CN115490266A - Preparation method of carbon-coated lithium manganate composite material - Google Patents
Preparation method of carbon-coated lithium manganate composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 185
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 88
- 238000000498 ball milling Methods 0.000 claims abstract description 67
- 238000001354 calcination Methods 0.000 claims abstract description 57
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 41
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000002696 manganese Chemical class 0.000 claims abstract description 25
- 239000002612 dispersion medium Substances 0.000 claims abstract description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 15
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 15
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 42
- 238000000227 grinding Methods 0.000 claims description 32
- 239000006185 dispersion Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 15
- 238000001694 spray drying Methods 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 17
- 239000011248 coating agent Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 8
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 239000011324 bead Substances 0.000 description 42
- 238000003801 milling Methods 0.000 description 21
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 229940099596 manganese sulfate Drugs 0.000 description 7
- 235000007079 manganese sulphate Nutrition 0.000 description 7
- 239000011702 manganese sulphate Substances 0.000 description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 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 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 4
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 230000005536 Jahn Teller effect Effects 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- KVGMATYUUPJFQL-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++] KVGMATYUUPJFQL-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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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
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
The invention belongs to the technical field of inorganic materials, and particularly relates to a preparation method of a carbon-coated lithium manganate composite material. The invention provides a preparation method of a carbon-coated lithium manganate composite material, which comprises the following steps: carrying out first ball milling on inorganic manganese salt, an organic carbon source and a first dispersion medium to obtain a first ball-milled material; in protective gas, performing first calcination on the first ball mill to obtain carbon-coated mangano-manganic oxide; carrying out second ball milling on the carbon-coated manganous-manganic oxide, the inorganic lithium salt, the inorganic carbon source and a second dispersion medium to obtain a second ball milling material; and carrying out second calcination on the second ball-milled material to obtain the carbon-coated lithium manganate composite material. According to the invention, the inorganic carbon source and the inorganic carbon source are sequentially adopted for coating twice, so that the uniform distribution of carbon elements on the periphery of lithium manganate can be ensured, and compared with the traditional one-time inorganic carbon mixed coating, the coating gain effect is obvious, so that the rate capability and the cycle performance of a lithium manganate product can be obviously improved.
Description
Technical Field
The invention belongs to the technical field of inorganic materials, and particularly relates to a preparation method of a carbon-coated lithium manganate composite material.
Background
Lithium manganate material (LiMn) 2 O 4 ) As a positive electrode material of a lithium ion battery, the lithium ion battery is widely applied to the fields of communication, electric tools, electric bicycles, electric automobile power batteries and the like. For the production method of the lithium manganate material, the mainstream synthesis method in the prior art is a high-temperature solid phase method, namely, solid compounds such as oxides of lithium and manganese or carbonates are selected, uniformly mixed according to a certain proportion, and are burnt at high temperature to react to generate the lithium manganate material; manganese dioxide and lithium carbonate are used as raw materials, and spinel-shaped lithium manganate can be generated after high-temperature calcination. The high-temperature solid phase method process has the characteristics of low cost, low technical threshold and the like, but the prepared lithium manganate material has the Jahn-Teller effect, so that LiMn is caused 2 O 4 Poor electrochemical properties such as cycle, rate, pressure drop, etc., have been limiting LiMn 2 O 4 Short sheets of material application.
In order to inhibit the reduction of the electrical properties of a product caused by the Jahn-Teller effect of spinel-shaped lithium manganate, the spinel-shaped lithium manganate is generally subjected to carbon coating at present, specifically, a manganese source, a lithium source and an inorganic carbon source are mixed and then calcined to obtain the carbon-coated lithium manganate, and the carbon-coated lithium manganate has better rate and cycle performance compared with the spinel-shaped lithium manganate, but the coating effect of the current carbon coating method is poor, and the obtained carbon-coated lithium manganate product still has a certain Jahn-Teller effect and influences LiMn 2 O 4 Electrochemical performance.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a carbon-coated lithium manganate composite material. The preparation method provided by the invention has a good coating effect, and can effectively improve the rate capability and the cycle performance of lithium manganate.
