WO2022237327A1 - Procédé de dopage et de revêtement de matériau d'électrode positive ternaire, matériau d'électrode positive ternaire et batterie au lithium-ion - Google Patents

Procédé de dopage et de revêtement de matériau d'électrode positive ternaire, matériau d'électrode positive ternaire et batterie au lithium-ion Download PDF

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WO2022237327A1
WO2022237327A1 PCT/CN2022/082373 CN2022082373W WO2022237327A1 WO 2022237327 A1 WO2022237327 A1 WO 2022237327A1 CN 2022082373 W CN2022082373 W CN 2022082373W WO 2022237327 A1 WO2022237327 A1 WO 2022237327A1
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positive electrode
electrode material
ternary
ternary positive
silicate
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PCT/CN2022/082373
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English (en)
Chinese (zh)
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万江涛
张宁
张勇杰
刘满库
李子郯
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蜂巢能源科技股份有限公司
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Publication of WO2022237327A1 publication Critical patent/WO2022237327A1/fr

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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M4/50—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
    • 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 disclosure relates to the technical field of new energy, and relates to a doping and coating method of a ternary positive electrode material, a ternary positive electrode material and a lithium ion battery.
  • High-nickel ternary cathode materials with high specific capacity, high cycle stability and high safety have been a research hotspot in recent years.
  • Doping and coating modification are necessary means to realize the above-mentioned properties of high-nickel ternary cathode materials.
  • the best doping method is to add nano-metal oxides or hydroxides and mix them uniformly before calcining, which requires additional abrasives, mixing and other processes, the operation is complicated, and the mixing effect is average; while coating is also adding nano-metal element materials to mix and sinter , the operation is equally complicated; it is difficult to guarantee the uniformity of all batches.
  • Existing high-nickel materials are generally doped with zirconium, titanium, aluminum, tungsten, magnesium, scandium, vanadium, calcium, strontium, barium, gallium, indium, etc., which improves the structural stability and conductivity of the material to a certain extent.
  • metal oxides such as zirconium, titanium, aluminum, tungsten, magnesium, scandium, vanadium, calcium, strontium, barium, gallium, indium and other metal oxides, most of the material and electrolyte are isolated, which greatly reduces the gas production.
  • the present disclosure provides a method for doping and coating a ternary positive electrode material, the method comprising the following steps:
  • the amount of silicate used in step (1) accounts for 0.05% to 0.5% of the total mass of the inner core of the ternary positive electrode material, such as 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35% , 0.4% or 0.5%, etc.
  • the final doping effect can be regulated by adjusting the amount of doping metal source and silicate used in step (1).
  • the final coating effect can be regulated.
  • non-metal element silicon and other metal elements for example, at least one of calcium, magnesium, aluminum, titanium, tungsten, zirconium, scandium, etc.
  • metal elements for example, at least one of calcium, magnesium, aluminum, titanium, tungsten, zirconium, scandium, etc.
  • wash and dealkalize in a saturated silicate solution and at the same time carry out precipitation of various metal elements to achieve coating, to achieve the double effect of dealkalization and coating.
  • the whole doping and coating process is carried out in the solution by wet precipitation
  • the finished method saves cumbersome grinding and mixing operations, the method is simple to operate, the uniformity of doping and coating is guaranteed, and at the same time, it is beneficial to appropriately reduce the cost.
  • the prepared positive electrode material has a good doping and coating effect, which can effectively solve the problem of gas production, improve cycle performance, and have no abnormalities in electrical performance testing.
  • the method provided by an embodiment of the present disclosure is especially suitable for a high specific capacity, high cycle stability, high safety and high nickel ternary positive electrode material system.
  • ternary materials are unstable at the grain boundaries of the secondary particles after preparation and sintering. After multiple cycles, cracks first appear at the grain boundaries, and the electrolyte enters the interior of the crystal through the continuously generated cracks. Oxidation-reduction reactions occur rapidly in a short period of time, a large amount of gas is produced and new cracks continue to be generated in large quantities, and the performance of the battery also drops sharply, causing safety hazards. How to stabilize the crystal interface of polycrystalline high-nickel and delay the formation of cracks The process is also a problem that must be solved to ensure the high specific capacity, high cycle stability and high safety of high-nickel ternary cathode materials.
