CN114497479B - High-compaction high-performance lithium iron phosphate positive electrode material and preparation method thereof - Google Patents
High-compaction high-performance lithium iron phosphate positive electrode material and preparation method thereof Download PDFInfo
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- CN114497479B CN114497479B CN202111668249.6A CN202111668249A CN114497479B CN 114497479 B CN114497479 B CN 114497479B CN 202111668249 A CN202111668249 A CN 202111668249A CN 114497479 B CN114497479 B CN 114497479B
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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 153
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 60
- 238000005056 compaction Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 90
- 239000002002 slurry Substances 0.000 claims abstract description 52
- 238000005245 sintering Methods 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 43
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 39
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 35
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 35
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 35
- 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
- 239000010936 titanium Substances 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 20
- 238000000227 grinding 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
- 238000002156 mixing Methods 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 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
- 238000010902 jet-milling Methods 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000010405 anode material Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 4
- 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
- 239000004721 Polyphenylene oxide Substances 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000843 powder Substances 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 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 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
- 238000012360 testing method Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 230000001788 irregular Effects 0.000 description 3
- 239000011164 primary particle Substances 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
- 238000005253 cladding Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011163 secondary particle Substances 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
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035515 penetration Effects 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- -1 titanium ions Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a high-compaction high-performance lithium iron phosphate positive electrode material and a preparation method thereof, wherein large-granularity ferric phosphate and small-granularity ferric phosphate are selected, a nonionic emulsifier is added to optimize the preparation of slurry, a titanium-containing compound and carbon are added to carry out primary sintering at different temperatures to modify the material to obtain two lithium iron phosphate materials, the two materials are mixed according to a certain proportion, so that particles with different sizes, different shapes, looseness and compactness are mutually filled, secondary sintering is carried out to ensure that carbon net and titanium-containing compound of the two materials are mutually penetrated, and the high-compaction high-performance lithium iron phosphate positive electrode material is obtained, wherein the compaction density is 2.66g/cm 3 The capacity of 0.1C charge-discharge gram of the button cell prepared by the method reaches more than 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 positive electrode 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 lithium iron phosphate positive electrode material is an important component of a lithium ion battery, has high charge and discharge efficiency, good cycle stability, is more durable, high in safety and low in price, and is rich in resources, and is valued more widely, so that the lithium iron phosphate positive electrode material is widely researched and applied. But the energy density of the battery system formed by the battery is low, so that the application of the battery system in a power battery is limited; the capacity of lithium iron phosphate on the current market is close to the theoretical value, the lifting space is not large, and therefore the energy density of the lithium iron phosphate can be improved by improving the compacted density of the lithium iron phosphate.
For example, CN 103618083B discloses a method for producing a high-capacity and high-compaction lithium iron phosphate positive electrode material, which effectively realizes improvement of the compaction density, electrochemical gram capacity and cycle performance of lithium iron phosphate by preparing the high-capacity and high-compaction lithium iron phosphate positive electrode material by adopting a method of multiple compaction and sintering; the method has the defects that the primary crystal phase formed after the primary sintering is unfavorable for the deep penetration of the dopant and the cladding to the material, so that the effect of improving the material performance by the dopant and the cladding is poor, the repeated compaction and the repeated sintering are needed, the process is complicated, the manufacturing difficulty is high, and the batch implementation is unfavorable.
CN 108011104A discloses a high-compaction-density lithium iron phosphate positive electrode material and a preparation method thereof, wherein two particle slurries, namely a large particle slurry and a small particle slurry, are selected, mixed according to a certain proportion in a grinding stage, and then are respectively subjected to drying treatment and heat treatment to prepare the high-compaction-density lithium iron phosphate. The true density of the lithium iron phosphate is 3.60g/cm 3 The method can improve the compaction density to a certain extent, but the compaction density still can not break through 2.60g/cm 3 。
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a high-compaction high-performance lithium iron phosphate positive electrode material, wherein the compaction density of the lithium iron phosphate positive electrode material is 2.66g/cm 3 According to the method, the capacity of the button battery manufactured by the lithium iron phosphate positive electrode material for detecting 0.1C charge and discharge g reaches more than 163.9 mAh/g.
