WO2024093679A1 - 一种正极材料及包括该正极材料的正极片和电池 - Google Patents
一种正极材料及包括该正极材料的正极片和电池 Download PDFInfo
- Publication number
- WO2024093679A1 WO2024093679A1 PCT/CN2023/125242 CN2023125242W WO2024093679A1 WO 2024093679 A1 WO2024093679 A1 WO 2024093679A1 CN 2023125242 W CN2023125242 W CN 2023125242W WO 2024093679 A1 WO2024093679 A1 WO 2024093679A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- electrode material
- battery
- present disclosure
- lithium
- Prior art date
Links
Classifications
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- 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
- H01M4/50—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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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 present invention belongs to the technical field of batteries, and in particular relates to a positive electrode material and a positive electrode sheet and a battery comprising the positive electrode material.
- the capacity of the positive electrode material plays a vital role in the capacity of lithium-ion batteries.
- an important way is to increase its charge and discharge voltage.
- the positive electrode material will face a series of unfavorable changes such as unstable crystal structure, rapid capacity decay and greatly reduced cycle performance. Therefore, it is a very critical task to develop a lithium-ion battery positive electrode material with high specific capacity, high voltage platform, good cycle performance and stable interface at high voltage.
- the present disclosure provides a positive electrode material, a positive electrode sheet and a battery comprising the positive electrode material, wherein the positive electrode material belongs to the P63mc space group and has an O2 phase stacking structure.
- the positive electrode material has high specific capacity, good interface stability and cycle stability at high voltage, and the use of the positive electrode material can improve the gram capacity, cycle performance, rate performance and energy density of the battery.
- a positive electrode material which is a lithium transition metal oxide including Li element, Na element, K element, Co element and optionally A element and/or M element, wherein the A element is selected from at least one of B and P, and the M element is selected from at least one of Al, Mg, Ti, Mn, Te, Ni, W, Nb, Zr, La and Y.
- the molar amount of the K element in the positive electrode material is z
- the molar amount of the Co element in the positive electrode material is 1-a-b
- the molar amount of the A element in the positive electrode material is a
- the molar amount of the M element in the positive electrode material is b
- the ratio of z to 1-a is 0 ⁇ z/1-a ⁇ 0.05
- the optional may be selected or not selected.
- the molar amount z of the K element in the positive electrode material per unit mole is 0 ⁇ z ⁇ 0.05, for example, z is 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.010, 0.012, 0.015, 0.018, 0.020, 0.022, 0.024, 0.025, 0.026, 0.028, 0.030, 0.032, 0.034, 0.035, 0.036, 0.038, 0.04, 0.042, 0.043, 0.045, 0.046, 0.048 or 0.049.
- the electrochemical kinetics and rate performance during the charge and discharge process can be improved, and the polarization phenomenon can be reduced, so that the battery has higher gram capacity, coulombic efficiency, rate performance and cycle performance.
- the molar amount a of element A per unit mole of positive electrode material is 0 ⁇ a ⁇ 0.05, for example, a is 0, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.010, 0.012, 0.015, 0.018, 0.020, 0.022, 0.024, 0.025, 0.026, 0.028, 0.030, 0.032, 0.034, 0.035, 0.036, 0.038, 0.04, 0.042, 0.043, 0.045, 0.046, 0.048 or 0.049.
- the A element is selected from at least one of B and P, preferably B.
- the B element and the P element have a fluxing effect, so that the morphology of the positive electrode material is a single crystal or polycrystalline spherical morphology with a large particle size.
- the morphology of the positive electrode material is a single crystal morphology.
- the B element can make the structure of the positive electrode material more stable, and can stabilize the interface between the positive electrode material and the electrolyte during the charge and discharge process, which is beneficial to improving the cycle performance of the battery.
- the B and P elements can significantly increase the gram capacity and compaction density of the positive electrode material, which is beneficial to improving the energy density and rate performance of the battery.
- the molar amount b of the M element per unit mole of the positive electrode material is 0 ⁇ b ⁇ 0.1, for example, b is 0, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.010, 0.012, 0.015, 0.018, 0.020, 0.022, 0.024, 0.025, 0.026, 0.028, 0.030, 0.032, 0.034, 0.035, 0.04, 0.045, 0.05, 0.055, 0.06, 0.065, 0.07, 0.075, 0.08, 0.085, 0.09 or 0.095.
