WO2023030403A1 - 一种复合材料及其制备方法和锂离子电池正极材料 - Google Patents

一种复合材料及其制备方法和锂离子电池正极材料 Download PDF

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WO2023030403A1
WO2023030403A1 PCT/CN2022/116295 CN2022116295W WO2023030403A1 WO 2023030403 A1 WO2023030403 A1 WO 2023030403A1 CN 2022116295 W CN2022116295 W CN 2022116295W WO 2023030403 A1 WO2023030403 A1 WO 2023030403A1
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source
composite material
lithium
cobalt
nickel
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French (fr)
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王亚州
张树涛
李子郯
王壮
马加力
白艳
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Svolt Energy Technology Co Ltd
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Svolt Energy Technology Co Ltd
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Priority to US18/557,379 priority patent/US20240140820A1/en
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    • 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
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    • 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
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    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to the technical field of lithium ion batteries, in particular, to a composite material, a preparation method thereof, and a positive electrode material of lithium ion batteries.
  • Lithium-ion batteries are popular for their advantages such as high working voltage, high specific energy, long cycle life and low pollution.
  • the commonly used positive electrode materials are lithium cobalt oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, lithium iron phosphate, and high-voltage lithium nickel manganese oxide. Cobalt is expensive, and lithium cobalt oxide and lithium nickel cobalt manganese oxide are used in power batteries, which pose a greater safety hazard. Lithium manganese oxide, lithium nickel manganese oxide, and lithium iron phosphate are ideal cathode materials for lithium-ion power batteries. Although the lithium manganese oxide material has low cost and good safety performance, its specific capacity is relatively low.
  • the cycle life is not ideal.
  • doping can effectively improve its high-temperature cycle performance, especially Ni-doped LiNi 0.5 Mn 1.5 O 4 , which makes the valence of manganese higher than 3.5, which can effectively inhibit Mn dissolution, JahnTeller distortion effect and lattice instability.
  • the discharge voltage platform is as high as 4.7V, making it an ideal cathode material for power batteries.
  • lithium nickel manganese oxide material can significantly improve the capacity of lithium nickel manganese oxide, but its cycle performance needs to be improved.
  • the first type is to mix nickel salt solution and manganese salt solution in a certain proportion, then add hydroxide or carbonate to form a precursor by co-precipitation, and then add lithium The salt is calcined to form lithium nickel manganese oxide.
  • the second type is to use nickel oxide, manganese oxide and lithium salt for mixed calcination to prepare lithium nickel manganese oxide.
  • lithium nickel manganese oxide particles generally prepared by simple solid-phase ball milling method are relatively large (7um ⁇ 16um), contain more heterogeneous components, and the specific capacity is not high, so the charge-discharge curve of the material is difficult to present.
  • a single charging and discharging platform has poor cycle performance. The reason is still that the uniformity of raw material mixing is not good.
  • the disclosure provides a method for preparing a composite material, comprising the following steps:
  • the mixture of manganese source, nickel source, lithium source and cobalt source is subjected to the first calcination treatment to obtain cobalt-doped lithium nickel manganese oxide; the mixture of the cobalt-doped lithium nickel manganese oxide and silicon dioxide is subjected to the second Calcination treatment.
  • the manganese source includes trimanganese tetraoxide.
  • the particle size D50 of the manganese source is 2-4 ⁇ m.
  • the nickel source includes nickel oxide.
  • the particle size D50 of the nickel source is 8-10 ⁇ m.
  • the lithium source includes lithium carbonate.
  • the particle size D50 of the lithium source is 8-10 ⁇ m.
  • the cobalt source comprises cobalt hydroxide and/or cobalt oxide.
  • the atomic molar ratio of the lithium source, nickel source and manganese source in terms of Li, Ni and Mn is (1.01-1.05):(0.4-0.475):(1.525-1.6).
  • the atomic molar ratio of the cobalt source and the nickel source in terms of Co and Ni is (0.03 ⁇ 0.06):1.
  • the preparation method of described nickel oxide comprises the following steps:
  • the nickel oxide suspension was ground to a particle size D50 of 300-800 nm, and then freeze-dried.
  • the solid content of nickel oxide is 25% to 35%
  • the freeze-drying temperature is -20-40°C
  • the freeze-drying vacuum is 3-10Pa.
  • the mass ratio of the cobalt-doped lithium nickel manganese oxide to the silicon dioxide is 1: (0.005-0.02);
  • the particle size of the silicon dioxide is 10-20 nm.
  • the first calcination treatment includes the following steps:
  • the mixture of the manganese source, the nickel source, the lithium source and the cobalt source is heated to a temperature of 800-950°C and kept at 800-950°C.
  • the incubation time is 10-12 hours.
  • the first calcination treatment is performed in an air atmosphere, and the flow rate of the air is 18-22 L/min.
  • the heating rate during the process of heating to a temperature of 800-950° C. is 2-4° C./min.
  • the mixture of the manganese source, the nickel source, the lithium source and the cobalt source is firstly subjected to stirring treatment, and then to the first calcination treatment.
  • the rotational speed of the stirring treatment is 1800-2200 rpm, and the time of the stirring treatment is 15-25 minutes.
