CN114843488A - Positive electrode active material, electrochemical device, and electronic device - Google Patents
Positive electrode active material, electrochemical device, and electronic device Download PDFInfo
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- CN114843488A CN114843488A CN202210674341.1A CN202210674341A CN114843488A CN 114843488 A CN114843488 A CN 114843488A CN 202210674341 A CN202210674341 A CN 202210674341A CN 114843488 A CN114843488 A CN 114843488A
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- 239000002245 particle Substances 0.000 claims abstract description 59
- 238000009826 distribution Methods 0.000 claims abstract description 26
- 239000011247 coating layer Substances 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 11
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 9
- 229920000515 polycarbonate Polymers 0.000 claims description 9
- 239000004417 polycarbonate Substances 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
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- 239000002033 PVDF binder Substances 0.000 claims description 5
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- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 87
- 239000011248 coating agent Substances 0.000 abstract description 23
- 238000000576 coating method Methods 0.000 abstract description 23
- 238000005245 sintering Methods 0.000 description 34
- 238000012360 testing method Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 15
- 239000010941 cobalt Substances 0.000 description 13
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- 238000000034 method Methods 0.000 description 13
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- 239000000047 product Substances 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000011164 primary particle Substances 0.000 description 7
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000006182 cathode active material Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
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- 239000006256 anode slurry Substances 0.000 description 2
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
- H01M4/483—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
- H01M4/525—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)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a positive active material, an electrochemical device and an electronic device, wherein the positive active material comprises a positive active material inner core and a coating layer coated on the surface of the positive active material inner core, the positive active material inner core comprises doped ions, and the coating layer comprises amorphous oxide; the particle size distribution D of the positive electrode active material n 10、D v 50、D v 90 and D FW Satisfies the following conditions: d n 10>1.2μm，3μm<D v 50<5μm，2μm<D FW <4μm，1.5<(D v 90‑D n 10)/D FW <2.5. The invention adopts specific elements and components for doping and coating, optimizes the grain diameter of the material,the capacity, rate capability, cycle performance and low-temperature performance of the prepared electrochemical device are further improved.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a positive electrode active material, an electrochemical device and electronic equipment.
Background
The ternary layered material is a lithium ion battery anode active material with wide application, has higher theoretical specific capacity and reaction platform voltage, and also has excellent reaction kinetics performance. The widely applied ternary layered material generally contains higher cobalt content, and cobalt ore is increasingly short of supply and demand as a rare mineral resource, so that the problem of limited cobalt ore resource can be solved by reducing the cobalt content in the ternary layered material, and the production cost of the battery is reduced.
The low-cobalt ternary material is a main scheme for reducing the cost of the lithium ion battery at present, but the reduction of the cobalt element can cause the problems of reduced compaction density, reduced capacity, deteriorated low-temperature performance, increased high-temperature cycle resistance and the like; in addition, the low-cobalt ternary material can generate more serious Li during sintering preparation + /Ni 2+ And mixed drainage is adopted, the initial capacity exertion of the material is reduced, the phase change of the bulk phase and the surface of the material is further serious in the circulation process, a rock salt phase is formed, and the circulation performance of the low-cobalt material is greatly deteriorated. Therefore, the performance of the battery is ensured while the production cost is reduced, and the method is a great problem in the development process of the ternary layered material.
