WO2006136050A1 - Oxyde de lithium composite a composants multiples contenant du nickel et du cobalt, procede pour sa fabrication, son utilisation en tant que matiere active d'electrode positive pour une batterie secondaire au lithium et pile secondaire au lithium - Google Patents

Oxyde de lithium composite a composants multiples contenant du nickel et du cobalt, procede pour sa fabrication, son utilisation en tant que matiere active d'electrode positive pour une batterie secondaire au lithium et pile secondaire au lithium Download PDF

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WO2006136050A1
WO2006136050A1 PCT/CN2005/000884 CN2005000884W WO2006136050A1 WO 2006136050 A1 WO2006136050 A1 WO 2006136050A1 CN 2005000884 W CN2005000884 W CN 2005000884W WO 2006136050 A1 WO2006136050 A1 WO 2006136050A1
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cobalt
nickel
positive electrode
lithium
oxide
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PCT/CN2005/000884
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Chinese (zh)
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Song Sheng Fang
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Shenzhen Bak Battery Co., Ltd
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Priority to PCT/CN2005/000884 priority Critical patent/WO2006136050A1/fr
Publication of WO2006136050A1 publication Critical patent/WO2006136050A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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
    • C01P2006/40—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
    • 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
    • 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 relates to the field of high energy electrochemistry, and in particular to a multicomponent oxide containing cobalt and nickel, a preparation method thereof and the use thereof in a lithium ion secondary battery.
  • lithium cobalt oxide has been the first choice for commercial lithium ion battery cathode materials due to its excellent properties, such as high specific capacity, good cycle performance and excellent processing behavior.
  • cobalt is a rare metal, and its resources are scarce.
  • a new cathode material that is more energy efficient, environmentally friendly, and long lasting.
  • the phase reaction method is a process in which the material to be reacted is mixed by machine grinding, and then it is sintered.
  • One of the outstanding advantages of this method is that the industrialization is simple and the production process cost is not high.
  • the disadvantage is that the precursor material is difficult to mix uniformly, resulting in uneven product composition and performance, especially when the reaction components are large.
  • the material is easy to freeze during pulping, and the slurry storage time is not frozen for a short time; the compactness of the pole piece is low, and the formed pole piece is hard, particularly brittle and easily broken, so that the volume specific energy of the material Lower, poor processing behavior.
  • the object of the present invention is to provide a cobalt-nickel-containing multicomponent oxide Li a (Ni b Co c ) M ⁇ having a uniform particle size distribution and a high volume specific energy of the material. c 0 2 .
  • Another object of the present invention is to provide a cobalt-nickel-containing multicomponent oxide having a simple preparation process and high handleability.
  • Li a (Ni b Co c ) M 1-bc 0 2 is prepared by using the multi-component oxide prepared above as a positive electrode material, and the prepared slurry has good fluidity and uniformity, and the slurry is stored. The freezing time is long, the processing behavior of the pole piece is good, and the cycle performance and capacity retention of the battery can be improved.
  • Multi-component oxide containing cobalt and nickel The preparation method comprises the following steps:
  • Ni-Co-M composite hydroxide Forming a Ni-Co-M composite hydroxide, aging, separating, washing, and drying to obtain a precursor
  • step (e) Heat treatment step
  • the product obtained in the step (d) is a lithium composite oxide having a heat treatment temperature of 650 to 850 ° C and a heat treatment time of 5 to 18 hours.
  • the metal M salt is at least one metal oxide selected from the group consisting of iron (Fe;), aluminum (Al), manganese (Mn), titanium (Ti), copper (Cu), and calcium (Ca) or a metal salt thereof.
  • the buffer solution consists of ammonia and an amine salt or ammonia and a weak acid.
  • the pH of the buffer solution in the step (a) is 8-11.
