CN115535991A - Nanocrystalline phosphoric acid series anode material and preparation method thereof - Google Patents
Nanocrystalline phosphoric acid series anode material and preparation method thereof Download PDFInfo
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- CN115535991A CN115535991A CN202211193912.6A CN202211193912A CN115535991A CN 115535991 A CN115535991 A CN 115535991A CN 202211193912 A CN202211193912 A CN 202211193912A CN 115535991 A CN115535991 A CN 115535991A
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- 150000003016 phosphoric acids Chemical class 0.000 title claims abstract description 39
- 239000010405 anode material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 98
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 60
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 52
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 49
- 239000007774 positive electrode material Substances 0.000 claims description 35
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 29
- 238000000498 ball milling Methods 0.000 claims description 20
- 235000006408 oxalic acid Nutrition 0.000 claims description 20
- 239000010406 cathode material Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 15
- 239000012798 spherical particle Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008213 purified water Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 238000003837 high-temperature calcination Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 229910014985 LiMnxFe1-xPO4 Inorganic materials 0.000 claims description 6
- 229910014982 LiMnxFe1−xPO4 Inorganic materials 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 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 abstract description 19
- 239000013078 crystal Substances 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- 229910019142 PO4 Inorganic materials 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000000227 grinding Methods 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- 229910016168 LiMn1-xFexPO4 Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011163 secondary particle Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 2
- MWUMAVZMOMGITB-UHFFFAOYSA-J P(=O)(O)(O)[O-].[Fe+2].[Mn+2].P(=O)(O)(O)[O-].P(=O)(O)(O)[O-].P(=O)(O)(O)[O-] Chemical compound P(=O)(O)(O)[O-].[Fe+2].[Mn+2].P(=O)(O)(O)[O-].P(=O)(O)(O)[O-].P(=O)(O)(O)[O-] MWUMAVZMOMGITB-UHFFFAOYSA-J 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 2
- 238000010902 jet-milling Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- 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
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Abstract
The invention relates to the technical field of lithium ion battery material preparation, and discloses a nanocrystalline phosphoric acid series anode material and a preparation method thereof; the nanocrystalline phosphoric acid series anode material prepared by the invention has high finished product purity, the single crystal particles are all nanocrystalline particles, and the nanocrystalline phosphoric acid series anode material can be used for preparing monocrystalline particle nano lithium manganese iron phosphate, can effectively improve the conductivity of the lithium manganese iron phosphate, and solves the problem that the conductivity of lithium manganese iron phosphate serving as a battery anode material in the prior art is poor.
Description
Technical Field
The invention relates to the technical field of lithium ion battery material preparation, in particular to a nanocrystalline phosphoric acid series anode material and a preparation method thereof.
Background
The new generation of olivine structure material lithium manganese phosphate (LiMnPO 4) has higher charge and discharge potential and the same theoretical capacity as LiFePO4, so the energy density of the material is greatly improved compared with LiFePO 4. However, most studies show that MnPO4 as a metastable substance does not exist stably like FePO4, so that pure LiMnPO4 material generally cannot be completely delithiated to generate MnPO4 through an electrochemical reaction process, and theoretical capacity is difficult to fully exert. Because the structures of LiMnPO4 and LiFePO4 are the same, mn and Fe can be mutually substituted in any proportion to generate a solid solution with LiMnxFe1-xPO4 as a molecular formula, namely the lithium iron manganese phosphate material; the LiMn1-xFexPO4 cathode material is a battery cathode material capable of effectively improving lithium iron phosphate at present due to good safety performance, low price, environmental protection and long service life; the LiMn1-xFexPO4 material has poor electronic conductivity, and if the size of primary particles is not effectively controlled, the electronic conductivity is increased, so that the electrochemical performance is poor.
Disclosure of Invention
The invention aims to provide a nanocrystalline phosphoric acid series positive electrode material and a preparation method thereof, and aims to solve the problem that lithium manganese iron phosphate serving as a battery positive electrode material in the prior art is poor in conductivity.