Disclosure of Invention
In view of the disadvantages of the prior art, an object of the present invention is to provide a positive electrode active material, an electrochemical device, and an electronic apparatus. According to the invention, specific elements and components are doped and coated, and the particle size and the crystal structure of the material are regulated and controlled, so that the particle size of the material is optimized, the micro powder content and the large particle number of the material are reduced, the rate capability and the storage performance of the material are improved, and the capacity, the cycle performance and the low-temperature performance of the prepared electrochemical device are further improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a positive electrode active material, including a positive electrode active material core and a coating layer coated on a surface of the positive electrode active material core, wherein the positive electrode active material core includes dopant ions therein, and the coating layer includes an amorphous oxide;
the particle size distribution D of the positive electrode active material n 10、D v 50、D v 90 and D FW Satisfies the following conditions: d n 10>1.2μm，3μm<D v 50<5μm，2μm<D fw <4μm，1.5<(D v 90-D n 10)/D FW <2.5。
Particle size distribution D of positive electrode active material in the invention n 10>1.2 μm, for example, 1.21 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2.0 μm, 2.2 μm, 2.4 μm, 2.6 μm, etc., 3 μm<D v 50<5 μm, for example, 3.1 μm, 3.2 μm, 3.4 μm, 3.6 μm, 3.8 μm, 4 μm, 4.2 μm, 4.4 μm, 4.6 μm, 4.8 μm, 4.9 μm, or the like, 2 μm<D fw <4 μm, for example, 2.1 μm, 2.2 μm, 2.4 μm, 2.6 μm, 2.8 μm, 3 μm, 3.2 μm, 3.4 μm, 3.6 μm, 3.8 μm, or 3.9 μm, 1.5. mu.m<(D v 90-D n 10)/D FW <2.5, for example, 1.51, 1.6, 1.8, 2, 2.2, 2.4, 2.49, etc.
The prepared positive active material comprises a positive active material inner core containing doped ions and an amorphous oxide coating layer, and the particle size and distribution of the material are regulated and controlled through the synergistic effect of the doped ions and the coating components, so that the structure of the material is optimized, the micro powder and agglomeration of the material are reduced, and the capacity performance, rate performance and cycle performance of the material can be improved; meanwhile, the coating layer contains amorphous oxide, and an amorphous coating substance is selected, so that the coating layer with a good coating state can be formed at a lower temperature, the capacity is improved, the interface resistance of the material is improved, the polarization is reduced, and the low-temperature performance of the material is improved. The positive active material has the advantages of uniform particle distribution, low micro powder content, reduced agglomeration, small number of large particles, and good low-temperature performance, capacity performance, rate performance and cycle performance.
In the present invention, the particle size distribution D of the first sintered product is n 10、D v 50、D v 90 and D FW Are all as known in the art, wherein D n 10 represents a particle diameter corresponding to 10% of the number distribution of the material particles; d v 50, also known as the average or median particle diameter, represents the particle diameter corresponding to 50% of the volume distribution of the material particles; d v 90 represents the particle size corresponding to 90% of the volume distribution of the material particles; d FW Refers to the difference between two particle size values corresponding to half the maximum height of the particle size distribution curve of the material.
Preferably, theThe positive electrode active material core includes Li a Ni b Co c Mn 1-b-c-d M d O 2 Wherein 1. ltoreq. a.ltoreq.1.2, for example 1, 1.01, 1.02, 1.05, 1.08, 1.1, 1.15 or 1.2 etc., 0.5. ltoreq. b.ltoreq.0.6, for example 0.5, 0.52, 0.54, 0.56, 0.58 or 0.6 etc., 0.03. ltoreq. c.ltoreq.0.2, for example 0.03, 0.05, 0.1, 0.15 or 0.2 etc., M comprises Al.
The invention can stabilize the crystal structure, improve the cycle performance of the low-cobalt ternary material (i.e. the cobalt content is more than or equal to 0.03 and less than or equal to 0.2) and improve the comprehensive electrochemical performance of the material by doping the ion aluminum and regulating and controlling the particle size.
Preferably, the amorphous oxide comprises amorphous titanium oxide.
Preferably, the molar ratio of the positive electrode active material core to the coating layer is 1 (0.008 to 0.01), and may be, for example, 1:0.008, 1:0.0085, 1:0.009, 1:0.0095, or 1:0.01, or the like.
The invention adopts the coating layer with proper content, can further improve the capacity of the anode active material, improve the resistance of the interface and improve the low-temperature performance of the material.
As a preferable technical scheme of the cathode active material of the present invention, the preparation method of the cathode active material comprises the following steps:
(1) mixing the positive active material precursor, a lithium source and an M source to obtain a mixture, and performing first sintering on the mixture at 930-980 ℃ to obtain a first sintered product;
(2) crushing the first sintered product, wherein the particle size distribution D of the crushed first sintered product n 10、D v 50、D v 90 and D FW Satisfies the following conditions: d n 10>1.2μm，3μm<D v 50<5μm，2μm<D FW <4μm，1.5<(D v 90-D n 10)/D FW <2.5；
(3) And mixing the crushed first sintering product with an amorphous oxide, and performing second sintering to obtain the cathode active material.