  • the temperature of the coprecipitation reaction in the step (b) is 40-80 ° C, and the stirring speed of the stirrer during the reaction is At 240-1 OOO rpm, the pH of the solution during the reaction is 10-12, and the time of the coprecipitation reaction is 4-10 hours.
  • the above-mentioned cobalt-nickel-containing multi-component oxide is used as a positive electrode material of a lithium ion secondary battery.
  • a lithium ion battery comprising a positive electrode sheet, and a positive electrode active material on the positive electrode sheet contains the above-mentioned cobalt-nickel-containing multicomponent oxide.
  • the preparation method of the invention adopts the coprecipitation reaction, the element components of the material are mixed at the atomic level to form an ellipsoidal particle having a uniform particle size, and is easy to be separated, and can be obtained by coprecipitation after washing, precipitation and sintering.
  • the resulting ellipsoidal particles are similar in particle uniformity.
  • the XRD test results show that the active material is a layered structure, the crystal form is well developed, and no other impurity peaks appear, that is, the doped ions are distributed in the layered crystal structure.
  • the results of SEM test show that the particle size distribution of the material is uniform, and it is an ellipsoidal structure with an average particle size of 5-16 ⁇ ⁇ and a tap density of 2.15-2.35g/cm 3 .
  • the multi-component oxide containing cobalt and nickel is used.
  • the prepared slurry has good fluidity and uniformity, and the slurry storage time is long, and the processing behavior of the pole piece is good.
  • the electrochemical performance test shows that the cycle performance, capacity retention and processing behavior of the pole piece are all There is a great improvement, and the specific capacity is also improved. 3.
  • the preparation method is not only simple in process, but also has the characteristics of high process operability, good production repeatability, good product uniformity, easy to realize industrialization, and relatively low cost. low.
  • Fig. 1 is an X-ray diffraction chart (XRD) of a positive electrode active material for a lithium ion secondary battery prepared in Example 1.
  • XRD X-ray diffraction chart
  • FIG. 2 is a scanning electron micrograph (SEM:) of a positive electrode active material of a lithium ion secondary battery prepared in Example 1.
  • 3 is a graph showing the first charge and discharge curves of the positive electrode active material of the lithium ion secondary battery prepared in Example 1.
  • 4 is a graph showing charge and discharge cycle performance of a lithium ion secondary battery positive electrode active material prepared in Example 1.
  • a method for preparing a multi-component oxide containing cobalt and nickel is to prepare a mixed solution of nickel-cobalt and metal M with ammonia in an ammonia-amine salt or an ammonia-weak acid buffer solution having a pH of 8-11, and then Simultaneously adding to the reaction kettle simultaneously with the lye to carry out a coprecipitation reaction, wherein the coprecipitation reaction time is 4-10 hours, the reaction temperature is 40-80 ° C, and the stirring speed is 240-1000 rpm to form a Ni-Co-M composite.
  • Ni-Co-M composite hydroxide Hydroxide, aging, separation and washing of Ni-Co-M composite hydroxide, to obtain ellipsoidal Ni-Co-M composite hydroxide particles with uniform particle size, high density and excellent electrochemical performance; Drying the Ni-Co-M composite hydroxide particles in an air atmosphere at a drying temperature of 60-120 Torr or under vacuum for 16-36 hours, mixing with lithium hydroxide or lithium salt, and heat-treating the mixture at 240-550 Torr. 3-7 hours; then heat-treating the mixture at 650-850 Torr for 5-18 hours to obtain a multi-component oxide containing cobalt nickel.
  • the reaction is incomplete.
  • the reaction is completed after a long time (>10h). Prolonging the reaction time reduces the production efficiency.
  • the stirring speed is too slow ( ⁇ 240ipm), the mixing is uneven, and the reaction is not complete. If the stirring speed is too fast (>1000 rpm), the particles of the generated material will be too fine, which will affect the structure of the product. If the temperature during sintering is lower than 650'C, the material will be incompletely sintered and the crystallization will be incomplete. If it is higher than 85CTC, the structure will be destroyed.
