether nonionic emulsifier.
More specifically, the polyether type nonionic emulsifier can be one or more of polyvinyl methyl ether, polyvinyl ethyl ether, polyoxyethylene polyoxypropylene ether, naphthol polyoxyethylene ether and polyvinyl isobutyl ether.
The titanium-containing compound can inhibit the growth of particles in the sintering process and enable the particles to be aggregated and compact, the compaction density of the material can be improved, the particles formed after sintering at a lower temperature are smaller, the particles can be mutually filled with the large particles obtained in the step S1, and the compaction density of the material is improved again. Preferably, in step s2, the titanium-containing compound is one or more of titanium tetrachloride, titanium trichloride, titanium oxychloride, tetrabutyl titanate, and ammonium fluorotitanate.
Preferably, in the step S1. or/and the step S2. the molar ratio of the lithium source to the ferric phosphate is 1: 01-1.02: 1.
Preferably, in the step S1, the mass ratio of the carbon source to the iron phosphate is 1: 50-1: 25.
Preferably, in the step S1, the non-ionic emulsifier accounts for 0.1-0.2% of the total mass of the lithium source, the iron phosphate and the carbon source.
Preferably, in the step S1, the pure water is added according to the proportion that the solid content of the mixed slurry is 40-60%.
Preferably, in the step S2, the pure water is added according to the proportion that the solid content of the mixed slurry is 40-60%.
Preferably, in the step S1 and the step S2, the heat preservation time is 10-12 h.
In the invention, the sintering conditions can be selected by referring to the existing lithium iron phosphate anode material. Preferably, in the step S4, the sintering temperature is 400-600 ℃, and the heat preservation time is 4-6 h.
A high-compaction high-performance lithium iron phosphate cathode material is prepared by adopting the method.
Compared with the prior art, the invention realizes the following beneficial effects:
the invention discloses a high-compaction high-performance lithium iron phosphate positive electrode material which is prepared by preparing two lithium iron phosphate materials with different particle sizes and appearances and mixing and sintering the two lithium iron phosphate materials in proportion. The compacted density of the lithium iron phosphate cathode material is 2.66g/cm3The charge-discharge gram capacity of 0.1C detected by a button battery prepared from the material reaches more than 163.9mAh/g, and the button battery has high compaction performance and high electrical performance.
Drawings
Fig. 1 is an SEM electron microscope scan of the lithium iron phosphate positive electrode material of example 4;
fig. 2 is an SEM electron microscope scan of the lithium iron phosphate positive electrode material of comparative example 1.
Detailed Description
The present invention is further described in detail below with reference to specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention. The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.
In the examples, lithium carbonate (Sichuan Chang and Hua Li technology Co., Ltd.), iron phosphate (Dayuandong sunshine New energy Co., Ltd.), polyvinyl methyl ether (Shanghai boundary Ming Biotech Co., Ltd.), polyvinyl ethyl ether (Shanghai boundary Ming Biotech Co., Ltd.), polyethylene glycol (Kyowa Denda New Material Co., Ltd.), tetrabutyl titanate (Wuhan Ji Industrial promotion chemical Co., Ltd.), titanium tetrachloride (Wuhan Ji Industrial promotion chemical Co., Ltd.) were used.
