WO2018090956A1 - Positive electrode material for high voltage lithium battery, battery, preparation method therefor and use thereof - Google Patents

Positive electrode material for high voltage lithium battery, battery, preparation method therefor and use thereof Download PDF

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WO2018090956A1
WO2018090956A1 PCT/CN2017/111393 CN2017111393W WO2018090956A1 WO 2018090956 A1 WO2018090956 A1 WO 2018090956A1 CN 2017111393 W CN2017111393 W CN 2017111393W WO 2018090956 A1 WO2018090956 A1 WO 2018090956A1
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positive electrode
lithium
electrode material
cobalt
manganese
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PCT/CN2017/111393
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French (fr)
Chinese (zh)
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梅铭
许国成
向黔新
李阳兴
李路
周朝毅
王丽娟
彭鹏
黄昕
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贵州振华新材料有限公司
华为技术有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/362—Composites
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the field of lithium ion secondary batteries, and in particular to a positive electrode material for a high voltage type lithium ion secondary battery.
  • the present invention also relates to a method of producing the positive electrode material, and a power type lithium ion secondary battery having improved electrochemical performance made of the positive electrode material.
  • Lithium-ion secondary batteries are widely used as power sources for various mobile devices due to their high energy density, high operating voltage, long cycle life, etc., energy storage power plants, even in aviation, aerospace, marine, automotive, medical equipment, etc. The field is gradually replacing other traditional batteries.
  • the output of energy is usually realized by the transfer of lithium ions, which involves electron transfer between a plurality of solid/liquid porous media such as a positive electrode, a negative electrode, a separator, an electrolyte, etc.
  • a plurality of solid/liquid porous media such as a positive electrode, a negative electrode, a separator, an electrolyte, etc.
  • Lithium battery electric vehicles such as Toyota, Japan, Tesla electric vehicles, etc.
  • electric storage stations which have appeared in recent years, are characterized by a large amount of lithium with high energy density.
  • Ion batteries are stored together in a centralized manner, and are used for charging and discharging through a power management system.
  • the energy density of the lithium ion secondary battery (including the volume energy density Wh/L and the weight energy density Wh/kg) has been a key area of close attention of various manufacturers and application terminal customers.
  • the output voltage of the lithium battery is related to the positive and negative electrodes.
  • the same lithium cobaltate cathode has a working voltage of 3.8 volts for the graphite anode platform and 2.2 volts for the lithium titanate anode platform.
  • the corresponding energy density will also be higher.
  • the current operating voltage range of lithium cobaltate to graphite anode is 3.0 ⁇ 4.2V, if the operating voltage range is increased to 3.0-4.25V, the corresponding high voltage battery, the corresponding cathode material is high voltage Type cathode material.
  • the working voltage of the lithium battery is improved, and its main purpose is to increase the energy density of the lithium ion secondary battery.
  • the voltage is increased by 0.05V
  • the energy density of the lithium battery cell can be increased from 530Wh/L to about 580Wh/L, and the volume is increased slightly by the amount of the negative electrode.
  • the energy density is increased by about 5 to 7%, which is very spectacular.
  • 4G mobile phones in the 3C field mostly use 4.35V lithium batteries, and the battery capacity is above 1.5Ah. Five manufacturers also provide fast charging technology.
  • the operating voltage of the above lithium ion secondary battery is only increased by 0.05-0.2 V, there are new requirements for the material and structure of the lithium ion secondary battery, and reversible safety at high voltage is also a challenge.
  • the positive electrode material when the working voltage is increased, it means that part of the lithium involved in the positive electrode material participates in the intercalation and deintercalation of lithium.
  • the theoretical specific capacity is 274 mAh/g according to the molecular formula LiCoO2.
  • the cathode materials currently used are lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium manganate and other materials. According to the national energy policy and energy density roadmap, the most commercially valuable in the field of power batteries is high.
  • the voltage is ordinary ternary, etc., and the energy density of the pack can reach 140 wh/kg at 3.0-4.2 V working voltage. If the voltage is increased to 4.4-4.6 volts, the energy density of the pack volume can reach the same under other application systems. 200-230Wh/kg.
  • the ternary material contains nickel and manganese, and the cost advantage is obvious.
  • coated LCO25 (CN102891307A), mixed with lithium cobalt oxide to form a dual platform (CN102610810A), doped with a metal element (CN102074700A) and the like as lithium cobaltate.
  • the technical problem to be solved by the present invention is that the termination voltage and energy density of the positive electrode material of the lithium ion secondary battery in the prior art need to be further improved.
  • the general working voltage is 1.5 to 2.5V. If the working voltage is 1.5 to 2.8V, the upper limit of the working voltage is increased, that is, the high voltage.
  • the working condition; similarly, the graphite 10 electrode to the ternary electrode generally has a working voltage of 3.0 to 4.2 V, and if the operating voltage is 3.0 to 4.8 V, it is a high voltage use condition.
  • the large specific surface area of the material means that the contact area between the material body and the electrolyte is larger, more reaction surfaces may participate in side reactions. Controlling the specific surface area is therefore the key to preparing high voltage cathode materials.
  • the material usually does not coat other elements with a specific capacity and high efficiency for the first time. After coating other elements, the coating material cannot be deintercalated/intercalated or the amount of insertion/extraction is small, the specific capacity and the first time Efficiency is reduced, but safety performance is improved, so a comprehensive balance of specific capacity and cycle/safety performance is required.
  • the object of the invention is to develop a universal high-voltage cathode material, balance the electrochemical performance and high-voltage cycle/safety performance of the lithium ion secondary battery by controlling the specific surface area of the material, and adopt the precursor 20 body preparation and the cathode material synthesis process.
  • a spherical or potato type and secondary spherical type positive electrode material is prepared, and the positive electrode material is applied to a lithium ion secondary battery.
  • the present invention also provides a power type lithium ion secondary battery including the following: an electrode, an electrolyte, a separator, and a container.
  • the electrode comprises a positive electrode and a negative electrode
  • the positive electrode comprises a positive current collector and a positive active material layer coated on the positive current collector
  • the negative electrode comprises a negative current collector and a negative active material layer coated on the negative current collector
  • It may be a simple microporous solid insulating layer
  • the container is a container having a certain form of a positive electrode, a negative electrode, a separator, and an electrolyte.
  • the structure of the positive electrode material of the present invention is Li[LixMnaNibCoc]O2 ⁇ MyOz, wherein -0.05 ⁇ x ⁇ 0.3, abc is greater than 0.02 and less than 0.9, M is a metal element other than lithium, nickel, cobalt, manganese and MyOz is a kind meets the A composite oxide type ionic conductor composed of a valence, 0.13 ⁇ ⁇ ⁇ 0.3, 0 ⁇ y4 ⁇ 3, 0 ⁇ z ⁇ 5, and 0.9 ⁇ x + a + b + c ⁇ 1.4.
  • the positive electrode material can be applied to a lithium ion secondary battery in a power type electric vehicle, a mobile storage power source, and an energy storage power station device.
  • the preparation method is simple and feasible, and the high voltage use performance of the product is significantly improved.
  • the present invention proposes the following technical solutions:
  • a positive electrode material for a lithium ion secondary battery wherein the positive electrode material has a structural formula of Li[LixMnaNibCoc]O2 ⁇ MyOz, wherein -0.05 ⁇ x ⁇ 0.3, abc is greater than 0.02 and less than 0.9; M is lithium, nickel, cobalt, manganese
  • the metal element other than MyOz is a composite oxide conforming to the valence composition, 0.13 ⁇ ⁇ ⁇ 0.3, 0 ⁇ y ⁇ 3, 0 ⁇ z ⁇ 5, and 0.9 ⁇ x + a + b + c ⁇ 1.4.
  • the above values of a, b, and c satisfy: a, b, c is 0.325 to 0.345; or a, c is 0.042 to 0.055, and b is 0.85 to 0.95; or a, c is 0.05 to 0.15, And b is 0.75 to 0.85; or a, c is 0.140 to 0.155 and b is 0.65 to 0.75; or a, c is 0.15 to 0.25 and b is 0.55 to 0.65; or a, c is 0.245 to 0.265 and b is 0.45 to ⁇ 0.55; or a and b are 0.35 to 0.45, and c is 0.15 to 0.25; or a is 0.45 to 0.55, b is 0.25 to 0.35, and c is 0.15 to 0.25.
  • the above M is selected from one or more selected from the group consisting of magnesium, titanium, lanthanum, lanthanoid, zirconium and aluminum.
  • the above M content is more than 0 or less than 0.43 wt% of the content of the positive electrode material.
  • M is uniformly mixed with the oxide of M and the lithium nickel cobalt manganese oxide composition, or M is uniformly coated with the oxide of M.
  • the positive electrode material is formed on the surface of the nickel-cobalt-manganese-acid composition, or M is uniformly coated on the surface of the M-nickel-cobalt-manganate composition with an oxide of M.
  • the above positive electrode material has a particle diameter D50 of 3.2 to 9 ⁇ m.
  • the above positive electrode material has a specific surface area of from 0.49 to 0.76 m 2 /g.
  • the present invention also provides a method for preparing a positive electrode material, which is characterized in that a particle size of 2-9.2 ⁇ m is obtained by a nickel, cobalt, manganese, M or a precursor synthesis process containing nickel, cobalt and manganese.
  • a precursor having a surface area of 6.5-13.2 m 2 /g then, the precursor is mixed with a lithium source, and subjected to demagnetization, primary sintering, primary pulverization, secondary sintering, secondary pulverization, and secondary demagnetization to obtain a positive electrode material;
  • Metal elements other than lithium, nickel, cobalt, and manganese are other than lithium, nickel, cobalt, and manganese.
  • the temperature of one sintering is 800-880 ° C, and the time of one sintering is 15-20 hours.
  • the secondary sintering temperature is 750-880 ° C, and the secondary sintering time is 15-18 hours.
  • the primary pulverization and the secondary pulverization comprise a polyurethane ball mill for 5-7 hours.
  • the source of M is a salt containing element M or an oxide containing element M or a hydroxide containing element M, preferably a soluble organic or inorganic salt.
  • the oxide has a particle size of ⁇ 100 ⁇ m.
  • the introduction of M may be added during the synthesis of the precursor, during the mixing of the precursor with the lithium salt, or during the preparation of the semi-finished material of the positive electrode material.
  • the invention also provides a lithium lithium ion secondary battery cathode material obtained by the above preparation method, wherein the cathode material has the structural formula Li[LixMnaNibCoc]O2 ⁇ MyOz, wherein -0.05 ⁇ x ⁇ 0.3, abc is greater than 0.02 and less than 0.9.
  • M is a metal element other than lithium
  • MyOz is a composite oxide having a valence composition, 0 ⁇ ⁇ ⁇ 0.3, 0 ⁇ y ⁇ 3, 0 ⁇ z ⁇ 5, and 0.9 ⁇ x +a+b+c ⁇ 1.4.
  • the present invention also provides a lithium ion secondary battery prepared by using the above positive electrode material.
  • the above lithium ion secondary battery uses a carbon material or lithium titanate as a negative electrode, and the carbon material is preferably graphite.
  • the lithium ion secondary battery has a voltage operating upper limit of 2.8-4.8 V depending on the different negative electrode materials.
  • the above lithium ion secondary battery uses lithium titanate as a negative electrode material, and its upper limit of voltage operation is 2.8 V, or a carbon material is used as a negative electrode material, and its upper limit of voltage operation is 4.8 V.
  • the present invention also provides a mobile storage device using the above-described lithium ion secondary battery.
  • the present invention also provides an energy storage power station using the above-described lithium ion secondary battery or the above-described mobile storage device.
  • Figure 1-1 is a scanning electron micrograph of the embodiment (comparative example) 2-3, and the magnification is 3000 times.
  • Figure 1-2 is a scanning electron micrograph of Example 2-1, and the magnification is 3000 times.
  • 1-3 is a scanning electron micrograph of the embodiment (comparative example) 3-3, and the magnification is 3000 times.
  • Figure 1-4 is a scanning electron micrograph of Example 3-1, and the magnification is 3000 times.
  • Fig. 3 shows the results of the voltage cycling test of the example and the comparative example.
  • the graphite was used as the negative electrode, and the cycle test operating voltage was 3.0-4.8 V, 1 C/1 C, and the cycle temperature was 60 °C.
  • the object of the present invention is to develop a universal high-voltage positive electrode material by controlling the particle size and specific surface area of the synthetic material, balancing the electrochemical performance output and high voltage cycle/safety performance, and developing the positive electrode material. Used in lithium ion secondary batteries.
  • the structure of the positive electrode material is Li[LixMnaNibCoc]O2 ⁇ MyOz, wherein -0.05 ⁇ x ⁇ 150.3, abc is greater than 0.02 and less than 0.9, 0.13 ⁇ 0.3, 0 ⁇ y ⁇ 3, 0 ⁇ z ⁇ 5, and 0.9 ⁇ x+a+b+c ⁇ 1.4.
  • M is a metal element other than lithium, nickel, cobalt, manganese;
  • MyOz is a composite oxide constituting a valence composition, usually an ionic conductor, and the source of MyOz is a salt containing element M or an oxide containing M.
  • the salts are preferably soluble organic or inorganic salts, preferably having a particle size of ⁇ 100 ⁇ m.
  • M is preferably one or more selected from the group consisting of magnesium, titanium, lanthanum, lanthanoid, zirconium and aluminum.
  • the source of M is preferably one or more selected from the group consisting of nano magnesium hydroxide, nano magnesium oxide, nano cerium oxide, nano alumina, nano titanium dioxide, n-tetrabutyl titanate, zirconium nitrate, cerium nitrate, and cerium nitrate.
  • the hydroxide product containing manganese, cobalt and nickel is prepared by coprecipitation method, and a precursor having a particle size of 2-9.2 ⁇ m and a specific surface area of 6.5-13.2 m 2 /g is obtained by a precursor synthesis process; the precursor is mixed with a lithium source.
  • the positive electrode material of the invention is obtained by demagnetization, primary sintering, primary pulverization, secondary sintering, secondary pulverization, and secondary demagnetization.
  • Manganese, cobalt, and nickel are derived from salts containing manganese, cobalt, and nickel, and preferably sulfates containing manganese, cobalt, and nickel.
  • the lithium source may be one or more of lithium carbonate, lithium hydroxide monohydrate, lithium acetate, and lithium fluoride.
  • the method for preparing a positive electrode material of the present invention includes the following steps:
  • Step 1 Prepare the precursor, including the following three steps:
  • Step 1 Prepare a salt solution containing manganese cobalt nickel
  • a salt containing manganese, cobalt and nickel is dissolved in deionized water to prepare a manganese-containing cobalt-nickel salt solution having a solid content of 25 to 435 wt% at a target molar ratio.
  • the dropping time is 4-12 hours, and after the completion of the dropwise addition, the powder or slurry containing M is added in an amount of 0 to 30% by weight of the salt of nickel-cobalt-manganese added, and the mixture is aged for 20-36 hours under stirring to obtain A suspension dispersion of the precursor.
  • the suspension dispersion prepared in step 2 is demagnetized, and the filter cake is obtained by centrifugation, and the filter cake is repeatedly washed with deionized water for 7-10 times until the impurity content is within the acceptable range of the standard, and the filter cake is taken out and dried by vacuum.
  • the machine was dried at 105-130 ° C and sieved through a 325 mesh stainless steel sieve to obtain a precursor.
  • Process 2 cathode material synthesis including the following two steps:
  • the precursor is uniformly mixed with the lithium source, and then subjected to demagnetization, sintering, and ball milling to obtain a semi-finished product of the positive electrode material.
  • solubility of lithium salt it can be divided into a wet preparation process and a dry process.
  • the precursor is sequentially added in a weight ratio of 100: (60 to 90), and the lithium salt is dispersed in a dry state at a normal temperature in a high-speed mixer, and the dispersed powder is demagnetized by a rotary demagnetizer having a strength of 8000 GS.
  • the powder after demagnetization is transferred to a ceramic crucible and placed in a muffle furnace, sintered in an air or oxygen atmosphere at 800-870 ° C for 15-20 hours, and the sintered material is ball milled by a polyurethane ball mill for 5-7 hours to prepare a cathode material.
  • Semi finished product is performed by a weight ratio of 100: (60 to 90), and the lithium salt is dispersed in a dry state at a normal temperature in a high-speed mixer, and the dispersed powder is demagnetized by a rotary demagnetizer having a strength of 8000 GS.
  • the powder after demagnetization is transferred to a ceramic crucible and placed in a mu
  • the semi-finished product of the positive electrode material and the powder containing M are re-introduced into the ball mill at a weight ratio of 100: (0 to 30), and then doped and coated, and then the doped powder is separately placed in a muffle furnace, in air or
  • the high temperature treatment is carried out in an oxygen atmosphere at 750-880 ° C for 15-18 hours, and the treated powder is ball milled by a ball mill for 5-7 hours, then demagnetized by a rotary demagnetizer (8000GS), and sieved with a 325 mesh stainless steel mesh. After that, a positive electrode material was obtained.
  • the positive electrode material prepared by the method for preparing a positive electrode material of the invention has the structural formula of Li[LixMnaNibCoc]O2 ⁇ MyOz, wherein -0.05 ⁇ x ⁇ 0.3, abc is greater than 0.02 and less than 0.9, and M is a metal other than lithium, nickel, cobalt and manganese.
  • the element and MyOz is a composite oxide conforming to the valence composition, 0 ⁇ ⁇ ⁇ 0.3, 0 ⁇ y ⁇ 3, 0 ⁇ z ⁇ 5, and 0.9 ⁇ x + a + b + c ⁇ 1.4.
  • Table 2 List of equipment information used in the examples
  • the ammonia gas is replaced by ammonia gas for 30 minutes, then the sodium hydroxide solution and the ammonia solution are added dropwise for 10 minutes, and the pH of the solution is adjusted to about 12.3, and the salt solution containing nickel, cobalt and manganese, ammonia solution and sodium hydroxide are simultaneously added. Solution.
  • the reaction temperature of the control solution was 55 ° C ⁇ 5 ° C.
  • the dropping time was 4 hours.
  • 1.88 kg of nano magnesium hydroxide powder was added, and 2.2 kg of nano cerium oxide slurry (solid content 20%) was aged under stirring for 30 hours, and then pumped by a diaphragm pump. Centrifuge in a centrifuge, add pipe demagnetizer (10000GS) to the pumping line, and repeatedly clean the filter cake with deionized water for 7 times until the impurity content is within the acceptable range.
  • the ammonia gas shielding gas was replaced by the ammonia gas for 30 minutes, and then the sodium hydroxide solution and the ammonia aqueous solution were added dropwise for 10 minutes, and the pH of the solution was adjusted to about 11.8, and the salt solution containing nickel, cobalt and manganese, the ammonia solution and the sodium hydroxide were simultaneously added dropwise. Solution.
  • the reaction temperature of the solution was controlled to be 60 ° C ⁇ 5 ° C. The dropping time was 6 hours.
  • nanometer titanium oxide dispersion solid content: 20% by weight
  • zirconium nitrate pentahydrate was aged under stirring for 40 hours, and then pumped into the pump by a pressure pump.
  • the solid-liquid separation in the plate and frame filter press adding the pipe demagnetizer (11000GS) on the pumping pipeline, and repeatedly cleaning the filter cake with deionized water for 6 times until the impurity content is within the acceptable range, after removing the filter cake It was dried by a vacuum disc dryer (temperature 105 ° C ⁇ 2 h), and filtered into a precursor product by a 5 325 mesh stainless steel mesh to obtain 10 kg of NCM955 precursor product, the product particle size was 8.8 ⁇ m, and the specific surface was 6.5 m 2 / g, the tap density is 1.7 g/cm3, and the magnetic substance is 77 ppb.
