CN114843488B - 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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- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 239000006182 cathode active material Substances 0.000 claims abstract description 4
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 10
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- 230000000694 effects Effects 0.000 description 9
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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
- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a positive electrode active material, an electrochemical device and electronic equipment, wherein the positive electrode active material comprises a positive electrode active material inner core and a coating layer coated on the surface of the positive electrode active material inner core, the positive electrode active material inner core comprises doped ions, and the coating layer comprises amorphous oxide; particle size distribution D of the cathode active material n 10、D v 50、D v 90 and D FW The method meets the following conditions: d (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 to carry out doping cladding, optimizes the particle size of the material, and further improves the capacity, the multiplying power performance, the cycle performance and the low-temperature performance of the prepared electrochemical device.
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 has excellent reaction dynamics performance. The ternary layered material widely used at present generally contains higher cobalt content, and cobalt ore is increasingly supplied and supplied 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 meanwhile, 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 cobalt element can bring the problems of reduced compaction density, reduced capacity, deteriorated low-temperature performance, increased high-temperature circulating resistance and the like; in addition, the low-cobalt ternary material can generate more serious Li during sintering preparation + /Ni 2+ The mixing and discharging can reduce the initial capacity exertion of the material, the phase change of the bulk phase and the surface of the material can be further serious in the circulation process, and rock salt phase is formed, so that the circulation performance of the low-cobalt material is greatly deteriorated. Therefore, the production cost is reduced, the performance of the battery is ensured, and the ternary lamellar material is a great difficulty in the research and development process.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a positive electrode active material, an electrochemical device and an electronic device. According to the invention, specific elements and components are doped and coated, the particle size and crystal structure of the material are regulated and controlled, 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.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a positive electrode active material, where the positive electrode active material includes a positive electrode active material core and a coating layer coated on a surface of the positive electrode active material core, the positive electrode active material core includes doped ions, and the coating layer includes amorphous oxide;
particle size distribution D of the cathode active material n 10、D v 50、D v 90 and D FW The method meets the following conditions: d (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 the cathode active Material in the present invention n 10>1.2 μm may be, 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 or 2.6 μm, etc., 3 μm<D v 50<5 μm may be, 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 or 4.9 μm, etc., 2 μm<D fw <4 μm may be, 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, etc., 1.5<(D v 90-D n 10)/D FW <2.5 may be, for example, 1.51, 1.6, 1.8, 2, 2.2, 2.4, or 2.49, etc.
The positive electrode active material prepared by the method comprises a positive electrode active material 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, the multiplying power performance and the cycle performance of the material can be improved; meanwhile, the coating layer contains amorphous oxide, and amorphous coating substances are selected, so that the coating layer with a good coating state can be formed at a lower temperature, the capacity is increased, the interface resistance of the material is improved, the polarization is reduced, and the low-temperature performance of the material is improved. The positive electrode active material has the advantages of uniform particle distribution, low micro powder content, reduced agglomeration, less large particle number, and good low-temperature performance, capacity performance, rate performance and cycle performance.
The particle size distribution D of the first sintered product in the present invention n 10、D v 50、D v 90 and D FW Are all in the meaning known in the art, wherein D n 10 represents the particle size corresponding to 10% of the number distribution of the material particles; d (D) v 50, also known as the average particle size or median particle size, represents the particle size corresponding to 50% of the volume distribution of the material particles; d (D) v 90 represents the particle size corresponding to 90% of the volume distribution of the material particles; d (D) FW Refers to the difference between two corresponding particle size values at half the maximum height of the particle size distribution curve of the material.
Preferably, the positive electrode active material core includes Li a Ni b Co c Mn 1-b-c-d M d O 2 Where 1.ltoreq.a.ltoreq.1.2, may be, 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, may be, for example, 0.5, 0.52, 0.54, 0.56, 0.58, or 0.6, etc., 0.03.ltoreq.c.ltoreq.0.2, may be, for example, 0.03, 0.05, 0.1, 0.15, or 0.2, etc., M includes Al.
