CN114873650B - Positive electrode material precursor, positive electrode material, preparation method of positive electrode material and lithium ion battery - Google Patents
Positive electrode material precursor, positive electrode material, preparation method of positive electrode material and lithium ion battery Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 58
- 239000002243 precursor Substances 0.000 title claims abstract description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 29
- 238000002360 preparation method Methods 0.000 title claims description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 35
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 34
- 239000000956 alloy Substances 0.000 claims abstract description 34
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 33
- 239000010405 anode material Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 31
- 150000003624 transition metals Chemical class 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910006025 NiCoMn Inorganic materials 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000010406 cathode material Substances 0.000 description 20
- 238000002474 experimental method Methods 0.000 description 20
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 20
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 20
- 239000002002 slurry Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000005520 cutting process Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 10
- 239000012467 final product Substances 0.000 description 10
- 239000011888 foil Substances 0.000 description 10
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 10
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 10
- 229910052751 metal Chemical class 0.000 description 10
- 239000002184 metal Chemical class 0.000 description 10
- 239000011812 mixed powder Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000010532 solid phase synthesis reaction Methods 0.000 description 5
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 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 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
-
- 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
- H01M4/48—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a positive electrode material precursor, which is a transition metal simple substance or a transition metal alloy, wherein the transition metal simple substance is selected from one or more of Ni, co and Mn, and the transition metal alloy is selected from one or more of NiCo alloy, niMn alloy and NiCoMn alloy. The invention directly takes transition metal (Ni, co, mn) powder or alloy powder thereof as a precursor of the anode material, and the anode material is sintered after being mixed with a lithium source, so that the prepared anode material has good crystal and better electrochemical performance. In addition, the positive electrode material prepared by the method has high tap density, simple manufacturing process, environment friendliness and low cost, and is convenient for mass production.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a positive electrode material precursor, a positive electrode material, a preparation method of the positive electrode material and a lithium ion battery.
Background
Under the multiple pressures of shortage of global resources and environmental pollution and under the positive call of the national double-carbon strategy, the development of a green and environment-friendly novel energy source becomes significant. As is well known, lithium ion battery technology is widely used in various fields such as automobiles, energy storage, 3C fields, etc., as a novel energy storage technology. The lithium ion battery and the material thereof have great research value due to the advantages of high working voltage, high energy density and the like of the lithium ion battery.
Because the positive electrode material occupies an important position in the cost of the lithium ion battery, the use cost of the lithium ion battery is greatly reduced by adopting a more economical positive electrode material or improving the synthesis process of the lithium ion battery, and the process of replacing the traditional energy source by the lithium ion battery can be accelerated and promoted. The current method for synthesizing the positive electrode material of the lithium ion battery comprises the following steps: high temperature solid phase method, hydrothermal method, sol-gel method, coprecipitation method, spray pyrolysis, etc.; the high-temperature solid-phase method for synthesizing the lithium ion battery anode material is low in cost, environment-friendly and convenient for mass production.
The conventional high-temperature solid phase method is to mix and sinter a metal oxide or a metal salt serving as a precursor and a lithium source to prepare the lithium ion battery anode material, wherein the precursor has a relatively complicated preparation process, such as the precursor is prepared by using a high-temperature solid phase method and a coprecipitation method.
In the patent CN 1102806C, a two-step solid phase method is adopted to synthesize a lithium cobaltate anode material, wherein a cobalt compound is used as a precursor and is mixed and sintered with a lithium source compound; in patent CN 1485278a, it is proposed to react aqueous ammonia as a complexing agent and sodium hydroxide as a precipitant with a metal salt solution to obtain a spherical cobalt hydroxide precursor by precipitation, and then synthesize a lithium cobaltate cathode material by high-temperature solid phase reaction. The method in the patent is also widely applied to the anode materials of the multi-element lithium ion batteries. However, the preparation process of the method is complicated when the precursor is prepared, and the further development of the method in a lithium ion battery is limited.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a positive electrode material precursor, a positive electrode material, a preparation method thereof and a lithium ion battery.
The invention provides a positive electrode material precursor, which is a transition metal simple substance or a transition metal alloy, wherein the transition metal simple substance is selected from one or more of Ni, co and Mn, and the transition metal alloy is selected from one or more of NiCo alloy, niMn alloy and NiCoMn alloy.