The present invention is achieved as described above, and in a first aspect, the present invention provides a method for producing a nanocrystalline phosphoric acid-based positive electrode material, including:
a preparation method of a nanocrystalline phosphoric acid series anode material comprises the following steps:
s1: burdening the raw materials; the raw materials comprise iron powder, manganese powder, phosphoric acid, oxalic acid and lithium carbonate;
s2: adding the iron powder, the manganese powder, the phosphoric acid and the oxalic acid into purified water, heating and stirring to generate a primary material;
s3: performing primary ball milling treatment on the primary material to generate a secondary material;
s4: adding the lithium carbonate into the secondary material, and performing secondary ball milling treatment to generate a tertiary material;
s5: performing spray granulation treatment on the third material to generate spherical particle powder;
s6: and carrying out high-temperature calcination and heat preservation treatment on the spherical particle powder to generate the nanocrystalline phosphoric acid series anode material.
In one embodiment, the proportioning standard of the raw materials in S1 is that the molar ratio of four elements of lithium, manganese, iron and phosphorus is 1: x:1-x:1, wherein x is more than 0 and less than 1.
In one embodiment, the S2 includes:
s21: dissolving the phosphoric acid and the oxalic acid in purified water to prepare a mixed acid solution;
s22: adding the iron powder and the manganese powder into the mixed acid solution;
s23: and heating and stirring the mixed acid solution added with the iron powder and the manganese powder to generate the primary material.
In one embodiment, the particle size of the iron and manganese powders is <100 μm.
In one embodiment, the heating temperature in S2 is 50-65 ℃, and the reaction time of stirring in S2 is 10-15 hours.
In one embodiment, the reaction time of the primary ball milling treatment in S3 is 5 to 8 hours.
In one embodiment, the reaction time of the secondary ball milling treatment in S4 is 3 to 6 hours.
In one embodiment, the temperature of the high-temperature calcination in S6 is 500-700 ℃, and the heat preservation time in S6 is 6-20 hours.
In a second aspect, the invention provides a nanocrystalline phosphoric acid series anode material, which is prepared by the preparation method of the nanocrystalline phosphoric acid series anode material in the first aspect, and the chemical general formula of the nanocrystalline phosphoric acid series anode material is LiMnxFe1-xPO4, wherein x is more than 0 and less than 1.
In a third aspect, the present invention provides a lithium battery made of the nanocrystalline phosphoric acid-based positive electrode material provided in the second aspect.
The invention provides a nanocrystalline phosphoric acid series anode material and a preparation method thereof, and the nanocrystalline phosphoric acid series anode material has the following beneficial effects:
1. the invention provides a method for preparing a phosphate LiMn1-xFexPO4 anode material with low cost by one-step process, the prepared nanocrystalline phosphate anode material has high finished product purity, the single crystal particles are all nano-scale particles, the nanocrystalline phosphate anode material can be used for preparing monocrystalline particle nano lithium manganese iron phosphate, the conductivity of the nanocrystalline particle nano lithium manganese iron phosphate can be effectively improved, and the problem that the conductivity of lithium manganese iron phosphate serving as a battery anode material in the prior art is poor is solved.
2. The nanocrystalline battery-grade lithium manganese iron phosphate cathode material prepared by using the cheap metal powder and the industrial phosphoric acid as transition metal and a phosphorus source and adopting the chemical humidifying method preparation process has the characteristics of low price of raw materials, fine preparation process, capability of preparing various products by the same process, reduction of processing cost, no waste discharge and dust in the production process, environmental friendliness, excellent performance and suitability for industrial continuous production.
Drawings
Fig. 1 is a schematic diagram illustrating specific steps of a method for preparing a nanocrystalline phosphoric acid-based positive electrode material according to an embodiment of the present invention;
fig. 2 is a schematic diagram of a specific step of a method S2 for preparing a nanocrystalline phosphoric acid-based positive electrode material according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The same or similar reference numerals in the drawings of the present embodiment correspond to the same or similar components; in the description of the present invention, it should be understood that if there is an orientation or positional relationship indicated by the terms "upper", "lower", "left", "right", etc. based on the orientation or positional relationship shown in the drawings, it is only for convenience of describing the present invention and simplifying the description, but it is not intended to indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and therefore, the terms describing the positional relationship in the drawings are only used for illustrative purposes and are not to be construed as limiting the present patent, and the specific meaning of the terms may be understood by those skilled in the art according to specific circumstances.