  • Example 1 Positive active material Preparation and performance structure testing
  • Nickel (Ni) was taken at a molar ratio of 0.75:0.1, and a total of 8.5 moles of cobalt (Co) sulfate was slowly stirred under constant stirring.
  • Add 10L of nickel-cobalt-ammonium complex solution by adding ammonia and ammonium sulfate to a buffer solution of pH 10, and mix it with 10L, 2.2M NaOH and 0.1M A1 2 (S04) 3 with constant stirring.
  • the mixed aqueous solution was slowly dropped into a reaction vessel containing 7 L of an aqueous solution and adjusted to a pH of 11 with a 2.2 M pure NaOH solution at a reaction temperature of 40 V and a stirring speed of 400 rpm.
  • Ni-Co-Al composite hydroxide was separated, aged for 2 hours, washed with distilled water several times, dried at 80 ° C for 16 hours, ground and sieved to obtain a precursor, and the water was accurately measured and carbonated.
  • the structure and morphology test results of the product obtained in this example The XRD pattern is shown in Figure la, similar to the XRD pattern of LiCo0 2 , the peak intensity ratio of 1003/1104 is as high as 1.9 or more, the structural peaks 006 and 102 and the peaks 008 and 110 Both tend to exist as independent peaks, so it can be considered that the synthesized product has a layered structure and the crystal form is well developed, the structure is complete, and the defects are few.
  • the SEM spectrum showed that the particle shape of the synthesized product was ellipsoidal, the size was uniform, the average particle size was 5-16 ⁇ ⁇ , and the tap density of the powder was 2.19 g/cm 3 .
  • the electrochemical performance of the product has been tested on a button cell made with a Xinwei low current tester.
  • the negative electrode of the button battery is metal lithium
  • the separator is glass fiber filter paper
  • the positive electrode is made of synthetic product.
  • the positive electrode sheet is prepared similarly to the large battery pole piece method, that is, 92 parts of the product of the invention, 4 parts of conductive agent, and sticky
  • the mixture of 4 parts of polyvinylidene fluoride (PVdF) and a suitable amount of solvent N-methylpyrrolidone (NMP) was mixed and stirred to obtain a paddle, and then coated on aluminum foil with a single side of about 160 um thick, dried, compacted.
  • PVdF polyvinylidene fluoride
  • NMP solvent N-methylpyrrolidone
  • the battery was charged to 4.3 volts at a constant current of 0.1 C, and discharged at a constant current of 0.1 C to 2.75 volts after constant voltage charging at 4.3 V.
  • the first charge specific capacity of the positive electrode material of the present invention was measured to be 196.2258 mAh/g, and the first discharge specific capacity was 167.2495.
  • Example 2 Positive active material Preparation and performance structure test molar ratio of 0.85:0.1:0.02:0.01 Take nickel (Ni), cobalt (Co), manganese (Mn), copper (Cu) sulfate total 9.8 moles slowly added under constant stirring conditions 10L of nickel, cobalt, manganese, copper and ammonia mixed complex solution was prepared from a buffer solution of pH 9 prepared by ammonia water and ammonium sulfate. There was a 7 L aqueous solution and the pH was adjusted to 10 in a 2.2 M pure NaOH solution, the reaction temperature was 50 ° C, and the stirring speed was 600 rpm.
  • the Ni-Co-Mn-Cu composite hydroxide was separated, aged for 1 hour, washed several times with distilled water, dried at 100 Torr for 10 hours, ground and sieved to obtain a precursor, and the water was accurately measured.
  • the structure and morphology test results of the product obtained in this example The XRD pattern is similar to the XRD pattern of Example 1, the peak intensity ratio of 1003/1104 is as high as 1.6 or more, and the structural peaks 006 and 102 and peaks 008 and 110 tend to be independent peaks. Existence, it can be considered that the synthesized product has a layered structure and the crystal form is well developed, the structure is complete, and the defects are few.