  • the second calcination treatment includes the following steps:
  • the mixture of cobalt-doped lithium nickel manganese oxide and silicon dioxide is heated to 500-700° C., and heat preservation treatment is carried out under the condition of 500-700° C.
  • the time for the heat preservation treatment is 10-12 hours.
  • the second calcination treatment is performed in an air atmosphere, and the flow rate of the air is 18-22 L/min.
  • the heating rate during the process of heating to a temperature of 500-700° C. is 2-4° C./min.
  • the mixture of cobalt-doped lithium nickel manganese oxide and silicon dioxide is firstly subjected to stirring treatment, and then to the second calcination treatment.
  • the rotational speed of the stirring treatment is 1800-2200 rpm, and the time of the stirring treatment is 15-25 minutes.
  • the composite material prepared by the preparation method of the composite material.
  • a lithium ion battery positive electrode material is mainly prepared from the composite material.
  • Fig. 1 is the scanning electron micrograph that obtains composite material in embodiment 1;
  • Fig. 2 is the cycle performance test result figure of the battery that composite material is prepared
  • Fig. 3 is the relationship diagram between the constant current charging ratio and the discharge current of the battery prepared by the composite material
  • Fig. 4 is a graph showing the relationship between the discharge capacity retention rate and the discharge current of the battery prepared from the composite material.
  • the present disclosure relates to a preparation method of a composite material, comprising the following steps:
  • the mixture of manganese source, nickel source, lithium source and cobalt source is subjected to the first calcination treatment to obtain cobalt-doped lithium nickel manganese oxide; the mixture of cobalt-doped lithium nickel manganese oxide and silicon dioxide is subjected to the second calcination treatment .
  • the mechanism of solid-phase calcination of oxides to synthesize lithium nickel manganese oxide is based on manganese oxide.
  • the lithium salt is first intercalated and reacted to form lithium manganese oxide, and then the nickel oxide is gradually embedded in lithium manganate to form lithium nickel manganese oxide. Therefore, the present disclosure starts from the reaction mechanism of preparing lithium nickel manganese oxide by calcination of oxides, and prepares a spinel lithium nickel manganese oxide composite material with a small particle size through a new preparation method.
  • the above preparation method can not only facilitate the intercalation of nickel oxide, but also help to form a lithium nickel manganese oxide composite material with less impurity phases, and can effectively improve the capacity and rate performance of the lithium nickel manganese oxide composite material.
  • Lithium nickel manganese oxide with small particle size has a large specific surface area, and there are many side reactions in contact with the electrolyte. Therefore, the present disclosure uses nano- SiO2 for coating to protect the cycle performance of lithium nickel manganese oxide
  • the manganese source includes trimanganese tetraoxide (Mn 3 O 4 ).
  • the particle size D50 of the manganese source is 2-4 ⁇ m.
  • the particle size D50 of the manganese source can also be selected as 2.2 ⁇ m, 2.5 ⁇ m, 2.7 ⁇ m, 3 ⁇ m, 3.2 ⁇ m, 3.5 ⁇ m, 3.7 ⁇ m or 3.9 ⁇ m.
  • the lithium nickel manganese oxide particles prepared by using 3um Mn 3 O 4 as the substrate reaction are also smaller, so Co-doped SiO 2 coated lithium nickel manganese oxide with a particle size ranging from 1um to 3um is obtained. Both the cycle performance and the rate performance have been greatly improved, especially the rate performance.
  • the material can charge and discharge at a current of 40C with a capacity retention rate of 96.24%, and at a current of 80C it has a capacity retention rate of 82.58%. rate, which will mean that electric vehicles will be charged to 80% in less than 1 minute, which has a very large competitive advantage.
  • the nickel source includes nickel oxide (NiO).
  • the particle size D50 of the nickel source is 8-10 ⁇ m.
  • the lithium source includes lithium carbonate (Li 2 CO 3 ).
  • the particle size D50 of the lithium source is 8-10 ⁇ m.
  • the particle size D50 of the lithium source can also be selected as 8.2 ⁇ m, 8.5 ⁇ m, 8.7 ⁇ m, 9 ⁇ m, 9.2 ⁇ m, 9.5 ⁇ m, 9.7 ⁇ m or 9.9 ⁇ m.
  • the cobalt source includes cobalt hydroxide and/or cobalt oxide.
  • the atomic molar ratios of the lithium source, the nickel source and the manganese source in terms of Li, Ni and Mn are (1.01-1.05):(0.4-0.475):(1.525-1.6).
  • the atomic molar ratio of lithium source, nickel source and manganese source in terms of Li, Ni and Mn is (1.01 ⁇ 1.05):(0.4 ⁇ 0.475):(1.525 ⁇ 1.6), and 1.01 :0.4:1.525, 1.02:0.42:1.53, 1.04:0.45:1.55, 1.04:0.46:1.57, or 1.05:0.475:1.6.
  • the atomic molar ratio of the cobalt source and the nickel source in terms of Co and Ni is (0.03 ⁇ 0.06):1.
