WO2021129130A1 - 铝包覆前驱体及其制备方法和应用 - Google Patents

铝包覆前驱体及其制备方法和应用 Download PDF

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WO2021129130A1
WO2021129130A1 PCT/CN2020/124789 CN2020124789W WO2021129130A1 WO 2021129130 A1 WO2021129130 A1 WO 2021129130A1 CN 2020124789 W CN2020124789 W CN 2020124789W WO 2021129130 A1 WO2021129130 A1 WO 2021129130A1
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precursor
aluminum
salt
metal salt
concentration
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French (fr)
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张勇杰
万江涛
任海朋
张宁
朱金鑫
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Svolt Energy Technology Co Ltd
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Svolt Energy Technology Co Ltd
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Priority to US17/789,043 priority Critical patent/US20230033278A1/en
Priority to EP20907658.7A priority patent/EP4023609A4/en
Publication of WO2021129130A1 publication Critical patent/WO2021129130A1/zh
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    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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Definitions

  • the present disclosure relates to the field of lithium batteries, for example, to an aluminum-coated precursor and a preparation method and application thereof.
  • Lithium-ion batteries play an important role in daily life.
  • the development of the new energy automobile industry has put forward new requirements for lithium-ion batteries, and the improvement of its energy density is imminent.
  • the lithium-rich manganese-based cathode material has a high specific capacity of 250mAh/g ⁇ 350mAh/g, and is low in price, environmentally friendly, and has high research value.
  • the preparation of the existing lithium-rich manganese-based cathode material is generally divided into two steps. The first step is the preparation of the lithium-rich precursor; the second step is the sintering of the precursor.
  • the physical characteristics of lithium-rich manganese-based materials such as morphology, particle size distribution, and tap density largely depend on the precursor.
  • the lithium-rich manganese-based precursors currently on the market have small particle sizes and low tap density ( ⁇ 1.5g/cm 3 ), poor sphericity and other issues.
  • the present disclosure provides an aluminum-coated precursor and a preparation method and application thereof.
  • An embodiment of the present disclosure provides an aluminum-coated precursor, the chemical formula of the precursor is xMCO 3 ⁇ (1-x)Al(OH) 3 , where M is at least one of nickel, cobalt, and manganese , X is 0.995 to 0.999, such as 0.995, 0.996, 0.997, 0.998 or 0.999.
  • the aluminum-coated precursor has the advantages of controllable particle size, uniform particle size distribution, high sphericity, smooth particle surface, high tap density, resistance to breakage, excellent electrochemical performance and energy density, and at the same time
  • the positive electrode material prepared by using the precursor has higher specific capacity, excellent cycle performance and electrochemical discharge performance.
  • the precursor particle size is 6-15 ⁇ m, for example, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, or 15 ⁇ m, etc.
  • the tap density is not less than 1.8 g/cm 3 , Such as 1.81g/cm 3 , 1.82g/cm 3 , 1.83g/cm 3 , 1.84g/cm 3 , 1.85g/cm 3 , 1.86g/cm 3 , 1.87g/cm 3 , 1.88g/cm 3 , 1.89g/cm 3 or 1.9g/cm 3 etc.
  • a method for preparing the precursor including:
  • the aging material is sequentially subjected to iron removal, solid-liquid separation, washing and drying, so as to obtain an aluminum coating precursor.
  • carbon dioxide is continuously introduced, and then metal salt and precipitating agent are added.
  • the continuous introduction of carbon dioxide can adjust the pH of the system and maintain the inert environment of the system to prevent co-precipitation.
  • the metal elements are oxidized, and the sphericity of the precursor can be improved, and the conductive agent can improve the magnification performance of the material, and then the prefabricated particles and water are mixed and slurried to continuously pass the metal salt and precipitant into the slurry.
  • Carbon dioxide and complexing agent can reduce the reaction speed of the system and inhibit the formation of new particles in the system.
  • the metal salt and precipitating agent use small particles of prefabricated particles as seeds for co-precipitation reaction.
  • the process continues to introduce precipitant and carbon dioxide to continue to maintain the pH stability of the system, and then obtain a dense precursor, and then mix the obtained reaction liquid containing the precursor with the aluminum salt for aging and stirring.
  • the role of aluminum in the precipitant The precipitate is formed on the surface of the precursor and uniformly attached to the surface of the precursor.
  • the above-mentioned particles with controllable particle size, uniform particle size distribution, high sphericity, and smooth particle surface can be prepared by the subsequent steps of iron removal, solid-liquid separation, washing and drying.
  • An aluminum-coated precursor with high tap density, resistance to breakage, excellent electrochemical performance and energy density, and a positive electrode material prepared by using the precursor has high specific capacity, excellent cycle performance and electrochemical discharge performance.
  • the metal salt and the precipitating agent are rapidly mixed (mixing is completed within 10 seconds), and then sealed and allowed to stand to obtain prefabricated particles.
  • the continuous introduction of carbon dioxide in the process can adjust the pH of the system, maintain the inert environment of the system, prevent the metal elements from being oxidized during the co-precipitation process, and improve the sphericity of the precursor, while the conductive agent can improve the rate performance of the material.
  • step (2) provided by an embodiment of the present disclosure, the metal salt and the precipitating agent are co-precipitated with small preformed particles as seeds in the process, and at the same time, the process is continuously fed with carbon dioxide to continue to maintain the pH of the system Stable, and then get a dense precursor.
  • the reaction solution obtained above is mixed and reacted with the aluminum salt and then subjected to aging and stirring.
  • the aluminum element in the aluminum salt reacts with the precipitating agent and then precipitates on the surface of the precursor. After the material, the precursor can be more stable through the coating of aluminum element.
  • step (4) the aging material obtained above is sequentially subjected to iron removal, solid-liquid separation, washing and drying to obtain an aluminum-coated precursor.
  • iron removal, solid-liquid separation, washing and drying in this step are all conventional operations in the precursor preparation process, and those skilled in the art can make selections according to actual needs, and will not be repeated here.
  • the metal salt includes at least one of a soluble nickel salt, a soluble manganese salt, and a soluble cobalt salt.
  • the concentration of the metal salt is 80-400g/L, for example, 80g/L, 100g/L, 150g/L, 200g/L, 250g/L, 300g/L , 350g/L or 400g/L, etc.
  • the soluble nickel salt is at least one selected from nickel chloride, nickel nitrate and nickel sulfate.
  • the soluble cobalt salt is at least one selected from cobalt chloride, cobalt nitrate and cobalt sulfate.
  • the soluble manganese salt is at least one selected from the group consisting of manganese chloride, manganese nitrate and manganese sulfate.
  • the flow rate of the carbon dioxide is 0.1-0.5L/min, for example, 0.1L/min, 0.15L/min, 0.2L/min, 0.25L/min, 0.3L/min. min, 0.35L/min, 0.4L/min, 0.45L/min or 0.5L/min, etc.
  • the flow rate of carbon dioxide is 0.1-0.5L/min. If the flow rate of carbon dioxide is too high, it will increase the instability of the system and cause gas waste.
  • the flow rate range of the carbon dioxide in the application can effectively maintain the system An inert environment meets the needs of the reaction.
  • the molar ratio of the metal salt to the precipitating agent is 1:(2-3.5), for example, 1:2, 1:2.1, 1:2.2, 1:2.3 , 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3.0, 1:3.1, 1:3.2, 1:3.3, 1:3.4 or 1:3.5, etc.
  • the molar ratio of the metal salt to the precipitating agent is 1:(2-3.5). If the precipitating agent ratio is too high, it is easy to generate new crystal nuclei in the system and easily cause pH fluctuations.
  • the amount of the conductive agent is 10-50g, such as 10g, 15g, 20g, 25g, 30g, 35g, 40g, 45g or 50g etc. Too high a concentration of conductive agent will cause a decrease in the specific capacity of the material.
  • the precipitating agent is at least one selected from sodium carbonate, ammonium bicarbonate, sodium hydroxide and sodium bicarbonate.