  • the SEM spectrum was similar to the SEM spectrum of Example 1, and it was shown that the particle shape of the synthesized product was ellipsoidal, the size was uniform, the average particle size was 6-12 ⁇ , and the tap density of the powder was 2.24 g/cm 3 .
  • the electrochemical performance of the product has been tested with a Xinwei small current tester.
  • the material has a first charge specific capacity of 192.4837 mAh/g, a first discharge specific capacity of 173.5134 mAh/g, and a coulombic efficiency of 90.14%. After 100 cycles, the capacity retention rate is 98.13%, and the reversible capacity is 170.26S7 mAh/g.
  • the pulping and coating process of the pole piece are good. No gelation occurs after 48 hours of slurry placement. The surface of the sheet is smooth and there is no dropping.
  • Example 3 Positive active material Preparation and performance structure test molar ratio of 0.75:0.15:0.03:0.02:0.05 Take nickel (Ni), cobalt (Co), iron (Fe), titanium (Ti), manganese (Mn) sulfate total 10 mol Under the condition of constant stirring, slowly add a buffer solution of pH 8 prepared from ammonia water and boric acid to prepare 10L of mixed complex solution, and mix it with 10L, 2.2M NaOH while slowly stirring. A 7 L aqueous solution was placed and the pH was adjusted to 10.5 with a 2.2 M pure NaOH solution at a reaction temperature of 60 ° C and a stirring speed of 800 rpm.
  • the Ni-Co-Mn-Fe-Ti composite hydroxide was separated, aged for 3 hours, washed with distilled water several times, and then dried at 6 (TC for 24 hours, ground and sieved to obtain a precursor, accurately measured
  • the water is mixed with anhydrous lithium nitrate at a ratio of 1:1.04 and placed in an intelligent control muffle furnace.
  • the temperature is raised to 500 5 at 5 ° C/min in dry air and the temperature is maintained for 3 hours for the first heat treatment.
  • the temperature was raised to 780 Torr at 5 ° C / min and the temperature was kept for 16 hours to carry out sintering, followed by natural cooling to room temperature, grinding, sieving and classification to obtain a positive electrode active material.
  • the structure and morphology test results of the product obtained in this example The XRD pattern is similar to the XRD pattern of Example 1, the peak intensity ratio of 1003/1104 is about 1.7, and the structural peaks 006 and 102 and peaks 008 and 110 tend to be independent peaks. Existence, it can be considered that the synthesized product has a layered structure and the crystal form is well developed, the structure is complete, and the defects are few.
  • the SEM spectrum is similar to the SEM spectrum of Example 1. The SEM spectrum shows that the particle shape of the synthesized product is ellipsoidal, the size is uniform, the average particle size is 4-13 m, and the tap density of the powder is 2.26 g/cm 3 .
  • the electrochemical performance of the product has been tested with a Xinwei small current tester for the button cell.
  • the first charge specific capacity of the material is 193.7749 mAh/g, the first discharge specific capacity is 164.783 mAh/g, and the coulombic efficiency is 85.02. %; After 100 cycles, the capacity retention rate was 96.47%, and the reversible capacity was 158.9327 mAh/g.
  • the pulping and coating process of the pole piece were good. No gel appeared after 48 hours of slurry placement. The surface of the sheet is smooth and there is no dropping.
  • Example 4 Preparation and performance of positive active material LiNi ⁇ Coi A ⁇ Mno.osC Structural test: Nickel (Ni), cobalt (Co), aluminum (Al), manganese (taken by molar ratio 0.65:0.2:0.1:0.05) Mn) sulfate total 10 moles Under the condition of constant stirring, slowly add a buffer solution of pH 8.5 prepared by ammonia water and ammonium sulfate to obtain 10L of mixed ammonia complex solution. Under continuous stirring, it is simultaneously slow with 10L, 2.2M NaOH aqueous solution.
