WO2023160450A1 - Matériau d'électrode positive de batterie au lithium-ion à haute teneur en nickel ayant une sécurité thermique et son procédé de préparation - Google Patents

Matériau d'électrode positive de batterie au lithium-ion à haute teneur en nickel ayant une sécurité thermique et son procédé de préparation Download PDF

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WO2023160450A1
WO2023160450A1 PCT/CN2023/076392 CN2023076392W WO2023160450A1 WO 2023160450 A1 WO2023160450 A1 WO 2023160450A1 CN 2023076392 W CN2023076392 W CN 2023076392W WO 2023160450 A1 WO2023160450 A1 WO 2023160450A1
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positive electrode
ion battery
sintering
electrode material
nickel
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Chinese (zh)
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宗博
于建
戚洪亮
孟祥鹤
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宁波容百新能源科技股份有限公司
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/52—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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

Definitions

  • the invention belongs to the technical field of lithium-ion batteries, and in particular relates to a high-nickel lithium-ion battery cathode material with thermal safety and a preparation method thereof.
  • Lithium-ion battery is one of the most important devices for energy storage applications. It has the advantages of high energy density and cycle efficiency, low self-discharge, and no memory effect. It has broad application prospects in power batteries, and with the With the progress of society, the demand for energy is gradually increasing the requirements for lithium batteries.
  • the layered lithium-ion material composed of nickel-cobalt-manganese elements has developed rapidly in recent years due to the synergistic effect of the three elements on the material, especially the ternary material with high nickel and low cobalt, which not only provides high energy density but also reduces The various costs brought by the element cobalt have been studied by people.
  • the ensuing high-nickelization brings about the instability of the material structure, there will be differences in the crystal structure such as Li/Ni mixed arrangement, and the harsh conditions of the preparation process will lead to a capacity difference.
  • the theoretical specific capacity is more, and the high nickel three
  • the thermal decomposition temperature of the element material decreases continuously while the capacity is increased, which has the disadvantage that it is easy to decompose when heated within 350°C, which leads to an increase in safety hazards.
  • High-nickel cathode materials can provide high capacity and are favored by people, but safety issues have always restricted the wide application of high-nickel materials. In vehicular applications, where temperatures can become uncontrolled and cause fires and even explosions.
  • the cathode material is one of the core components of lithium-ion batteries to provide energy, so it is very important to develop cathode materials with high energy density and excellent thermal stability.
  • the technical problem to be solved by the present invention is to provide a thermally safe high-nickel lithium-ion battery cathode material and its preparation method and application.
  • the high-nickel lithium-ion battery cathode material provided by the invention has high energy density and Excellent thermal stability.
  • the invention provides a high-nickel lithium-ion positive electrode material and method with a secondary sintering process containing thermally stable element MTd and elements with similar properties coated.
  • the invention provides a high-nickel lithium-ion battery positive electrode material with thermal safety, the general chemical formula is Li 1+x Ni a Co b Mn c M Td O 2 ;
  • M T is selected from Al, One or more of Zr, Si, Ti, Mg, W, Mo, P, Ta, Ce, Nb, Mn, Y and F;
  • the anode material of the high-nickel lithium-ion battery is spherical particles, and the thermally stable element M T presents a reduced level from the surface of the spherical particles to the interior of the spherical particles.
  • the surface of the positive electrode material of the high-nickel lithium ion battery is coated with one or more compounds of amphoteric elements.
  • the material structure is loose inside, and the surface layer particles are arranged in a divergent shape;
  • the normal plane of the major diameter of the surface layer particles and the normal plane of the major diameter of the inner particles present a vertical relationship in three-dimensional space.
  • the molar ratio of Li to metal ions is 1.00-1.08;
  • the particle compressive strength of the positive electrode material is ⁇ 89.8Mpa
  • the particle diameter distribution mode of the positive electrode material is between 0.34 and 0.60 ⁇ m;
  • the average unit cell volume of the positive electrode material is between.
  • the present invention also provides a method for preparing the above-mentioned high-nickel lithium-ion battery cathode material with thermal safety, comprising the following steps:
  • the first additive contains one or more elements of Al, Zr, Si, Ti, Mg, W, Mo, P, Ta, Ce, Nb, Mn, Y and F.
  • the oxygen-containing gas is an oxygen-containing atmosphere with an oxygen content ⁇ 98 vol%.
  • the sintering temperature is 650-850°C
  • the sintering heating rate is 2°C/min-10°C/min
  • the sintering holding time is ⁇ 20h.