  • the ammonia gas shielding gas is replaced by the ammonia gas for 30 minutes, and then the sodium hydroxide solution and the ammonia aqueous solution are added dropwise for 10 minutes, and the pH of the solution is adjusted to about 12.1, and the salt solution containing nickel, cobalt and manganese, the ammonia solution and the hydrogen are simultaneously added dropwise.
  • Sodium oxide solution was 63 ° C ⁇ 5 ° C.
  • the dropping time was 8 hours, and 0.85 kg of nano magnesium hydroxide powder and 33.85 kg of cerium nitrate hexahydrate were added after completion of the dropwise addition, and 29.15 kg of nano titanium dioxide dispersion (solid content: 20% by weight) was aged under stirring. Hours, then use the diaphragm pump to pump into the centrifuge for solid-liquid separation, add pipe demagnetizer (9800GS) on the pumping line, and repeatedly wash the filter cake with deionized water 7 times until the impurity content is within the qualified range.
  • pipe demagnetizer (9800GS) pipe demagnetizer
  • the filter cake was taken out and dried by a vacuum pan dryer (temperature 105 ° C ⁇ 2 h), and filtered into a precursor product by a 325 mesh stainless steel mesh to obtain 91.3 kg of a NCM 523 precursor product, and the product particle size was 9.2 ⁇ m.
  • the specific surface was 9.5 m 2 /g, the tap density was 1.9 g/cm 3 , and the magnetic substance was 90 ppb.
  • the ammonia gas shielding gas was replaced by the ammonia gas for 30 minutes, and then the sodium hydroxide solution and the ammonia aqueous solution were added dropwise for 10 minutes, and the pH of the solution was adjusted to about 11.8, and the salt solution containing nickel, cobalt and manganese, the ammonia solution and the sodium hydroxide were simultaneously added dropwise. Solution.
  • the reaction temperature of the control solution was 65 ⁇ 5 °C.
  • the dropping time is 6 hours.
  • 0.5 kg of nano-magnesia powder is added and aged for 35 hours under stirring, and then pumped into the plate and frame filter press by a pressure pump to separate the solid and liquid, on the pumping line.
  • the magnet was demagnetized (11000 GS), and the filter cake was washed 7 times with reverse 5 multiplexed deionized water until the impurity content was within the acceptable range.
  • the filter cake was taken out and dried by a vacuum disc dryer (temperature 105 ° C ⁇ 2 h).
  • the precursor product was filtered through a 325 mesh stainless steel mesh to obtain a NCM46846 precursor product having a particle size of 4.5 ⁇ m, a specific surface of 5.6 m 2 /g, a tap density of 2.0 g/cm 3 and a magnetic substance of 176 ppb.
  • the ammonia gas is replaced by ammonia gas for 30 minutes, then the sodium hydroxide solution and the ammonia solution are added dropwise for 10 minutes, and the pH of the solution is adjusted to about 12.3, and the salt solution containing nickel, cobalt and manganese, ammonia solution and sodium hydroxide are simultaneously added. Solution.
  • the reaction temperature of the control solution was 55 ° C ⁇ 5 ° C.
  • the dropping time was 4 hours.
  • 0.57 kg of nano-magnesia was added under stirring, and 6.4 kg of nano-titanium dioxide slurry (solid content: 20% by weight) was aged for 30 hours, and then pumped into the centrifuge with a diaphragm pump. Centrifugal separation in the machine, adding pipe demagnetizer (10000GS) to the pumping line, and repeatedly cleaning the filter cake with 20 deionized water for 7 times until the impurity content is within the acceptable range, the filter cake is taken out and then vacuum dryer is used.
  • the ammonia gas shielding gas was replaced by the ammonia gas for 30 minutes, and then the sodium hydroxide solution and the ammonia aqueous solution were added dropwise for 10 minutes, and the pH of the solution was adjusted to about 11.8, and the salt solution containing nickel, cobalt and manganese, the ammonia solution and the sodium hydroxide were simultaneously added dropwise. Solution.
  • the reaction temperature of the solution was controlled to be 60 ° C ⁇ 5 ° C.
  • the dropping time is 6 hours, and after the completion of the dropwise addition, the temperature is aged for 40 hours in the state of stirring, and then pumped into the plate and frame filter press by a pressure pump to separate the solid and liquid, and the pipe demagnetizer is added to the pumping pipe.
  • the ammonia gas shielding gas was replaced by the ammonia gas for 30 minutes, and then the sodium hydroxide solution and the ammonia aqueous solution were added dropwise for 10 minutes, and the pH of the solution was adjusted to about 12.1, and the salt solution containing nickel, cobalt and manganese, the ammonia solution and the sodium hydroxide were simultaneously added dropwise. Solution.
  • the reaction temperature of the control solution was 63 ° C ⁇ 5 ° C.
  • the dropping time is 8 hours.
  • 1.7 kg of nano-magnesia powder is added, and 28.5 kg of cerium nitrate hexahydrate powder is aged under stirring for 20 hours, and then pumped into the centrifuge with a diaphragm pump.
  • pipe demagnetizer (9800GS) on the pumping line, and repeatedly clean the filter cake with deionized water for 10 times until the impurity content is within the acceptable range. Remove the filter cake and dry it with a vacuum disc dryer.
  • the product particle size was 5.9 ⁇ m
  • the specific surface was 6.8 m 2 /g
  • the tap density was 1.6 g. /cm3
  • the magnetic substance is 110 ppb.
  • the ammonia gas shielding gas 5 is replaced by the ammonia gas for 5 minutes, and then the sodium hydroxide solution and the ammonia aqueous solution are added dropwise for 10 minutes, and the pH of the solution is adjusted to about 12.3, and the salt solution containing nickel-cobalt-manganese is simultaneously added, the ammonia solution and the hydroxide are added.
  • Sodium solution At the same time, the reaction temperature of the control solution was 65 ° C ⁇ 5 ° C. The dropping time is 8 hours.
  • the product particle size is 8.5 ⁇ m
  • the specific surface is 7.2 m 2 / g
  • the tap density is 1.6. g/cm3
  • the magnetic substance is 123 ppb.
  • the ammonia gas shielding gas was replaced by the ammonia gas for 30 minutes, and then the sodium hydroxide solution and the ammonia aqueous solution were added dropwise for 10 minutes, and the pH of the solution was adjusted to about 12.1, and the salt solution containing nickel, cobalt and manganese, the ammonia solution and the sodium hydroxide were simultaneously added dropwise. Solution.
  • the reaction temperature of the solution was controlled to be 50 ° C ⁇ 5 ° C. The dropping time is 5 hours.
  • the solid-liquid separation in the plate and frame filter press adding the pipe demagnetizer (11000GS) on the pumping pipeline, and repeatedly cleaning the filter cake with deionized water for 6 times until the impurity content is within the acceptable range, after removing the filter cake It was dried by a vacuum disc dryer (temperature: 105 ° C ⁇ 2 h), and filtered into a precursor product by a 325 mesh stainless steel mesh to obtain 25.2 kg of NCM 502525 precursor product, the product particle size was 4.3 ⁇ m, and the specific surface was 10.8 m 2 / g, the tap density is 1.7 g/cm3, and the magnetic substance is 145 ppb.
  • the obtained positive electrode material has a specific surface area: 0.49 m 2 /g, an average particle diameter D50: 4.5 ⁇ m, and the structural formula is:
  • the obtained positive electrode material has a specific surface area: 0.65 m 2 /g, and 5 average particle diameter D 50: 3.2 ⁇ m, and the structural formula is:
  • the obtained positive electrode material has a specific surface area of 0.56 m220/g, an average particle diameter D50 of 8.2 ⁇ m, and a structural formula:
  • the obtained positive electrode material has a specific surface area: 2.2 m 2 /g, an average particle diameter D50: 8.9 ⁇ m, and the structural formula is:
  • the obtained positive electrode material has a specific surface area: 0.7 m 2 /g, an average particle diameter D50: 4.8 ⁇ m, and the structural formula is:
  • the obtained positive electrode material has a specific surface area: 0.76 m 2 /g, an average particle diameter D50: 9.0 ⁇ m, and the structural formula is:
  • Example 1-4 17.8kg of the precursor of Example 1-4 was added in sequence, and 7.6kg of lithium carbonate was initially mixed into a powder, and then transferred to a high-speed mixer for dispersion in a dry state at normal temperature.
  • the dispersed powder was a rotary demagnetizer with a strength of 8000 GS. Demagnetization.
  • the powder after demagnetization was transferred to a ceramic crucible and placed in a muffle furnace.
  • the prepared powder was subjected to a first sintering treatment at 800 ° C for 15 hours in an air atmosphere, and the sintered material was cooled and ball milled for 6 hours using a polyurethane ball mill.
  • a positive electrode material semi-finished product is obtained
  • the steel mesh screen is sieved to obtain the positive electrode material of the invention.
  • the obtained positive electrode material was 20.1 kg.
  • the positive electrode material semi-finished product is placed in a muffle furnace, and the second sintering treatment is performed at 800 ° C ⁇ 15 h in an oxygen atmosphere, and the powder after the treatment cooling 5 is ball milled by a ball mill for 6 hours, and then a rotary demagnetizer (8000 GS) is used.
  • the demagnetization was carried out and sieved with a 325 mesh stainless steel mesh to obtain 20.2 kg of the positive electrode material of the invention.
  • the obtained positive electrode material had a specific surface area of 0.79 m 2 /g, an average particle diameter D50 of 10.1 ⁇ m, and a structural formula of Li[Li-0.1Mn0.043Ni0.915Co0.044]O2.
  • the obtained positive electrode material has a specific surface area: 2.00 m 2 /g, an average particle diameter D50: 6.3 ⁇ m, and the structural formula is:
  • Example 5 ICP Element Content Detection Simultaneously, the positive electrode material powder prepared in Example 2-1, Example 3-1, Example (Comparative Example) 2-3, and Example (Comparative Example) 3-3 was subjected to ICP. The detection and detection of the doping coating element content gave the results as shown in Table 3.
  • Example 2-1 Example 3-1
  • Example 2-3 Example 3-3
  • Aluminum (Al) (wt%) 0.0013 0.0014 0.0008 0.0013 Copper (Cu) (wt%) 0.0005 0.0005 0.0005 0.0005 0.0004 Iron (Fe) (wt%) 0.0055 0.0059 0.0054 0.0028 ⁇ (La) (wt%) 0.0001 0.0001 0.0008 0.0001
  • Titanium (Ti) (wt%) 0.0013 0.0507 0.0440 0.0666 ⁇ (Y) (wt%) 0.0172 0.0043 0.1627 0.0006
  • Zirconium (Zr) (wt%) 0.0005 0.1051 0.0002 0.0001 Sulfur (S) (wt%) 0.0039 0.0020 0.0024 0.0100 Phosphorus (P) (wt%) 0.0021 0.0041 0.0029 0.0032
  • the doping/coating elements are present in the trace elements of the material, and the content thereof accounts for (0.0 to 0.43)% by weight of the bulk positive electrode material, and the elements are individually between 20 and 4000 ppm in ppm, indicating that The doping and cladding process is feasible, indicating that the doping/coating element can be better combined with the bulk positive electrode material.
  • Example 6 Preparation of Half-Battery and Evaluation of Electrochemical Performance 70 g of N-methylpyrrolidone (NMP) was weighed into an experimental disperser vessel, stirring was started, and 5 g of polyvinylidene fluoride (PVDF Solef 56020) was added with stirring. After the powder and other adhesives are completely dissolved, 5 g of conductive carbon powder (SP) is weighed and added to the above solution, and after high-speed dispersion for 60 minutes, respectively, Example 2-1, Example 3-1, and Examples (Comparative Example) 2-3, 90 g of the positive electrode material powder prepared in Example (Comparative Example) 3-3 was added to the above solution, and after dispersing for 0.5 h, the stirring speed was lowered to discharge.
  • NMP N-methylpyrrolidone
  • PVDF Solef 56020 polyvinylidene fluoride
  • the aluminum foil having a thickness of 16 ⁇ m was taken as a current collector, and the prepared slurry was uniformly coated on a copper foil and dried in a dry box to form a pole piece, and the baking temperature was 105 ° C, and the baking time was 1 h.
  • the dried pole piece was compacted into a pole piece having a compacted density of 3.3 g/cm 3 of active material in the pole piece, an active thickness of about 85 ⁇ m, and a total thickness of about 100 ⁇ m.
  • the CR 2032 type button half-cell was prepared, the counter electrode was a metal lithium sheet, the electrolyte was LBC301, the button type half-cell was assembled in a high-purity argon gas-filled glove box, and the button-type half-cell was allowed to stand for 10 hours on the machine test. The detection result of Fig. 2 is obtained.
  • the material button cell using the cladding/doping process has a stable curve, a high platform, and is uncoated/doped (Example 3-3) or an excessive coating (Example 2 3)
  • the invention still emits electricity smoothly, and the comparative ratio is accompanied by a rapid drop in voltage during discharge, which is not good for practical electrochemical applications, indicating that it is not coated or Excessive coating affects the specific capacity. This may be because the ionic conductor layer is too thick, or a side reaction occurs on the surface of the positive electrode material in the absence of doping and coating, which offsets the free insertion and extraction of lithium.
  • the positive electrode material powder prepared in Example 2-1, Example 3-1, Example 2-3, Example 2-5, and Example 3-3 was prepared as a positive electrode active material by a square battery to have a capacity of 2.0. Ah around the power battery. Making a full battery is mainly used to investigate high voltage cycling and safety effects.
  • the applicable varieties are the 954261 aluminum plastic film flexible packaging battery, which has a battery thickness of 9.5 mm, a length of 4.2 mm and a width of 6.1 mm.
  • the battery design capacity is 2.0Ah.
  • the preparation of the positive electrode tab is usually made by preparing a slurry, coating, cold pressing, slitting, etc., and the effective positive active material in the pole piece
  • the mass content was 95%
  • the pole piece coating weight was 0.21 g/cm3
  • the pole piece coating width was 38 mm
  • the total electrode active material area was 0.050 m2
  • the pole piece compaction density was 53.6 g/cm3 based on the active material.
  • the preparation method of the negative electrode sheet is usually prepared through a process of preparing a slurry, coating, cold pressing, slitting, and the like.
  • the prepared electrode sheet has an effective negative electrode active material (artificial graphite) content of 95.5%, a pole piece coating weight of 0.130 g/cm 2 , and a pole piece coating width of 40 mm, and a pole piece active material.
  • the total area is 0.051 m2
  • the compact density of the pole piece is 1.6 g/cm3 based on the active material
  • the lithium titanate is used as the negative electrode active material
  • the content of the effective negative electrode active material (lithium titanate) after preparation is 90.0%.
  • the pole piece coating weight was 0.275 g/cm2, the pole piece coating width was 40 mm, the total electrode active material area was 0.051 m2, and the pole piece compaction density was 1.8 g/cm3 based on the active material.
  • the positive electrode sheet, the separator film, the negative electrode sheet and the like are sequentially wound into a bare cell, and the bare cell is inspected and loaded into a punched aluminum plastic film and heat-sealed 1 (about 135 ° C ⁇ 5 s, width 5 ⁇ 8mm), injection (electrolyte: LIB302, 3.2g / only), and then in the LIP-10AHB06 high temperature formation machine (lithium titanate negative battery formation voltage 0-2.5V, graphite negative lithium battery formation voltage 0 ⁇ 3.85 V, 0.2C), heat seal 2 (about 135 ° C ⁇ 5 s, width 5 ⁇ 8 mm), capacity test (lithium titanate negative battery test voltage 1.5-2.8V, graphite negative lithium battery test voltage 3.0 ⁇ 4.2V, 0.5 C), select quality qualified batteries for subsequent performance evaluation.
  • the positive electrode sheet of the above embodiment can be freely combined with a graphite negative electrode sheet and a lithium titanate negative electrode sheet to prepare a graphite negative electrode lithium ion secondary battery and a lithium titanate negative electrode lithium ion secondary battery, except that the battery formation and capacity testing processes are different.
  • Example 2-1, Example 3-1, Example 2-3, Example 3-3 the battery was made of graphite as a negative electrode, and Example 2-5 was made of lithium titanate as a negative electrode. .
  • the graphite 5 negative electrode lithium battery prepared in the example was placed in an oven at 60 ° C, and the electrode was connected to a 1 C/1 C, 3.0-4.8 V cycle test on a LIP-10AHB06 type high temperature forming machine, and the high temperature cycle result of FIG. 3 was obtained.
  • the lithium titanate negative electrode lithium battery prepared in the example was placed in an oven at 60 ° C, and the electrode was connected to a 1 C/1 C, 1.5-2.8 V cycle test on a LIP-10AHB06 type high temperature forming machine to obtain a high 10 temperature of FIG. Loop results.
  • Example thickness Internal resistance Open circuit voltage Capacity loss Example 2-1 6.76% 3.26% -2.79% -1.35%
  • Example 3-1 4.57% 3.33% -3.61% -1.76%
  • Example 2-3 35.10% 27.90% -3.80% -2.10%
  • Example 3-3 57.82% 48.83% -7.78% -6.08%
  • Example 2-5 34.37% 2.20% -1.39% -1.41%
  • Example thickness Internal resistance Open circuit voltage Capacity loss Example 2-1 29.30% 30.20% -7.20% -6.50% Example 3-1 36.60% 38.10% -13.10% -6.30% Example 2-3 105.10% 83.20% -22.50% -12.40% Example 3-3 120.80% 177.10% -39.80% -18.20% Example 2-5 38.50% 26.70% -4.43% -8.20%
  • the present invention provides a method for preparing a high-voltage positive electrode material, and a beneficial improvement result of the preparation of the method. Due to limitations and limitations of experimental demonstration, the process of the present invention can also be combined with existing patents.
  • the beneficial revelation together to advance the preparation technology of the high voltage positive electrode material is not limited to the specific embodiments described above, and all of the disclosed and undisclosed cases do not affect the essence of the present invention.

Abstract

Disclosed are a positive electrode material for a high voltage lithium battery, a battery, a preparation method therefor and the use thereof. The structural formula of the positive electrode material is Li[LixMnaNibCoc]O2·αMyOz, wherein -0.05 < x < 0.3, a, b and c are all greater than 0.02 and less than 0.9, M is a metal element other than lithium, nickel, cobalt and manganese, and MyOz is a composite oxide complying with valence composition, 0.13 ≤ α ≤ 0.3, 0 < y ≤ 3, 0 < z ≤ 5, and 0.9 < x+a+b+c < 1.4. The positive electrode material is obtained by using a precursor synthesis process and a doping and coating technique and by crushing twice, demagnetizating twice and sintering twice. A lithium ion secondary battery prepared using the positive electrode material has the advantages of a stable structure, a good electrolyte applicability, etc. Lithium ion secondary batteries prepared using different negative electrodes have a good cycle stability in a maximum operating voltage range of 2.8-4.8 V, and are applicable in the fields of long-lasting lithium battery applications such as electric vehicles (xEV) and energy storage systems (ESS).

Description

高电压锂电池正极材料、电池及制法和应用High voltage lithium battery cathode material, battery and preparation method and application thereof 技术领域Technical field
本发明涉及锂离子二次电池领域，具体涉及一种高电压型锂离子二次电池的正极材料。本发明还涉及该正极材料的制备方法，以及用该正极材料制成的电化学性能得到改善的动力型锂离子二次电池。The present invention relates to the field of lithium ion secondary batteries, and in particular to a positive electrode material for a high voltage type lithium ion secondary battery. The present invention also relates to a method of producing the positive electrode material, and a power type lithium ion secondary battery having improved electrochemical performance made of the positive electrode material.
