CN110165178B - Lithium battery positive electrode material, preparation method thereof and lithium battery containing positive electrode material - Google Patents
Lithium battery positive electrode material, preparation method thereof and lithium battery containing positive electrode material Download PDFInfo
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- CN110165178B CN110165178B CN201910439213.7A CN201910439213A CN110165178B CN 110165178 B CN110165178 B CN 110165178B CN 201910439213 A CN201910439213 A CN 201910439213A CN 110165178 B CN110165178 B CN 110165178B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007774 positive electrode material Substances 0.000 title claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 53
- 239000011149 active material Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010405 anode material Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 15
- 239000010406 cathode material Substances 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 21
- 239000005416 organic matter Substances 0.000 claims description 16
- 239000000919 ceramic Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000010000 carbonizing Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- -1 nickel cobalt aluminum Chemical compound 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 15
- 239000011248 coating agent Substances 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 238000005253 cladding Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 26
- 239000010410 layer Substances 0.000 description 19
- 229910052786 argon Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000007664 blowing Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 238000007873 sieving Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000007600 charging Methods 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 3
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium battery anode material, a preparation method thereof and a lithium battery containing the anode material. The method comprises the steps of coating a porous carbon layer on the surface of an active material, mixing the porous carbon coated active material with a liquid metal organic substance, mixing solid and liquid, enabling the liquid metal organic substance to be uniformly coated on the surface of the porous carbon coated active material, reacting the metal liquid organic substance with water vapor, sintering at high temperature, and dehydrating to obtain the Al2O3In-situ deposited on the pores of the porous carbon layer and the carbon layer, and Al2O3Can "nail" on porous carbon layer surface steadily to reach better cladding effect, and can make active substance and electrolyte separate, reduce the side reaction of cathode material and electrolyte, simultaneously, the electric conductivity of cathode material has been strengthened to middle porous carbon layer, has effectively improved the first coulomb efficiency, cycle performance and the rate capability ability of battery.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a lithium battery positive electrode material, a preparation method thereof and a lithium battery containing the positive electrode material.
Background
The lithium ion battery anode material has poor conductivity, so that the rate performance of the lithium ion battery anode material is poor, a layer of conductive carbon is usually coated on the surface of the lithium ion battery anode material, or a large amount of conductive agents such as carbon black or carbon tubes are added when pole pieces are prepared by homogenizing, but the specific surface area of the conductive carbon or the conductive agents added in the homogenizing process is large, so that the side reaction with electrolyte is increased, in addition, the lithium ion battery anode material is easy to react with the electrolyte to form a stable SEI film in the charging and discharging process, and although the stable SEI film can play a role in stabilizing the battery cycle, limited lithium ions in the battery are also consumed, so that the primary efficiency and the cycle performance of the anode material are influenced.
To solve the above problem, the cathode material is usually coated with an electrochemically stable coating layer so that the cathode material is separated from the electrolyte, and Al2O3Ceramics as electronic insulationThe ceramic layer can well hinder side reactions between the electrolyte and the conductive agent, and although the existing atomic deposition method can achieve good coating, the cost is too high, and the actual production is not facilitated.
There is a need to provide a more efficient, simple and low cost Al2O3The coating method lays a foundation for further application of the coated anode material.
Disclosure of Invention
The invention aims to provide a lithium battery anode material, a preparation method thereof and a lithium battery comprising the anode material2O3Can be deposited relatively uniformly in the pores of the porous carbon layer and the carbon layer, and Al2O3Can be stably nailed on the surface of the porous carbon layer (see figure 1).
The method comprises the following specific steps:
the invention aims to provide a lithium battery anode material, which is in a core-shell structure, wherein a core part is an active material, and a shell part is composed of a porous carbon layer and ceramic sediments, and the ceramic sediments are deposited in holes of the porous carbon layer and on the surface of the carbon layer.
Preferably, the thickness of the porous carbon layer is 10nm to 5 μm; more preferably 500nm to 1 μm.