The invention further aims at providing a preparation method of the high-compaction high-performance lithium iron phosphate positive electrode material.
The preparation method of the 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, ferric phosphate, a nonionic 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 jet milling to obtain a first lithium iron phosphate material;
s2, preparing a second lithium iron phosphate material: mixing pure water, a lithium source, ferric 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 to 0.8 percent 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 the mass ratio of 1:1-1:4 to obtain a lithium iron phosphate mixed material;
s4, preparing a lithium iron phosphate positive electrode material: and S3, performing 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 nonionic emulsifier and a carbon source are added in the preparation of the first lithium iron phosphate material, the slurry is in an emulsified state under the action of the nonionic emulsifier, so that particles are mutually agglomerated, and the first lithium iron phosphate material which is large in particles wrapped by a carbon network, irregular in appearance, loose and porous is obtained by performing primary sintering at a higher temperature (790-840 ℃); adding a titanium-containing compound into 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 into material particles of the slurry, and performing primary sintering at 730-780 ℃ to obtain the second lithium iron phosphate material with small particles coated by metal titanium ions, regular morphology and compact particles; by mixing the two lithium iron phosphate materials, they will fill each other, and interpenetrate in the secondary sintering to increase the compacted density and overall performance.
In step S1 or S2, the ground particles produce quasi-spherical secondary particles composed of primary particles in the sintering process, and the agglomerated secondary particles are opened and independently exist in a separated primary particle state through the jet milling in step S1 or S2. The primary particles with smaller volumes are not destroyed by adopting the jet milling mode.
Preferably, in step s1 and/or 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 improvement of the finishing performance of the lithium iron phosphate material is facilitated. The carbon source can be selected from carbon sources for preparing lithium iron phosphate particles conventionally, preferably, in the 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 and enable the particles to be aggregated and compacted in the sintering process, so that the compacted density of the material can be improved, and the particles formed after sintering at a lower temperature are smaller, and can be mutually filled with the large particles obtained in S1, so that the compacted 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 fluotitanate.
Preferably, in the step S1 and/or 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 ferric phosphate is 1:50-1:25.
Preferably, in the step S1, the nonionic emulsifier accounts for 0.1 to 0.2 percent of the total mass of the lithium source, the ferric 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 slurry is 40-60% after mixing.
Preferably, in the step S2, the pure water is added according to the proportion that the solid content of the slurry is 40-60% after mixing.
Preferably, in the step S1 and the step S2, the heat preservation time is 10-12 h.
In the invention, sintering conditions can be selected with reference 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.
The high-compaction high-performance lithium iron phosphate positive electrode material is prepared by adopting the method.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a high-compaction high-performance lithium iron phosphate positive electrode material, which is prepared by mixing and sintering two lithium iron phosphate materials with different particle sizes and morphologies according to a proportion. The compacted density of the lithium iron phosphate positive electrode material is 2.66g/cm 3 The prepared button battery has the charge-discharge gram capacity reaching more than 163.9mAh/g when being used for detecting 0.1C, and has high compaction performance and high electrical performance.
Drawings
FIG. 1 is a SEM scanning image of a 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 invention is further illustrated in detail below in connection with specific examples which are provided solely for the purpose of illustration and are not intended to limit the scope of the invention. The test methods used in the following examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are those commercially available.
In the examples, lithium carbonate (Sichuan and Hua Li technologies Co., ltd.), ferric phosphate (Ruta Dong Yang New energy Co., ltd.), polyvinyl methyl ether (Shanghai Ming Biotechnology Co., ltd.), polyvinyl ethyl ether (Shanghai Ming Biotechnology Co., ltd.), polyethylene glycol (Guangzhou Germany New Material Co., ltd.), tetrabutyl titanate (Wuhan Ji Ye L chemical Co., ltd.), titanium tetrachloride (Wuhan Ji Ye L chemical Co., ltd.) were used.
