CN115504511A - Collinear production method of anode material - Google Patents
Collinear production method of anode material Download PDFInfo
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- CN115504511A CN115504511A CN202211188010.3A CN202211188010A CN115504511A CN 115504511 A CN115504511 A CN 115504511A CN 202211188010 A CN202211188010 A CN 202211188010A CN 115504511 A CN115504511 A CN 115504511A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000010405 anode material Substances 0.000 title abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 120
- 239000000463 material Substances 0.000 claims abstract description 102
- 239000007774 positive electrode material Substances 0.000 claims abstract description 34
- 238000001354 calcination Methods 0.000 claims abstract description 32
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 31
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010406 cathode material Substances 0.000 claims abstract description 21
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 33
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 33
- 238000001816 cooling Methods 0.000 claims description 17
- 238000009423 ventilation Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000004321 preservation Methods 0.000 description 19
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 12
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/006—Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- 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
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of anode materials, and particularly relates to a collinear production method of an anode material. The invention provides a collinear production method of a positive electrode material, which comprises the following steps: placing a first cathode precursor material into a first sagger, placing a second cathode precursor material into a second sagger, stacking the first sagger and the second sagger in sequence from top to bottom, and then placing the sagger and the second sagger into a roller furnace for calcining to respectively obtain a first cathode material and a second cathode material; the first positive electrode precursor material comprises a trimanganese tetroxide or nickel cobalt manganese ternary precursor; the second positive electrode precursor material includes manganese dioxide. The collinear production method provided by the invention can be used for obtaining the anode material with stable performance.
Description
Technical Field
The invention belongs to the technical field of anode materials, and particularly relates to a collinear production method of an anode material.
Background
The roller furnace has the working principle that products to be sintered are directly or indirectly placed on a roller rod, and can sequentially advance through the continuous rotation of the roller rod, so that the products to be sintered are calcined, and the roller furnace is the main equipment for producing the lithium battery anode material at present.
In the conventional process of calcining the anode material, in order to pursue low energy consumption, a sintering method of a roller furnace is generally set to be an upper layer and a lower layer, namely, after the material to be sintered is filled in a sagger, the sagger is stacked into two layers, and then the sagger enters the roller furnace to be calcined. However, the temperature of the upper layer and the lower layer is controlled when the roller furnace is used for calcining, ventilation treatment is needed, and the material to be calcined cannot be in complete uniform contact with the atmosphere in the furnace due to the isolation of the supporting body, so that the calcining atmosphere of the material to be calcined in the sagger on the upper layer and the sagger on the lower layer is changed, and the performance of the sintered product obtained on the upper layer and the lower layer is unstable.
Disclosure of Invention
The invention aims to provide a collinear production method of a cathode material, and the method provided by the invention can be used for obtaining the cathode material with stable performance.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a collinear production method of a positive electrode material, which comprises the following steps:
placing a first cathode precursor material in a first sagger, placing a second cathode precursor material in a second sagger, stacking the first sagger and the second sagger in sequence from top to bottom, and then placing the stacked sagger and the second sagger in a roller furnace for calcination to respectively obtain a first cathode material and a second cathode material;
the first positive electrode precursor material comprises trimanganese tetroxide or a nickel-cobalt-manganese ternary precursor;
the second positive electrode precursor material includes manganese dioxide.
Preferably, the first positive electrode precursor material further includes lithium carbonate.
Preferably, the mass ratio of the manganous-manganic oxide to the lithium carbonate is 1:0.255 to 0.27;
the mass ratio of the nickel-cobalt-manganese ternary precursor to the lithium carbonate is 1:0.4 to 0.43.
Preferably, the second positive electrode precursor material further includes lithium carbonate;
the mass ratio of manganese dioxide to lithium carbonate is 1:0.215 to 0.23.
Preferably, when the first positive electrode precursor material is manganous-manganic oxide and lithium carbonate, the calcination temperature of the first positive electrode precursor material is 760 to 780 ℃;
when the first anode precursor material is a nickel-cobalt-manganese ternary precursor and lithium carbonate, the calcination temperature of the first anode precursor material is 820-920 ℃.
Preferably, the calcination temperature of the second positive electrode precursor material is 780 to 850 ℃.