Example 1
S1, preparing a first lithium iron phosphate material: putting pure water, lithium carbonate, iron phosphate, polyvinyl methyl ether and polyethylene glycol into a reaction kettle, stirring, dispersing and emulsifying, conveying the emulsified slurry to a sand mill, grinding until the granularity D50 is 0.50 mu m, spray-drying the slurry to obtain dry powder, placing the powder in a box-type furnace in inert atmosphere for primary sintering, and then carrying out air flow crushing on the sintered material to obtain a first lithium iron phosphate material; wherein the molar ratio of the added lithium carbonate to the added iron phosphate is 1.01:1, the weight of the added water is 50% according to the solid content of the slurry, the mass percentage of the added polyethylene glycol to the iron phosphate is 3.0%, the added polyvinyl methyl ether to the total weight of the slurry is 0.1%, the temperature of primary sintering is 810 ℃, and the heat preservation time is 12 hours;
s2, preparing a second lithium iron phosphate material: putting pure water, lithium carbonate, iron phosphate and tetrabutyl titanate into a reaction kettle, stirring and dispersing, conveying the dispersed slurry to a sand mill, grinding until the granularity D50 is 0.50 mu m, carrying out spray drying on the slurry to obtain dried powder, placing the powder in a box furnace in an inert atmosphere, carrying out primary sintering, and then carrying out jet milling on the sintered material to obtain a second lithium iron phosphate material; wherein the molar ratio of the added lithium carbonate to the added iron phosphate is 1.01:1, the weight of the added water is 50% according to the solid content of the slurry, the added tetrabutyl titanate accounts for 0.6% of the mass of the iron phosphate, the temperature of primary sintering is 760 ℃, and the heat preservation time is 10 hours;
s3, preparing a lithium iron phosphate mixed material: mixing the first lithium iron phosphate material and the second lithium iron phosphate material according to the mass ratio of 1:3 to obtain a lithium iron phosphate mixed material;
s4, preparing a lithium iron phosphate anode material: and S3, carrying out secondary sintering on the lithium iron phosphate mixed material in the step in a box type furnace in inert atmosphere, wherein the sintering temperature is 500 ℃, and the heat preservation time is 5 hours, so as to obtain the high-compaction high-performance lithium iron phosphate cathode material 1.
Example 2
The steps are the same as those in the embodiment 1, except that in the step s3, the first lithium iron phosphate material and the second lithium iron phosphate material are mixed in a mass ratio of 1:1, and the obtained lithium iron phosphate positive electrode material 2 is obtained.
Example 3
The steps are the same as those in embodiment 1, except that in step s3, the first lithium iron phosphate material and the second lithium iron phosphate material are mixed in a mass ratio of 1:2, and the obtained lithium iron phosphate positive electrode material 3 is obtained.
Example 4
The steps are the same as those in embodiment 1, except that in step s3, the first lithium iron phosphate material and the second lithium iron phosphate material are mixed in a mass ratio of 1:4, and the obtained lithium iron phosphate positive electrode material 4 is obtained.
Example 5
S1, preparing a first lithium iron phosphate material: putting pure water, lithium carbonate, iron phosphate, polyvinyl ether and polyethylene glycol into a reaction kettle, stirring, dispersing and emulsifying, conveying the emulsified slurry to a sand mill, grinding until the granularity D50 is 0.60 mu m, spray-drying the slurry to obtain dry powder, placing the powder in a box furnace in inert atmosphere for primary sintering, and then carrying out air flow crushing on the sintered material to obtain a first lithium iron phosphate material; wherein the molar ratio of the added lithium carbonate to the added iron phosphate is 1.01:1, the weight of the added water is 50% according to the solid content of the slurry, the mass percentage of the added polyethylene glycol to the iron phosphate is 4.0%, the added polyvinyl methyl ether to the total weight of the slurry is 0.2%, the temperature of primary sintering is 840 ℃, and the heat preservation time is 12 hours;
s2, preparing a second lithium iron phosphate material: putting pure water, lithium carbonate, iron phosphate and tetrabutyl titanate into a reaction kettle, stirring and dispersing, conveying the dispersed slurry to a sand mill, grinding until the granularity D50 is 0.60 mu m, carrying out spray drying on the slurry to obtain dried powder, placing the powder in a box furnace in an inert atmosphere, carrying out primary sintering, and then carrying out jet milling on the sintered material to obtain a second lithium iron phosphate material; wherein the molar ratio of the added lithium carbonate to the added iron phosphate is 1.01:1, the weight of the added water is 50% according to the solid content of the slurry, the added tetrabutyl titanate accounts for 0.8% of the mass of the iron phosphate, the temperature of primary sintering is 780 ℃, and the heat preservation time is 10 hours;
s3, preparing a lithium iron phosphate mixed material: mixing the first lithium iron phosphate material and the second lithium iron phosphate material according to a mass ratio of 1:3 to obtain a lithium iron phosphate mixed material;
s4, preparing a lithium iron phosphate anode material: and S3, carrying out secondary sintering on the lithium iron phosphate mixed material in the step in a box furnace in an inert atmosphere, wherein the sintering temperature is 500 ℃, and the heat preservation time is 5 hours, so as to obtain the high-compaction high-performance lithium iron phosphate cathode material 5.