背景技术Background technique
锂离子二次电池由于具有能量密度高、工作电压高、循环寿命长等优点,而被广泛用作各种移动设备的电源,储能电站,甚至在航空、航天、航海、汽车、医疗设备等领域中逐步取代其他的传统电池。Lithium-ion secondary batteries are widely used as power sources for various mobile devices due to their high energy density, high operating voltage, long cycle life, etc., energy storage power plants, even in aviation, aerospace, marine, automotive, medical equipment, etc. The field is gradually replacing other traditional batteries.
在锂离子化学电源体系中,通常是由锂离子的转移实现能量的输出,其涉及到正极,负极,隔离膜,电解质等多种固/液体多孔介质之间的电子转移“(锂离子电池的电化学阻抗谱分析”,庄全超；等《化学进展》2010.22(6)P 1044-1057),充放电电压过高时,锂离子脱出/嵌入驱动力过大,长期使用会带来严重的循环衰减及安全问题。In a lithium-ion chemical power system, the output of energy is usually realized by the transfer of lithium ions, which involves electron transfer between a plurality of solid/liquid porous media such as a positive electrode, a negative electrode, a separator, an electrolyte, etc. (Li-ion battery Electrochemical impedance spectroscopy analysis, Zhuang Quanchao; et al., Progress in Chemistry, 2010.22(6)P 1044-1057), when the charge and discharge voltage is too high, the lithium ion extraction/embedding driving force is too large, and long-term use will bring serious cyclic attenuation. And security issues.
近年来出现的锂电池电动车(如日本丰田产普瑞斯,美国特斯拉公司产的特斯拉电动车等),以及电贮存能站等,其使用特点是将大量能量密度高的锂离子电池集中存放在一起,通过电能管理***进行充放电等使用。在上述电池设备的商业化过程中,锂离子二次电池的能量密度(包括体积能量密度Wh/L和重量能量密度Wh/kg)一直是各生产厂商及应用终端客户密切关注的重点领域。锂电池的输出工作电压与正极，负极均有关，相同的钴酸锂正极，对石墨负极平台工作电压是3.8伏，对钛酸锂负极平台工作电压是2.2伏，相应的能量密度也会有较大的变化，目前钴酸锂对石墨负极的工作电压范围为3.0～4.2V,如将其工作电压范围提高至3.0-4.25V,则相应的即为高电压电池，相应的正极材料为高电压型正极材料。Lithium battery electric vehicles (such as Toyota, Japan, Tesla electric vehicles, etc.), and electric storage stations, which have appeared in recent years, are characterized by a large amount of lithium with high energy density. Ion batteries are stored together in a centralized manner, and are used for charging and discharging through a power management system. In the commercialization of the above-mentioned battery equipment, the energy density of the lithium ion secondary battery (including the volume energy density Wh/L and the weight energy density Wh/kg) has been a key area of close attention of various manufacturers and application terminal customers. The output voltage of the lithium battery is related to the positive and negative electrodes. The same lithium cobaltate cathode has a working voltage of 3.8 volts for the graphite anode platform and 2.2 volts for the lithium titanate anode platform. The corresponding energy density will also be higher. Large changes, the current operating voltage range of lithium cobaltate to graphite anode is 3.0 ~ 4.2V, if the operating voltage range is increased to 3.0-4.25V, the corresponding high voltage battery, the corresponding cathode material is high voltage Type cathode material.
提升锂电池的工作电压意义不言而喻，其主要目的即为提升锂离子二次电池的能量密度。同样以上述钴酸锂对石墨负极锂离子二次电池为例，电压提升0.05V,锂电池电芯的能量密度可以从530Wh/L提升到580Wh/L左右，在略增加负极用量的情况下体积能量密度提升约5～7％，因而非常可观，目前3C领域4G手机大都开始采用4.35V锂电池，电池的容量在1.5Ah以上，5部分厂家还结合提供了快充技术。It is self-evident that the working voltage of the lithium battery is improved, and its main purpose is to increase the energy density of the lithium ion secondary battery. Taking the above lithium cobaltate as an example for the graphite negative electrode lithium ion secondary battery, the voltage is increased by 0.05V, and the energy density of the lithium battery cell can be increased from 530Wh/L to about 580Wh/L, and the volume is increased slightly by the amount of the negative electrode. The energy density is increased by about 5 to 7%, which is very impressive. At present, 4G mobile phones in the 3C field mostly use 4.35V lithium batteries, and the battery capacity is above 1.5Ah. Five manufacturers also provide fast charging technology.
尽管上述锂离子二次电池的工作电压仅提升0.05-0.2V,但对锂离子二次电池的材料及结构均有新的要求，在高的电压下可逆使用安全性也是一个挑战。就正极材料而言，当工作电压升高时，意味着部分参与正极材料的结构锂参与了锂的嵌入和脱出，以钴酸锂为例，按分子式LiCoO2计算，其理论比容量为274mAh/g,在4.2V应用下约138～140mAh/g比容量，即只有0.5mol右的锂参与了可逆反应，在4.35V应用条件下约170-172mAh/g的比容量Although the operating voltage of the above lithium ion secondary battery is only increased by 0.05-0.2 V, there are new requirements for the material and structure of the lithium ion secondary battery, and reversible safety at high voltage is also a challenge. As for the positive electrode material, when the working voltage is increased, it means that part of the lithium involved in the positive electrode material participates in the intercalation and deintercalation of lithium. Taking lithium cobaltate as an example, the theoretical specific capacity is 274 mAh/g according to the molecular formula LiCoO2. , in the 4.2V application, about 138 ~ 140mAh / g specific capacity, that is, only 0.5mol of right lithium participates in the reversible reaction, the specific capacity of about 170-172mAh / g under the 4.35V application conditions
发挥，约0.62mol的锂参与了可逆循环，意味着脱锂后的陶瓷结构氧化物结构空位结构缺陷更多，在此条件下如何保证结构稳定是一个非常大的挑战。At present, about 0.62 mol of lithium participates in the reversible cycle, which means that there are more defects in the vacancy structure of the ceramic structure oxide structure after delithiation, and how to ensure structural stability under such conditions is a very big challenge.
对于电解质而言也是一个挑战，电解质原料水分及氢氟酸含量越低电解质耐电压越高，但考虑到电解质原料的合成反应中的反应平衡，并不能保证电解质原料中不含有上 述杂质。It is also a challenge for the electrolyte. The lower the electrolyte raw material moisture and hydrofluoric acid content, the higher the electrolyte withstand voltage, but considering the equilibrium of the reaction in the synthesis reaction of the electrolyte raw material, there is no guarantee that the electrolyte raw material does not contain Said impurities.
因此针对上述组成结构的每个组成进行改进是高电压锂离子电池急需要解决的问题。许多已公开的文献及专利均给出了各自的解决方案。Therefore, improvement of each composition of the above-described constituent structures is an urgent problem to be solved by a high-voltage lithium ion battery. Many published documents and patents have given their respective solutions.
在xEV/ESS领域，目前使用的正极材料有磷酸铁锂，镍钴锰酸锂，锰酸锂等材料，根据国家的能源方针及能量密度路线图，在动力电池领域最有商业价值的是高电压普通三元等，其在3.0-4.2V工作电压下pack能量密度可达140wh/kg,如升高电压至4.4～4.6伏，则在其他应用体系不变的情况下pack体积能量密度可达200-230Wh/kg。同钴酸锂相比，三元材料含有镍和锰，成本优势明显，针对三元材料在高电压的应用主要有如下技术路线：包覆LCO25(CN102891307A)，与钴酸锂混合使用形成双平台(CN102610810A),同钴酸锂一样掺杂金属元素(CN102074700A)等。In the field of xEV/ESS, the cathode materials currently used are lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium manganate and other materials. According to the national energy policy and energy density roadmap, the most commercially valuable in the field of power batteries is high. The voltage is ordinary ternary, etc., and the energy density of the pack can reach 140 wh/kg at 3.0-4.2 V working voltage. If the voltage is increased to 4.4-4.6 volts, the energy density of the pack volume can reach the same under other application systems. 200-230Wh/kg. Compared with lithium cobalt oxide, the ternary material contains nickel and manganese, and the cost advantage is obvious. For the application of ternary materials in high voltage, the following technical routes are mainly included: coated LCO25 (CN102891307A), mixed with lithium cobalt oxide to form a dual platform (CN102610810A), doped with a metal element (CN102074700A) and the like as lithium cobaltate.
发明内容Summary of the invention
本发明所解决的技术问题是：以往技术中锂离子二次电池的正极材料的终止电压和能量密度有待进一步提高。The technical problem to be solved by the present invention is that the termination voltage and energy density of the positive electrode material of the lithium ion secondary battery in the prior art need to be further improved.
上述专利就各自研究的领域公开的解决方案和措施，可以作为本发明的有益启示和参考。但锂离子二次电池材料的应用搭配涉及诸多环节，因此还需要开发一类普适性高电压正极材料，尤其是三元系材料，能够依据不同负极在循环最高工作电压2.8V～4.8V 5范围内安全使用。本发明基于开发适用于不同负极体系的一种普适性高电压使用(应用工作电压上限2.8V～4.8V)材料需要，对材料制备，性能及应用作了详细的说明。所述普适性高电压使用，以钛酸锂电极对三元电极而言，一般工作电压为1.5～2.5V,如果工作电压为1.5～2.8V时，其工作电压上限提高，即为高电压使用工况；同样的，以石墨10电极对三元电极而言，一般工作电压3.0～4.2V,如果工作电压为3.0～4.8V，则为高电压使用工况。The above-mentioned patents disclose the solutions and measures disclosed in the respective research fields, which can be used as useful inspiration and reference for the present invention. However, the application of lithium ion secondary battery materials involves many links. Therefore, it is necessary to develop a class of universal high-voltage cathode materials, especially ternary materials, which can be circulated at a maximum working voltage of 2.8V to 4.8V according to different anodes. Safe use within the scope. The invention is based on the development of a universal high voltage use (application working voltage upper limit 2.8V ~ 4.8V) material suitable for different negative electrode systems, and the material preparation, performance and application are described in detail. The universal high voltage is used. When the lithium titanate electrode is used for the ternary electrode, the general working voltage is 1.5 to 2.5V. If the working voltage is 1.5 to 2.8V, the upper limit of the working voltage is increased, that is, the high voltage. The working condition; similarly, the graphite 10 electrode to the ternary electrode generally has a working voltage of 3.0 to 4.2 V, and if the operating voltage is 3.0 to 4.8 V, it is a high voltage use condition.
由于材料的比表面积地大意味着材料本体与电解质接触面积更大，有更多的反应面有可能会参与发生副反应。因此控制比表面积是制备高电压正极材料的关键。另外，作为锂离子正极材料，通常材料不包覆其他元素比容量及首次效率较高，包覆其他元素后由于包覆材料不能脱/嵌锂或者是嵌入/脱出量较少，比容量及首次效率均下降，但安全性能提升，因而需要在比容量及循环/安全性能方面作综合平衡量考虑。Since the large specific surface area of the material means that the contact area between the material body and the electrolyte is larger, more reaction surfaces may participate in side reactions. Controlling the specific surface area is therefore the key to preparing high voltage cathode materials. In addition, as a lithium ion positive electrode material, the material usually does not coat other elements with a specific capacity and high efficiency for the first time. After coating other elements, the coating material cannot be deintercalated/intercalated or the amount of insertion/extraction is small, the specific capacity and the first time Efficiency is reduced, but safety performance is improved, so a comprehensive balance of specific capacity and cycle/safety performance is required.
本发明的目的在于:开发一种普适型高电压正极材料，通过控制材料比表面积，平衡锂离子二次电池电化学性能和高电压循环/安全性能，采用前驱20体制备、正极材料合成工序制备一次球型或土豆型及二次球型颗粒正极材料，并将该正极材料应用于锂离子二次电池中。The object of the invention is to develop a universal high-voltage cathode material, balance the electrochemical performance and high-voltage cycle/safety performance of the lithium ion secondary battery by controlling the specific surface area of the material, and adopt the precursor 20 body preparation and the cathode material synthesis process. A spherical or potato type and secondary spherical type positive electrode material is prepared, and the positive electrode material is applied to a lithium ion secondary battery.
同时本发明还提供了一种动力型锂离子二次电池,该锂离子二次电池包括以下部分:电极、电解质、隔膜、容器。其中电极包括正极和负极,正极包括正极集流器和涂覆在正极集流器上的正极活性物质层；负极包括负极集流器和涂覆在负极集流器上的负极活性物质层；隔膜可以是单纯的多微孔固体绝缘层,容器是正极、负极、隔膜、电解质的具备一定形态的包容体。Meanwhile, the present invention also provides a power type lithium ion secondary battery including the following: an electrode, an electrolyte, a separator, and a container. Wherein the electrode comprises a positive electrode and a negative electrode, the positive electrode comprises a positive current collector and a positive active material layer coated on the positive current collector; the negative electrode comprises a negative current collector and a negative active material layer coated on the negative current collector; It may be a simple microporous solid insulating layer, and the container is a container having a certain form of a positive electrode, a negative electrode, a separator, and an electrolyte.
本发明的正极材料结构式为Li[LixMnaNibCoc]O2·αMyOz,其中-0.05＜x＜0.3,a.b.c均大于0.02并小于0.9，M为除锂、镍、钴、锰以外的金属元素且MyOz是一种符合 化合价组成的复合氧化物型离子导体，0.13≤α≤0.3,0＜y4≤3,0＜z≤5,并且0.9＜x+a+b+c＜1.4。The structure of the positive electrode material of the present invention is Li[LixMnaNibCoc]O2·αMyOz, wherein -0.05<x<0.3, abc is greater than 0.02 and less than 0.9, M is a metal element other than lithium, nickel, cobalt, manganese and MyOz is a kind meets the A composite oxide type ionic conductor composed of a valence, 0.13 ≤ α ≤ 0.3, 0 < y4 ≤ 3, 0 < z ≤ 5, and 0.9 < x + a + b + c < 1.4.
该正极材料可应用于动力型电动车、移动存贮电源、储能电站设备中的锂离子二次电池，该制备方法工艺简单可行，产品高电压使用性能得以显著提升。The positive electrode material can be applied to a lithium ion secondary battery in a power type electric vehicle, a mobile storage power source, and an energy storage power station device. The preparation method is simple and feasible, and the high voltage use performance of the product is significantly improved.
具体来说，本发明提出了如下技术方案：Specifically, the present invention proposes the following technical solutions:
一种锂离子二次电池用正极材料，该正极材料结构式为Li[LixMnaNibCoc]O2·αMyOz,其中-0.05＜x＜0.3,a.b.c均大于0.02并小于0.9；M为除锂、镍、钴、锰以外的金属元素且MyOz是一种符合化合价组成的复合氧化物，0.13≤α≤0.3,0＜y≤3,0＜z≤5,并且0.9＜x+a+b+c＜1.4。A positive electrode material for a lithium ion secondary battery, wherein the positive electrode material has a structural formula of Li[LixMnaNibCoc]O2·αMyOz, wherein -0.05<x<0.3, abc is greater than 0.02 and less than 0.9; M is lithium, nickel, cobalt, manganese The metal element other than MyOz is a composite oxide conforming to the valence composition, 0.13 ≤ α ≤ 0.3, 0 < y ≤ 3, 0 < z ≤ 5, and 0.9 < x + a + b + c < 1.4.
优选的是，上述a,b,c的取值满足：a,b,c为0.325～0.345；或a,c为0.042～0.055，并且b为0.85～0.95；或a,c为0.05～0.15，并且b为0.75～0.85；或a,c为0.140～0.155并且b为0.65～0.75；或a,c为0.15～0.25并且b为0.55～0.65；或a,c为0.245～0.265并且b为0.45～0.55；或a和b为0.35～0.45，并且c为0.15～0.25；或a为0.45～0.55，b为0.25～0.35，c为0.15～0.25。Preferably, the above values of a, b, and c satisfy: a, b, c is 0.325 to 0.345; or a, c is 0.042 to 0.055, and b is 0.85 to 0.95; or a, c is 0.05 to 0.15, And b is 0.75 to 0.85; or a, c is 0.140 to 0.155 and b is 0.65 to 0.75; or a, c is 0.15 to 0.25 and b is 0.55 to 0.65; or a, c is 0.245 to 0.265 and b is 0.45 to ～ 0.55; or a and b are 0.35 to 0.45, and c is 0.15 to 0.25; or a is 0.45 to 0.55, b is 0.25 to 0.35, and c is 0.15 to 0.25.
优选的是，上述M选自镁，钛，钇，镧系元素，锆和铝中的一种以上。Preferably, the above M is selected from one or more selected from the group consisting of magnesium, titanium, lanthanum, lanthanoid, zirconium and aluminum.
优选的是，上述M含量占正极材料含量的为大于0小于等于0.43wt％优选的是，M以M的氧化物与镍钴锰酸锂组合物均匀混合，或者M以M的氧化物均匀包覆于镍钴锰酸锂组合物表面上，或者M以M的氧化物均匀包覆于M镍钴锰酸锂组合物表面上形成所述正极材料。Preferably, the above M content is more than 0 or less than 0.43 wt% of the content of the positive electrode material. Preferably, M is uniformly mixed with the oxide of M and the lithium nickel cobalt manganese oxide composition, or M is uniformly coated with the oxide of M. The positive electrode material is formed on the surface of the nickel-cobalt-manganese-acid composition, or M is uniformly coated on the surface of the M-nickel-cobalt-manganate composition with an oxide of M.
优选的是，上述正极材料粒径D50为3.2-9μm。Preferably, the above positive electrode material has a particle diameter D50 of 3.2 to 9 μm.
优选的是，上述正极材料比表面积为0.49-0.76m2/g。Preferably, the above positive electrode material has a specific surface area of from 0.49 to 0.76 m 2 /g.
另外，本发明还提供一种正极材料的制备方法，其特征在于，通过含镍、钴、锰、M或含镍、钴、锰的前驱体合成工艺，制得粒径2-9.2μm、比表面积6.5-13.2m2/g的前驱体；接着，将前驱体与锂源混合，经除磁、一次烧结、一次粉碎、二次烧结、二次粉碎、二次除磁工序得到正极材料；M为除锂、镍、钴、锰以外的金属元素。In addition, the present invention also provides a method for preparing a positive electrode material, which is characterized in that a particle size of 2-9.2 μm is obtained by a nickel, cobalt, manganese, M or a precursor synthesis process containing nickel, cobalt and manganese. a precursor having a surface area of 6.5-13.2 m 2 /g; then, the precursor is mixed with a lithium source, and subjected to demagnetization, primary sintering, primary pulverization, secondary sintering, secondary pulverization, and secondary demagnetization to obtain a positive electrode material; Metal elements other than lithium, nickel, cobalt, and manganese.
优选的是，所述的方法中，一次烧结的温度为800-880℃，一次烧结的时间为15-20小时。Preferably, in the method, the temperature of one sintering is 800-880 ° C, and the time of one sintering is 15-20 hours.
优选的是，所述的方法中，二次烧结的温度为750-880℃，二次烧结的时间为15-18小时。Preferably, in the method, the secondary sintering temperature is 750-880 ° C, and the secondary sintering time is 15-18 hours.
优选的是，所述的方法中，一次粉碎和二次粉碎包括聚氨酯球磨机球磨5-7小时。Preferably, in the method, the primary pulverization and the secondary pulverization comprise a polyurethane ball mill for 5-7 hours.
优选的是，所述的方法中，M的来源为含元素M的盐类或者含元素M的氧化物或者含元素M的氢氧5化物，所述盐类优选为可溶性有机或无机盐。Preferably, in the method, the source of M is a salt containing element M or an oxide containing element M or a hydroxide containing element M, preferably a soluble organic or inorganic salt.