Preferably, the thickness of the ceramic deposit is 1-100 nm; more preferably 5 to 10 nm.
Preferably, the ceramic deposit is selected from Al2O3。
Preferably, the active material is at least one selected from nickel cobalt manganese ternary material (NCM), nickel cobalt aluminum ternary material (NCA), lithium iron phosphate (LFP), Lithium Manganese Oxide (LMO), and Lithium Nickel Manganese Oxide (LNMO).
Another object of the present invention is to provide a method for preparing the above cathode material, comprising the steps of:
1) mixing the active material, an organic matter and a pore-forming agent, and then carbonizing to obtain a porous carbon-coated active material;
2) and under the condition of isolating oxygen, mixing the porous carbon-coated active material with the liquid metal organic matter, introducing water vapor for reaction, and depositing sintered ceramic sediments on the surface of the porous carbon-coated active material to obtain the lithium battery cathode material.
Preferably, the mass ratio of the active material, the organic matter and the pore-forming agent in the step 1) is 100: (10-30): (5-10); more preferably 100: (15-20): (6-8).
Preferably, the particle size of the nickel-cobalt-manganese ternary material (NCM), the nickel-cobalt-aluminum ternary material (NCA), the lithium iron phosphate (LFP), the Lithium Manganate (LMO) and the Lithium Nickel Manganate (LNMO) is 5-25 μm, and more preferably, the particle size is 10-15 μm.
Preferably, the carbonization temperature in the step 1) is 400-600 ℃; more preferably 450 to 550 ℃.
Preferably, the carbonization time in the step 1) is 0.5-10 h; more preferably 4-8 h.
Preferably, the active material, the organic matter and the pore-forming agent in the step 1) are mixed in a rotary furnace; preferably, the rotating speed of the rotary kiln is 5-50 rpm/min.
Preferably, the organic substance in step 1) is selected from at least one of glucose, citric acid, stearic acid, phthalic anhydride.
Preferably, the pore-forming agent is at least one selected from ammonium bicarbonate and urea.
Preferably, step 1) further comprises sieving with a 325-mesh sieve to obtain the porous carbon-coated active material.
Preferably, the mass ratio of the liquid metal organic matter to the active material in the step 2) is (1-2): 100, respectively; more preferably (1.5-1.8): 100.
preferably, the mass ratio of the water vapor introduction amount to the active material is (5-10): 100, respectively; more preferably 6: 100.
preferably, the reaction time of the liquid metal organic matter and the water vapor in the step 2) is 1-4 h; more preferably 1.5 to 2 hours.
Preferably, the sintering temperature in the step 2) is 800-950 ℃; more preferably 900 deg.c.
Preferably, the sintering reaction time in the step 2) is 5-10 h; more preferably 6 to 8 hours.
Preferably, the liquid metallorganics are selected from trimethylaluminum.
The invention also provides a lithium battery which comprises the cathode material.
The invention has the beneficial effects that:
the method comprises the steps of coating a porous carbon layer on the surface of an active material, mixing the porous carbon coated active material with a liquid metal organic substance, mixing solid and liquid, enabling the liquid metal organic substance to be uniformly coated on the surface of the porous carbon coated active material, reacting the metal liquid organic substance with water vapor, sintering at high temperature, and dehydrating to obtain the Al2O3In-situ deposited on the pores of the porous carbon layer and the carbon layer, and Al2O3The lithium ion battery can be stably nailed on the surface of the porous carbon layer, so that a better coating effect is achieved, active substances are separated from electrolyte, side reactions of the anode material and the electrolyte are reduced, meanwhile, the lithium ion battery is favorable for the insertion and the extraction of lithium ions, and the conductivity of the anode material can be further improved by the porous carbon layer, so that the first coulomb efficiency, the cycle performance and the rate capability of the battery are effectively improved.