In order to solve the technical problem, the invention provides a preparation method of a carbon-coated lithium manganate composite material, which comprises the following steps:
carrying out first ball milling on inorganic manganese salt, an organic carbon source and a first dispersion medium to obtain a first ball milling material;
in protective gas, performing first calcination on the first ball-milled material to obtain carbon-coated mangano-manganic oxide;
carrying out second ball milling on the carbon-coated manganous-manganic oxide, the inorganic lithium salt, the inorganic carbon source and a second dispersion medium to obtain a second ball milling material;
and carrying out secondary calcination on the second ball-milled material to obtain the carbon-coated lithium manganate composite material.
Preferably, after the first ball-milled material is obtained and before the first calcining, spray drying is performed on the first ball-milled material to obtain spherical precursor particles; and the first calcining is to perform the first calcining on the spherical precursor particles to obtain the carbon-coated manganous-manganic oxide.
Preferably, the carbon-coated trimanganese tetroxide has a D50 of 6 to 8 μm.
Preferably, the molar ratio of the carbon-coated manganous manganic oxide to the inorganic lithium salt is 1 (1.02-1.08); and in the second ball-milling material, the content of the inorganic carbon source is 50-100 ppm.
Preferably, the temperature of the first calcination is 1000-1300 ℃, and the holding time of the first calcination is 5-7 h.
Preferably, the inorganic carbon source includes graphene and/or carbon nanotubes.
Preferably, the temperature of the second calcination is 750-780 ℃, the holding time of the second calcination is 23-30 h, the second calcination is carried out in flowing air, and the flow velocity of the air is 15-30 m 3 /h。
Preferably, the second ball milling comprises the following steps:
carrying out 21 st ball milling on the carbon-coated manganous-manganic oxide and inorganic lithium salt to obtain a 21 st ball grinding material;
dispersing the inorganic carbon source in the second dispersion medium to obtain an inorganic carbon source dispersion liquid; the solid content of the inorganic carbon source dispersion liquid is 1-3%;
and carrying out 22 nd ball milling on the 21 st ball grinding material and the inorganic carbon source dispersion liquid.
Preferably, the mass ratio of the inorganic manganese salt to the organic carbon source is 100 (1-2); the ratio of the mass of the first dispersion medium to the total mass of the inorganic manganese salt and the organic carbon source is (1.5-2.5): 1.
Preferably, the second calcining step is to obtain a sintering material, and the second calcining step further comprises the step of mechanically grinding and grading the sintering material to obtain the carbon-coated lithium manganate composite material: the grading frequency of the mechanical mill is 20-30 Hz, and the feeding frequency of the mechanical mill is 5-15Hz; the D50 of the carbon-coated lithium manganate composite material is 10-16 mu m.
The invention provides a preparation method of a carbon-coated lithium manganate composite material, which comprises the following steps: carrying out first ball milling on inorganic manganese salt, an organic carbon source and a first dispersion medium to obtain a first ball milling material; in protective gas, performing first calcination on the first ball mill to obtain carbon-coated mangano-manganic oxide; carrying out second ball milling on the carbon-coated manganous-manganic oxide, the inorganic lithium salt, the inorganic carbon source and a second dispersion medium to obtain a second ball milling material; and carrying out second calcination on the second ball-milled material to obtain the carbon-coated lithium manganate composite material. The preparation method provided by the invention carries out the first carbon coating on inorganic manganese salt which is one of raw materials for preparing lithium manganate: carrying out ball milling by adopting inorganic manganese salt, an organic carbon source and a first dispersion medium to ensure that the inorganic manganese salt is fully coated by the organic carbon source and then calcined, wherein during the first calcination, the inorganic manganese salt is decomposed at high temperature to generate trimanganese tetroxide, and simultaneously, the organic carbon source is decomposed at high temperature, hydrogen and oxygen in the organic carbon source are separated, and the generated carbon simple substance can be adsorbed on the surface of the trimanganese tetroxide; and then performing ball milling and secondary calcination on the obtained carbon-coated manganous-manganic oxide, inorganic lithium salt, an inorganic carbon source and a second dispersion medium, and performing secondary carbon coating in the process of synthesizing the lithium manganate to obtain the carbon-coated lithium manganate composite material. In conclusion, the method adopts twice carbon coating, organic carbon is respectively adopted to coat the manganous oxide when the manganous oxide is prepared by calcining the inorganic manganese salt, the inorganic carbon source is used to coat the lithium manganate again when the lithium manganate is synthesized, the coating effect is ensured, the inorganic carbon source and the inorganic carbon source are sequentially adopted to coat the manganous oxide twice, the carbon elements can be ensured to be uniformly distributed around the lithium manganate, and compared with the traditional one-time inorganic carbon mixed coating, the coating gain effect is obvious, so the rate performance and the cycle performance of the lithium manganate product can be obviously improved.