Preferably, the mass ratio of the first positive electrode precursor material to the second positive electrode precursor material is 1:3 to 4.
Preferably, the roller furnace comprises an heating area, a heat preservation area and a cooling area which are connected in sequence.
Preferably, the heat preservation time of the heat preservation area is 10-15 h.
Preferably, the heating area and the cooling area are independently ventilated;
the ventilation rate of the heating area is 4 cubic/min; the ventilation rate of the cooling area is 20 cubic/min.
The invention provides a collinear production method of a positive electrode material, which comprises the following steps: placing a first cathode precursor material in a first sagger, placing a second cathode precursor material in a second sagger, stacking the first sagger and the second sagger in sequence from top to bottom, and then placing the stacked sagger and the second sagger in a roller furnace for calcination to respectively obtain a first cathode material and a second cathode material; the first positive electrode precursor material comprises a trimanganese tetroxide or nickel cobalt manganese ternary precursor; the second positive electrode precursor material includes manganese dioxide. In the present invention, the second cathode precursor material located in the second sagger releases oxygen during the calcination process, while the first cathode precursor material located in the first sagger requires oxygen to participate during the calcination process. Therefore, oxygen released from the second sagger can go up to the first sagger to participate in the calcination of the first cathode precursor material, so that the calcination atmosphere discharged from the first sagger and the second sagger is more uniform, and finally, the cathode precursor material in the first sagger and the cathode precursor material in the second sagger can be calcined to obtain the cathode material with stable performance.
Drawings
Fig. 1 is an SEM image of the first positive electrode material obtained in example 1;
fig. 2 is an SEM image of the first positive electrode material obtained in comparative example 1;
fig. 3 is a graph showing cycle characteristics of the first positive electrode materials obtained in examples 1 to 2 and comparative examples 1 to 2.
Detailed Description
The invention provides a collinear production method of a positive electrode material, which comprises the following steps:
placing a first cathode precursor material into a first sagger, placing a second cathode precursor material into a second sagger, stacking the first sagger and the second sagger in sequence from top to bottom, and then placing the sagger and the second sagger into a roller furnace for calcining to respectively obtain a first cathode material and a second cathode material;
the first positive electrode precursor material comprises a trimanganese tetroxide or nickel cobalt manganese ternary precursor;
the second positive electrode precursor material includes manganese dioxide.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
In the present invention, the first positive electrode precursor material includes a trimanganese tetroxide or a nickel-cobalt-manganese ternary precursor. In the present invention, the first positive electrode precursor material also preferably includes lithium carbonate.
In the present invention, the mass ratio of the manganous-manganic oxide to the lithium carbonate is preferably 1:0.255 to 0.27, more preferably 1:0.258 to 0.268, more preferably 1:0.26 to 0.265.
In the present invention, the first positive electrode precursor material preferably further includes an additive. In the present invention, when the first positive electrode precursor material includes trimanganese tetroxide, the additive is preferably aluminum hydroxide and niobium pentoxide; the mass of the aluminum hydroxide is preferably 2 to 3 percent of the total mass of the first positive electrode precursor material; the mass of the niobium pentoxide is preferably 0.5 to 1% of the total mass of the first positive electrode precursor material.
In the present invention, when the first positive electrode precursor material includes trimanganese tetroxide and lithium carbonate, the calcination temperature of the first positive electrode precursor material is preferably 760 to 780 ℃, more preferably 765 to 775 ℃, and still more preferably 768 to 770 ℃. In the present invention, when the first positive electrode precursor material is trimanganese tetroxide and lithium carbonate, the calcined product of the first positive electrode precursor material is lithium manganate.
In the invention, the nickel-cobalt-manganese ternary precursor is preferably a 811-type nickel-cobalt-manganese ternary precursor, a 622-type nickel-cobalt-manganese ternary precursor or a 523-type nickel-cobalt-manganese ternary precursor. In the invention, the mass ratio of the nickel-cobalt-manganese ternary precursor to the lithium carbonate is preferably 1:0.4 to 0.43, more preferably 1:0.42.
in the invention, when the first cathode precursor material comprises a nickel-cobalt-manganese ternary precursor, the additive is preferably niobium pentoxide; the mass of the niobium pentoxide is preferably 0.1 to 0.2% of the total mass of the first positive electrode precursor material.