Drawings
FIG. 1 is a schematic structural diagram of a lithium battery positive electrode material prepared by the present invention;
fig. 2 is SEM images of the positive electrode material before and after coating in example 6 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples. It will also be understood that the following examples are included merely for purposes of further illustrating the invention and are not to be construed as limiting the scope of the invention, as the invention extends to insubstantial modifications and adaptations of the invention following in the light of the principles set forth herein. The specific process parameters and the like of the following examples are also only one example of suitable ranges, and the skilled person can make a selection within the suitable ranges through the description herein, and are not limited to the specific data of the following examples.
Example 1
A preparation method of a lithium battery positive electrode material comprises the following steps:
1) NCM811, glucose and ammonium bicarbonate are mixed according to the mass ratio of 100: 30: 10, uniformly mixing, putting into a return furnace with the rotation speed of 45rpm/min, heating to 400 ℃, carbonizing for 8 hours, cooling to room temperature, and sieving by a 325-mesh sieve to obtain a porous carbon-coated active material;
2) putting the porous carbon-coated active material into a rotary furnace to rotate at the rotating speed of 20rpm/min, introducing argon for 2 hours, and then extruding trimethyl aluminum into a cavity of the rotary furnace, wherein the mass ratio of the trimethyl aluminum to NCM811 is 2: stirring for 2h 100, continuously introducing argon gas, and blowing water vapor into the cavity, wherein the mass ratio of the blowing amount of the water vapor to the NCM811 is 5: 100, reacting trimethylaluminum with water vapor for 2 hours, continuously introducing argon, heating the rotary furnace to 950 ℃, sintering and dehydrating, keeping the temperature for 10 hours, and naturally cooling to room temperature to obtain the lithium battery cathode material.
Example 2
A preparation method of a lithium battery positive electrode material comprises the following steps:
1) NCM811, glucose and ammonium bicarbonate are mixed according to the mass ratio of 100: 20: 8, uniformly mixing, then putting into a return furnace with the rotating speed of 45rpm/min, heating to 600 ℃, carbonizing for 6 hours, then cooling to room temperature, and sieving with a 325-mesh sieve to obtain a porous carbon-coated active material;
2) putting the porous carbon-coated active material into a rotary furnace to rotate at the rotating speed of 20rpm/min, introducing nitrogen for 2 hours, and then extruding trimethylaluminum into a cavity of the rotary furnace, wherein the mass ratio of the trimethylaluminum to NCM811 is 1.5: stirring for 1h, continuously introducing nitrogen and blowing water vapor into the cavity, wherein the mass ratio of the blowing amount of the water vapor to the NCM811 is 6: 100, reacting trimethylaluminum with water vapor for 1.5h, continuously introducing nitrogen, heating the rotary furnace to 900 ℃ for sintering and dehydrating, preserving heat for 10h, and naturally cooling to room temperature to obtain the lithium battery cathode material.
Example 3
A preparation method of a lithium battery positive electrode material comprises the following steps:
1) NCM811, citric acid and ammonium bicarbonate are mixed according to the mass ratio of 100: 25: 8, uniformly mixing, then putting into a return furnace with the rotating speed of 40rpm/min, heating to 500 ℃, carbonizing for 5 hours, then cooling to room temperature, and sieving with a 325-mesh sieve to obtain a porous carbon-coated active material;
2) putting the porous carbon-coated active material into a rotary furnace to rotate at the rotating speed of 15rpm/min, introducing nitrogen for 2 hours, and then extruding trimethylaluminum into a cavity of the rotary furnace, wherein the mass ratio of the trimethylaluminum to NCM811 is 2: stirring for 2h 100, continuously introducing nitrogen and blowing water vapor into the cavity, wherein the mass ratio of the blowing amount of the water vapor to the NCM811 is 8: 100, reacting trimethylaluminum with water vapor for 2 hours, continuously introducing nitrogen, heating the rotary furnace to 800 ℃, sintering and dehydrating, keeping the temperature for 8 hours, and naturally cooling to room temperature to obtain the lithium battery cathode material.