  • the atomic molar ratio of the cobalt source and the nickel source in terms of Co and Ni can also be selected from 0.035:1, 0.036:1, 0.035:1, 0.038:1, 0.04:1, 0.042:1, 0.045 :1, 0.0475:1, 0.05:1, 0.052:1, or 0.055:1.
  • the preparation method of nickel oxide comprises the following steps:
  • the nickel oxide suspension was ground to a particle size D50 of 300-800 nm, and then freeze-dried.
  • the nickel oxide obtained by using grinding technology combined with freeze-drying technology helps to form lithium nickel manganese oxide with less impurity phase.
  • the suspension of nickel oxide is ground to a particle size D50 of 300-800nm, and can also be selected from 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm.
  • the solid content of the nickel oxide in the nickel oxide suspension is 25%-35%.
  • the solid content of nickel oxide is 25%-35%, and may also be 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33% or 34%.
  • the freeze-drying temperature is -20-40° C.
  • the vacuum degree of the freeze-drying is 3-10 Pa.
  • freeze-drying technology helps to prevent the secondary agglomeration of NiO during the drying process.
  • the freeze-drying temperature is -20°C to -40°C, and can also be selected from -21°C, -22°C, -23°C, -24°C, -25°C, -26°C, -27°C, -28°C, -29°C, -30°C, -31°C, -32°C, -33°C, -34°C, -35°C, -36°C, -37°C, -38°C, -39°C or -40°C °C.
  • This disclosure limits grinding to a particle size D50 of 300-800nm, a solid content of nickel oxide of 25%-35%, and a freeze-drying temperature of -20-40°C.
  • the combination of the above conditions can make the obtained nano-nickel oxide have Excellent dispersion, using the prepared nano-NiO to calcine to prepare lithium nickel manganese oxide helps to reduce the heterogeneous phase of oxide calcination to prepare lithium nickel manganese oxide, and can obtain lithium nickel manganese oxide with a particle size of 1-3um. . Less impurity phase helps to improve the cycle stability of the material, and the small particle size of 1-3um is conducive to the full play of the capacity of lithium nickel manganese oxide.
  • the mass ratio of cobalt-doped lithium nickel manganese oxide to silicon dioxide is 1:(0.005 ⁇ 0.02).
  • SiO 2 as a coating agent will form Li 2 SiO 3 with very good ion conductivity on the surface of lithium nickel manganese oxide.
  • Li 2 SiO 3 and The doping of Co element produces a synergistic effect, which can simultaneously improve the ionic conductivity and electronic conductivity of the lithium nickel manganese oxide composite material, and greatly improve the rate performance of the lithium nickel manganese oxide material;
  • the formed Li 2 SiO 3 can be combined with the high-voltage electrolyte
  • the HF produced in the reaction can prevent HF from corroding the positive electrode material, improve the structural stability of lithium nickel manganese oxide, and improve the cycle performance of the material.
  • the mass ratio of cobalt-doped lithium nickel manganese oxide to silicon dioxide is 1: (0.005-0.02), and 1:0.006, 1:0.007, 1:0.008, 1:0.009, 1:0.01, 1:0.011, 1:0.012, 1:0.013, 1:0.014, 1:0.015, 1:0.016, 1:0.017, 1:0.018, or 1:0.019.
  • the particle size of the silica is 10-20 nm.
  • the particle size of silicon dioxide can also be selected from 11nm, 11.5nm, 12nm, 12.5nm, 13nm, 13.5nm, 14nm, 14.5nm, 15nm, 15.5nm, 16nm, 166.5nm, 17nm, 17.5nm , 18nm, 18.5nm, 19nm or 19.5nm.
  • the first calcination treatment comprises the following steps:
  • the mixture of manganese source, nickel source, lithium source and cobalt source is heated to a temperature of 800-950°C, and kept at 800-950°C.
  • the mixture of manganese source, nickel source, lithium source and cobalt source is heated to a temperature of 800-950°C, and can also be selected from 810°C, 820°C, 830°C, 840°C, 850°C, 860°C, 870°C, 880°C, 890°C, 900°C, 910°C, 920°C, 930°C or 940°C; keep warm at 800-950°C, you can also choose 810°C, 820°C, 830°C, 840°C, 850°C °C, 860°C, 870°C, 880°C, 890°C, 900°C, 910°C, 920°C, 930°C or 940°C.
  • the time for keeping warm is 10-12 hours.
  • the incubation time can also be selected to be 10.5h, 11h or 12h.
  • the first calcination treatment is performed under an air atmosphere, and the flow rate of the air is 18-22 L/min.
  • the air flow rate is 18-22 L/min, and 18.5 L/min, 19 L/min, 19.5 L/min, 20 L/min, 20.5 L/min or 21 L/min can also be selected.
  • the heating rate during the process of heating to a temperature of 800-950° C. is 2-4° C./min.
  • the heating rate is 2-4°C/min, and can also be selected from 2.2°C/min, 2.5°C/min, 2.7°C/min, 3°C/min, 3.2°C/min, 3.5°C/min or 3.7°C/min.
  • the present disclosure adopts an appropriate first calcination temperature, heating rate, heat preservation time and air flow to match, thereby making the lithium nickel manganese oxide impurity content less, which is beneficial to improve the cycle performance of the battery material.