优选的是，所述的方法中，氧化物的粒径＜100μm。Preferably, in the method, the oxide has a particle size of <100 μm.
优选的是，所述的方法中，M的引入可以在前驱体合成过程中，也可以在前驱体与锂盐的混合过程中，还可以在正极材料半成品制备阶段添加。Preferably, in the method, the introduction of M may be added during the synthesis of the precursor, during the mixing of the precursor with the lithium salt, or during the preparation of the semi-finished material of the positive electrode material.
本发明还提供一种锂锂离子二次电池正极材料，通过上述制备方法得到，10该正极材料结构式为Li[LixMnaNibCoc]O2·αMyOz,其中-0.05＜x＜0.3,a.b.c均大于0.02并小于0.9，M为除锂、镍、钴、锰以外的金属元素且MyOz是一种符合化合价组成的复合氧化物，0＜α≤0.3,0＜y≤3,0＜z≤5,并且0.9＜x+a+b+c＜1.4。 The invention also provides a lithium lithium ion secondary battery cathode material obtained by the above preparation method, wherein the cathode material has the structural formula Li[LixMnaNibCoc]O2·αMyOz, wherein -0.05<x<0.3, abc is greater than 0.02 and less than 0.9. M is a metal element other than lithium, nickel, cobalt, manganese and MyOz is a composite oxide having a valence composition, 0 < α ≤ 0.3, 0 < y ≤ 3, 0 < z ≤ 5, and 0.9 < x +a+b+c<1.4.
本发明还提供一种锂离子二次电池，采用上述正极材料制备得到。The present invention also provides a lithium ion secondary battery prepared by using the above positive electrode material.
优选的是，上述锂离子二次电池采用碳材料或钛酸锂作为负极，其中碳材料优选石墨。Preferably, the above lithium ion secondary battery uses a carbon material or lithium titanate as a negative electrode, and the carbon material is preferably graphite.
优选的是，上述锂离子二次电池依据不同的负极材料其电压工作上限为2.8-4.8V。Preferably, the lithium ion secondary battery has a voltage operating upper limit of 2.8-4.8 V depending on the different negative electrode materials.
优选的是，上述锂离子二次电池，以钛酸锂为负极材料，其电压工作上限为2.8V，或者以碳材料为负极材料，其电压工作上限为4.8V。Preferably, the above lithium ion secondary battery uses lithium titanate as a negative electrode material, and its upper limit of voltage operation is 2.8 V, or a carbon material is used as a negative electrode material, and its upper limit of voltage operation is 4.8 V.
本发明还提供一种移动式存储设备，采用了上述的锂离子二次电池。The present invention also provides a mobile storage device using the above-described lithium ion secondary battery.
本发明还提供一种储能电站，采用了上述锂离子二次电池或上述的移动式储存设备。The present invention also provides an energy storage power station using the above-described lithium ion secondary battery or the above-described mobile storage device.
本发明实施例的优点将会在下面的说明书中部分阐明，一部分根据说明书是显而易见的，或者可以通过本发明实施例的实施而获知。The advantages of the embodiments of the present invention will be set forth in part in the description which follows.
附图说明DRAWINGS
图1-1为实施例(对比例)2-3扫描电镜图，放大倍数为3000倍。Figure 1-1 is a scanning electron micrograph of the embodiment (comparative example) 2-3, and the magnification is 3000 times.
图1-2为实施例2-1扫描电镜图，放大倍数为3000倍。Figure 1-2 is a scanning electron micrograph of Example 2-1, and the magnification is 3000 times.
图1-3为实施例(对比例)3-3扫描电镜图，放大倍数为3000倍。1-3 is a scanning electron micrograph of the embodiment (comparative example) 3-3, and the magnification is 3000 times.
图1-4为实施例3-1扫描电镜图，放大倍数为3000倍。Figure 1-4 is a scanning electron micrograph of Example 3-1, and the magnification is 3000 times.
图2为实施例及对比例扣式半电池检测结果，工作电压为3.0-4.35V。2 is a test result of the embodiment and the comparative button type half-cell, and the working voltage is 3.0-4.35V.
图3为实施例及对比例高5电压循环检测结果，以石墨为负极，循环测试工作电压为3.0-4.8V,1C/1C,循环温度为60℃。Fig. 3 shows the results of the voltage cycling test of the example and the comparative example. The graphite was used as the negative electrode, and the cycle test operating voltage was 3.0-4.8 V, 1 C/1 C, and the cycle temperature was 60 °C.
图4为实施例及对比例高电压循环检测结果，以钛酸锂为负极，循环测试工作电压为1.5-2.8V,1C/1C,循环温度为60℃。4 is an example and a comparative high voltage cycle detection result, using lithium titanate as a negative electrode, and the cycle test working voltage is 1.5-2.8 V, 1 C/1 C, and the cycle temperature is 60 ° C.
具体实施方式detailed description
如上所述，本发明的目的在于：通过控制合成材料的粒径和比表面积，平衡电化学性能输出及高电压循环/安全性能，开发一种普适型高电压正极材料，并将该正极材料应用于锂离子二次电池中。As described above, the object of the present invention is to develop a universal high-voltage positive electrode material by controlling the particle size and specific surface area of the synthetic material, balancing the electrochemical performance output and high voltage cycle/safety performance, and developing the positive electrode material. Used in lithium ion secondary batteries.
该正极材料结构式为Li[LixMnaNibCoc]O2·αMyOz,其中-0.05＜x＜150.3,a.b.c均大于0.02并小于0.9，0.13≤α≤0.3,0＜y≤3,0＜z≤5,并且0.9＜x+a+b+c＜1.4。M为除锂、镍、钴、锰以外的金属元素；MyOz是一种符合化合价组成的复合氧化物，通常为离子导体，MyOz的来源为含元素M的盐类或者含M的氧化物，所述盐类优选为可溶性有机或无机盐，所述氧化物优选为粒径＜100μm。M优选自镁，钛，钇，镧系元素，锆，铝中的一种以上。M的来源优选自纳米氢氧化镁、纳米氧化镁、纳米氧化钇、纳米氧化铝、纳米二氧化钛、钛酸正四丁酯、硝酸锆、硝酸镧和硝酸钇中的一种以上。The structure of the positive electrode material is Li[LixMnaNibCoc]O2·αMyOz, wherein -0.05<x<150.3, abc is greater than 0.02 and less than 0.9, 0.13≤α≤0.3, 0<y≤3, 0<z≤5, and 0.9< x+a+b+c<1.4. M is a metal element other than lithium, nickel, cobalt, manganese; MyOz is a composite oxide constituting a valence composition, usually an ionic conductor, and the source of MyOz is a salt containing element M or an oxide containing M. The salts are preferably soluble organic or inorganic salts, preferably having a particle size of <100 μm. M is preferably one or more selected from the group consisting of magnesium, titanium, lanthanum, lanthanoid, zirconium and aluminum. The source of M is preferably one or more selected from the group consisting of nano magnesium hydroxide, nano magnesium oxide, nano cerium oxide, nano alumina, nano titanium dioxide, n-tetrabutyl titanate, zirconium nitrate, cerium nitrate, and cerium nitrate.
利用共沉淀法制得含锰钴镍的氢氧化物产物，通过前驱体合成工艺，制得粒径2-9.2μm、比表面积6.5-13.2m2/g的前驱体；将前驱体与锂源混合，经除磁、一次烧结、一次粉碎、二次烧结、二次粉碎、二次除磁工序得到发明物正极材料。锰、钴、镍来源于含锰、钴、镍元素的盐，优选含锰、钴、镍元素的硫酸盐。锂源可为碳酸锂、单水氢氧化锂、醋酸锂和氟化锂一种以上。 The hydroxide product containing manganese, cobalt and nickel is prepared by coprecipitation method, and a precursor having a particle size of 2-9.2 μm and a specific surface area of 6.5-13.2 m 2 /g is obtained by a precursor synthesis process; the precursor is mixed with a lithium source. The positive electrode material of the invention is obtained by demagnetization, primary sintering, primary pulverization, secondary sintering, secondary pulverization, and secondary demagnetization. Manganese, cobalt, and nickel are derived from salts containing manganese, cobalt, and nickel, and preferably sulfates containing manganese, cobalt, and nickel. The lithium source may be one or more of lithium carbonate, lithium hydroxide monohydrate, lithium acetate, and lithium fluoride.
总的来说，本发明的正极材料制备方法包括如下工序：In general, the method for preparing a positive electrode material of the present invention includes the following steps:
工序1 制备前驱体，包括以下3个步骤： Step 1 Prepare the precursor, including the following three steps:
步骤1 配制含锰钴镍的盐溶液 Step 1 Prepare a salt solution containing manganese cobalt nickel
将含锰、钴、镍的盐溶于去离子水中，按目标摩尔比制备固含量为25-435重量％的含锰钴镍的盐溶液。A salt containing manganese, cobalt and nickel is dissolved in deionized water to prepare a manganese-containing cobalt-nickel salt solution having a solid content of 25 to 435 wt% at a target molar ratio.
步骤2制备含前驱体的悬浮分散液Step 2 Preparation of Suspension Dispersion Containing Precursor
在容器中放入一部分上述含锰钴镍的盐溶液的10％～43％作为打底溶液，在搅拌状态下通入氨气保护气置换30min,再开始滴加质量浓度为5％的氢氧化钠溶液及质量浓度8％氨水溶液10min,调节溶液pH为12左右即开始同时滴加剩余含锰钴镍的盐溶液，氨水溶液及氢氧化钠溶液。同时控制溶液的反应温度为45-75℃。滴加时间为4-12小时，滴加完成后再按加入镍钴锰的盐的重量的0～30％添加含M的粉末或浆料在搅拌状态下保温陈化20-36小时，得到含前驱体的悬浮分散液。10% to 43% of the above manganese-cobalt-containing salt solution is placed in the container as a primer solution, and the ammonia gas is purged for 30 minutes under stirring, and then the dropwise addition of 5% by weight of hydroxide is started. The sodium solution and the mass concentration of 8% ammonia solution for 10 minutes, and the pH of the solution is adjusted to about 12, and the remaining salt solution containing manganese, cobalt and nickel, ammonia solution and sodium hydroxide solution are simultaneously added dropwise. At the same time, the reaction temperature of the solution was controlled to be 45-75 °C. The dropping time is 4-12 hours, and after the completion of the dropwise addition, the powder or slurry containing M is added in an amount of 0 to 30% by weight of the salt of nickel-cobalt-manganese added, and the mixture is aged for 20-36 hours under stirring to obtain A suspension dispersion of the precursor.
步骤3 制备前驱体Step 3 Preparation of the precursor
将步骤2制备的悬浮分散液除磁,离心分离得到滤饼，同时反复用去离子水清洗滤饼7-10次，直到杂质含量在符合标准的合格范围内，将滤饼取出后用真空干燥机在105-130℃烘干，并用325目不锈钢筛过筛得到前驱体。The suspension dispersion prepared in step 2 is demagnetized, and the filter cake is obtained by centrifugation, and the filter cake is repeatedly washed with deionized water for 7-10 times until the impurity content is within the acceptable range of the standard, and the filter cake is taken out and dried by vacuum. The machine was dried at 105-130 ° C and sieved through a 325 mesh stainless steel sieve to obtain a precursor.
工序2正极材料合成，包括以下两个步骤：Process 2 cathode material synthesis, including the following two steps:
步骤1正极材料半成品合成 Step 1 Synthesis of semi-finished material of cathode material
将前驱体与锂源均匀混合，然后经除磁，烧结，再经球磨粉碎得到正极材料半成品。根据锂盐可溶性可分为湿法制备工艺和干法制备工艺。The precursor is uniformly mixed with the lithium source, and then subjected to demagnetization, sintering, and ball milling to obtain a semi-finished product of the positive electrode material. According to the solubility of lithium salt, it can be divided into a wet preparation process and a dry process.
湿法制备工艺。按重量比为100:(35～60):(60～130)依次添加前驱体，锂盐，去离子水等制备成浆料，再转移到高速搅拌机在常温下进行分散，分散后的浆料采用强度为8000GS的管式除磁器除磁。除磁后的浆料采用烘箱烘干后，再转移到陶瓷钵中放入马弗炉，再在空气或氧气气氛中800-870℃烧结15-20小时，烧结后的物料再用聚氨酯球磨机球磨5-7小时制备得到正极材料半成品。Wet preparation process. According to the weight ratio of 100: (35 ~ 60): (60 ~ 130) sequentially added precursor, lithium salt, deionized water, etc. to prepare a slurry, and then transferred to a high-speed mixer to disperse at room temperature, the dispersed slurry The tube demagnetizer with a strength of 8000 GS is demagnetized. After demagnetization, the slurry is dried in an oven, transferred to a ceramic crucible and placed in a muffle furnace, and then sintered in an air or oxygen atmosphere at 800-870 ° C for 15-20 hours. The sintered material is then ball milled with a polyurethane ball mill. A semi-finished product of the positive electrode material is prepared in 5-7 hours.
干法制备工艺。按重量比为100:(60～90)依次添加前驱体，锂盐到高速混料机在常温干态下进行分散，分散后的粉体采用强度为8000GS的旋转除磁器除磁。除磁后的粉体转移到陶瓷钵中放入马弗炉，在空气或氧气气氛中800-870℃烧结15-20小时，烧结后的物料再用聚氨酯球磨机球磨5-7小时制备得到正极材料半成品。Dry preparation process. The precursor is sequentially added in a weight ratio of 100: (60 to 90), and the lithium salt is dispersed in a dry state at a normal temperature in a high-speed mixer, and the dispersed powder is demagnetized by a rotary demagnetizer having a strength of 8000 GS. The powder after demagnetization is transferred to a ceramic crucible and placed in a muffle furnace, sintered in an air or oxygen atmosphere at 800-870 ° C for 15-20 hours, and the sintered material is ball milled by a polyurethane ball mill for 5-7 hours to prepare a cathode material. Semi finished product.
步骤2 正极材料合成Step 2 Synthesis of positive electrode material
正极材料半成品与含M的粉末按5重量比100:(0～30)分别重新投入到球磨机后进行掺杂包覆，再将掺杂好的粉体分别放入马弗炉中，在空气或氧气气氛中750-880℃进行高温处理15-18小时，再将处理后的粉体用球磨机球磨5-7小时后，采用旋转除磁器(8000GS)进行除磁，并用325目不锈钢筛网过筛后得到正极材料。The semi-finished product of the positive electrode material and the powder containing M are re-introduced into the ball mill at a weight ratio of 100: (0 to 30), and then doped and coated, and then the doped powder is separately placed in a muffle furnace, in air or The high temperature treatment is carried out in an oxygen atmosphere at 750-880 ° C for 15-18 hours, and the treated powder is ball milled by a ball mill for 5-7 hours, then demagnetized by a rotary demagnetizer (8000GS), and sieved with a 325 mesh stainless steel mesh. After that, a positive electrode material was obtained.
本发明的正极材料制备方法制备的正极材料结构式为Li[LixMnaNibCoc]O2·αMyOz,其中-0.05＜x＜0.3,a.b.c均大于0.02并小于0.9，M为除锂、镍、钴、锰以外的金属元素且MyOz是一种符合化合价组成的复合氧化物，0＜α≤0.3,0＜y≤3,0＜z≤5,并且0.9＜x+a+b+c＜1.4。The positive electrode material prepared by the method for preparing a positive electrode material of the invention has the structural formula of Li[LixMnaNibCoc]O2·αMyOz, wherein -0.05<x<0.3, abc is greater than 0.02 and less than 0.9, and M is a metal other than lithium, nickel, cobalt and manganese. The element and MyOz is a composite oxide conforming to the valence composition, 0 < α ≤ 0.3, 0 < y ≤ 3, 0 < z ≤ 5, and 0.9 < x + a + b + c < 1.4.
下面通过具体实施例来说明本发明的正极材料的制备方法、以及正极材料的各项性 能，以及用该正极材料制成的锂离子二次电池的电化学性能。Hereinafter, the preparation method of the positive electrode material of the present invention and the properties of the positive electrode material will be described by way of specific examples. The electrochemical performance of a lithium ion secondary battery made of the positive electrode material.
实施例中所用到各试剂和仪器来源如下：The sources of each reagent and instrument used in the examples are as follows:
表1:实施例中用到的试剂及型号信息表Table 1: Reagents and model information sheets used in the examples
Figure PCTCN2017111393-appb-000001
Figure PCTCN2017111393-appb-000001
表2：实施例所用到的设备信息一览表Table 2: List of equipment information used in the examples
Figure PCTCN2017111393-appb-000002
Figure PCTCN2017111393-appb-000002
实施例1 前驱体制备Example 1 Precursor Preparation
实施例1-1Example 1-1
称取100kg去离子水于搅拌罐中，再分别称取18.26kg七水硫酸钴,17.59kg六水硫酸镍,10.95kg 5单水硫酸锰溶解于水中，配制含镍钴锰的盐溶液。同时配制约50kg质量浓度为5％的氨水溶液，以及约50kg质量浓度为8％的氢氧化钠溶液，再开启200L塑料搅拌罐，提前放入约20kg含镍钴锰的盐溶液打底，在搅拌状态下通入氨气保护气置换30min,再开始滴加氢氧化钠溶液及氨水溶液10min,调节溶液pH为12.3左右即开始同时滴加含镍钴锰的盐溶液，氨水溶液及氢氧化钠溶液。Weigh 100 kg of deionized water in a stirred tank, and weigh 18.26 kg of cobalt sulfate heptahydrate, 17.59 kg of nickel sulfate hexahydrate, and 10.95 kg of manganese sulfate monohydrate dissolved in water to prepare a salt solution containing nickel cobalt manganese. At the same time, prepare about 50kg of ammonia solution with a concentration of 5%, and about 50kg of sodium hydroxide solution with a concentration of 8%, then open a 200L plastic stirred tank, and put about 20kg of salt solution containing nickel-cobalt-manganese in advance. Under the stirring state, the ammonia gas is replaced by ammonia gas for 30 minutes, then the sodium hydroxide solution and the ammonia solution are added dropwise for 10 minutes, and the pH of the solution is adjusted to about 12.3, and the salt solution containing nickel, cobalt and manganese, ammonia solution and sodium hydroxide are simultaneously added. Solution.
同时控制溶液的反应温度为55℃±5℃。滴加时间为4小时，滴加完成后再加入1.88kg纳米氢氧化镁粉末，2.2kg纳米氧化钇浆料(固含量20％)在搅拌状态下保温陈化30小时，再用隔膜泵泵入到离心机中离心分离，在泵入管路上加装管道除磁器除磁(10000GS),同时反复用去离子水清洗滤饼7次，直到杂质含量在合格范围内，将滤饼取 出后用真空干燥机烘干(温度130℃×2h)，并用325目不锈钢筛网过滤成前驱体成品，得到NCM111型前驱体产物19.97kg，产物粒径为2.0μm,比表面为13.2m2/g,振实密度为2.2g/cm3,磁性物质为153ppb。At the same time, the reaction temperature of the control solution was 55 ° C ± 5 ° C. The dropping time was 4 hours. After the addition was completed, 1.88 kg of nano magnesium hydroxide powder was added, and 2.2 kg of nano cerium oxide slurry (solid content 20%) was aged under stirring for 30 hours, and then pumped by a diaphragm pump. Centrifuge in a centrifuge, add pipe demagnetizer (10000GS) to the pumping line, and repeatedly clean the filter cake with deionized water for 7 times until the impurity content is within the acceptable range. After drying, it was dried by a vacuum dryer (temperature: 130 ° C × 2 h), and filtered into a precursor product by a 325 mesh stainless steel mesh to obtain 19.97 kg of a precursor product of NCM 111 type, the product particle size was 2.0 μm, and the specific surface was 13.2 m 2 / g, the tap density is 2.2 g/cm3, and the magnetic substance is 153 ppb.
