CN115207324B - Composite nickel-rich positive electrode active material, preparation and application thereof - Google Patents
Composite nickel-rich positive electrode active material, preparation and application thereof Download PDFInfo
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- CN115207324B CN115207324B CN202210981068.7A CN202210981068A CN115207324B CN 115207324 B CN115207324 B CN 115207324B CN 202210981068 A CN202210981068 A CN 202210981068A CN 115207324 B CN115207324 B CN 115207324B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 96
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000000654 additive Substances 0.000 claims abstract description 48
- 230000000996 additive effect Effects 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 23
- 239000011149 active material Substances 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 5
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- 239000006183 anode active material Substances 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 description 30
- 208000028659 discharge Diseases 0.000 description 9
- 238000007599 discharging Methods 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 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
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- -1 lithium organic acid Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/36—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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of lithium ion battery anode materials, and particularly relates to a composite nickel-rich anode active material, which comprises a nickel-rich active material and an additive; the additive is at least one of BiNiO 3、PbNiO3. The invention also relates to a positive electrode material containing the positive electrode active material, a positive electrode and a lithium ion battery. The use of the additive can effectively relieve the lattice cracks of the nickel-rich active material caused by the phase change from H2 to H3 in the charge-discharge process, and improve the electrochemical performance, particularly the electrochemical performance under high current.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to the field of lithium ion battery anode materials.
Background
There is a continuing and urgent need for battery technology that provides more energy in a shorter period of time while maintaining low cost and improved safety. The application of the ultra-high nickel (Ni is more than or equal to 0.8) layered oxide in the lithium ion battery is benefited, and the electric automobile shows a continuous voyage mileage enough to compete with the traditional automobile; however, long charging times have hindered their widespread success. The capacity of the ultra-high nickel positive electrode material is close to or even more than 200mAhg < -1 >, the cost is effectively controlled (cobalt reduction) and the characteristics meet the development trend of lithium ion batteries of electric automobiles. However, the increasingly stringent rapid charge requirements make the use of ultra-high nickel challenging.
During the extraction of lithium ions (corresponding to the battery charging process), the ultra-high nickel positive electrode material undergoes a series of phase changes: h1→m→h2→h3. The present commercial nickel-rich positive electrode materials are generally made into spherical secondary particles composed of primary particles distributed randomly, which can cause ion movement in the secondary particles to be macroscopically represented as isotropic, which is not a significant problem in response to a low current density, but such a configuration does not cause significant problems in response to a low current density, and the problem of rapid increase in current density is caused to occur, and the problem of excessive polarization is caused to occur at a high level, which may lead to a large capacity fading.
Although improvements for high nickel cathode materials have been widely reported, these improvements are not based on milder conditions (lower nickel content or low rate conditions), but there are few studies on rapid charge improvement for ultra-high nickel cathode materials. Currently, many researchers have suggested lowering the charge cut-off voltage, lowering the nickel content and depth of discharge to mitigate damage (cracking) to the material structure.
In view of the foregoing, cracks generated in the cathode material during the charge and discharge process have seriously affected the application of the cathode material, and it is necessary to provide a lithium ion cathode material that reduces the cracks during the charge and discharge process.
Disclosure of Invention
In order to solve the problems that the nickel-rich positive electrode active material is easy to generate inter-crystal cracks, the electrochemical performance is not ideal, and the like, the first aim of the invention is to provide a composite nickel-rich positive electrode active material, which aims to solve the problem of inter-crystal cracks of the nickel-rich positive electrode material, and improve the electrochemical performance of the nickel-rich positive electrode active material, particularly the electrochemical performance under high current.
The second object of the invention is to provide a preparation method and application of the composite nickel-rich positive electrode active material.
The third object of the present invention is to provide a positive electrode material, a positive electrode and a lithium ion battery comprising the composite nickel-rich positive electrode active material.
The special H2-H3 phase change process of the high-nickel positive electrode material enables the high-nickel positive electrode material to be easier to generate lattice cracks in the charge-discharge stage, so that the electrochemical performance of the high-nickel positive electrode material is greatly influenced, in particular the structural stability and the electrochemical performance of the high-nickel positive electrode material under high current are influenced, and aiming at the problem, the invention provides the following improvement scheme, which specifically comprises the following steps:
A composite nickel-rich positive electrode active material comprises a nickel-rich active material and an additive;
The additive is at least one of BiNiO 3、PbNiO3.