  • a reaction vessel containing 7 L of an aqueous solution and adjusting its pH to 11.5 with a 2.2 M pure NaOH solution was added dropwise, the reaction temperature was 70 V, and the stirring speed was 300 rpm.
  • the Ni-Co-Al-Mn composite hydroxide was separated, aged for 4 hours, washed with distilled water for several times, and then dried at 120 ° C for 8 hours. After grinding and sieving, the precursor was prepared and the water was accurately measured.
  • lithium hydroxide monohydrate LiOH * H 2 0
  • molar ratio 1 1.07 mixed grinding and placed in an intelligent control muffle furnace, in a dry air at 2 ° C / min to 400 ⁇ and constant temperature for 6 hours
  • the first heat treatment was carried out, and then the temperature was raised to 770 Torr at 2 ° C / min and the temperature was kept for 24 hours to carry out sintering, followed by natural cooling to room temperature, grinding, sieving and classification to obtain a positive electrode active material.
  • the structure and morphology test results of the product obtained in this example The XRD pattern is similar to the XRD pattern of Example 1, the peak intensity ratio of 1003/1104 is about 1.4, and the structural peaks 006 and 102 and peaks 008 and 110 tend to be independent peaks. Existence, it can be considered that the synthesized product has a layered structure and the crystal form is well developed, the structure is complete, and the defects are few.
  • the SEM spectrum was similar to the SEM spectrum of Example 1, and it was shown that the particle shape of the synthesized product was ellipsoidal, the size was uniform, the average particle size was 4-18 um, and the tap density of the powder was 2.17 g/cm 3 .
  • the electrochemical performance of the product was tested with a Xinwei small current tester.
  • the material has a first charge specific capacity of 189.6044 mAh/g, a first discharge specific capacity of 165.2592 m Ah7g, and a coulombic efficiency of 87.16%. After 100 cycles, the capacity retention rate was 96.13%, and the reversible capacity was 158.8637 mAh/g.
  • the pulping and coating process of the pole piece were good. No gel appeared after 48 hours of slurry placement. The surface of the pole piece was produced. Smooth, no missing material.
  • Example 5 Preparation and performance of positive active material LiNio ⁇ CoojAlo Mno.cnCuo.iHCao.oi ⁇ Structural test molar ratio 0.65:0.3:0.02:0.01:0.01:0.01 Take nickel (Ni), cobalt (Co), aluminum (Al), manganese (Mn;), copper (Cu) and calcium (Ca) sulfates a total of 10 moles under constant stirring conditions slowly added to the buffer solution of pH 3 ⁇ 11 11 prepared from ammonia and oxalate A mixed ammonia complex solution of 10L was obtained, and while continuously stirring, it was slowly dropped into a 7 L aqueous solution with 10 L of a 2.2 M aqueous solution of NaOH, and the pH was adjusted to 11.0 with a 2.2 M pure NaOH solution.
  • the reaction temperature was 55 ° C and the stirring speed was 900 rpm.
  • the Ni-Co-Al-Mn-Cu-Ca composite hydroxide was separated, aged for 3 hours, washed several times with distilled water, dried at 50 ° C for 30 hours, ground and sieved to obtain a precursor, which was accurately measured.
  • the anhydrous lithium nitrate is mixed with 1:1.07 and placed in an intelligent control muffle furnace.
  • the first heat treatment is carried out in a dry air at TC/min to 550 ° C and constant temperature for 8 hours.
  • the temperature was raised to 770 ° C at 2 ° C / min and the temperature was kept for 20 hours to carry out sintering, followed by natural cooling to room temperature, grinding, sieving and classification to obtain a positive electrode active material. .
  • the structure and morphology test results of the product obtained in this example The XRD pattern is similar to the XRD pattern of Example 1, the peak intensity ratio of 1003/1104 is about 1.4, and the structural peaks 006 and 102 and peaks 008 and 110 tend to be independent peaks. Existence, it can be considered that the synthesized product has a layered structure and the crystal form is well developed, the structure is complete, and the defects are few.