Example 1
S1, preparing a first lithium iron phosphate material: adding pure water, lithium carbonate, ferric phosphate, polyvinyl methyl ether and polyethylene glycol into a reaction kettle, stirring, dispersing and emulsifying, conveying the emulsified slurry to a sand mill, grinding the slurry to a granularity D50 of 0.50 mu m, spray-drying the slurry to obtain dry powder, sintering the powder in a box-type furnace in inert atmosphere for one time, and carrying out jet milling on the sintered material to obtain a first lithium iron phosphate material; wherein the mol ratio of the added lithium carbonate to the ferric phosphate is 1.01:1, the weight of the added water is 50 percent according to the solid content of the slurry, the added polyethylene glycol accounts for 3.0 percent of the mass of the ferric phosphate, the added polyvinyl methyl ether accounts for 0.1 percent of the total weight of the slurry, the primary sintering temperature is 810 ℃, and the heat preservation time is 12 hours;
s2, preparing a second lithium iron phosphate material: adding pure water, lithium carbonate, ferric phosphate and tetrabutyl titanate into a reaction kettle, stirring and dispersing, conveying the dispersed slurry to a sand mill, grinding the slurry to the granularity D50 of 0.50 mu m, performing spray drying on the slurry to obtain dry powder, sintering the powder in a box-type furnace in inert atmosphere for one time, and performing jet milling on the sintered material to obtain a second lithium iron phosphate material; wherein the mol ratio of the added lithium carbonate to the ferric phosphate is 1.01:1, the weight of the added water is 50 percent according to the solid content of the slurry, the added tetrabutyl titanate accounts for 0.6 percent of the mass of the ferric phosphate, the primary sintering temperature 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 a mass ratio of 1:3 to obtain a lithium iron phosphate mixed material;
s4, preparing a lithium iron phosphate positive electrode material: and S3, performing secondary sintering on the lithium iron phosphate mixed material in the step S3 in a box-type furnace with 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 1.
Example 2
The procedure is the same as in example 1, except that in step s3, the mass ratio of the first lithium iron phosphate material to the second lithium iron phosphate material is 1:1, and the lithium iron phosphate positive electrode material 2 is obtained.
Example 3
The procedure is the same as in example 1, except that in step s3, the mass ratio of the first lithium iron phosphate material to the second lithium iron phosphate material is 1:2, and the lithium iron phosphate positive electrode material 3 is obtained.
Example 4
The procedure is the same as in example 1, except that in step s3, the mass ratio of the first lithium iron phosphate material to the second lithium iron phosphate material is 1:4, and the lithium iron phosphate positive electrode material 4 is obtained.
Example 5
S1, preparing a first lithium iron phosphate material: adding pure water, lithium carbonate, ferric phosphate, polyvinyl diethyl ether and polyethylene glycol into a reaction kettle, stirring, dispersing and emulsifying, conveying the emulsified slurry to a sand mill, grinding to a granularity D50 of 0.60 mu m, spray-drying the slurry to obtain dry powder, sintering the powder in a box-type furnace in inert atmosphere for one time, and carrying out jet milling on the sintered material to obtain a first lithium iron phosphate material; wherein the mol ratio of the added lithium carbonate to the ferric phosphate is 1.01:1, the weight of the added water is 50 percent according to the solid content of the slurry, the added polyethylene glycol accounts for 4.0 percent of the mass of the ferric phosphate, the added polyvinyl methyl ether accounts for 0.2 percent of the total weight of the slurry, the primary sintering temperature is 840 ℃, and the heat preservation time is 12 hours;
s2, preparing a second lithium iron phosphate material: adding pure water, lithium carbonate, ferric phosphate and tetrabutyl titanate into a reaction kettle, stirring and dispersing, conveying the dispersed slurry to a sand mill, grinding the slurry to the granularity D50 of 0.60 mu m, performing spray drying on the slurry to obtain dry powder, sintering the powder in a box-type furnace in inert atmosphere for one time, and performing jet milling on the sintered material to obtain a second lithium iron phosphate material; wherein the mol ratio of the added lithium carbonate to the ferric phosphate is 1.01:1, the weight of the added water is 50 percent according to the solid content of the slurry, the added tetrabutyl titanate accounts for 0.8 percent of the mass of the ferric phosphate, the primary sintering temperature 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 positive electrode material: and S3, performing secondary sintering on the lithium iron phosphate mixed material in the step S3 in a box-type furnace with 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 5.