Further, after the first ball-milled material is obtained and before the first calcining, the method further comprises the steps of carrying out spray drying on the first ball-milled material to obtain spherical precursor particles, and carrying out the first calcining on the spherical precursor particles to obtain the carbon-coated mangano-manganic oxide. According to the invention, the ball-milled material is subjected to spray drying before the first calcination to obtain the spherical precursor, which is beneficial to the coating effect of carbon single substances on the mangano-manganic oxide during the first calcination.
Drawings
FIG. 1 is a graph showing a particle size distribution of a carbon-coated lithium manganate composite material prepared in example 1;
FIG. 2 is an electron micrograph of a carbon-coated lithium manganate composite prepared in example 1;
FIG. 3 is a graph of the capacity and capacity retention of cells having the same design capacity of 2000mAh, discharged at 1C and 15C rates for the materials prepared in example 1 and comparative example 1;
fig. 4 is a result of a thermal stability performance test of the materials prepared in example 1 and comparative example 1.
Detailed Description
The invention provides a preparation method of a carbon-coated lithium manganate composite material, which comprises the following steps:
carrying out first ball milling on inorganic manganese salt, an organic carbon source and a first dispersion medium to obtain a first ball-milled material;
in protective gas, performing first calcination on the first ball mill to obtain carbon-coated mangano-manganic oxide;
carrying out second ball milling on the carbon-coated manganous-manganic oxide, the inorganic lithium salt, the inorganic carbon source and a second dispersion medium to obtain a second ball milling material;
and carrying out second calcination on the second ball-milled material to obtain the carbon-coated lithium manganate composite material.
In the present invention, the starting materials are all commercially available products well known to those skilled in the art unless otherwise specified.
The method comprises the step of carrying out first ball milling on inorganic manganese salt, an organic carbon source and a first dispersion medium to obtain a first ball milling material.
In the present invention, the inorganic manganese salt is particularly preferably manganese sulfate.
In the present invention, the inorganic manganese salt is preferably a high-purity inorganic manganese salt.
In the present invention, the purity of the inorganic manganese salt is preferably not less than 98%.
In the present invention, the inorganic manganese salt is preferably electrolytic manganese.
In the present invention, the purity of the inorganic manganese salt is preferably not less than 92%.
In the present invention, the inorganic carbon source is particularly preferably glucose.
In the present invention, the first dispersion medium is particularly preferably water.
In the present invention, the water is particularly preferably distilled water.
In the present invention, the mass ratio of the inorganic manganese salt to the organic carbon source is preferably 100 (1 to 2), more preferably 100 (1.2 to 1.5).
In the present invention, the ratio of the mass of the first dispersion medium to the total mass of the inorganic manganese salt and the organic carbon source is preferably (1.5 to 2.5): 1, and more preferably (1.8 to 2.3): 1.
In the present invention, the charging sequence of the first ball mill is preferably: and sequentially filling inorganic manganese salt, an organic carbon source and a first dispersion medium into a ball milling tank.
In the present invention, the rotation speed of the first ball mill is preferably 25 to 30r/min, and more preferably 26 to 28r/min.
In the present invention, the time of the first ball milling is preferably 1.5 to 3 hours, and more preferably 2 hours.
In the present invention, the ball-to-material ratio of the first ball mill is preferably (1 to 1.2): 1.