Preferably, the transition metal element is in the form of a powder having a particle size of 1nm to 100. Mu.m, preferably 1nm to 10. Mu.m.
The invention also provides a positive electrode material prepared from the lithium source and the positive electrode material precursor.
Preferably, the lithium source is selected from lithium hydroxide, lithium carbonate or lithium nitrate, and the molar ratio of the positive electrode material precursor to the lithium source is 1:1-1:1.1.
Preferably, the particle size of the positive electrode material is 1nm to 100. Mu.m, preferably 50nm to 50. Mu.m.
The invention also provides a preparation method of the positive electrode material, which comprises the following steps:
Mixing a lithium source and a positive electrode material precursor, and then sintering at a high temperature to obtain a sintered product;
And annealing the sintered product, and grinding and sieving to obtain the positive electrode material.
Preferably, the high-temperature sintering environment is oxygen or air atmosphere;
the high-temperature sintering method comprises the following steps:
Heating to 400-600 ℃ at a heating rate of 2-10 ℃/min, and preserving heat for 3-10 h;
Then heating to 700-1000 ℃ at a heating rate of 2-10 ℃/min, and preserving heat for 8-20 h.
Preferably, the annealing is naturally cooled to room temperature under oxygen or air atmosphere.
Preferably, the screen is a 200-500 mesh screen.
The invention also provides a lithium ion battery, which comprises the positive electrode material.
Compared with the prior art, the invention provides a positive electrode material precursor, which is a transition metal simple substance or a transition metal alloy, wherein the transition metal simple substance is selected from one or more of Ni, co and Mn, and the transition metal alloy is selected from one or more of NiCo alloy, niMn alloy and NiCoMn alloy. The invention directly takes transition metal (Ni, co, mn) powder or alloy powder thereof as a precursor of the anode material, and the anode material is sintered after being mixed with a lithium source, so that the prepared anode material has good crystal and better electrochemical performance. In addition, the positive electrode material prepared by the method has high tap density, simple manufacturing process, environment friendliness and low cost, and is convenient for mass production.
Drawings
FIG. 1a is a scanning electron microscope picture of a lithium cobaltate layered cathode material prepared in example 1;
Fig. 1b is a relationship between specific discharge capacity and number of discharge turns at 0.2C magnification of the lithium cobaltate layered cathode materials prepared in examples 1 to 4;
FIG. 1c is a xrd graph of the lithium cobaltate layered cathode material prepared in example 1;
FIG. 2a is a scanning electron microscope image of the lithium nickelate layered cathode material prepared in example 5;
Fig. 2b is a relationship between specific discharge capacity and number of discharge turns of the lithium nickelate layered cathode materials prepared in examples 5 to 8 at 0.2C magnification;
FIG. 2c is a xrd graph of the lithium nickelate layered cathode material prepared in example 5;
FIG. 3a is a scanning electron microscope picture of NCM811 layered positive electrode material prepared in example 9;
fig. 3b is a relationship between specific discharge capacity and number of discharge turns at 0.2C magnification of NCM811 layered cathode materials prepared in example 9 and example 10;
FIG. 3c is xrd of the NCM811 layered positive electrode material prepared in example 9.
Detailed Description
The invention provides a positive electrode material precursor, which is a transition metal simple substance or a transition metal alloy, wherein the transition metal simple substance is selected from one or more of Ni, co and Mn, and the transition metal alloy is selected from one or more of NiCo alloy, niMn alloy and NiCoMn alloy.
In the present invention, the elemental transition metal is in the form of a powder having a particle diameter of 1nm to 100. Mu.m, preferably 1nm to 10. Mu.m, more preferably 1nm, 5nm, 10nm, 50nm, 100nm, 500nm, 1. Mu.m, 5 μm, 10. Mu.m, or any value between 1nm and 10. Mu.m. In the invention, the transition metal powder has uniform particle size, less impurities, high purity and purity of more than or equal to 98 percent.
The transition metal alloy is in the form of a powder having a particle size of 1nm to 100. Mu.m, preferably 1nm to 10. Mu.m, more preferably 1nm, 5nm, 10nm, 50nm, 100nm, 500nm, 1. Mu.m, 5. Mu.m, 10. Mu.m, or any value between 1nm and 10. Mu.m.
The source of the transition metal simple substance or the transition metal alloy is not particularly limited, and the transition metal simple substance or the transition metal alloy is generally sold or prepared by self.
