CN116986574A - Preparation method of high-compaction-density lithium iron manganese phosphate - Google Patents
Preparation method of high-compaction-density lithium iron manganese phosphate Download PDFInfo
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- CN116986574A CN116986574A CN202311139197.2A CN202311139197A CN116986574A CN 116986574 A CN116986574 A CN 116986574A CN 202311139197 A CN202311139197 A CN 202311139197A CN 116986574 A CN116986574 A CN 116986574A
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- lithium iron
- manganese phosphate
- iron manganese
- phosphate
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- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 title claims abstract description 119
- 238000005056 compaction Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 101
- 238000002156 mixing Methods 0.000 claims abstract description 44
- 238000001354 calcination Methods 0.000 claims abstract description 42
- 238000000227 grinding Methods 0.000 claims abstract description 32
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 30
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 20
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 20
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 20
- 239000011343 solid material Substances 0.000 claims abstract description 16
- 238000001694 spray drying Methods 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 16
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims abstract description 10
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims abstract description 10
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 21
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910021389 graphene Inorganic materials 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 9
- 229940099596 manganese sulfate Drugs 0.000 claims description 9
- 239000011702 manganese sulphate Substances 0.000 claims description 9
- 235000007079 manganese sulphate Nutrition 0.000 claims description 9
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 9
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims 12
- 239000002245 particle Substances 0.000 abstract description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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- 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
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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
- H01M4/58—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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The preparation method of the high-compaction-density lithium iron manganese phosphate comprises the following steps: step one: adding lithium hydroxide, manganese oxalate, ferric phosphate and cobalt phosphate into pure water, grinding and mixing for 1-3h; step two: drying the suspension obtained after grinding and mixing in a spray drying mode; step three: calcining the dried solid material at 650-770 ℃ for 7-9h, cooling after calcining, and crushing by adopting air flow to obtain a second lithium iron manganese phosphate material. The invention prepares the high compaction density lithium iron manganese phosphate by mixing three lithium iron manganese phosphate materials with different particle diameters, and the compaction density can reach 2.8g/cm 3 Above, thereby can effectual improvement lithium iron manganese phosphate's electric capacity to improve lithium iron manganese phosphate's duration, be convenient for the popularization and the application of lithium iron manganese phosphate battery.
Description
Technical Field
The invention belongs to the field of lithium iron manganese phosphate, and particularly relates to a preparation method of high-compaction-density lithium iron manganese phosphate.
Background
Along with the development of society, the living standard of people is continuously improved, and meanwhile, the environmental pollution phenomenon is also increasingly serious, so that the demand for new energy is also increasingly rising. At presentLithium batteries are widely popularized and applied as new energy batteries, china is in the leading position in the research and development of lithium batteries, the anode materials of the lithium batteries mainly comprise lithium iron phosphate, lithium manganate, ternary series and the like, the research and development focus is always on ternary lithium batteries because of limited performances of the lithium iron phosphate and the lithium manganate, but the lithium iron phosphate has higher safety and longer service life due to the safety problem and the manufacturing cost in recent years, the characteristic of low raw material cost gradually returns to the research and development line, and the lithium manganese phosphate is developed on the basis of the lithium iron phosphate and has higher energy density which is 15% -20% higher than that of the lithium iron phosphate by adding manganese element, so that a higher voltage platform is provided, but the lithium manganese phosphate and the lithium iron phosphate have the same defects that the compaction density is too low and the compaction density which is 4g/cm relative to that of the ternary lithium battery 3 The compacted density of the lithium iron manganese phosphate and the lithium iron phosphate is generally 2-2.4g/cm 3 The higher the compaction density is, the higher the theoretical capacitance is, so the lower the compaction density of the lithium iron manganese phosphate is, the lower the theoretical capacitance is, the endurance is affected, and the popularization and application of the lithium iron manganese phosphate battery are affected.
Disclosure of Invention
The invention provides a preparation method of high-compaction-density lithium iron manganese phosphate, which is used for solving the defects in the prior art.