  • step A it also includes crushing and sieving the sintered product, washing with water and drying to obtain the washed material;
  • the water-washed material is mixed with the second additive for the second sintering, and after sieving, the high-nickel lithium-ion battery positive electrode material is obtained.
  • the washing temperature is ⁇ 40°C, and the mass ratio of water to material is (0.5-3):1;
  • the free lithium content in the washing material needs to be ⁇ 1400ppm.
  • the second additive is selected from one or more amphoteric compounds
  • the atmosphere condition of the second sintering is an oxygen-containing atmosphere, the sintering temperature is ⁇ 600°C, the sintering time is ⁇ 15h, and the sintering heating rate is 2°C/min ⁇ 10°C/min.
  • the surface of the washing material is coated with amphoteric elements, and the coating amount is below 5000 ppm.
  • the surface and internal M T of the positive electrode material particles have non-uniform characteristics, and the material particles are essentially high-nickel NCM ternary materials inside, while other parts of the material are NCMM T high-nickel quaternary materials.
  • the addition of cations MT on the surface of the particles to maintain the electrical neutrality of the matrix will also bring O 2- , this effect inhibits the escape of [O] during the charging process, and replaces part of the framework ions and fills the lattice voids , which effectively inhibits the development of the internal stress of the lattice, thereby improving the stability of the crystal structure of the high-nickel cathode material; on the basis of maintaining the capacity, this structure is not only conducive to inhibiting the surface side reactions of the primary particles but also effectively improving lithium intercalation and desorption. Stress relief for ionic processes.
  • the anode material of the high-nickel lithium ion battery provided by the invention has a high thermal decomposition temperature, a low harmful effect of doping elements on the internal crystal structure of spherical particles, and a high discharge capacity.
  • Fig. 1 is the preparation process flow chart of high-nickel lithium-ion battery cathode material provided by the present invention
  • Fig. 2 is the sectional view of high nickel ternary precursor Ni 0.86 Co 0.06 Mn 0.08 (OH) 2 ;
  • Fig. 3 is the sectional view of the high-nickel lithium-ion battery cathode material that the present invention prepares;
  • Fig. 4 is the SEM photo of the high-nickel lithium ion battery cathode material that the present invention prepares
  • Fig. 5 is the diameter width distribution histogram of the visible primary particle of high-nickel lithium ion battery cathode material in Fig. 4;
  • Fig. 6 is the individual value figure of embodiment 1 and comparative example 1;
  • Fig. 7 is the box plot of embodiment 1 and comparative example 1;
  • Fig. 8 is the charging and discharging curve of embodiment 1;
  • Fig. 9 is the DSC curve of embodiment 1;
  • Fig. 10 is the DSC curve of embodiment 2;
  • Fig. 11 is the charging and discharging curve of comparative example 1;
  • Fig. 12 is the DSC curve of comparative example 1;
  • Fig. 13 is the SEM picture of comparative example 6;
  • FIG. 14 is a histogram of primary particles of Comparative Example 6.
  • the invention provides a high-nickel lithium-ion battery cathode material with thermal safety, the general chemical formula is Li 1+x Ni a Co b Mn c M Td O 2 ;
  • 0.01 ⁇ x preferably 0.03, 0.05, 0.06, or any value between 0.01 and 0.08;
  • 0.03 ⁇ b ⁇ 0.1 preferably 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, or any value between 0.03 and 0.1;
  • 0.5 ⁇ c/b ⁇ 1 preferably 0.5, 0.6, 0.7, 0.8, 0.9, 1, or any value between 0.5 and 1;
  • 0.006 ⁇ d ⁇ 0.016 preferably 0.006, 0.008, 0.010, 0.012, 0.014, 0.016, or any value between 0.006 and 0.016;
  • M T is selected from one or more of Al, Zr, Si, Ti, Mg, W, Mo, P, Ta, Ce, Nb, Mn, Y and F, preferably one or both of Al and Zr kind.
  • the anode material of the high-nickel lithium-ion battery is spherical particles, and the thermally stable element M T presents a reduced level from the surface of the spherical particles to the interior of the spherical particles.
  • the M T presents a gradually decreasing level from the surface layer to the inside in the longitudinal section of the spherical particle;
  • the surface of the positive electrode material of the high-nickel lithium ion battery is coated with one or more compounds of amphoteric elements.
  • the elements MT and NCM that can improve the thermal stability of the material
  • the precursor particles are mixed and then sintered at high temperature.