  • the concentration of sodium carbonate is 50-200g/L, for example, 50g/L, 60g/L, 70g/L, 80g/L, 90g/L, 100g/L , 110g/L, 120g/L, 130g/L, 140g/L, 150g/L, 160g/L, 170g/L, 180g/L, 190g/L or 200g/L etc.
  • the concentration of ammonium bicarbonate is 50-200 g/L, for example, 50 g/L, 60 g/L, 70 g/L, 80 g/L, 90 g/L, 100 g/L L, 110g/L, 120g/L, 130g/L, 140g/L, 150g/L, 160g/L, 170g/L, 180g/L, 190g/L or 200g/L, etc.
  • the concentration of the sodium hydroxide is 50-200g/L, for example 50g/L, 60g/L, 70g/L, 80g/L, 90g/L, 100g/L L, 110g/L, 120g/L, 130g/L, 140g/L, 150g/L, 160g/L, 170g/L, 180g/L, 190g/L or 200g/L, etc.
  • the concentration of sodium bicarbonate is 50-200 g/L, such as 50 g/L, 60 g/L, 70 g/L, 80 g/L, 90 g/L, 100 g/L L, 110g/L, 120g/L, 130g/L, 140g/L, 150g/L, 160g/L, 170g/L, 180g/L, 190g/L or 200g/L, etc.
  • the temperature of the precipitation reaction is 30 to 80°C, for example, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C or 80°C, etc.
  • the sealed and standing time is 12-24h, such as 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h etc.
  • the conductive agent is at least one of glucose and fructose.
  • the particle size of the prefabricated particles is 1 to 2 ⁇ m, for example, it can be 1.0 ⁇ m, 1.1 ⁇ m, 1.2 ⁇ m, 1.3 ⁇ m, 1.4 ⁇ m, 1.5 ⁇ m, 1.6 ⁇ m, 1.7 ⁇ m. ⁇ m, 1.8 ⁇ m, 1.9 ⁇ m or 2.0 ⁇ m, etc.
  • the solid content of the slurry is 50-100 g/L, such as 50 g/L, 55 g/L, 60 g/L, 65 g/L, 70 g/L, 75 g/L L, 80g/L, 85g/L, 90g/L, 95g/L or 100g/L, etc.
  • the solid content of the slurry is 50-100 g/L. If the solid content of the slurry is too high, the growth rate of the particles in the system will be slow, and a precursor within the particle size range of the application cannot be obtained.
  • the stirring speed is 350-800 rpm, for example, 350 rpm, 400 rpm, 450 rpm, 500 rpm, 550 rpm, 600 rpm, 650 rpm, 700 rpm, 750 rpm or 800 rpm.
  • the temperature of the co-precipitation reaction is 30-60°C, and the time is 5-150h, such as 5h, 10h, 20h, 30h, 40h, 50h, 60h, 70h, 80h, 90h, 100h, 110h, 120h, 130h, 140h or 150h, etc.; pH is 6-8, such as 6.0, 6.2, 6.4, 6.6, 6.8, 7.0, 7.2, 7.4, 7.6, 7.8 or 8.0.
  • the present disclosure by controlling the temperature, time, and pH of the co-precipitation reaction process within the scope of the application, a precursor with high sphericity can be obtained, and the pH of the system needs to be adjusted to 9 or higher in the prior art. Compared with the precursor with the particle size of the application, the application greatly reduces the amount of alkali in the system, and at the same time inhibits the oxidation of manganese during the reaction, which is suitable for large-scale production.
  • the continuous flow rate of the metal salt is 100-500 mL/h, such as 100 mL/h, 150 mL/h, 200 mL/h, 250 mL/h, 300 mL/h, 350 mL /h, 400mL/h, 450mL/h or 500mL/h, etc.;
  • the flow rate of the precipitation agent is 100-500mL/h, such as 100mL/h, 150mL/h, 200mL/h, 250mL/h, 300mL/h, 350mL/h, 400mL/h, 450mL/h or 500mL/h, etc.
  • the flow rate of the carbon dioxide is 0.25 ⁇ 0.6L/min, such as 0.25L/min, 0.3L/min, 0.35L/min, 0.4L/min , 0.45L/min, 0.5L/min, 0.55L/min or 0.6L/min, etc.
  • the solid content of the liquid after the reaction is 30-500 g/L, for example, 30 g/L, 100 g/L, 150 g/L, 200 g/L, 250 g/L, 300 g /L, 350g/L, 400g/L, 450g/L or 500g/L, etc.
  • step (2) the complexing agent is continuously introduced with stirring.
  • the purpose of adding the complexing agent is to reduce the reaction speed of the system in the process and inhibit the formation of new particles in the system.
  • the process further includes the continuous introduction of the complexing agent with stirring.
  • the complexing agent is ammonia or ammonium bicarbonate.
  • the concentration of the complexing agent is 10-50g/L, such as 10g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L L or 50g/L etc.
  • the volume ratio of the post-reaction liquid to the aluminum salt is (10-20):1, such as 10:1, 11:1, 12:1, 13: 1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1 or 20:1, etc.
  • the volume ratio of the post-reaction liquid to the aluminum salt is (10-20):1, and this mixing ratio can ensure that sufficient aluminum is coated on the precursor, thereby improving the precursor The stability.
  • the aluminum salt is at least one of aluminum chloride and aluminum sulfate.
  • the concentration of the aluminum salt is 10-50g/L, such as 10g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L , 40g/L, 45g/L or 50g/L etc.
  • the rotational speed of the aging and stirring is 200-300rpm, such as 200rpm, 210rpm, 220rpm, 230rpm, 240rpm, 250rpm, 260rpm, 270rpm, 280rpm, 290rpm or 300rpm, etc.; time It is 0.5-5h, such as 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h.
  • a method for preparing a positive electrode material which includes:
  • the precursor is the aluminum-coated precursor described in an embodiment or an aluminum-coated precursor obtained by the method described in an embodiment.
  • the aluminum with controllable particle size, uniform particle size distribution, high sphericity, smooth particle surface, high tap density, resistance to breakage, excellent electrochemical performance and energy density is obtained by combining the foregoing aluminum with controllable particle size, uniform particle size distribution, high sphericity, smooth particle surface, high tap density, and excellent electrochemical performance and energy density.
  • the coating precursor is mixed with the lithium salt for primary sintering and secondary sintering. During the primary sintering process, the lithium ions enter the precursor material to combine to form the lithium salt cathode material, and the secondary sintering makes the sintering process more complete.
  • a positive electrode material with higher specific capacity, excellent cycle performance and electrochemical discharge performance can be prepared.
  • step (a) provided by an embodiment of the present disclosure, the above-mentioned precursor or the precursor obtained by the above-mentioned method is mixed with the lithium salt for a single sintering, so that the lithium ions in the lithium salt enter the interior of the precursor and combine to form a lithium salt cathode material , That is, a sintering material.
  • step (b) provided by an embodiment of the present disclosure, the primary sintered material obtained above is crushed and then subjected to secondary sintering, so that the lithium salt that did not enter the precursor body during the primary sintering process further migrates into the precursor body, ensuring the sintering process The reaction is more complete, and the cathode material is obtained.
  • the molar ratio of the precursor material to the lithium salt is 1:(1.02 ⁇ 1.08), such as 1:1.02, 1:1.03, 1:1.04, 1: 1.05, 1:1.06, 1:1.07 or 1:1.08, etc.
  • the temperature of the primary sintering is 450-600°C, and the time is 4-6h, such as 4.0h, 4.2h, 4.4h, 4.6h, 4.8h, 5.0h, 5.2h, 5.4h, 5.6h, 5.8h or 6.0h, etc.
  • the primary sintering temperature is 450-600°C. If the temperature is too low, some lithium ions cannot enter the precursor to form a lithium salt cathode material. If the temperature is too high, energy will be wasted. Therefore, the use of this sintering temperature can not only ensure that lithium ions can migrate into the interior of the precursor to generate lithium salt cathode materials, but also avoid energy waste.