In the present invention, when the first cathode precursor material includes a nickel-cobalt-manganese ternary precursor and lithium carbonate, the calcination temperature of the first cathode precursor material is preferably 780 to 850 ℃, more preferably 790 to 840 ℃, and more preferably 800 to 830 ℃.
In the invention, when the first positive electrode precursor material comprises a nickel-cobalt-manganese ternary precursor and lithium carbonate, a calcined product of the first positive electrode precursor material is a nickel-cobalt-manganese ternary positive electrode material. In the present invention, the nickel-cobalt-manganese ternary positive electrode material is preferably a 811-type nickel-cobalt-manganese ternary positive electrode material (NCM 811), a 622-type nickel-cobalt-manganese ternary positive electrode material (NCM 622), or a 523-type nickel-cobalt-manganese ternary positive electrode material (NCM 5232).
In the present invention, the second positive electrode precursor material includes manganese dioxide. In the present invention, the second positive electrode precursor material also preferably includes lithium carbonate. In the present invention, the mass ratio of manganese dioxide to lithium carbonate is preferably 1:0.215 to 0.23, more preferably 1:0.218 to 0.228, more preferably 1: 0.220-0.225.
In the present invention, the second positive electrode precursor material preferably further includes an additive. In the present invention, the additive preferably includes aluminum hydroxide and niobium pentoxide. In the present invention, the mass of the aluminum hydroxide is preferably 2 to 3% of the total mass of the second positive electrode precursor material; the mass of the niobium pentoxide is preferably 0.5 to 1% of the total mass of the second positive electrode precursor material.
In the present invention, the calcination temperature of the second positive electrode precursor material is preferably 780 to 850 ℃, more preferably 790 to 840 ℃, and still more preferably 800 to 830 ℃. In the invention, the calcined product of the second positive electrode precursor material is lithium manganate.
In the present invention, the mass ratio of the first positive electrode precursor material to the second positive electrode precursor material is preferably 1:3 to 4.
In the present invention, the first sagger is preferably 330 × 70mm in size. In the invention, when the first positive electrode precursor material is manganous-manganic oxide and lithium carbonate, the addition amount of the first positive electrode precursor material in the first sagger is preferably 2-5 kg; the thickness is preferably 20mm. In the invention, when the first positive electrode precursor material is a nickel-cobalt-manganese ternary precursor and lithium carbonate, the addition amount of the first positive electrode precursor material in the first sagger is preferably 2-5 kg; the thickness is preferably 25mm.
In the present invention, the second sagger is preferably 330 × 120mm in size. In the present invention, the amount of the second positive electrode precursor material added to the second sagger is preferably 8 to 12kg; the thickness is preferably 80mm.
In the invention, the roller furnace preferably comprises an heating area, a heat preservation area and a cooling area which are connected in sequence. In the present invention, the length of each of the heating zone and the cooling zone is preferably 0.4 to 0.6 times the length of the heat-retaining zone.
In the invention, the heating area is preferably ventilated; the ventilation volume of the warming region is preferably 4 cubic/minute.
In the present invention, the holding section is preferably subjected to upper-layer temperature control and lower-layer temperature control. In the present invention, the temperature of the upper layer temperature control is the same as the calcination temperature of the first positive electrode precursor material, and details are not repeated herein. In the present invention, the temperature of the lower layer controlled temperature is the same as the calcination temperature of the second positive electrode precursor material, and will not be described herein again. In the present invention, the holding time in the holding section is preferably 10 to 15 hours, more preferably 11 to 14 hours, and still more preferably 12 to 13 hours. In the present invention, the holding section is not ventilated.
In the invention, the cooling area is preferably ventilated; the ventilation rate of the cooling area is preferably 20 cubic/min.
In the present invention, the conveying speed of the roller furnace is preferably 2m/h.
After the calcination is complete, the invention also preferably includes independently post-treating the product in the first sagger and the product in the second sagger; the post-treatment preferably comprises dispersing, demagnetizing and sieving in sequence. The dispersing, demagnetizing and sieving processes are not particularly limited in the present invention, and may be performed by processes well known to those skilled in the art.
In another embodiment of the present invention, after obtaining the first positive electrode material and the second positive electrode material, the present invention preferably further comprises mixing the first positive electrode material and the second positive electrode material, and using the obtained mixture as the positive electrode material.