  • the M T element gradually infiltrates from the high-concentration area into the low-concentration area, and the material particles are realized by surface doping in the crystal lattice of the polycrystalline nickel-cobalt-manganese ternary positive electrode matrix.
  • the characteristics of surface and internal MT are uneven, the material particles are essentially high-nickel NCM ternary materials inside, and the surface part of the material is NCMM T high-nickel quaternary materials.
  • the interior of the material structure is arranged randomly, and the surface layer particles are arranged in a divergent shape;
  • the normal plane of the major diameter of the particles in the surface layer and the normal plane of the major diameter of the inner particles present a vertical relationship in three-dimensional space.
  • the particle compressive strength of the positive electrode material is ⁇ 89.8Mpa
  • the mode of the particle diameter distribution of the positive electrode material is between 0.34 and 0.60 ⁇ m; wherein, the mode of the particle diameter distribution refers to the width of the primary particle diameter on the measurement scale of length, width and height in three-dimensional space. If it is not within this range, it will not be able to maintain the thermal stability of the crystal structure. Smaller particles are more likely to undergo heat transfer after heating, and more primary particle diameter distributions are greater than the upper limit of this range, which is more likely to cause spherical particles to collapse.
  • the average unit cell volume of the positive electrode material is between, preferably, the unit cell volume after surface doping is
  • the present invention also provides a method for preparing the above-mentioned high-nickel lithium-ion battery cathode material with thermal safety, comprising the following steps:
  • the lithium source, the high-nickel precursor and the first additive are mixed and then sintered under oxygen-containing gas conditions to obtain a high-nickel lithium-ion battery positive electrode material.
  • the lithium source is selected from one or more of lithium hydroxides, hydrated hydroxides and carbonates;
  • the high-nickel ternary precursor is selected from nickel-cobalt-manganese hydroxide, nickel-cobalt-manganese coprecipitated hydroxide;
  • the first additive contains one or more elements of Al, Zr, Si, Ti, Mg, W, Mo, P, Ta, Ce, Nb, Mn, Y and F.
  • the additive contains no less than one dopant ion, Mg 2+ , Ti 4+ , Zr 4+ , Si 4+ , W 6+ , Al 3+ , Mo 6 + , P 5+ , Ta 5+ , Ce 3+ , Nb 5+ , Mn 4+ , Y 3+ and F - etc.
  • the first additive is preferably a compound containing one or more of the above elements.
  • the molar ratio range of Li to metal elements other than lithium is 1.00 ⁇ 1.15.
  • the mixed material is sintered under the condition of oxygen-containing gas, and the oxygen-containing gas is an oxygen-containing atmosphere with an oxygen content ⁇ 98 vol%.
  • the obtained mixed material is loaded into a sagger after being tested for uniformity, and the mixed material is sintered in an oxygen-containing atmosphere with an oxygen content ⁇ 98 vol%.
  • the sintering temperature is 650-850°C, preferably 650, 700, 750, 800, 850°C, preferably any value between 650-850°C, and the heating rate of the sintering is 2°C/min-10°C/min min is preferably 2, 4, 6, 8, 10, or any value between 2°C/min-10°C/min, and the sintering holding time is ⁇ 20h.
  • the sintering step after the sintering step, it also includes crushing and sieving the sintered product, washing with water and drying to obtain the washed material;
  • the water-washed material is mixed with the second additive for the second sintering, and after sieving, the high-nickel lithium-ion battery positive electrode material is obtained.
  • crushing adopts the sequence of first using the equipment of jaw crusher and then mechanical crushing.
  • the specific method of the sieving is known to those skilled in the art.
  • the powder obtained by sieving is washed with water and dried to obtain a washed material.
  • the washing conditions the washing temperature is ⁇ 40°C, the mass ratio of water to material is (0.5 ⁇ 3):1, the washing speed is 300 ⁇ 400r/min, and the washing time is 10 ⁇ 20min; Dry in a vacuum drying oven, the vacuum drying temperature is 120°C, not lower than 4h, pass through oxygen, and sieve to ensure that the free lithium content in the dried material needs to be ⁇ 1400ppm.
  • the water washing is carried out by means of weakened water washing. That is to dissolve a certain quality of lithium hydroxide in pure water first, and then add the material to the solution to reduce the structural remodeling of the surface of the water-washed particles, reduce the loss of residual lithium on the surface, and have a positive effect on subsequent thermal safety
  • the water-washed material is mixed with a second additive for second sintering.