Example 6
S1, preparing a first lithium iron phosphate material: adding pure water, lithium carbonate, ferric phosphate, polyvinyl methyl ether and polyethylene glycol into a reaction kettle, stirring, dispersing and emulsifying, conveying the emulsified slurry to a sand mill, grinding the slurry to a granularity D50 of 0.55 mu m, spray-drying the slurry to obtain dry powder, sintering the powder in a box-type furnace in inert atmosphere for one time, and carrying out jet milling on the sintered material to obtain a first lithium iron phosphate material; wherein the mol ratio of the added lithium carbonate to the ferric phosphate is 1.01:1, the weight of the added water is 50 percent according to the solid content of the slurry, the added carbon source accounts for 2.0 percent of the mass of the ferric phosphate, the added nonionic emulsifier accounts for 0.1 percent of the total weight of the slurry, the primary sintering temperature is 790 ℃, and the heat preservation time is 12 hours;
s2, preparing a second lithium iron phosphate material: adding pure water, lithium carbonate, ferric phosphate and titanium tetrachloride into a reaction kettle, stirring and dispersing, conveying the dispersed slurry to a sand mill, grinding the slurry to a granularity D50 of 0.55 mu m, spray-drying the slurry to obtain dry powder, sintering the powder in a box-type furnace in inert atmosphere for one time, and performing jet milling on the sintered material to obtain a second lithium iron phosphate material; wherein the mol ratio of the added lithium source to the ferric phosphate is 1.01:1, the weight of the added water is 50 percent according to the solid content of the slurry, the added tetrabutyl titanate accounts for 0.4 percent of the mass of the ferric phosphate, the primary sintering temperature 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 a mass ratio of 1:3 to obtain a lithium iron phosphate mixed material;
s4, preparing a lithium iron phosphate positive electrode material: and S3, performing secondary sintering on the lithium iron phosphate mixed material in the step S3 in a box-type furnace with 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
Pure water, lithium carbonate, ferric phosphate, tetrabutyl titanate and polyethylene glycol are put into a reaction kettle to be stirred and dispersed, the dispersed slurry is conveyed to a sand mill to be ground to the granularity D50 of 0.50 mu m, the slurry is subjected to spray drying to obtain dry powder, the powder is sintered for one time in a box-type furnace in inert atmosphere, and then the sintered material is subjected to jet milling to obtain the lithium iron phosphate material 7.
Wherein the mol ratio of the added lithium source to the ferric phosphate is 1.01:1, the weight of the added water is 50 percent according to the solid content of the slurry, the added carbon source accounts for 3.0 percent of the mass of the ferric phosphate, the added titanium-containing compound accounts for 0.6 percent of the mass of the ferric phosphate, the added nonionic emulsifier accounts for 0.1 percent of the total weight of the slurry, the primary sintering temperature is 810 ℃, and the heat preservation time is 12 hours;
comparative example 2
The procedure is the same as in example 1, except that in step s3, the mass ratio of the first lithium iron phosphate material to the second lithium iron phosphate material is 1:5, and the lithium iron phosphate positive electrode material 8 is obtained.
Comparative example 3
The procedure is the same as in example 1, except that in step s2, tetrabutyl titanate is added to obtain a mass percentage of 1.0% of the iron phosphate, and the lithium iron phosphate cathode material 9 is obtained.