In the present invention, when the positive electrode precursor material in the first sagger includes manganomanganic oxide, the mass ratio of the first positive electrode material to the second positive electrode material when mixed is 1:3 to 4.
In the present invention, when the positive electrode precursor material in the first sagger includes a nickel-cobalt-manganese ternary precursor, the mass ratio of the first positive electrode material to the second positive electrode material when mixing is 1:3 to 4.
The collinear production method of the anode material provided by the invention does not need ventilation in the heat preservation area, the roller furnace is in natural air pressure balance, and the heat energy in the furnace body is not taken away too much, so that the energy consumption is lower. In the present invention, when the first positive electrode precursor material includes trimanganese tetroxide and lithium carbonate, the energy consumption for producing each ton of positive electrode material is preferably 70% to 80% of that in non-collinear production.
In the invention, when the first cathode precursor material comprises a nickel-cobalt-manganese ternary precursor and lithium carbonate, the energy consumption for producing each ton of cathode materials is preferably 60-70% of that in non-collinear production.
In order to further illustrate the present invention, the following describes in detail a co-linear production method of a positive electrode material provided by the present invention with reference to the drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing 1000kg of manganous-manganic oxide, 260kg of lithium carbonate, 35kg of aluminum hydroxide and 7kg of niobium pentoxide to obtain a first positive electrode precursor material; loading the obtained first positive electrode precursor material into a plurality of first saggers with the size of 330 × 70mm, wherein the mass of the first positive electrode precursor material in each first sagger is 2kg;
mixing 1000kg of manganese dioxide, 230kg of lithium carbonate, 30kg of aluminum hydroxide and 7kg of niobium pentoxide to obtain a second positive electrode precursor material; loading the obtained second positive electrode precursor material into a plurality of second saggers with the size of 330 × 120mm, wherein the mass of the second positive electrode precursor material in each second sagger is 8kg;
according to the sequence from top to bottom, a plurality of first saggers and a plurality of second saggers are stacked and placed, and then the saggers and the second saggers are placed into a roller furnace together for calcination (the length of an heating area is 10m, the length of a heat preservation area is 25m, and the length of a cooling area is 10 m), wherein the transmission speed of the roller furnace is 2m/h, and the ventilation volume of the heating area is 4 cubic meters per minute; the temperature of the upper layer of the heat preservation area is 770 ℃, the temperature of the lower layer is 800 ℃, and the heat preservation time is 13h; the ventilation volume of the cooling area is 20 cubic/min;
and after the calcination is finished, respectively dispersing, demagnetizing and screening the product in the first sagger and the product in the second sagger to respectively obtain a first positive electrode material and a second positive electrode material.
Example 2
1000kg of 622 type nickel cobalt manganese hydroxide, 420kg of lithium carbonate and 2kg of niobium pentoxide are mixed to obtain a first positive electrode precursor material; loading the obtained first positive electrode precursor material into a plurality of first saggers with the size of 330 × 70mm, wherein the mass of the first positive electrode precursor material in each first sagger is 2kg;
mixing 1000kg of manganese dioxide, 230kg of lithium carbonate, 30kg of aluminum hydroxide and 7kg of niobium pentoxide to obtain a second positive electrode precursor material; loading the obtained second positive electrode precursor material into a plurality of second saggers with the size of 330 × 120mm, wherein the mass of the second positive electrode precursor material in each second sagger is 8kg;
according to the sequence from top to bottom, a plurality of first saggers and a plurality of second saggers are stacked and placed, and then the saggers and the second saggers are placed into a roller furnace together for calcination (the length of an heating area is 10m, the length of a heat preservation area is 25m, and the length of a cooling area is 10 m), wherein the transmission speed of the roller furnace is 2m/h, and the ventilation volume of the heating area is 4 cubic meters per minute; the temperature of the upper layer of the heat preservation area is 890 ℃, the temperature of the lower layer is 850 ℃, and the heat preservation time is 11h; the ventilation volume of the cooling area is 20 cubic/min;
and after the calcination is finished, respectively dispersing, demagnetizing and screening the product in the first sagger and the product in the second sagger to respectively obtain a first positive electrode material and a second positive electrode material.