In the present invention, a positive electrode active material precursor, a lithium source, and an M source are mixedSintering to realize doping of the positive active material, controlling the temperature of the first sintering within 930-980 ℃, optimizing the particle sizes of primary particles and secondary particles of the material, preventing the material from being difficult to crush or damaging the electrochemical performance of the crushed material, and crushing the material to D after sintering at the temperature n 10>1.2μm、3μm<D v 50<5μm、2μm<D FW <4μm，1.5<(D v 90-D n 10)/D FW <2.5, the particle size of the secondary particles of the material can be further optimized, the particle size distribution of the material is controlled, and the content of the micro particles in the positive active material is effectively reduced, so that the problem of gas generation deterioration in the circulation and storage processes of the material is solved, the positive active material has lower interface resistance, and agglomeration between the particles of the material is inhibited, so that the rate capability and the low-temperature power performance of the battery are improved. In addition, the surface of the crushed first sintering product is coated with the amorphous oxide, the amorphous oxide has stronger activity, a good coating effect can be realized at a low temperature, the appearance of the material is optimized, the size and the particle size of the material are further regulated and controlled, and the capacity, the cycle performance and the low-temperature performance of the material are jointly improved by matching the crushed first sintering product with good size and appearance.
According to the invention, specific elements and components are doped and coated, and a specific primary sintering temperature and a specific crushing process are matched, so that the particle sizes of primary particles and secondary particles of the material are optimized in a low-cost mode, the micro powder content and the number of large particles of the material are reduced, the obtained positive active material has uniform particle distribution and higher powder compaction density, and the positive pole piece has more uniform surface density and higher compaction density, so that the capacity performance and the energy density of an electrochemical device can be further improved.
In the present invention, the temperature of the first sintering is 930 ℃ to 980 ℃, and may be, for example, 930 ℃, 935 ℃, 940 ℃, 945 ℃, 950 ℃, 955 ℃, 960 ℃, 965 ℃, 970 ℃, 975 ℃, 980 ℃, or the like.
Particle size distribution D of the first sintered product n 10>1.2 μm, for example, 1.21 μm, 1.3 μm, 1.4 μm, 1.5 μmm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2.0 μm, 2.2 μm, 2.4 μm, 2.6 μm, etc., 3 μm<D v 50<5 μm, for example, may be 3.1 μm, 3.2 μm, 3.4 μm, 3.6 μm, 3.8 μm, 4 μm, 4.2 μm, 4.4 μm, 4.6 μm, 4.8 μm or 4.9 μm, etc., 2 μm<D FW <4 μm, for example, 2.1 μm, 2.2 μm, 2.4 μm, 2.6 μm, 2.8 μm, 3 μm, 3.2 μm, 3.4 μm, 3.6 μm, 3.8 μm, or 3.9 μm, 1.5. mu.m<(D v 90-D n 10)/D FW <2.5, for example, 1.51, 1.6, 1.8, 2, 2.2, 2.4, 2.49, etc.
Preferably, the amorphous oxide comprises amorphous titanium oxide, the amorphous titanium oxide has high activity, and the material formed by coating the surface of the material by combining the preparation method has good appearance, can also improve the storage performance of the material, and prevents the problem of gas generation deterioration of the material in the circulation and storage processes.
Preferably, the chemical formula of the positive electrode active material precursor is Ni x Co y Mn 1-x-y (OH) 2 Wherein 0.55 ≦ x ≦ 0.60, such as 0.55, 0.56, 0.57, 0.58, 0.59, or 0.6, etc., and 0.05 ≦ y ≦ 0.15, such as 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, or 0.15, etc., and mixing the low-cobalt ternary material Ni x Co y Mn 1-x-y (OH) 2 The lithium-ion secondary battery cathode active material is subjected to first sintering with a lithium source and an M source, and is subjected to second sintering with an amorphous oxide after being crushed, so that the low-cobalt ternary material is doped and coated, the low-capacity problem of the low-cobalt material can be improved, the production cost is reduced, the low-temperature performance cycle and the storage performance of the material are balanced, and the cathode active material with good electrochemical comprehensive performance is obtained.