The invention also provides a positive electrode material prepared from the lithium source and the positive electrode material precursor.
In the invention, the lithium source is selected from lithium hydroxide, lithium carbonate or lithium nitrate, and the molar ratio of the positive electrode material precursor to the lithium source is 1:1-1:1.1. The excess lithium is used to compensate for the small loss of lithium during sintering.
In the present invention, the particle size of the positive electrode material is 1nm to 100. Mu.m, preferably 50nm to 50. Mu.m, more preferably 50nm, 100nm, 500nm, 1. Mu.m, 5. Mu.m, 10. Mu.m, 50. Mu.m, or any value between 50nm and 50. Mu.m.
The invention also provides a preparation method of the positive electrode material, which comprises the following steps:
Mixing a lithium source and a positive electrode material precursor, and then sintering at a high temperature to obtain a sintered product;
And annealing the sintered product, and grinding and sieving to obtain the positive electrode material.
According to the invention, a lithium source and a positive electrode material precursor are mixed and then sintered at a high temperature to obtain a sintered product.
The lithium source and the positive electrode material precursor are mixed and placed in a heating device, and in the invention, the heating device is preferably a tube furnace.
Then, sintering is performed at high temperature under oxygen or air atmosphere. In the present invention, the high temperature sintering process is divided into two stages:
The first stage presintering to decompose the lithium source completely, heating to 400-600 deg.c at the heating rate of 2-10 deg.c/min and maintaining for 3-10 hr. Wherein the heating rate is preferably any value between 2, 4, 6, 8, 10 or 2-10 ℃/min; the temperature of the heating is preferably 400, 450, 500, 550, 600 or any value between 400 and 600 ℃, and the time of the heat preservation is preferably 3,4, 5, 6, 7, 8, 9, 10 or any value between 3 and 10 hours.
And synthesizing a layered anode material of the lithium ion battery in the second stage of high-temperature process, heating to 700-1000 ℃ at a heating rate of 2-10 ℃/min, and preserving heat for 8-20 h. Wherein the heating rate is preferably 2, 4, 6, 8, 10, or any value between 2 and 10 ℃/min, more preferably any value between 3 and 5 ℃/min; the temperature of the heating is preferably 700, 800, 900, 1000, or any value between 700 and 1000 ℃, and the time of the heat preservation is preferably 8, 10, 12, 14, 16, 18, 20, or any value between 8 and 20 hours.
After the high-temperature sintering process is finished, the sintered product is naturally cooled to room temperature in oxygen or air for annealing. In the present invention, the room temperature is defined as 25.+ -. 5 ℃.
The annealed material is ground and sieved, and the grinding method is not particularly limited in the present invention, and may be any method known to those skilled in the art. Screening through a 200-500-mesh sieve according to actual needs to obtain the anode material with uniform particle size.
The invention also provides a lithium ion battery, which comprises the positive electrode material.
The positive electrode material prepared by the invention has the following advantages:
(1) According to the invention, transition metal (Ni, co and Mn) simple substance powder or alloy (such as NiCo, niMn, niCoMn alloy) powder thereof is used as a precursor of the lithium ion battery anode material, and is directly mixed with a lithium source to rapidly prepare the lithium ion battery layered anode material, so that the preparation cost of the precursor of the lithium ion battery layered anode material is greatly saved, and the production period is shortened;
(2) The invention uses transition metal (Ni, co, mn) simple substance powder or alloy (such as NiCo, niMn, niCoMn alloy) powder thereof as the precursor of the lithium ion battery anode material, avoids generating waste water and causing environmental pollution when processing the precursor of the lithium ion battery layered anode material, saves more resources, and is a novel preparation method of the lithium ion battery anode material with environmental protection, economy and high efficiency.
(3) The equipment and the method related in the preparation method of the positive electrode material are simple and easy to operate, and are suitable for large-scale production.
(4) The lithium ion layered anode material prepared by the invention has excellent electrochemical performance, good cycle performance, higher specific discharge capacity and higher tap density (more than 2.25g/cm 3).
In order to further understand the present invention, the following examples are provided to illustrate a positive electrode material precursor, a positive electrode material, a preparation method thereof, and a lithium ion battery, and the scope of the present invention is not limited by the following examples.
The following raw materials, unless otherwise specified, are all commercially available products.