Example 4
A preparation method of a lithium battery positive electrode material comprises the following steps:
1) NCM811, citric acid and urea are mixed according to the mass ratio of 100: 20: 8, uniformly mixing, then putting into a return furnace with the rotating speed of 35rpm/min, heating to 600 ℃, carbonizing for 4 hours, then cooling to room temperature, and sieving with a 325-mesh sieve to obtain a porous carbon-coated active material;
2) putting the porous carbon-coated active material into a rotary furnace to rotate at the rotating speed of 15rpm/min, introducing argon for 1h, extruding trimethylaluminum into a cavity of the rotary furnace, wherein the mass ratio of the trimethylaluminum to NCM811 is 1.5: stirring for 2h 100, continuously introducing argon gas, and blowing water vapor into the cavity, wherein the mass ratio of the blowing amount of the water vapor to the NCM811 is 8: and (3) 100, keeping the reaction time of trimethylaluminum and water vapor at 2h, continuously introducing argon, heating the rotary furnace to 900 ℃ for sintering and dehydrating, keeping the temperature for 6h, and naturally cooling to room temperature to obtain the lithium battery cathode material.
Example 5
A preparation method of a lithium battery positive electrode material comprises the following steps:
1) mixing NCM811, a hard acid ester and ammonium bicarbonate according to a mass ratio of 100: 30: 6, uniformly mixing, then putting into a return furnace with the rotation speed of 45rpm/min, heating to 400 ℃, carbonizing for 6 hours, then cooling to room temperature, and sieving with a 325-mesh sieve to obtain a porous carbon-coated active material;
2) putting the porous carbon-coated active material into a rotary furnace to rotate at the rotating speed of 20rpm/min, introducing argon for 2 hours, and then extruding trimethylaluminum into a cavity of the rotary furnace, wherein the mass ratio of the trimethylaluminum to NCM811 is 1: stirring for 2h 100, continuously introducing argon gas, and blowing water vapor into the cavity, wherein the mass ratio of the blowing amount of the water vapor to the NCM811 is 6: 100, reacting trimethylaluminum with water vapor for 2 hours, continuously introducing argon, heating the rotary furnace to 950 ℃, sintering and dehydrating, keeping the temperature for 8 hours, and naturally cooling to room temperature to obtain the lithium battery cathode material.
Example 6
A preparation method of a lithium battery positive electrode material comprises the following steps:
1) NCM811, glucose and urea are mixed according to the mass ratio of 100: 20: 5, uniformly mixing, then putting into a return furnace with the rotation speed of 45rpm/min, heating to 400 ℃, carbonizing for 6 hours, then cooling to room temperature, and sieving by a 325-mesh sieve to obtain a porous carbon-coated active material;
2) putting the porous carbon-coated active material into a rotary furnace to rotate at the rotating speed of 8rpm/min, introducing argon for 2h, and then extruding trimethylaluminum into a cavity, wherein the mass ratio of the trimethylaluminum to NCM811 is 1: stirring for 2h 100, continuously introducing argon gas, and blowing water vapor into the cavity, wherein the mass ratio of the blowing amount of the water vapor to the NCM811 is 8: and (3) 100, keeping the reaction time of trimethylaluminum and water vapor at 2h, continuously introducing argon, heating the rotary furnace to 900 ℃ for sintering and dehydrating, keeping the temperature for 6h, and naturally cooling to room temperature to obtain the lithium battery cathode material.
Comparative example 1
Commercially available carbon-coated NCM811 was used as the positive electrode material, and the particle size D50 was 16 μm.
Comparative example 2
The preparation method is the same as example 6 except that only porous carbon coating is performed.
Comparative example 3
The preparation method is the same as example 6, except that only Al is carried out without porous carbon coating2O3And (4) coating.
1. And (4) SEM test:
SEM tests were performed on samples of the positive electrode material of example 6 before and after coating, and the results are shown in fig. 2;
as can be seen from fig. 2: obvious crystal lattice stripes can be seen on the surface of the anode material before coating, and the crystal lattice stripes disappear on the surface of the coated anode material, and a layer of amorphous substance with uniform thickness (dotted line part in the figure) is replaced by the amorphous substance, namely amorphous carbon and Al2O3The clad layer, that is, the shell portion of the positive electrode material prepared in the present invention.