  • the mixture of the manganese source, the nickel source, the lithium source and the cobalt source is firstly subjected to stirring treatment, and then to the first calcination treatment.
  • the manganese source, the nickel source, and the lithium source are firstly mixed, and then mixed with the cobalt source.
  • the rotational speed of the stirring treatment is 1800-2200 rpm, and the time of the stirring treatment is 15-25 minutes.
  • the rotating speed of stirring treatment is 1800 ⁇ 2200rpm, and 1850rpm, 1870rpm, 1900rpm, 1920rpm, 1950rpm or 1970rpm can also be selected; the time of stirring treatment can also be selected from 16min, 17min, 18min, 19min, 20min, 21min, 22min, 23min or 24min.
  • the second calcination treatment comprises the following steps:
  • the mixture of cobalt-doped lithium nickel manganese oxide and silicon dioxide is heated to 500-700°C, and heat preservation treatment is carried out under the condition of 500-700°C.
  • the mixture of cobalt-doped lithium nickel manganese oxide and silicon dioxide is heated to 500-700°C, and can also be selected from 510°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C, 680°C or 690°C.
  • the time for the heat preservation treatment is 10-12 hours.
  • the incubation time can also be selected to be 10.5h, 11h or 11.5h.
  • the second calcination treatment is performed under an air atmosphere, and the flow rate of the air is 18-22 L/min.
  • the air flow rate can also be selected to be 18.2L/min, 18.5L/min, 18.7L/min, 19L/min, 19.2L/min, 19.5L/min or 19.7L/min.
  • the heating rate during heating to a temperature of 500-700° C. is 2-4° C./min.
  • the heating rate is 2-4°C/min, and can also be selected from 2.2°C/min, 2.5°C/min, 2.7°C/min, 3°C/min, 3.2°C/min, 3.5°C/min or 3.7°C/min.
  • the mixture of cobalt-doped lithium nickel manganese oxide and silicon dioxide is first subjected to a stirring treatment, and then to a second calcination treatment.
  • the rotating speed of stirring treatment is 1800 ⁇ 2200rpm, and the time of stirring treatment is 15 ⁇ 25min. In one embodiment, the rotating speed of stirring treatment is 1800 ⁇ 2200rpm, and 1850rpm, 1870rpm, 1900rpm, 1920rpm, 1950rpm or 1970rpm can also be selected; the time of stirring treatment can also be selected from 16min, 17min, 18min, 19min, 20min, 21min, 22min, 23min or 24min.
  • the present disclosure also relates to a composite material obtained by the above composite material preparation method.
  • the lithium nickel manganese oxide composite material of the present disclosure not only has super cycle stability, but also can be charged and discharged at a super large rate.
  • the present disclosure also relates to a lithium-ion battery cathode material, which is mainly prepared from the above composite material.
  • the ion battery cathode material of the present disclosure can better improve the cycle stability and conductivity of the lithium ion battery.
  • Fig. 2 is the cycle performance test result figure of the battery that composite material is prepared; Wherein, (c) in Fig. 2 is the relationship diagram of capacity retention rate and number of cycles; (d) in Fig. 2 is discharge specific capacity and cycle Diagram of the number of circles.
  • Fig. 3 is a graph showing the relationship between the constant current charging ratio and the discharging current of the battery prepared from the composite material.
  • Fig. 4 is a graph showing the relationship between the discharge capacity retention rate and the discharge current of the battery prepared from the composite material.
  • FIG. 4 see the rate performance in Table 2 for the specific values of the discharge capacity retention rates of Comparative Example 1 and Example 1 at different discharge currents.