In the invention, the ball milling beads used in the first ball milling comprise first-stage ball matching milling beads, second-stage ball matching milling beads and third-stage ball matching milling beads, the particle size of the first-stage ball matching milling beads is preferably 15mm, the particle size of the second-stage ball matching milling beads is 20mm, and the particle size of the third-stage ball matching milling beads is 25mm; the preferred mass ratio of the first-stage ball-matching grinding beads to the second-stage ball-matching grinding beads to the third-stage ball-matching grinding beads is 3.
After the first ball-milled material is obtained and before the first calcination, the method preferably further comprises the steps of spray-drying the first ball-milled material to obtain spherical precursor particles, and performing the first calcination on the spherical precursor particles to obtain the carbon-coated mangano-manganic oxide.
In the present invention, the temperature of the spray drying is preferably 110 to 120 ℃, more preferably 112 to 115 ℃.
In the present invention, the spray drying is preferably carried out in a spray tower.
After the first ball-milling material or the spherical precursor particles are obtained, the first ball-milling material or the spherical precursor particles are subjected to first calcination in a protective gas to obtain the carbon-coated manganous-manganic oxide.
In the present invention, the temperature of the first calcination is preferably 1000 to 1300 ℃, more preferably 1100 to 1250 ℃.
In the present invention, the holding time for the first calcination is preferably 5 to 7 hours, and more preferably 5.5 to 6 hours.
In the present invention, the protective gas is preferably an inert gas or nitrogen, more preferably nitrogen.
In the present invention, the first calcination is preferably performed in a rotary kiln.
In the present invention, when the first calcined raw material is preferably a spherical precursor particle, the shape of the carbon-coated trimanganese tetroxide is preferably spherical.
In the invention, during the first calcination, the inorganic manganese salt is decomposed at high temperature to generate manganomanganic oxide, and in the process, the organic carbon source is decomposed at high temperature, and hydrogen and oxygen are separated, so that carbon elements can be uniformly adsorbed around the manganomanganic oxide.
In the invention, after the carbon-coated manganous-manganic oxide is obtained and before the second ball milling, the invention also comprises the step of carrying out airflow milling classification on the carbon-coated manganous-manganic oxide to obtain homogenized carbon-coated manganous-manganic oxide, wherein the D50 of the homogenized carbon-coated manganous-manganic oxide is 6-8 mu m.
In the present invention, the D50 of the homogenized carbon-coated trimanganese tetroxide is preferably 6 to 8 μm, more preferably 6.5 to 7.5 μm.
After the carbon-coated manganous manganic oxide or the homogenized carbon-coated manganous manganic oxide is obtained, the carbon-coated manganous manganic oxide or the homogenized carbon-coated manganous manganic oxide, the inorganic lithium salt, the inorganic carbon source and a second dispersion medium are subjected to second ball milling to obtain a second ball milling material.
In the present invention, the inorganic lithium salt is specifically lithium carbonate.
In the present invention, the inorganic carbon source preferably includes graphene and/or carbon nanotubes.
In the present invention, the second dispersion medium is particularly preferably N-methylpyrrolidone (NMP).
In the present invention, the molar ratio of the carbon-coated mangano-manganic oxide to the inorganic lithium salt is preferably 1 (1.02 to 1.08), and more preferably 1 (1.03 to 1.06).
In the present invention, the content of the inorganic carbon source in the second ball-milled material is preferably 50 to 100ppm, and more preferably 60 to 90ppm.
In the present invention, the second ball milling preferably includes the steps of:
carrying out third ball milling on the carbon-coated manganous-manganic oxide and the inorganic lithium salt to obtain a third ball grinding material;
dispersing the inorganic carbon source in the second dispersion medium to obtain an inorganic carbon source dispersion liquid; the solid content of the inorganic carbon source dispersion liquid is 1-3%;
and carrying out fourth ball milling on the third ball grinding material and the inorganic carbon source dispersion liquid.
The carbon-coated manganous-manganic oxide and inorganic lithium salt are subjected to third ball milling to obtain a third ball grinding material.
In the present invention, the third ball milling row is preferably performed in a star ball mill.