Example 6
S1, preparing a first lithium iron phosphate material: putting pure water, lithium carbonate, iron phosphate, polyvinyl methyl ether and polyethylene glycol into a reaction kettle, stirring, dispersing and emulsifying, conveying the emulsified slurry to a sand mill, grinding until the granularity D50 is 0.55 mu m, spray-drying the slurry to obtain dry powder, placing the powder in a box-type furnace in inert atmosphere for primary sintering, and then carrying out air flow crushing on the sintered material to obtain a first lithium iron phosphate material; wherein the molar ratio of the added lithium carbonate to the added iron phosphate is 1.01:1, the weight of the added water is 50% according to the solid content of the slurry, the mass percentage of the added carbon source to the iron phosphate is 2.0%, the added nonionic emulsifier to the total weight of the slurry is 0.1%, the temperature of primary sintering is 790 ℃, and the heat preservation time is 12 hours;
s2, preparing a second lithium iron phosphate material: adding pure water, lithium carbonate, iron phosphate and titanium tetrachloride into a reaction kettle, stirring and dispersing, conveying the dispersed slurry to a sand mill, grinding until the granularity D50 is 0.55 mu m, performing spray drying on the slurry to obtain dried powder, placing the powder in a box furnace in an inert atmosphere, performing primary sintering, and performing jet milling on the sintered material to obtain a second lithium iron phosphate material; wherein the molar ratio of the added lithium source to the iron phosphate is 1.01:1, the weight of the added water is 50% according to the solid content of the slurry, the added tetrabutyl titanate accounts for 0.4% of the mass of the iron phosphate, the temperature of primary sintering is 730 ℃, and the heat preservation time is 10 hours;
s3, preparing a lithium iron phosphate mixed material: mixing the first lithium iron phosphate material and the second lithium iron phosphate material according to the mass ratio of 1:3 to obtain a lithium iron phosphate mixed material;
s4, preparing a lithium iron phosphate anode material: and S3, carrying out secondary sintering on the lithium iron phosphate mixed material in the step in a box furnace in an inert atmosphere, wherein the sintering temperature is 500 ℃, and the heat preservation time is 5 hours, so as to obtain the high-compaction high-performance lithium iron phosphate anode material 6.
Comparative example 1
Putting pure water, lithium carbonate, iron phosphate, tetrabutyl titanate and polyethylene glycol into a reaction kettle, stirring and dispersing, conveying the dispersed slurry to a sand mill, grinding until the granularity D50 is 0.50 mu m, carrying out spray drying on the slurry to obtain dry powder, placing the powder into a box furnace in an inert atmosphere for primary sintering, and then carrying out jet milling on the sintered material to obtain the lithium iron phosphate material 7.
Wherein the molar ratio of the added lithium source to the iron phosphate is 1.01:1, the weight of the added water is 50% according to the solid content of the slurry, the added carbon source accounts for 3.0% of the mass of the iron phosphate, the added titanium-containing compound accounts for 0.6% of the mass of the iron phosphate, the added nonionic emulsifier accounts for 0.1% of the total weight of the slurry, the temperature of primary sintering is 810 ℃, and the heat preservation time is 12 hours;
comparative example 2
The steps are the same as those in embodiment 1, except that in step s3, the first lithium iron phosphate material and the second lithium iron phosphate material are mixed in a mass ratio of 1:5, and the obtained lithium iron phosphate positive electrode material 8 is obtained.
Comparative example 3
The steps are the same as those of the embodiment 1, except that in the step s2, tetrabutyl titanate is added to account for 1.0% by mass of the iron phosphate, and the lithium iron phosphate anode material 9 is obtained.
Comparative example 4
The steps are the same as those in the embodiment 1, except that in the step s2, tetrabutyl titanate is added to account for 0.2% by mass of the iron phosphate, and the lithium iron phosphate positive electrode material 10 is obtained.
Comparative example 5
The steps are the same as those in example 1, except that in step s1, the sintering temperature is 850 ℃, and the lithium iron phosphate positive electrode material 11 is obtained.
Comparative example 6
The steps are the same as those in the embodiment 1, except that in the step s2, the sintering temperature is 720 ℃, and the lithium iron phosphate positive electrode material 12 is obtained.