Preferably, the lithium source comprises lithium hydroxide.
Preferably, the M source comprises an aluminum source, and the aluminum source doped in the material can stabilize the crystal structure and improve the material cycling performance.
Preferably, the aluminium source comprises alumina, which may be, for example, micron-sized alumina (particle size D50 of 0.2 to 0.8 μm).
The molar ratio of the lithium source to the ternary material precursor is (1 to 1.1):1, and may be, for example, 1:1, 1.02:1, 1.04:1, 1.06:1, 1.08:1, or 1.1:1, etc.
Preferably, the molar ratio of the positive electrode active material precursor to the M source is 1 (0.008 to 0.01), and may be, for example, 1:0.008, 1:0.0085, 1:0.009, 1:0.0095, or 1:0.01, or the like.
Preferably, the molar ratio of the first sintered product to the amorphous oxide is 1 (0.008 to 0.01), and may be, for example, 1:0.008, 1:0.0085, 1:0.009, 1:0.0095, or 1:0.01, or the like.
According to the invention, the M element with proper content is doped, the amorphous oxide with specific content is coated, the amorphous coating substance is selected, and the high activity of the amorphous substance is utilized to coat at a lower temperature, so that a coating layer with a better coating state can be formed, the capacity is improved, the interface resistance of the material is improved, the polarization is reduced, and the low-temperature performance of the material is improved.
Preferably, the mixing speed in step (1) is 750r/min to 850r/min, such as 750r/min, 780r/min, 800r/min, 820r/min or 850 r/min.
Preferably, before the first sintering in step (1), the mixture is pre-sintered at 400 to 500 ℃, for example, 400, 420, 440, 450, 460, 480 or 500 ℃, to better melt the lithium salt, thereby further improving the uniformity, capacity and cycle performance of the sintered product.
Preferably, the pre-sintering time is 2.5h to 3.5h, for example, 2.5h, 2.6h, 2.8h, 3h, 3.2h, 3.5h, etc.
Preferably, the temperature rise rate of the pre-sintering is 2.5 ℃/min to 3.5 ℃/min, and may be, for example, 2.5 ℃/min, 2.8 ℃/min, 3 ℃/min, 3.2 ℃/min, 3.5 ℃/min or the like.
Preferably, the time of the first sintering is 8h to 12h, for example, 8h, 9h, 10h, 11h, 12h, or the like.
Preferably, the temperature increase rate of the first sintering is 5 ℃/min to 7 ℃/min, and for example, it may be 5 ℃/min, 5.5 ℃/min, 6 ℃/min, 6.5 ℃/min, or 7 ℃/min. The purpose of controlling the migration and diffusion rate of the doping elements can be achieved by controlling the temperature rising rate of the pre-sintering and the first sintering.
In a preferred embodiment of the preparation method of the present invention, the temperature of the second sintering is 250 to 350 ℃, and may be, for example, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, or the like.
According to the invention, the material is sintered at a proper second sintering temperature, so that the amorphous oxide is coated on the surface of the material, a better coating effect can be realized at a low temperature of 250-350 ℃, the capacity of the material is improved, and the capacity performance of the material is influenced when the second sintering temperature is higher.
Preferably, the time of the second sintering is 4h to 6h, for example, 4h, 4.5h, 5h, 5.5h or 6h, etc.
Preferably, the mixing speed in step (3) is 450r/min to 550r/min, such as 450r/min, 480r/min, 500r/min, 520r/min, 540r/min or 550 r/min.
Preferably, the mixing time in step (3) is 15min to 25min, such as 15min, 16min, 18min, 20min, 22min, 24min or 25 min.
In a second aspect, the present invention provides an electrochemical device comprising the positive electrode active material according to the first aspect in a positive electrode thereof.
The positive active material has uniform particles, low micro powder content, proper granularity of primary particles and secondary particles and low number of large particles, and the electrochemical device prepared by the positive active material has high capacity, high coulombic efficiency, good cycle performance and good low-temperature performance.