  • the temperature of the secondary sintering is 700-850°C, and the time is 15-25h, such as 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h , 24h or 25h, etc.
  • An embodiment of the present disclosure provides a cathode material, which is prepared by the method of claim 6 or 7.
  • the chemical formula of the cathode material is Li(Li a Ni m Co n Mn (1-abmn) Al b )O 2 , where a is 0.05 to 0.35, b is 0.005 to 0.01, and m is 0.01 to 0.25, n is 0.01 to 0.25, for example, a is 0.05, 0.1, 0.15, 0.2, 0.25, 0.3 or 0.35, etc., b is 0.005, 0.006, 0.007, 0.008, 0.009 or 0.01, etc., m is 0.01, 0.05, 0.1 , 0.15, 0.2 or 0.25, etc., n is 0.01, 0.05, 0.1, 0.15, 0.2 or 0.25, etc.
  • the positive electrode material has a relatively high specific capacity and excellent cycle performance and electrochemical discharge performance.
  • the present disclosure provides a lithium battery in an embodiment, and the lithium battery has the cathode material described in an embodiment.
  • the lithium battery has a long cycle life on the basis of a high specific energy.
  • the present disclosure provides an automobile, and the automobile has the lithium battery described in an embodiment.
  • the vehicle loaded with the above-mentioned lithium battery with high specific energy and long cycle life has excellent endurance, so as to meet the needs of consumers.
  • FIG. 1 is a schematic flow chart of a method for preparing an aluminum-coated precursor according to an embodiment of the present disclosure
  • FIG. 2 is a schematic diagram of a method for preparing a cathode material according to an embodiment of the present disclosure
  • FIG. 3 is a scanning electron micrograph of an aluminum-coated precursor prepared in an embodiment of the present disclosure
  • FIG. 5 is a graph showing the first charge and discharge curve of a button battery made of a positive electrode material prepared in an embodiment of the present disclosure at 0.1C.
  • the present disclosure provides an aluminum-coated precursor whose chemical formula is xMCO 3 (1-x) ⁇ Al(OH) 3 , where M is at least one of nickel, cobalt, and manganese One, x is 0.995 to 0.999.
  • the aluminum-coated precursor has the advantages of controllable particle size, uniform particle size distribution, high sphericity, smooth particle surface, high tap density, resistance to breakage, excellent electrochemical performance and energy density, and a positive electrode prepared by using the precursor
  • the material has high specific capacity and excellent cycle performance and electrochemical discharge performance.
  • the precursor of this composition has high specific discharge capacity and stability.
  • the particle size of the precursor is 6-15 ⁇ m, and the tap density is not less than 1.8g/cm 3 .
  • the present disclosure provides a method for preparing the foregoing aluminum-coated precursor. As shown in FIG. 1, the method includes:
  • the precipitating agent is selected from at least one of sodium carbonate, ammonium bicarbonate, sodium hydroxide and sodium bicarbonate, wherein the concentration of sodium carbonate is 50-200g/L, the bicarbonate The concentration of ammonium is 50-200 g/L, the concentration of sodium hydroxide is 50-200 g/L, and the concentration of sodium bicarbonate is 50-200 g/L.
  • the molar ratio of the metal salt to the precipitating agent is 1: (2-3.5), and the amount of the conductive agent is 10-50 g based on the total amount of 1 L of the metal salt and the precipitating agent.
  • the flow rate of continuous introduction of carbon dioxide is 0.1-0.5L/min
  • the temperature of the precipitation reaction is 30-80°C
  • the sealed and standing time is 12-24h
  • the obtained prefabricated particles have a particle size of 1-2 ⁇ m.
  • S200 Mix the prefabricated particles with water to obtain a slurry, and then continue to pass in the metal salt, the precipitant and the carbon dioxide to perform a co-precipitation reaction with stirring, so as to obtain a post-reaction liquid.
  • the solid content of the slurry obtained by mixing the prefabricated particles and water is 50-100 g/L, the stirring speed is 350-800 rpm, the co-precipitation reaction temperature is 30-60° C., the time is 5-150 h, and the pH is 6-8.
  • the flow rate of metal salt is 100 ⁇ 500mL/h
  • the flow rate of continuous precipitant is 100 ⁇ 500mL/h
  • the flow rate of continuous carbon dioxide is 0.25 ⁇ 0.6L/min
  • the solid content of the liquid after the reaction is controlled to 30 ⁇ 500g/L.
  • the aluminum salt is at least one of aluminum chloride and aluminum sulfate, the concentration of the aluminum salt is 10-50g/L, the mass ratio of the liquid to the aluminum salt after the reaction is (10-20):1, and the rotation speed of the aging and stirring is 200 ⁇ 300rpm, the time is 0.5 ⁇ 5h.
  • the present disclosure provides a method for preparing a positive electrode material. As shown in FIG. 2, the method includes:
  • the lithium salt is selected from hydrogen At least one of lithium oxide and lithium carbonate, the molar ratio of the precursor material to the lithium salt is 1:(1.02 ⁇ 1.08), the temperature of one sintering is 450 ⁇ 600°C, and the time is 4 ⁇ 6h.
  • step Sa crushing the primary sintered material obtained in step Sa and then performing secondary sintering, so that the lithium salt that did not enter the precursor body during the primary sintering process further migrates into the precursor body, ensuring that the sintering process reacts more fully, and the cathode material is obtained.
  • the second sintering is at 700 ⁇ 850°C, and the time is 15 ⁇ 25h.
  • the present disclosure provides a cathode material, which is prepared by the above-mentioned method.
  • the present disclosure provides a lithium battery having the above-mentioned cathode material.
  • the present disclosure provides an automobile having the above-mentioned lithium battery.
  • the method of preparing the aluminum-coated precursor is as follows:
  • the aging material obtained above is sequentially subjected to iron removal, solid-liquid separation, washing and drying to obtain an aluminum-coated precursor with a particle size of 8 ⁇ m, the chemical formula of which is (Mn 0.6 Ni 0.2 Co 0.18 )CO 3 ⁇ 0.02 Al(OH) 3 has a tap density of 1.8 g/cm 3 .
  • the method of preparing the cathode material is as follows:
  • Figure 3 and Figure 4 are the scanning electron micrographs of the precursor material. It can be seen that the precursor material obtained by this method has a spherical structure, uniform particle size distribution and smooth surface, and the particle size distribution of the precursor is detected by a laser particle sizer. The particle size distribution is uniform.
  • the positive electrode material is mixed with SP (carbon black conductive agent) and PVDF (polyvinylidene fluoride), and NMP (N-methylpyrrolidone) is used as a solvent to pulp and stir for several hours to prepare a lithium ion half-cell.
  • SP carbon black conductive agent
  • PVDF polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • the charge and discharge test was carried out with a blue battery tester at 4.8V, and the 0.1C discharge gram capacity of the product was 305mAh (Figure 5 is the 0.1C charge and discharge curve of the lithium-ion half-cell battery), and the 1.0C discharge capacity is 230 ⁇ 240mAh, 50 The cycle capacity retention rate is 92%.
  • the method of preparing the aluminum-coated precursor is as follows:
  • the concentration of manganese is 300g/L, and then in the presence of the conductive agent fructose, carbon dioxide is continuously introduced at a flow rate of 0.5L/min, and then the mixed metal salt is quickly mixed with a sodium hydroxide solution with a concentration of 50g/L (Complete the mixing within 10 seconds, where the molar ratio of mixed metal salt and sodium hydroxide is 1:3.5, and based on the total amount of 1L mixed metal salt and sodium hydroxide, the amount of conductive agent fructose is 30g), Sealed and allowed to stand for 18h at °C to obtain prefabricated particles with a particle size of 1.5 ⁇ m;
  • the aging material obtained above is sequentially subjected to iron removal, solid-liquid separation, washing and drying to obtain an aluminum-coated precursor with a particle size of 10 ⁇ m, the chemical formula of which is (Mn 0.7 Ni 0.2 Co 0.09 )CO 3 ⁇ 0.01 Al(OH) 3 has a tap density of 1.8 g/cm 3 .