The invention is realized by the following technical scheme:
the preparation method of the high-compaction-density lithium iron manganese phosphate comprises the following steps:
step one: preparing a first lithium iron manganese phosphate material, a second lithium iron manganese phosphate material and a third lithium iron manganese phosphate material;
step two: mixing a first lithium iron manganese phosphate material, a second lithium iron manganese phosphate material and a third lithium iron manganese phosphate material according to the proportion of 1:2-4:4-6;
step three: after the mixing is completed, crushing, and calcining the mixed material at the temperature of 630-750 ℃ for 6-12h;
step four: and cooling after the calcination is finished, crushing and sub-packaging to obtain the high-compaction density lithium iron manganese phosphate material.
The preparation method of the high-compaction-density lithium iron manganese phosphate comprises the following steps:
step one: adding pure water into the graphene-coated nano lithium phosphate material, manganese sulfate and ferric phosphate, grinding and mixing for 2-4h;
step two: drying the suspension obtained after grinding and mixing in a spray drying mode;
step three: calcining the dried solid material at 780-830 ℃ for 6-8 hours, cooling after calcining, and crushing by adopting air flow to obtain the first lithium iron manganese phosphate material.
According to the preparation method of the high-compaction-density lithium iron manganese phosphate, the preparation method of the graphene-coated nano lithium phosphate material comprises the steps of immersing the nano lithium phosphate material in a graphene solution, carrying out coating operation in a coprecipitation mode, filtering after coating is completed, and drying to obtain the graphene-coated nano lithium phosphate material.
According to the preparation method of the high-compaction-density lithium iron manganese phosphate, the mass ratio of the graphene-coated nano lithium phosphate material to the manganese sulfate to the ferric phosphate is 5:2:1, and the addition amount of the pure water is 5-8 times of the total mass of the nano lithium phosphate material, the manganese sulfate and the ferric phosphate.
The preparation method of the high-compaction-density lithium iron manganese phosphate comprises the following steps of:
step one: adding lithium hydroxide, manganese oxalate, ferric phosphate and cobalt phosphate into pure water, grinding and mixing for 1-3h;
step two: drying the suspension obtained after grinding and mixing in a spray drying mode;
step three: calcining the dried solid material at 650-770 ℃ for 7-9h, cooling after calcining, and crushing by adopting air flow to obtain a second lithium iron manganese phosphate material.
According to the preparation method of the high-compaction-density lithium iron manganese phosphate, the mass ratio of the lithium hydroxide to the manganese oxalate to the iron phosphate to the cobalt phosphate is 4:1:3:1, and the addition amount of the pure water is 6-10 times of the total mass of the lithium hydroxide to the manganese oxalate to the iron phosphate to the cobalt phosphate.
The preparation method of the high-compaction-density lithium iron manganese phosphate comprises the following steps of:
step one: adding lithium carbonate, manganese phosphate and ferric phosphate into pure water, grinding and mixing for 2-3h;
step two: drying the suspension obtained after grinding and mixing in a spray drying mode;
step three: calcining the dried solid material at 620-740 ℃ for 6-9h, cooling after calcining, and crushing by adopting air flow to obtain the third lithium iron manganese phosphate material.
According to the preparation method of the high-compaction-density lithium iron manganese phosphate, the mass ratio of the lithium carbonate to the manganese phosphate to the iron phosphate is 4:2:4, and the addition amount of the pure water is 5-7 times of the total mass of the lithium carbonate, the manganese phosphate and the iron phosphate.
According to the preparation method of the high-compaction-density lithium iron manganese phosphate, in the second step, the first lithium iron manganese phosphate material, the second lithium iron manganese phosphate material and the third lithium iron manganese phosphate material are mixed and refined and ground by adopting a ball mill.
The preparation method of the high-compaction-density lithium iron manganese phosphate comprises the step four of carrying out crushing operation by adopting air flow.