In the present invention, the rotation speed of the third ball mill is preferably 30 to 40r/min.
In the present invention, the time of the third ball milling is preferably 30min;
in the present invention, the ball/material ratio of the third ball mill is preferably (1 to 1.2): 1.
In the invention, the particle size of the ball milling beads used in the third ball milling preferably comprises a first-stage ball-matching milling bead, a second-stage ball-matching milling bead and a third-stage ball-matching milling bead, the particle size of the first-stage ball-matching milling bead is preferably 15mm, the particle size of the second-stage ball-matching milling bead is 20mm, and the particle size of the third-stage ball-matching milling bead is 25mm; the preferred mass ratio of the first-stage ball-matching grinding beads to the second-stage ball-matching grinding beads to the third-stage ball-matching grinding beads is 3.
Dispersing the inorganic carbon source in the second dispersion medium to obtain an inorganic carbon source dispersion liquid; the solid content of the inorganic carbon source dispersion liquid is 1-3%.
In the present invention, the dispersion is preferably carried out in a high-speed stirrer.
In the present invention, the dispersion is preferably carried out under stirring conditions, and the rotation speed of the stirring is preferably 2000 to 4000r/min, more preferably 2500 to 3500r/min.
In the present invention, the time for the dispersion is preferably 20min.
In the present invention, the solid content of the inorganic carbon source dispersion is preferably 1 to 3%, more preferably 1.5 to 2.5%.
After the third ball grinding material and the inorganic carbon source dispersion liquid are obtained, the third ball grinding material and the inorganic carbon source dispersion liquid are subjected to fourth ball milling.
In the present invention, the fourth ball milling is preferably performed in a planetary ball mill.
In the present invention, the rotation speed of the fourth ball mill is preferably 30 to 40r/min.
In the present invention, the time of the fourth ball milling is preferably 90min.
In the present invention, the ball-to-material ratio of the fourth ball mill is preferably (1 to 1.2): 1.
In the invention, the particle size of the ball milling beads used in the fourth ball milling preferably comprises first-stage ball-matching milling beads, second-stage ball-matching milling beads and third-stage ball-matching milling beads, the particle size of the first-stage ball-matching milling beads is preferably 15mm, the particle size of the second-stage ball-matching milling beads is 20mm, and the particle size of the third-stage ball-matching milling beads is 25mm; the preferred mass ratio of the first-stage ball-matching grinding beads to the second-stage ball-matching grinding beads to the third-stage ball-matching grinding beads is 3.
According to the invention, the inorganic carbon is preferably dispersed in the second dispersion matrix to obtain the inorganic carbon source dispersion liquid, and then the third ball grinding material and the inorganic carbon source dispersion liquid are subjected to fourth ball milling, so that the inorganic carbon source and the third ball grinding material can be uniformly mixed during the fourth ball milling.
After a second ball-milled material is obtained, carrying out second calcination on the second ball-milled material to obtain the carbon-coated lithium manganate composite material.
In the present invention, the temperature of the second calcination is preferably 750 to 780 ℃, more preferably 760 to 775 ℃.
In the present invention, the holding time for the second calcination is preferably 23 to 30 hours, and more preferably 25 to 28 hours.
In the present invention, the second calcination is preferably carried out in flowing air, the flow rate of which is preferably 15 to 30m 3 H, more preferably 18 to 25m 3 /h。
In the present invention, the second calcination is preferably carried out in a roller kiln.
The second ball-milled material is preferably transferred into a closed sagger for the second calcination.
In the present invention, the mass of the second ball-milling material transferred into the 1 and closed sagger is preferably 2 to 3kg.
In the invention, the second calcination is performed to obtain a sintering material, and the invention preferably further comprises the step of performing mechanical grinding classification on the sintering material to obtain the carbon-coated lithium manganate composite material.
In the present invention, the classification frequency of the mechanical mill classification is preferably 20 to 30Hz, more preferably 23 to 26Hz.
In the present invention, the feeding frequency of the mechanical mill stage is preferably 5 to 15Hz, more preferably 6 to 12Hz.