  • a method for preparing a composite material comprising the steps of:
  • Li 2 CO 3 , NiO, and Mn 3 O 4 are mixed according to the Li:Ni:Mn atomic molar ratio of 1.05:0.4:1.6, wherein the particle size D50 of Mn 3 O 4 is 3 ⁇ m, and Li 2 CO 3
  • the particle size D50 9 ⁇ m; in addition, according to the Ni:Co atomic molar ratio of 1:0.06, add Co(OH) 2 , and use a mixing agitator at 2000 rpm to stir for 20 minutes; the above-mentioned mixed and stirred material is calcined, and the calcining method includes : Under the air atmosphere, the air flow rate is 20L/min, the heating rate is 4°C/min, the temperature is raised to 950°C, the temperature is kept for 12 hours, the temperature is naturally cooled, and the material is collected;
  • a method for preparing a composite material comprising the steps of:
  • Li 2 CO 3 , NiO, and Mn 3 O 4 are mixed according to the Li:Ni:Mn atomic molar ratio of 1.05:0.4:1.6, wherein the particle size D50 of Mn 3 O 4 is 3 ⁇ m, and Li 2 CO 3
  • the particle size D50 9 ⁇ m; in addition, according to the Ni:Co atomic molar ratio of 1:0.04, add Co(OH) 2 , and use a mixing agitator at 2000 rpm to stir for 20 minutes; the above-mentioned mixed and stirred materials are calcined, and the calcining method includes : In the air atmosphere, the air flow rate is 20L/min, the heating rate is 2°C/min, the temperature is raised to 800°C, the temperature is kept for 10 hours, the temperature is naturally cooled, and the material is collected;
  • a method for preparing a composite material comprising the steps of:
  • Li 2 CO 3 , NiO, and Mn 3 O 4 are mixed according to the Li:Ni:Mn atomic molar ratio of 1.05:0.4:1.6, wherein the particle size D50 of Mn 3 O 4 is 3 ⁇ m, and Li 2 CO 3
  • the particle size D50 9 ⁇ m; in addition, according to the Ni:Co atomic molar ratio of 1:0.05, add Co(OH) 2 , and use a mixing agitator at 2000 rpm to stir for 20 minutes; the above-mentioned mixed and stirred materials are calcined, and the calcining method includes : Under the air atmosphere, the air flow rate is 20L/min, the heating rate is 3°C/min, the temperature is raised to 900°C, the temperature is kept for 11 hours, the temperature is naturally cooled, and the material is collected;
  • Li 2 CO 3 , NiO, and Mn 3 O 4 are mixed according to the Li:Ni:Mn atomic molar ratio of 1.05:0.4:1.6, wherein the particle size D50 of Mn 3 O 4 is 3 ⁇ m, and Li 2 CO 3
  • the particle size D50 9 ⁇ m; in addition, according to the Ni:Co atomic molar ratio of 1:0.06, add Co(OH) 2 , and use a mixing agitator at 2000 rpm to stir for 20 minutes; the above-mentioned mixed and stirred material is calcined, and the calcining method includes : Under the air atmosphere, the air flow rate is 20L/min, the heating rate is 4°C/min, the temperature is raised to 950°C, the temperature is kept for 12 hours, the temperature is naturally lowered, and the material is collected.
  • Li 2 CO 3 , NiO, and Mn 3 O 4 are mixed according to the Li:Ni:Mn atomic molar ratio of 1.05:0.4:1.6, wherein the particle size D50 of Mn 3 O 4 is 3 ⁇ m, and Li 2 CO 3
  • the particle size D50 9 ⁇ m; use a mixing agitator at 2000 rpm to stir for 20min; the above-mentioned mixed and stirred material is calcined, and the calcining method includes: 20L/min air flow rate under air atmosphere, 4°C/min heating rate, heating to 950°C, keep warm for 12 hours, cool down naturally, and collect materials;
  • the button batteries prepared by the materials in Example 1, Comparative Example 1, and Comparative Example 2 were tested using a blue electric tester.
  • the voltage range was 3.5V-5V, 0.1C charge and discharge for one cycle, and then 0.5C constant current constant Voltage charging, the cut-off current is 0.05C, constant current discharge is performed at 1C current, and the cycle is 50 cycles, and the relevant data of parameters such as the first discharge capacity, the first Coulombic efficiency, the 100th cycle discharge capacity, and the 100th cycle capacity retention rate are obtained.
  • the button batteries prepared by the cobalt-free thick electrodes in Example 1, Comparative Example 1, and Comparative Example 2 were tested with a blue electric tester.
  • the voltage range was 3.5V-5V, and the constant current and constant voltage charging was carried out with a current of 0.5C.
  • the charging cut-off current is 0.05C; the constant current discharge is carried out at 0.5C, 1C, 2C, 5C, 10C, 20C, 40C, 80C, and 0.5C respectively, and the discharge cut-off voltage is 3.5V.
  • the initial discharge capacity of Comparative Example 1 is 125.5mAh/g
  • the initial discharge capacity of Comparative Example 2 is 120.9mAh/g
  • the small particle size lithium nickel manganese oxide composite material prepared by the method of Example 1 The specific capacity can be increased to 133.8mAh/g; the first effect can be increased to 94.8%, and the small particle size lithium nickel manganese oxide composite material of the present disclosure can increase the capacity retention rate to 98.13% after 100 cycles.
  • the capacity retention rate of the composite material in Comparative Example 1 at 80C rate discharge performance is 64.1%, and the capacity retention rate of the composite material in Comparative Example 2 at 80C rate discharge performance is 46.2%.
  • the capacity retention rate of the composite material in Example 1 was increased to 81.8% at 80C rate discharge performance, and the constant current charging ratio at 80C was increased to 79.2%.
  • the lithium nickel manganese oxide composite material prepared by the disclosed method can not only improve the cycle performance of the battery, but also provide more transmission channels for lithium ions and electrons, greatly improving the rate performance of the battery.
  • the electric charge is about 80%, which means that the electric car will be charged to 80% in less than 1 minute, which is very competitive.
  • the present disclosure provides a composite material, a preparation method thereof, and a positive electrode material of a lithium-ion battery.
  • the disclosed method improves material stability and electronic conductivity by combining Co doping, and the small particle size lithium nickel manganese oxide prepared by nano-NiO ensures full play of capacity, and SiO2 is used as a coating agent to improve the ionic conductivity and electronic conductivity of the material.
  • the composite material not only has super cycle stability, but also can be charged and discharged at a super large rate.