In an alternative embodiment, the present invention provides a method for detecting whether a positive active material according to the present invention is contained in an electrochemical device, comprising:
splitting the sample of the electrochemical device to obtain a positive electrode, washing the positive electrode by using a solvent, drying, coating the surface of the positive electrode with a knife to obtain active substance powder, cutting the active substance powder into sections of particles by using CP, and scanning electronsObserving the morphology of the active substance powder with a microscope, performing line scanning or surface scanning with EDS, and determining the particle size distribution D of the material with a laser particle size analyzer n 10、D v 50、D v 90 and D FW Obtaining the distribution and structure of elements in the active substance powder and the particle size distribution of the material;
when the test result shows that the active material powder has the particles divided into the kernel and the coating, the kernel contains Ni, Co, Mn and Al, the coating contains Ti, the particles are uniformly distributed, and the particle size distribution of the particles meets D n 10>1.2μm，3μm<D v 50<5μm，2μm<D FW <4μm，1.5<(D v 90-D n 10)/D FW <2.5, it was confirmed that the positive electrode of the electrochemical device sample contained the positive electrode active material of the present invention.
Preferably, the positive electrode further comprises a conductive agent and a binder.
Preferably, the conductive agent includes conductive carbon black (SP) and/or Carbon Nanotubes (CNT).
Preferably, the binder comprises polyvinylidene fluoride (PVDF).
In an alternative embodiment, the present invention provides a method for preparing the positive electrode, including:
and mixing the positive active material, the conductive agent, the binder and the solvent to obtain positive slurry, coating the positive slurry on an aluminum foil, drying and rolling to obtain the positive electrode.
Preferably, the mass ratio of the positive electrode active material, the SP, the CNT and the PVDF is (96 to 98):1:1:1, and may be, for example, 96:1:1:1, 96.5:1:1:1, 97:1:1:1, 97.5:1:1:1 or 98:1:1:1, etc.
Preferably, the temperature of the drying is 50 ℃ to 70 ℃, for example, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, 62 ℃, 64 ℃, 68 ℃ or 70 ℃ and the like.
In an alternative embodiment, the electrochemical device is a lithium ion battery.
In an alternative embodiment, the negative electrode of the electrochemical device comprises graphite, SP, carboxymethyl cellulose (CMC) and styrene-butadiene rubber (SBR) in a mass ratio of (90 to 99):1:1.5:2, for example, 90:1:1.5:2, 92:1:1.5:2, 94:1:1.5:2, 96:1:1.5:2, 98:1:1.5:2 or 99:1:1.5:2, etc.
Preferably, the electrochemical device further includes an electrolyte and a separator.
Preferably, the electrolyte includes a lithium salt and a solvent.
Preferably, the lithium salt includes LiPF 6 。
Preferably, the lithium salt is contained in an amount of 4 wt% to 24 wt%, for example, 4 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, or 24 wt%, etc., based on 100 wt% of the mass of the electrolyte.
Preferably, the solvent comprises any one of or a combination of at least two of Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC) and Polycarbonate (PC), and may be, for example, a combination of EC and EMC, a combination of DMC and PC, a combination of EC, EMC and DMC, or a combination of EC, EMC, DMC and PC, or the like.
Preferably, the mass ratio of EC, EMC, DMC and PC in the solvent is (2 to 4): (3 to 5): (2 to 4): (0 to 1), the selection range (2 to 4) of EC may be, for example, 2, 2.5, 3, 3.5, or 4, etc., the selection range (3 to 5) of EMC may be, for example, 3, 3.5, 4, 4.5, or 5, etc., the selection range (2 to 4) of DMC may be, for example, 2, 2.5, 3, 3.5, or 4, etc., the selection range (0 to 1) of PC may be, for example, 0, 0.1, 0.2, 0.3, 0.5, 0.7, or 1, etc., and when PC is 0, it means that PC is not contained in the solvent.
Preferably, the separator is a PE-based film.
Preferably, the thickness of the separator is 8 μm to 12 μm, and may be, for example, 8 μm, 8.5 μm, 9 μm, 9.5 μm, 10 μm, 10.5 μm, 11 μm, 11.5 μm, 12 μm, or the like.