In the present invention, the D50 of the carbon-coated lithium manganate composite material is preferably 10 to 16 μm, and more preferably 12 to 14 μm.
In the invention, after the carbon-coated lithium manganate composite material is obtained, the carbon-coated lithium manganate composite material is preferably screened and then packaged.
In the present invention, the screen mesh for screening is preferably 280 mesh, and the screen underflow of the present invention is packed.
According to the invention, the carbon elements can be uniformly distributed on the periphery of the lithium manganate by adopting two different coating modes, and compared with the traditional one-time inorganic carbon mixed coating, the lithium manganate coated lithium manganate has an obvious gain effect.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Weighing manganese sulfate (with purity of more than or equal to 98%) and an organic carbon source (glucose) according to a mass ratio of 100, adding the manganese sulfate and the organic carbon source into a ball mill, adding distilled water, wherein the mass of the manganese sulfate and the organic carbon source is 2 times of the total mass of the manganese sulfate and the organic carbon source, starting ball milling, wherein the ball-to-material ratio is preferably 1;
conveying the first ball-milled material to a spray tower for spray drying, wherein the spray drying temperature is 120 ℃; placing the mixture after spray drying into a rotary kiln for high-temperature calcination, wherein the calcination temperature is 1300 ℃, the heat preservation time is 7 hours, and nitrogen is introduced in the sintering process to obtain spherical carbon-coated manganic manganous oxide;
carrying out particle homogenization treatment on the spherical carbon-coated manganous-manganic oxide by airflow milling classification to obtain homogenized carbon-coated manganous-manganic oxide, wherein D50 is 6-8 mu m;
placing the homogenized carbon-coated manganous manganic oxide and lithium carbonate into a planetary ball mill for mixing, wherein the molar ratio of the homogenized carbon-coated manganous manganic oxide to the lithium carbonate is 1.02, the ball material ratio is preferably 1, the mass ratio of ball grinding beads with the particle size of 15mm to ball grinding beads with the particle size of 20mm to ball grinding beads with the particle size of 55mm is 3;
adding an inorganic carbon source (graphene) into NMP for dispersing to obtain an inorganic carbon source dispersion liquid, wherein the solid content is 3%, and a high-speed stirrer is used for dispersing at the speed of 4000r/min for 20min;
adding the inorganic carbon source dispersion liquid into a planetary ball mill containing homogenized carbon-coated trimanganese tetroxide and lithium carbonate, wherein the addition amount is 100ppm after the homogenized carbon-coated trimanganese tetroxide, lithium carbonate and the inorganic carbon source dispersion liquid are mixed; performing ball-milling mixing, wherein the ball-material ratio is preferably 1, the mass ratio of ball-milling beads with the particle size of 15mm to ball-milling beads with the particle size of 20mm to ball-milling beads with the particle size of 55mm is 3; obtaining a second ball-milled material;
adding the second ball-milled material into sagger, 3kg per sagger, calcining in roller kiln at 780 deg.C for 30 hr with air flow of 20m 3 H; and (3) mechanically grinding and dispersing the cooled calcined material, wherein the frequency of a grading wheel is 25Hz, the frequency of a feeder is 5, dispersing the material until the D50 is 10-16 mu m, and packaging the material after passing through a 280-mesh screen.
Example 2
The preparation method is basically the same as that of the embodiment 1, except that: the inorganic carbon source is carbon nanotubes.