According to the research of the invention, through the use of the additive, the crystal lattice crack of the nickel-rich active material caused by the phase change from H2 to H3 in the charge-discharge process can be effectively relieved, and the electrochemical performance, particularly the electrochemical performance under high current, is improved.
In the invention, the nickel-rich active material is a positive electrode active material with Ni more than or equal to 0.8 (the Ni accounts for more than or equal to 80mol percent of the content of transition metal); preferably Li wNi1-x-y CoxMnyO2, w is more than or equal to 0.98 and less than or equal to 1.15,0, x is more than or equal to 0.20, y is more than or equal to 0 and less than or equal to 0.20, and 1-x-y is more than or equal to 0.8 (preferably 0.8-1); further preferably at least one of NCM83, NCM88, NCM92, NCA88, NCA 92.
In the present invention, the additives preferably include BiNiO 3 and PbNiO 3. According to the invention, the components in the combination are used as the additive, so that the synergistic effect is achieved, the lattice cracks caused by the phase transition from H2 to H3 of the nickel-rich material can be further synergistically relieved, the electrochemical performance is further improved, and the electrochemical performance under high current is particularly improved.
Preferably, in the additive, the weight ratio of BiNiO 3 to PbNiO 3 is 1-5:1.
In the invention, the additive also comprises an auxiliary additive, wherein the auxiliary additive is at least one of zirconia, tungsten oxide, strontium oxide and alumina. In the invention, at least one of BiNiO 3、PbNiO3 and the auxiliary additive are combined, so that the cycle performance of the composite nickel-rich positive electrode active material can be further improved.
Preferably, the additive is added in an amount of 0.05 to 1wt% relative to the nickel-rich active material; preferably 0.3 to 0.8Wt%, more preferably 0.3 to 0.5Wt%; wherein the addition amount of the auxiliary additive is less than or equal to 0.5%; preferably 0.1 to 0.3%.
Preferably, the composite nickel-rich positive electrode active material is a material with a coating structure, and further comprises a coating material, wherein the coating material coats the nickel-rich active material and the additive. Preferably, the coating material is an oxide of at least one element of Co, al, W, ce, nb, B, ti, mg, zr.
The composite nickel-rich positive electrode active material with the preferable coating structure has a core-shell structure, wherein the core is the composite of the nickel-rich active material and the additive, and the shell coating the core is the coating material. The invention discovers that the core-shell structure material is favorable for further combining and cooperating with the additive, and can further improve the performance of the nickel-rich material.
Preferably, in the composite nickel-rich positive electrode active material, the content of the coating material is 0.05-1 wt%; preferably 0.1 to 0.5wt%.
The invention also provides a preparation method of the composite nickel-rich positive electrode active material, which is obtained by compounding the nickel-rich active material and the additive.
The invention relates to a preferable in-situ preparation method, which comprises the following steps: mixing a nickel-rich precursor, a lithium source and an additive, and calcining to obtain the nickel-rich precursor;
Preferably, the nickel-rich precursor is a nickel-rich hydroxide capable of obtaining the nickel-rich active material; for example, the chemical formula of the nickel-rich precursor is Ni 1-x-y CoxMny(OH)2, x is more than or equal to 0 and less than or equal to 0.20, and y is more than or equal to 0 and less than or equal to 0.20; the 1-x-y is greater than or equal to 0.8 (preferably 0.8-1).
The lithium source is at least one of lithium hydroxide, lithium carbonate, lithium nitrate and lithium organic acid (such as lithium acetate).
The molar ratio of Li in the transition metal and the lithium source of the nickel-rich precursor (also called lithium distribution ratio, for example, me/Li ratio) is 1:1.02 to 1.1.
In the present invention, the temperature of the calcination process is 700 to 900 ℃, and more preferably 750 to 800 ℃.
Preferably, the calcination time is 7 to 20 hours.