  • the method of preparing the cathode material is as follows:
  • the precursor material obtained by this method has a spherical structure, a uniform particle size distribution and a smooth surface, and the particle size distribution of the precursor is detected by a laser particle sizer and the particle size distribution is further found to be uniform.
  • the positive electrode material was mixed with SP (carbon black conductive agent) and PVDF (polyvinylidene fluoride), and NMP (N-methylpyrrolidone) was used as a solvent to pulp and stir for several hours to prepare a lithium ion half-cell, using a blue battery tester
  • the charge-discharge test was carried out at 4.8V, and the 0.1C discharge gram capacity of the product was 295-305mAh, the 1.0C discharge capacity was 230-235mAh, and the 50-week cycle capacity retention rate was 88%.
  • the method of preparing the aluminum-coated precursor is as follows:
  • Nickel nitrate, cobalt nitrate and manganese nitrate are mixed according to the molar ratio of nickel, cobalt and manganese to 0.2:0.19:0.6 to obtain a mixed metal salt, and the concentrations of nickel nitrate, cobalt nitrate and manganese nitrate in the mixed metal salt are all 200g/L, then in the presence of the conductive agent glucose, the carbon dioxide is continuously introduced at a flow rate of 0.3L/min, and then the mixed metal salt is quickly mixed with a sodium carbonate solution with a concentration of 100g/L (the mixing is completed within 10 seconds, Among them, the molar ratio of the mixed metal salt to sodium carbonate is 1:2.8, and based on the total amount of 1L of mixed metal salt and sodium carbonate, the amount of conductive agent glucose is 25g), and then seal and stand at 50°C for 20h to obtain the particle size Prefabricated particles of 1.8 ⁇ m;
  • the aging material obtained above is sequentially subjected to iron removal, solid-liquid separation, washing and drying to obtain an aluminum-coated precursor with a particle size of 15 ⁇ m, the chemical formula of which is (Mn 0.6 Ni 0.2 Co 0.19 )CO 3 ⁇ 0.01 Al(OH) 3 has a tap density of 1.9 g/cm 3 .
  • the method of preparing the cathode material is as follows:
  • the precursor material obtained by this method has a spherical structure, a uniform particle size distribution and a smooth surface, and the particle size distribution of the precursor is detected by a laser particle sizer, and the particle size distribution is further found to be uniform.
  • the positive electrode material is mixed with SP (carbon black conductive agent), PVDF (polyvinylidene fluoride), and NMP (N-methylpyrrolidone) is used as a solvent to pulp and stir for several hours to prepare a lithium ion half-cell.
  • SP carbon black conductive agent
  • PVDF polyvinylidene fluoride
  • NMP N-methylpyrrolidone

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Abstract

一种铝包覆前驱体及其制备方法，其中，所述铝包覆前驱体化学式为xMCO 3(1-x)·Al(OH) 3，其中，M 为镍、钴和锰中的至少之一，x为0.995～0.999。该铝包覆前驱体具有粒度可控且粒度分布均匀、球形度高、颗粒表面光滑、振实密度高、不易破碎、电化学性能和能量密度优异的优势。

Description

铝包覆前驱体及其制备方法和应用 技术领域
本公开涉及锂电池领域，例如涉及一种铝包覆前驱体及其制备方法和应用。
背景技术
锂离子电池在日常生活中发挥着重要作用，新能源汽车行业的发展对锂离子电池提出了新的要求，其能量密度的提升迫在眉睫。富锂锰基正极材料拥有250mAh/g～350mAh/g的高比容量，且价格较低，环境友好，具有较高的研究价值。现有的富锂锰基正极材料的制备一般分为两步，第一步是富锂前驱体的制备；第二步是前驱体的烧结。富锂锰基材料的物理特征如：形貌、粒度分布、振实密度等很大程度上取决于前驱体，然而目前市场上的富锂锰基前驱体存在着粒度小、振实低(≤1.5g/cm 3)、球型度差等问题。
因此，现有的富锂锰基前驱体有待改进。
发明内容
本公开提供一种铝包覆前驱体及其制备方法和应用。
本公开在一实施例中提供一种铝包覆前驱体，所述前驱体化学式为xMCO 3·(1-x)Al(OH) 3，其中，M为镍、钴和锰中的至少之一，x为0.995～0.999，例如0.995、0.996、0.997、0.998或0.999等。