- the M element is used to replace part of the Co element.
- the structure of the cobalt layer can be stabilized, thereby improving the stability of the overall structure of the positive electrode material.
- the molar amount y of the Na element in unit mole of the positive electrode material is 0 ⁇ y ⁇ 0.03, for example, y is 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.010, 0.012, 0.015, 0.018, 0.020, 0.022, 0.024, 0.025, 0.026 or 0.028.
- a supporting effect can be played on the layered structure of the positive electrode material, which is beneficial to the insertion and extraction of lithium ions.
- the chemical formula of the positive electrode material is:
- z/1-a is within the range specified in the present invention, it means that the doping amount of K element is limited to a certain range, within which the radius of K ion>the radius of Li ion, which plays a certain supporting role on the skeleton of the layered structure, promotes the deintercalation of Li ions, and is beneficial to the performance of gram capacity and the improvement of cycle performance.
- z/1-a exceeds the range, it means that more Li is replaced by K element, and the loss of Li leads to a significant decrease in its gram capacity.
- the value of n in the chemical formula of the positive electrode material is different in different delithiation states, including the positive electrode sheet of the positive electrode material before sorting, the value of n in the positive electrode material in the powder state is 0.95-1.02; the positive electrode sheet of the positive electrode material after sorting (voltage range is 3.6V-4.0V), the value of n in the positive electrode material is 0.70-1.0.
- the positive electrode material has an O2 phase stacking structure and belongs to the P63mc space group, which is a layered structure. Compared with the existing O3 phase stacking structure, it has a larger interlayer spacing, so it is easier to deintercalate and extract lithium ions.
- the positive electrode material has a polycrystalline morphology or a single crystal morphology, the polycrystalline morphology has a more excellent rate performance, and the single crystal morphology has a greater compaction density.
- the Dv50 of the positive electrode material is 12 ⁇ m to 20 ⁇ m, for example, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m or 20 ⁇ m.
- the Dv50 of the positive electrode material can be tested using a laser particle size analyzer.
- Dv50 refers to the particle size corresponding to when the cumulative volume particle size distribution percentage of a sample reaches 50%.
- the packing density of the positive electrode material can be increased, thereby increasing the capacity of the battery.
- m ⁇ 2 for example, 2 to 8, such as 2 to 5, such as 2, 3, 4, 5, 6, 7 or 8.
- the gram capacity of the positive electrode material is ⁇ 210 mAh/g (button cell, upper voltage limit ⁇ 4.50 V (relative to lithium)).
- the present disclosure also provides a method for preparing the above-mentioned positive electrode material, the method comprising the following steps:
- the first step is to synthesize a compound Na x K z Co 1-ab A a M b O 2 containing Co, Na, K, optionally A and optionally M, wherein 0.68 ⁇ x ⁇ 0.74, and the definitions of z, a, b, A and M are as described above;
- the method for preparing the positive electrode material comprises the following steps:
- step 2) calcining the mixture of step 1) at high temperature to obtain a compound with a chemical formula of Na x K z Co 1-ab A a M b O 2 ;
- step 3 mixing the compound of step 2 ) with the lithium - containing compound in a solvent to carry out an ion exchange reaction, and washing and drying the reaction product after the reaction is completed to obtain the positive Extreme material.
- step 1) the mixing time is ⁇ 4h.
- the mixing is, for example, at least one of high-speed stirring, ball milling, and sand milling.
- step 1) the mixing is performed using, for example, a high-speed mixing device, a sand mill, a ball mill, a plowshare mixing device, or an oblique mixing device. If a medium (such as water or alcohol or other solvent medium) is added during the ball milling or sand milling process, a drying process is required after the mixing.
- a medium such as water or alcohol or other solvent medium
- the cobalt-containing compound is selected from cobalt hydroxide, cobalt trioxide, doped cobalt trioxide, cobaltous oxide, cobalt oxyhydroxide, cobalt nitrate, cobalt sulfate and the like.