The following describes the implementation of the present invention in detail with reference to specific embodiments.
Referring to FIG. 1, a preferred embodiment of the present invention is provided.
In a first aspect, the present invention provides a method for preparing a nanocrystalline phosphoric acid-based positive electrode material, comprising:
s1: and (4) burdening the raw materials.
Specifically, the invention prepares a phosphoric acid series cathode material, namely LiMn x Fe 1-x PO 4 (ii) a As can be seen, liMn x Fe 1- x PO 4 Five elements, i.e., lithium (Li), manganese (Mn), iron (Fe), phosphorus (P), and oxygen (O), are included, and thus, it is necessary to provide the five elements in a raw material for preparing a phosphoric acid-based positive electrode material.
More specifically, the lithium element is derived from lithium carbonate (Li 2CO 3), the iron element is derived from iron powder, the manganese element is derived from manganese powder, and the phosphorus element is derived from phosphoric acid (H2 CO 3) 3 PO 4 ) The oxygen is derived from phosphoric acid and oxalic acid (H) 2 C 2 O 4 )。
It is understood that the finally prepared product LiMn x Fe 1-x PO 4 The proportions of lithium, manganese, iron and phosphorus are fixed values, and the proportions of iron powder, manganese powder, phosphoric acid, oxalic acid and lithium carbonate in the raw materials fluctuate within a certain range on the premise of considering consumption in the preparation process.
More specifically, the proportion standard of the raw materials is that the molar ratio of four elements of lithium, manganese, iron and phosphorus is 1: x:1-x:1,0 < x <1, namely the molar ratio of lithium element, manganese element, iron element and phosphorus element in the iron powder, manganese powder, phosphoric acid, oxalic acid and lithium carbonate in the raw materials is 1: x:1-x: x is more than 1,0 and less than 1, wherein, the phosphorus element can be properly excessive, which is beneficial to the reaction of manganese metal and iron, and the grinding reaction speed can also be improved in the grinding process.
S2: adding iron powder, manganese powder, phosphoric acid and oxalic acid into purified water, heating and stirring to generate a primary material.
Specifically, raw materials prepared according to a predetermined ratio need to be mixed, and the mixture is heated and stirred to generate a primary material, wherein the primary material is a mixture of manganese iron dihydrogen phosphate and manganese iron dihydrogen phosphate.
More specifically, the heating temperature is 50-65 ℃ and the reaction time with stirring is 10-15 hours.
S3: and performing ball milling treatment on the primary material to generate a secondary material.
Specifically, the generated primary material is added into a high-energy ball mill for ball milling treatment.
In the ball milling treatment, the hard balls are strongly collided, ground and stirred with the raw material by using the rotation or vibration of the ball mill to crush the powder into nano-sized particles, and the ball milling treatment can be realized by the high-energy ball mill.
More specifically, after the high-energy ball mill performs ball milling treatment on the primary material, a secondary material is generated.
More specifically, the reaction time of the ball-milling treatment is 5 to 15 hours.
S4: and adding lithium carbonate into the secondary material, and performing secondary ball milling treatment to generate a tertiary material.
Specifically, the chemical general formula of the secondary material is MnxFe1-xPO4, and the phosphate-based positive electrode material to be prepared by the invention is also lack of Li, so lithium carbonate is added to add lithium element.
More specifically, the time of the secondary ball milling treatment is 3 to 6 hours.
Different from the preparation method of the nanocrystalline lithium manganese iron phosphate precursor, the nanocrystalline phosphoric acid-series positive electrode material prepared by the invention contains lithium element, and the lithium element is added in a ball milling mode before high-temperature calcination and heat preservation treatment.