Example 1 preparation of lithium cobalt oxide layered cathode Material
Cobalt metal simple substance powder (particle size is 1 micron) and lithium hydroxide monohydrate are mixed according to a mole ratio of 1:1.05, fully mixing, placing the mixed powder in a tube furnace, heating to 500 ℃ at a speed of 3 ℃/min in an oxygen atmosphere for presintering, and preserving heat for 5 hours; then heating to 850 ℃ at a rate of 5 ℃/min and preserving the heat for 10 hours. And taking out the lithium cobalt oxide positive electrode material after natural annealing of the tube furnace, grinding, sieving through a 300-mesh sieve, and obtaining the sieved lithium cobalt oxide powder as a final product, wherein the picture of a scanning electron microscope of the lithium cobalt oxide layered positive electrode material prepared in the embodiment 1 is shown in fig. 1 a. Referring to fig. 1c, fig. 1c is a xrd pattern of a lithium cobaltate layered cathode material prepared in example 1.
The above product was prepared according to 8:1:1 respectively mixing with PVDF and carbon black according to a proportion, wherein the total mass of the mixture is 1g, adding 2.3g of N-methyl pyrrolidone, fully stirring to obtain uniform slurry, coating the slurry on an aluminum foil, drying, cutting into pieces, adding a proper amount of electrolyte in a glove box to assemble a button cell, and carrying out a charge-discharge experiment on a test platform. The charge-discharge voltage interval is 2.8V-4.3V, and the charge-discharge experiment is carried out under the 0.2C multiplying power. Referring to FIG. 1b, the label is "novel lithium cobaltate 1-850 ℃". The graph shows that the lithium cobaltate positive electrode material prepared by the method has higher discharge capacity and excellent cycle performance.
Example 2 preparation of lithium cobalt oxide layered cathode Material
Cobalt metal simple substance powder (particle size is 1 micron) and lithium hydroxide monohydrate are mixed according to a mole ratio of 1:1.05, fully mixing, placing the mixed powder in a tube furnace, heating to 500 ℃ at a speed of 3 ℃/min in an oxygen atmosphere for presintering, and preserving heat for 5 hours; then heating to 900 ℃ at a speed of 5 ℃/min and preserving heat for 10 hours. And (3) taking out the lithium cobalt oxide anode material after natural annealing in the tube furnace, grinding, sieving through a 300-mesh sieve, and obtaining the screened lithium cobalt oxide powder as a final product.
The above product was prepared according to 8:1:1 respectively mixing with PVDF and carbon black according to a proportion, wherein the total mass of the mixture is 1g, adding 2.3g of N-methyl pyrrolidone, fully stirring to obtain uniform slurry, coating the slurry on an aluminum foil, drying, cutting into pieces, adding a proper amount of electrolyte in a glove box to assemble a button cell, and carrying out a charge-discharge experiment on a test platform. The charge-discharge voltage interval is 2.8V-4.3V, and the charge-discharge experiment is carried out under the 0.2C multiplying power. Referring to FIG. 1b, labeled "New lithium cobaltate-900 ℃".
Example 3 preparation of lithium cobalt oxide layered cathode Material
Cobalt oxide powder (particle size 5 μm) and lithium hydroxide monohydrate were mixed in a molar ratio of 1:1.05, fully mixing, placing the mixed powder in a tube furnace, heating to 500 ℃ at a speed of 3 ℃/min in an oxygen atmosphere for presintering, and preserving heat for 5 hours; then heating to 900 ℃ at a speed of 5 ℃/min and preserving heat for 10 hours. And (3) taking out the lithium cobalt oxide anode material after natural annealing in the tube furnace, grinding, sieving through a 300-mesh sieve, and obtaining the screened lithium cobalt oxide powder as a final product. The preparation is referred to as "commercial lithium cobalt oxide" in the figures, as it is made by commercial conventional methods.
The above product was prepared according to 8:1:1 respectively mixing with PVDF and carbon black according to a proportion, wherein the total mass of the mixture is 1g, adding 2.3g of N-methyl pyrrolidone, fully stirring to obtain uniform slurry, coating the slurry on an aluminum foil, drying, cutting into pieces, adding a proper amount of electrolyte in a glove box to assemble a button cell, and carrying out a charge-discharge experiment on a test platform. The charge-discharge voltage interval is 2.8V-4.3V, and the charge-discharge experiment is carried out under the 0.2C multiplying power. Referring to FIG. 1b, this is labeled "commercial lithium cobaltate-900℃". As can be seen from FIG. 1b, the cycling performance of commercial lithium cobalt oxide is inferior to "novel lithium cobalt oxide 1-850 ℃ using the present process".