Example 3
Weighing manganese sulfate (with the purity of more than or equal to 98%) and an organic carbon source (glucose) according to a mass ratio of 100, adding into a ball mill, then adding distilled water, wherein the mass of the distilled water is 2 times of the total mass of the manganese sulfate and the organic carbon source, starting ball milling, and carrying out ball milling for 2 hours at a speed of 25-30 r/min, wherein the ball-to-material ratio is preferably 1;
conveying the first ball-milled material to a spray tower for spray drying, wherein the spray drying temperature is 120 ℃; placing the mixture after spray drying into a rotary kiln for high-temperature calcination, wherein the calcination temperature is 1000 ℃, the heat preservation time is 6 hours, and nitrogen is introduced during the sintering process to obtain spherical carbon-coated manganous manganic oxide;
carrying out particle homogenization treatment on the spherical carbon-coated manganous-manganic oxide by airflow milling classification to obtain homogenized carbon-coated manganous-manganic oxide, wherein D50 is 6-8 mu m;
placing the homogenized carbon-coated manganous manganic oxide and lithium carbonate into a planetary ball mill for mixing, wherein the molar ratio of the homogenized carbon-coated manganous manganic oxide to the lithium carbonate is 1.08, the ball-to-material ratio is preferably 1, the mass ratio of ball grinding beads with the particle diameter of 15mm to ball grinding beads with the particle diameter of 20mm to ball grinding beads with the particle diameter of 55mm is 3;
adding an inorganic carbon source (graphene) into NMP for dispersing to obtain an inorganic carbon source dispersion liquid, wherein the solid content is 3%, and a high-speed stirrer is used for dispersing at the speed of 4000r/min for 20min;
adding the inorganic carbon source dispersion liquid into a planetary ball mill containing homogenized carbon-coated trimanganese tetroxide and lithium carbonate, wherein the inorganic carbon source content is 100ppm after the homogenized carbon-coated trimanganese tetroxide, the lithium carbonate and the inorganic carbon source dispersion liquid are mixed; performing ball milling and mixing, wherein the ball material ratio is preferably 1, the mass ratio of ball milling beads with the particle size of 15mm to ball milling beads with the particle size of 20mm to ball milling beads with the particle size of 55mm is 3; obtaining a second ball-milled material;
adding the second ball-milled material into sagger, 3kg per sagger, calcining in roller kiln at 750 deg.C for 30 hr with air flow of 20m 3 H; and (3) mechanically grinding and dispersing the cooled calcined material, wherein the frequency of a grading wheel is 25Hz, the frequency of a feeder is 5, dispersing the material until the D50 is 10-16 mu m, and packaging the material after passing through a 280-mesh screen.
Example 4
The preparation method is basically the same as that of the embodiment 1, except that: the inorganic carbon source is carbon nanotubes.
Comparative example 1
Carrying out particle homogenization treatment on the spherical trimanganese tetroxide by classification of an air flow mill to obtain homogenized trimanganese tetroxide, wherein D50 is 6-8 mu m;
placing homogenized trimanganese tetroxide and lithium carbonate into a planetary ball mill for mixing, wherein the molar ratio of the homogenized trimanganese tetroxide to the lithium carbonate is 1; obtaining a ball-milled material;
adding ball-milling material into sagger, 3kg per sagger, calcining in roller kiln at 780 deg.C for 30 hr with air flow of 20m 3 H; mechanically grinding and dispersing the calcined and cooled material, wherein the frequency of a grading wheel is 25Hz, the frequency of a feeder is 5, dispersing the material until the D50 is 10-16 mu m, and sieving the material by a 280-mesh sieve to obtain lithium manganate particles;
carrying out secondary mixing on the lithium manganate particles and glucose, wherein the mass ratio is 100;
conveying the ball-milled material to a spray tower for spray drying, wherein the spray drying temperature is 120 ℃; and (3) putting the sprayed mixture into a rotary kiln for calcining, wherein the calcining temperature is 500 ℃, the heat preservation time is 7 hours, nitrogen is introduced in the sintering process to obtain spherical carbon-coated lithium manganate, and finally, the spherical carbon-coated lithium manganate is subjected to high-speed dispersion, sieving and packaging.
Test example 1
The results of the strength test analysis of the carbon-coated lithium manganate composite material prepared in example 1 are shown in fig. 1, and it can be seen from fig. 1 that the particle size of the carbon-coated lithium manganate composite material obtained in example 1 of the present invention is more concentrated by controlling the particle size in the preparation process of trimanganese tetraoxide.
Electron microscope analysis is performed on the carbon-coated lithium manganate composite material prepared in example 1, and an SEM (scanning electron microscope) scanning image of the product prepared in example 1 is shown in fig. 2; as can be seen from fig. 2, the carbon-coated lithium manganate composite material prepared in embodiment 1 of the present invention has a good coating effect.