It can be understood that the primary material is subjected to primary ball milling treatment in the high-energy ball mill to generate a secondary material, and then lithium carbonate is added into the high-energy ball mill and subjected to secondary ball milling treatment, so that lithium element reacts with the secondary material to generate a tertiary material.
More specifically, the lithium carbonate also comprises a carbon element, in the secondary ball milling, the lithium element in the lithium carbonate reacts with the secondary material to generate a tertiary material, and the carbon element in the lithium carbonate is coated on the surface of the tertiary material, so that the single crystal size of the material is reduced, and the electrochemical performance of the nanocrystalline phosphoric acid series positive electrode material prepared by the method is effectively improved.
S5: and carrying out spray granulation treatment on the third material to generate spherical particle powder.
Specifically, spray granulation is a granulation method in which a slurry or a solution is sprayed into a granulation tower, and the slurry or the solution is dried and agglomerated by hot air spray, thereby obtaining spherical granules. The method is widely used for producing catalysts with various particle sizes or other particles with required particle sizes. The method is suitable for experiments and small-scale production, and the particle balls have good precision and uniform particles.
It is understood that, in the present invention, the tertiary material is subjected to spray granulation, and the tertiary material can be manufactured into spherical granular powder.
S6: and carrying out high-temperature calcination and heat preservation treatment on the spherical particle powder to generate the nanocrystalline phosphoric acid series anode material.
Specifically, the nanocrystalline manganese iron phosphate prepared by the invention is spherical particles with the average single crystal particle size of less than 100nm and the average secondary particle size of 15-35 μm, and the spherical particle powder generated in S5 cannot meet the standard, so that the spherical particle powder needs to be subjected to high-temperature calcination and heat preservation treatment to generate the nanocrystalline phosphoric acid series anode material meeting the standard.
More specifically, the temperature of the high-temperature calcination is 500 ℃ to 700 ℃.
More specifically, when the calcining temperature reaches the requirement, the heat preservation treatment is carried out for 6 to 20 hours, and it can be understood that the nanocrystalline phosphoric acid series cathode material can be generated only by preserving the heat for 6 to 20 hours under the temperature condition of 500 to 700 ℃.
It should be noted that the nanocrystalline material is a material composed of crystals having a nanoscale size (1 to 10 nm), and more specifically, the crystals are a structure in which a large number of microscopic substance units (atoms, ions, molecules, etc.) are arranged in order according to a certain rule.
As can be seen from the figure, the nanocrystalline phosphoric acid series anode material and LiFePO prepared by the invention 4 Property gap of (2):
the nanocrystalline phosphoric acid series anode material prepared by the invention has the advantages of high performance and high performance of LiFePO 4 The same theoretical capacity, and higher energy density and charge-discharge potential.
The invention provides a method for preparing a phosphate LiMn1-xFexPO4 cathode material by a low-cost one-step process, which has the following beneficial effects:
1. the invention provides a method for preparing a phosphate LiMn1-xFexPO4 cathode material by a low-cost one-step process, the prepared nanocrystalline phosphate cathode material has high finished product purity, the single crystal particles are nano-scale particles, and the nanocrystalline phosphate cathode material can be used for preparing monocrystalline particle nano lithium manganese iron phosphate, can effectively improve the conductivity of the lithium manganese iron phosphate and solves the problem of poor conductivity of the lithium manganese iron phosphate as a battery cathode material in the prior art.
2. The nanocrystalline battery-grade lithium iron manganese phosphate anode material prepared by using the cheap metal powder and industrial phosphoric acid as transition metal and a phosphorus source and adopting a chemical humidifying method preparation process has the characteristics of low price of raw materials, fine preparation process, capability of preparing various products by the same process, reduction of processing cost, no waste discharge and dust in the production process, environmental friendliness, excellent performance and suitability for industrial continuous production.
3. In the invention, carbon element is introduced to react and is coated on the surface of the tertiary material, so that the single crystal size of the material is reduced, and the electrochemical performance of the nanocrystalline phosphoric acid series anode material prepared by the invention is effectively improved.
Referring to FIG. 2:
in some embodiments, S2 comprises:
s21: phosphoric acid and oxalic acid are dissolved in purified water to produce a mixed acid solution.