- the sodium-containing compound is selected from sodium oxide, sodium carbonate, sodium nitrate, sodium hydroxide, sodium bicarbonate, sodium sulfate, and the like.
- the potassium-containing compound is selected from potassium oxide, potassium carbonate, potassium nitrate, potassium hydroxide, potassium bicarbonate, potassium sulfate and the like.
- the compound containing A is selected from an oxide of B, an oxide of P, a hydroxide of B, a hydroxide of P, an acid of B, an acid of P, a salt of B or a salt of P.
- the compound containing A is selected from boric acid and phosphoric acid.
- the compound containing M is selected from oxides, hydroxides or salts of Al, Mg, Ti, Mn, Te, Ni, W, Nb, Zr, La and Y.
- the compound containing M is selected from basic magnesium carbonate, magnesium hydroxide, zirconium oxide, aluminum oxide, aluminum hydroxide, yttrium oxide, lanthanum oxide, aluminum phosphate, sodium pyrophosphate, sodium tungstate, lanthanum fluoride, etc.
- the calcination temperature is 700-900° C.
- the calcination time is 8-50 hours
- the calcination is carried out in air or oxygen atmosphere.
- the high temperature calcination is to put the mixed material into the crucible, Place it in a muffle furnace, tunnel furnace, roller kiln, tubular furnace or other high temperature sintering equipment for high temperature calcination.
- the lithium-containing compound is selected from lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium hydroxide, lithium nitrate, lithium carbonate, and the like.
- the solvent is selected from water or an organic solution.
- the mass ratio of the lithium-containing compound to the compound having the chemical formula Na x K z Co 1-ab A a M b O 2 is ⁇ 1, preferably 1-3.
- the mass ratio of the solvent to the compound of the chemical formula Na x K z Co 1-ab A a M b O 2 is ⁇ 5, preferably 20-150.
- the reaction equipment for carrying out the ion exchange reaction comprises a closed container equipment with a sealing function and a stirring capability, such as a wet coating reaction equipment and a coprecipitation reaction equipment.
- step 3 the ion exchange reaction is carried out under stirring conditions, the stirring speed is 10 rpm to 200 rpm, the reaction temperature is 70 to 125° C., and the reaction time is ⁇ 5 hours, such as 10 to 15 hours.
- the drying temperature is 80-180° C.
- the drying time is ⁇ 10 hours.
- the equipment used in the drying process may be a blast oven, a vacuum drying oven, a rotary kiln, a disc dryer, an oven, etc.
- the present disclosure also provides a positive electrode sheet, which includes the positive electrode material mentioned above.
- the positive electrode sheet includes a positive electrode current collector and an active material layer, wherein the active material layer is coated on at least one side surface of the positive electrode current collector, and the active material layer includes the above-mentioned positive electrode material.
- the positive electrode sheet includes a positive electrode current collector, a safety layer and an active material layer
- the safety layer is coated on at least one side surface of the positive electrode current collector
- the active material layer is coated on the surface of the safety layer
- the active material layer includes the above-mentioned positive electrode material
- the safety coating includes an iron-containing compound (such as lithium iron phosphate, Lithium phosphate), aluminum-containing compounds (such as alumina ceramics) and other non-conductive safety dielectric materials.
- an iron-containing compound such as lithium iron phosphate, Lithium phosphate
- aluminum-containing compounds such as alumina ceramics
- the active material layer further includes a conductive agent and a binder.
- the mass percentage of each component in the active material layer is: 70wt% to 99wt% of positive electrode material, 0.5wt% to 15wt% of conductive agent, and 0.5wt% to 15wt% of binder.
- the mass percentage of each component in the active material layer is: 80wt% to 98wt% of positive electrode material, 1wt% to 10wt% of conductive agent, and 1wt% to 10wt% of binder.
- the conductive agent is selected from at least one of conductive carbon black, acetylene black, Ketjen black, conductive graphite, carbon nanotubes (single-walled carbon nanotubes and/or multi-walled carbon nanotubes), and carbon fibers (such as conductive carbon fibers).
- the binder is selected from at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyacrylate lithium (PAA-Li).
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- PAA-Li polyacrylate lithium
- the present disclosure also provides a battery, wherein the battery comprises the above-mentioned positive electrode material, or the battery comprises the above-mentioned positive electrode sheet.