The invention has the advantages that: the invention prepares the high compaction density lithium iron manganese phosphate by mixing three lithium iron manganese phosphate materials with different particle diameters, and the compaction density can reach 2.8g/cm 3 Above, thereby can effectual improvement lithium iron manganese phosphate's electric capacity to improve lithium iron manganese phosphate's duration, be convenient for the popularization and the application of lithium iron manganese phosphate battery.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it will be obvious that the drawings in the following description are some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
Fig. 1 is an SEM image of example 1.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the high-compaction-density lithium iron manganese phosphate comprises the following steps:
step one: preparing a first lithium iron manganese phosphate material, a second lithium iron manganese phosphate material and a third lithium iron manganese phosphate material;
the preparation method for preparing the first lithium iron manganese phosphate material comprises the following steps:
step one: soaking a nano lithium phosphate material in a graphene solution, performing coating operation in a coprecipitation mode, filtering after coating is completed, and drying to obtain a graphene-coated nano lithium phosphate material;
step two: weighing 5kg of graphene-coated nano lithium phosphate material, 2kg of manganese sulfate and 1kg of ferric phosphate, adding 40kg of pure water, grinding and mixing for 2 hours;
step three: drying the suspension obtained after grinding and mixing in a spray drying mode;
step four: calcining the dried solid material at 780 ℃ for 6 hours, cooling after calcining, and crushing by adopting air flow to obtain the first lithium iron manganese phosphate material.
The preparation method for preparing the second lithium iron manganese phosphate material comprises the following steps:
step one: adding 54kg of pure water into 4kg of lithium hydroxide, 1kg of manganese oxalate, 3kg of ferric phosphate and 1kg of cobalt phosphate, grinding and mixing for 1h;
step two: drying the suspension obtained after grinding and mixing in a spray drying mode;
step three: and calcining the dried solid material at 650 ℃ for 7 hours, cooling after calcining, and crushing by adopting air flow to obtain a second lithium iron manganese phosphate material.
The preparation method for preparing the third lithium iron manganese phosphate material comprises the following steps:
step one: adding 50kg of pure water into 4kg of lithium carbonate, 2kg of manganese phosphate and 4kg of ferric phosphate, grinding and mixing for 2 hours;
step two: drying the suspension obtained after grinding and mixing in a spray drying mode;
step three: calcining the dried solid material at 620 ℃ for 6 hours, cooling after calcining, and crushing by adopting air flow to obtain the third lithium iron manganese phosphate material.
Step two: mixing a first lithium iron manganese phosphate material, a second lithium iron manganese phosphate material and a third lithium iron manganese phosphate material according to the proportion of 1:2:4;
step three: after the mixing is completed, crushing, and calcining the mixed material for 6 hours at the temperature of 630 ℃;
step four: and cooling after the calcination is finished, crushing and sub-packaging to obtain the high-compaction density lithium iron manganese phosphate material.
Example 2
The preparation method of the high-compaction-density lithium iron manganese phosphate comprises the following steps:
step one: preparing a first lithium iron manganese phosphate material, a second lithium iron manganese phosphate material and a third lithium iron manganese phosphate material;
the preparation method for preparing the first lithium iron manganese phosphate material comprises the following steps:
step one: soaking a nano lithium phosphate material in a graphene solution, performing coating operation in a coprecipitation mode, filtering after coating is completed, and drying to obtain a graphene-coated nano lithium phosphate material;
step two: weighing 5kg of graphene-coated nano lithium phosphate material, 2kg of manganese sulfate and 1kg of ferric phosphate, adding 64kg of pure water, grinding and mixing for 4 hours;
step three: drying the suspension obtained after grinding and mixing in a spray drying mode;
step four: calcining the dried solid material at 830 ℃ for 8 hours, cooling after calcining, and crushing by adopting air flow to obtain the first lithium iron manganese phosphate material.
The preparation method for preparing the second lithium iron manganese phosphate material comprises the following steps:
step one: adding 90kg of pure water into 4kg of lithium hydroxide, 1kg of manganese oxalate, 3kg of ferric phosphate and 1kg of cobalt phosphate, grinding and mixing for 3 hours;
step two: drying the suspension obtained after grinding and mixing in a spray drying mode;
step three: calcining the dried solid material at 770 ℃ for 9 hours, cooling after calcining, and crushing by adopting air flow to obtain a second lithium iron manganese phosphate material.