本公开提供的一实施例中，铝包覆前驱体具有粒度可控且粒度分布均匀、球形度高、颗粒表面光滑、振实密度高、不易破碎、电化学性能和能量密度优异的优势，同时采用该前驱体制备得到的正极材料具有较高的比容量以及优异的循环性能和电化学放电性能。
在一实施例中，所述前驱体粒径为6～15μm，例如6μm、7μm、8μm、9μm、10μm、11μm、12μm、13μm、14μm或15μm等，振实密度不低于1.8g/cm 3，例如1.81g/cm 3、1.82g/cm 3、1.83g/cm 3、1.84g/cm 3、1.85g/cm 3、1.86g/cm 3、1.87g/cm 3、1.88g/cm 3、1.89g/cm 3或1.9g/cm 3等。
本公开在一实施例中提供一种制备所述前驱体的方法，包括：
(1)在导电剂存在下，持续通入二氧化碳，将金属盐与沉淀剂混合进行沉淀反应，然后密封静置，以便得到预造粒子；
(2)将所述预造粒子与水混合得到浆料，然后伴随着搅拌，同时持续通入所述金属盐、所述沉淀剂和所述二氧化碳进行共沉淀反应，以便得到反应后液；
(3)将所述反应后液与铝盐混合反应后进行陈化搅拌，以便得到陈化后料；
(4)将所述陈化后料依次进行除铁、固液分离、洗涤和干燥，以便得到铝包覆前驱体。
本公开提供的一实施例中，首先在导电剂存在下，持续通入二氧化碳，再加入金属盐与沉淀剂，二氧化碳的持续通入可以调节体系pH，并且可维持体系的惰性环境，防止共沉淀过程中金属元素被氧化，且可改善前驱体的球型度，而导电剂可以提高材料的倍率性能，然后将预造粒子与水混合调浆得到的浆料中持续通入金属盐、沉淀剂、二氧化碳和络合剂，络合剂可降低体系反应速度，抑制体系中新颗粒的生成，金属盐和沉淀剂在该过程中以小颗粒的预造粒子为晶种进行共沉淀反应，同时该过程持续通入沉淀剂和二氧化碳，以继续维持体系pH稳定，进而得到密实的前驱体，再将得到的含有前驱体的反应后液与铝盐混合进行陈化搅拌，铝元素在沉淀剂的作用下生成沉淀并均匀的附着在前驱体表面，最后经后续的除铁、固液分离、洗涤和干燥工序，即可制备得到上述具有粒度可控且粒度分布均匀、球形度高、颗粒表面光滑、振实密度高、不易破碎、电化学性能和能量密度优异的铝包覆前驱体，同时采用该前驱体制备得到的正极材料具有较高的比容量以及优异的循环性能和电化学放电性能。
本公开一实施例提供的步骤步骤(1)中，在导电剂存在下，将金属盐与沉淀剂迅速混合(10秒以内完成混合)，然后密封静置，得到预造粒子。该过程二氧化碳的持续通入可以调节体系pH，并且可维持体系的惰性环境，防止共沉淀过程中金属元素被氧化，且可改善前驱体的球型度，而导电剂可以提高材料的倍率性能。
本公开一实施例提供的步骤(2)中，金属盐和沉淀剂在该过程中以小颗粒的预造粒子为晶种进行共沉淀反应，同时该过程持续通入二氧化碳，以继续维持体系pH稳定，进而得到密实的前驱体。
本公开一实施例提供的步骤(3)中，将上述得到的反应液与铝盐混合反应后进行陈化搅拌，铝盐中的铝元素与沉淀剂反应后沉淀到前驱体表面，到陈化 后料，经过铝元素的包覆可使前驱体更加稳定。
本公开一实施例提供的步骤(4)中，将上述得到的陈化后料依次进行除铁、固液分离、洗涤和干燥，得到铝包覆前驱体。需要说明的是，该步骤中除铁、固液分离、洗涤和干燥均为制备前驱体过程的常规操作，本领域技术人员可以根据实际需要进行选择，此处不再赘述。
在一实施例中，在步骤(1)中，所述金属盐包括可溶性镍盐、可溶性锰盐和可溶性钴盐中的至少之一。
在一实施例中，在步骤(1)中，所述金属盐的浓度为80～400g/L，例如80g/L、100g/L、150g/L、200g/L、250g/L、300g/L、350g/L或400g/L等。
在一实施例中，在步骤(1)中，所述可溶性镍盐为选自氯化镍、硝酸镍和硫酸镍中的至少之一。
在一实施例中，在步骤(1)中，所述可溶性钴盐为选自氯化钴、硝酸钴和硫酸钴中的至少之一。
在一实施例中，在步骤(1)中，所述可溶性锰盐为选自氯化锰、硝酸锰和硫酸锰中的至少之一。
在一实施例中，在步骤(1)中，所述二氧化碳的流速为0.1～0.5L/min，例如0.1L/min、0.15L/min、0.2L/min、0.25L/min、0.3L/min、0.35L/min、0.4L/min、0.45L/min或0.5L/min等。
本公开提供的一实施例中，二氧化碳的流速为0.1～0.5L/min，若二氧化碳流速过高会增加体系的不稳定性且造成气体的浪费，而本申请流速范围的二氧化碳可以有效维持体系的惰性环境，满足反应需要。
在一实施例中，在步骤(1)中，所述金属盐与所述沉淀剂的摩尔比为1:(2～3.5)，例如1:2、1:2.1、1:2.2、1:2.3、1:2.4、1:2.5、1:2.6、1:2.7、1:2.8、1:2.9、1:3.0、1:3.1、1:3.2、1:3.3、1:3.4或1:3.5等。
本公开提供的一实施例中，金属盐与所述沉淀剂的摩尔比为1:(2～3.5)，若沉淀剂比例太高容易使体系产生新的晶核，且容易造成pH的波动。
在一实施例中，在步骤(1)中，基于1L所述金属盐和所述沉淀剂的总量，所述导电剂的用量为10～50g，例如10g、15g、20g、25g、30g、35g、40g、45g或50g等。太高浓度的导电剂会造成材料比容量的下降。
在一实施例中，在步骤(1)中，所述沉淀剂为选自碳酸钠、碳酸氢铵、氢 氧化钠和碳酸氢钠中的至少之一。
在一实施例中，在步骤(1)中，所述碳酸钠的浓度为50～200g/L，例如50g/L、60g/L、70g/L、80g/L、90g/L、100g/L、110g/L、120g/L、130g/L、140g/L、150g/L、160g/L、170g/L、180g/L、190g/L或200g/L等。
在一实施例中，在步骤(1)中，所述碳酸氢铵的浓度为50～200g/L，例如50g/L、60g/L、70g/L、80g/L、90g/L、100g/L、110g/L、120g/L、130g/L、140g/L、150g/L、160g/L、170g/L、180g/L、190g/L或200g/L等。
在一实施例中，在步骤(1)中，所述氢氧化钠的浓度为50～200g/L，例如50g/L、60g/L、70g/L、80g/L、90g/L、100g/L、110g/L、120g/L、130g/L、140g/L、150g/L、160g/L、170g/L、180g/L、190g/L或200g/L等。
在一实施例中，在步骤(1)中，所述碳酸氢钠的浓度为50～200g/L，例如50g/L、60g/L、70g/L、80g/L、90g/L、100g/L、110g/L、120g/L、130g/L、140g/L、150g/L、160g/L、170g/L、180g/L、190g/L或200g/L等。
在一实施例中，在步骤(1)中，所述沉淀反应的温度为30～80℃，例如30℃、35℃、40℃、45℃、50℃、55℃、60℃、65℃、70℃、75℃或80℃等。
在一实施例中，在步骤(1)中，所述密封静置的时间为12～24h，例如12h、13h、14h、15h、16h、17h、18h、19h、20h、21h、22h、23h或24h等。
在一实施例中，在步骤(1)中，所述导电剂为葡萄糖和果糖中的至少之一。
在一实施例中，在步骤(1)中，所述预造粒子粒径为1～2μm，例如可以是1.0μm、1.1μm、1.2μm、1.3μm、1.4μm、1.5μm、1.6μm、1.7μm、1.8μm、1.9μm或2.0μm等。
在一实施例中，在步骤(2)中，所述浆料的固含量为50～100g/L，例如50g/L、55g/L、60g/L、65g/L、70g/L、75g/L、80g/L、85g/L、90g/L、95g/L或100g/L等。
本公开提供的一实施例中，浆料的固含量为50～100g/L，若该浆料固含量过高，体系中颗粒的生长速度慢，无法得到本申请粒径范围的前驱体。
在一实施例中，在步骤(2)中，所述搅拌转速为350～800rpm，例如350rpm、400rpm、450rpm、500rpm、550rpm、600rpm、650rpm、700rpm、750rpm或800rpm等。