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Abstract

一种复合材料及其制备方法和锂离子电池正极材料。该复合材料的制备方法，包括以下步骤：将锰源、镍源、锂源和钴源的混合物进行第一煅烧处理，得到钴掺杂的镍锰酸锂；将所述钴掺杂的镍锰酸锂与二氧化硅的混合物进行第二煅烧处理。该复合材料的制备方法，通过结合Co掺杂来提高材料稳定性和电子导电性，SiO 2作为包覆剂以提高复合材料的离子导电性和防止HF腐蚀，形成稳定界面；该方法有助于镍氧化物的嵌入，形成含有较少杂相的镍锰酸锂复合材料，能够有效的提高镍锰酸锂复合材料的容量和倍率性能。

Description

一种复合材料及其制备方法和锂离子电池正极材料
相关申请的交叉引用
本申请要求于2021年08月31日提交中国专利局的申请号为2021110106286、名称为“一种复合材料及其制备方法和锂离子电池正极材料”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本公开涉及锂离子电池技术领域，具体而言，涉及一种复合材料及其制备方法和锂离子电池正极材料。
背景技术
近年来，随着车企对电池企业的要求日益增高，高比能量、长寿命、低成本的正极材料及其制备的电池被迫切需要。锂离子电池以其工作电压高、比能量大、循环寿命长、污染小等优势备受欢迎。
目前普遍使用的正极材料分别是钴酸锂、锰酸锂、镍钴锰酸锂、磷酸铁锂以及高电压镍锰酸锂等。钴价格昂贵，且钴酸锂、镍钴锰酸锂用于动力电池的安全隐患较大。锰酸锂、镍锰酸锂以及磷酸铁锂是锂离子动力电池较为理想的正极材料。锰酸锂材料虽然成本低，安全性能好，但比容量相对偏低，由于Mn的溶解、Jahn-Teller畸变效应以及晶格的不稳定，导致循环寿命尤其是高温循环性能不理想。研究表明，掺杂可有效改善其高温循环性能，尤其是Ni掺杂的LiNi 0.5Mn 1.5O 4，使得锰的价位高于3.5，能够有效抑制Mn溶解、JahnTeller畸变效应以及晶格的不稳定性，并且放电电压平台高达4.7V，成为一款理想的动力电池正极材料。
此外，为了进一步提高容量和改善循环性能，研究表明，通过控制颗粒大小，小粒径镍锰酸锂材料能够明显提高镍锰酸锂的容量，但其循环性能需要进行提高。目前制备镍锰酸锂的方法主要有两大类，第一类是用镍盐溶液和锰盐溶液按一定的比例混合， 然后加入氢氧化物或碳酸盐进行共沉淀形成前驱体再加入锂盐煅烧形成镍锰酸锂。第二类就是用镍的氧化物、锰的氧化物和锂盐进行混合煅烧制备镍锰酸锂。以上两种制备镍锰酸锂的方法中，用镍的氧化物、锰的氧化物和锂盐进行混合煅烧制备镍锰酸锂成本优势非常显著，但对于组成元素复杂的目标产物不适合，根据文献报道的结果，一般由简单的固相球磨法制备得到的镍锰酸锂颗粒较大(7um～16um)，含有较多的杂相成分，比容量不高，材料的充放电曲线很难呈现单一的充放电平台，循环性能较差。究其原因，仍然是原料混合的均匀性不好。
因此，急需一种具有高容量和优异循环性能的复合材料。
申请内容
本公开提供一种复合材料的制备方法，包括以下步骤：
将锰源、镍源、锂源和钴源的混合物进行第一煅烧处理，得到钴掺杂的镍锰酸锂；将所述钴掺杂的镍锰酸锂与二氧化硅的混合物进行第二煅烧处理。
在一种实施方式中，所述锰源包括四氧化三锰。
在一种实施方式中，所述锰源的粒径D50为2～4μm。
在一种实施方式中，所述镍源包括氧化镍。
在一种实施方式中，所述镍源的粒径D50为8～10μm。
在一种实施方式中，所述锂源包括碳酸锂。
在一种实施方式中，所述锂源的粒径D50为8～10μm。
在一种实施方式中，所述钴源包括氢氧化钴和/或氧化钴。
在一种实施方式中，所述锂源、镍源和锰源分别以Li、Ni和Mn计的原子摩尔比为(1.01～1.05):(0.4～0.475):(1.525～1.6)。
在一种实施方式中，所述钴源和镍源分别以Co和Ni计的原子摩尔比为(0.03～0.06):1。
在一种实施方式中，所述氧化镍的制备方法包括以下步骤：
将氧化镍的悬浊液研磨至粒径D50为300～800nm后进行冷冻干燥。
在一种实施方式中，所述氧化镍的悬浊液中，氧化镍的固含量为25％～35％；
在一种实施方式中，所述冷冻干燥的温度为-20～-40℃，所述冷冻干燥的真空度为3～10Pa。
在一种实施方式中，所述钴掺杂的镍锰酸锂和所述二氧化硅的质量比为1：(0.005～0.02)；
在一种实施方式中，所述二氧化硅的粒径为10～20nm。
在一种实施方式中，所述第一煅烧处理包括以下步骤：
所述锰源、镍源、锂源和钴源的混合物加热至温度为800～950℃，并于800～950℃条件下进行保温。
在一种实施方式中，所述保温的时间为10～12h。