- the battery further includes a negative electrode sheet, a separator and an electrolyte.
- the electrolyte includes a lithium salt and an organic solvent.
- the organic solvent is selected from at least one of ethylene carbonate (abbreviated as EC), diethyl carbonate (abbreviated as DEC), propylene carbonate (abbreviated as PC), and fluoroethylene carbonate (abbreviated as FEC).
- EC ethylene carbonate
- DEC diethyl carbonate
- PC propylene carbonate
- FEC fluoroethylene carbonate
- the electrolyte further includes an additive, and the additive includes 2,4-butane sultone.
- the chemical structural formula of the 2,4-butane sultone is:
- the content of 2,4-butane sultone accounts for 0.1wt% to 10wt% of the total content of the electrolyte, for example, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, 2.2wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.8wt%, 3wt%, 3.3wt%, 3.5wt%, 3.8wt%, 4wt%, 4.2wt%, 4.5wt%, 4.8wt%, 5wt%, 6wt%, 7wt%,
- the additive helps to form a film, so that the cycle performance of the battery is improved to a certain extent.
- the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer, wherein the negative electrode active material layer is coated on at least one side surface of the negative electrode current collector, and the negative electrode active material layer includes a negative electrode active material, a conductive agent, and a binder.
- the mass percentage of each component in the negative electrode active material layer is: 70wt% to 99wt% of negative electrode active material, 0.5wt% to 15wt% of conductive agent, and 0.5wt% to 15wt% of binder.
- the mass percentage of each component in the negative electrode active material layer is: 80wt% to 98wt% of negative electrode active material, 1wt% to 10wt% of conductive agent, and 1wt% to 10wt% of binder.
- the negative electrode active material is selected from one or a combination of artificial graphite, natural graphite, hard carbon, mesophase carbon microbeads, lithium titanate, silicon carbon, and silicon oxide.
- the diaphragm is selected from a material with polypropylene as the base material, or a rubber-coated diaphragm with ceramic coated on one side or both sides thereof.
- the discharge capacity obtained is defined as C 0 mAh/g
- the discharge capacity in the voltage range from the start of discharge to 4.4V is defined as C 1 mAh/g
- the capacity in the voltage range of 3.8V-3.7V is defined as C 2
- the discharge capacity of this positive electrode material at 0.1C satisfies C 1 /C 0 ⁇ 9%, C 2 /C 0 ⁇ 25%.
- the present disclosure provides a positive electrode material and a positive electrode sheet and a battery including the positive electrode material.
- the positive electrode material has a special phase structure that is significantly different from conventional lithium cobalt oxide materials.
- the positive electrode material can show multiple small charge and discharge platforms during the charge and discharge process.
- the positive electrode material provided by the present disclosure has advantages in electrochemical performance, including: under the same charge and discharge cut-off voltage and charge and discharge rate conditions, the positive electrode material has higher gram capacity and cycle performance.
- the positive electrode material compound disclosed in the present disclosure has a higher gram capacity and better cycle performance.
- the battery disclosed herein due to the use of the positive electrode material disclosed herein, can have good cycle stability and higher gram capacity under higher voltage conditions such as 4.50V, and can meet the demand for lightweight use of high-end digital products.
- FIG. 1 is an XRD diagram of the positive electrode material of Example 1.
- FIG. 2 is a SEM image of the positive electrode material of Example 1.
- FIG. 3 is a SEM image of the positive electrode material of Example 6.
- FIG. 4 is a charge and discharge curve diagram of the button cell of Example 1.
- the cathode material provided in the present disclosure is used to characterize the characteristic peaks of the cathode material by X-ray diffraction (XRD), and is used to characterize the molar content of each element in the chemical formula by inductively coupled plasma spectrometer (ICP).
- XRD X-ray diffraction
- ICP inductively coupled plasma spectrometer
- the positive electrode material provided in the present disclosure is characterized by being assembled with a negative electrode sheet and an electrolyte into a full battery or a button battery.
- the preparation method of the positive electrode material comprises the following steps:
- the preparation method of the positive electrode active material comprises the following steps:
- the two substances were placed in a high-speed mixing device using the same stirring equipment as in the embodiment.