Example 4 preparation of lithium cobalt oxide layered cathode Material
Cobalt metal simple substance powder (particle size is 10 microns) and lithium hydroxide monohydrate are mixed according to a mole ratio of 1:1.05, fully mixing, placing the mixed powder in a tube furnace, heating to 500 ℃ at a speed of 3 ℃/min in an oxygen atmosphere for presintering, and preserving heat for 5 hours; then heating to 900 ℃ at a speed of 5 ℃/min and preserving heat for 10 hours. And (3) taking out the lithium cobalt oxide anode material after natural annealing in the tube furnace, grinding, sieving through a 300-mesh sieve, and obtaining the screened lithium cobalt oxide powder as a final product. The preparation is referred to as "commercial lithium cobalt oxide" in the figures, as it is made by commercial conventional methods.
The above product was prepared according to 8:1:1 respectively mixing with PVDF and carbon black according to a proportion, wherein the total mass of the mixture is 1g, adding 2.3g of N-methyl pyrrolidone, fully stirring to obtain uniform slurry, coating the slurry on an aluminum foil, drying, cutting into pieces, adding a proper amount of electrolyte in a glove box to assemble a button cell, and carrying out a charge-discharge experiment on a test platform. The charge-discharge voltage interval is 2.8V-4.3V, and the charge-discharge experiment is carried out under the 0.2C multiplying power. Referring to FIG. 1b, the label is "novel lithium cobaltate 2-850 ℃". As can be seen from fig. 1b, the lithium cobaltate positive electrode materials prepared by using the metal simple substance powder with different particle sizes have certain electrochemical properties, and the properties may be related to the particle sizes of the metal simple substance powder.
Example 5 preparation of lithium Nickel oxide layered cathode Material
The nickel metal simple substance powder (particle size is 1 micron) and lithium hydroxide monohydrate are mixed according to the mole ratio of 1:1.05, fully mixing, placing the mixed powder in a tube furnace, heating to 500 ℃ at a speed of 3 ℃/min in an oxygen atmosphere for presintering, and preserving heat for 5 hours; then heating to 800 ℃ at a speed of 5 ℃/min and preserving heat for 10 hours. And taking out the lithium cobaltate anode material after natural annealing in the tube furnace, grinding, sieving through a 300-mesh sieve, and obtaining the sieved lithium cobaltate powder as a final product, wherein the picture of a scanning electron microscope of the lithium nickelate layered anode material prepared in the embodiment 5 is shown in fig. 2 a. Referring to fig. 2c, fig. 2c is a xrd graph of the lithium nickelate layered cathode material prepared in example 5.
The above product was prepared according to 8:1:1 respectively mixing with PVDF and carbon black according to a proportion, wherein the total mass of the mixture is 1g, adding 2.3g of N-methyl pyrrolidone, fully stirring to obtain uniform slurry, coating the slurry on an aluminum foil, drying, cutting into pieces, adding a proper amount of electrolyte in a glove box to assemble a button cell, and carrying out a charge-discharge experiment on a test platform. The charge-discharge voltage interval is 2.8V-4.3V, and the charge-discharge experiment is carried out under the 0.2C multiplying power. The results are shown in FIG. 2b, labeled "New lithium Nickel-800-1.05". The graph shows that the lithium nickelate positive electrode material prepared by the method has higher discharge capacity and excellent cycle performance.
Example 6 preparation of lithium Nickel oxide layered cathode Material
The nickel metal simple substance powder (particle size is 1 micron) and lithium hydroxide monohydrate are mixed according to the mole ratio of 1:1.05, fully mixing, placing the mixed powder in a tube furnace, heating to 500 ℃ at a speed of 3 ℃/min in an oxygen atmosphere for presintering, and preserving heat for 5 hours; then heating to 850 ℃ at a rate of 5 ℃/min and preserving the heat for 10 hours. And (3) taking out the lithium cobalt oxide anode material after natural annealing in the tube furnace, grinding, sieving through a 300-mesh sieve, and obtaining the screened lithium cobalt oxide powder as a final product.