The invention can stabilize the crystal structure, improve the cycle performance of the low cobalt ternary material (namely, 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 through doping the ionic 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 1:0.008, 1:0.0085, 1:0.009, 1:0.0095, 1:0.01, or the like, for example.
The invention adopts the coating layer with proper content, can further improve the capacity of the positive electrode active material, improve the interface resistance and improve the low-temperature performance of the material.
As a preferable technical scheme of the positive electrode active material, the preparation method of the positive electrode active material comprises the following steps:
(1) Mixing a positive electrode 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 The method meets the following conditions: d (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 amorphous oxide, and performing second sintering to obtain the positive electrode active material.
In the invention, the precursor of the positive electrode active material, the lithium source and the M source are mixed and sintered to realize the doping of the positive electrode active material, at the moment, the temperature of the first sintering is controlled within the range of 930 ℃ to 980 ℃, the particle sizes of primary particles and secondary particles of the material can be optimized, the crushing difficulty of the material is prevented or the electrochemical performance of the crushed material is damaged, and the material is crushed 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 granularity of the secondary particles of the material can be further optimized, and the material is controlledThe particle size distribution effectively reduces the content of tiny particles in the positive electrode active material, thereby improving the problems of gas production deterioration in the material circulation and storage process, being beneficial to enabling the positive electrode active material to have lower interface resistance and inhibiting the agglomeration among the particles of the material, and further improving the rate performance and low-temperature power performance of the battery. In addition, the surface of the crushed first sintering product is coated with amorphous oxide, the amorphous oxide has stronger activity, good coating effect can be realized at low temperature, the morphology of the material is optimized, the regulation and control of the size and the particle size of the material are further realized, and the capacity, the circulation performance and the low-temperature performance of the material are jointly improved by matching with the crushed first sintering product with good size and morphology.
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 granularity of primary particles and secondary particles of the material is optimized in a low-cost manner, the content of micro powder and the number of large particles of the material are reduced, the obtained anode active material has uniform particle distribution and higher powder compaction density, and the anode plate has more uniform surface density and higher compaction density, so that the capacity performance and 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 930 ℃, 935 ℃, 940 ℃, 945, 950 ℃, 955 ℃, 960 ℃, 965 ℃, 970 ℃, 975 ℃, 980 ℃, or the like, for example.
Particle size distribution D of the first sintered product n 10>1.2 μm may be, 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 or 2.6 μm, etc., 3 μm<D v 50<5 μm may be, 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 or 4.9 μm, etc., 2 μm<D FW <4 μm may be, 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, etc., 1.5<(D v 90-D n 10)/D FW <2.5 may be, for example, 1.51, 1.6, 1.8, 2, 2.2, 2.4, or 2.49, etc.
Preferably, the amorphous oxide comprises amorphous titanium oxide, the amorphous titanium oxide has higher activity, and the material formed by coating the surface of the material has better morphology by combining the preparation method of the invention, and can also improve the storage performance of the material and prevent the problem of gas production deterioration of the material in the circulating and storage processes.
Preferably, the positive electrode active material precursor has a chemical formula of Ni x Co y Mn 1-x-y (OH) 2 Wherein 0.55.ltoreq.x.ltoreq.0.60, which may be, for example, 0.55, 0.56, 0.57, 0.58, 0.59 or 0.6 etc., 0.05.ltoreq.y.ltoreq.0.15, which may be, for example, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14 or 0.15 etc., the low cobalt ternary material Ni x Co y Mn 1-x-y (OH) 2 The preparation method comprises the steps of carrying out first sintering with a lithium source and an M source, crushing and carrying out second sintering with an amorphous oxide, so that doping and cladding of the low-cobalt ternary material are realized, 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 anode 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 doping the aluminum source in the material can stabilize the crystal structure and improve the cycle performance of the material.