According to the preparation method of the composite nickel-rich positive electrode active material with the coating structure, a calcined product is immersed in a coating precursor material solution, solid-liquid separation is carried out, and the second calcination treatment is carried out, so that the composite nickel-rich positive electrode active material with the coating structure is prepared. Preferably, the temperature of the second calcination may be adjusted according to the difference of the coating materials, for example, may be 230 to 780 ℃, and further may be 250 to 500 ℃;
preferably, the second calcination is for a period of 4 to 10 hours.
The invention also provides application of the composite nickel-rich positive electrode active material, which is used as a positive electrode active material for preparing a lithium ion battery. It is used as a positive electrode active material for preparing a positive electrode of a lithium ion battery in a preferred application.
In the invention, the composite nickel-rich positive electrode active material can be manufactured into lithium ion batteries and components thereof based on the existing means. For example, the composite nickel-rich positive electrode active material, the binder and the conductive agent are pulped by a solvent, then coated on a current collector, and dried and solidified to obtain the positive electrode. In addition, the positive electrode, the diaphragm and the negative electrode can be stacked and assembled to form a battery core, the battery core is arranged in a battery shell, and electrolyte is injected to form the lithium ion battery.
The invention also provides a positive electrode material containing the composite nickel-rich positive electrode active material.
The positive electrode material further comprises components which can be added by a person skilled in the lithium battery field, such as at least one of a conductive agent and a binder.
The invention also provides a positive electrode containing the composite nickel-rich positive electrode active material, which comprises a current collector and a positive electrode material containing the composite nickel-rich positive electrode active material, wherein the positive electrode material is compounded on the surface of the current collector.
The invention also provides a lithium ion battery, which comprises a positive electrode containing the composite nickel-rich positive electrode active material.
Advantageous effects
1. The invention provides a composite nickel-rich positive electrode active material containing the additive, which can effectively relieve the problem of lattice cracks easily occurring in the nickel-rich material, and is beneficial to improving the electrochemical performance of the nickel-rich material, in particular to improving the electrochemical performance of the nickel-rich material under high current.
2. The invention adopts BiNiO 3 and PbNiO 3 of the combination as the additive, which is helpful for synergy and further improves the crack problem of the nickel-rich material. In addition, the auxiliary additive and/or the cladding structure are/is matched, so that the problem of cracking of the nickel-rich material is further improved.
3. The method has simple process, and the prepared material has excellent electrochemical performance, is suitable for large-scale application and is easy to popularize.
Drawings
FIG. 1 is a graph showing the specific capacity of the positive electrode material prepared in example 1
FIG. 2 is an SEM image of the positive electrode material prepared in example 1;
FIG. 3 is a comparison of XRD patterns before and after 50 cycles of the positive electrode material prepared in example 1
FIG. 4 is a slice diagram of the positive electrode material prepared in example 1 before circulation;
FIG. 5 is a slice view of the positive electrode material prepared in example 1 after 50 cycles;
Detailed Description
Example 1
Step 1: weighing ternary precursor Ni 0.83 Co0.05Mn0.12(OH)2 and battery grade lithium hydroxide monohydrate according to a molar ratio of Li to Me (Me is the total molar quantity of Ni, co and Mn) of 1.05, putting the ternary precursor Ni 0.83 Co0.05Mn0.12(OH)2 and the battery grade lithium hydroxide into a high-speed mixer, taking a first additive (1000 ppmBiNiO 3、1000ppmPbNiO3) accounting for 0.2% of the mass fraction of the ternary precursor, adding 2000ppmZrO (auxiliary additive) into the high-speed mixer, mixing at a high speed for 20min, putting the uniformly mixed primary mixture into an atmosphere furnace, heating to 750 ℃ from room temperature under the oxygen concentration of more than or equal to 90%, preserving heat for 15h, naturally cooling, crushing and sieving to obtain primary crushed materials, wherein the average particle size D50 of the primary crushed materials is 10.80 mu m, and the free lithium content is less than or equal to 2800ppm.