The above product was prepared according to 8:1:1 respectively mixing with PVDF and carbon black according to a proportion, wherein the total mass of the mixture is 1g, adding 2.3g of N-methyl pyrrolidone, fully stirring to obtain uniform slurry, coating the slurry on an aluminum foil, drying, cutting into pieces, adding a proper amount of electrolyte in a glove box to assemble a button cell, and carrying out a charge-discharge experiment on a test platform. The charge-discharge voltage interval is 2.8V-4.3V, and the charge-discharge experiment is carried out under the 0.2C multiplying power. The results are shown in FIG. 2b, labeled "novel lithium nickelate-850 ℃ -1.05".
Example 7 preparation of lithium Nickel oxide layered cathode Material
The nickel metal simple substance powder (particle size is 1 micron) and lithium hydroxide monohydrate are mixed according to the mole ratio of 1:1.03, fully mixing, placing the mixed powder in a tube furnace, heating to 500 ℃ at a speed of 3 ℃/min in an oxygen atmosphere for presintering, and preserving heat for 5 hours; then heating to 800 ℃ at a speed of 5 ℃/min and preserving heat for 10 hours. And (3) taking out the lithium cobaltate anode material after natural annealing in the tube furnace, grinding, sieving through a 300-mesh sieve, and obtaining the screened lithium nickelate powder as a final product.
The above product was prepared according to 8:1:1 respectively mixing with PVDF and carbon black according to a proportion, wherein the total mass of the mixture is 1g, adding 2.3g of N-methyl pyrrolidone, fully stirring to obtain uniform slurry, coating the slurry on an aluminum foil, drying, cutting into pieces, adding a proper amount of electrolyte in a glove box to assemble a button cell, and carrying out a charge-discharge experiment on a test platform. The charge-discharge voltage interval is 2.8V-4.3V, and the charge-discharge experiment is carried out under the 0.2C multiplying power. The results are shown in FIG. 2b, labeled "New lithium Nickel-800-1.03".
Example 8 preparation of lithium Nickel oxide layered cathode Material
Nickel oxide powder (particle size 1 micron) was mixed with lithium hydroxide monohydrate in a molar ratio of 1:1.05, fully mixing, placing the mixed powder in a tube furnace, heating to 500 ℃ at a speed of 3 ℃/min in an oxygen atmosphere for presintering, and preserving heat for 5 hours; then heating to 800 ℃ at a speed of 5 ℃/min and preserving heat for 10 hours. And (3) taking out the lithium cobaltate anode material after natural annealing in the tube furnace, grinding, sieving through a 300-mesh sieve, and obtaining the screened lithium nickelate powder as a final product.
The above product was prepared according to 8:1:1 respectively mixing with PVDF and carbon black according to a proportion, wherein the total mass of the mixture is 1g, adding 2.3g of N-methyl pyrrolidone, fully stirring to obtain uniform slurry, coating the slurry on an aluminum foil, drying, cutting into pieces, adding a proper amount of electrolyte in a glove box to assemble a button cell, and carrying out a charge-discharge experiment on a test platform. The charge-discharge voltage interval is 2.8V-4.3V, and the charge-discharge experiment is carried out under the 0.2C multiplying power. The results are shown in FIG. 2b, labeled "commercial lithium nickel oxide-800-1.05". As can be seen from FIG. 2b, the cycling stability of "commercial lithium nickelate-800-1.05" is slightly poorer than the novel lithium nickelate prepared using the present method.
Example 9 preparation of Nickel cobalt lithium manganate layered cathode Material
Nickel cobalt manganese alloy (nickel cobalt manganese ratio is 8:1:1) powder (particle size is 5 microns) and lithium hydroxide monohydrate are mixed according to a mole ratio of 1:1.05, fully mixing, placing the mixed powder in a tube furnace, heating to 500 ℃ at a speed of 3 ℃/min in an oxygen atmosphere for presintering, and preserving heat for 5 hours; then heating to 800 ℃ at a speed of 5 ℃/min and preserving heat for 10 hours. And after the tube furnace is naturally annealed, taking out the lithium cobaltate anode material, grinding, sieving through a 300-mesh sieve, and obtaining the screened NCM811 anode powder which is the final product, wherein the picture of a Scanning Electron Microscope (SEM) of the NCM811 layered anode material prepared in the embodiment 9 is shown in the figure 3 a.