Preferably, the aluminum source comprises aluminum oxide, which may be, for example, micron-sized aluminum oxide (particle size D50 of 0.2 μm to 0.8 μm).
The molar ratio of the lithium source to the ternary material precursor is (1 to 1.1): 1, which 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 and the M source is 1 (0.008 to 0.01), for example, 1:0.008, 1:0.0085, 1:0.009, 1:0.0095, or 1:0.01, etc.
Preferably, the molar ratio of the first sintered product to the amorphous oxide is 1 (0.008 to 0.01), for example, 1:0.008, 1:0.0085, 1:0.009, 1:0.0095, 1:0.01, or the like.
According to the invention, the amorphous coating material is selected, and the high activity of the amorphous material is utilized to coat the amorphous material at a lower temperature, so that a coating layer with a better coating state can be formed, the capacity is increased, the interface resistance of the material is improved, the polarization is reduced, and the low-temperature performance of the material is improved.
Preferably, the rotational speed of the mixing in step (1) is 750r/min to 850r/min, and may be, for example, 750r/min, 780r/min, 800r/min, 820r/min, 850r/min, or the like.
Preferably, before the first sintering in the step (1), the mixture is pre-sintered at 400 ℃ to 500 ℃, for example, 400 ℃, 420 ℃, 440 ℃, 450 ℃, 460 ℃, 480 ℃ or 500 ℃ and the like, so that lithium salt is better melted, and uniformity, capacity and cycle performance of the sintered product are further improved.
Preferably, the pre-sintering time is 2.5h to 3.5h, for example, 2.5h, 2.6h, 2.8h, 3h, 3.2h, or 3.5h, etc.
Preferably, the temperature rise rate of the pre-sintering is 2.5 ℃ to 3.5 ℃ per minute, for example, 2.5 ℃ per minute, 2.8 ℃ per minute, 3 ℃ per minute, 3.2 ℃ per minute, 3.5 ℃ per minute, 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 rise rate of the first sintering is 5 ℃/min to 7 ℃/min, and may be, for example, 5 ℃/min, 5.5 ℃/min, 6 ℃/min, 6.5 ℃/min, 7 ℃/min, or the like. The purpose of controlling the migration and diffusion rate of the doping element can be achieved by controlling the temperature rising rates of the pre-sintering and the first sintering.
As a preferable mode of the production 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 ℃.
According to the invention, the proper second sintering temperature is adopted for sintering, so that amorphous oxide is coated on the surface of the material, a better coating effect can be realized at the low temperature of 250-350 ℃, the capacity of the material is improved, and the capacity performance of the material can be influenced when the second sintering temperature is higher.
Preferably, the second sintering time is 4h to 6h, for example, 4h, 4.5h, 5h, 5.5h, 6h, or the like.
Preferably, the rotational speed of the mixing in step (3) is 450r/min to 550r/min, for example, 450r/min, 480r/min, 500r/min, 520r/min, 540r/min, 550r/min, etc.
Preferably, the mixing time in the step (3) is 15 to 25min, for example, 15min, 16min, 18min, 20min, 22min, 24min or 25min, etc.
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 of the electrochemical device.
The anode active material has uniform particles, low micro powder content, proper particle size of primary particles and secondary particles, small number of large particles, and high capacity, coulomb efficiency, good cycle performance and low temperature performance.
In an alternative embodiment, the instant invention provides a method for detecting whether an electrochemical device comprises the positive electrode active material of the instant invention, comprising:
splitting the electrochemical device sample to obtain a positive electrode, washing the positive electrode with a solvent, drying, scraping the surface of the positive electrode to obtain active substance powder, cutting the active substance powder into sections of particles by using CP, observing the appearance of the active substance powder by using a scanning electron microscope, performing line scanning or surface scanning by matching with EDS, and measuring the particle size distribution D of the material by using a laser particle size analyzer n 10、D v 50、D v 90 and D FW Obtaining the distribution, structure and particle size distribution of the elements in the active material powder;
when the test results show that the particles in the active material powder are divided into an inner core and a coating layer, wherein the inner core contains Ni, co, mn, al, the coating layer 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 includes 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 electrode active material, the conductive agent, the binder and the solvent to obtain positive electrode slurry, coating the positive electrode slurry on an aluminum foil, drying and rolling to obtain the positive electrode.