The preparation method for preparing the third lithium iron manganese phosphate material comprises the following steps:
step one: adding 70kg of pure water into 4kg of lithium carbonate, 2kg of manganese phosphate and 4kg of ferric phosphate, grinding and mixing for 3 hours;
step two: drying the suspension obtained after grinding and mixing in a spray drying mode;
step three: calcining the dried solid material at 740 ℃ for 9 hours, cooling after calcining, and crushing by adopting air flow to obtain the third lithium iron manganese phosphate material.
Step two: mixing a first lithium iron manganese phosphate material, a second lithium iron manganese phosphate material and a third lithium iron manganese phosphate material according to the proportion of 1:4:6;
step three: after the mixing is completed, crushing, and calcining the mixed material for 12 hours at the temperature of 750 ℃;
step four: and cooling after the calcination is finished, crushing and sub-packaging to obtain the high-compaction density lithium iron manganese phosphate material.
Example 3
The preparation method of the high-compaction-density lithium iron manganese phosphate comprises the following steps:
step one: preparing a first lithium iron manganese phosphate material, a second lithium iron manganese phosphate material and a third lithium iron manganese phosphate material;
the preparation method for preparing the first lithium iron manganese phosphate material comprises the following steps:
step one: soaking a nano lithium phosphate material in a graphene solution, performing coating operation in a coprecipitation mode, filtering after coating is completed, and drying to obtain a graphene-coated nano lithium phosphate material;
step two: weighing 5kg of graphene-coated nano lithium phosphate material, 2kg of manganese sulfate and 1kg of ferric phosphate, adding 52kg of pure water, grinding and mixing for 3 hours;
step three: drying the suspension obtained after grinding and mixing in a spray drying mode;
step four: and calcining the dried solid material at the temperature of 805 ℃ for 7 hours, cooling after calcining, and crushing by adopting air flow to obtain the first lithium iron manganese phosphate material.
The preparation method for preparing the second lithium iron manganese phosphate material comprises the following steps:
step one: adding 80kg of pure water into 4kg of lithium hydroxide, 1kg of manganese oxalate, 3kg of ferric phosphate and 1kg of cobalt phosphate, grinding and mixing for 2 hours;
step two: drying the suspension obtained after grinding and mixing in a spray drying mode;
step three: calcining the dried solid material at 710 ℃ for 8 hours, cooling after calcining, and crushing by adopting air flow to obtain a second lithium iron manganese phosphate material.
The preparation method for preparing the third lithium iron manganese phosphate material comprises the following steps:
step one: adding 60 pure water into 4kg of lithium carbonate, 2kg of manganese phosphate and 4kg of ferric phosphate, grinding and mixing for 2.5 hours;
step two: drying the suspension obtained after grinding and mixing in a spray drying mode;
step three: calcining the dried solid material at 680 ℃ for 7.5 hours, cooling after calcining, and crushing by adopting air flow to obtain the third lithium iron manganese phosphate material.
Step two: mixing a first lithium iron manganese phosphate material, a second lithium iron manganese phosphate material and a third lithium iron manganese phosphate material according to the proportion of 1:3:5;
step three: after the mixing is completed, crushing, and calcining the mixed material for 9 hours at 680 ℃;
step four: and cooling after the calcination is finished, crushing and sub-packaging to obtain the high-compaction density lithium iron manganese phosphate material.
Verification test
The high-compaction density lithium iron manganese phosphate materials prepared in examples 1-3 were subjected to performance testing, and the conventional lithium iron manganese phosphate electrode plates were used as control examples, and the performance testing results are shown in table one.