Comparative example 1
Mixing 1000kg of manganous-manganic oxide, 260kg of lithium carbonate, 35kg of aluminum hydroxide and 7kg of niobium pentoxide to obtain a manganous-manganic oxide precursor material; the obtained trimanganese tetroxide precursor material was loaded into a number of first saggers (the mass of trimanganese tetroxide precursor material in each sagger was 2 kg) with a size of 330 × 70mm and a number of second saggers (the mass of trimanganese tetroxide precursor material in each sagger was 8 kg) with a size of 330 × 70mm, respectively;
the method comprises the following steps of (1) stacking a plurality of first saggers and a plurality of second saggers in sequence from top to bottom, and then putting the saggers and the second saggers into a roller furnace together for calcination (the length of a heating area is 10m, the length of a heat preservation area is 25m, and the length of a cooling area is 10 m), wherein the transmission speed of the roller furnace is 2m/h, and the ventilation volume of the heating area is 4 cubic meters per minute; the temperature of the upper layer of the heat preservation area is 770 ℃, the temperature of the lower layer is 770 ℃, the heat preservation time is 13h, and the ventilation volume of the heat preservation area is 4 cubic/min; the ventilation rate of the cooling area is 20 cubic/min;
and after the calcination is finished, respectively dispersing, demagnetizing and screening the product in the first sagger and the product in the second sagger to respectively obtain a first positive electrode material and a second positive electrode material.
Comparative example 2
1000kg of 622 type nickel cobalt manganese hydroxide, 420kg of lithium carbonate and 2kg of niobium pentoxide are mixed to obtain 622 type nickel cobalt lithium manganate precursor material; respectively loading the obtained 622 type nickel cobalt lithium manganate precursor material into a plurality of first saggers (the mass of the 622 type nickel cobalt lithium manganate precursor material in each sagger is 2 kg) with the size of 330 x 70mm and a plurality of second saggers (the mass of the 622 type nickel cobalt lithium manganate precursor material in each sagger is 8 kg) with the size of 330 x 70mm;
according to the sequence from top to bottom, a plurality of first saggers and a plurality of second saggers are stacked and placed, and then the saggers and the second saggers are placed into a roller furnace together for calcination (the length of an heating area is 10m, the length of a heat preservation area is 25m, and the length of a cooling area is 10 m), wherein the transmission speed of the roller furnace is 2m/h, and the ventilation volume of the heating area is 4 cubic meters per minute; the temperature of the upper layer of the heat preservation area is controlled to be 890 ℃, the temperature of the lower layer is controlled to be 890 ℃, the heat preservation time is 11 hours, and the oxygen amount introduced into the heat preservation area is 5 cubic/minute; the ventilation volume of the cooling area is 20 cubic/min;
and after the calcination is finished, respectively dispersing, demagnetizing and screening the product in the first sagger and the product in the second sagger to obtain a first positive electrode material and a second positive electrode material.
Performance testing
Test example 1
Scanning electron microscope tests are carried out on the first cathode materials obtained in example 1 and comparative example 1, wherein an SEM image of the first cathode material obtained in example 1 is shown in figure 1, an SEM image of the first cathode material obtained in comparative example 1 is shown in figure 2, and it can be seen from figures 1 and 2 that the cathode material prepared in example 1 is complete in particle, uniform in primary grain growth, and forms a better modified spinel morphology of truncated octahedron, so that the cathode material has better electrochemical performance.
Test example 2
Preparing a positive electrode by taking the first positive electrode material obtained in the embodiment 1-2 and the first positive electrode material obtained in the comparative example 1-2 as active materials, taking metal lithium as a negative electrode, and taking conventional 1mol/L lithium ion battery electrolyte as electrolyte to prepare a button cell; then, the assembled battery was subjected to a constant current charge-discharge cycle test at a rate of 1C, and the test results are shown in fig. 3, in which the abscissa is the cycle number and the ordinate is the specific capacity (mAh · g) -1 )。
From fig. 3, it can be seen that the specific capacity of the cathode material prepared by the collinear production method provided by the present invention is increased by 10 to 20% compared with the cathode material prepared in the comparative example.