Comparative example 7
The steps are the same as those in example 1, except that in step s1. and step s2. the particles in the slurry are ground to a particle size D50 of 0.40 μm, and the obtained material is a lithium iron phosphate positive electrode material.
Comparative example 8
The steps are the same as those in example 1, except that in step s1. and step s2. the slurry is ground until the particle size D50 of the particles in the slurry is 0.70 μm, and the obtained lithium iron phosphate positive electrode material is obtained.
Comparative example 9
The procedure is the same as in example 1, except that in step s1, the slurry is ground until the particle size D50 of the particles in the slurry is 0.40 μm, and the obtained lithium iron phosphate positive electrode material is obtained.
Comparative example 10
The procedure is the same as in example 1, except that in step s2, the slurry is ground until the particle size D50 of the particles in the slurry is 0.80 μm, and the obtained lithium iron phosphate positive electrode material is obtained.
Comparative example 11
The steps are the same as those in the embodiment 1, except that in the step s2, tetrabutyl titanate is not added in the preparation of the second lithium iron phosphate material, and the obtained lithium iron phosphate positive electrode material is obtained.
Comparative example 12
The steps are the same as those in embodiment 1, except that in step s1, polyvinyl methyl ether is not added in the preparation of the first lithium iron phosphate material, and the obtained lithium iron phosphate positive electrode material is obtained.
Performance testing
The lithium iron phosphate positive electrode materials prepared in the above examples and comparative examples were subjected to a compaction density test, and were prepared into button cells, and electrical performance tests were performed thereon, with the test results shown in table 1:
TABLE 1
As can be seen from Table 1, the compacted density of the lithium iron phosphate cathode material prepared by the method of the invention is 2.66g/cm3The button cell prepared from the lithium iron phosphate positive electrode material has 0.1C discharge capacity higher than 163.9mAh/g and 1C discharge capacity higher than 149.8mAh/g, and effectively improves the compacted density and comprehensive performance of the lithium iron phosphate positive electrode material. It can be seen from comparison between example 1 and comparative example 1 that the compacted density of the lithium iron phosphate cathode material prepared by the method of the present invention is significantly increased, because the lithium iron phosphate material with large particle size, irregular morphology and loose particles and the lithium iron phosphate material with small particle size, regular morphology and dense particles are prepared in the preparation process of the present invention, and then the two lithium iron phosphate materials are mixed to fill each other, and the two lithium iron phosphate materials are interpenetrated in the secondary sintering process to improve the compacted density and the overall performance. As can be seen by comparing comparative example 2 with example 1, in step s3, the first lithium iron phosphate material and the second lithium iron phosphate material are mixed in a ratioWhen the ratio is not 1: 1-1: 4, the performance of the prepared lithium iron phosphate positive electrode material is reduced, and the compaction density is 2.63g/cm3And the 0.1C discharge capacity is 163.0 mAh/g.
As can be seen by comparing comparative examples 3-4 with example 1, when the addition amount of the titanium-containing compound is not 0.4-0.8% of the mass of the iron phosphate in the step S2, the compaction density of the prepared lithium iron phosphate cathode material is not higher than 2.60g/cm3The button cell prepared from the material has 0.1C discharge capacity not higher than 163.2 mAh/g.
As can be seen by comparing the comparative example 5 with the example 1, in the step S1, when the sintering temperature is not 790-840 ℃, the compaction density of the prepared lithium iron phosphate cathode material is not higher than 2.59g/cm3The button cell prepared from the material has 0.1C discharge capacity not higher than 161.4 mAh/g.
As can be seen by comparing the comparative example 6 with the example 1, in the step S2, when the sintering temperature is not 730-780 ℃, the compaction density of the prepared lithium iron phosphate cathode material is not higher than 2.56g/cm3The button cell prepared from the material has 0.1C discharge capacity not higher than 161.9 mAh/g.
As can be seen by comparing comparative examples 7-10 with example 1, in the steps S1. and S2. the grinding particle size D50 is too small or too large, and the compaction density of the prepared lithium iron phosphate cathode material is not higher than 2.62g/cm3The button cell prepared from the material has 0.1C discharge capacity not higher than 162.0 mAh/g.