实施例1-2Example 1-2
称取30kg去离子水于搅拌罐中，再分别称取0.97kg七水硫酸钴,18.86kg六水硫酸镍,0.57kg单水硫酸锰溶解于水中，配制含镍钴锰的盐溶液。同时配制约10kg质量浓度为5％的氨水溶液，以及约10kg质量浓度为8％的氢氧化钠溶液，再开启100L塑料搅拌罐，提前放入约20kg含镍钴锰的盐溶液打底，在搅拌状态下通入氨气保护气置换30min,再开始滴加氢氧化钠溶液及氨水溶液10min,调节溶液pH为11.8左右即开始同时滴加含镍钴锰的盐溶液，氨水溶液及氢氧化钠溶液。同时控制溶液的反应温度为60℃±5℃。滴加时间为6小时，滴加完成后再加入5.0kg纳米氧化钛分散液(固含量20wt％)，5.0kg五水硝酸锆在搅拌状态下保温陈化40小时，再用压力泵泵入到板框压滤机中固液分离，在泵入管路上加装管道除磁器除磁(11000GS),同时反复用去离子水清洗滤饼6次，直到杂质含量在合格范围内，将滤饼取出后用真空盘式干燥机烘干(温度105℃×2h)，并用5 325目不锈钢筛网过滤成前驱体成品，得到NCM955型前驱体产物10kg，产物粒径为8.8μm,比表面为6.5m2/g,振实密度为1.7g/cm3,磁性物质为77ppb。Weigh 30 kg of deionized water in a stirred tank, and weigh 0.97 kg of cobalt sulfate heptahydrate, 18.86 kg of nickel sulfate hexahydrate, and 0.57 kg of manganese sulfate monohydrate dissolved in water to prepare a salt solution containing nickel cobalt manganese. At the same time, prepare about 10kg of ammonia solution with a concentration of 5%, and about 10kg of sodium hydroxide solution with a concentration of 8%, then open a 100L plastic stirred tank, and put about 20kg of salt solution containing nickel-cobalt-manganese in advance. Under the stirring state, the ammonia gas shielding gas was replaced by the ammonia gas for 30 minutes, and then the sodium hydroxide solution and the ammonia aqueous solution were added dropwise for 10 minutes, and the pH of the solution was adjusted to about 11.8, and the salt solution containing nickel, cobalt and manganese, the ammonia solution and the sodium hydroxide were simultaneously added dropwise. Solution. At the same time, the reaction temperature of the solution was controlled to be 60 ° C ± 5 ° C. The dropping time was 6 hours. After the completion of the dropwise addition, 5.0 kg of nanometer titanium oxide dispersion (solid content: 20% by weight) was added, and 5.0 kg of zirconium nitrate pentahydrate was aged under stirring for 40 hours, and then pumped into the pump by a pressure pump. The solid-liquid separation in the plate and frame filter press, adding the pipe demagnetizer (11000GS) on the pumping pipeline, and repeatedly cleaning the filter cake with deionized water for 6 times until the impurity content is within the acceptable range, after removing the filter cake It was dried by a vacuum disc dryer (temperature 105 ° C × 2 h), and filtered into a precursor product by a 5 325 mesh stainless steel mesh to obtain 10 kg of NCM955 precursor product, the product particle size was 8.8 μm, and the specific surface was 6.5 m 2 / g, the tap density is 1.7 g/cm3, and the magnetic substance is 77 ppb.
实施例1-3Examples 1-3
称取700kg去离子水于搅拌罐中，再分别称取41.66kg七水硫酸钴,98.45kg六水硫酸镍,36.14kg单水硫酸锰溶解于水中，配制含镍钴锰的盐溶液。同时配制总重量约200kg质量浓度为5％的氨水溶液，以及约200kg质量浓度为8％的氢氧化钠溶液，再开启1000L塑料搅拌罐，提前放入约250kg含镍钴锰的盐溶液打底，在搅拌状态下通入氨气保护气置换30min,再开始滴加氢氧化钠溶液及氨水溶液10min,调节溶液pH为12.1左右即开始同时滴加含镍钴锰的盐溶液，氨水溶液及氢氧化钠溶液。同时控制溶液的反应温度为63℃±5℃。滴加时间为8小时，滴加完成后再加入0.85kg纳米氢氧化镁粉末，及33.85kg六水硝酸镧，29.15kg纳米二氧化钛分散液(固含量20重量％)在搅拌状态下保温陈化36小时，再用隔膜泵泵入到离心机中固液分离，在泵入管路上加装管道除磁器除磁(9800GS),同时反复用去离子水清洗滤饼7次，直到杂质含量在合格范围内，将滤饼取出后用真空盘式干燥机烘干(温度105℃×2h)，并用325目不锈钢筛网过滤成前驱体成品，得到NCM523型前驱体产物91.3kg，产物粒径为9.2μm,比表面为9.5m2/g,振实密度为1.9g/cm3,磁性物质为90ppb。Weigh 700 kg of deionized water in a stirred tank, and weigh 41.66 kg of cobalt sulfate heptahydrate, 98.45 kg of nickel sulfate hexahydrate, and 36.14 kg of manganese sulfate monohydrate dissolved in water to prepare a salt solution containing nickel-cobalt-manganese. At the same time, a total weight of about 200kg of ammonia solution with a concentration of 5%, and about 200kg of sodium hydroxide solution with a concentration of 8%, and then open a 1000L plastic stirred tank, and put about 250kg of nickel-cobalt-manganese salt solution in advance. Under the agitation state, the ammonia gas shielding gas is replaced by the ammonia gas for 30 minutes, and then the sodium hydroxide solution and the ammonia aqueous solution are added dropwise for 10 minutes, and the pH of the solution is adjusted to about 12.1, and the salt solution containing nickel, cobalt and manganese, the ammonia solution and the hydrogen are simultaneously added dropwise. Sodium oxide solution. At the same time, the reaction temperature of the control solution was 63 ° C ± 5 ° C. The dropping time was 8 hours, and 0.85 kg of nano magnesium hydroxide powder and 33.85 kg of cerium nitrate hexahydrate were added after completion of the dropwise addition, and 29.15 kg of nano titanium dioxide dispersion (solid content: 20% by weight) was aged under stirring. Hours, then use the diaphragm pump to pump into the centrifuge for solid-liquid separation, add pipe demagnetizer (9800GS) on the pumping line, and repeatedly wash the filter cake with deionized water 7 times until the impurity content is within the qualified range. The filter cake was taken out and dried by a vacuum pan dryer (temperature 105 ° C × 2 h), and filtered into a precursor product by a 325 mesh stainless steel mesh to obtain 91.3 kg of a NCM 523 precursor product, and the product particle size was 9.2 μm. The specific surface was 9.5 m 2 /g, the tap density was 1.9 g/cm 3 , and the magnetic substance was 90 ppb.
实施例1-4Examples 1-4
称取120kg去离子水于搅拌罐中，再分别称取4.39kg七水硫酸钴,24.05kg六水硫酸镍,15.23kg单水硫酸锰溶解于水中，配制含镍钴锰的盐溶液。同时配制约120kg质量浓度为5％的氨水溶液，以及约120kg质量浓度为8％的氢氧化钠溶液，再开启500L塑料搅拌罐，提前放入约60kg含镍钴锰的盐溶液打底，在搅拌状态下通入氨气保护气置换30min,再开始滴加氢氧化钠溶液及氨水溶液10min,调节溶液pH为11.8左右即开始同时滴加含镍钴锰的盐溶液，氨水溶液及氢氧化钠溶液。同时控制溶液的反应温度为65±5℃。滴加时间为6小时，滴加完成后再加入0.5kg纳米氧化镁粉末在搅拌状态下保温陈化35小时，再用压力泵泵入到板框压滤机中固液分离，在泵入管路上加装管道除 磁器除磁(11000GS),同时反5复用去离子水清洗滤饼7次，直到杂质含量在合格范围内，将滤饼取出后用真空盘式干燥机烘干(温度105℃×2h)，并用325目不锈钢筛网过滤成前驱体成品，得到NCM46846型前驱体产物，产物粒径为4.5μm,比表面为5.6m2/g,振实密度为2.0g/cm3,磁性物质为176ppb。Weigh 120 kg of deionized water in a stirred tank, and weigh 4.39 kg of cobalt sulfate heptahydrate, 24.05 kg of nickel sulfate hexahydrate, and 15.23 kg of manganese sulfate monohydrate dissolved in water to prepare a salt solution containing nickel cobalt manganese. At the same time, prepare about 120kg of ammonia solution with a concentration of 5%, and about 120kg of sodium hydroxide solution with a concentration of 8%, then open a 500L plastic stirred tank, and put about 60kg of salt solution containing nickel-cobalt-manganese in advance. Under the stirring state, the ammonia gas shielding gas was replaced by the ammonia gas for 30 minutes, and then the sodium hydroxide solution and the ammonia aqueous solution were added dropwise for 10 minutes, and the pH of the solution was adjusted to about 11.8, and the salt solution containing nickel, cobalt and manganese, the ammonia solution and the sodium hydroxide were simultaneously added dropwise. Solution. At the same time, the reaction temperature of the control solution was 65 ± 5 °C. The dropping time is 6 hours. After the completion of the dropwise addition, 0.5 kg of nano-magnesia powder is added and aged for 35 hours under stirring, and then pumped into the plate and frame filter press by a pressure pump to separate the solid and liquid, on the pumping line. Adding pipes The magnet was demagnetized (11000 GS), and the filter cake was washed 7 times with reverse 5 multiplexed deionized water until the impurity content was within the acceptable range. The filter cake was taken out and dried by a vacuum disc dryer (temperature 105 ° C × 2 h). The precursor product was filtered through a 325 mesh stainless steel mesh to obtain a NCM46846 precursor product having a particle size of 4.5 μm, a specific surface of 5.6 m 2 /g, a tap density of 2.0 g/cm 3 and a magnetic substance of 176 ppb.
实施例(对比例)1-5Examples (Comparative) 1-5
称取100kg去离子水于搅拌罐中，再分别称取13.34kg七水硫酸钴,12.89kg六水硫酸镍,8.0kg单水硫酸锰溶解于水中，配制含镍钴锰的盐溶液。同时配制约50kg质量浓度为5％的氨水溶液，以及约50kg质量浓度为8％的氢氧化钠溶液，再开启200L塑料搅拌罐，提前放入约20kg含镍钴锰的盐溶液打底，在搅拌状态下通入氨气保护气置换30min,再开始滴加氢氧化钠溶液及氨水溶液10min,调节溶液pH为12.3左右即开始同时滴加含镍钴锰的盐溶液，氨水溶液及氢氧化钠溶液。同时控制溶液的反应温度为55℃±5℃。100 kg of deionized water was weighed into a stirred tank, and 13.34 kg of cobalt sulfate heptahydrate, 12.89 kg of nickel sulfate hexahydrate, and 8.0 kg of manganese sulfate monohydrate were weighed and dissolved in water to prepare a salt solution containing nickel cobalt manganese. At the same time, prepare about 50kg of ammonia solution with a concentration of 5%, and about 50kg of sodium hydroxide solution with a concentration of 8%, then open a 200L plastic stirred tank, and put about 20kg of salt solution containing nickel-cobalt-manganese in advance. Under the stirring state, the ammonia gas is replaced by ammonia gas for 30 minutes, then the sodium hydroxide solution and the ammonia solution are added dropwise for 10 minutes, and the pH of the solution is adjusted to about 12.3, and the salt solution containing nickel, cobalt and manganese, ammonia solution and sodium hydroxide are simultaneously added. Solution. At the same time, the reaction temperature of the control solution was 55 ° C ± 5 ° C.
滴加时间为4小时，滴加完成后再在搅拌状态下添加0.57kg纳米氧化镁，6.4kg纳米二氧化钛浆料(固含量20重量％)保温陈化30小时，再用隔膜泵泵入到离心机中离心分离，在泵入管路上加装管道除磁器除磁(10000GS),同时反复用20去离子水清洗滤饼7次，直到杂质含量在合格范围内，将滤饼取出后用真空干燥机烘干(温度130℃×2h)，并用325目不锈钢筛网过滤成前驱体成品，得到NCM111型前驱体产物14.83kg，产物粒径为2.0μm,比表面为13.2m2/g,振实密度为2.2g/cm3,磁性物质为153ppb。The dropping time was 4 hours. After the completion of the dropwise addition, 0.57 kg of nano-magnesia was added under stirring, and 6.4 kg of nano-titanium dioxide slurry (solid content: 20% by weight) was aged for 30 hours, and then pumped into the centrifuge with a diaphragm pump. Centrifugal separation in the machine, adding pipe demagnetizer (10000GS) to the pumping line, and repeatedly cleaning the filter cake with 20 deionized water for 7 times until the impurity content is within the acceptable range, the filter cake is taken out and then vacuum dryer is used. Drying (temperature 130 ° C × 2 h), and filtering into a precursor product with a 325 mesh stainless steel mesh to obtain 14.83 kg of NCM111 precursor product, the product particle size is 2.0 μm, the specific surface is 13.2 m 2 / g, and the tap density is 2.2 g/cm3, the magnetic substance was 153 ppb.
实施例(对比例)1-6Examples (Comparative) 1-6
称取30kg去离子水于搅拌罐中，再分别称取1.3kg七水硫酸钴,25.33kg六水硫酸镍,0.77kg单水硫酸锰溶解于水中，配制含镍钴锰的盐溶液溶液。同时配制约10kg质量浓度为5％的氨水溶液，以及约10kg质量浓度为8％的氢氧化钠溶液，再开启100L塑料搅拌罐，提前放入约20kg含镍钴锰的盐溶液打底，在搅拌状态下通入氨气保护气置换30min,再开始滴加氢氧化钠溶液及氨水溶液10min,调节溶液pH为11.8左右即开始同时滴加含镍钴锰的盐溶液，氨水溶液及氢氧化钠溶液。同时控制溶液的反应温度为60℃±5℃。滴加时间为6小时，滴加完成后搅拌状5态下保温陈化40小时，再用压力泵泵入到板框压滤机中固液分离，在泵入管路上加装管道除磁器除磁(11000GS),同时反复用去离子水清洗滤饼6次，直到杂质含量在合格范围内，将滤饼取出后用真空盘式干燥机烘干(温度105℃×2h)，并用325目不锈钢筛网过滤成前驱体成品，得到NCM955型前驱体产物9.63kg，产物粒径为9.8μm,比表面为10 6.3m2/g,振实密度为1.8g/cm3,磁性物质为90ppb。Weigh 30 kg of deionized water in a stirred tank, and weigh 1.3 kg of cobalt sulfate heptahydrate, 25.33 kg of nickel sulfate hexahydrate, and 0.77 kg of manganese sulfate monohydrate dissolved in water to prepare a solution solution of nickel-cobalt-manganese salt solution. At the same time, prepare about 10kg of ammonia solution with a concentration of 5%, and about 10kg of sodium hydroxide solution with a concentration of 8%, then open a 100L plastic stirred tank, and put about 20kg of salt solution containing nickel-cobalt-manganese in advance. Under the stirring state, the ammonia gas shielding gas was replaced by the ammonia gas for 30 minutes, and then the sodium hydroxide solution and the ammonia aqueous solution were added dropwise for 10 minutes, and the pH of the solution was adjusted to about 11.8, and the salt solution containing nickel, cobalt and manganese, the ammonia solution and the sodium hydroxide were simultaneously added dropwise. Solution. At the same time, the reaction temperature of the solution was controlled to be 60 ° C ± 5 ° C. The dropping time is 6 hours, and after the completion of the dropwise addition, the temperature is aged for 40 hours in the state of stirring, and then pumped into the plate and frame filter press by a pressure pump to separate the solid and liquid, and the pipe demagnetizer is added to the pumping pipe. (11000GS), while repeatedly cleaning the filter cake with deionized water for 6 times until the impurity content is within the acceptable range, take out the filter cake and dry it with a vacuum disc dryer (temperature 105 °C × 2 h), and use 325 mesh stainless steel sieve The mesh was filtered into a precursor product to obtain 9.63 kg of NCM955 precursor product, the product particle size was 9.8 μm, the specific surface was 10 6.3 m 2 /g, the tap density was 1.8 g/cm 3 , and the magnetic substance was 90 ppb.
实施例1-7Example 1-7
称取700kg去离子水于搅拌罐中，再分别称取23.7kg七水硫酸钴,183.5kg六水硫酸镍,14.0kg单水硫酸锰溶解于水中，配制含镍钴锰的盐溶液溶液。同时配制约200kg质量浓度为5％的氨水溶液，以及约200kg质量浓度为8％的氢氧化钠溶液，再开启1000L塑料搅拌罐，提前放入约250kg含镍钴锰的盐溶液打底，在搅拌状态下通入氨气保护气置换30min,再开始滴加氢氧化钠溶液及氨水溶液10min,调节溶液pH为12.1左右即开始同时滴加含镍钴锰的盐溶液，氨水溶液及氢氧化钠溶液。同时控制溶液的反应温度为63℃±5℃。 Weigh 700 kg of deionized water in a stirred tank, and weigh 23.7 kg of cobalt sulfate heptahydrate, 183.5 kg of nickel sulfate hexahydrate, and 14.0 kg of manganese sulfate monohydrate dissolved in water to prepare a solution solution containing nickel cobalt manganese. At the same time, prepare about 200kg of ammonia solution with a concentration of 5%, and about 200kg of sodium hydroxide solution with a concentration of 8%, then open a 1000L plastic stirred tank, and put about 250kg of salt solution containing nickel-cobalt-manganese in advance. Under the stirring state, the ammonia gas shielding gas was replaced by the ammonia gas for 30 minutes, and then the sodium hydroxide solution and the ammonia aqueous solution were added dropwise for 10 minutes, and the pH of the solution was adjusted to about 12.1, and the salt solution containing nickel, cobalt and manganese, the ammonia solution and the sodium hydroxide were simultaneously added dropwise. Solution. At the same time, the reaction temperature of the control solution was 63 ° C ± 5 ° C.
滴加时间为8小时，滴加完成后再加入1.7kg纳米氧化镁粉末，及28.5kg六水硝酸钇粉末在搅拌状态下保温陈化20小时，再用隔膜泵泵入到离心机中固液分离，在泵入管路上加装管道除磁器除磁(9800GS),同时反复用去离子水清洗滤饼10次，直到杂质含量在合格范围内，将滤饼取出后用真空盘式干燥机烘干(温度105℃×2h)，并用325目不锈钢筛网过滤成前驱体成品，得到NCM811型前驱体产物94.6kg，产物粒径为5.9μm,比表面为6.8m2/g,振实密度为1.6g/cm3,磁性物质为110ppb。The dropping time is 8 hours. After the addition is completed, 1.7 kg of nano-magnesia powder is added, and 28.5 kg of cerium nitrate hexahydrate powder is aged under stirring for 20 hours, and then pumped into the centrifuge with a diaphragm pump. Separate, add pipe demagnetizer (9800GS) on the pumping line, and repeatedly clean the filter cake with deionized water for 10 times until the impurity content is within the acceptable range. Remove the filter cake and dry it with a vacuum disc dryer. (temperature 105 ° C × 2 h), and filtered into a precursor product by a 325 mesh stainless steel mesh to obtain 94.6 kg of NCM811 precursor product, the product particle size was 5.9 μm, the specific surface was 6.8 m 2 /g, and the tap density was 1.6 g. /cm3, the magnetic substance is 110 ppb.