In the present invention, a method of assembling an electrochemical device using the cathode, the anode and the separator is the prior art, and those skilled in the art can assemble the electrochemical device by referring to the method disclosed in the prior art. Taking a lithium ion battery as an example, a positive electrode, a diaphragm and a negative electrode are sequentially wound or stacked to form a battery core, the battery core is placed in a battery case, electrolyte is injected, formation and packaging are performed, and the electrochemical device is obtained.
In a third aspect, the present invention provides an electronic device comprising an electrochemical device according to the second aspect.
The electronic device according to the present invention may be, for example, a mobile computer, a portable phone, a memory card, a liquid crystal television, an automobile, a motorcycle, a motor, a timepiece, a camera, or the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) the prepared positive active material comprises a positive active material inner core containing doped ions and an amorphous oxide coating layer, and the particle size and distribution of the material are regulated and controlled through the synergistic effect of the doped ions and the coating components, so that the structure of the material is optimized, the micro powder and agglomeration of the material are reduced, and the capacity performance, rate performance and cycle performance of the material can be improved; meanwhile, the coating containing amorphous oxide is matched, so that the coating temperature is reduced, the coating effect is optimized, the capacity is improved, the interface resistance of the material is improved, the polarization is reduced, and the low-temperature performance of the material is improved.
(2) The invention optimizes the specific primary sintering temperature and crushing process, optimizes the particle size of the primary particles and the secondary particles of the material, controls the particle size distribution of the material, reduces the content of micro powder and the number of large particles of the material, obtains the anode active material with uniform particle distribution, improves the problem of gas generation deterioration in the circulation and storage processes of the material, reduces the interface resistance, and reduces the agglomeration among the particles of the material, thereby improving the rate capability, the capacity, the cycle performance and the low-temperature performance of the battery.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The present embodiment provides a positive electrode active material including a positive electrode active material core Li 1.06 Ni 0.55 Co 0.12 Mn 0.322 Al 0.008 O 2 And a coating layer coated on the surface of the core of the positive electrode active material, the coating layer being amorphous titanium oxide, and a cathode active material comprising the sameThe particle size distribution of the positive electrode active material is D n 10 is 1.4 μm, D v 90 is 6.3 μm, D v 50 is 3.6 μm, D FW Was 2.1.
The embodiment also provides a preparation method of the positive electrode active material, which comprises the following steps:
(1) respectively weighing LiOH and a precursor Ni of the positive active material according to the molar ratio of 1.06:1 0.55 Co 0.1 Mn 0.35 (OH) 2 Placing in a high-speed mixer for standby, and then mixing according to micron-grade alumina and Ni 0.55 Co 0.1 Mn 0.35 (OH) 2 Weighing micron-sized alumina in a molar ratio of 0.01:1, placing the micron-sized alumina in a high-speed mixer, stirring at a rotating speed of 800r/min until no white point exists in the high-speed mixer, and obtaining a mixture;
(2) loading the mixture into a sagger, controlling the heating rate, firstly heating to 450 ℃ at 3 ℃/min, pre-sintering for 3h, then heating to 950 ℃ at 6 ℃/min, and carrying out first sintering for 10h in the air to obtain a first sintering product Li 1.06 Ni 0.55 Co 0.12 Mn 0.322 Al 0.008 O 2 ；
(3) Mixing Li 1.06 Ni 0.55 Co 0.12 Mn 0.322 Al 0.008 O 2 (ii) a Crushing to obtain granules D n 10 is 1.4 μm, D v 90 is 6.3 μm, D v 50 is 3.6 μm, D FW Is 2.1;
(4) crushing Li 1.06 Ni 0.55 Co 0.12 Mn 0.322 Al 0.008 O 2 And nano-scale amorphous titanium oxide (the grain diameter D50 is 0.6um, recorded as c-TiO NSs) is placed in a high-speed mixer according to the molar ratio of 1:0.01 and is uniformly mixed, the rotating speed is 500r/min during mixing, the mixing time is 20min, then the mixed materials are placed in a sagger and sintered for 5h in air at 300 ℃, and the anode active material is obtained.