Step 2: taking the primary crushed material as a matrix, washing with water (solid-to-liquid ratio is 1:1, washing time is 30 min), drying (moisture content is less than or equal to 0.1 wt), coating (HBO 3) with 2000ppm (0.2%), mixing at high speed for 20min by a high-speed mixer, then carrying out secondary calcination in air atmosphere, heating to 250 ℃, preserving heat for 8h, naturally cooling, and then carrying out crushing, sieving and demagnetizing to obtain the high-nickel NCM lithium ion battery anode material LiNi 0.83 Co0.05Mn0.12 O2 product, wherein the average particle size D50 is 10.60um, and the free lithium content is less than or equal to 1500ppm.
The obtained product is subjected to battery assembly and buckling test, and the specific method comprises the following steps: weighing the prepared anode material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 90:5:5, adding NMP (N-methylpyrrolidone), mixing at high speed for 15min by a deaeration machine to prepare slurry, uniformly coating the slurry on an aluminum foil, and preparing a pole piece by using a scraper with the scale of 100 mu m; and then the pole piece is put into a vacuum drying oven at 80 ℃ for baking, and the anode piece with the diameter of 14mm is cut into the anode piece through tabletting and punching after the drying. According to the negative electrode shell and the lithium sheet, 3 drops of DEC/EC (volume ratio is 1:1) electrolyte are dripped into a needle cylinder, a celgard2500 diaphragm is dripped into the needle cylinder, 3 drops of DEC/EC (volume ratio is 1:1) electrolyte are dripped into the needle cylinder, and the positive electrode sheet and the positive electrode shell are assembled in the glove box filled with argon in sequence. And (3) carrying out cycle performance test on the assembled button cell under the charging system of 3.0-4.3V and 0.5C/1C. The test results are shown in figure 1.
The product of example 1, under conditions of 3.0-4.3v,0.1c, first discharge capacity: 212mAh/g;3.0-4.3V of the total voltage,
The capacity retention rate at room temperature for 50 weeks under the condition of 0.5C/1C is as follows: 99.8%. The cycle retention at high temperature (45 ℃) for 50 weeks was 98.9%. At high magnification, the cycle retention rate after 1C,2C,4C,8C charge and discharge is 90%.
Example 2
The difference compared to example 1 is only that the first additive contains BiNiO 3 alone, and the amount of the first additive added is the same as example 1 (i.e., biNiO 3 is 2000 ppm). The battery and electrochemical performance measurements were performed as in example 1, with the following results:
The capacity retention rate at room temperature for 50 weeks under the condition of 0.5C/1C is as follows: 98.8%. The cycle retention at high temperature (45 ℃) for 50 weeks was 97.3%. At high magnification, the cycle retention rate after 1C,2C,4C and 8C charge and discharge is 86%.
Example 3
The difference compared with example 1 is only that the first additive contains PbNiO 3 alone, and the addition amount of the first additive is the same as example 1 (PbNiO 3 is 2000 ppm). The battery and electrochemical performance measurements were performed as in example 1, with the following results:
the capacity retention rate at room temperature for 50 weeks under the condition of 0.5C/1C is as follows: 98.5%. The cycle retention at high temperature (45 ℃) for 50 weeks was 97.1%. At high magnification, the cycle retention rate after charging and discharging of 1C,2C,4C and 8C is 85.4%.
Example 4
The only difference compared to example 1 is that no auxiliary additives are added, and other processes and parameters are the same as in example 1.
The capacity retention rate at room temperature for 50 weeks under the condition of 0.5C/1C is as follows: 98.1% and a cycle retention of 96.5% at high temperature (45 ℃) for 50 weeks. At high magnification, the cycle retention rate after charging and discharging of 1C,2C,4C and 8C is 85.2%.
Example 5
The difference compared to example 1 is only that the first additive was added at a level of 0.5% (BiNiO 3 to 2500ppm, pbNiO 3 to 2500 ppm). Other operations and parameters were the same as in example 1.
Electrochemical measurements were carried out according to the procedure of example 1, and the capacity retention rate at room temperature for 50 weeks was: 99.1% and a cycle retention of 97.5% at high temperature (45 ℃) for 50 weeks. At high magnification, the cycle retention rate after charging and discharging of 1C,2C,4C and 8C is 87.2%.