实施例1-8Example 1-8
称取30kg去离子水于搅拌罐中，再分别称取3.7kg七水硫酸钴,17.0kg六水硫酸镍,2.2kg单水硫酸锰溶解于水中，配制含镍钴锰的盐溶液溶液。同时配制约10kg质量浓度为5％的氨水溶液，以及约10kg质量浓度为8％的氢氧化钠溶液，再开启100L塑料搅拌罐，提前放入约20kg含镍钴锰的盐溶液打底，在搅拌状态下通入氨气保护气5置换30min,再开始滴加氢氧化钠溶液及氨水溶液10min,调节溶液pH为12.3左右即开始同时滴加含镍钴锰的盐溶液，氨水溶液及氢氧化钠溶液。同时控制溶液的反应温度为65℃±5℃。滴加时间为8小时，滴加完成后再加入2.0kg五水硝酸锆及0.2kg钛酸酯溶液在搅拌状态下保温陈化32小时，再用压力泵泵入到板框压滤机中固液分离，在泵入管路上加装管道除磁器除磁(11000GS),同时反复用去离子水清洗滤饼10次，直到杂质含量在合格范围内，将滤饼取出后用真空盘式干燥机烘干(温度105℃×2h)，并用325目不锈钢筛网过滤成前驱体成品，得到NCM71515型前驱体产物9.1kg，产物粒径为8.5μm,比表面为7.2m2/g,振实密度为1.6g/cm3,磁性物质为123ppb。Weigh 30 kg of deionized water in a stirred tank, and weigh 3.7 kg of cobalt sulfate heptahydrate, 17.0 kg of nickel sulfate hexahydrate, and 2.2 kg of manganese sulfate monohydrate in water to prepare a solution solution containing nickel-cobalt-manganese. At the same time, prepare about 10kg of ammonia solution with a concentration of 5%, and about 10kg of sodium hydroxide solution with a concentration of 8%, then open a 100L plastic stirred tank, and put about 20kg of salt solution containing nickel-cobalt-manganese in advance. Under the agitation state, the ammonia gas shielding gas 5 is replaced by the ammonia gas for 5 minutes, and then the sodium hydroxide solution and the ammonia aqueous solution are added dropwise for 10 minutes, and the pH of the solution is adjusted to about 12.3, and the salt solution containing nickel-cobalt-manganese is simultaneously added, the ammonia solution and the hydroxide are added. Sodium solution. At the same time, the reaction temperature of the control solution was 65 ° C ± 5 ° C. The dropping time is 8 hours. After the completion of the dropwise addition, 2.0 kg of zirconium nitrate pentahydrate and 0.2 kg of titanate solution are added and aged for 32 hours under stirring, and then pumped into the plate and frame filter press by a pressure pump. Separate the liquid, add pipe demagnetizer to the pumping line (11000GS), and repeatedly clean the filter cake with deionized water for 10 times until the impurity content is within the acceptable range. Remove the filter cake and bake it with a vacuum disc dryer. Dry (temperature 105 ° C × 2 h), and filtered into a precursor product with a 325 mesh stainless steel mesh to obtain 9.1 kg of NCM71515 precursor product, the product particle size is 8.5 μm, the specific surface is 7.2 m 2 / g, and the tap density is 1.6. g/cm3, the magnetic substance is 123 ppb.
实施例1-9Example 1-9
称取180kg去离子水于搅拌罐中，再分别称取18.7kg七水硫酸钴,32.4kg六水硫酸镍,10.8kg单水硫酸锰溶解于水中，配制含镍钴锰的盐溶液溶液。同时配制约120kg质量浓度为5％的氨水溶液，以及约120kg质量浓度为8％的氢氧化钠溶液，再开启500L塑料搅拌罐，提前放入约60kg含镍钴锰的盐溶液打底，在搅拌状态下通入氨气保护气置换30min,再开始滴加氢氧化钠溶液及氨水溶液10min,调节溶液pH为12.1左右即开始同时滴加含镍钴锰的盐溶液，氨水溶液及氢氧化钠溶液。同时控制溶液的反应温度为50℃±5℃。滴加时间为5小时，滴加完成后再加入2.8kg六水硝酸钇，2.3kg钛酸正四丁酯钛酸正四丁酯溶液在搅拌状态下保温陈化35小时，再用压力泵泵入到板框压滤机中固液分离，在泵入管路上加装管道除磁器除磁(11000GS),同时反复用去离子水清洗滤饼6次，直到杂质含量在合格范围内，将滤饼取出后用真空盘式干燥机烘干(温度105℃×2h)，并用325目不锈钢筛网过滤成前驱体成品，得到NCM502525型前驱体产物25.2kg，产物粒径为4.3μm,比表面为10.8m2/g,振实密度为1.7g/cm3,磁性物质为145ppb。180 kg of deionized water was weighed into a stirred tank, and 18.7 kg of cobalt sulfate heptahydrate, 32.4 kg of nickel sulfate hexahydrate, and 10.8 kg of manganese sulfate monohydrate were weighed and dissolved in water to prepare a solution solution of nickel-cobalt-manganese salt solution. At the same time, prepare about 120kg of ammonia solution with a concentration of 5%, and about 120kg of sodium hydroxide solution with a concentration of 8%, then open a 500L plastic stirred tank, and put about 60kg of salt solution containing nickel-cobalt-manganese in advance. Under the stirring state, the ammonia gas shielding gas was replaced by the ammonia gas for 30 minutes, and then the sodium hydroxide solution and the ammonia aqueous solution were added dropwise for 10 minutes, and the pH of the solution was adjusted to about 12.1, and the salt solution containing nickel, cobalt and manganese, the ammonia solution and the sodium hydroxide were simultaneously added dropwise. Solution. At the same time, the reaction temperature of the solution was controlled to be 50 ° C ± 5 ° C. The dropping time is 5 hours. After the completion of the dropwise addition, 2.8 kg of lanthanum nitrate hexahydrate is added, and 2.3 kg of tetrabutylammonium titanate titanate solution is aged under stirring for 35 hours, and then pumped into the pump by a pressure pump. The solid-liquid separation in the plate and frame filter press, adding the pipe demagnetizer (11000GS) on the pumping pipeline, and repeatedly cleaning the filter cake with deionized water for 6 times until the impurity content is within the acceptable range, after removing the filter cake It was dried by a vacuum disc dryer (temperature: 105 ° C × 2 h), and filtered into a precursor product by a 325 mesh stainless steel mesh to obtain 25.2 kg of NCM 502525 precursor product, the product particle size was 4.3 μm, and the specific surface was 10.8 m 2 / g, the tap density is 1.7 g/cm3, and the magnetic substance is 145 ppb.
实施例2(湿法合成正极材料)Example 2 (wet synthesis of positive electrode material)
实施例2-1Example 2-1
依次添加实施例1-1制得的前驱体19.8kg，去离子水17kg，单水氢氧化锂7.8kg制备成浆料，再转移到高速搅拌机在常温下进行分散，分散后的浆料采用强度为8000GS的管式除磁器除磁。除磁后的浆料采用烘箱烘干后，再转移到陶瓷钵中放入马弗炉，制得的粉体在空气气氛中按880℃×15h进行第10 1次烧结处理。烧结后的物料冷却后再用聚氨酯球磨机球磨6小时制备得到正极材料半成品。 19.8 kg of the precursor prepared in Example 1-1, 17 kg of deionized water, and 7.8 kg of lithium hydroxide monohydrate were sequentially added to prepare a slurry, which was then transferred to a high-speed mixer for dispersion at room temperature, and the dispersed slurry was subjected to strength. Demagnetize the tubular demagnetizer for 8000GS. The demagnetized slurry was dried in an oven, transferred to a ceramic crucible and placed in a muffle furnace, and the obtained powder was subjected to a 1011th sintering treatment at 880 ° C × 15 h in an air atmosphere. After the sintered material was cooled, it was ball milled for 6 hours with a polyurethane ball mill to prepare a semi-finished product of the positive electrode material.
再向正极材料半成品补加2.21kg钛酸正四丁酯重新投入到球磨机后进行掺杂包覆，再将掺杂好的粉体进行初步烘干后，放入马弗炉中，在空气或氧气气氛中分别按880℃×15h进行第2次烧结处理，再将处理冷却后的粉体用球磨机球磨6小时后，采用旋转除磁器(8000GS)进行除磁，并用325目不锈钢筛网过筛后得到正极材料19.8kg。Then add 2.21kg of n-tetrabutyl titanate to the semi-finished product of the positive electrode material and re-inject it into the ball mill to dope coating. Then the doped powder is initially dried and put into the muffle furnace, in air or oxygen. The second sintering treatment was carried out at 880 ° C × 15 h in the atmosphere, and the powder after the treatment was ball milled by a ball mill for 6 hours, and then demagnetized by a rotary demagnetizer (8000 GS) and sieved with a 325 mesh stainless steel mesh. A positive electrode material of 19.8 kg was obtained.
得到的正极材料比表面积：0.49m2/g，平均粒径D50：4.5μm，结构式为：The obtained positive electrode material has a specific surface area: 0.49 m 2 /g, an average particle diameter D50: 4.5 μm, and the structural formula is:
Li[Li-0.05Mn0.329Ni0.341Co0.33]O2·0.1MgO·0.02TiO2·0.01Y2O3。Li[Li-0.05Mn0.329Ni0.341Co0.33]O2·0.1MgO·0.02TiO2·0.01Y2O3.
实施例2-2Example 2-2
依次添加实施例1-3制得的前驱体91.3kg，去离子水67kg，单水氢氧化锂32.8kg制备成浆料，再转移到高速搅拌机在常温下进行分散，分散后的浆料采用强度为8000GS的管式除磁器除磁。除磁后的浆料采用烘箱烘干后，再转移到陶瓷钵中放入马弗炉，制得的粉体在空气氛中按870℃×16h进行第125次烧结处理。烧结后的物料冷却后再用聚氨酯球磨机球磨6小时制备得到正极材料半成品。91.3 kg of the precursor prepared in Example 1-3, 67 kg of deionized water and 32.8 kg of lithium hydroxide monohydrate were sequentially added to prepare a slurry, which was then transferred to a high-speed mixer for dispersion at room temperature, and the dispersed slurry was used in strength. Demagnetize the tubular demagnetizer for 8000GS. The demagnetized slurry was dried in an oven, transferred to a ceramic crucible and placed in a muffle furnace, and the obtained powder was subjected to a 125th sintering treatment at 870 ° C × 16 h in an air atmosphere. After the sintered material was cooled, it was ball milled for 6 hours with a polyurethane ball mill to prepare a semi-finished product of the positive electrode material.
再向正极材料半成品补加30kg六水硝酸镧及40kg去离子水重新投入到球磨机后进行掺杂包覆，再将掺杂好的粉体进行初步烘干后，放入马弗炉中，在空气气氛中按870℃×16h进行第2次烧结处理，再将处理冷却后的粉体用球磨机球磨6小时后，采用旋转除磁器(8000GS)进行除磁，并用325目不锈钢筛网过筛后得到正极材料100.2kg。Then add 30kg of lanthanum nitrate hexahydrate and 40kg of deionized water to the semi-finished material of the positive electrode material and re-inject it into the ball mill for doping and coating, then pre-dry the doped powder and put it into the muffle furnace. The second sintering treatment was carried out in an air atmosphere at 870 ° C × 16 h, and the treated powder was ball milled by a ball mill for 6 hours, then demagnetized by a rotary demagnetizer (8000 GS), and sieved with a 325 mesh stainless steel mesh. 100.2 kg of a positive electrode material was obtained.
得到的正极材料比表面积：0.65m2/g，5平均粒径D50：3.2μm，结构式为：The obtained positive electrode material has a specific surface area: 0.65 m 2 /g, and 5 average particle diameter D 50: 3.2 μm, and the structural formula is:
Li[Li0.07Mn0.29Ni0.508Co0.201]O2·0.02MgO·0.1La2O3·0.1TiO2。Li[Li0.07Mn0.29Ni0.508Co0.201]O2·0.02MgO·0.1La2O3·0.1TiO2.
实施例(对比例)2-3Examples (Comparative) 2-3
依次添加实施例1-5制得的前驱体14.8kg，去离子水18kg，碳酸锂8.1kg制备成浆料，再转移到高速搅拌机在常温下进行分散，分散后的浆料采用强度为8000GS的管式除磁器除磁。除磁后的浆料采用烘箱烘干后，再转移到陶瓷钵中放入马弗炉，制得的粉体在空气气氛中按880℃×15h进行第1次烧结处理。烧结后的物料冷却后再用聚氨酯球磨机球磨6小时制备得到正极材料半成品。14.8 kg of the precursor prepared in Example 1-5, 18 kg of deionized water and 8.1 kg of lithium carbonate were sequentially added to prepare a slurry, which was then transferred to a high-speed mixer for dispersion at room temperature, and the dispersed slurry was used at a strength of 8000 GS. Tube demagnetizer demagnetization. The demagnetized slurry was dried in an oven, transferred to a ceramic crucible and placed in a muffle furnace, and the obtained powder was subjected to a first sintering treatment at 880 ° C × 15 h in an air atmosphere. After the sintered material was cooled, it was ball milled for 6 hours with a polyurethane ball mill to prepare a semi-finished product of the positive electrode material.
再向正极材料半成品补加14.14kg六水硝酸钇与20kg去离子水，重新投入到球磨机后进行掺杂包覆，再将掺杂好的粉体进行初步烘干后，放入马弗炉中，在空气气氛中按880℃×15h进行第2次烧结处理，再将处理冷却后的粉体用球磨机球磨6小时后，采用旋转除磁器(8000GS)进行除磁，并用325目不锈钢筛网过筛后得到正极材料20kg。Further add 14.14kg of lanthanum nitrate hexahydrate and 20kg of deionized water to the semi-finished product of the positive electrode material, re-inject it into the ball mill, dope coating, and then pre-pow the doped powder into the muffle furnace. The second sintering treatment was carried out in an air atmosphere at 880 ° C × 15 h, and the treated powder was ball milled by a ball mill for 6 hours, and then demagnetized by a rotary demagnetizer (8000 GS) and sieved with a 325 mesh stainless steel mesh. After the sieve, 20 kg of a positive electrode material was obtained.
得到的正极材料比表面积：0.56m220/g，平均粒径D50：8.2μm，结构式为：The obtained positive electrode material has a specific surface area of 0.56 m220/g, an average particle diameter D50 of 8.2 μm, and a structural formula:
Li[Li0.35Mn0.329Ni0.341Co0.33]O2·0.1MgO·0.12TiO2·0.13Y2O3。Li[Li0.35Mn0.329Ni0.341Co0.33]O2·0.1MgO·0.12TiO2·0.13Y2O3.
实施例2-4Example 2-4
依次添加实施例1-8制得的前驱体9.1kg，去离子水5.7kg，单水氢氧化锂4.0kg制备成浆料，再转移到高速搅拌机在常温下进行分散，分散后的浆料采用强度为8000GS的管式除磁器除磁。除磁后的浆料采用烘箱烘干后，再转移到陶瓷钵中放入马弗炉，制得的粉体在氧气气氛中按830℃×16h进行第1次烧结处理。烧结后的物料冷却后再用聚氨酯球磨机球磨6小时制备得到正极材料半成品。9.1 kg of the precursor prepared in Example 1-8, 5.7 kg of deionized water and 4.0 kg of lithium hydroxide monohydrate were sequentially added to prepare a slurry, which was then transferred to a high-speed mixer for dispersion at room temperature, and the dispersed slurry was used. The tube demagnetizer with a strength of 8000 GS is demagnetized. The demagnetized slurry was dried in an oven, transferred to a ceramic crucible and placed in a muffle furnace, and the obtained powder was subjected to a first sintering treatment at 830 ° C × 16 h in an oxygen atmosphere. After the sintered material was cooled, it was ball milled for 6 hours with a polyurethane ball mill to prepare a semi-finished product of the positive electrode material.
再向正极材料半成品补加0.6g钛酸正四丁酯，2.64kg五水硝酸锆与5.0kg去离子水，重新投入到球磨机后进行掺杂包覆，再将掺杂好的粉体进行初步烘干后，放入马弗炉中，在氧气气氛中按780℃×16h进行第2次烧结处理，再将处理冷却后的5粉体用 球磨机球磨6小时后，采用旋转除磁器(8000GS)进行除磁，并用325目不锈钢筛网过筛后得到正极材料10.2kg。Then add 0.6g of tetrabutyl titanate, 2.64kg of zirconium nitrate pentahydrate and 5.0kg of deionized water to the semi-finished product of the positive electrode material, re-inject it into the ball mill, dope coating, and then pre-bake the doped powder. After drying, it is placed in a muffle furnace, and the second sintering treatment is performed at 780 ° C × 16 h in an oxygen atmosphere, and the 5 powders after the treatment is cooled are used. After 6 hours of ball milling by a ball mill, demagnetization was carried out using a rotary demagnetizer (8000 GS), and sieved through a 325 mesh stainless steel mesh to obtain 10.2 kg of a positive electrode material.
得到的正极材料比表面积：2.2m2/g，平均粒径D50：8.9μm，结构式为：The obtained positive electrode material has a specific surface area: 2.2 m 2 /g, an average particle diameter D50: 8.9 μm, and the structural formula is:
Li[Li0.05Mn0.141Ni0.712Co0.144]O2·0.01TiO2·0.12ZrO2。Li[Li0.05Mn0.141Ni0.712Co0.144]O2·0.01TiO2·0.12ZrO2.
实施例2-5Example 2-5
依次添加实施例1-9制得的前驱体25.1kg，去离子水14.5kg，氟化锂8.1kg制备成浆料，再转移到高速搅拌机在常温下进行分散，分散后的浆料采用强度为8000GS的管式除磁器除磁。除磁后的浆料采用烘箱烘干后，再转移到陶瓷钵中放入马弗炉，制得的粉体在空气气氛中按830℃×16h进行第115次烧结处理。烧结后的物料冷却后再用聚氨酯球磨机球磨6小时制备得到正极材料半成品。25.1 kg of the precursor prepared in Example 1-9, 14.5 kg of deionized water, and 8.1 kg of lithium fluoride were sequentially added to prepare a slurry, which was then transferred to a high-speed mixer for dispersion at room temperature, and the dispersed slurry was subjected to strength. The 8000GS tubular demagnetizer is demagnetized. The demagnetized slurry was dried in an oven, transferred to a ceramic crucible and placed in a muffle furnace, and the obtained powder was subjected to a 115th sintering treatment at 830 ° C × 16 h in an air atmosphere. After the sintered material was cooled, it was ball milled for 6 hours with a polyurethane ball mill to prepare a semi-finished product of the positive electrode material.
再向正极材料半成品补加2.0g钛酸正四丁酯，2.0kg六水硝酸钇与14kg去离子水，重新投入到球磨机后进行掺杂包覆，再将掺杂好的粉体进行初步烘干后，放入马弗炉中，在空气气氛中按780℃×16h进行第2次烧结处理，再将处理冷却后的粉体用球磨机球磨6小时后，采用旋转除磁器(8000GS)进行除磁，并用325目不锈钢筛网过筛后得到正极材料30.2kg。Then add 2.0g of tetrabutyl titanate, 2.0kg of lanthanum nitrate hexahydrate and 14kg of deionized water to the semi-finished product of the positive electrode material, re-inject it into the ball mill, dope coating, and then pre-dry the doped powder. Thereafter, the mixture was placed in a muffle furnace, and subjected to a second sintering treatment at 780 ° C × 16 h in an air atmosphere, and the treated powder was ball milled by a ball mill for 6 hours, and then demagnetized by a rotary demagnetizer (8000 GS). And sifting with a 325 mesh stainless steel mesh to obtain 30.2 kg of a positive electrode material.