  • the second additive is selected from compounds including but not limited to M T elements.
  • the added amount of the second additive is ⁇ 5000ppm.
  • the atmosphere condition for the second sintering is an oxygen-containing atmosphere, the sintering temperature is 350-600°C, preferably Al 2 O 3 and B(OH) 3 ; the sintering time is ⁇ 15h, and the sintering heating rate is 2 °C/min-10°C/min, preferably 2, 4, 6, 8, 10, or any value between 2°C/min-10°C/min.
  • the sintered product is sieved to obtain a high-nickel lithium-ion battery cathode material with thermal safety.
  • Fig. 1 is a flow chart of the preparation process of the high-nickel lithium-ion battery positive electrode material provided by the present invention.
  • the present invention by controlling the type and amount of the additive MT , primary particles with a specific diameter and spherical particles with different arrangements of the surface layer and the interior, a high-nickel lithium-ion battery positive electrode material is obtained, and the high-nickel lithium-ion battery positive electrode
  • the material has high energy density and excellent thermal stability.
  • the method of the invention has low equipment requirements, is easy to industrialized production, easy to realize the conditions, and low processing cost;
  • the high-nickel material prepared by the method has a high thermal decomposition temperature, a low harmful effect of doping elements on the internal crystal structure of spherical particles, and a high discharge capacity;
  • the invention has lower requirements on the precursor, is easy to realize, and has lower raw material costs.
  • thermo safety means: the DSC decomposition temperature of the positive electrode material is improved, that is, the positive electrode material can be used in a higher temperature range Maintain chemical thermal stability inside, delay the occurrence of danger to a certain extent, after dismantling the fully charged half-battery, match the dried positive electrode sheet with a considerable amount of electrolyte and then conduct DSC detection, the peak value of the heat absorption / heat release The temperature is above 230.50°C; "high nickel” means: the molar content of Ni element in the polycrystalline nickel cobalt lithium manganese oxide matrix accounts for more than 80% of the molar weight of all metal elements. DSC uses a differential scanning calorimeter to characterize the phase safety temperature of the positive electrode material; the lithium-rich state is a state in which the ratio of lithium elements to metal elements is greater than 1.
  • thermally safe high-nickel lithium-ion battery positive electrode material provided by the present invention, its preparation method and application will be described below in conjunction with the examples, and the protection scope of the present invention is not limited by the following examples.
  • Fig. 2 is a cross-sectional view of the high-nickel ternary precursor Ni 0.86 Co 0.06 Mn 0.08 (OH) 2 ;
  • Fig. 3 is a cross-sectional view of the high-nickel lithium-ion battery cathode material prepared in the present invention.
  • the obtained positive electrode material was charged to 4.3V at 0.2C, and the cut-off current was 0.05C.
  • the battery was disassembled and the corresponding electrode pieces were cut out, and the corresponding quality of electrolyte was put into the crucible to simulate the environment under the working voltage of the material, and the DSC test was carried out.
  • the measured half capacity is 204.3mAh/g, and the DSC thermal decomposition temperature is 246.50°C.
  • the average compressive strength of the secondary spherical particles in the material is 125.3Mpa, and the minimum particle compressive strength is 89.8Mpa, as tested by the particle pressure tester.
  • Fig. 4 is a SEM photo of the high-nickel lithium-ion battery cathode material prepared in the present invention.
  • Fig. 5 is a histogram of the diameter width distribution of visible primary particles of the positive electrode material of the high-nickel lithium ion battery in Fig. 4 . It can be seen from Figure 5 that the widest particle size distribution is between 0.3 and 0.6 ⁇ m.
  • the sintering temperature is 380°C, 10h, the heating rate 2°C/min, after taking out, sieve and crush.
  • the measured half-capacity is 208.1mAh/g, and the DSC temperature is 220.32°C
  • Example 1 A two-sample t-test was carried out on Example 1 and Comparative Example 1 to verify whether the broad distribution of primary particle diameters on the surface of spherical particles is related to the thermal decomposition temperature of DSC. See Figures 6-7 and Table 1 for the results. Among them, Fig. 6 is the individual value diagram of sample 1 and sample 2, and Fig. 7 is the line box diagram of sample 1 and sample 2. Sample 1 is the high-nickel positive electrode material prepared in Example 1, and Sample 2 is the high-nickel material described in the comparative example; C2 in the figure represents Example 1, and C5 represents Comparative Example 1.