Comparative example 4
The procedure is the same as in example 1, except that in step s2, tetrabutyl titanate is added to obtain a mass percentage of 0.2% of the iron phosphate, and the lithium iron phosphate cathode material 10 is obtained.
Comparative example 5
The procedure was the same as in example 1, except that in step s1, the sintering temperature was 850 ℃, and a lithium iron phosphate positive electrode material 11 was obtained.
Comparative example 6
The procedure was the same as in example 1, except that in step s2, the sintering temperature was 720 ℃, and the lithium iron phosphate cathode material 12 was obtained.
Comparative example 7
The procedure was the same as in example 1, except that in step s1 and step s2, the particles in the slurry were ground to a particle size D50 of 0.40 μm, and a lithium iron phosphate positive electrode material was obtained.
Comparative example 8
The procedure was the same as in example 1, except that in step s1 and step s2, grinding was performed until the particle size D50 of the particles in the slurry was 0.70 μm, and a lithium iron phosphate positive electrode material was obtained.
Comparative example 9
The procedure was the same as in example 1, except that in step S1, grinding was performed until the particle size D50 of the particles in the slurry was 0.40. Mu.m, and a lithium iron phosphate positive electrode material was obtained.
Comparative example 10
The procedure was the same as in example 1, except that in step s2, grinding was performed until the particle size D50 of the particles in the slurry was 0.80 μm, and a lithium iron phosphate positive electrode material was obtained.
Comparative example 11
The procedure is the same as in example 1, except that in 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 of example 1, except that in step s1, no polyvinyl methyl ether is added in the preparation of the first lithium iron phosphate material, and the obtained lithium iron phosphate positive electrode material.
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 fabricated into button cells, which were subjected to an electrical property test, and the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the lithium iron phosphate positive electrode material prepared by the method of the present invention has a compacted density of 2.66g/cm 3 The button cell prepared by adopting the method has the discharge capacity of 0.1C higher than 163.9mAh/g and the discharge capacity of 1C higher than 149.8mAh/g, and the compaction density and the comprehensive performance of the lithium iron phosphate anode material are effectively improved. As can be seen from comparison of example 1 and comparative example 1, the compacted density of the lithium iron phosphate cathode material prepared by the method of the present invention is significantly improved, 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 compact particles are prepared in the preparation process of the present invention, and then the two lithium iron phosphate materials are mixed to be mutually filled, and the compacted density and the overall performance are improved by interpenetration in the secondary sintering. As can be seen from comparison of comparative example 2 and example 1, when the mixing ratio of the first lithium iron phosphate material and the second lithium iron phosphate material is not 1:1 to 1:4 in step S3, the performance of the prepared lithium iron phosphate positive electrode material is reduced, and the compacted density is 2.63g/cm 3 The 0.1C discharge capacity was 163.0mAh/g.
By comparison ofAs can be seen from comparative examples 3 to 4 and example 1, when the addition amount of the titanium-containing compound is not 0.4 to 0.8% by mass of the iron phosphate in the step S2, the compacted density of the obtained lithium iron phosphate positive electrode material is not higher than 2.60g/cm 3 The discharge capacity of 0.1C is not higher than 163.2mAh/g.
As can be seen from comparison of comparative example 5 and example 1, when the sintering temperature is not in the range of 790-840 ℃ in step S1, the compacted density of the prepared lithium iron phosphate positive electrode material is not higher than 2.59g/cm 3 The discharge capacity of 0.1C is not higher than 161.4mAh/g.
As can be seen from comparison of comparative example 6 and example 1, in step S2, when the sintering temperature is not within the range of 730-780 ℃, the compaction density of the prepared lithium iron phosphate positive electrode material is not higher than 2.56g/cm 3 The discharge capacity of 0.1C of the button cell prepared by adopting the method is not higher than 161.9mAh/g.