在一实施例中，在步骤(2)中，所述共沉淀反应温度为30～60℃，时间为 5～150h，例如5h、10h、20h、30h、40h、50h、60h、70h、80h、90h、100h、110h、120h、130h、140h或150h等；pH为6～8，例如6.0、6.2、6.4、6.6、6.8、7.0、7.2、7.4、7.6、7.8或8.0等。
本公开提供的一实施例中，通过控制共沉淀反应过程的温度、时间和pH在本申请范围内，可以得到球形度高的前驱体，并且与现有技术中需要调整体系pH为9以上才能得到本申请粒径的前驱体相比，本申请大幅减小了体系碱用量，同时抑制反应过程中锰被氧化，适合大规模生产。
在一实施例中，在步骤(2)中，持续通入所述金属盐流速为100～500mL/h，例如100mL/h、150mL/h、200mL/h、250mL/h、300mL/h、350mL/h、400mL/h、450mL/h或500mL/h等；所述沉淀剂的流速为100～500mL/h，例如100mL/h、150mL/h、200mL/h、250mL/h、300mL/h、350mL/h、400mL/h、450mL/h或500mL/h等；所述二氧化碳的流速为0.25～0.6L/min，例如0.25L/min、0.3L/min、0.35L/min、0.4L/min、0.45L/min、0.5L/min、0.55L/min或0.6L/min等。
在一实施例中，在步骤(2)中，所述反应后液的固含量为30～500g/L，例如30g/L、100g/L、150g/L、200g/L、250g/L、300g/L、350g/L、400g/L、450g/L或500g/L等。
在一实施例中，在步骤(2)中，伴随着搅拌，持续通入络合剂。加入络合剂的目的在于降低该过程体系反应速度，抑制体系中新颗粒的生成，该过程中进一步包括伴随着搅拌，持续通入络合剂。
在一实施例中，在步骤(2)中，所述络合剂为氨水或碳酸氢铵。
在一实施例中，所述络合剂浓度为10～50g/L，例如10g/L、15g/L、20g/L、25g/L、30g/L、35g/L、40g/L、45g/L或50g/L等。
在一实施例中，在步骤(3)中，所述反应后液与所述铝盐的体积比为(10～20):1，例如10:1、11:1、12:1、13:1、14:1、15:1、16:1、17:1、18:1、19:1或20:1等。
本公开提供的一实施例中，反应后液与所述铝盐的体积比为(10～20):1，该混合比例下可以保证足够的铝元素包覆在前驱体上，从而提高前驱体的稳定性。
在一实施例中，在步骤(3)中，所述铝盐为氯化铝和硫酸铝中的至少之一。
在一实施例中，在步骤(3)中，所述铝盐的浓度为10～50g/L，例如10g/L、15g/L、20g/L、25g/L、30g/L、35g/L、40g/L、45g/L或50g/L等。
在一实施例中，在步骤(3)中，所述陈化搅拌的转速为200～300rpm，例如200rpm、210rpm、220rpm、230rpm、240rpm、250rpm、260rpm、270rpm、280rpm、290rpm或300rpm等；时间为0.5～5h，例如0.5h、1h、1.5h、2h、2.5h、3h、3.5h、4h、4.5h或5h等。
本公开在一实施例中提供一种制备正极材料的方法，包括：
(a)将前驱体与锂盐混合进行一次烧结，以便得到一次烧结料；
(b)将所述一次烧结料破碎后进行二次烧结，以便得到正极材料；
其中，在步骤(a)中，所述前驱体为一实施例所述的铝包覆前驱体或采用一实施例所述的方法得到的铝包覆前驱体。
根据本公开一实施例提供的制备正极材料的方法通过将上述具有粒度可控且粒度分布均匀、球形度高、颗粒表面光滑、振实密度高、不易破碎、电化学性能和能量密度优异的铝包覆前驱体与锂盐混合进行一次烧结和二次烧结，其中，一次烧结过程中使得锂离子进入前驱体材料内部，结合生成锂盐正极材料，再经二次烧结使得烧结过程更为充分，从而制备得到具有较高的比容量以及优异的循环性能和电化学放电性能的正极材料。
本公开一实施例提供的步骤(a)中，将上述前驱体或上述方法得到的前驱体与锂盐混合进行一次烧结，使得锂盐中的锂离子进入前驱体内部，结合生成锂盐正极材料，即一次烧结料。
本公开一实施例提供的步骤(b)中，将上述得到的一次烧结料破碎后进行二次烧结，从而使得一次烧结过程未进入前驱体内部的锂盐进一步迁移进入前驱体内部，保证烧结过程反应更充分，得到正极材料。
在一实施例中，在步骤(a)中，所述前驱体材料与所述锂盐的摩尔比为1:(1.02～1.08)，例如1:1.02、1:1.03、1:1.04、1:1.05、1:1.06、1:1.07或1:1.08等。
在一实施例中，在步骤(a)中，所述一次烧结的温度为450～600℃，时间为4～6h，例如4.0h、4.2h、4.4h、4.6h、4.8h、5.0h、5.2h、5.4h、5.6h、5.8h或6.0h等。
本公开提供的一实施例中，一次烧结的温度为450～600℃，若该温度过低，使得部分锂离子不能进入前驱体内部而形成锂盐正极材料，而若温度过高则浪费能源。由此，采用该烧结温度不仅可以保证锂离子能够迁移进入前驱体内部生成锂盐正极材料，而且避免能源浪费。
在一实施例中，在步骤(b)中，所述二次烧结的温度为700～850℃，时间为15～25h，例如15h、16h、17h、18h、19h、20h、21h、22h、23h、24h或25h等。
本公开提供的一实施例中，本领域技术人员可以根据实际需要对一次烧结料破碎粒度进行选择，此处不再赘述。
本公开在一实施例中提供一种正极材料，所述正极材料采用权利要求6或7所述的方法制备得到。
在一实施例中，其中，所述正极材料的化学式为Li(Li aNi mCo nMn (1-a-b-m-n)Al b)O 2，其中a为0.05～0.35，b为0.005～0.01，m为0.01～0.25，n为0.01～0.25，例如a为0.05、0.1、0.15、0.2、0.25、0.3或0.35等，b为0.005、0.006、0.007、0.008、0.009或0.01等，m为0.01、0.05、0.1、0.15、0.2或0.25等，n为0.01、0.05、0.1、0.15、0.2或0.25等。
本公开提供的一实施例中，该正极材料具有较高的比容量以及优异的循环性能和电化学放电性能。
本公开在一实施例中提供一种锂电池，所述锂电池具有一实施例所述的正极材料。
本公开提供的一实施例中，该锂电池在具有高比能量的基础上具有长循环寿命。
本公开在一实施例中提供一种汽车，所述汽车具有一实施例所述的锂电池。
本公开提供的一实施例中，装载上述具有高比能量和长循环寿命锂电池的车辆具有优异的续航能力，从而满足消费者的使用需求。
附图说明
附图用来提供对本公开技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本公开的技术方案，并不构成对本公开技术方案的限制。
图1是本公开一实施例制备铝包覆前驱体的方法流程示意图；
图2是本公开一实施例制备正极材料的方法流程示意图；
图3是本公开一实施例制备得到的铝包覆前驱体扫描电镜图；
图4是本公开一实施例制备得到的铝包覆前驱体扫描电镜图；
图5是本公开一实施例制备得到的正极材料做成的扣式电池在0.1C的首次充放电曲线图。
具体实施例
下面结合附图并通过具体实施方式来进一步说明本公开的技术方案。
在一个实施例中，本公开提供了一种铝包覆前驱体，所述前驱体化学式为xMCO 3(1-x)·Al(OH) 3，其中，M为镍、钴和锰中的至少之一，x为0.995～0.999。该铝包覆前驱体具有粒度可控且粒度分布均匀、球形度高、颗粒表面光滑、振实密度高、不易破碎、电化学性能和能量密度优异的优势，同时采用该前驱体制备得到的正极材料具有较高的比容量以及优异的循环性能和电化学放电性能，该组成的前驱体具有较高的放电比容量和稳定性。上述前驱体粒径为6～15μm，振实密度不低于1.8g/cm 3。
在一个实施例中，本公开提供了一种制备上述铝包覆前驱体的方法，如图1所示，所述方法包括：