  • the SEM spectrum was similar to the SEM spectrum of Example 1, and it was shown that the particle shape of the synthesized product was a nan spherical shape with a uniform size, an average particle diameter of 5-17 P m, and a tap density of the powder of 2.21 g/cm 3 .
  • the electrochemical performance of the product has been tested with a Xinwei small current tester.
  • the material has a first charge specific capacity of 191.6174 mAh/g, a first discharge specific capacity of 166.7329 mAh/g, and a coulombic efficiency of 87.01%. After 100 cycles, the capacity retention rate is 94.88%, and the reversible capacity is 158.1962 mAlVg.
  • the pulping and coating process of the pole piece are good. No gel phenomenon occurs after the slurry is placed for 48 hours. The surface of the electrode piece is smooth. There is no dropping phenomenon.
  • 10 L of the mixed ammonia complex solution was prepared, and while continuously stirring, it was slowly dropped into a 7 L aqueous solution containing 10 L of 2.2 M NaOH solution and adjusted with 2.2 M pure NaOH solution.
  • the reaction temperature was 70 ° C and the stirring speed was 950 rpm.
  • the Ni-Co-Al-Mn composite hydroxide was separated, aged for 3 hours, washed with distilled water for several times, dried at 80 ° C for 24 hours, ground and sieved to obtain a precursor, and the water was accurately measured.
  • Waterless Lithium nitrate massage ratio 1: 1.05 was mixed and placed in an intelligent control muffle furnace, heated to 550 ° C at 5 ° C / min in dry air and heated for 8 hours for the first heat treatment, and then 2 ° C/min was heated to 770 ° C and kept at a constant temperature for 16 hours for sintering, and then naturally cooled to room temperature, ground, sieved and classified to obtain a positive electrode active material.
  • the structure and morphology test results of the product obtained in this example The XRD pattern is similar to the XRD pattern of Example 1, the peak intensity ratio of 1003/1104 is about 1.53, and the structural peaks 006 and 102 and peaks 008 and 110 tend to be independent peaks. Existence, it can be considered that the synthesized product has a layered structure and the crystal form is well developed, the structure is complete, and the defects are few.
  • the SEM spectrum was similar to the SEM spectrum of Example 1. It showed that the particle shape of the synthesized product was ellipsoidal, the size was uniform, the average particle size was 7-15 ⁇ ⁇ , and the tap density of the powder was 2.34 g/cm 3 .
  • the electrochemical performance of the product has been tested with a Xinwei small current tester.
  • the material has a first charge specific capacity of 192.7129 mAh/g, a first discharge specific capacity of 172.6642 mAh/g, and a coulombic efficiency of 89.60%. After 100 cycles, the capacity retention rate is 96.21%, and the reversible capacity is 166.1202 mAh/g.
  • the pulping and coating process of the pole piece are good. No gelation occurs after the paddle is placed for 96 hours. The surface is smooth and there is no material drop.

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un oxyde de lithium composite à composants multiples de formule Lia(NibCoc)M1-b-cO2, dans laquelle M est au moins un atome métallique sélectionné parmi le fer (Fe), l'aluminium (AL), le manganèse (Mn), le titane (Ti), le cuivre (Cu) et le calcium (Ca), et a = 0,97 ~ 1,07, 0,3 = b < 1, 0 < c = 0,5 et 0,8 = b + c < 1. Elle concerne également un procédé de fabrication de celui-ci. Le procédé comprend les étapes consistant à (a) produire une solution complexe de nickel, cobalt, métal M et d'ammoniaque dans une solution tampon ; (b) ajouter la solution complexe et une solution alcaline dans un réacteur, lentement, pour coprécipiter l'hydroxyde composite Ni-Co-M, puis effectuer un vieillissement, une séparation, un lavage et un séchage, puis un précurseur est obtenu ; (c) mélanger et broyer le précurseur conjointement avec un sel d'hydroxyde de lithium ou de lithium, puis traiter à chaud pour obtenir un produit fini. L'utilisation de l'oxyde de lithium composite en tant que matière active d'électrode positive pour une batterie secondaire au lithium et une batterie secondaire au lithium comportant cette matière active d'électrode positive sont proposées.