  • the above statistical results show that different particle size distributions have an impact on the thermal decomposition temperature of DSC.
  • the thermal safety performance of the high-nickel cathode material sample 1 prepared by the preparation process of the present invention is better than that of the sample 2.
  • the particle compressive strength of the positive electrode material is 85.9Mpa, and the mode of the particle size distribution of the positive electrode material is between 0.34 and 0.6 ⁇ m.
  • Ni 0.86 Co 0.06 Mn 0.08 (OH) 2 and LiOH ⁇ H 2 O according to the molar ratio of 1:1.08, and 1mol% Al(OH) 3 and 5000ppm ZrO 2 into a 10L high mixer for mixing. It is 1000r/min and lasts for 10-30min; after the first sintering at 850°C for 15h, washing with water, and second sintering, it is coated with 2000ppm boric acid and 1000ppm MnO 2 , and the DSC result is 245.2°C.
  • the molar ratio of Ni 0.86 Co 0.06 Mn 0.08 (OH) 2 and LiOH ⁇ H 2 O is 1:1.08
  • the stoichiometric ratio of transition metal ions is 0.15 aluminum hydroxide
  • the mass concentration of transition metal ions is 1000ppm Si(TEOS) and 2500ppm ZrO 2 are added to a 10L high mixer for mixing at a rate of 1000r/min for 10-30min; after sintering at 850°C for 15h for the first time, the heating rate is 2°C/min, Pass through a 325-mesh sieve and mechanically crush; then wash with water, the water-to-material ratio mass ratio is 1:0.5, the rotation speed is 360r/min, and the washing time is 30 minutes, put it in a vacuum oven for 4 hours at 120°C, take it out and add 2000ppm Boric acid is mixed evenly and then sintered for the second time.
  • the sintering temperature is 380°C for 10 hours
  • the heating rate is 2°C/min.
  • the molar ratio of Ni 0.86 Co 0.06 Mn 0.08 (OH) 2 and LiOH ⁇ H 2 O is 1:1.08, aluminum hydroxide with a stoichiometric ratio of 0.1 to transition metal ions, and a mass concentration of transition metal ions of 1000ppm MnO 2 , 500ppm Si and 3000ppm ZrO 2 were added to a 10L high mixer for mixing at a rate of 1000r/min for 10-30min; after sintering at 850°C for 15h for the first time, the heating rate was 2°C/min min, passed through a 325 mesh sieve, and mechanically crushed; then washed with water, the washing conditions were water-material ratio mass ratio 1:0.5, rotating speed 360r/min, washing time 30 minutes, put it in a vacuum oven for 4 hours at 120°C, took it out and added 2000ppm of boric acid, mixed evenly, and then sintered for the second time.
  • the sintering temperature was 380°C for 10 hours, and the heating rate was 2
  • Example 2 According to the test method of Example 1, the properties of the positive electrode materials in Examples 8-13 were measured, and the results are shown in Table 2.

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un matériau d'électrode positive de batterie au lithium-ion à haute teneur en nickel ayant une sécurité thermique, lequel matériau a la formule chimique générale Li1+xNiaCobMncMTdO2, dans laquelle 0,01 ≤ x ≤ 0,03, 0,8 ≤ a < 1, 0,03 ≤ b ≤ 0,1, 0,5 ≤ c/b ≤ 1, 0,006 ≤ d ≤ 0,016 et a + b + c + d = 1 ; et MT est choisi parmi un ou plusieurs éléments parmi Al, Zr, Si, Ti, Sr, Mg, W, Mo, P, Ta, Ce, Nb, Mn, Y et F. Le matériau d'électrode positive de batterie au lithium-ion à haute teneur en nickel est une particule sphérique et le niveau d'un élément thermiquement stable MT diminue de la surface de la particule sphérique à l'intérieur de la particule sphérique ; et la surface du matériau d'électrode positive de batterie au lithium-ion à haute teneur en nickel est revêtue d'un composé d'un ou plusieurs éléments amphotères. Le matériau d'électrode positive de batterie au lithium-ion à haute teneur en nickel selon la présente invention a une température de décomposition thermique élevée, l'effet nocif d'éléments de dopage sur la structure cristalline interne de la particule sphérique est relativement faible, et celui-ci a une capacité de décharge élevée.
PCT/CN2023/076392 2022-02-28 2023-02-16 Matériau d'électrode positive de batterie au lithium-ion à haute teneur en nickel ayant une sécurité thermique et son procédé de préparation WO2023160450A1 (fr)

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