S100：在导电剂存在下，持续通入二氧化碳，将金属盐与沉淀剂混合进行沉淀反应，然后密封静置，得到预造粒子。金属盐的浓度为80～400g/L，沉淀剂选自碳酸钠、碳酸氢铵、氢氧化钠和碳酸氢钠中的至少之一，其中，碳酸钠的浓度为50～200g/L，碳酸氢铵的浓度为50～200g/L，氢氧化钠的浓度为50～200g/L，碳酸氢钠的浓度为50～200g/L。金属盐与沉淀剂的摩尔比为1:(2～3.5)，基于1L金属盐和沉淀剂的总量，导电剂的用量为10～50g。该过程中持续通入二氧化碳的流速为0.1～0.5L/min，沉淀反应的温度为30～80℃，密封静置的时间为12～24h，得到的预造粒子粒径为1～2μm。
S200：将所述预造粒子与水混合得到浆料，然后伴随着搅拌，同时持续通入所述金属盐、所述沉淀剂和所述二氧化碳进行共沉淀反应，以便得到反应后液。预造粒子与水混合得到浆料的固含量为50～100g/L，搅拌转速为350～800rpm，共沉淀反应温度为30～60℃，时间为5～150h，pH为6～8。通入金属盐流速为100～500mL/h，持续通入沉淀剂的流速为100～500mL/h，持续通入二氧化碳的流速为0.25～0.6L/min，控制反应后液的固含量为30～500g/L。
S300：将上述得到的反应液与铝盐混合反应后进行陈化搅拌，铝盐中的铝元素与沉淀剂反应后沉淀到前驱体表面，得到陈化后料。铝盐为氯化铝和硫酸 铝中的至少之一，铝盐的浓度为10～50g/L，反应后液与铝盐的质量比为(10～20):1，陈化搅拌的转速为200～300rpm，时间为0.5～5h。
S400：将陈化后料依次进行除铁、固液分离、洗涤和干燥。
在一个实施例中，本公开提供了一种制备正极材料的方法，如图2所示，所述方法包括：
Sa：将上述前驱体或上述方法得到的前驱体与锂盐混合进行一次烧结，使得锂盐中的锂离子进入前驱体内部，结合生成锂盐正极材料，即一次烧结料；锂盐选自氢氧化锂和碳酸锂中的至少之一，前驱体材料与锂盐的摩尔比为1:(1.02～1.08)，一次烧结的温度为450～600℃，时间为4～6h。
Sb：将步骤Sa得到的一次烧结料破碎后进行二次烧结，从而使得一次烧结过程未进入前驱体内部的锂盐进一步迁移进入前驱体内部，保证烧结过程反应更充分，得到正极材料。二次烧结的700～850℃，时间为15～25h。
在一个实施例中，本公开提供了一种正极材料，所述正极材料采用上述所述的方法制备得到。
在一个实施例中，本公开提供了一种锂电池，所述锂电池具有上述正极材料。
在一个实施例中，本公开提供了一种汽车，所述汽车具有上述锂电池。
实施例1
制备铝包覆前驱体的方法如下：
(1)将硫酸镍、硫酸钴、硫酸锰按照镍钴锰元素摩尔比为0.2:0.18:0.6进行混合，得到混合金属盐，并且混合金属盐中硫酸镍、硫酸钴和硫酸锰的浓度均为400g/L，然后在导电剂葡萄糖存在下，按照流速为0.1L/min的流速持续通入二氧化碳，然后将混合金属盐与浓度为200g/L的氢氧化钠溶液快速混合(10秒内完成混合，其中，混合金属盐与氢氧化钠的摩尔比为1:2.0，同时基于1L混合金属盐和氢氧化钠的总量，导电剂葡萄糖的用量为20g)，然后在30℃密封静置12h，得到粒径为1.2μm的预造粒子；
(2)将上述得到的预造粒子与水混合得到浆料(固含量为200g/L)，然后 伴随着搅拌(搅拌转速为400rpm)，进行共沉淀反应，同时持续通入混合金属盐(流速为200mL/h)，碳酸氢钠(浓度为50～200g/L，流速为150～250mL/h)、二氧化碳(流速为0.25mL/min)，并且控制体系pH为7.5，反应60h，得到固含量为500g/L的反应后料；
(3)将反应后液与氯化铝混合后进行陈化搅拌，其中搅拌转速为300rpm，陈化时间为2h，得到陈化后料；
(4)将上述得到的陈化后料依次进行除铁、固液分离、洗涤和干燥，得到粒径8μm的铝包覆前驱体，其化学式为(Mn 0.6Ni 0.2Co 0.18)CO 3·0.02Al(OH) 3，其振实密度为1.8g/cm 3。
制备正极材料的方法如下：
Sa：将上述步骤(4)得到的铝包覆驱体与氢氧化锂按照摩尔比为1:1.06混合在空气气氛下于500℃进行一次烧结6h，得到一次烧结料；
Sb：将上述得到的一次烧结料破碎后在700℃进行二次烧结18h，得到化学式为Li(Li 0.2Ni 0.16Co 0.15Mn 0.48Al 0.014)O 2，压实密度为3.2g/cm 3。
结论：图3和图4为前驱体材料的扫描电镜图，可以看出该方法得到的前驱体材料具有球形结构、粒度分布均匀且表面光滑，并且使用激光粒度仪检测前驱体粒径分布进一步发现其粒度分布均匀，同时该正极材料与SP(炭黑导电剂)、PVDF(聚偏氟乙烯)混合，用NMP(N-甲基吡咯烷酮)为溶剂制浆搅拌数h制得锂离子半电池，采用蓝电测试仪在4.8V下进行充放电测试，得到产品0.1C放电克容量为305mAh(图5为该锂离子半电池电池0.1C充放电曲线)，1.0C放电容量为230～240mAh，50周循环容量保持率92％。
实施例2
制备铝包覆前驱体的方法如下：
(1)将氯化镍、氯化钴、氯化锰按照镍钴锰元素摩尔比为0.2:0.09:0.7进行混合，得到混合金属盐，并且混合金属盐中氯化镍、氯化钴和氯化锰的浓度均为300g/L，然后在导电剂果糖存在下，按照流速为0.5L/min的流速持续通入二氧化碳，然后将混合金属盐与浓度为50g/L的氢氧化钠溶液快速混合(10秒内完成混合，其中，混合金属盐与氢氧化钠的摩尔比为1:3.5，同时基于1L混合金 属盐和氢氧化钠的总量，导电剂果糖的用量为30g)，然后在80℃密封静置18h，得到粒径为1.5μm的预造粒子；
(2)将上述得到的预造粒子与水混合得到浆料(固含量为100g/L)，然后伴随着搅拌(搅拌转速为500rpm)，进行共沉淀反应，同时持续通入混合金属盐(流速为300mL/h)、碳酸钠(浓度为50～200g/L，流速为250～350mL/h)和二氧化碳(流速为0.4mL/min)，并且控制体系pH为8，反应50h，得到固含量为800g/L的反应后料；
(3)将反应后液与硫酸铝混合后进行陈化搅拌，其中搅拌转速为300rpm，陈化时间为2h，得到陈化后料；
(4)将上述得到的陈化后料依次进行除铁、固液分离、洗涤和干燥，得到粒径10μm的铝包覆前驱体，其化学式为(Mn 0.7Ni 0.2Co 0.09)CO 3·0.01Al(OH) 3，其振实密度为1.8g/cm 3。
制备正极材料的方法如下：
Sa：将上述步骤(4)得到的铝包覆驱体与碳酸锂按照摩尔比为1:1.06混合在空气气氛下于500℃进行一次烧结5h，得到一次烧结料；
Sb：将上述得到的一次烧结料破碎后在750℃进行二次烧结20h，得到化学式为Li(Li 0.2Ni 0.16Co 0.07Mn 0.56Al 0.008)O 2，压实密度为3.1g/cm 3。
结论：根据前驱体材料的扫描电镜图，可以看出该方法得到的前驱体材料具有球形结构、粒度分布均匀且表面光滑，并且使用激光粒度仪检测前驱体粒径分布进一步发现其粒度分布均匀，同时该正极材料与SP(炭黑导电剂)、PVDF(聚偏氟乙烯)混合，用NMP(N-甲基吡咯烷酮)为溶剂制浆搅拌数h制得锂离子半电池，采用蓝电测试仪在4.8V下进行充放电测试，得到产品0.1C放电克容量为295～305mAh，1.0C放电容量为230～235mAh，50周循环容量保持率88％。
实施例3
制备铝包覆前驱体的方法如下：
(1)将硝酸镍、硝酸钴、硝酸锰按照镍钴锰元素摩尔比为0.2:0.19:0.6进行混合，得到混合金属盐，并且混合金属盐中硝酸镍、硝酸钴和硝酸锰的浓度均 为200g/L，然后在导电剂葡萄糖存在下，按照流速为0.3L/min的流速持续通入二氧化碳，然后将混合金属盐与浓度为100g/L的碳酸钠溶液快速混合(10秒内完成混合，其中，混合金属盐与碳酸钠的摩尔比为1:2.8，同时基于1L混合金属盐和碳酸钠的总量，导电剂葡萄糖的用量为25g)，然后在50℃密封静置20h，得到粒径为1.8μm的预造粒子；
(2)将上述得到的预造粒子与水混合得到浆料(固含量为60g/L)，然后伴随着搅拌(搅拌转速为400rpm)，进行共沉淀反应，同时持续通入混合金属盐(流速为250mL/h)、碳酸氢钠(浓度为50～200g/L，流速为200～300mL/h)和二氧化碳(流速为0.6mL/min)和络合剂氨水(浓度为30g/L)，并且控制体系pH为6.5，反应50h，得到固含量为500g/L的反应后料；