Preferably, the mass ratio of the positive electrode active material, SP, CNT, and PVDF is (96 to 98): 1:1:1, 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 ℃, 70 ℃ or the like can be used.
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, carboxymethylcellulose (CMC), and Styrene Butadiene Rubber (SBR), the mass ratio of graphite, SP, CMC, and SBR being (90 to 99): 1.5:2, for example, may be 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 comprises a lithium salt and a solvent.
Preferably, the lithium salt comprises LiPF 6 。
Preferably, the lithium salt is contained in an amount of 4wt% to 24wt%, for example, 4wt%, 8wt%, 10wt%, 15wt%, 20wt%, 24wt%, or the like, based on 100wt% of the electrolyte.
Preferably, the solvent includes any one or a combination of at least two of Ethylene Carbonate (EC), ethylmethyl carbonate (EMC), dimethyl carbonate (DMC) and Polycarbonate (PC), 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, etc.
Preferably, the mass ratio of EC, EMC, DMC to 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, 4.5 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, the method of assembling an electrochemical device using the positive electrode, the negative electrode and the separator is the prior art, and those skilled in the art can assemble the electrochemical device by referring to the methods disclosed in the prior art. Taking a lithium ion battery as an example, sequentially winding or stacking a positive electrode, a diaphragm and a negative electrode to form a battery core, filling the battery core into a battery shell, injecting electrolyte, forming, and packaging to obtain the electrochemical device.
In a third aspect, the present invention provides an electronic device comprising the electrochemical apparatus according to the second aspect.
The electronic device according to the invention may be, for example, a mobile computer, a cellular phone, a memory card, a liquid crystal television, an automobile, a motorcycle, a motor, a timepiece, a camera, etc.
Compared with the prior art, the invention has the beneficial effects that:
(1) The positive electrode active material prepared by the method comprises a positive electrode active material 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, the multiplying power performance and the cycle performance of the material can be improved; meanwhile, the coating layer containing amorphous oxide is matched, so that the coating temperature is reduced, the coating effect is optimized, the capacity is increased, 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 specific primary sintering temperature and crushing process, optimizes the granularity of primary particles and secondary particles of the material, controls the particle size distribution of the material, reduces the micro powder content and the number of large particles of the material, obtains the anode active material with uniform particle distribution, improves the problem of gas production deterioration in the material circulation and storage process, reduces the interface resistance and reduces the agglomeration among the particles of the material, thereby improving the multiplying power performance, the capacity, the circulation performance and the low temperature performance of the battery.
Detailed Description
The technical scheme of the invention is further described by the following specific 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 inner core of the positive electrode active material, wherein the coating layer is amorphous titanium oxide, and the 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 mu m, D FW 2.1.
The embodiment also provides a preparation method of the positive electrode active material, which comprises the following steps:
(1) LiOH and a precursor Ni of the positive electrode active material are respectively weighed according to the mol 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 according to micron-sized alumina and Ni 0.55 Co 0.1 Mn 0.35 (OH) 2 The micron-sized alumina is weighed according to the molar ratio of 0.01:1 and placed in a high-speed mixer for stirring, the rotating speed is 800r/min, and the mixture is obtained after stirring until no white point exists in the high-speed mixer;
(2) Putting the mixture into a sagger, controlling the heating rate, firstly heating to 450 ℃ at 3 ℃/min, presintering for 3h, then heating to 950 ℃ at 6 ℃/min, and carrying out first sintering for 10h under 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) Li is mixed with 1.06 Ni 0.55 Co 0.12 Mn 0.322 Al 0.008 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Crushing to obtain particles D n 10 is 1.4 μm, D v 90 is 6.3 μm, D v 50 is 3.6 mu m, D FW 2.1;
(4) Crushing Li 1.06 Ni 0.55 Co 0.12 Mn 0.322 Al 0.008 O 2 And nanoscale amorphous titanium oxide (with the particle size D50 of 0.6um and marked as c-TiO NSs) are placed in a high-speed mixer in a molar ratio of 1:0.01 to be uniformly mixed, the rotating speed is 500r/min during mixing, the mixing time is 20min, and then the mixed materials are placed in a sagger and sintered for 5h at 300 ℃ air, so that the positive electrode active material is obtained.