The purified water is purified water from which impurities are removed, so that the neutralization reaction of alkaline substances existing in a common water source with phosphoric acid and oxalic acid can be avoided, and the phosphoric acid and the oxalic acid are prevented from being additionally consumed.
Specifically, phosphoric acid and oxalic acid are mixed and dissolved in purified water to make a mixed acid solution.
S22: adding iron powder and manganese powder into the mixed acid solution.
Specifically, iron powder and manganese powder are prepared according to a predetermined proportion and then can be added into the mixed acid solution.
S23: and heating and stirring the mixed acid solution added with the iron powder and the manganese powder to generate a primary material.
In particular, under the condition of high heat, the iron powder and the manganese powder can react with the mixed acid solution more efficiently.
More specifically, stirring is a commonly used operation in organic preparation experiments, and aims to enable reactants to be fully mixed so as to avoid side reactions or organic matter decomposition caused by nonuniform concentration, local overlarge and nonuniform heating of the reactants.
It will be appreciated that heating and stirring can be effective to promote the formation of a primary mass.
More specifically, the heating temperature is 50-65 ℃ and the reaction time with stirring is 10-15 hours.
In some embodiments, the particle size of the iron and manganese powders is <100 μm.
It can be understood that the fine iron powder and manganese powder can react with the mixed acid solution more efficiently, and if the particle diameter of the iron powder and manganese powder is too large, the contact area of the iron powder and manganese powder with the mixed acid solution per unit time is small, resulting in low reaction efficiency.
Based on the above embodiments, the present invention provides embodiments 1, 2 and 3 to provide specific embodiments with detailed data, so as to further explain the present invention:
example 1:
specifically, when the nanocrystalline phosphoric acid-based positive electrode material is LiMnxFe1-xPO4 (x = 0.5), li: mn x ：Fe 1-x The proportion of each element in P is 1:0.:5:0.5:1.
more specifically, 72.1kg of 85% phosphoric acid is selected as the phosphoric acid, and 6.5kg of oxalic acid is selected as the oxalic acid; the two are dissolved in purified water to prepare mixed acid solution.
More specifically, 17.4kg of manganese powder and 17.8kg of iron powder were used, and the particle sizes of both the manganese powder and the iron powder were less than 100 μm.
More specifically, the heating temperature is 50 ℃, the stirring and soaking time is 12 hours, and the obtained primary material is put into a high-energy mill for grinding reaction for 10 hours to generate a secondary material.
More specifically, 23.2kg of lithium carbonate and 10kg of glucose were further ground for 5 hours to produce a third batch.
More specifically, the third material is put into a centrifugal sprayer for spray drying treatment to obtain spherical particles of 15-35 μm.
More specifically, the spherical particle powder after spray drying is calcined in a sintering furnace filled with nitrogen at 600 ℃ and is kept warm for 13 hours to generate the nanocrystalline phosphoric acid series cathode material.
More specifically, the calcined nanocrystalline phosphoric acid series cathode material is subjected to jet milling treatment to obtain a spherical lithium ferric manganese phosphate cathode material with the monocrystal particle size of 80-200 nanometers and the secondary particle size range of 5-25 micrometers.
In addition, the nanocrystalline phosphoric acid-based positive electrode material obtained by high-temperature calcination and heat preservation has a monolithic structure, and in this case, the nanocrystalline phosphoric acid-based positive electrode material needs to be pulverized.
The jet milling is to carry out ultrafine grinding on solid materials by utilizing the energy of high-speed air flow or superheated steam, and can effectively crush the nanocrystalline phosphoric acid series anode material into a spherical lithium manganese iron phosphate anode material with the monocrystal particle size of 80-200 nanometers and the secondary particle size of 5-25 micrometers.
In example 1, by controlling the ratio of iron powder to manganese powder, li: mn x ：Fe 1-x The proportion of each element in P is 1:0.:5:0.5:1, which has good electrical conductivity and can be used as a positive electrode material for a lithium battery.