在一种实施方式中，所述第一煅烧处理于空气的气氛下进行，所述空气的流量为18～22L/min。
在一种实施方式中，所述加热至温度为800～950℃过程中的升温速率为2～4℃/min。
在一种实施方式中，所述锰源、镍源、锂源和钴源的混合物先进行搅拌处理，再进行所述第一煅烧处理。
在一种实施方式中，所述搅拌处理的转速为1800～2200rpm，所述搅拌处理的时间为15～25min。
在一种实施方式中，所述第二煅烧处理包括以下步骤：
所述钴掺杂的镍锰酸锂与二氧化硅的混合物加热升温至500～700℃，并与500～700℃条件下进行保温处理。
在一种实施方式中，所述保温处理的时间为10～12h。
在一种实施方式中，所述第二煅烧处理于空气的气氛下进行，所述空气的流量为18～22L/min。
在一种实施方式中，所述加热至温度为500～700℃过程中的升温速率为2～4℃/min。
在一种实施方式中，所述钴掺杂的镍锰酸锂与二氧化硅的混合物先进行搅拌处理，再进行所述第二煅烧处理。
在一种实施方式中，所述搅拌处理的转速为1800～2200rpm，所述搅拌处理的时间为15～25min。
所述的复合材料的制备方法制备得到的复合材料。
一种锂离子电池正极材料，主要由所述的复合材料制备得到。
附图说明
为了更清楚地说明本公开实施方式的技术方案，下面将对实施方式中所需要使用的附图作简单地介绍，应当理解，以下附图仅示例地表征本公开的实施方式，图中尺寸比例与实施方式的真实比例并不能直接对应，同时以下附图仅示出了本公开的某些实施方式，因此不应被看作是对范围的限定。
图1为实施例1中得到复合材料的扫描电镜图；
图2为复合材料制备得到的电池的循环性能测试结果图；
图3为复合材料制备得到的电池的恒电流充入比例与放电电流的关系图；
图4为复合材料制备得到的电池的放电容量保持率与放电电流的关系图。
具体实施方式
申请内容中实施方式的优点将会在下面的说明书实施方式部分阐明，一部分根据 说明书是显而易见的，或者可以通过本公开实施例的部分实施例而获得。
下面结合附图并通过一些实施方式来进一步说明本公开的技术方案。
为了使本公开的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本公开进行进一步详细说明。应当理解，此处所描述的实施例仅仅用以解释本公开，并不用于限定本公开。此外，下面所描述的本公开各个实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互组合。在不脱离本公开实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本公开实施例的保护范围。
本公开涉及一种复合材料的制备方法，包括以下步骤：
将锰源、镍源、锂源和钴源的混合物进行第一煅烧处理，得到钴掺杂的镍锰酸锂；将钴掺杂的镍锰酸锂与二氧化硅的混合物进行第二煅烧处理。
氧化物固相煅烧合成镍锰酸锂的机理是以锰氧化物为基底，锂盐先嵌入进行反应形成锰酸锂，然后镍氧化物逐步嵌入到锰酸锂内部，形成镍锰酸锂。因此本公开从氧化物煅烧制备镍锰酸锂的反应机理出发，通过一种新的制备方法，制备了一种小粒径的尖晶石镍锰酸锂复合材料。上述制备方法不仅能够有助于镍氧化物的嵌入，而且有助于形成杂相较少的镍锰酸锂复合材料，能够有效地提高镍锰酸锂复合材料的容量和倍率性能。小粒径的镍锰酸锂比表面积较大，与电解液接触产生的副反应较多，因此本公开采用纳米SiO 2进行包覆，保护了镍锰酸锂的循环性能。
在一种实施方式中，锰源包括四氧化三锰(Mn 3O 4)。
在一种实施方式中，锰源的粒径D50为2～4μm。
在这一种实施方式中，锰源的粒径D50还可以选择2.2μm、2.5μm、2.7μm、3μm、3.2μm、3.5μm、3.7μm或3.9μm。
以3um的Mn 3O 4为基底反应制备的镍锰酸锂颗粒也较小，因此得到了粒径范围在1um～3um的Co掺杂SiO 2包覆的镍锰酸锂。无论是循环性能或倍率性能都有一个很大的提高，特别是倍率性能，该材料能够在40C的电流下充放电拥有96.24％的容量保持 率，80C的电流下充放电拥有82.58％的容量保持率，这将意味着电动汽车将在不到1min的时间内充电到80％，具有非常大的竞争优势。
在一种实施方式中，镍源包括氧化镍(NiO)。
在一种实施方式中，镍源的粒径D50为8～10μm。
在一种实施方式中，锂源包括碳酸锂(Li 2CO 3)。
在一种实施方式中，锂源的粒径D50为8～10μm。
在一种实施方式中，锂源的粒径D50还可以选择8.2μm、8.5μm、8.7μm、9μm、9.2μm、9.5μm、9.7μm或9.9μm。
在一种实施方式中，钴源包括氢氧化钴和/或氧化钴。