Assembling of lithium ion battery
(1) Preparation of the positive electrode: the positive electrode active materials prepared in the examples and comparative examples of the present invention, SP, CNT, and PVDF were mixed with N-methylpyrrolidone (NMP) in a mass ratio of 97:1:1:1Stirring at high speed to obtain anode slurry, coating the anode slurry on aluminum foil, placing in a vacuum oven, and drying at 60 deg.C for 12 hr to obtain the final product with surface density of 18g/cm 2 The dried positive electrode is rolled, and the compaction density is 3.4g/cm 3 ；
(2) Preparation of a negative electrode: mixing graphite, SP, CMC and SBR according to a mass ratio of 95.5:1:1.5:2 to prepare slurry, coating the slurry on a copper foil, and rolling to obtain a negative electrode;
(3) preparing a lithium ion battery: 1M LiPF using the above positive and negative electrodes 6 The electrochemical device is assembled by using an electrolyte, wherein solvents in the electrolyte are Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) electrolyte in a mass ratio of 1:1:1, and a PE base film.
Second, performance test
(1) Particle size distribution test of the positive electrode active material: 0.5g of positive active material is taken by a Mickel S3500 instrument, external ultrasonic treatment is carried out, and a mixed solution of a dropper west region and deionized water is used for dissolving. The test cycle was repeated 3 times, the mean value was selected as the particle size data and D was recorded n 10，D v 50，D v 90。
(2) Testing of the lithium ion battery:
and (3) carrying out electrochemical performance test on the lithium ion battery by adopting a battery performance test system (equipment model: BTS05/10C8D-HP) of the Shenghong Electrical appliance component electric company Limited.
And testing the initial discharge specific capacity, the initial coulombic efficiency and the 800-circle capacity retention rate: and (3) placing the electrochemical device in a test cabinet for testing, testing the discharge capacity of the battery at 0.33 ℃ at 25 ℃, wherein the voltage window is 2.8V-4.4V, the obtained discharge specific capacity is the first discharge specific capacity, the charge specific capacity is divided by the discharge specific capacity to obtain the first coulombic efficiency, and after 800 cycles, the 800 th cycle discharge capacity is divided by the first cycle discharge capacity to obtain the 800 th cycle capacity retention rate.
Direct current internal resistance test (DCR): the electrochemical devices were placed in a test cabinet for testing at 25 ℃ for 30 seconds of DCR discharge at 50% SOC at 4C.
Low temperature capacity retention test: and (3) placing the electrochemical device in a test cabinet for testing, testing the discharge capacity of the battery at low temperature (-20 ℃) at 0.33C/0.33C circulation, stopping circulation after the capacity of the battery is attenuated to 80% of the initial capacity (80% SOH), and dividing the discharge capacity of 80% SOH by the discharge capacity of the 3 rd circle to obtain the capacity retention rate at-20 ℃.
Examples 2 to 9 and comparative examples 1 to 3 were carried out by changing parameters based on the procedure of example 1, and the specific changed parameters and test results are shown in tables 1 to 8 in which the particle size distribution is that of the positive electrode active material.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
As can be seen from comparison of example 1 with examples 4 to 7 in tables 3 to 4, sintering with appropriate contents of the positive electrode active material precursor, the M source, and the amorphous oxide in the present invention can further improve the capacity, coulombic efficiency, rate capability, and cycle performance of the material. In examples 4 and 5, the content of the M source is more or less, so that the capacity and the low-temperature performance are obviously reduced; example 6 too high coating amorphous state causes particle adhesion and poor flowability, thus affecting capacity and low temperature performance; example 7 the content of the coated amorphous titanium oxide is low, the capacity and DCR of the material are both low, and the cycle performance is also biased; thus, the capacity, coulombic efficiency, rate capability and cycle of example 1 were all optimized.