As can be seen from comparison between comparative example 11 and example 1, in step s2, tetrabutyl titanate is not added in the preparation of the second lithium iron phosphate material, and the compacted density of the prepared lithium iron phosphate positive electrode material is only 2.54g/cm3The button cell is prepared by adopting the material, and the 0.1C discharge capacity is 159.9 mAh/g.
As can be seen by comparing comparative example 12 with example 1, in step S2, polyvinyl methyl ether is not added in the preparation of the second lithium iron phosphate material, and the compacted density of the prepared lithium iron phosphate positive electrode material is only 2.51g/cm3The button cell is prepared by adopting the material, and the 0.1C discharge capacity is 159.1 mAh/g.
The lithium iron phosphate cathode material prepared by the method is subjected to morphology analysis by a scanning electron microscope, and an electron microscope image of the lithium iron phosphate cathode material prepared in example 4 is shown in fig. 1. As can be seen from fig. 1, the lithium iron phosphate positive electrode material includes two lithium iron phosphate materials, one of which has a large particle size, an irregular shape and loose particles, and the other of which has a small particle size, a regular shape and dense particles, and the two lithium iron phosphate materials are filled with each other, so that the compaction density of the lithium iron phosphate positive electrode material is improved.
An electron microscope image of the lithium iron phosphate cathode material prepared in comparative example 1 is shown in fig. 2. It can be seen from fig. 2 that the prepared lithium iron phosphate cathode material is loose, so that the compaction density is low.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a high-compaction high-performance lithium iron phosphate positive electrode material is characterized by comprising the following steps:
s1, preparing a first lithium iron phosphate material: mixing and emulsifying pure water, a lithium source, iron phosphate, a non-ionic emulsifier and a carbon source to obtain slurry, grinding until the particle size D50 of particles in the slurry is 0.50-0.60 mu m, drying, sintering at 790-840 ℃, and carrying out jet milling to obtain a first lithium iron phosphate material;
s2, preparing a second lithium iron phosphate material: mixing pure water, a lithium source, iron phosphate and a titanium-containing compound to obtain slurry, grinding until the particle size D50 of particles in the slurry is 0.50-0.60 mu m, drying, sintering at 730-780 ℃, and carrying out jet milling to obtain a second lithium iron phosphate material; the titanium-containing compound accounts for 0.4-0.8% of the mass of the ferric phosphate;
s3, preparing a lithium iron phosphate mixed material: mixing the first lithium iron phosphate material in the step S1 and the second lithium iron phosphate material in the step S2 according to a mass ratio of 1: 1-1: 4 to obtain a lithium iron phosphate mixed material;
s4, preparing a lithium iron phosphate anode material: and S3, carrying out secondary sintering on the lithium iron phosphate mixed material in the step S3 to obtain the lithium iron phosphate anode material.
2. The method for preparing the lithium iron phosphate cathode material according to claim 1, wherein in step s1. or/and step s2. the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium nitrate or lithium acetate.
3. The method for preparing the lithium iron phosphate cathode material according to claim 1, wherein in the step S1, the carbon source is one or more of glucose, starch, phenolic resin, polyvinyl alcohol and polyethylene glycol.
4. The method for preparing the lithium iron phosphate positive electrode material according to claim 1, wherein in step s1, the nonionic emulsifier is a polyether nonionic emulsifier.
5. The method for preparing the lithium iron phosphate cathode material according to claim 1, wherein in the step s2, the titanium-containing compound is one or more of titanium tetrachloride, titanium trichloride, titanium oxychloride, tetrabutyl titanate and ammonium fluotitanate.
6. The preparation method of the lithium iron phosphate positive electrode material according to claim 1, wherein in the step S1, the nonionic emulsifier accounts for 0.1-0.2% of the total mass of the lithium source, the iron phosphate and the carbon source.
7. The preparation method of the lithium iron phosphate cathode material according to claim 1, wherein in step S1. or/and S2. the molar ratio of the lithium source to the iron phosphate is 1.01: 1-1.02: 1.
8. The preparation method of the lithium iron phosphate positive electrode material as claimed in claim 1, wherein in the step S1 and the step S2, the heat preservation time is 10-12 h.
9. The preparation method of the lithium iron phosphate positive electrode material according to claim 1, wherein in the step S4, the sintering temperature is 400-600 ℃, and the heat preservation time is 4-6 hours.
10. A high-compaction high-performance lithium iron phosphate cathode material is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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