As can be seen from comparison of comparative examples 7 to 10 and example 1, when the grinding particle size D50 is too small or too large in steps S1, S2, the compacted density of the prepared lithium iron phosphate positive electrode material is not higher than 2.62g/cm 3 The discharge capacity of 0.1C is not higher than 162.0mAh/g.
As can be seen from comparison of comparative example 11 and example 1, in step S2, the second lithium iron phosphate material was prepared without tetrabutyl titanate, and the compacted density of the prepared lithium iron phosphate positive electrode material was only 2.54g/cm 3 The button cell is prepared by adopting the method, and the discharge capacity of 0.1C is 159.9mAh/g.
As can be seen from comparison of comparative example 12 and example 1, in step S2, the second lithium iron phosphate material was prepared without adding polyvinyl methyl ether, and the compacted density of the prepared lithium iron phosphate positive electrode material was only 2.51g/cm 3 The button cell is prepared by adopting the method, and the 0.1C discharge capacity is 159.1mAh/g.
The morphology analysis of the lithium iron phosphate positive electrode material prepared by the method is carried out by adopting a scanning electron microscope, and an electron microscope diagram of the lithium iron phosphate positive electrode material prepared in the example 4 is shown in figure 1. From fig. 1, it can be seen that the lithium iron phosphate positive electrode material contains two lithium iron phosphate materials, one of which has a large particle size, irregular morphology and loose particles, and the other of which has a small particle size, regular morphology and dense particles, and it can be seen that the two lithium iron phosphate materials are mutually filled, so that the compacted density of the lithium iron phosphate positive electrode material is improved.
An electron microscopic image of the lithium iron phosphate positive electrode material prepared in comparative example 1 is shown in fig. 2. It can be seen from fig. 2 that the lithium iron phosphate positive electrode material is relatively loose and thus has a relatively low compacted density.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the high-compaction high-performance lithium iron phosphate positive electrode material is characterized by comprising the following steps of:
s1, preparing a first lithium iron phosphate material: mixing and emulsifying pure water, a lithium source, ferric phosphate, a nonionic 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 jet milling to obtain a first lithium iron phosphate material;
s2, preparing a second lithium iron phosphate material: mixing pure water, a lithium source, ferric 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 to 0.8 percent 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 the mass ratio of 1:1-1:4 to obtain a lithium iron phosphate mixed material;
s4, preparing a lithium iron phosphate positive electrode material: and S3, performing secondary sintering on the lithium iron phosphate mixed material in the step S3 to obtain the lithium iron phosphate anode material.
2. The preparation method of the lithium iron phosphate positive electrode material according to claim 1, wherein in the step S1 and/or the step S2, the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate.
3. The method for preparing a lithium iron phosphate positive electrode 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 a 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 a lithium iron phosphate positive electrode 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 fluorotitanate.
6. The method for preparing a lithium iron phosphate positive electrode material according to claim 1, wherein in the step s1, the nonionic emulsifier accounts for 0.1 to 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 positive electrode material according to claim 1, wherein in the step S1 and/or the step S2, the molar ratio of the lithium source to the ferric phosphate is 1.01:1-1.02:1.
8. The method for preparing the lithium iron phosphate positive electrode material according to claim 1, wherein in the step S1 and the step S2, the heat preservation time is 10-12 hours.