Example 6
The difference compared to example 1 is only that the first additive was added in an amount of 0.1% (BiNiO 3 was 500ppm, pbNiO 3 was 500 ppm). Other operations and parameters were the same as in example 1.
Electrochemical measurements were carried out according to the procedure of example 1, and the capacity retention rate at room temperature for 50 weeks was: 98.2% and a cycle retention of 97.1% at high temperature (45 ℃) for 50 weeks. At high magnification, the cycle retention rate after charging and discharging of 1C,2C,4C and 8C is 86.4%.
Example 7
The only difference compared to example 1 is that the precursor type, in particular Ni 0.9 Co0.05Mn0.05(OH)2, is shifted. The preparation and electrochemical determination were carried out according to the procedure of example 1, with the following results: the capacity retention rate at room temperature for 50 weeks is: 99.6%. The cycle retention at high temperature (45 ℃) for 50 weeks was 98.3%. At high magnification, the cycle retention rate after 1C,2C,4C,8C charge and discharge is 89%.
Example 8
The only difference from example 1 is that the coating mode of step 2 is changed, and the difference step 2 is: the dry coating is directly carried out without washing. Other operations and parameters are the same as in the embodiments.
The preparation and electrochemical determination were carried out according to the procedure of example 1, with the following results: the capacity retention rate at room temperature for 50 weeks is: 98.6%. The cycle retention at high temperature (45 ℃) for 50 weeks was 97.2%. At high magnification, the cycle retention rate after charging and discharging of 1C,2C,4C and 8C is 87.1%.
Comparative example 1:
The only difference compared to example 1 is that no first additive is added.
The preparation and electrochemical determination were carried out according to the procedure of example 1, with the following results: the capacity retention rate at room temperature for 50 weeks is: 90.6%. The cycle retention at high temperature (45 ℃) for 50 weeks was 91.2%. At high magnification, the cycle retention rate after charging and discharging of 1C,2C,4C and 8C is 75.1%.
Comparative example 2:
The difference compared with example 1 is only that SrO is used instead of the first additive and the amount added is the same as the first additive.
The preparation and electrochemical determination were carried out according to the procedure of example 1, with the following results: the capacity retention rate at room temperature for 50 weeks is: 92.6%. The cycle retention at high temperature (45 ℃) for 50 weeks was 93.4%. At high magnification, the cycle retention rate after charging and discharging of 1C,2C,4C and 8C is 80.3 percent.
Claims (24)
1. The composite nickel-rich positive electrode active material is characterized by comprising a nickel-rich active material and an additive;
The additive is at least one of BiNiO 3、PbNiO3;
The method comprises the steps of mixing a nickel-rich precursor, a lithium source and an additive, and calcining to obtain the nickel-rich precursor; the temperature of the calcination process is 700-900 ℃.
2. The composite nickel-rich positive electrode active material according to claim 1, wherein the nickel-rich active material is Li wNi1-x-y CoxMnyO2, w is more than or equal to 0.98 and less than or equal to 1.15,0 and x is more than or equal to 0.20, y is more than or equal to 0 and less than or equal to 0.20, and 1-x-y is more than or equal to 0.8.
3. The composite nickel-rich positive electrode active material according to claim 1, wherein the nickel-rich active material is at least one of NCM83, NCM88, NCM92, NCA88, NCA 92.
4. The composite nickel-rich positive electrode active material of claim 1, wherein said additives are BiNiO 3 and PbNiO 3.
5. The composite nickel-rich positive electrode active material according to claim 4, wherein the weight ratio of BiNiO 3 to PbNiO 3 in the additive is 1-5:1.
6. The composite nickel-rich positive electrode active material according to any one of claims 1 to 5, further comprising an auxiliary additive, wherein the auxiliary additive is at least one of zirconia, tungsten oxide, strontium oxide, and alumina.
7. The composite nickel-rich positive electrode active material according to claim 6, wherein the additive is added in an amount of 0.05 to 1wt% relative to the nickel-rich active material; wherein the addition amount of the auxiliary additive is less than or equal to 0.5wt%.
8. The composite nickel-rich positive electrode active material according to claim 7, wherein the additive is added in an amount of 0.3-0.8 wt% relative to the nickel-rich active material; wherein the addition amount of the auxiliary additive is 0.1-0.3 wt%.