得到的正极材料比表面积：0.7m2/g，平均粒径D50：4.8μm，结构式为：The obtained positive electrode material has a specific surface area: 0.7 m 2 /g, an average particle diameter D50: 4.8 μm, and the structural formula is:
Li[Li0.2Mn0.25Ni0.483Co0.26]O2·0.05TiO2·0.18Y2O3。Li[Li0.2Mn0.25Ni0.483Co0.26]O2·0.05TiO2·0.18Y2O3.
实施例3(干法合成正极材料)Example 3 (dry synthesis of positive electrode material)
实施例3-1Example 3-1
依次添加实施例1-2前驱体10kg，碳酸锂3.75g到高速混料机在常温干态下进行分散，分散后的粉体采用强度为8000GS的旋转除磁器除磁。除磁后的粉体转移到陶瓷钵中放入马弗炉，制备的粉体在氧气气氛中按800℃×16h进行第1次烧结处理，烧结后的物料冷却再用聚氨酯球磨机球磨6小时制备得到正极材料半成品。10 kg of the precursor of Example 1-2 and 3.75 g of lithium carbonate were sequentially added to a high-speed mixer to be dispersed in a dry state at normal temperature, and the dispersed powder was demagnetized by a rotary demagnetizer having a strength of 8000 GS. The demagnetized powder was transferred to a ceramic crucible and placed in a muffle furnace. The prepared powder was subjected to a first sintering treatment in an oxygen atmosphere at 800 ° C × 16 h, and the sintered material was cooled and ball milled for 6 hours using a polyurethane ball mill. A positive electrode material semi-finished product is obtained
再向正极材料半成品补加2.75kg纳米二氧化钛分散液(固含量20重量％)重新投入到球磨机后进行掺杂5包覆，再将掺杂好的物料烘干成粉体放入马弗炉中，在氧气气氛中分别按800℃×16h进行第2次烧结处理，再将处理冷却后的粉体用球磨机球磨6小时后，采用旋转除磁器(8000GS)进行除磁，并用325目不锈钢筛网过筛后得到发明物正极材料10.1kg。Then add 2.75kg of nanometer titanium dioxide dispersion (solid content 20% by weight) to the semi-finished material of the positive electrode material, re-inject it into the ball mill, dope 5 coating, and then dry the doped material into powder into the muffle furnace. The second sintering treatment was carried out in an oxygen atmosphere at 800 ° C × 16 h, and the treated powder was ball milled by a ball mill for 6 hours, and then demagnetized by a rotary demagnetizer (8000 GS), and a 325 mesh stainless steel mesh was used. After sieving, 10.1 kg of the positive electrode material of the invention was obtained.
得到的正极材料比表面积：0.76m2/g，平均粒径D50：9.0μm，结构式为：The obtained positive electrode material has a specific surface area: 0.76 m 2 /g, an average particle diameter D50: 9.0 μm, and the structural formula is:
Li[Li0.3Mn0.043Ni0.915Co0.044]O2·0.05TiO2·0.15ZrO2·0.10TiO210。Li[Li0.3Mn0.043Ni0.915Co0.044]O2·0.05TiO2·0.15ZrO2·0.10TiO210.
实施例3-2Example 3-2
依次添加实施例1-4前驱体17.8kg，碳酸锂7.6kg初步混合成粉料，再转移到高速混料机在常温干态下进行分散，分散后的粉体采用强度为8000GS的旋转除磁器除磁。除磁后的粉体转移到陶瓷钵中放入马弗炉，制备的粉体在空气气氛中按800℃×15h进行第1次烧结处理，烧结后的物料冷却再用聚氨酯球磨机球磨6小时制备得到正极材料半成品。17.8kg of the precursor of Example 1-4 was added in sequence, and 7.6kg of lithium carbonate was initially mixed into a powder, and then transferred to a high-speed mixer for dispersion in a dry state at normal temperature. The dispersed powder was a rotary demagnetizer with a strength of 8000 GS. Demagnetization. The powder after demagnetization was transferred to a ceramic crucible and placed in a muffle furnace. The prepared powder was subjected to a first sintering treatment at 800 ° C for 15 hours in an air atmosphere, and the sintered material was cooled and ball milled for 6 hours using a polyurethane ball mill. A positive electrode material semi-finished product is obtained
再向正极材料半成品补加0.7kg纳米三氧化二铝及20kg去离子水重新投入到球磨机后进行掺杂包覆，再将掺杂好的物料烘干成粉体放入马弗炉中，在空气气氛中按800℃×15h进行第2次烧结处理，再将处理冷却后的粉体用球磨机球磨6小时后，采用旋转 除磁器(8000GS)进行除磁，并用325目不锈Then add 0.7kg of nanometer aluminum oxide and 20kg of deionized water to the semi-finished material of the positive electrode material, re-inject it into the ball mill, dope coating, and then dry the doped material into powder into the muffle furnace. The second sintering treatment was carried out in an air atmosphere at 800 ° C × 15 h, and the powder after the treatment cooling was ball milled by a ball mill for 6 hours, and then rotated. Demagnetizer (8000GS) for demagnetization and 325 mesh stainless
钢筛网过筛后得到发明物正极材料。得到的正极材料20.1kg。The steel mesh screen is sieved to obtain the positive electrode material of the invention. The obtained positive electrode material was 20.1 kg.
比表面积：0.68m2/g，平均粒径D50：8.6μm，结构式为：Specific surface area: 0.68 m 2 / g, average particle diameter D50: 8.6 μm, the structural formula is:
Li[Li0.05Mn0.456Ni0.463Co0.079]O2·0.03Al2O3·0.10MgO。Li[Li0.05Mn0.456Ni0.463Co0.079]O2·0.03Al2O3·0.10MgO.
实施例(对比例)3-3Example (Comparative Example) 3-3
依次添加实施例1-6前驱体9.63kg，碳酸锂6.9kg初步混合成粉料，再转移到高速混料机在常温干态下进行分散，分散后的粉体采用强度为8000GS的旋转除磁器除磁。除磁后的粉体转移到陶瓷钵中放入马弗炉，在氧气气氛中按800℃×15h进行第1次烧结处理，烧结后的物料冷却再用聚氨酯球磨机球磨6小时制备得到正极材料半成品。9.63 kg of the precursors of Examples 1-6 were added in sequence, and 6.9 kg of lithium carbonate was initially mixed into a powder, which was then transferred to a high-speed mixer for dispersion in a dry state at normal temperature. The dispersed powder was subjected to a rotary demagnetizer having a strength of 8000 GS. Demagnetization. The powder after demagnetization is transferred to a ceramic crucible and placed in a muffle furnace. The first sintering treatment is carried out in an oxygen atmosphere at 800 ° C for 15 h. The sintered material is cooled and ball milled for 6 hours using a polyurethane ball mill to obtain a semi-finished product of the positive electrode material. .
再将正极材料半成品放入马弗炉中，在氧气气氛中按800℃×15h进行第2次烧结处理，再将处理冷却5后的粉体用球磨机球磨6小时后，采用旋转除磁器(8000GS)进行除磁，并用325目不锈钢筛网过筛后得到发明物正极材料20.2kg。Then, the positive electrode material semi-finished product is placed in a muffle furnace, and the second sintering treatment is performed at 800 ° C × 15 h in an oxygen atmosphere, and the powder after the treatment cooling 5 is ball milled by a ball mill for 6 hours, and then a rotary demagnetizer (8000 GS) is used. The demagnetization was carried out and sieved with a 325 mesh stainless steel mesh to obtain 20.2 kg of the positive electrode material of the invention.
得到的正极材料比表面积：0.79m2/g，平均粒径D50：10.1μm，结构式为：Li[Li-0.1Mn0.043Ni0.915Co0.044]O2。The obtained positive electrode material had a specific surface area of 0.79 m 2 /g, an average particle diameter D50 of 10.1 μm, and a structural formula of Li[Li-0.1Mn0.043Ni0.915Co0.044]O2.
实施例3-4Example 3-4
依次添加实施例1-7前驱体94.6kg，碳酸锂60.4g到高速混料机在常温干态下进行分散，分散后的粉体采用强度为8000GS的旋转除磁器除磁。除磁后的粉体转移到陶瓷钵中放入马弗炉，制备的粉体在氧气气氛中按830℃×15 20h进行第1次烧结处理，烧结后的物料冷却再用聚氨酯球磨机球磨6小时制备得到正极材料半成品。94.6 kg of the precursor of Example 1-7 and 60.4 g of lithium carbonate were sequentially added to a high-speed mixer to be dispersed in a dry state at normal temperature, and the dispersed powder was demagnetized by a rotary demagnetizer having a strength of 8000 GS. The demagnetized powder was transferred to a ceramic crucible and placed in a muffle furnace. The prepared powder was subjected to a first sintering treatment at 830 ° C × 15 20 h in an oxygen atmosphere, and the sintered material was cooled and ball milled for 6 hours using a polyurethane ball mill. A semi-finished product of the positive electrode material is prepared.
再向正极材料半成品补加3.5kg纳米二氧化钛分散液(固含量20重量％)重新投入到球磨机后进行掺杂包覆，再将掺杂好的物料烘干成粉体放入马弗炉中，在氧气气氛中分别按760℃×16h进行第2次烧结处理，再将处理冷却后的粉体用球磨机球磨6小时后，采用旋转除磁器(8000GS)进行除磁，并用325目不锈钢筛网过筛后得到发明物正极材料100.2kg。Further adding 3.5 kg of nano titanium dioxide dispersion (solid content 20% by weight) to the semi-finished material of the positive electrode material, re-injecting into the ball mill, doping and coating, and then drying the doped material into a powder into a muffle furnace. The second sintering treatment was carried out in an oxygen atmosphere at 760 ° C × 16 h, and the treated powder was ball milled by a ball mill for 6 hours, and then demagnetized by a rotary demagnetizer (8000 GS) and sieved with a 325 mesh stainless steel mesh. After sieving, 100.2 kg of the positive electrode material of the invention was obtained.
得到的正极材料比表面积：2.00m2/g，平均粒径D50：6.3μm，结构式为：The obtained positive electrode material has a specific surface area: 2.00 m 2 /g, an average particle diameter D50: 6.3 μm, and the structural formula is:
Li[Li0.04Mn0.095Ni0.803Co0.097]O2·0.05MgO·0.08ZrO2。Li[Li0.04Mn0.095Ni0.803Co0.097]O2·0.05MgO·0.08ZrO2.
实施例4扫描电镜分析Example 4 Scanning electron microscopy analysis
将上述实施例2-1，实施例3-1，实施例(对比例)2-3，实施例(对比例)3-3制备得到的正极材料粉体分别进行扫描电镜SEM测试,得到图1的结果。The powders of the positive electrode materials prepared in the above Examples 2-1, 3-1, Examples (Comparative Examples) 2-3, and Examples (Comparative Examples) 3-3 were respectively subjected to scanning electron microscope SEM test to obtain FIG. the result of.
由图1-1至1-4可见，采用本发明技术同样的原料制备的对比例和实施例材料形貌上有较大的区别，实施例2-1与实施例(对比例)2-3为一次土豆型颗粒，实施例2-1的晶体颗粒更为圆润完美，实施例3-1与实施例(对比例)3-3为二次球形颗粒，实施例3-1中团聚成的二次颗粒更加紧密完好。在颗粒表面有一层均匀的包覆物，这有可5能是掺杂包覆元素对材料结构及形貌有一定和影响，一定程度上会诱导形成不同结构形貌的制成品。It can be seen from Figures 1-1 to 1-4 that the comparative examples prepared by using the same raw materials of the present invention have a large difference in morphology from the materials of the examples, and Examples 2-1 and Examples (Comparative Examples) 2-3 The crystal particles of Example 2-1 were more round and perfect for the primary potato type particles, and Example 3-1 and the Examples (Comparative Example) 3-3 were secondary spherical particles, and the agglomerated in Example 3-1. The secondary particles are more closely packed. There is a uniform coating on the surface of the particles. This has the effect that the doping and coating elements have a certain influence on the structure and morphology of the material, and to some extent, the finished products with different structural morphology are induced.
实施例5ICP元素含量检测同时对实施例2-1，实施例3-1，实施例(对比例)2-3，实施例(对比例)3-3制备得到的发明物正极材料粉体进行ICP检测，检测掺杂包覆元素含量，得到如表3所示结果。Example 5 ICP Element Content Detection Simultaneously, the positive electrode material powder prepared in Example 2-1, Example 3-1, Example (Comparative Example) 2-3, and Example (Comparative Example) 3-3 was subjected to ICP. The detection and detection of the doping coating element content gave the results as shown in Table 3.
表3 实施例及对比例ICP检测结果 Table 3 Example and Comparative Example ICP Test Results
元素element 单位unit 实施例2-1Example 2-1 实施例3-1Example 3-1 实施例2-3Example 2-3 实施例3-3Example 3-3
铝(Al)Aluminum (Al) (wt％)(wt%) 0.00130.0013 0.00140.0014 0.00080.0008 0.00130.0013
铜(Cu)Copper (Cu) (wt％)(wt%) 0.00050.0005 0.00050.0005 0.00050.0005 0.00040.0004
铁(Fe)Iron (Fe) (wt％)(wt%) 0.00550.0055 0.00590.0059 0.00540.0054 0.00280.0028
镧(La)镧(La) (wt％)(wt%) 0.00010.0001 0.00010.0001 0.00080.0008 0.00010.0001
镁(Mg)Magnesium (Mg) (wt％)(wt%) 0.02370.0237 0.00260.0026 0.01460.0146 0.00330.0033
钛(Ti)Titanium (Ti) (wt％)(wt%) 0.00130.0013 0.05070.0507 0.04400.0440 0.06660.0666
钇(Y)钇(Y) (wt％)(wt%) 0.01720.0172 0.00430.0043 0.16270.1627 0.00060.0006
锆(Zr)Zirconium (Zr) (wt％)(wt%) 0.00050.0005 0.10510.1051 0.00020.0002 0.00010.0001
硫(S)Sulfur (S) (wt％)(wt%) 0.00390.0039 0.00200.0020 0.00240.0024 0.01000.0100
磷(P)Phosphorus (P) (wt％)(wt%) 0.00210.0021 0.00410.0041 0.00290.0029 0.00320.0032
由表3可见，材料的微量元素中均出现了掺杂/包覆元素，且其含量占本体正极材料的(0.0～0.43)重量％，元素单独按ppm计在20-4000ppm之间，说明该掺杂包覆工艺是可行的，表明掺杂/包覆元素能与本体正极材料较好的结合在一起。It can be seen from Table 3 that the doping/coating elements are present in the trace elements of the material, and the content thereof accounts for (0.0 to 0.43)% by weight of the bulk positive electrode material, and the elements are individually between 20 and 4000 ppm in ppm, indicating that The doping and cladding process is feasible, indicating that the doping/coating element can be better combined with the bulk positive electrode material.
实施例6半电池制备及电化学性能评估称取70gN-甲基吡略烷酮(NMP)于实验用分散机容器中，开启搅拌，在搅拌的情况下加入5g聚偏氟乙烯(PVDF Solef 56020)粉末，等胶黏剂完全溶解后再称取5g导电碳粉(SP)加入到上述溶液中，高速分散60min后，分别取实施例2-1，实施例3-1，实施例(对比例)2-3，实施例(对比例)3-3制备的正极材料粉体90g加入到上述溶液中，分散0.5h后降低搅拌速度出料备用。Example 6 Preparation of Half-Battery and Evaluation of Electrochemical Performance 70 g of N-methylpyrrolidone (NMP) was weighed into an experimental disperser vessel, stirring was started, and 5 g of polyvinylidene fluoride (PVDF Solef 56020) was added with stirring. After the powder and other adhesives are completely dissolved, 5 g of conductive carbon powder (SP) is weighed and added to the above solution, and after high-speed dispersion for 60 minutes, respectively, Example 2-1, Example 3-1, and Examples (Comparative Example) 2-3, 90 g of the positive electrode material powder prepared in Example (Comparative Example) 3-3 was added to the above solution, and after dispersing for 0.5 h, the stirring speed was lowered to discharge.
取厚度为16μm铝箔作为集流体，将制备的浆料均匀涂布于铜箔上并在干燥箱中烘干成为极片，烘烤温度为105℃，烘烤时间为1h。The aluminum foil having a thickness of 16 μm was taken as a current collector, and the prepared slurry was uniformly coated on a copper foil and dried in a dry box to form a pole piece, and the baking temperature was 105 ° C, and the baking time was 1 h.
将烘干后的极片压实制成极片，极片中活性物质的压实密度为3.3g/cm3，活性物厚度约为85μm，总厚度约为100μm。制备CR 2032型扣式半电池，对电极为金属锂片，电解质为LBC301，扣式半电池在高纯氩气充气保护的手套箱中组装，扣式半电池制作后静置10h上机测试。得到图2的检测结果。The dried pole piece was compacted into a pole piece having a compacted density of 3.3 g/cm 3 of active material in the pole piece, an active thickness of about 85 μm, and a total thickness of about 100 μm. The CR 2032 type button half-cell was prepared, the counter electrode was a metal lithium sheet, the electrolyte was LBC301, the button type half-cell was assembled in a high-purity argon gas-filled glove box, and the button-type half-cell was allowed to stand for 10 hours on the machine test. The detection result of Fig. 2 is obtained.
由图2可见，采用了包覆/掺杂工艺的材料扣式电池曲线平稳，平台较高，同未包覆/掺杂(实施例3-3)或者是包覆物过量(实施例2-3)相比，在放电末期发明例仍旧能平稳的放出电量，而对比例在放电的过程中伴随着电压的快速下降，对于实际电化学应用而言并不好，说明未进行包覆或者是过度包覆均影响比容量的发挥，这有可能是离子导体层过厚，或者是在掺杂包覆缺失情况下正极材料表面发生了副反应，抵消了锂的自由嵌入和脱出。It can be seen from Fig. 2 that the material button cell using the cladding/doping process has a stable curve, a high platform, and is uncoated/doped (Example 3-3) or an excessive coating (Example 2 3) In comparison, at the end of the discharge, the invention still emits electricity smoothly, and the comparative ratio is accompanied by a rapid drop in voltage during discharge, which is not good for practical electrochemical applications, indicating that it is not coated or Excessive coating affects the specific capacity. This may be because the ionic conductor layer is too thick, or a side reaction occurs on the surface of the positive electrode material in the absence of doping and coating, which offsets the free insertion and extraction of lithium.
实施例7 全电池制备及性能评估Example 7 Full Battery Preparation and Performance Evaluation
将实施例2-1，实施例3-1，实施例2-3，实施例2-5，实施例3-3制备得到的正极材料粉体作为正极活性物质按方形电池设计制备成容量为2.0Ah左右动力电池。制作全电池主要用于考察高电压循环及安全性效果。其中所评估适用的品种为卷绕结构954261型铝塑膜软包装电池，制作的电池厚度为9.5mm，长度为4.2mm，宽度为6.1mm。电池设计容量为2.0Ah。The positive electrode material powder prepared in Example 2-1, Example 3-1, Example 2-3, Example 2-5, and Example 3-3 was prepared as a positive electrode active material by a square battery to have a capacity of 2.0. Ah around the power battery. Making a full battery is mainly used to investigate high voltage cycling and safety effects. The applicable varieties are the 954261 aluminum plastic film flexible packaging battery, which has a battery thickness of 9.5 mm, a length of 4.2 mm and a width of 6.1 mm. The battery design capacity is 2.0Ah.