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 all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. A collinear production method of a positive electrode material is characterized by comprising the following steps:
placing a first cathode precursor material into a first sagger, placing a second cathode precursor material into a second sagger, stacking the first sagger and the second sagger in sequence from top to bottom, and then placing the sagger and the second sagger into a roller furnace for calcining to respectively obtain a first cathode material and a second cathode material;
the first positive electrode precursor material comprises a trimanganese tetroxide or nickel cobalt manganese ternary precursor;
the second positive electrode precursor material includes manganese dioxide.
2. A co-linear production method according to claim 1, wherein the first positive electrode precursor material further comprises lithium carbonate.
3. The collinear production method according to claim 2, wherein the mass ratio of the trimanganese tetroxide to the lithium carbonate is 1:0.255 to 0.27;
the mass ratio of the nickel-cobalt-manganese ternary precursor to the lithium carbonate is 1:0.4 to 0.43.
4. A collinear production method according to claim 1, wherein said second positive electrode precursor material further includes lithium carbonate;
the mass ratio of manganese dioxide to lithium carbonate is 1:0.215 to 0.23.
5. The collinear production method according to claim 2, wherein when the first positive electrode precursor material includes trimanganese tetroxide and lithium carbonate, a calcination temperature of the first positive electrode precursor material is 760 to 780 ℃;
when the first positive electrode precursor material comprises a nickel-cobalt-manganese ternary precursor and lithium carbonate, the calcination temperature of the first positive electrode precursor material is 820-920 ℃.
6. A collinear production method according to claim 4, wherein the calcination temperature of the second positive electrode precursor material is 780 to 850 ℃.
7. A co-linear production method according to claim 1, wherein the mass ratio of the first positive electrode precursor material to the second positive electrode precursor material is 1:3 to 4.
8. A collinear production process according to claim 1, wherein the roller hearth furnace comprises an elevated temperature zone, a hold temperature zone, and a reduced temperature zone connected in series.
9. A collinear production process according to claim 8 wherein the hold time of the hold section is from 10 to 15 hours.
10. A collinear production method according to claim 8, wherein said temperature raising and cooling zones are independently ventilated;
the ventilation volume of the heating area is 4 cubic/min; the ventilation volume of the cooling area is 20 cubic/minute.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007227483A (en) * | 2006-02-21 | 2007-09-06 | Tdk Corp | Laminated ceramic element manufacturing method |
| CN108493447A (en) * | 2018-03-13 | 2018-09-04 | 乳源东阳光磁性材料有限公司 | Preparation method of high-quality high-nickel multi-element positive electrode material |
| CN112744874A (en) * | 2020-12-29 | 2021-05-04 | 无锡晶石新型能源股份有限公司 | Preparation method of low-energy-consumption high-nickel ternary material |
| CN214792563U (en) * | 2021-04-16 | 2021-11-19 | 阳泉银宇新材料有限责任公司 | Special sagger for lithium ion battery material |
| CN215002867U (en) * | 2021-05-26 | 2021-12-03 | 南通瑞翔新材料有限公司 | Sagger for sintering roller kiln for lithium battery ternary cathode material |
| CN113823764A (en) * | 2021-09-29 | 2021-12-21 | 北京当升材料科技股份有限公司 | Roller kiln for sintering anode material, multi-element anode material and preparation method thereof |
-
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- 2022-09-28 CN CN202211188010.3A patent/CN115504511A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007227483A (en) * | 2006-02-21 | 2007-09-06 | Tdk Corp | Laminated ceramic element manufacturing method |
| CN108493447A (en) * | 2018-03-13 | 2018-09-04 | 乳源东阳光磁性材料有限公司 | Preparation method of high-quality high-nickel multi-element positive electrode material |
| CN112744874A (en) * | 2020-12-29 | 2021-05-04 | 无锡晶石新型能源股份有限公司 | Preparation method of low-energy-consumption high-nickel ternary material |
| CN214792563U (en) * | 2021-04-16 | 2021-11-19 | 阳泉银宇新材料有限责任公司 | Special sagger for lithium ion battery material |
| CN215002867U (en) * | 2021-05-26 | 2021-12-03 | 南通瑞翔新材料有限公司 | Sagger for sintering roller kiln for lithium battery ternary cathode material |
| CN113823764A (en) * | 2021-09-29 | 2021-12-21 | 北京当升材料科技股份有限公司 | Roller kiln for sintering anode material, multi-element anode material and preparation method thereof |
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