9. The composite nickel-rich positive electrode active material according to claim 1, wherein the composite nickel-rich positive electrode active material is a material having a coating structure, further comprising a coating material, and wherein the coating material coats the nickel-rich active material and the additive.
10. The composite nickel-rich positive electrode active material according to claim 9, wherein the coating material is an oxide of at least one element of Co, al, W, ce, nb, B, ti, mg, zr.
11. A method for preparing the composite nickel-rich positive electrode active material according to any one of claims 1 to 10, which is characterized in that the nickel-rich precursor, a lithium source and an additive are mixed and then calcined;
the temperature of the calcination process is 700-900 ℃.
12. The method for preparing a composite nickel-rich positive electrode active material according to claim 11, wherein the calcination time is 7 to 20 hours.
13. The method for preparing the composite nickel-rich positive electrode active material according to any one of claims 9 to 10, which is characterized in that the preparation process of the composite nickel-rich positive electrode active material with the coating structure is as follows: the calcined product obtained by the preparation method of claim 11 or 12, and then the calcined product is immersed in the coating precursor material solution, and then subjected to solid-liquid separation and second calcination treatment, thereby obtaining the composite nickel-rich positive electrode active material with a coating structure.
14. The method for preparing a composite nickel-rich positive electrode active material according to claim 13, wherein the second calcination temperature is 230-780 ℃.
15. The method for preparing a composite nickel-rich positive electrode active material according to claim 13, wherein the second calcination time is 4-10 hours.
16. The use of the composite nickel-rich positive electrode active material according to any one of claims 1 to 10 or the composite nickel-rich positive electrode active material prepared by the preparation method according to any one of claims 11 to 15 as a positive electrode active material for preparing a lithium ion battery.
17. Use according to claim 16 as positive electrode active material for the preparation of a positive electrode for a lithium ion battery.
18. A lithium ion battery positive electrode material, characterized by comprising the composite nickel-rich positive electrode active material according to any one of claims 1 to 10 or the composite nickel-rich positive electrode active material prepared by the preparation method according to any one of claims 11 to 15.
19. The positive electrode material for a lithium ion battery according to claim 18, further comprising a conductive agent and a binder.
20. The positive electrode material of lithium ion battery according to claim 19, wherein the contents of the conductive agent and the binder are 5-15 wt% respectively.
21. A positive electrode for a lithium ion battery, comprising the positive electrode material according to any one of claims 18 to 20.
22. A lithium ion battery comprising the composite nickel-rich positive electrode active material according to any one of claims 1 to 10 or the composite nickel-rich positive electrode active material produced by the production method according to any one of claims 11 to 15.
23. The lithium-ion battery of claim 22, comprising the positive electrode material of any one of claims 18-20.
24. The lithium-ion battery of claim 23, comprising the positive electrode of claim 21.
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| JP2011138787A (en) * | 2011-02-25 | 2011-07-14 | Nec Corp | Positive electrode active material for secondary battery |
| CN103606671A (en) * | 2013-12-09 | 2014-02-26 | 湖南杉杉新材料有限公司 | Positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery and preparation method thereof |
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| KR102341409B1 (en) * | 2016-08-26 | 2021-12-20 | 삼성에스디아이 주식회사 | Composite positive electrode active material for lithium ion battery, preparing method thereof, and lithium ion battery including positive electrode comprising the same |
| CN106784798B (en) * | 2017-02-15 | 2020-01-14 | 中国科学院过程工程研究所 | Positive electrode active material, preparation method thereof, high-performance positive electrode slurry containing positive electrode active material and all-solid-state lithium ion battery |
| CN109599545A (en) * | 2018-12-04 | 2019-04-09 | 中国科学院青海盐湖研究所 | A kind of tertiary cathode material and preparation method thereof, lithium ion battery |
| US11581519B2 (en) * | 2019-04-10 | 2023-02-14 | Sk On Co., Ltd. | Post-treatment method of lithium secondary battery |
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| CN103606671A (en) * | 2013-12-09 | 2014-02-26 | 湖南杉杉新材料有限公司 | Positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery and preparation method thereof |
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