2. And (3) performance testing:
the positive electrode materials of examples 1 to 6 and comparative examples 1 to 3, SP, PVDF ═ 95.5: 2: 2.5, adding a proper amount of NMP as a dispersant to prepare slurry, then coating the slurry on an aluminum foil, performing vacuum drying and rolling to prepare a positive plate, taking metal lithium as a counter electrode, using 1mol/L electrolyte of a LiPF6 three-component mixed solvent (EC, DMC and EMC are mixed according to a volume ratio of 1: 1: 1), adopting a polypropylene microporous membrane as a diaphragm, assembling the diaphragm into a CR2016 type button cell in a glove box filled with argon, and performing charge and discharge tests on the button cell in a Neware cell test system of Shenzhen New Wien company, wherein the test conditions are as follows: at room temperature, the constant current charging and discharging of 0.1C, the charging and discharging voltage is limited to 3.0-4.3V in long-cycle test 1C charging and 1C discharging, and the result is shown in the following table 1:
TABLE 1
As can be seen from Table 1: the cycle capacity retention of the positive electrode materials of the examples was significantly improved relative to the comparative examples, which indicates that the double-layer coating of the present invention is more stable because Al2O3The double-layer coating can effectively ensure the intercalation and deintercalation of lithium ions on the premise of ensuring the cycle performance, although the double-layer coating is only improved by about 1-3 percent compared with the comparative example, the result is thatThe method belongs to the major breakthrough because of the great technical difficulty in the first time of improving the coulomb efficiency.
Claims (6)
1. A lithium battery positive electrode material is characterized in that: the anode material is of a core-shell structure, the core part of the anode material is an active material, the shell part of the anode material is composed of a porous carbon layer and ceramic deposits, and the ceramic deposits are deposited on holes of the porous carbon layer and the surface of the carbon layer; the ceramic deposit is selected from Al2O3(ii) a The active material is selected from at least one of nickel cobalt manganese ternary material, nickel cobalt aluminum ternary material, lithium iron phosphate, lithium manganate and lithium nickel manganese;
the preparation method of the cathode material comprises the following steps:
1) mixing the active material, an organic matter and a pore-forming agent, and then carbonizing to obtain a porous carbon-coated active material;
2) under the condition of isolating oxygen, mixing the porous carbon-coated active material with a liquid metal organic matter, introducing water vapor for reaction, and depositing sintered ceramic sediments on the surface of the porous carbon-coated active material to obtain a lithium battery anode material;
the liquid metal organic is selected from trimethylaluminum;
the mass ratio of the liquid metal organic matter to the active material in the step 2) is 1-2: 100, respectively; the mass ratio of the steam introduction amount of the steam reaction in the step 2) to the active material is 5-10: 100, respectively; the reaction time of the liquid metal organic matter and the water vapor in the step 2) is 1-4 h; the sintering temperature in the step 2) is 800-950 ℃; the sintering time in the step 2) is 5-10 h.
2. The positive electrode material according to claim 1, characterized in that: the thickness of the porous carbon layer is 10 nm-5 mu m; the thickness of the ceramic deposit is 1-100 nm.
3. The method for producing a positive electrode material according to claim 1 or 2, characterized in that: the method comprises the following steps:
1) mixing the active material, an organic matter and a pore-forming agent, and then carbonizing to obtain a porous carbon-coated active material;
2) under the condition of isolating oxygen, mixing the porous carbon-coated active material with a liquid metal organic matter, introducing water vapor for reaction, and depositing sintered ceramic sediments on the surface of the porous carbon-coated active material to obtain a lithium battery anode material;
the liquid metal organic is selected from trimethylaluminum;
in the step 2), the mass ratio of the liquid metal organic matter to the active material is 1-2: 100, respectively; the mass ratio of the steam introduction amount of the steam reaction in the step 2) to the active material is 5-10: 100, respectively; in the step 2), the reaction time of the liquid metal organic matter and the water vapor is 1-4 h; the sintering temperature in the step 2) is 800-950 ℃; the sintering time in the step 2) is 5-10 h.