Example 2:
specifically, when the nanocrystalline phosphoric acid-based positive electrode material is LiNixFe1-xPO4 (x = 0.5), li: ni x ：Fe 1-x The proportion of each element in P is 1:0.:5:0.5:1.
more specifically, 71.3kg of 85% phosphoric acid is selected as the phosphoric acid, and 6.5kg of oxalic acid is selected as the oxalic acid; the two are dissolved in purified water to prepare mixed acid solution.
More specifically, 18.47kg of manganese powder and 17.661kg of iron powder were used, and the particle sizes of both the manganese powder and the iron powder were less than 100 μm.
More specifically, the heating temperature is 50 ℃, the stirring and soaking time is 12 hours, and the obtained primary material is put into a high-energy mill for grinding reaction for 10 hours to generate a secondary material.
More specifically, 23.41kg of lithium carbonate and 10kg of glucose were further ground for 5 hours to produce a third batch.
More specifically, the third material is put into a centrifugal sprayer for spray drying treatment to obtain spherical particles of 15-35 μm.
More specifically, the spherical particle powder after spray drying is calcined in a sintering furnace filled with nitrogen at 600 ℃ and is kept warm for 13 hours to generate the nanocrystalline phosphoric acid series cathode material.
More specifically, the calcined nanocrystalline phosphoric acid series cathode material is subjected to air flow crushing treatment to obtain a spherical lithium ferric manganese phosphate cathode material with the monocrystal particle size of 80-200 nanometers and the secondary particle size range of 5-25 micrometers.
Unlike example 1, in example 2, a nanocrystalline phosphoric acid-based positive electrode material was produced using a nickel element instead of a manganese element, and the nanocrystalline phosphoric acid-based positive electrode material had a chemical general formula of LiNixFe1-xPO4, has good electrical conductivity, and can be used as a positive electrode material for a lithium battery, and Ni in the nanocrystalline phosphoric acid-based positive electrode material can be replaced with manganese.
Example 3:
specifically, when the nanocrystalline phosphoric acid-based positive electrode material is LiMnxFe1-xPO4 (x = 0), li: mn: fe x The proportion of each element in P is 1:0:1:1.
more specifically, 71.97kg of 85% phosphoric acid is selected as the phosphoric acid, and 6.5kg of oxalic acid is selected as the oxalic acid; the two are dissolved in purified water to prepare mixed acid solution.
More specifically, 35.65kg of iron powder is used, and the particle sizes of the iron powder are all less than 100 μm.
More specifically, the heating temperature is 50 ℃, the stirring and soaking time is 12 hours, and the obtained primary material is put into a high-energy mill for grinding reaction for 10 hours to generate a secondary material.
More specifically, 23.41kg of lithium carbonate and 10kg of glucose were further ground for 5 hours to produce a third batch.
More specifically, the third material is put into a centrifugal sprayer for spray drying treatment to obtain spherical particles of 15-35 μm.
More specifically, the spherical particle powder after spray drying is calcined in an air furnace at 600 ℃ and is kept warm for 13 hours to generate the nanocrystalline phosphoric acid series cathode material.
More specifically, the nanocrystalline phosphoric acid series anode material is subjected to airflow crushing treatment to generate a spherical lithium manganese iron phosphate precursor with the single crystal particle size of 80-200 nanometers and the secondary particle size of 5-25 micrometers.
In example 3, no manganese powder is added, only iron powder is added to produce a nanocrystalline phosphoric acid-based positive electrode material, the chemical general formula of which is LiFePO4, which has good conductivity and can serve as a positive electrode material of a lithium battery, and the preparation method of example 3 requires less materials than those of examples 1 and 2, so that the preparation process is simpler.
In a second aspect, the invention provides a nanocrystalline phosphoric acid series anode material, which is prepared by the preparation method of the nanocrystalline phosphoric acid series anode material in the first aspect, and the chemical general formula of the nanocrystalline phosphoric acid series anode material is LiMnxFe1-xPO4, wherein x is more than 0 and less than 1.