1. Assembly of lithium ion batteries
(1) Preparation of positive electrode: the positive electrode active materials, SP, CNT and PVDF prepared in the examples and the comparative examples are mixed with azomethyl pyrrolidone (NMP) according to the mass ratio of 97:1:1:1, the mixture is stirred at high speed to obtain positive electrode slurry, the positive electrode slurry is coated on aluminum foil, and the aluminum foil is placed in a vacuum oven and dried for 12 hours at 60 ℃ to obtain the positive electrode slurry with the surface density of 18g/cm 2 The dried positive electrode is rolled to a compaction density of 3.4g/cm 3 ；
(2) Preparation of the negative electrode: mixing graphite, SP, CMC and SBR according to the mass ratio of 95.5:1:1.5:2 to prepare slurry, coating the slurry on copper foil, and rolling to obtain a negative electrode;
(3) Preparation of a lithium ion battery: the positive electrode and the negative electrode are adoptedPolar, 1M LiPF 6 And the electrolyte comprises Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and dimethyl carbonate (DMC) electrolyte with a mass ratio of 1:1:1 as solvents, and a PE base film, and the electrochemical device is obtained through assembly.
2. Performance testing
(1) Particle size distribution testing of positive electrode active material: a Michael S3500 apparatus was used to take 0.5g of positive electrode active material, and external ultrasonic treatment was performed using a mixed solution of the Xiyan area of a dropper dissolved in deionized water. Test cycle 3 times, select average value as granularity data, record D n 10，D v 50，D v 90。
(2) Testing of lithium ion batteries:
electrochemical performance testing was performed on lithium ion batteries using a Cheng Hong Electrical Co., ltd battery performance test System (device model: BTS05/10C 8D-HP).
First discharge specific capacity, first coulombic efficiency and 800 cycles capacity retention test: placing the electrochemical device in a test cabinet for testing, wherein the discharge capacity of the test battery is 2.8V to 4.4V at the temperature of 25 ℃ at the temperature of 0.33 ℃, the obtained discharge specific capacity is the first discharge specific capacity, the discharge specific capacity divided by the discharge specific capacity is the first coulomb efficiency, and the 800 th discharge capacity divided by the first discharge capacity after 800 circles are circulated, so that the 800-circle capacity retention rate is obtained.
Direct current internal resistance test (DCR): the electrochemical device was placed in a test cabinet for testing, and the cell was tested for 30 seconds of discharge DCR at 50% soc at 4C at 25 ℃.
Low temperature capacity retention test: and placing the electrochemical device in a test cabinet for testing, testing the discharge capacity of the battery at the low temperature (-20 ℃) when the battery circulates at 0.33/0.33 ℃, stopping circulating after the capacity of the battery is attenuated to 80 percent (80 percent SOH) of the initial capacity, and dividing the discharge capacity of the 80 percent SOH by the discharge capacity of the 3 rd circle to obtain the capacity retention rate at the temperature of minus 20 ℃.