4. The production method according to claim 3, characterized in that: the mass ratio of the active material, the organic matter and the pore-forming agent in the step 1) is 100: 10-30: 5-10; the carbonization temperature in the step 1) is 400-600 ℃; the carbonization time in the step 1) is 0.5-10 h.
5. The production method according to claim 3, characterized in that: in the step 1), the organic matter is at least one selected from glucose, citric acid, stearic acid, phthalic anhydride and phthalic anhydride; in the step 1), the pore-forming agent is selected from at least one of ammonium bicarbonate and urea.
6. A lithium battery, characterized by: the lithium battery includes the positive electrode material according to claim 1 or 2.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105355911A (en) * | 2015-11-28 | 2016-02-24 | 中信大锰矿业有限责任公司大新锰矿分公司 | Preparation method of aluminum oxide coated lithium nickel manganese cobalt cathode material |
| JP2017212123A (en) * | 2016-05-26 | 2017-11-30 | トヨタ自動車株式会社 | Electrode body |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103078081B (en) * | 2013-01-15 | 2016-04-06 | 宁德新能源科技有限公司 | Surface coated anode active material of lithium ion battery particle and preparation method thereof |
| US20150162602A1 (en) * | 2013-12-10 | 2015-06-11 | GM Global Technology Operations LLC | Nanocomposite coatings to obtain high performing silicon anodes |
| CN104201323B (en) * | 2014-07-07 | 2016-08-17 | 上海电力学院 | The preparation method of alumina-coated lithium cobaltate cathode material |
| CN104716312B (en) * | 2015-03-11 | 2017-03-22 | 中国科学院化学研究所 | Silicon-carbon composite material for lithium ion battery, preparation method and application of silicon-carbon composite material |
| US10326142B2 (en) * | 2015-09-15 | 2019-06-18 | GM Global Technology Operations LLC | Positive electrode including discrete aluminum oxide nanomaterials and method for forming aluminum oxide nanomaterials |
| CN105576220B (en) * | 2016-03-21 | 2018-03-30 | 河北工业大学 | A kind of preparation method of cellular carbon-coated LiFePO 4 for lithium ion batteries positive electrode |
| KR101865382B1 (en) * | 2016-04-20 | 2018-06-07 | 울산과학기술원 | Surface-treated positive active material, method for surface-treating positive active material, and electrochemical devices including the same surface-treated positive active material |
| KR102591512B1 (en) * | 2016-09-30 | 2023-10-23 | 삼성전자주식회사 | Negative active material, lithium secondary battery including the material, and method for manufacturing the material |
| CN108390022B (en) * | 2017-12-29 | 2020-12-25 | 桑德新能源技术开发有限公司 | Carbon-metal oxide composite coated lithium battery ternary positive electrode material, preparation method thereof and lithium battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105355911A (en) * | 2015-11-28 | 2016-02-24 | 中信大锰矿业有限责任公司大新锰矿分公司 | Preparation method of aluminum oxide coated lithium nickel manganese cobalt cathode material |
| JP2017212123A (en) * | 2016-05-26 | 2017-11-30 | トヨタ自動車株式会社 | Electrode body |
Non-Patent Citations (2)
| Title |
|---|
| Effects of Atomic Layer Deposition of Al2O3 on the Li[Li0.20Mn0.54Ni0.13Co0.13]O2 Cathode for Lithium-Ion Batteries;Yoon Seok Jung等;《Journal of The Electrochemical Society》;20111101;第158卷(第12期);第A1298-A1302页 * |
| Structure and Electrochemical Performance of LiFePO4/C Cathode Materials Coated with Nano Al2O3 for Lithium-ion Battery;ZHAO Shi-Xi等;《无机材料学报》;20130704;第28卷(第11期);第1265-1269页 * |
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