- the mixing program was set to mix at 300 rpm for 3 minutes, at 500 rpm for 5 minutes, and at 1000 rpm for 10 minutes.
- the mixture was taken out and it was confirmed that there were no white lithium carbonate spots in the mixture.
- the mixture was considered to be uniform;
- the preparation method of the positive electrode active material includes the following steps:
- the two substances were placed in a high-speed mixing device using the same stirring device as in the embodiment.
- the mixing program was set to mix at 300 rpm for 3 minutes, at 500 rpm for 5 minutes, and at 1000 rpm for 10 minutes. The mixture was taken out and it was confirmed that there were no white spots of lithium carbonate in the mixture. The mixture was considered to be uniform.
- step 1 The preparation method of the positive electrode material sample 18# is the same as that of Example 1, which will not be repeated here. The only difference is step 1:
- step 1 The preparation method of the positive electrode material sample 19# is the same as that of Example 1, which will not be repeated here. The only difference is step 1:
- Table 1 Chemical composition ratios of positive electrode materials and the amounts of raw materials used in Examples 1-11 and Comparative Examples 3-4
- the positive electrode materials prepared in the above embodiments and comparative examples are assembled into a lithium ion battery, which includes a positive electrode sheet, a negative electrode sheet, a separator between the positive electrode sheet and the negative electrode sheet, and an electrolyte.
- the charging cut-off voltage of the battery disclosed in the present invention is 4.5V.
- the preparation process of the lithium ion battery is as follows:
- the positive electrode material, conductive carbon black and PVDF were mixed in a weight ratio of 96%:2%:2% to obtain a positive electrode slurry by dispersion.
- the slurry was coated on an aluminum foil current collector and rolled to obtain a positive electrode sheet.
- EC ethylene carbonate
- DEC diethyl carbonate
- PC propylene carbonate
- FEC fluoroethylene carbonate
- LiPF 6 lithium hexafluorophosphate
- 2,4-butane sultone 2%.
- the prepared lithium-ion battery is subjected to a cycle performance test, and the cycle performance test process is as follows:
- the lithium-ion battery is charged to 4.50V at a constant current of 1C, then charged to 4.50V at a constant voltage of 0.05C, and then discharged to 3.0V at a discharge rate of 1C.
- This charge and discharge cycle is repeated 500 times.
- the discharge capacity at the first cycle and the discharge capacity at the 500th cycle are measured, and the capacity retention rate after the cycle is calculated.
- the calculation formula is:
- Capacity retention rate after cycles (discharge capacity at the 500th cycle)/(discharge capacity at the first cycle) ⁇ 100%.
- buttons-type batteries were assembled into button-type batteries after XRD testing.
- the preparation method of button cells is as follows:
- the positive electrode material is mixed with conductive carbon black (SP) and PVDF in a weight ratio of 80%:10%:10%, and a positive electrode slurry is obtained by dispersion.
- the slurry is coated on an aluminum foil current collector, and a positive electrode sheet is prepared by rolling.
- EC ethylene carbonate
- DEC diethyl carbonate
- PC propylene carbonate
- Fluorinated ethylene carbonate (abbreviated as FEC) accounting for 5% of the total mass of the electrolyte
- LiPF 6 lithium hexafluorophosphate
- 2,4-butane sultone accounting for 2% of the total content of the electrolyte
- Example 16a 2,4-butane sultone accounts for 0.1 wt% of the total content of the electrolyte
- Example 16b 2,4-butane sultone accounts for 10 wt% of the total content of the electrolyte
- Example 16d 2,4-Butane sultone accounts for 15 wt% of the total content of the electrolyte.
- the button cell After the button cell is made, it is left to stand for 4 hours under normal conditions, and then the first charge and discharge capacity test is carried out.
- the test conditions are: 0.1C charging to 4.5V, constant voltage charging to 0.025C, and then standing for 3 minutes, and then 0.1C discharge to 3.0V, and the first discharge capacity, first charge capacity, and first efficiency are recorded respectively.
- the discharge capacity obtained is defined as C 0 mAh/g
- the discharge capacity in the voltage range from the beginning of discharge to 4.4V is defined as C 1 mAh/g
- the capacity in the voltage range of 3.8V-3.7V is defined as C 2 in the discharge capacity
- C 1 /C 0 and C 2 /C 0 are calculated.