The above product was prepared according to 8:1:1 respectively mixing with PVDF and carbon black according to a proportion, wherein the total mass of the mixture is 1g, adding 2.3g of N-methyl pyrrolidone, fully stirring to obtain uniform slurry, coating the slurry on an aluminum foil, drying, cutting into pieces, adding a proper amount of electrolyte in a glove box to assemble a button cell, and carrying out a charge-discharge experiment on a test platform. The charge-discharge voltage interval is 2.8V-4.3V, and the charge-discharge experiment is carried out under the 0.2C multiplying power. Referring to fig. 3b, labeled "novel NCM811". The graph shows that the NCM811 positive electrode material prepared by the method has higher discharge capacity and excellent cycle performance.
Example 10 preparation of Nickel cobalt lithium manganate layered cathode Material
The molar ratio of purchased NCM811 (i.e., nickel cobalt manganese element ratio of 8:1:1) hydroxide precursor (particle size 5 microns) to lithium hydroxide monohydrate was 1:1.05, fully mixing, placing the mixed powder in a tube furnace, heating to 500 ℃ at a speed of 3 ℃/min in an oxygen atmosphere for presintering, and preserving heat for 5 hours; then heating to 800 ℃ at a speed of 5 ℃/min and preserving heat for 10 hours. And after the tube furnace is naturally annealed, taking out the lithium cobalt oxide anode material, grinding, sieving through a 300-mesh sieve, and obtaining the screened NCM811 anode powder which is the final product.
The above product was prepared according to 8:1:1 respectively mixing with PVDF and carbon black according to a proportion, wherein the total mass of the mixture is 1g, adding 2.3g of N-methyl pyrrolidone, fully stirring to obtain uniform slurry, coating the slurry on an aluminum foil, drying, cutting into pieces, adding a proper amount of electrolyte in a glove box to assemble a button cell, and carrying out a charge-discharge experiment on a test platform. The charge-discharge voltage interval is 2.8V-4.3V, and the charge-discharge experiment is carried out under the 0.2C multiplying power. Referring to FIG. 3b, labeled "commercial NCM811". From the figure, the cycling performance of the NCM811 positive electrode material prepared by the commercial preparation method is slightly poorer than that of the novel NCM811 prepared by the method.
Table 1 tap density data for different materials of examples 1 to 10.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the positive electrode material is characterized by comprising the following steps of:
mixing a lithium source and a positive electrode material precursor, and then performing two-stage high-temperature sintering to obtain a sintering product;
annealing the sintered product, and grinding and sieving to obtain a layered anode material;
The positive electrode material precursor is a transition metal simple substance or a transition metal alloy, wherein the transition metal simple substance is selected from one or more of Ni, co and Mn, and the transition metal alloy is selected from one or more of NiCo alloy, niMn alloy and NiCoMn alloy;
the two-stage high-temperature sintering environment is oxygen or air atmosphere;
the two-stage high-temperature sintering method comprises the following steps:
Heating to 400-600 ℃ at a heating rate of 2-10 ℃/min, and preserving heat for 3-10 h;
And then heating to 700-1000 ℃ at a heating rate of 2-10 ℃/min, and preserving heat for 8-20 h.
2. The preparation method according to claim 1, wherein the transition metal simple substance is in the form of powder, and the particle size of the powder is 1 nm-100 μm.
3. The method according to claim 2, wherein the particle size of the powder is 1nm to 10 μm.
4. The method of claim 1, wherein the lithium source is selected from the group consisting of lithium hydroxide, lithium carbonate, and lithium nitrate.
5. The method of claim 1, wherein the molar ratio of the positive electrode material precursor to the lithium source is 1:1 to 1:1.1.
6. The method according to claim 1, wherein the particle size of the positive electrode material is 1nm to 100 μm.
7. The method according to claim 1, wherein the particle size of the positive electrode material is 50nm to 50 μm.
8. The method according to claim 1, wherein the annealing is performed under oxygen or air atmosphere, and the annealing is performed naturally to room temperature.
9. The method of claim 1, wherein the sieving is through a 200-500 mesh screen.
10. A lithium ion battery, characterized by comprising the positive electrode material prepared by the preparation method of any one of claims 1 to 9.
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