List one
As can be seen from Table 1 and FIG. 1, the high-compaction density lithium iron manganese phosphate materials prepared in examples 1-3 of the present invention had higher compaction densities than the comparative examples, both at 2.8g/cm 3 The voltage platform, the theoretical energy density and the theoretical specific capacity are higher than those of the comparative example, so that the compaction density and the electrical property of the high-compaction-density lithium iron manganese phosphate material prepared by the invention are higher than those of the existing lithium iron manganese phosphate electrode plate, the defect of the existing lithium iron manganese phosphate electrode plate can be effectively overcome, and the high-compaction-density lithium iron manganese phosphate material is convenient for the wide popularization and application of the lithium iron manganese phosphate electrode plate.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of high-compaction-density lithium iron manganese phosphate is characterized by comprising the following steps of: the method comprises the following steps:
step one: preparing a first lithium iron manganese phosphate material, a second lithium iron manganese phosphate material and a third lithium iron manganese phosphate material;
step two: mixing a first lithium iron manganese phosphate material, a second lithium iron manganese phosphate material and a third lithium iron manganese phosphate material according to the proportion of 1:2-4:4-6;
step three: after the mixing is completed, crushing, and calcining the mixed material at the temperature of 630-750 ℃ for 6-12h;
step four: and cooling after the calcination is finished, crushing and sub-packaging to obtain the high-compaction density lithium iron manganese phosphate material.
2. The method for preparing the high-compaction-density lithium iron manganese phosphate according to claim 1, which is characterized in that: the preparation method of the first lithium iron manganese phosphate material in the first step comprises the following steps:
step one: adding pure water into the graphene-coated nano lithium phosphate material, manganese sulfate and ferric phosphate, grinding and mixing for 2-4h;
step two: drying the suspension obtained after grinding and mixing in a spray drying mode;
step three: calcining the dried solid material at 780-830 ℃ for 6-8 hours, cooling after calcining, and crushing by adopting air flow to obtain the first lithium iron manganese phosphate material.
3. The method for preparing the high-compaction-density lithium iron manganese phosphate according to claim 2, which is characterized in that: the preparation method of the graphene-coated nano lithium phosphate material comprises the steps of immersing the nano lithium phosphate material in a graphene solution, carrying out coating operation in a coprecipitation mode, filtering after coating is completed, and drying to obtain the graphene-coated nano lithium phosphate material.
4. The method for preparing the high-compaction-density lithium iron manganese phosphate according to claim 2, which is characterized in that: the mass ratio of the graphene-coated nano lithium phosphate material to the manganese sulfate to the ferric phosphate is 5:2:1, and the addition amount of the pure water is 5-8 times of the total mass of the nano lithium phosphate material to the manganese sulfate to the ferric phosphate.
5. The method for preparing the high-compaction-density lithium iron manganese phosphate according to claim 1, which is characterized in that: the preparation method of the second lithium iron manganese phosphate material comprises the following steps:
step one: adding lithium hydroxide, manganese oxalate, ferric phosphate and cobalt phosphate into pure water, grinding and mixing for 1-3h;
step two: drying the suspension obtained after grinding and mixing in a spray drying mode;
step three: calcining the dried solid material at 650-770 ℃ for 7-9h, cooling after calcining, and crushing by adopting air flow to obtain a second lithium iron manganese phosphate material.
6. The method for preparing high-compaction-density lithium iron manganese phosphate according to claim 5, wherein the method comprises the following steps: the mass ratio of the lithium hydroxide to the manganese oxalate to the iron phosphate to the cobalt phosphate is 4:1:3:1, and the addition amount of the pure water is 6-10 times of the total mass of the lithium hydroxide, the manganese oxalate, the iron phosphate and the cobalt phosphate.
7. The method for preparing the high-compaction-density lithium iron manganese phosphate according to claim 1, which is characterized in that: the preparation method of the third lithium iron manganese phosphate material comprises the following steps:
step one: adding lithium carbonate, manganese phosphate and ferric phosphate into pure water, grinding and mixing for 2-3h;
step two: drying the suspension obtained after grinding and mixing in a spray drying mode;
step three: calcining the dried solid material at 620-740 ℃ for 6-9h, cooling after calcining, and crushing by adopting air flow to obtain the third lithium iron manganese phosphate material.
8. The method for preparing high-compaction-density lithium iron manganese phosphate according to claim 5, wherein the method comprises the following steps: the mass ratio of the lithium carbonate to the manganese phosphate to the iron phosphate is 4:2:4, and the addition amount of the pure water is 5-7 times of the total mass of the lithium carbonate to the manganese phosphate to the iron phosphate.