- the lithium-ion battery assembled with the positive electrode material prepared in the present disclosure can enable the lithium-ion battery to achieve a higher discharge capacity per gram under high voltage while taking into account excellent cycle performance, and can meet people's demand for thinner lithium-ion batteries.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
Claims (15)
- 一种正极材料,其特征在于,所述正极材料为包括Li元素、Na元素、K元素、Co元素以及可选地包括A元素和/或M元素的锂过渡金属氧化物,所述A元素选自B和P中的至少一种,所述M元素选自Al、Mg、Ti、Mn、Te、Ni、W、Nb、Zr、La和Y中的至少一种。
- 根据权利要求1所述的正极材料,其特征在于,单位摩尔正极材料中K元素的摩尔量为z,单位摩尔正极材料中Co元素的摩尔量为1-a-b,单位摩尔正极材料中A元素的摩尔量a,单位摩尔正极材料中M元素的摩尔量为b,所述z和1-a的比值为0<z/1-a<0.05。
- 根据权利要求1或2所述的正极材料,其特征在于,单位摩尔正极材料中K元素的摩尔量z为0<z<0.05;和/或,单位摩尔正极材料中Na元素的摩尔量y为0<y<0.03。
- 根据权利要求1-3任一项所述的正极材料,其特征在于,单位摩尔正极材料中A元素的摩尔量a为0≤a<0.05;和/或,单位摩尔正极材料中M元素的摩尔量b为0≤b<0.1。
- 根据权利要求1-4任一项所述的正极材料,其特征在于,所述正极材料的化学式为:Lin-y-zNayKzCo1-a-bAaMbO2,其中,0.95≤n≤1.02,0<y<0.03,0<z<0.05,0≤a<0.05,0≤b<0.1,且0<z/1-a<0.05。
- 根据权利要求1-5任一项所述的正极材料,其特征在于,所述正极材料具有O2相堆积结构,属于P63mc空间群。
- 根据权利要求1-6任一项所述的正极材料,其特征在于,所述正极材料具有多晶形貌或具有单晶形貌。
- 根据权利要求1-6任一项所述的正极材料,其特征在于,通过X射线衍射测试,所述正极材料至少包括002晶面(2θ=18.6°±0.5°)特征峰、102晶面(2θ=41.7°±0.5°)特征峰和103晶面(2θ=47.1°±0.5°)特征峰。
- 根据权利要求1-6任一项所述的正极材料,其特征在于,通过X射线衍射测试,所述正极材料的101晶面(2θ=38.2°±0.2°)特征峰和004晶面(2θ=37.6°±0.2°)特征峰的峰强度的比值m≥2。
- 根据权利要求1-9任一项所述的正极材料,其特征在于,所述正极材料的Dv50为12μm~20μm。
- 根据权利要求1-10任一项所述的正极材料,其特征在于,所述正极材料的克容量为≥210mAh/g。
- 一种正极片,所述正极片包括权利要求1-11任一项所述的正极材料。
- 一种电池,其特征在于,所述电池包括权利要求1-11任一项所述的正极材料,或者,所述电池包括权利要求12所述的正极片。
- 根据权利要求13所述的电池,其特征在于,所述电池在3.0~4.5V电压下,首次进行0.1C充放电时,得到的放电容量定义为C0mAh/g,从放电开始到4.4V电压范围内的放电容量定义为C1mAh/g,放电容量中3.8V~3.7V电压范围内的容量定义为C2,则此正极材料0.1C下的放电容量满足C1/C0≥9%,C2/C0≥25%。
- 根据权利要求13或14所述的电池,其特征在于,所述电池还包括电解液,所述电解液还包括添加剂,所述添加剂包括2,4-丁烷磺内酯;优选地,所述2,4-丁烷磺内酯的含量占电解液总含量的0.1wt%~10wt%。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP23884611.7A EP4542678A1 (en) | 2022-11-01 | 2023-10-18 | Positive electrode material, positive electrode sheet comprising same, and battery |
US18/922,257 US20250046813A1 (en) | 2022-11-01 | 2024-10-21 | Positive electrode material, and positive electrode plate and battery including positive electrode material |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211358612.9A CN116093271A (zh) | 2022-11-01 | 2022-11-01 | 一种正极材料及包括该正极材料的正极片和电池 |
CN202211358612.9 | 2022-11-01 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US18/922,257 Continuation US20250046813A1 (en) | 2022-11-01 | 2024-10-21 | Positive electrode material, and positive electrode plate and battery including positive electrode material |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2024093679A1 true WO2024093679A1 (zh) | 2024-05-10 |