It can be understood that the nanocrystalline phosphoric acid-series positive electrode material prepared by the method for preparing the nanocrystalline phosphoric acid-series positive electrode material provided by the first aspect has high finished product purity, the single crystal particles are all nano-scale particles, and the nanocrystalline phosphoric acid-series positive electrode material can be used for preparing monocrystalline particle nano lithium manganese iron phosphate, can effectively improve the conductivity of the lithium manganese iron phosphate, and solves the problem that the conductivity of the lithium manganese iron phosphate serving as a battery positive electrode material in the prior art is poor.
In addition, the raw materials of the nanocrystalline phosphoric acid anode material are metal powder and industrial phosphoric acid which are low in price, the preparation process is fine, and various products can be prepared by the same process, so that the processing cost is reduced, no waste or dust is generated in the production process, the nanocrystalline phosphoric acid anode material is green and environment-friendly, has excellent performance, and is suitable for industrial continuous production.
In a third aspect, the present invention provides a lithium battery made of a nanocrystalline phosphoric acid-based positive electrode material.
It can be understood that the nanocrystalline phosphoric acid-based positive electrode material provided by the second aspect has the advantages of good conductivity and low price, so that a lithium battery prepared by using the nanocrystalline phosphoric acid-based positive electrode material provided by the second aspect can be compressed to be cost on the premise of ensuring quality, and thus has price advantage.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method for preparing a nanocrystalline phosphoric acid series anode material is characterized by comprising the following steps:
s1: preparing raw materials; the raw materials comprise iron powder, manganese powder, phosphoric acid, oxalic acid and lithium carbonate;
s2: adding the iron powder, the manganese powder, the phosphoric acid and the oxalic acid into purified water, heating and stirring to generate a primary material;
s3: performing primary ball milling treatment on the primary material to generate a secondary material;
s4: adding the lithium carbonate into the secondary material, and performing secondary ball milling treatment to generate a tertiary material;
s5: carrying out spray granulation treatment on the third material to generate spherical particle powder;
s6: and carrying out high-temperature calcination and heat preservation treatment on the spherical particle powder to generate the nanocrystalline phosphoric acid series anode material.
2. The method for preparing a nanocrystalline phosphoric acid series cathode material according to claim 1, wherein the proportioning standard of the raw materials in S1 is that the molar ratio of four elements of lithium, manganese, iron and phosphorus is 1: x:1-x:1, wherein x is more than 0 and less than 1.
3. The method according to claim 1, wherein S2 comprises:
s21: dissolving the phosphoric acid and the oxalic acid in purified water to prepare a mixed acid solution;
s22: adding the iron powder and the manganese powder into the mixed acid solution;
s23: and heating and stirring the mixed acid solution added with the iron powder and the manganese powder to generate the primary material.
4. The method according to claim 1, wherein the particle diameters of the iron powder and the manganese powder are less than 100 μm.
5. The method for preparing a nanocrystalline phosphoric acid-based positive electrode material according to claim 1, wherein the heating temperature in S2 is 50-65 ℃, and the reaction time of stirring in S2 is 10-15 hours.
6. The method for preparing a nanocrystalline phosphoric acid-based positive electrode material according to claim 1, wherein the reaction time of the primary ball milling treatment in S3 is 5 to 8 hours.
7. The method for preparing a nanocrystalline phosphoric acid-based positive electrode material according to claim 1, wherein the reaction time of the secondary ball milling treatment in S4 is 3 to 6 hours.
8. The method for preparing a nanocrystalline phosphoric acid-based positive electrode material according to claim 1, wherein the temperature of the high-temperature calcination in S6 is 500 ℃ to 700 ℃, and the time of the heat preservation in S6 is 6 hours to 20 hours.
9. A nanocrystalline phosphoric acid series anode material is characterized in that the nanocrystalline phosphoric acid series anode material is prepared by the preparation method of the nanocrystalline phosphoric acid series anode material according to claims 1-8, the chemical general formula of the nanocrystalline phosphoric acid series anode material is LiMnxFe1-xPO4, wherein x is more than 0 and less than 1.
10. A lithium battery, characterized in that it is made of a nanocrystalline phosphoric acid based positive electrode material according to claim 9.
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