  • the silicate is used to stabilize the grain boundary between the primary particles of the positive electrode by co-doping with the silicate and the metal source, and after the dealkalization coating process is completed, the dehydrated silicate (such as lithium silicate) can automatically generate a better protective film during the drying process; saturated silicate solution can inhibit the reverse dissolution of silicate in the material, so the introduction of silicate doping and coating It further plays a role in stabilizing the material structure and enhancing the coating effect, and improves the safety performance and cycle performance of the material.
  • the dehydrated silicate such as lithium silicate
  • the doping metal in the doping metal source in step (1) includes at least one of calcium, magnesium, aluminum, titanium, tungsten, zirconium and scandium, and the doping metal in step (1)
  • the amount of the source accounts for 0.05%-0.5% of the total mass of the core of the ternary cathode material, such as 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4% or 0.5%.
  • the anion of the doping metal source is not limited, for example, it may be sulfate, nitrate or chloride.
  • the silicate in step (1) includes at least one of sodium silicate and lithium silicate.
  • the co-precipitation method can be carried out with reference to related technologies, and is not specifically limited.
  • the one-step co-precipitation method described in step (1) to prepare the ternary cathode material precursor includes:
  • the lye includes sodium hydroxide solution and/or potassium hydroxide solution.
  • the preparation concentration is 0.1mol/L ⁇ 1mol/L (such as 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.5mol/L, 0.7mol/L, 0.8mol/L or 1mol/L, etc. ) soluble nickel salt, cobalt salt, manganese salt mixed solution, the concentration described here is the total metal cation concentration in the mixed solution;
  • the molar ratio of nickel-cobalt-manganese is not particularly limited.
  • the molar content of nickel in the precursor is greater than or equal to 80%, it is called a high-nickel ternary positive electrode material precursor, and the prepared ternary positive electrode material is a high-nickel ternary positive electrode material.
  • the method of an embodiment of the present disclosure has a better effect on improving the electrochemical performance of the high-nickel ternary positive electrode material.
  • the preparation concentration is 5g/L ⁇ 50g/L (such as 5g/L, 6g/L, 8g/L, 10g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L L, 45g/L or 50g/L, etc.) doped metal source solution
  • the doped metal source can be a single type, also can be a combination of two or more, the type can be at least one of titanium, aluminum, magnesium, for example Sulphate, the concentration described here is the total metal cation concentration in the mixed solution;
  • the preparation concentration is 0.1mol/L ⁇ 1mol/L (such as 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.5mol/L, 0.7mol/L, 0.8mol/L or 1.0mol/L, etc.) Silicate solution, a single type of silicate, or a combination of two or more, the concentration described here is the total metal cation concentration in the mixed solution;
  • the strong base solution includes Sodium solution and/or potassium hydroxide solution;
  • the primary sintering temperature in step (1) is 650°C to 850°C, such as 650°C, 680°C, 700°C, 725°C, 750°C, 775°C, 800°C, 820°C, 840°C Or 850°C, etc.; the time for the primary sintering is 10h-20h, such as 10h, 12h, 13h, 15h, 16h, 18h, 19h or 20h.
  • the lithium source is used in an appropriate excess.
  • the molar ratio of the lithium source and the precursor of the ternary cathode material is 1.02 ⁇ 1.06, such as 1.02, 1.03, 1.04, 1.05 or 1.06.
  • the product obtained by the first sintering is crushed after the first sintering.
  • the metal elements in the metal salt include at least one of zirconium, titanium, aluminum, tungsten, magnesium, scandium, vanadium, calcium, strontium, barium, gallium and indium.
  • the amount of metal salt used accounts for 0.05% to 0.5% of the total mass of the inner core of the ternary positive electrode material, such as 0.05%, 0.08%, 0.1%, 0.15%, 0.2% %, 0.25%, 0.3%, 0.35%, 0.4%, 0.45% or 0.5%, etc.
  • the step of cleaning in step (2) includes: using a silicate saturated solution as the bottom liquid, mixing the inner core of the ternary positive electrode material with the bottom liquid, and the liquid-solid ratio is 1: 1 ⁇ 5:1 (such as 1:1, 2:1, 3:1, 3.5:1, 4:1 or 5:1, etc.), the mixing time is 20min ⁇ 60min (such as 20min, 25min, 30min, 35min, 40min , 45min, 50min, 55min or 60min, etc.), in the mixing process, the concentration of 10g/L ⁇ 50g/L (such as 10g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L or 50g/L, etc., where the concentration is the total metal cation concentration in the metal salt solution) for precipitation coating.
  • a silicate saturated solution such as 1:1, 2:1, 3:1, 3.5:1, 4:1 or 5:1, etc.
  • the mixing time is 20min ⁇ 60min (such as 20min, 25min, 30
  • the water content after dehydration in step (2) is less than 5wt%, such as 4.5wt%, 4wt%, 3wt%, 2.5wt%, 2wt%, 1wt% or 0.5wt%.
  • the water content after the dehydration in step (2) is 1wt%-5wt%.
  • the dehydration in step (2) is achieved by feeding nitrogen gas into the dehydration process.
  • a step of pre-drying is carried out after dehydration in step (2) and before secondary sintering, the temperature of the pre-drying is 150°C-220°C, such as 150°C, 160°C, 170°C, 180°C , 200°C, 210°C or 220°C, etc.; the pre-drying time is 3h to 12h, such as 3h, 4h, 5h, 6h, 8h, 9h, 10h, 11h or 12h; the pre-drying time is up to the moisture content of the material Less than 0.05wt%, such as 0.04wt%, 0.03wt% or 0.02wt%, etc.
  • the dehydrated silicate (such as lithium silicate) can automatically form a better protective film during the drying process, and a more stable protective film can be obtained by pre-drying under the above conditions.
  • the present disclosure does not specifically limit the equipment used for pre-drying, for example, a double-cone dryer may be used.
  • the atmosphere of the secondary sintering in step (2) is an oxygen-containing atmosphere
  • the temperature of the secondary sintering is 400°C to 700°C, such as 400°C, 450°C, 500°C, 550°C, 600°C °C, 650 °C or 700 °C, etc.
  • the time for the secondary sintering is 2h to 15h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 10h, 12h, or 15h.
  • the volume content of oxygen in the oxygen-containing atmosphere is greater than 80%, such as 82%, 85%, 90%, 95%, 98%, 99% or 100%.
  • the present disclosure provides a ternary positive electrode material prepared by the above method, the ternary positive electrode material includes a core of the ternary positive electrode material co-doped with silicon and doped metal elements, and is coated on the Metal oxides on the surface of the inner core.
  • the silicon element exists in the form of silicate.
  • the metal oxide coated on the surface of the inner core includes at least one of oxides of zirconium, titanium, aluminum, tungsten, magnesium, scandium, vanadium, calcium, strontium, barium, gallium and indium.
  • the total mass concentration of the doped element silicon and the doped metal element is 500ppm-5000ppm, such as 500ppm, 600ppm, 650ppm, 700ppm, 800ppm, 900ppm, 1000ppm, 1250ppm, 1500ppm , 1600ppm, 1800ppm, 2000ppm, 2300ppm, 2600ppm, 2800ppm, 3000ppm, 3500ppm, 3700ppm, 4000ppm, 4200ppm, 4500ppm or 5000ppm, etc.; 900ppm, 1000ppm, 1250ppm, 1500ppm, 1600ppm, 1800ppm, 2000ppm, 2300ppm, 2600ppm, 2800ppm, 3000ppm, 3500ppm, 3700ppm, 4000ppm, 4200ppm, 4500ppm or 5000ppm etc.
  • the mass concentration of the metal oxide coated on the surface of the inner core is 500ppm-5000ppm, such as 500ppm, 600ppm, 650ppm, 700ppm, 800ppm, 900ppm, 1000ppm, 1250ppm, 1500ppm ⁇ 1600ppm ⁇ 1800ppm ⁇ 2000ppm ⁇ 2300ppm ⁇ 2600ppm ⁇ 2800ppm ⁇ 3000ppm ⁇ 3500ppm ⁇ 3700ppm ⁇ 4000ppm ⁇ 4200ppm ⁇ 4500ppm ⁇ 5000ppm ⁇ ; ⁇ 500ppm ⁇ 5000ppm, ⁇ 500ppm ⁇ 600ppm ⁇ 650ppm ⁇ 700ppm ⁇ 800ppm , 900ppm, 1000ppm, 1250ppm, 1500ppm, 1600ppm, 1800ppm, 2000ppm, 2300ppm, 2600ppm, 2800ppm, 3000ppm, 3500ppm, 3700ppm, 4000ppm, 4200ppm, 4500ppm or 5000ppm, etc.
  • the present disclosure provides a lithium ion battery, including a positive electrode, a negative electrode and a separator, and the positive electrode adopts the above-mentioned ternary positive electrode material.
  • This embodiment provides a method for doping and covering a ternary positive electrode material, including the following steps:
  • Precursor synthesis first weigh soluble nickel salt, soluble cobalt salt and soluble manganese salt according to the molar ratio of 8:1:1 to prepare nickel-cobalt-manganese ternary mixed solution A (the total metal cation concentration in mixed solution A is 0.6mol /L); the zirconium chloride solution B of preparation 10g/L, the zirconium chloride in this solution B accounts for 0.2% of the gross mass of a sintered material H; the sodium silicate solution C of preparation 0.5mol/L, this solution C The sodium silicate in accounts for 0.2% of the total mass of one-fired material H;
  • Pre-drying Use a double-cone dryer to pre-dry at 150°C for 5 hours. After drying, put it into a sagger for secondary sintering.
  • Coating secondary sintering Weigh a certain amount of the pre-dried sample and calcinate at 700° C. for 8 hours in an oxygen atmosphere to obtain secondary sintering material I.
  • This embodiment provides a method for doping and covering a ternary positive electrode material, including the following steps:
  • Precursor synthesis first weigh soluble nickel salt, soluble cobalt salt and soluble manganese salt according to the molar ratio of 83:11:6 to prepare nickel-cobalt-manganese ternary mixed solution A (the total metal cation concentration in mixed solution A is 0.5mol /L); prepare 20g/L titanium nitrate solution B, the titanium nitrate in the solution B accounts for 0.15% of the total mass of the material H; prepare the sodium silicate solution C of 0.8mol/L, the silicic acid in the solution C Sodium accounts for 0.25% of the total mass of the first-fired material H;
  • the particle size is about 9.5um.
  • Pre-drying Use a double-cone dryer to pre-dry at 180°C for 5 hours. After drying, put it into a sagger for secondary sintering.
  • Coating secondary sintering Weigh a certain amount of the pre-dried sample and calcinate at 550° C. for 9 hours in an oxygen atmosphere to obtain secondary sintering material I.
  • Precursor synthesis first weigh soluble nickel salt, soluble cobalt salt and soluble manganese salt according to the molar ratio of 88:9:3 to prepare nickel-cobalt-manganese ternary mixed solution A (the total metal cation concentration in mixed solution A is 0.8mol /L); prepare 30g/L aluminum sulfate solution B, the aluminum sulfate in this solution B accounts for 0.15% of the gross mass of one-fired material H; prepare the lithium silicate solution C of 0.1mol/L, the silicon in this solution C Lithium acid accounts for 0.1% of the total mass of the first-fired material H;
  • the particle size is about 9.5um.
  • 3Dealkalization coating put the one-calcined material H in a three-in-one washing machine, add an appropriate amount of pure water to prepare a saturated lithium silicate solution, the liquid-solid ratio is 3:1, stir and wash for 50 minutes, and add 30g dropwise during the process /L zirconium chloride solution for precipitation coating, the zirconium chloride in the zirconium chloride solution accounts for 0.15% of the total mass of the first-fired material H, and then nitrogen gas is fed into it for rapid dehydration, and after dehydration, it is confirmed that the moisture content is less than 5wt%.
  • Pre-drying Use a double-cone dryer to pre-dry at 170°C for 6 hours. After drying, put it into a sagger for secondary sintering.
  • Coating secondary sintering Weigh a certain amount of the pre-dried sample and calcinate at 600° C. for 6 hours in an oxygen atmosphere to obtain secondary sintering material I.
  • This embodiment provides a method for doping and covering a ternary positive electrode material, including the following steps:
  • Precursor synthesis first weigh soluble nickel salt, soluble cobalt salt and soluble manganese salt according to the molar ratio of 8:1:1 to prepare nickel-cobalt-manganese ternary mixed solution A (the total metal cation concentration in mixed solution A is 0.6mol /L); the zirconium chloride solution B of preparation 20g/L, the zirconium chloride in this solution B accounts for 0.1% of the gross mass of a sintered material H; the lithium silicate solution C of preparation 0.5mol/L, this solution C Lithium silicate in accounts for 0.3% of the gross mass of one-fired material H;
  • Pre-drying use a double-cone dryer to pre-dry at 165°C for 8 hours. After drying, put it into a sagger for secondary sintering.
  • Coating secondary sintering Weigh a certain amount of the pre-dried sample and calcinate at 500° C. for 10 h in an oxygen atmosphere to obtain secondary sintering material I.
  • Example 1 The difference from Example 1 is that the sodium silicate in the solution C in step 1 accounts for 0.02% of the total mass of the first-fired material H.
  • Example 1 The difference from Example 1 is that the sodium silicate in the solution C in step 1 accounts for 1% of the total mass of the first-fired material H.
  • step 1. does not add sodium silicate.
  • Example 1 The difference from Example 1 is that the step 3 dealkalization coating is not carried out, but only water washing is carried out.
  • the positive electrode materials prepared in various examples and comparative examples were used to prepare positive electrode sheets, and assembled into all-electric soft packs for electrochemical performance testing, wherein the negative electrode active material was graphite, and the results are shown in Table 1. specific:
  • Discharge capacity test at 25°C, the charge rate is 0.33C, and the discharge rate is 0.33C.
  • Cycle test Under the condition of 25°C, the charge rate is 0.5C, the discharge rate is 1C, and the capacity retention rate after 600 cycles is tested.
  • Example 1 From the comparison between Example 1 and Examples 5-6, it can be seen that the amount of silicate added in the doping stage will affect the doping effect, and then affect the electrochemical performance of the ternary positive electrode material. If the amount of silicate used is too small, it will This will lead to a decrease in cycle performance, an increase in gas production, and a decrease in the first effect; if the amount of silicate is used too much, it will lead to a decrease in capacity and a decrease in the first effect.
  • Example 1 From the comparison of Example 1 and Comparative Example 1, it can be seen that if only metal is used for doping but no silicate is used for doping, the cycle will be deteriorated, the gas production will be increased, and the first effect will be reduced.
  • Example 1 From the comparison of Example 1 and Comparative Example 2, it can be seen that the present disclosure replaces conventional water washing by dealkalization coating, which is beneficial to improve cycle stability and reduce gas production.

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  • Electrochemistry (AREA)
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Abstract

La présente invention concerne un procédé de dopage et de revêtement de matériau d'électrode positive ternaire, un matériau d'électrode positive ternaire et une batterie au lithium-ion. Le procédé consiste à : préparer un précurseur de matériau d'électrode positive ternaire au moyen d'un procédé de co-précipitation en une étape, nettoyer un produit fritté à l'aide d'une solution saturée de silicate en tant que solution de base après la réalisation d'un frittage primaire, ajouter un sel métallique dans un procédé de nettoyage pour effectuer un revêtement par précipitation, et réaliser un frittage secondaire après déshydratation. Le procédé est simple en fonctionnement, l'uniformité de dopage et de revêtement est garantie, et en même temps, les coûts sont correctement réduits.
PCT/CN2022/082373 2021-05-12 2022-03-23 Procédé de dopage et de revêtement de matériau d'électrode positive ternaire, matériau d'électrode positive ternaire et batterie au lithium-ion WO2022237327A1 (fr)

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