(3)将反应后液与氯化铝混合后进行陈化搅拌，其中搅拌转速为300rpm，陈化时间为2h，得到陈化后料；
(4)将上述得到的陈化后料依次进行除铁、固液分离、洗涤和干燥，得到粒径15μm的铝包覆前驱体，其化学式为(Mn 0.6Ni 0.2Co 0.19)CO 3·0.01Al(OH) 3，其振实密度为1.9g/cm 3。
制备正极材料的方法如下：
Sa：将上述步骤(4)得到的铝包覆驱体与氢氧化锂按照摩尔比为1:1.02混合在空气气氛下于550℃进行一次烧结5h，得到一次烧结料；
Sb：将上述得到的一次烧结料破碎后在800℃进行二次烧结20h，得到化学式为Li(Li 0.2Ni 0.16Co 0.15Mn 0.48Al 0.008)O 2，压实密度为3.2g/cm 3。
结论：根据前驱体材料的扫描电镜图可以看出该方法得到的前驱体材料具有球形结构、粒度分布均匀且表面光滑，并且使用激光粒度仪检测前驱体粒径分布进一步发现其粒度分布均匀，同时该正极材料与SP(炭黑导电剂)、PVDF(聚偏氟乙烯)混合，用NMP(N-甲基吡咯烷酮)为溶剂制浆搅拌数h制得锂离子半电池，采用蓝电测试仪在4.8V下进行充放电测试，得到产品0.1C放电克容量为255～260mAh，1.0C放电容量为205～208mAh，50周循环容量保持率84％。

Claims (40)

  1. 一种铝包覆前驱体，所述前驱体化学式为xMCO 3(1-x)·Al(OH) 3，其中，M为镍、钴和锰中的至少之一，x为0.995～0.999。
  2. 根据权利要求1所述的前驱体，其中，所述前驱体粒径为6～15μm，振实密度不低于1.8g/cm 3。
  3. 一种制备权利要求1或2所述前驱体的方法，包括：
    (1)在导电剂存在下，持续通入二氧化碳，将金属盐与沉淀剂混合进行沉淀反应，然后密封静置，以便得到预造粒子；
    (2)将所述预造粒子与水混合得到浆料，然后伴随着搅拌，同时持续通入所述金属盐、所述沉淀剂和所述二氧化碳进行共沉淀反应，以便得到反应后液；
    (3)将所述反应后液与铝盐混合反应后进行陈化搅拌，以便得到陈化后料；
    (4)将所述陈化后料依次进行除铁、固液分离、洗涤和干燥，以便得到铝包覆前驱体。
  4. 根据权利要求3所述的方法，其中，在步骤(1)中，所述金属盐包括可溶性镍盐、可溶性锰盐和可溶性钴盐中的至少之一。
  5. 根据权利要求3或4所述的方法，其中，在步骤(1)中，所述金属盐的浓度为80～400g/L。
  6. 根据权利要求4或5所述的方法，其中，在步骤(1)中，所述可溶性镍盐为选自氯化镍、硝酸镍和硫酸镍中的至少之一。
  7. 根据权利要求4-6任一项所述的方法，其中，在步骤(1)中，所述可溶性钴盐为选自氯化钴、硝酸钴和硫酸钴中的至少之一。
  8. 根据权利要求4-7任一项所述的方法，其中，在步骤(1)中，所述可溶性锰盐为选自氯化锰、硝酸锰和硫酸锰中的至少之一。
  9. 根据权利要求3-8任一项所述的方法，其中，在步骤(1)中，所述二氧化碳的流速为0.1～0.5L/min。
  10. 根据权利要求3-9任一项所述的方法，其中，在步骤(1)中，所述金属盐与所述沉淀剂的摩尔比为1：(2～3.5)。
  11. 根据权利要求3-10任一项所述的方法，其中，在步骤(1)中，基于1L所述金属盐和所述沉淀剂的总量，所述导电剂的用量为10～50g。
  12. 根据权利要求3-11任一项所述的方法，其中，在步骤(1)中，所述沉淀剂为选自碳酸钠、碳酸氢铵、氢氧化钠和碳酸氢钠中的至少之一。
  13. 根据权利要求12所述的方法，其中，在步骤(1)中，所述碳酸钠的浓度为50～200g/L。
  14. 根据权利要求12或13所述的方法，其中，在步骤(1)中，所述碳酸氢铵的浓度为50～200g/L。
  15. 根据权利要求12-14任一项所述的方法，其中，在步骤(1)中，所述氢氧化钠的浓度为50～200g/L。
  16. 根据权利要求12-15任一项所述的方法，其中，在步骤(1)中，所述碳酸氢钠的浓度为50～200g/L。
  17. 根据权利要求3-16任一项所述的方法，其中，在步骤(1)中，所述沉淀反应的温度为30～80℃。
  18. 根据权利要求3-17任一项所述的方法，其中，在步骤(1)中，所述密封静置的时间为12～24h。
  19. 根据权利要求3-18任一项所述的方法，其中，在步骤(1)中，所述导电剂为葡萄糖和果糖中的至少之一。
  20. 根据权利要求3-19任一项所述的方法，其中，在步骤(1)中，所述预造粒子粒径为1～2μm。
  21. 根据权利要求3-20任一项所述的方法，其中，在步骤(2)中，所述浆料的固含量为50～100g/L。
  22. 根据权利要求3-21任一项所述的方法，其中，在步骤(2)中，所述搅拌转速为350～800rpm。
  23. 根据权利要求3-22任一项所述的方法，其中，在步骤(2)中，所述共沉淀反应温度为30～60℃，时间为5～150h，pH为6～8。
  24. 根据权利要求3-23任一项所述的方法，其中，在步骤(2)中，持续通入所述金属盐流速为100～500mL/h，所述沉淀剂的流速为100～500mL/h，所述二氧化碳的流速为0.25～0.6L/min。
  25. 根据权利要求3-24任一项所述的方法，其中，在步骤(2)中，所述反应后液的固含量为30～500g/L。
  26. 根据权利要求3-25任一项所述的方法，其中，在步骤(2)中，伴随着搅拌，持续通入络合剂。
  27. 根据权利要求26所述的方法，其中，在步骤(2)中，所述络合剂为 氨水或碳酸氢铵。
  28. 根据权利要求26或27所述的方法，其中，所述络合剂浓度为10～50g/L。
  29. 根据权利要求3-28任一项所述的方法，其中，在步骤(3)中，所述反应后液与所述铝盐的体积比为(10～20):1。
  30. 根据权利要求3-29任一项所述的方法，其中，在步骤(3)中，所述铝盐为氯化铝和硫酸铝中的至少之一。
  31. 根据权利要求3-30任一项所述的方法，其中，在步骤(3)中，所述铝盐的浓度为10～50g/L。
  32. 根据权利要求3-31任一项所述的方法，其中，在步骤(3)中，所述陈化搅拌的转速为200～300rpm，时间为0.5～5h。
  33. 一种制备正极材料的方法，包括：
    (a)将前驱体与锂盐混合进行一次烧结，以便得到一次烧结料；
    (b)将所述一次烧结料破碎后进行二次烧结，以便得到正极材料，
    其中，在步骤(a)中，所述前驱体为权利要求1或2中所述的铝包覆前驱体或采用权利要求3-32任一项所述的方法得到的铝包覆前驱体。
  34. 根据权利要求33所述的方法，其中，在步骤(a)中，所述前驱体材料与所述锂盐的摩尔比为1：(1.02～1.08)。
  35. 根据权利要求33或34所述的方法，其中，在步骤(a)中，所述一次烧结的温度为450～600℃，时间为4～6h。
  36. 根据权利要求33-35任一项所述的方法，其中，在步骤(b)中，所述二次烧结的温度为700～850℃，时间为15～25h。
  37. 一种正极材料，所述正极材料采用权利要求33-36任一项所述的方法制备得到。
  38. 根据权利要求37所述的方法，其中，所述正极材料的化学式为Li(Li aNi mCo nMn (1-a-b-m-n)Al b)O 2，其中a为0.05～0.35，b为0.005～0.01，m为0.01～0.25，n为0.01～0.25。
  39. 一种锂电池，所述锂电池具有权利要求37或38所述的正极材料。
  40. 一种汽车，所述汽车具有权利要求39所述的锂电池。
PCT/CN2020/124789 2019-12-27 2020-10-29 铝包覆前驱体及其制备方法和应用 Ceased WO2021129130A1 (zh)

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