Family
ID=86199821
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2023/125242 WO2024093679A1 (zh) | 2022-11-01 | 2023-10-18 | 一种正极材料及包括该正极材料的正极片和电池 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20250046813A1 (zh) |
EP (1) | EP4542678A1 (zh) |
CN (1) | CN116093271A (zh) |
WO (1) | WO2024093679A1 (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117747808A (zh) * | 2022-09-13 | 2024-03-22 | 珠海冠宇电池股份有限公司 | 一种正极材料及包括该正极材料的正极片和电池 |
CN116093271A (zh) * | 2022-11-01 | 2023-05-09 | 珠海冠宇电池股份有限公司 | 一种正极材料及包括该正极材料的正极片和电池 |
WO2025081483A1 (zh) * | 2023-10-20 | 2025-04-24 | 东莞新能源科技有限公司 | 一种正极材料、电化学装置和电子装置 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000294241A (ja) * | 1999-04-09 | 2000-10-20 | Mitsui Mining & Smelting Co Ltd | 非水電解液二次電池正極材料及びそれを用いた非水電解液二次電池 |
JP2000323140A (ja) * | 1999-05-17 | 2000-11-24 | Mitsui Mining & Smelting Co Ltd | 非水電解液二次電池正極材料及びそれを用いた非水電解液二次電池 |
CN105518912A (zh) * | 2013-07-11 | 2016-04-20 | 株式会社三德 | 用于非水电解质二次电池的正极活性材料以及使用所述正极活性材料的正极和二次电池 |
US20160141606A1 (en) * | 2014-11-19 | 2016-05-19 | Samsung Sdi Co., Ltd. | Positive active material for rechargeable lithium battery, method of preparing same, and rechargeable lithium battery including same |
US20160276665A1 (en) * | 2013-11-22 | 2016-09-22 | Mitsui Mining & Smelting Co., Ltd. | Spinel-Type Lithium Metal Composite Oxide |
CN112768687A (zh) * | 2021-01-21 | 2021-05-07 | 中国科学院长春应用化学研究所 | 锂位掺杂改性的锂离子电池用高镍低钴三元正极材料及其制备方法 |
CN113517418A (zh) * | 2021-06-25 | 2021-10-19 | 倪尔福 | 钠离子二次电池及其制备方法 |
CN114141999A (zh) * | 2021-10-26 | 2022-03-04 | 华中科技大学 | 耐高温高电压复合钴酸锂正极材料及其制备方法和应用 |
CN116093271A (zh) * | 2022-11-01 | 2023-05-09 | 珠海冠宇电池股份有限公司 | 一种正极材料及包括该正极材料的正极片和电池 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114613968A (zh) * | 2022-03-29 | 2022-06-10 | 珠海冠宇电池股份有限公司 | 一种正极材料及包括该正极材料的电池 |
-
2022
- 2022-11-01 CN CN202211358612.9A patent/CN116093271A/zh active Pending
-
2023
- 2023-10-18 WO PCT/CN2023/125242 patent/WO2024093679A1/zh active Application Filing
- 2023-10-18 EP EP23884611.7A patent/EP4542678A1/en active Pending
-
2024
- 2024-10-21 US US18/922,257 patent/US20250046813A1/en active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000294241A (ja) * | 1999-04-09 | 2000-10-20 | Mitsui Mining & Smelting Co Ltd | 非水電解液二次電池正極材料及びそれを用いた非水電解液二次電池 |
JP2000323140A (ja) * | 1999-05-17 | 2000-11-24 | Mitsui Mining & Smelting Co Ltd | 非水電解液二次電池正極材料及びそれを用いた非水電解液二次電池 |
CN105518912A (zh) * | 2013-07-11 | 2016-04-20 | 株式会社三德 | 用于非水电解质二次电池的正极活性材料以及使用所述正极活性材料的正极和二次电池 |