9. The method for preparing a 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 h.
10. A high-compaction high-performance lithium iron phosphate cathode material, characterized in that the high-compaction high-performance lithium iron phosphate cathode material is prepared by the preparation method according to any one of claims 1 to 9.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008159495A (en) * | 2006-12-26 | 2008-07-10 | Hitachi Maxell Ltd | Positive electrode active material for lithium ion secondary battery and manufacturing method thereof |
| CN102013489A (en) * | 2010-10-28 | 2011-04-13 | 河北工业大学 | Metallic titanium doped carbon-coating lithium iron phosphate and preparation method thereof |
| CN108011104A (en) * | 2017-12-12 | 2018-05-08 | 桑顿新能源科技有限公司 | A kind of high compacted density lithium iron phosphate positive material and preparation method thereof |
| CN108163828A (en) * | 2018-01-02 | 2018-06-15 | 乳源东阳光磁性材料有限公司 | A kind of preparation method of spherical lithium iron phosphate anode material |
| CN109192948A (en) * | 2018-08-29 | 2019-01-11 | 深圳市德方纳米科技股份有限公司 | A kind of high compacted density LiFePO4 and preparation method thereof |
| CN109301179A (en) * | 2018-08-22 | 2019-02-01 | 江苏元景锂粉工业有限公司 | A kind of lithium battery lithium iron phosphate positive material and preparation method thereof |
| CN111668464A (en) * | 2020-05-11 | 2020-09-15 | 乳源东阳光磁性材料有限公司 | Lithium iron phosphate coated nickel-cobalt-aluminum ternary cathode material and preparation method and application thereof |
| CN113086959A (en) * | 2021-02-26 | 2021-07-09 | 雅安锂盛新能企业管理中心(有限合伙) | High-compaction low-temperature lithium iron phosphate material, lithium battery positive plate and preparation method thereof |
| CN113562714A (en) * | 2021-07-16 | 2021-10-29 | 贝特瑞（天津）纳米材料制造有限公司 | High-compaction-density lithium iron phosphate and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110091772A1 (en) * | 2008-03-31 | 2011-04-21 | Yuji Mishima | Process for producing lithium iron phosphate particles, lithium iron phosphate particles having olivine type structure, and positive electrode sheet and non-aqueous solvent-based secondary battery using the lithium iron phosphate particles |
-
2021
- 2021-12-30 CN CN202111668249.6A patent/CN114497479B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008159495A (en) * | 2006-12-26 | 2008-07-10 | Hitachi Maxell Ltd | Positive electrode active material for lithium ion secondary battery and manufacturing method thereof |
| CN102013489A (en) * | 2010-10-28 | 2011-04-13 | 河北工业大学 | Metallic titanium doped carbon-coating lithium iron phosphate and preparation method thereof |
| CN108011104A (en) * | 2017-12-12 | 2018-05-08 | 桑顿新能源科技有限公司 | A kind of high compacted density lithium iron phosphate positive material and preparation method thereof |
| CN108163828A (en) * | 2018-01-02 | 2018-06-15 | 乳源东阳光磁性材料有限公司 | A kind of preparation method of spherical lithium iron phosphate anode material |
| CN109301179A (en) * | 2018-08-22 | 2019-02-01 | 江苏元景锂粉工业有限公司 | A kind of lithium battery lithium iron phosphate positive material and preparation method thereof |
| CN109192948A (en) * | 2018-08-29 | 2019-01-11 | 深圳市德方纳米科技股份有限公司 | A kind of high compacted density LiFePO4 and preparation method thereof |
| CN111668464A (en) * | 2020-05-11 | 2020-09-15 | 乳源东阳光磁性材料有限公司 | Lithium iron phosphate coated nickel-cobalt-aluminum ternary cathode material and preparation method and application thereof |
| CN113086959A (en) * | 2021-02-26 | 2021-07-09 | 雅安锂盛新能企业管理中心(有限合伙) | High-compaction low-temperature lithium iron phosphate material, lithium battery positive plate and preparation method thereof |
| CN113562714A (en) * | 2021-07-16 | 2021-10-29 | 贝特瑞（天津）纳米材料制造有限公司 | High-compaction-density lithium iron phosphate and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Effects of titanium incorporation on phase and electrochemical performance in LiFePO4 cathode material";Wang, ZH et al.;《ELECTROCHIMICA ACTA》;第78卷;576-584 * |
| "Ti含量对掺杂磷酸铁锂正极材料性能影响的研究";许昕;《安徽化工》;第44卷(第6期);全文 * |
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