PCT/CN2005/000884 2005-06-20 2005-06-20 Oxyde de lithium composite a composants multiples contenant du nickel et du cobalt, procede pour sa fabrication, son utilisation en tant que matiere active d'electrode positive pour une batterie secondaire au lithium et pile secondaire au lithium WO2006136050A1 (fr)

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CN108630915A (zh) * 2018-03-27 2018-10-09 四川大学 一种高性能镍钴铝酸锂正极材料及其制备方法
CN111517377A (zh) * 2020-04-28 2020-08-11 蜂巢能源科技有限公司 高镍三元正极材料前驱体、高镍三元正极材料及其制备方法
CN112299494A (zh) * 2020-10-29 2021-02-02 格林爱科(荆门)新能源材料有限公司 一种镍钴氢氧化物材料的制备方法
CN114751467A (zh) * 2022-04-29 2022-07-15 福安青美能源材料有限公司 一种定向提高镍钴锰三元前驱体比表面积的陈化方法
CN114887481A (zh) * 2022-03-08 2022-08-12 江苏理工学院 一种VOCs的催化降解方法

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US8540961B2 (en) 2005-04-13 2013-09-24 Lg Chem, Ltd. Method of preparing material for lithium secondary battery of high performance
US7939049B2 (en) 2005-04-13 2011-05-10 Lg Chem, Ltd. Cathode material containing Ni-based lithium transition metal oxide
US7939203B2 (en) 2005-04-13 2011-05-10 Lg Chem, Ltd. Battery containing Ni-based lithium transition metal oxide
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US8426066B2 (en) 2005-04-13 2013-04-23 Lg Chem, Ltd. Material for lithium secondary battery of high performance
US8450013B2 (en) 2005-04-13 2013-05-28 Lg Chem, Ltd. Material for lithium secondary battery of high performance
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US9416024B2 (en) 2005-04-13 2016-08-16 Lg Chem, Ltd. Method of preparing material for lithium secondary battery of high performance
WO2007129854A1 (fr) 2006-05-10 2007-11-15 Lg Chem, Ltd. Procédé de préparation de matière pour batterie secondaire au lithium haute performance
EP2016637A4 (fr) * 2006-05-10 2010-02-03 Lg Chemical Ltd Procédé de préparation de matière pour batterie secondaire au lithium haute performance
CN108630915B (zh) * 2018-03-27 2022-10-11 四川大学 一种高性能镍钴铝酸锂正极材料及其制备方法
CN108630915A (zh) * 2018-03-27 2018-10-09 四川大学 一种高性能镍钴铝酸锂正极材料及其制备方法
CN111517377A (zh) * 2020-04-28 2020-08-11 蜂巢能源科技有限公司 高镍三元正极材料前驱体、高镍三元正极材料及其制备方法
CN112299494A (zh) * 2020-10-29 2021-02-02 格林爱科(荆门)新能源材料有限公司 一种镍钴氢氧化物材料的制备方法
CN114887481A (zh) * 2022-03-08 2022-08-12 江苏理工学院 一种VOCs的催化降解方法
CN114887481B (zh) * 2022-03-08 2023-08-22 江苏理工学院 一种VOCs的催化降解方法
CN114751467A (zh) * 2022-04-29 2022-07-15 福安青美能源材料有限公司 一种定向提高镍钴锰三元前驱体比表面积的陈化方法
CN114751467B (zh) * 2022-04-29 2024-04-02 福安青美能源材料有限公司 一种定向提高镍钴锰三元前驱体比表面积的陈化方法

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