正极极片制备通常由制备浆料，涂布及冷压，分切等工艺制成，极片中有效正极活性物 质含量为95％，极片涂布重量为0.21g/cm3，极片涂布宽度为38mm，极片活性物质总面积为0.050m2，极片压实密度以活性物质计为53.6g/cm3。The preparation of the positive electrode tab is usually made by preparing a slurry, coating, cold pressing, slitting, etc., and the effective positive active material in the pole piece The mass content was 95%, the pole piece coating weight was 0.21 g/cm3, the pole piece coating width was 38 mm, the total electrode active material area was 0.050 m2, and the pole piece compaction density was 53.6 g/cm3 based on the active material.
负极片的制备方法通常经由制备浆料，涂布，冷压，分切等工序制备。采用人造石墨作为负极活性物质时，制备后的极片有效负极活性物质(人造石墨)含量为95.5％，极片涂布重量为0.130g/cm2，极片涂布宽度为40mm，极片活性物质总面积为0.051m2，极片压实密度以活性物质计为1.6g/cm3；采用钛酸锂作为负极活性物质时，制备后的极片有效负极活性物质(钛酸锂)含量为90.0％，极片涂布重量为0.275g/cm2，极片涂布宽度为40mm，极片活性物质总面积为0.051m2，极片压实密度以活性物质计为1.8g/cm3。The preparation method of the negative electrode sheet is usually prepared through a process of preparing a slurry, coating, cold pressing, slitting, and the like. When artificial graphite is used as the negative electrode active material, the prepared electrode sheet has an effective negative electrode active material (artificial graphite) content of 95.5%, a pole piece coating weight of 0.130 g/cm 2 , and a pole piece coating width of 40 mm, and a pole piece active material. The total area is 0.051 m2, the compact density of the pole piece is 1.6 g/cm3 based on the active material, and when the lithium titanate is used as the negative electrode active material, the content of the effective negative electrode active material (lithium titanate) after preparation is 90.0%. The pole piece coating weight was 0.275 g/cm2, the pole piece coating width was 40 mm, the total electrode active material area was 0.051 m2, and the pole piece compaction density was 1.8 g/cm3 based on the active material.
将正极片，隔离膜，负极片等按顺序卷绕制备成裸电芯，裸电芯检验合格后装入冲好坑的铝塑膜中并进行热封1(约135℃×5s，宽度5～8mm)，注液(电解液：LIB302，3.2g/只)，然后在LIP-10AHB06型高温化成机化成(钛酸锂负极电池化成电压0-2.5V，石墨负极锂电池化成电压0～3.85V，0.2C)，热封2(约135℃×5s，宽度5～8mm)，进行容量测试(钛酸锂负极电池测试电压1.5-2.8V，石墨负极锂电池测试电压3.0～4.2V，0.5C)，挑选质量合格的电芯用于后续性能评估。上述实施例正极片可与石墨负极片及钛酸锂负极片自由组合制备成石墨负极锂离子二次电池和钛酸锂负极锂离子二次电池，只是电池的化成及容量测试流程不同。The positive electrode sheet, the separator film, the negative electrode sheet and the like are sequentially wound into a bare cell, and the bare cell is inspected and loaded into a punched aluminum plastic film and heat-sealed 1 (about 135 ° C × 5 s, width 5 ~ 8mm), injection (electrolyte: LIB302, 3.2g / only), and then in the LIP-10AHB06 high temperature formation machine (lithium titanate negative battery formation voltage 0-2.5V, graphite negative lithium battery formation voltage 0 ~ 3.85 V, 0.2C), heat seal 2 (about 135 ° C × 5 s, width 5 ~ 8 mm), capacity test (lithium titanate negative battery test voltage 1.5-2.8V, graphite negative lithium battery test voltage 3.0 ~ 4.2V, 0.5 C), select quality qualified batteries for subsequent performance evaluation. The positive electrode sheet of the above embodiment can be freely combined with a graphite negative electrode sheet and a lithium titanate negative electrode sheet to prepare a graphite negative electrode lithium ion secondary battery and a lithium titanate negative electrode lithium ion secondary battery, except that the battery formation and capacity testing processes are different.
将检测合格的石墨负极锂电池电芯每组取2-3只，在室温条件(23℃±2℃)下恒温2h，然后在LIP-10AHB06型高温化成机上按0.5C放电至3.0V，放电完毕静置30s，取出电芯检测电芯厚度、内阻等指标，再重新上架按0.5C25充电至4.2V，再以20mA小电流CV至截止电压为4.2V，重新取出电池量测厚度，端电压及内阻，组装的钛酸锂负极锂电池电芯测试环境温度同上，电芯0.5C放电截止电压为1.5V，然后静置30s，取出电芯测量电芯厚度、内阻等指标，再重新上架按0.5C充电至2.5V，再以20mA小电流恒压(CV)至截止电压2.5V，重新取出电芯量测厚度，端电压及内阻。然后将电芯静置2小时后放入60℃及85℃烘箱中进行高温存储试验，期间可取出电芯量测厚度，电压，电阻的变化。得到表4及表5的结果。表4和表5中，实施例2-1，实施例3-1，实施例2-3，实施例3-3以石墨为负极制作电池，实施例2-5以钛酸锂为负极制作电池。Take 2-3 pieces of qualified graphite negative electrode lithium battery cells in each group, and keep them at room temperature (23 °C ± 2 °C) for 2 h, then discharge to 0.5 V at 0.5 C on LIP-10AHB06 high-temperature forming machine, discharge. After standing for 30s, take out the cell to check the thickness of the cell, internal resistance and other indicators, and then re-seat to 0.5C25 to 4.2V, then 20mA low current CV to cutoff voltage is 4.2V, re-extract the battery measurement thickness, end Voltage and internal resistance, assembled lithium titanate negative lithium battery battery test environment temperature is the same as above, cell 0.5C discharge cut-off voltage is 1.5V, then stand for 30s, take out the cell to measure cell thickness, internal resistance and other indicators, and then Reload the rack and charge it to 2.5V according to 0.5C, and then take the small current constant voltage (CV) of 20mA to the cutoff voltage of 2.5V, and then take out the measured thickness, terminal voltage and internal resistance of the battery. Then, the cell was allowed to stand for 2 hours, and then placed in an oven at 60 ° C and 85 ° C for high-temperature storage test, during which the cell was taken out to measure changes in thickness, voltage, and resistance. The results of Tables 4 and 5 were obtained. In Tables 4 and 5, Example 2-1, Example 3-1, Example 2-3, Example 3-3, the battery was made of graphite as a negative electrode, and Example 2-5 was made of lithium titanate as a negative electrode. .
将实施例制备的石墨5负极锂电池放入60℃烘箱中，电极接入到在LIP-10AHB06型高温化成机上进行1C/1C，3.0-4.8V循环检测，得到图3的高温循环结果。The graphite 5 negative electrode lithium battery prepared in the example was placed in an oven at 60 ° C, and the electrode was connected to a 1 C/1 C, 3.0-4.8 V cycle test on a LIP-10AHB06 type high temperature forming machine, and the high temperature cycle result of FIG. 3 was obtained.
将实施例制备的钛酸锂负极锂电池及放入60℃烘箱中，电极接入到在LIP-10AHB06型高温化成机上进行1C/1C，1.5-2.8V循环检测，得到图4的高10温循环结果。The lithium titanate negative electrode lithium battery prepared in the example was placed in an oven at 60 ° C, and the electrode was connected to a 1 C/1 C, 1.5-2.8 V cycle test on a LIP-10AHB06 type high temperature forming machine to obtain a high 10 temperature of FIG. Loop results.
85℃/4h 满充电压下储存性能结果表4Storage performance at 85°C/4h full charge. Table 4
实施例Example 厚度thickness 内阻Internal resistance 开路电压Open circuit voltage 容量损失Capacity loss
实施例2-1Example 2-1 6.76％6.76% 3.26％3.26% -2.79％-2.79% -1.35％-1.35%
实施例3-1Example 3-1 4.57％4.57% 3.33％3.33% -3.61％-3.61% -1.76％-1.76%
实施例2-3Example 2-3 35.10％35.10% 27.90％27.90% -3.80％-3.80% -2.10％-2.10%
实施例3-3Example 3-3 57.82％57.82% 48.83％48.83% -7.78％-7.78% -6.08％-6.08%
实施例2-5Example 2-5 34.37％34.37% 2.20％2.20% -1.39％-1.39% -1.41％-1.41%
60℃/30d 储存性能结果表560°C/30d Storage Performance Results Table 5
实施例Example 厚度thickness 内阻Internal resistance 开路电压Open circuit voltage 容量损失Capacity loss
实施例2-1Example 2-1 29.30％29.30% 30.20％30.20% -7.20％-7.20% -6.50％-6.50%
实施例3-1Example 3-1 36.60％36.60% 38.10％38.10% -13.10％-13.10% -6.30％-6.30%
实施例2-3Example 2-3 105.10％105.10% 83.20％83.20% -22.50％-22.50% -12.40％-12.40%
实施例3-3Example 3-3 120.80％120.80% 177.10％177.10% -39.80％-39.80% -18.20％-18.20%
实施例2-5Example 2-5 38.50％38.50% 26.70％26.70% -4.43％-4.43% -8.20％-8.20%
由图3，图4，表4，表5可见，采用了合适掺杂/包覆元素处理的正极材料组装的不同负极锂离子二次电池在高电压下循环性能优越，在高温满电压存储条件下电芯厚度及内阻变化较小，表明采用包覆/掺杂的正极材料界面稳定，与电解质之间发生的副反应较少，有利于改善锂电池在高电压使用状况下电极界面的恶化/劣化，保证极片在循环过程中始终有电解质浸润和足够的锂离子嵌入/脱出通道，从而提高锂离子电池在高电压下的循环性能，提升了锂电池的体积/重量能量密度，拓展了锂离子二次电池的应用范围和应用场景。As can be seen from Fig. 3, Fig. 4, Table 4, and Table 5, different negative electrode lithium ion secondary batteries assembled with a suitable doping/coating element treated positive electrode material have superior cycle performance at high voltage, and are stored at high temperature full voltage. The thickness and internal resistance of the lower cell are small, indicating that the interface of the coated/doped cathode material is stable, and fewer side reactions occur with the electrolyte, which is beneficial to improve the deterioration of the electrode interface of the lithium battery under high voltage use conditions. / Deterioration, ensuring that the pole piece always has electrolyte infiltration and sufficient lithium ion insertion/extraction channels during the cycle, thereby improving the cycle performance of the lithium ion battery at high voltage, increasing the volume/weight energy density of the lithium battery, and expanding the Application range and application scenarios of lithium ion secondary batteries.
综上所述，本发明提供了一5种制备高电压正极材料的方法，以及本方法制备物的有益改善结果，限于篇幅及实验论证认识的局限，本发明的工序也可以与已有专利的有益启示一起推动高电压正极材料的制备技术进展，并不局限于上述特定的实施方式，所有已揭示和未揭示的案例不影响本发明的实质内容。In summary, the present invention provides a method for preparing a high-voltage positive electrode material, and a beneficial improvement result of the preparation of the method. Due to limitations and limitations of experimental demonstration, the process of the present invention can also be combined with existing patents. The beneficial revelation together to advance the preparation technology of the high voltage positive electrode material is not limited to the specific embodiments described above, and all of the disclosed and undisclosed cases do not affect the essence of the present invention.
尽管已描述了本发明的优选实施例，但本领域内的技术人员一旦得知了基本创造性概念，则可对这些实施例作出另外的变更和修改。所以，所附权利要求意欲解释为包括优选实施例以及落入本发明范围的所有变更和修改。While the preferred embodiment of the invention has been described, it will be understood that Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and the modifications and
显然，本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内，则本发明也意图包含这些改动和变型在内。 It is apparent that those skilled in the art can make various modifications and variations to the invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention cover the modifications and modifications of the invention

Claims (16)

  1. 一种锂离子二次电池用正极材料，其特征在于：A cathode material for a lithium ion secondary battery, characterized in that:
    该正极材料结构式为Li[LixMnaNibCoc]O2·αMyOz，The positive electrode material has the structural formula Li[LixMnaNibCoc]O2·αMyOz,
    其中-0.05＜x＜0.3,a.b.c均大于0.02并小于0.9；Wherein -0.05<x<0.3, a.b.c is greater than 0.02 and less than 0.9;
    M为除锂、镍、钴、锰以外的金属5元素且MyOz是一种符合化合价组成的复合氧化物，0.13≤α≤0.3,0＜y≤3,0＜z≤5,并且0.9＜x+a+b+c＜1.4。M is a metal 5 element other than lithium, nickel, cobalt, manganese and MyOz is a composite oxide having a valence composition, 0.13 ≤ α ≤ 0.3, 0 < y ≤ 3, 0 < z ≤ 5, and 0.9 < x +a+b+c<1.4.
  2. 根据权利要求1所述的正极材料，其中，a,b,c的取值满足：a,b,c为0.325～0.345；或The positive electrode material according to claim 1, wherein a, b, and c have values of: a, b, and c are from 0.325 to 0.345;
    a,c为0.042～0.055，并且b为0.85～0.95；或a, c is 0.042 to 0.055, and b is 0.85 to 0.95; or
    a,c为0.05～0.15，并且b为0.75～0.85；或a, c is 0.05 to 0.15, and b is 0.75 to 0.85; or
    a,c为0.140～0.155并且b为0.65～0.75；或a, c is 0.140 to 0.155 and b is 0.65 to 0.75; or
    a,c为10 0.15～0.25并且b为0.55～0.65；或a,c为0.245～0.265并且b为0.45～0.55；或a, c is 10 0.15 to 0.25 and b is 0.55 to 0.65; or a, c is 0.245 to 0.265 and b is 0.45 to 0.55;
    a和b为0.35～0.45，并且c为0.15～0.25；或a为0.45～0.55，b为0.25～0.35，c为0.15～0.25。a and b are from 0.35 to 0.45, and c is from 0.15 to 0.25; or a is from 0.45 to 0.55, b is from 0.25 to 0.35, and c is from 0.15 to 0.25.
  3. 根据权利要求1或2所述的正极材料，其中，所述M选自镁，钛，钇，镧系元素，锆和铝中的一种以上。The cathode material according to claim 1 or 2, wherein the M is at least one selected from the group consisting of magnesium, titanium, lanthanum, lanthanoid, zirconium and aluminum.
  4. 根据权利要求1-3任一项所述的正极材料，其中，所述M含量占正极材料含量的为大于0小于等于0.43wt％The cathode material according to any one of claims 1 to 3, wherein the M content is more than 0 or less than 0.43 wt% of the content of the cathode material.
  5. 根据权利要求1-4任一项所述的正极材料，其中，M以M的氧化物与镍钴锰酸锂组合物均匀混合，或者M以M的氧化物均匀包覆于镍钴锰酸锂组合物表面上，或者M以M的氧化物均匀包覆于M镍钴锰酸锂组合物表面上形成所述正极材料。The positive electrode material according to any one of claims 1 to 4, wherein M is uniformly mixed with the oxide of M and the lithium nickel cobalt manganese oxide composition, or M is uniformly coated with lithium oxide of M cobalt lithium manganese oxide. The positive electrode material is formed on the surface of the composition, or M is uniformly coated on the surface of the M nickel cobalt manganese manganate composition with an oxide of M.
  6. 根据权利要求1-5任一项所述的正极材料，其中，所述正极材料粒径D50为3.2-9μm。The cathode material according to any one of claims 1 to 5, wherein the cathode material has a particle diameter D50 of from 3.2 to 9 μm.
  7. 根据权利要求1-6任一项所述的正极材料，其中，所述正极材料比表面积为0.49-0.76m2/g。The cathode material according to any one of claims 1 to 6, wherein the cathode material has a specific surface area of from 0.49 to 0.76 m 2 /g.
  8. 权利要求1-7中任一项所述正极材料的制备方法，其特征在于，通过含镍、钴、锰、M或含镍、钴、锰的前驱体合成工艺，制得粒径2-9.2μm、比表面积6.5-13.2m2/g的前驱体；The method for preparing a positive electrode material according to any one of claims 1 to 7, characterized in that the particle size of 2-9.2 is obtained by a synthesis process of a precursor containing nickel, cobalt, manganese, M or nickel, cobalt and manganese. a precursor having a μm and a specific surface area of 6.5-13.2 m 2 /g;
    接着，将前驱体与锂源混合，经除磁、一次烧结、一次粉碎、二次烧结、二次粉碎、二次除磁工序得到正极材料；Next, the precursor is mixed with a lithium source, and subjected to demagnetization, primary sintering, primary pulverization, secondary sintering, secondary pulverization, and secondary demagnetization to obtain a positive electrode material;
    M为除锂、镍、钴、锰以外的金属元素。M is a metal element other than lithium, nickel, cobalt, and manganese.
  9. 根据权利要求8所述的制备方法，其中，M的来源为含元素M的盐类或者含元素M的氧化物或者含元素M的氢氧化物，所述盐类优选为可溶性有机或无机盐。The production method according to claim 8, wherein the source of M is a salt containing element M or an oxide containing element M or a hydroxide containing element M, and the salt is preferably a soluble organic or inorganic salt.
  10. 根据权利要求9所述的制备方法，所述氧化物的粒径＜100μm。The production method according to claim 9, wherein the oxide has a particle diameter of <100 μm.
  11. 根据权利要求8-10任一项所述的制备方法，其中，M的引入可以在前驱体合成过程中，也可以在前驱体与锂盐的混合过程中，还可以在正极材料半成品制备阶段添加。The preparation method according to any one of claims 8 to 10, wherein the introduction of M may be carried out during the synthesis of the precursor, or during the mixing of the precursor with the lithium salt, or during the preparation of the semi-finished product of the positive electrode material. .
  12. 一种锂离子二次电池正极材料，通过权利要求8-11任一项所述的制备方法得到， 其特征在于，所述锂离子二次电池正极材料结构式为Li[LixMnaNibCoc]O2·αMyOz，A cathode material for a lithium ion secondary battery obtained by the preparation method according to any one of claims 8-11, The structure of the cathode material of the lithium ion secondary battery is Li[LixMnaNibCoc]O2·αMyOz,
    其中-0.05＜x＜0.3,a.b.c均大于0.02并小于0.9，Wherein -0.05<x<0.3, a.b.c is greater than 0.02 and less than 0.9,
    M为除锂、镍、钴、锰以外的金属元素；M is a metal element other than lithium, nickel, cobalt, manganese;
    MyOz是一种符合化合价组成的复合氧化物，0＜α≤0.3,0＜y≤3,0＜z≤5,并且0.9＜x+a+b+c＜1.4。MyOz is a composite oxide conforming to the valence composition, 0 < α ≤ 0.3, 0 < y ≤ 3, 0 < z ≤ 5, and 0.9 < x + a + b + c < 1.4.
  13. 一种锂离子二次电池，其特征在于，采用权利要求1-7或12任一项所述的正极材料制备得到。A lithium ion secondary battery produced by using the positive electrode material according to any one of claims 1 to 7 or 12.
  14. 根据权利要求13所述的锂离子二次电池，其特征在于，采用碳材料或钛酸锂作为负极，其中碳材料优选石墨。The lithium ion secondary battery according to claim 13, wherein a carbon material or lithium titanate is used as the negative electrode, and the carbon material is preferably graphite.
  15. 一种移动式存储设备，其特征在于，采用了权利要求13或14所述的锂离子二次电池。A mobile storage device characterized by using the lithium ion secondary battery according to claim 13 or 14.
  16. 一种储能电站，其特征在于，采用了权利要求13或14所述的锂离子二次电池或权利要求15所述的移动式储存设备。 An energy storage power station characterized by using the lithium ion secondary battery according to claim 13 or 14, or the mobile storage device according to claim 15.
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