Examples 2 to 9 and comparative examples 1 to 3 were subjected to parameter modification based on the step of example 1, and the specifically modified 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 3
TABLE 4 Table 4
As can be seen from comparison of examples 1 and 4 to 7 in tables 3 to 4, sintering with appropriate amounts 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. The higher or lower M source content of examples 4 and 5 significantly reduces capacity and low temperature performance; example 6 coating amorphous state too high, can cause particle adhesion, mobility deterioration, thus affecting capacity and low temperature performance; example 7 coated amorphous titanium oxide has lower content, lower material capacity and DCR, and also has deviation in cycle performance; thus, the capacity, coulombic efficiency, rate capability, and cycle were all optimized for example 1.
TABLE 5
TABLE 6
As can be seen from comparison of examples 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, primary particles of the material grow larger, secondary particles are generated by agglomeration of the primary particles, the secondary particles are difficult to crush during crushing, the content of micro powder after crushing is more, the electrochemical performance of the material is also influenced, 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 coulomb efficiency, the 800-cycle capacity retention rate, the DCR and the low-temperature capacity retention rate of comparative examples 1 to 2 are all worse than those of example 1; when the second sintering temperature is low, the amorphous titanium oxide coating effect is deviated to affect the morphology of the material, and when the second sintering temperature is high, the capacity of the material is affected, so that the overall electrochemical performance of examples 8 to 9 is slightly inferior to that of example 1.
TABLE 7
TABLE 8
As can be seen from the comparison between the examples 1 and 3 in tables 7 to 8, the amorphous oxide is adopted in the example 1, which has higher activity, can realize good coating effect at low temperature, optimize the morphology of the material, further realize the regulation and control of the size and particle diameter of the material, and cooperate with the crushed first sintering product with good size and morphology to jointly improve the capacity, cycle performance and low temperature performance of the material, while the conventional titanium oxide is adopted in the comparative example 3 for sintering, so that the prepared positive electrode active material has poorer capacity and cycle stability.
From examples 1 to 9, it can be seen that the present invention further improves the capacity, cycle performance and low temperature performance of the prepared electrochemical device by doping and coating specific elements and components, adjusting and controlling the particle size and crystal structure of the material, optimizing the particle size of the material, reducing the micro powder content and large particle number of the material, improving the rate capability and storage performance of the material.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (10)
1. The positive electrode active material is characterized by comprising a positive electrode active material inner core and a coating layer coated on the surface of the positive electrode active material inner core, wherein the positive electrode active material inner core comprises doped ions, and the coating layer comprises amorphous oxide;
particle size distribution D of the cathode active material n 10、D v 50、D v 90 and D FW Simultaneously satisfies: 1.2 μm<D n 10≤2.2μm，3μm<D v 50<5μm，2μm<D FW <4μm，1.5<(D v 90-D n 10)/D FW <2.4。
2. The positive electrode active material according to claim 1, characterized in thatThe 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 1.2,0.5, b is more than or equal to 0.6,0.03, c is more than or equal to 0.2,0.005, d is more 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 a molar ratio of the positive electrode active material core to the coating layer is 1 (0.008 to 0.01).
5. An electrochemical device, characterized in that the positive electrode of the electrochemical device includes the positive electrode active material according to any one of claims 1 to 4 therein.
6. The electrochemical device of claim 5, further comprising a conductive agent and a binder in the positive electrode, wherein the conductive agent and the binder satisfy any one of the following conditions (a) to (b):
(a) The conductive agent comprises conductive carbon black and/or carbon nano tubes;
(b) The binder comprises polyvinylidene fluoride.
7. The electrochemical device of claim 5, further comprising an electrolyte and a separator.
8. The electrochemical device of claim 7, wherein the electrolyte comprises a lithium salt and a solvent that satisfy any one of the following conditions (c) to (e):
(c) The lithium salt comprises LiPF 6 ；
(d) The lithium salt content is 4wt% to 24wt%, based on 100wt% of the electrolyte;
(e) The solvent includes any one or a combination of at least two of ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate and 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 μm to 12 μm.
10. An electronic device, characterized in that it comprises an electrochemical apparatus according to any one of claims 5 to 9.
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