US20160276665A1 (en) * | 2013-11-22 | 2016-09-22 | Mitsui Mining & Smelting Co., Ltd. | Spinel-Type Lithium Metal Composite Oxide |
US20160141606A1 (en) * | 2014-11-19 | 2016-05-19 | Samsung Sdi Co., Ltd. | Positive active material for rechargeable lithium battery, method of preparing same, and rechargeable lithium battery including same |
CN112768687A (zh) * | 2021-01-21 | 2021-05-07 | 中国科学院长春应用化学研究所 | 锂位掺杂改性的锂离子电池用高镍低钴三元正极材料及其制备方法 |
CN113517418A (zh) * | 2021-06-25 | 2021-10-19 | 倪尔福 | 钠离子二次电池及其制备方法 |
CN114141999A (zh) * | 2021-10-26 | 2022-03-04 | 华中科技大学 | 耐高温高电压复合钴酸锂正极材料及其制备方法和应用 |
CN116093271A (zh) * | 2022-11-01 | 2023-05-09 | 珠海冠宇电池股份有限公司 | 一种正极材料及包括该正极材料的正极片和电池 |
Also Published As
Publication number | Publication date |
---|---|
EP4542678A1 (en) | 2025-04-23 |
US20250046813A1 (en) | 2025-02-06 |
CN116093271A (zh) | 2023-05-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11996555B2 (en) | Ternary cathode material, preparation method therefor, and lithium ion battery | |
JP6380608B2 (ja) | リチウム複合化合物粒子粉末の製造方法、リチウム複合化合物粒子粉末を非水電解質二次電池に用いる方法 | |
JP5879761B2 (ja) | リチウム複合化合物粒子粉末及びその製造方法、並びに非水電解質二次電池 | |
WO2020043140A1 (zh) | 三元正极材料及其制备方法、锂离子电池 | |
WO2022199389A1 (zh) | 硅氧复合负极材料及其制备方法、锂离子电池 | |
KR20180031556A (ko) | 구형 또는 구형-유사 리튬 이온 배터리 캐소드 재료 및 이의 제조 방법 및 적용 | |
US20250070159A1 (en) | Positive electrode active material and its use | |
CN114613992B (zh) | 一种正极材料、电池、电子设备 | |
WO2024093679A1 (zh) | 一种正极材料及包括该正极材料的正极片和电池 | |
CN114573041B (zh) | 一种正极材料的制备方法 | |
WO2023155930A1 (zh) | 锂离子电池正极材料及其制备方法 | |
CN117121235A (zh) | 锂二次电池正极活性材料和包含它的锂二次电池 | |
CN106910887A (zh) | 一种富锂锰基正极材料、其制备方法及包含该正极材料的锂离子电池 | |
WO2024119936A1 (zh) | 一种正极活性材料及其应用 | |
CN116470022A (zh) | 一种利用铈改性的钠离子电池层状正极材料及其制备方法 | |
JP2011249293A (ja) | リチウム遷移金属化合物及びその製造方法、並びにリチウムイオン電池 | |
WO2010126677A1 (en) | Lithium-ion electrochemical cell | |
WO2024146611A1 (zh) | 一种锂离子电池 | |
JP2025501057A (ja) | 正極活物質及びリチウムイオン電池 | |
CN115995550A (zh) | 一种正极活性材料及其应用 | |
CN113437285B (zh) | 一种钾离子二次电池正极材料及其制备方法和应用 | |
JP2006196293A (ja) | 非水系電解質二次電池用正極活物質の製造方法、非水系電解質二次電池用正極活物質および非水系電解質二次電池 | |
CN119400847B (zh) | 复合正极材料、正极极片和电池 | |
WO2024045937A1 (zh) | 一种正极活性材料及其应用 | |
WO2025123972A1 (zh) | 正极材料及正极浆料、锂离子电池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 23884611 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023884611 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2023884611 Country of ref document: EP Effective date: 20250116 |
|
WWP | Wipo information: published in national office |
Ref document number: 2023884611 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |