WO2021120040A1 - 一种高密度铝掺杂氧化钴的制备方法 - Google Patents

一种高密度铝掺杂氧化钴的制备方法 Download PDF

Info

Publication number
WO2021120040A1
WO2021120040A1 PCT/CN2019/126213 CN2019126213W WO2021120040A1 WO 2021120040 A1 WO2021120040 A1 WO 2021120040A1 CN 2019126213 W CN2019126213 W CN 2019126213W WO 2021120040 A1 WO2021120040 A1 WO 2021120040A1
Authority
WO
WIPO (PCT)
Prior art keywords
aluminum
cobalt
doped
reaction
solution
Prior art date
Application number
PCT/CN2019/126213
Other languages
English (en)
French (fr)
Inventor
许开华
蒋振康
张爱青
李炳忠
王超
许东伟
Original Assignee
格林美（江苏）钴业股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 格林美（江苏）钴业股份有限公司 filed Critical 格林美（江苏）钴业股份有限公司
Priority to JP2022538225A priority Critical patent/JP7369298B2/ja
Priority to EP19956195.2A priority patent/EP4079691A4/en
Priority to KR1020227021476A priority patent/KR20220116461A/ko
Publication of WO2021120040A1 publication Critical patent/WO2021120040A1/zh
Priority to US17/842,761 priority patent/US12006228B2/en

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—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
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
    • 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
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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 preparation of cobalt oxide, and specifically relates to a method for preparing high-density aluminum doped cobalt oxide.
  • lithium-ion batteries As a new type of energy, lithium-ion batteries have the advantages of high energy, long life, low pollution, etc., and are widely used in mobile phones, computers, electric vehicles, national defense and other fields; 3C electronic products require lightness and compactness, and the corresponding batteries need to have high Energy density, the cathode material directly determines the performance of the final lithium-ion battery, and lithium cobalt oxide, as the most important cathode material for 3C electronic products, its energy density determines the energy density of the lithium-ion battery to a certain extent; high voltage Lithium cobalt oxide has the characteristics of high gram capacity, and has a higher energy density than conventional lithium cobalt oxide, which is the main direction of lithium cobalt oxide research and development in the future.
  • the present application provides a method for preparing high-density aluminum-doped cobalt oxide, which solves the problem of uneven aluminum doping and low tap density in the aluminum-doped cobalt oxide prepared by the prior art, resulting in the production of The cycle performance and charge-discharge performance of the battery are not good.
  • a method for preparing high-density aluminum doped cobalt oxide includes the following steps:
  • Step 1 Add the cobalt salt solution, lye and oxidant into the reactor for co-precipitation reaction.
  • D50 reaches 2.0-2.5 ⁇ m
  • D50 reaches 3.5-4.0 ⁇ m, Stop adding the aluminum-cobalt solution and keep other conditions unchanged and continue the reaction until the D50 reaches the required particle size, stop the reaction to obtain aluminum-containing cobalt oxyhydroxide slurry;
  • Step 2 The aluminum-containing cobalt oxyhydroxide slurry obtained in Step 2 is aged, dehydrated, washed, and dried to obtain aluminum-containing cobalt oxyhydroxide powder;
  • Step 3 calcining the aluminum-containing cobalt oxyhydroxide powder obtained in step 3 to obtain high-density aluminum-doped cobalt oxide.
  • the specific method is:
  • the D50 when the D50 reaches 3.5-4.0 ⁇ m, stop adding the aluminum-cobalt solution and continue adding the cobalt salt solution.
  • the overflowing slurry is thickened, and the supernatant is Exhaust, and return the thick slurry to the reactor to continue the reaction until the D50 reaches the required particle size, stop the reaction.
  • the feed rate of the cobalt salt solution is 220-260 L/h
  • the feed rate of the lye is 50-150 L/h
  • the feed rate of the oxidant is 20- 30L/h
  • the stirring speed during the feeding is 300-600rpm.
  • the concentration of cobalt ions in the cobalt salt solution is 120-140 g/L
  • the concentration of the liquid caustic soda is 80-150 g/L
  • the oxidant is in air, oxygen or hydrogen peroxide. At least one.
  • the concentration of cobalt in the aluminum-cobalt solution is 120-140 g/L, and the ratio of the concentration of cobalt ions to the concentration of aluminum ions in the aluminum-cobalt solution is 100:0.5-1.
  • the cobalt salt solution and the aluminum-cobalt solution both contain a complexing agent, and the ratio of the concentration of cobalt ions in the cobalt salt solution to the concentration of the complexing agent is 0.04-0.1; the cobalt ions in the aluminum-cobalt solution The ratio of the concentration of the complexing agent to the concentration of the complexing agent is 0.04-0.1.
  • the reaction kettle contains a bottom liquid with a pH value of 9.0-11.
  • the washing uses 80-90°C deionized water for washing, and the drying temperature is 120-180°C.
  • the calcination temperature is 500-750°C, and the calcination time is 10-20h.
  • the method further includes washing and drying the high-density aluminum-doped cobalt oxide obtained in step 3.
  • the present invention adopts a method of first adding a cobalt salt solution for co-precipitation reaction, and when a certain particle size is reached, then adding an aluminum-cobalt solution for co-precipitation reaction, so that the doped aluminum element can be perfectly embedded and oxidized.
  • the tap density and uniformity of aluminum-doped cobalt oxide are thereby effectively improved, and the cycle performance and charge-discharge performance of the battery are improved.
  • FIG. 1 is an XRD comparative analysis diagram of high-density aluminum-doped cobalt oxide and undoped cobalt oxide obtained in Example 1 of the present invention.
  • the present invention uses a laser particle size analyzer to measure the particle size in the process of producing aluminum-doped cobalt oxide and the particle size of the finally obtained aluminum-doped cobalt oxide particles.
  • the chemical reagents used in the embodiments of the present invention unless otherwise specified, All are obtained through conventional commercial channels.
  • An embodiment of the present invention provides a method for preparing high-density aluminum-doped cobalt oxide, and the method includes the following steps:
  • Step 1 Add the cobalt salt solution, lye and oxidant into the reactor containing the bottom solution with pH value of 9.0-11 for co-precipitation reaction.
  • D50 reaches 2.0-2.5 ⁇ m
  • stop adding the aluminum-cobalt solution and continue to add the cobalt salt solution.
  • the overflowing slurry is thickened, and the supernatant is outside
  • return the concentrated slurry to the reaction kettle to continue the reaction until the D50 reaches the required particle size, stop the reaction to obtain an aluminum-containing cobalt oxyhydroxide slurry;
  • the feed rate of the cobalt salt solution is 220-260L/h, preferably 240L/h; the feed rate of the lye is 50-150L/h, preferably 100L/h; the feed rate of the oxidant is 20 ⁇ 30L/h, preferably 245L/h; the stirring speed during the feeding is 300-600rpm, preferably 500rpm; the concentration of cobalt ion in the cobalt salt solution is 120-140g/L, preferably 130g/L
  • the concentration of the liquid caustic soda is 80-150g/L, preferably 100g/L, the oxidant is at least one of air, oxygen or hydrogen peroxide;
  • the cobalt salt is one of cobalt chloride, cobalt sulfate, and cobalt nitrate Species, preferably cobalt sulfate;
  • the aluminum salt in the aluminum cobalt solution is aluminum sulfate or aluminum nitrate, preferably aluminum sulfate; the ratio of the
  • Step 2 The aluminum-containing cobalt oxyhydroxide slurry obtained in Step 2 is aged, dehydrated, washed, and dried to obtain aluminum-containing cobalt oxyhydroxide powder; wherein the washing is performed with deionized water at 80-90°C, The drying temperature is 120-180°C;
  • Step 3 Calcining the aluminum-containing cobalt oxyhydroxide powder obtained in step 3 at 500-750°C for 10-20 hours to obtain high-density aluminum-doped cobalt oxide;
  • the method further includes washing and drying the high-density aluminum-doped cobalt oxide obtained in step 3.
  • the high-density aluminum-doped cobalt oxide provided by Embodiment 1 of the present invention is prepared through the following steps:
  • Step 1 Add the cobalt sulfate solution with a concentration of 130g/L, the lye with a concentration of 100g/L, and air at a stirring rate of 500rpm at a feed rate of 240L/h, 100L/h, and 25L/h.
  • Co-precipitation reaction is carried out in a reactor with pure water of 9.0-11.
  • an aluminum-cobalt sulfate solution with a ratio of cobalt ion concentration to aluminum ion concentration of 100:0.8 is added to the reaction system.
  • D50 reaches 3.8 ⁇ m, stop adding aluminum cobalt sulfate solution and continue adding cobalt sulfate solution.
  • Step 2 The aluminum-containing cobalt oxyhydroxide slurry obtained in Step 2 is aged, dehydrated, washed, and dried to obtain aluminum-containing cobalt oxyhydroxide powder;
  • the washing uses 80-90°C deionized water for washing, and the drying temperature is 150°C;
  • Step 3 The aluminum-containing cobalt oxyhydroxide powder obtained in step 3 was calcined at 600°C for 15 hours, washed with deionized water at 80-90°C, and dried at 150°C to obtain high-density aluminum doped oxidation cobalt.
  • the high-density aluminum-doped cobalt oxide provided by Embodiment 1 of the present invention is prepared through the following steps:
  • Step 1 Add the cobalt sulfate solution with a concentration of 130g/L, the lye with a concentration of 100g/L, and air at a stirring rate of 500rpm at a feed rate of 240L/h, 100L/h, and 25L/h.
  • Co-precipitation reaction is carried out in a reactor with pure water of 9.0-11.
  • an alumino-cobalt sulfuric acid solution with a ratio of the concentration of cobalt ions to the concentration of aluminum ions of 100:0.8 is added to the reaction system for reaction.
  • D50 reaches 3.5 ⁇ m, stop adding aluminum cobalt sulfate solution and continue adding cobalt sulfate solution.
  • Step 2 The aluminum-containing cobalt oxyhydroxide slurry obtained in Step 2 is aged, dehydrated, washed, and dried to obtain aluminum-containing cobalt oxyhydroxide powder;
  • the washing uses 80-90°C deionized water for washing, and the drying temperature is 150°C;
  • Step 3 The aluminum-containing cobalt oxyhydroxide powder obtained in step 3 was calcined at 500°C for 20 hours, washed with deionized water at 80-90°C, and dried at 150°C to obtain high-density aluminum-doped cobalt oxide .
  • the high-density aluminum-doped cobalt oxide provided by Embodiment 1 of the present invention is prepared through the following steps:
  • Step 1 Add the cobalt sulfate solution with a concentration of 130g/L, lye with a concentration of 100g/L, and air at a stirring rate of 500 rpm to add the pH value at a feed rate of 240L/h, 100L/h, and 25L/h.
  • the co-precipitation reaction is carried out in a reactor with a bottom solution of 9.0-11.
  • D50 reaches 2.5 ⁇ m
  • an aluminum-cobalt sulfate solution with a ratio of the concentration of cobalt ion to the concentration of aluminum ion of 100:0.8 is added to the reaction system.
  • the cobalt sulfate solution and the aluminum cobalt sulfate solution used both contain an ammonia complexing agent, and the ratio of the concentration of cobalt ion in the cobalt acid solution to the concentration of the ammonia complexing agent is 0.07; the cobalt in the aluminum cobalt sulfate solution The ratio of ion concentration to ammonia complexing agent concentration is 0.07;
  • Step 2 The aluminum-containing cobalt oxyhydroxide slurry obtained in Step 2 is aged, dehydrated, washed, and dried to obtain aluminum-containing cobalt oxyhydroxide powder;
  • the washing uses 80-90°C deionized water for washing, and the drying temperature is 150°C;
  • Step 3 The aluminum-containing cobalt oxyhydroxide powder obtained in step 3 was calcined at 750°C for 10 hours, washed with deionized water at 80-90°C, and dried at 150°C to obtain high-density aluminum doped oxidation cobalt.
  • the aluminum-doped cobalt oxide provided in this comparative example is prepared by the following method:
  • Step 1 Add the cobalt sulfate solution, liquid caustic soda and oxidant of the same concentration in Example 1 into the reactor containing the bottom liquid at the same feed rate and simultaneously add sodium metaaluminate.
  • the overflowing slurry is thickened, the supernatant is drained, and the thick slurry is returned to the reactor to continue the reaction until the D50 reaches the 5 ⁇ m particle size, the reaction is stopped.
  • Steps 2 and 3 are the same as those stated in Example 1, and finally aluminum-doped cobalt oxide is obtained.
  • the aluminum content, tap density, and specific surface area of the aluminum-doped cobalt oxide prepared in Example 1 to Example 3 and the comparative example were tested.
  • the test results are as follows:
  • the aluminum content in the aluminum-doped cobalt oxide obtained in the present invention is much greater than the aluminum content in the aluminum-doped cobalt oxide prepared in the comparative example.
  • the aluminum-doped cobalt oxide obtained in the present invention contains The tap density and specific surface area are much higher than the tap density and specific surface area of the aluminum-doped cobalt oxide obtained in the comparative example.
  • the aluminum-doped cobalt oxide obtained in the embodiment of the present invention and the aluminum-doped cobalt oxide obtained in the comparative example were respectively assembled into lithium cobalt oxide batteries, and their electrochemical performance was tested. The results are shown in the following table.
  • Table 1 is the test data of the specific discharge capacity and the capacity retention rate after cycling of the lithium cobalt oxide battery assembled by using the aluminum-doped cobalt oxide obtained in Examples 1-3 and the comparative example
  • the present invention adopts the method of adding cobalt salt solution for co-precipitation reaction, and then adding aluminum-cobalt solution for co-precipitation reaction when a certain particle size is reached, so that the doped aluminum element can be perfectly embedded in the cobalt oxide crystals.
  • the tap density of aluminum-doped cobalt oxide is as high as 2.36g/cm 3
  • the specific surface area is as high as 6.8m 2 /g, which effectively improves the tap density and uniformity of aluminum-doped cobalt oxide, and improves the battery’s Cycle performance, charge and discharge performance, and current density.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

一种高密度铝掺杂氧化钴的制备方法，该方法包括如下步骤：1)将钴盐溶液、碱液以及氧化剂加入反应釜中进行反应，当D50达到2.0～2.5μm后，向反应体系中加入铝钴溶液进行反应，当D50达到3.5～4.0μm后，停止加入铝钴溶液且保持其他条件不变继续反应直至D50达到所需粒径时，停止反应，获得含铝羟基氧化钴浆料；2)对上述含铝羟基氧化钴浆料进行陈化、脱水、洗涤、干燥，获得含铝羟基氧化钴粉末；3)对上述含铝羟基氧化钴粉末进行煅烧，获得目标物。通过采用上述制备方法，能够使得掺杂铝元素完美地嵌入氧化钴晶格中，从而有效的提高了铝掺杂氧化钴的振实密度和均匀性，提高电池的循环性能和充放电性能。

Description

一种高密度铝掺杂氧化钴的制备方法 技术领域
本发明属于氧化钴的制备技术领域，具体涉及一种高密度铝掺杂氧化钴的制备方法。
背景技术
作为新型能源的锂离子电池具有高能量、长寿命、低污染等优点，被广泛用于手机、计算机、电动车、国防等多种领域；3C电子产品要求轻便、小巧，相应的电池需要具备高能量密度，其中正极材料直接决定了最终锂离子电池的性能，而钴酸锂作为现在最主要的3C电子产品用正极材料，其能量密度在一定程度上决定了锂离子电池的能量密度；高电压钴酸锂具有高克容量的特性，相比常规钴酸锂具有更高的能量密度，是未来钴酸锂研究开发的主要方向。
发明内容
有鉴于此，本申请提供一种高密度铝掺杂氧化钴的制备方法，解决了现有技术制备得到的铝掺杂氧化钴中铝元素掺杂不均匀、振实密度低，从而导致制作成的电池的循环性能和充放电性能不佳的问题。
为达到上述目的，本发明的技术方案是这样实现的：一种高密度铝掺杂氧化钴的制备方法，该方法包括如下步骤：
步骤1、将钴盐溶液、碱液以及氧化剂加入反应釜中进行共沉淀反应，当D50达到2.0～2.5μm后，向反应体系中加入铝钴溶液进行反应，当D50达到3.5～4.0μm后，停止加入铝钴溶液且保持其他条件不变继续反应直至D50达到所需粒径时，停止反应，获得含铝羟基氧化钴浆料；
步骤2、对步骤2获得的含铝羟基氧化钴浆料进行陈化、脱水、洗涤、干燥，获得含铝羟基氧化钴粉末；
步骤3、对步骤3获得的含铝羟基氧化钴粉末进行煅烧，获得高密度铝掺杂氧化钴。
优选地，所述步骤1中，当D50达到3.5～4.0μm后，停止加入铝钴溶液且保持其他条件不变继续反应直至D50达到所需粒径时，停止反应，具体方法为：
优选地，当D50达到3.5～4.0μm后，停止加入铝钴溶液且继续加入钴盐溶液，当所述反应釜内的液位到达溢流后，对溢流出的浆料进行浓密，上清液外排，并将浓浆返回至所述反应釜中继续反应，直至D50达到所需粒径时，停止反应。
优选地，所述步骤1中，所述钴盐溶液的进料速度为220～260L/h，所述碱液的进料速度为50～150L/h，所述氧化剂的进料速度为20～30L/h，所述进料时的搅拌速度为300～600rpm。
优选地，所述步骤1中，所述钴盐溶液中钴离子的浓度为120～140g/L，所述液碱的浓度为80～150g/L，所述氧化剂为空气、氧气或双氧水中的至少一种。
优选地，所述步骤1中，所述铝钴溶液中钴的浓度为120～140g/L，所述铝钴溶液中钴离子的浓度与铝离子的浓度之比为100:0.5～1。
优选地，所述钴盐溶液和铝钴溶液中均含有络合剂，所述钴盐溶液中钴离子的浓度与络合剂的浓度之比为0.04～0.1；所述铝钴溶液中钴离子的浓度与络合剂的浓度之比为0.04～0.1。
优选地，所述步骤1中，所述反应釜中含有pH值为9.0～11的底液。
优选地，所述步骤2中，所述洗涤采用80～90℃的去离子水进行洗涤，所述干燥的温度为120～180℃。
优选地，所述步骤3中，所述煅烧的温度为500～750℃，煅烧的时间为10～20h。优选地，该方法还包括对步骤3获得的高密度铝掺杂氧化钴进行洗涤和烘干。
与现有技术相比，本发明通过采用先加入钴盐溶液进行共沉淀反应，待达到一定粒径时，再加入铝钴溶液进行共沉淀反应的方法，能够使得掺杂铝元素完美地嵌入氧化钴晶格中，从而有效的提高了铝掺杂氧化钴的振实密度和均匀性，提高电池的循环性能和充放电性能。
附图说明
图1是本发明实施例1获得的高密度铝掺杂氧化钴与未掺杂氧化钴的XRD对比分析图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合具体实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明采用激光粒度分析仪测定生成铝掺杂氧化钴过程中的颗粒粒径以及最终获得的铝掺杂氧化钴的颗粒的粒径，本发明实施例所使用的化学试剂，如无特殊说明，均通过常规商业途径获得。
本发明实施例提供的一种高密度铝掺杂氧化钴的制备方法，该方法包括如下步骤：
步骤1、将钴盐溶液、碱液以及氧化剂加入含有pH值为9.0～11的底液的反应釜中进行共沉淀反应，当D50达到2.0～2.5μm后，向反应体系中加入铝钴溶液进行反应，当D50达到3.5～4.0μm后，停止加入铝钴溶液且继续加入钴盐溶液，当所述反应釜内的液位到达溢流后，对溢流出的浆料进行浓密，上清液 外排，并将浓浆返回至所述反应釜中继续反应，直至D50达到所需粒径时，停止反应，获得含铝羟基氧化钴浆料；
其中，钴盐溶液的进料速度为220～260L/h，优选为240L/h；碱液的进料速度为50～150L/h，优选为100L/h；所述氧化剂的进料速度为20～30L/h，优选为245L/h；所述进料时的搅拌速度为300～600rpm，优选为500rpm；所述钴盐溶液中钴离子的浓度为120～140g/L，优选为130g/L；所述液碱的浓度为80～150g/L，优选为100g/L，所述氧化剂为空气、氧气或双氧水中的至少一种；钴盐为氯化钴、硫酸钴、硝酸钴中的一种，优选为硫酸钴；铝钴溶液中的铝盐为硫酸铝或硝酸铝，优选为硫酸铝；铝钴溶液中钴离子的浓度与铝离子的浓度之比为100:0.5～1，优选为100:0.85；所述钴盐溶液和铝钴溶液中均含有络合剂，所述钴盐溶液中钴离子的浓度与络合剂的浓度之比为0.04～0.1，优选为0.07；所述铝钴溶液中钴离子的浓度与络合剂的浓度之比为0.04～0.1，优选为0.07；络合剂为氨水、乙二胺、乙二胺四乙酸二钠、柠檬酸中的至少一种，优选为氨水。
步骤2、对步骤2获得的含铝羟基氧化钴浆料进行陈化、脱水、洗涤、干燥，获得含铝羟基氧化钴粉末；其中，所述洗涤采用80～90℃的去离子水进行洗涤，所述干燥的温度为120～180℃；
步骤3、在500～750℃下对步骤3获得的含铝羟基氧化钴粉末进行煅烧10～20h，获得高密度铝掺杂氧化钴；
进一步地，该方法还包括对步骤3获得的高密度铝掺杂氧化钴进行洗涤和烘干。
为了能够更好的解释本发明方案，下面结合具体实施例作进一步说明。
实施例1
本发明实施例1提供的一种高密度铝掺杂氧化钴是通过如下步骤制备得到的：
步骤1、在搅拌速率为500rpm将浓度为130g/L的硫酸钴溶液、浓度为100g/L的碱液以及空气分别以240L/h、100L/h、25L/h的进料速度加入含有pH值为9.0～11的纯水的反应釜中进行共沉淀反应，当D50达到2.2μm后，向反应体系中加入钴离子的浓度与铝离子的浓度之比为100:0.8的铝钴硫酸盐溶液进行反应，当D50达到3.8μm后，停止加入铝钴硫酸盐溶液且继续加入硫酸钴溶液，当所述反应釜内的液位到达溢流后，对溢流出的浆料进行浓密，上清液外排，并将浓浆返回至所述反应釜中继续反应，直至D50达到所需5μm粒径时，停止反应，获得含铝羟基氧化钴浆料；
其中，所用的硫酸钴溶液和铝钴硫酸盐溶液中均含有络合剂，硫酸钴溶液中钴离子的浓度与氨水络合剂的浓度之比为0.07；所述铝钴硫酸盐溶液中钴离子的浓度与氨水络合剂的浓度之比为0.07；
步骤2、对步骤2获得的含铝羟基氧化钴浆料进行陈化、脱水、洗涤、干燥，获得含铝羟基氧化钴粉末；
其中，洗涤采用80～90℃的去离子水进行洗涤，干燥的温度为150℃；
步骤3、在600℃下对步骤3获得的含铝羟基氧化钴粉末进行煅烧15h，，再采用80～90℃的去离子水进行洗涤，再150℃下进行干燥、获得高密度铝掺杂氧化钴。
实施例2
本发明实施例1提供的一种高密度铝掺杂氧化钴是通过如下步骤制备得到的：
步骤1、在搅拌速率为500rpm将浓度为130g/L的硫酸钴溶液、浓度为 100g/L的碱液以及空气分别以240L/h、100L/h、25L/h的进料速度加入含有pH值为9.0～11的纯水的反应釜中进行共沉淀反应，当D50达到2.0μm后，向反应体系中加入钴离子的浓度与铝离子的浓度之比为100:0.8的铝钴硫酸溶液进行反应，当D50达到3.5μm后，停止加入铝钴硫酸盐溶液且继续加入硫酸钴溶液，当反应釜内的液位到达溢流后，对溢流出的浆料进行浓密，上清液外排，并将浓浆返回至所述反应釜中继续反应，直至D50达到所需4μm粒径时，停止反应，获得含铝羟基氧化钴浆料；
其中，所用的硫酸钴溶液和铝钴硫酸盐溶液中均含有氨水络合剂，硫酸钴溶液中钴离子的浓度与氨水络合剂的浓度之比为0.07；所述铝钴硫酸盐溶液中钴离子的浓度与氨水络合剂的浓度之比为0.07；
步骤2、对步骤2获得的含铝羟基氧化钴浆料进行陈化、脱水、洗涤、干燥，获得含铝羟基氧化钴粉末；
其中，洗涤采用80～90℃的去离子水进行洗涤，干燥的温度为150℃；
步骤3、在500℃下对步骤3获得的含铝羟基氧化钴粉末进行煅烧20h，再采用80～90℃的去离子水进行洗涤，再150℃下进行干燥、获得高密度铝掺杂氧化钴。
实施例3
本发明实施例1提供的一种高密度铝掺杂氧化钴是通过如下步骤制备得到的：
步骤1、在搅拌速率为500rpm将浓度为130g/L的硫酸钴溶液、浓度为100g/L的碱液以及空气分别以240L/h、100L/h、25L/h的进料速度加入含有pH值为9.0～11的底液的反应釜中进行共沉淀反应，当D50达到2.5μm后，向反应体系中加入钴离子的浓度与铝离子的浓度之比为100:0.8的铝钴硫酸盐溶 液进行反应，当D50达到4μm后，停止加入铝钴硫酸盐溶液且继续加入硫酸钴溶液，当反应釜内的液位到达溢流后，对溢流出的浆料进行浓密，上清液外排，并将浓浆返回至所述反应釜中继续反应，直至D50达到所需6μm粒径时，停止反应，获得含铝羟基氧化钴浆料；
其中，所用的硫酸钴溶液和铝钴硫酸盐溶液中均含有氨水络合剂，酸钴溶液中钴离子的浓度与氨水络合剂的浓度之比为0.07；所述铝钴硫酸盐溶液中钴离子的浓度与氨水络合剂的浓度之比为0.07；
步骤2、对步骤2获得的含铝羟基氧化钴浆料进行陈化、脱水、洗涤、干燥，获得含铝羟基氧化钴粉末；
其中，洗涤采用80～90℃的去离子水进行洗涤，干燥的温度为150℃；
步骤3、在750℃下对步骤3获得的含铝羟基氧化钴粉末进行煅烧10h，，再采用80～90℃的去离子水进行洗涤，再150℃下进行干燥、获得高密度铝掺杂氧化钴。
为了验证通过本实施例制备得到的高密度铝掺杂氧化钴中铝元素是否均匀的掺杂至氧化钴中，现对实施例1获得的铝掺杂氧化钴以及未掺杂氧化钴进行XRD检测，如图1所示，从图1中可以看出，本发明获得的高密度铝掺杂氧化钴与未掺杂氧化钴的峰型完全吻合，且没有杂峰，表明本发明铝元素全部均匀的掺杂至氧化钴晶格中了。
对比例
本对比例提供的铝掺杂氧化钴通过以下方法制得：
步骤1，将实施例1中同浓度的硫酸钴溶液、液碱、氧化剂分别以相同的进料速度并流加入至含有底液的反应釜中，且同时加入偏铝酸钠，当所述反应釜内的液位到达溢流后，对溢流出的浆料进行浓密，上清液外排，并将浓浆返 回至所述反应釜中继续反应，直至D50达到5μm粒径时，停止反应，获得含铝羟基氧化钴浆料；
步骤2和步骤3均与实施例1中所陈述的相同，最终获得铝掺杂氧化钴。
对本实施例1-实施例3以及对比例制备得到的铝掺杂氧化钴中铝含量、振实密度以及比表面积进行测试，检测结果如下所示：
  铝含量/％ 振实密度(g/cm 3) 比表面积(m 2/g)
实施例1 0.54 2.36 5.76
实施例2 0.36 2.18 6.8
实施例3 0.45 2.45 5.6
对比例 0.25 1.58 3.08
从表1中的数据可知，本发明获得的铝掺杂氧化钴中铝的含量远大于对比例制备得到的铝掺杂氧化钴中铝的含量，此外，本发明获得的铝掺杂氧化钴的振实密度和比表面积远高于对比例获得的铝掺杂氧化钴的振实密度和比表面积。
检测例
将本发明实施例获得的铝掺杂氧化钴以及对比例获得的铝掺杂氧化钴分别组装成钴酸锂电池，并对其进行电化学性能检测，结果显示如下表。
表1为采用实施例1-3以及对比例获得的铝掺杂氧化钴组装成的钴酸锂电池的放电比容量以及循环后容量保持率的检测数据
Figure PCTCN2019126213-appb-000001
Figure PCTCN2019126213-appb-000002
综上所述，本发明通过采用先加入钴盐溶液进行共沉淀反应，待达到一定粒径时，再加入铝钴溶液进行共沉淀反应的方法，能够使得掺杂铝元素完美地嵌入氧化钴晶格中，使得铝掺杂氧化钴的振实密度高达2.36g/cm 3，比表面积高达6.8m 2/g，从而有效的提高了铝掺杂氧化钴的振实密度和均匀性，提高电池的循环性能、充放电性能以及电流密度。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求的保护范围为准。

Claims (10)

  1. 一种高密度铝掺杂氧化钴的制备方法，其特征在于，该方法包括如下步骤：
    步骤1、将钴盐溶液、碱液以及氧化剂加入反应釜中进行共沉淀反应，当D50达到2.0～2.5μm后，向反应体系中加入铝钴溶液进行反应，当D50达到3.5～4.0μm后，停止加入铝钴溶液且保持其他条件不变继续反应直至D50达到所需粒径时，停止反应，获得含铝羟基氧化钴浆料；
    步骤2、对步骤2获得的含铝羟基氧化钴浆料进行陈化、脱水、洗涤、干燥，获得含铝羟基氧化钴粉末；
    步骤3、对步骤3获得的含铝羟基氧化钴粉末进行煅烧，获得高密度铝掺杂氧化钴。
  2. 根据权利要求1所述的一种高密度铝掺杂氧化钴的制备方法，其特征在于，所述步骤1中，当D50达到3.5～4.0μm后，停止加入铝钴溶液且保持其他条件不变继续反应直至D50达到所需粒径时，停止反应，具体方法为：
    当D50达到3.5～4.0μm后，停止加入铝钴溶液且继续加入钴盐溶液，当所述反应釜内的液位到达溢流后，对溢流出的浆料进行浓密，上清液外排，并将浓浆返回至所述反应釜中继续反应，直至D50达到所需粒径时，停止反应。
  3. 根据权利要求2所述的一种高密度铝掺杂氧化钴的制备方法，其特征在于，所述步骤1中，所述钴盐溶液的进料速度为220～260L/h，所述碱液的进料速度为50～150L/h，所述氧化剂的进料速度为20～30L/h，所述进料时的搅拌速度为300～600rpm。
  4. 根据权利要求3所述的一种高密度铝掺杂氧化钴的制备方法，其特征在于，所述步骤1中，所述钴盐溶液中钴离子的浓度为120～140g/L，所述液碱的 浓度为80～150g/L，所述氧化剂为空气、氧气或双氧水中的至少一种。
  5. 根据权利要求4所述的一种高密度铝掺杂氧化钴的制备方法，其特征在于，所述步骤1中，所述铝钴溶液中钴的浓度为120～140g/L，所述铝钴溶液中钴离子的浓度与铝离子的浓度之比为100:0.5～1。
  6. 根据权利要求5所述的一种高密度铝掺杂氧化钴的制备方法，其特征在于，所述钴盐溶液和铝钴溶液中均含有络合剂，所述钴盐溶液中钴离子的浓度与络合剂的浓度之比为0.04～0.1；所述铝钴溶液中钴离子的浓度与络合剂的浓度之比为0.04～0.1。
  7. 根据权利要求6所述的一种高密度铝掺杂氧化钴的制备方法，其特征在于，所述步骤1中，所述反应釜中含有pH值为9.0～11的底液。
  8. 根据权利要求7所述的一种高密度铝掺杂氧化钴的制备方法，其特征在于，所述步骤2中，所述洗涤采用80～90℃的去离子水进行洗涤，所述干燥的温度为120～180℃。
  9. 根据权利要求8所述的一种高密度铝掺杂氧化钴的制备方法，其特征在于，所述步骤3中，所述煅烧的温度为500～750℃，煅烧的时间为10～20h。
  10. 根据权利要求1-9任意一项所述的一种高密度铝掺杂氧化钴的制备方法，其特征在于，该方法还包括对步骤3获得的高密度铝掺杂氧化钴进行洗涤和烘干。
PCT/CN2019/126213 2019-12-17 2019-12-18 一种高密度铝掺杂氧化钴的制备方法 WO2021120040A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2022538225A JP7369298B2 (ja) 2019-12-17 2019-12-18 高密度なアルミニウムドープ酸化コバルトの調製方法
EP19956195.2A EP4079691A4 (en) 2019-12-17 2019-12-18 PROCESS FOR PREPARING HIGH-DENSITY ALUMINUM-DOPED COBALT OXIDE
KR1020227021476A KR20220116461A (ko) 2019-12-17 2019-12-18 고밀도 알루미늄이 도핑된 산화코발트의 제조 방법
US17/842,761 US12006228B2 (en) 2019-12-17 2022-06-16 Preparation method for high density aluminum doped cobalt oxide

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201911303146.2 2019-12-17
CN201911303146.2A CN112993243A (zh) 2019-12-17 2019-12-17 一种高密度铝掺杂氧化钴的制备方法

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US17/842,761 Continuation US12006228B2 (en) 2019-12-17 2022-06-16 Preparation method for high density aluminum doped cobalt oxide

Publications (1)

Publication Number Publication Date
WO2021120040A1 true WO2021120040A1 (zh) 2021-06-24

Family

ID=76342438

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/126213 WO2021120040A1 (zh) 2019-12-17 2019-12-18 一种高密度铝掺杂氧化钴的制备方法

Country Status (6)

Country Link
US (1) US12006228B2 (zh)
EP (1) EP4079691A4 (zh)
JP (1) JP7369298B2 (zh)
KR (1) KR20220116461A (zh)
CN (1) CN112993243A (zh)
WO (1) WO2021120040A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113697865A (zh) * 2021-08-27 2021-11-26 湖南中伟新能源科技有限公司 一种四氧化三钴及其制备方法和锂离子电池
CN113772746A (zh) * 2021-09-01 2021-12-10 荆门市格林美新材料有限公司 一种高振实掺铝小粒径四氧化三钴的制备方法
CN115465898A (zh) * 2022-09-19 2022-12-13 陕西红马科技有限公司 一种仿生法制备空心球四氧化三钴的方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113800572B (zh) * 2021-08-24 2023-09-15 南通金通储能动力新材料有限公司 一种表面致密内部疏松的羟基氧化钴及其制备方法
CN114988489B (zh) * 2022-05-30 2023-11-21 荆门市格林美新材料有限公司 一种氧化亚钴及其制备方法和应用
CN114873652B (zh) * 2022-06-02 2023-06-20 兰州理工大学 一种高振实密度钴氧化物的制备方法
CN114940515B (zh) * 2022-06-15 2023-11-03 荆门市格林美新材料有限公司 一种铝掺杂的碳酸钴及其制备方法和应用
CN116426144A (zh) * 2022-12-29 2023-07-14 北京星驰恒动科技发展有限公司 耐辐照热控填料和防静电热控涂层及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020024041A1 (en) * 2000-07-14 2002-02-28 Matsushita Electric Industrial Co., Ltd Method for producing a positive electrode active material for an alkaline storage battery
EP2824200A1 (en) * 2012-03-05 2015-01-14 Sunshine Kaidi New Energy Group Co., Ltd Process for the comprehensive recovery of metal cobalt, ruthenium and aluminum from waste catalyst co-ru/al2o3 in fischer-tropsch synthesis
CN107863525A (zh) * 2017-10-23 2018-03-30 兰州金川新材料科技股份有限公司 一种梯度掺杂钴酸锂的制备方法
CN108298596A (zh) * 2018-04-03 2018-07-20 兰州金川新材料科技股份有限公司 一种大粒度掺杂四氧化三钴的制备方法
US20190169042A1 (en) * 2016-12-21 2019-06-06 Lg Chem, Ltd. Metal-doped cobalt precursor for preparing positive electrode active material for secondary battery
CN110071275A (zh) * 2019-04-23 2019-07-30 金川集团股份有限公司 一种包覆金属四氧化三钴的制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4305613B2 (ja) 2001-08-03 2009-07-29 戸田工業株式会社 非水電解質二次電池用正極活物質並びに非水電解質二次電池
DE60232570D1 (de) * 2001-08-03 2009-07-23 Toda Kogyo Corp Aktives Kathodenmaterial aus Kobaltoxidpartikeln für nicht-wässrige-Elektrolyt-Sekundärzelle und Herstellungsverfahren dafür, und nicht-wässrige-Elektrolyt-Sekundärzelle
CN108217753B (zh) * 2016-12-14 2020-07-28 天津国安盟固利新材料科技股份有限公司 一种梯度掺杂四氧化三钴材料及其制备方法
CN108011101B (zh) * 2017-11-28 2020-04-03 衢州华友钴新材料有限公司 一种大粒径均匀掺铝四氧化三钴的制备方法
CN108649219B (zh) * 2018-05-14 2021-09-24 荆门市格林美新材料有限公司 一种大粒径掺铝四氧化三钴的制备方法
CN109354075B (zh) * 2018-09-30 2020-10-09 衢州华友钴新材料有限公司 一种小粒径均匀掺铝球形四氧化三钴的制备方法
CN109411749B (zh) * 2018-10-30 2020-10-09 中伟新材料股份有限公司 掺Al大颗粒四氧化三钴以及其制备方法
CN110078132A (zh) * 2019-04-23 2019-08-02 金川集团股份有限公司 一种间歇性包覆制备掺杂四氧化三钴的方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020024041A1 (en) * 2000-07-14 2002-02-28 Matsushita Electric Industrial Co., Ltd Method for producing a positive electrode active material for an alkaline storage battery
EP2824200A1 (en) * 2012-03-05 2015-01-14 Sunshine Kaidi New Energy Group Co., Ltd Process for the comprehensive recovery of metal cobalt, ruthenium and aluminum from waste catalyst co-ru/al2o3 in fischer-tropsch synthesis
US20190169042A1 (en) * 2016-12-21 2019-06-06 Lg Chem, Ltd. Metal-doped cobalt precursor for preparing positive electrode active material for secondary battery
CN107863525A (zh) * 2017-10-23 2018-03-30 兰州金川新材料科技股份有限公司 一种梯度掺杂钴酸锂的制备方法
CN108298596A (zh) * 2018-04-03 2018-07-20 兰州金川新材料科技股份有限公司 一种大粒度掺杂四氧化三钴的制备方法
CN110071275A (zh) * 2019-04-23 2019-07-30 金川集团股份有限公司 一种包覆金属四氧化三钴的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4079691A4 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113697865A (zh) * 2021-08-27 2021-11-26 湖南中伟新能源科技有限公司 一种四氧化三钴及其制备方法和锂离子电池
CN113772746A (zh) * 2021-09-01 2021-12-10 荆门市格林美新材料有限公司 一种高振实掺铝小粒径四氧化三钴的制备方法
CN115465898A (zh) * 2022-09-19 2022-12-13 陕西红马科技有限公司 一种仿生法制备空心球四氧化三钴的方法
CN115465898B (zh) * 2022-09-19 2024-01-30 陕西红马科技有限公司 一种仿生法制备空心球四氧化三钴的方法

Also Published As

Publication number Publication date
CN112993243A (zh) 2021-06-18
JP7369298B2 (ja) 2023-10-25
KR20220116461A (ko) 2022-08-23
EP4079691A1 (en) 2022-10-26
JP2023507209A (ja) 2023-02-21
US12006228B2 (en) 2024-06-11
US20220315444A1 (en) 2022-10-06
EP4079691A4 (en) 2024-01-17

Similar Documents

Publication Publication Date Title
WO2021120040A1 (zh) 一种高密度铝掺杂氧化钴的制备方法
CN108172799A (zh) 一种核壳结构锂离子电池的三元正极材料及其制备方法
CN103972499B (zh) 一种改性的镍钴铝酸锂正极材料及其制备方法
CN111916727B (zh) 一种双离子湿法掺杂的三元高镍正极材料及其制备方法
CN104900869B (zh) 碳包覆镍钴铝三元正极材料的制备方法
CN108134064B (zh) 一种正极材料前驱体及其制备方法和正极材料
CN109301189B (zh) 一种类单晶型高镍多元材料的制备方法
CN108899480A (zh) 一种长循环寿命高比容量镍钴铝正极材料及其制备方法
CN113793927B (zh) 一种锂离子电池三元正极材料及其制备方法
EP4234498A1 (en) Doped high-nickel ternary material and preparation method therefor
CN105374997B (zh) 一种复合材料包覆镍锰酸锂的制备方法
CN111916701B (zh) 一种包覆型正极材料及其制备方法和用途
CN103715422B (zh) 电解法制备锂离子电池的高镍系正极材料的方法
WO2022237393A1 (zh) 磷酸铁锂的制备方法
CN109616658B (zh) 一种硒、硫酸根共掺杂高镍正极材料及其制备方法和应用
CN103746108A (zh) 空心镍锰酸锂结构掺杂锂离子电池正极材料的制备方法
CN109065864B (zh) 碳/氧化锡/石墨烯复合材料及其制备方法和应用
CN112713263B (zh) 一种偏磷酸盐包覆钴酸锂材料的制备方法及包含其的锂离子电池
CN111446416B (zh) 多级结构相结TiO2复合石墨烯负极材料的制备及应用
CN116750809A (zh) 一种改性的三元正极材料及其制备方法
WO2023071411A1 (zh) 掺杂型磷酸钒钠及其制备方法和应用
CN115974153A (zh) 一种低温制备含有氧缺陷氧化钒的方法
CN105895893B (zh) 一种锂钼钒氧化物锂离子电池正极材料及其制备方法
CN105047923A (zh) 一种锂离子电池负极材料钒酸铜锂及其制备方法
CN111675249A (zh) 一种铜负载三元纳米带正极材料的制备方法及其产品和应用

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: 19956195

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022538225

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2019956195

Country of ref document: EP

Effective date: 20220718