9. The method for preparing the high-compaction-density lithium iron manganese phosphate according to claim 1, which is characterized in that: in the second step, the first lithium iron manganese phosphate material, the second lithium iron manganese phosphate material and the third lithium iron manganese phosphate material are mixed and refined and ground by adopting a ball mill.
10. The method for preparing the high-compaction-density lithium iron manganese phosphate according to claim 1, which is characterized in that: in the fourth step, the crushing operation is carried out by adopting air flow.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2614634A1 (en) * | 2007-12-14 | 2009-06-14 | Phostech Lithium Inc. | Lithium iron phosphate cathode materials with enhanced energy density and power performance |
| CN109244391A (en) * | 2018-08-22 | 2019-01-18 | 江苏元景锂粉工业有限公司 | A kind of nitrogen mixes carbon coating iron manganese phosphate lithium material and preparation method thereof |
| CN109250698A (en) * | 2018-08-22 | 2019-01-22 | 江苏元景锂粉工业有限公司 | A kind of high-tap density lithium iron manganese phosphate anode material and its preparation method and application |
| CN113659133A (en) * | 2021-07-09 | 2021-11-16 | 江苏乐能电池股份有限公司 | Preparation method of high-compaction lithium ferric manganese phosphate cathode material |
| CN115010108A (en) * | 2022-06-15 | 2022-09-06 | 浙江格派钴业新材料有限公司 | Preparation method of high-compaction lithium iron manganese phosphate cathode material for lithium ion battery |
| CN115924874A (en) * | 2022-12-23 | 2023-04-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of solid-phase high-compaction lithium manganese iron phosphate cathode material and product thereof |
| CN116216685A (en) * | 2023-03-24 | 2023-06-06 | 宜都兴发化工有限公司 | Rapid preparation method of spherical lithium iron manganese phosphate anode material |
| CN116598466A (en) * | 2023-06-20 | 2023-08-15 | 河北九丛科技有限公司 | Preparation method of metal oxide uniformly doped battery-level lithium manganese iron phosphate |
-
2023
- 2023-09-05 CN CN202311139197.2A patent/CN116986574A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2614634A1 (en) * | 2007-12-14 | 2009-06-14 | Phostech Lithium Inc. | Lithium iron phosphate cathode materials with enhanced energy density and power performance |
| CN109244391A (en) * | 2018-08-22 | 2019-01-18 | 江苏元景锂粉工业有限公司 | A kind of nitrogen mixes carbon coating iron manganese phosphate lithium material and preparation method thereof |
| CN109250698A (en) * | 2018-08-22 | 2019-01-22 | 江苏元景锂粉工业有限公司 | A kind of high-tap density lithium iron manganese phosphate anode material and its preparation method and application |
| CN113659133A (en) * | 2021-07-09 | 2021-11-16 | 江苏乐能电池股份有限公司 | Preparation method of high-compaction lithium ferric manganese phosphate cathode material |
| CN115010108A (en) * | 2022-06-15 | 2022-09-06 | 浙江格派钴业新材料有限公司 | Preparation method of high-compaction lithium iron manganese phosphate cathode material for lithium ion battery |
| CN115924874A (en) * | 2022-12-23 | 2023-04-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of solid-phase high-compaction lithium manganese iron phosphate cathode material and product thereof |
| CN116216685A (en) * | 2023-03-24 | 2023-06-06 | 宜都兴发化工有限公司 | Rapid preparation method of spherical lithium iron manganese phosphate anode material |
| CN116598466A (en) * | 2023-06-20 | 2023-08-15 | 河北九丛科技有限公司 | Preparation method of metal oxide uniformly doped battery-level lithium manganese iron phosphate |
Non-Patent Citations (1)
| Title |
|---|
| 李志军;王红英;汤伟杰;罗大为;: "锂离子电池正极材料LiMnPO_4的制备及改性研究进展", 《电源技术》, no. 03, pages 616 - 619 * |
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