TABLE 5
TABLE 6
As can be seen from the comparison of example 1 with examples 8 to 9 and comparative examples 1 to 2 in tables 5 and 6, the temperature of the first sintering and the temperature of the second sintering in the present invention affect the particle size distribution of the material and further affect the electrochemical properties of the material. When the temperature of the first sintering is higher, the growth of primary particles of the material is larger, the primary particles are agglomerated to generate secondary particles, the secondary particles are difficult to crush during crushing, the content of micro powder after crushing is higher, and the electrochemical performance of the material is also influenced, and when the temperature of the first sintering is lower, the primary particles of the material are smaller, and the smaller particles are difficult to crush, so that the first discharge specific capacity, the first coulombic efficiency, the 800-cycle capacity retention ratio, the DCR and the low-temperature capacity retention ratio of the comparative examples 1 to 2 are all inferior to those of the example 1; when the second sintering temperature is lower, the coating effect of the amorphous titanium oxide is deviated, which affects the morphology of the material, and when the second sintering temperature is higher, the capacity of the material is affected, so that the comprehensive electrochemical performance of examples 8 to 9 is slightly worse than that of example 1.
TABLE 7
TABLE 8
As can be seen from comparison between the example 1 and the comparative example 3 in tables 7 to 8, the amorphous oxide used in the example 1 of the present invention has higher activity, and can achieve a good coating effect at a low temperature, optimize the morphology of the material, further achieve control of the size and the particle size of the material, and cooperate with the first crushed sintered product having good size and morphology to improve the capacity, the cycle performance, and the low-temperature performance of the material, while the conventional titanium oxide used in the comparative example 3 is sintered, and the capacity and the cycle stability of the prepared positive active material are poorer.
In summary, in embodiments 1 to 9, it can be seen that, by doping and coating specific elements and components, and adjusting and controlling the particle size and crystal structure of the material, the particle size of the material is optimized, the content of the fine powder and the number of large particles of the material are reduced, the rate capability and storage performance of the material are improved, and the capacity, cycle performance and low-temperature performance of the prepared electrochemical device are further improved.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The positive active material is characterized by comprising a positive active material inner core and a coating layer coated on the surface of the positive active material inner core, wherein the positive active material inner core comprises doped ions, and the coating layer comprises an amorphous oxide;
the particle size distribution D of the positive electrode active material n 10、D v 50、D v 90 and D FW Satisfies the following conditions: d n 10>1.2μm，3μm<D v 50<5μm，2μm<D FW <4μm，1.5<(D v 90-D n 10)/D FW <2.5。
2. The positive electrode active material according to claim 1, wherein the positive electrode active material core comprises Li a Ni b Co c Mn 1-b-c-d M d O 2 Wherein a is more than or equal to 1 and less than or equal to 1.2, b is more than or equal to 0.5 and less than or equal to 0.6, c is more than or equal to 0.03 and less than or equal to 0.2, d is more than or equal to 0.005 and less than or equal to 0.01, and M comprises Al.
3. The positive electrode active material according to claim 1, wherein the amorphous oxide comprises amorphous titanium oxide.
4. The positive electrode active material according to claim 1, wherein the molar ratio of the positive electrode active material core to the clad is 1 (0.008 to 0.01).
5. An electrochemical device, characterized in that a positive electrode of the electrochemical device comprises the positive electrode active material according to any one of claims 1 to 4.
6. The electrochemical device according to claim 5, further comprising a conductive agent and a binder in the positive electrode, the conductive agent and the binder satisfying any one of the following conditions (a) to (b):
(a) the conductive agent comprises conductive carbon black and/or carbon nanotubes;
(b) the binder includes polyvinylidene fluoride.
7. The electrochemical device of claim 5, further comprising an electrolyte and a separator.
8. The electrochemical device according to claim 7, wherein the electrolyte includes a lithium salt and a solvent, and the lithium salt and the solvent satisfy any one of the following conditions (c) to (e):
(c) the lithium salt comprises LiPF 6 ；
(d) The content of the lithium salt is 4-24 wt% based on 100 wt% of the electrolyte;
(e) the solvent comprises any one of ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate and polycarbonate or the combination of at least two of the ethylene carbonate, the ethyl methyl carbonate, the dimethyl carbonate and the polycarbonate.
9. The electrochemical device according to claim 7, wherein the separator satisfies any one of the following conditions (f) to (g):
(f) the diaphragm is a PE base film;
(g) the thickness of the separator is 8 to 12 μm.
10. An electronic device, characterized in that it comprises an electrochemical device according to any one of claims 5 to 9.
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