Test example 2
The carbon-coated lithium manganate composite prepared in example 1 and the carbon-coated lithium manganate prepared in comparative example 1 are respectively designed into cells with the same capacity of 2000mAh, and under the conditions of 1C rate discharge and 15C rate discharge, the rate performance and cycle performance of the carbon-coated lithium manganate composite prepared in example 1 and the carbon-coated lithium manganate prepared in comparative example 1 are tested, and the test results are shown in fig. 3, which can be obtained from fig. 3: compared with the carbon-coated lithium manganate prepared in the comparative example 1, the carbon-coated lithium manganate composite material prepared in the embodiment 1 of the present invention has higher capacity and capacity retention rate, and meanwhile, a test of storing at a high temperature (60 ℃) for 7 days shows that the embodiment 1 can effectively solve the defect of high-temperature storage performance of lithium manganate, and the test result is shown in fig. 4, and can be obtained from fig. 4: compared with the carbon-coated lithium manganate prepared in the comparative example 1, the carbon-coated lithium manganate composite material prepared in the embodiment 1 of the invention has no obvious gas expansion phenomenon at high temperature.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. The preparation method of the carbon-coated lithium manganate composite material is characterized by comprising the following steps of:
carrying out first ball milling on inorganic manganese salt, an organic carbon source and a first dispersion medium to obtain a first ball milling material;
in protective gas, performing first calcination on the first ball-milled material to obtain carbon-coated mangano-manganic oxide;
carrying out second ball milling on the carbon-coated manganous-manganic oxide, the inorganic lithium salt, the inorganic carbon source and a second dispersion medium to obtain a second ball milling material;
and carrying out second calcination on the second ball-milled material to obtain the carbon-coated lithium manganate composite material.
2. The preparation method according to claim 1, wherein after obtaining the first ball-milled material and before performing the first calcination, the method further comprises spray-drying the first ball-milled material to obtain spherical precursor particles; the first calcination is to perform the first calcination on the spherical precursor particles to obtain the carbon-coated mangano-manganic oxide.
3. The method according to claim 1, wherein the carbon-coated trimanganese tetroxide has a D50 of 6 to 8 μm.
4. The preparation method of claim 1, wherein the molar ratio of the carbon-coated manganous manganic oxide to the inorganic lithium salt is 1 (1.02-1.08); and in the second ball-milling material, the content of the inorganic carbon source is 50-100 ppm.
5. The preparation method according to claim 1, wherein the temperature of the first calcination is 1000 to 1300 ℃, and the holding time of the first calcination is 5 to 7 hours.
6. The method according to claim 1 or 4, wherein the inorganic carbon source comprises graphene and/or carbon nanotubes.
7. The method according to claim 1 or 4, wherein the temperature of the second calcination is 750 to 780 ℃, the holding time of the second calcination is 23 to 30 hours, the second calcination is performed in flowing air, and the flow rate of the air is 15 to 30m 3 /h。
8. The method of manufacturing according to claim 1 or 4, characterized in that the second ball milling comprises the following steps:
carrying out 21 st ball milling on the carbon-coated manganous-manganic oxide and inorganic lithium salt to obtain a 21 st ball grinding material;
dispersing the inorganic carbon source in the second dispersion medium to obtain an inorganic carbon source dispersion liquid; the solid content of the inorganic carbon source dispersion liquid is 1-3%;
and carrying out 22 nd ball milling on the 21 st ball grinding material and the inorganic carbon source dispersion liquid.
9. The method according to claim 1, wherein the mass ratio of the inorganic manganese salt to the organic carbon source is 100 (1-2); the ratio of the mass of the first dispersion medium to the total mass of the inorganic manganese salt and the organic carbon source is (1.5-2.5): 1.
10. The preparation method according to claim 1, wherein the second calcination is performed to obtain a sintered material, and further comprising the step of mechanically grinding and grading the sintered material to obtain the carbon-coated lithium manganate composite material: the grading frequency of the mechanical mill is 20-30 Hz, and the feeding frequency of the mechanical mill is 5-15Hz; the D50 of the carbon-coated lithium manganate composite material is 10-16 mu m.
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