在一种实施方式中，锂源、镍源和锰源分别以Li、Ni和Mn计的原子摩尔比为(1.01～1.05):(0.4～0.475):(1.525～1.6)。
在一种实施方式中，锂源、镍源和锰源分别以Li、Ni和Mn计的原子摩尔比为(1.01～1.05):(0.4～0.475):(1.525～1.6)，还可以选择1.01:0.4:1.525、1.02:0.42:1.53、1.04:0.45:1.55、1.04:0.46:1.57或1.05:0.475:1.6。
在一种实施方式中，钴源和镍源分别以Co和Ni计的原子摩尔比为(0.03～0.06):1。
在一种实施方式中，钴源和镍源分别以Co和Ni计的原子摩尔比还可以选择0.035:1、0.036:1、0.035:1、0.038:1、0.04:1、0.042:1、0.045:1、0.0475:1、0.05:1、0.052:1或0.055:1。
在一种实施方式中，氧化镍的制备方法包括以下步骤：
将氧化镍的悬浊液研磨至粒径D50为300～800nm后进行冷冻干燥。
通过采用研磨技术结合冷冻干燥技术得到的氧化镍，有助于形成杂相较少的镍锰酸锂。
在一种实施方式中，氧化镍的悬浊液研磨至粒径D50为300～800nm，还可以选择 350nm、400nm、450nm、500nm、550nm、600nm、650nm、700nm、750nm。
在一种实施方式中，氧化镍的悬浊液中，氧化镍的固含量为25％～35％。
在一种实施方式中，氧化镍的固含量为25％～35％，还可以选择26％、27％、28％、29％、30％、31％、32％、33％或34％。
在一种实施方式中，冷冻干燥的温度为-20～-40℃，冷冻干燥的真空度为3～10Pa。
采用冷冻干燥技术有助于防止NiO在干燥过程中的二次团聚。
在一种实施方式中，冷冻干燥的温度为-20～-40℃，还可以选择-21℃、-22℃、-23℃、-24℃、-25℃、-26℃、-27℃、-28℃、-29℃、-30℃、-31℃、-32℃、-33℃、-34℃、-35℃、-36℃、-37℃、-38℃、-39℃或-40℃。
本公开限定研磨至粒径D50为300～800nm、氧化镍的固含量为25％～35％、冷冻干燥的温度为-20～-40℃，通过上述条件的配合可使得到的纳米氧化镍具有优异的分散性，使用制得的纳米NiO煅烧制备镍锰酸锂有助于减少氧化物煅烧制备镍锰酸锂的杂相，且能够得到粒径在1～3um小粒径的镍锰酸锂。杂相少有助于提高材料的循环稳定性，1～3um的小粒径有利于镍锰酸锂容量的充分发挥。
在一种实施方式中，钴掺杂的镍锰酸锂和二氧化硅的质量比为1：(0.005～0.02)。
使用SiO 2对镍锰酸锂进行包覆，有两大优点：(1)SiO 2作为包覆剂会在镍锰酸锂表面形成离子导电性非常好的Li 2SiO 3，Li 2SiO 3与Co元素掺杂产生协同效应，能够同时提高镍锰酸锂复合材料的离子导电和电子导电性，大大提高镍锰酸锂材料的倍率性能；(2)形成的Li 2SiO 3能够与高压电解液中产生的HF进行反应，防止HF对正极材料的腐蚀，提高了镍锰酸锂的结构稳定性，提高材料的循环性能。
在一种实施方式中，钴掺杂的镍锰酸锂和二氧化硅的质量比为1：(0.005～0.02)，还可以选择1:0.006、1:0.007、1:0.008、1:0.009、1:0.01、1:0.011、1:0.012、1:0.013、1:0.014、1:0.015、1:0.016、1:0.017、1:0.018或1:0.019。
在一种实施方式中，二氧化硅的粒径为10～20nm。
在一种实施方式中，二氧化硅的粒径还可以选择11nm、11.5nm、12nm、12.5nm、13nm、13.5nm、14nm、14.5nm、15nm、15.5nm、16nm、166.5nm、17nm、17.5nm、18nm、18.5nm、19nm或19.5nm。
在一种实施方式中，第一煅烧处理包括以下步骤：
锰源、镍源、锂源和钴源的混合物加热至温度为800～950℃，并于800～950℃条件下进行保温。
在一种实施方式中，锰源、镍源、锂源和钴源的混合物加热至温度为800～950℃，还可以选择810℃、820℃、830℃、840℃、850℃、860℃、870℃、880℃、890℃、900℃、910℃、920℃、930℃或940℃；于800～950℃条件下进行保温，还可以选择810℃、820℃、830℃、840℃、850℃、860℃、870℃、880℃、890℃、900℃、910℃、920℃、930℃或940℃。
在一种实施方式中，保温的时间为10～12h。
在一种实施方式中，保温的时间还可以选择10.5h、11h或12h。
在一种实施方式中，第一煅烧处理于空气的气氛下进行，空气的流量为18～22L/min。
在一种实施方式中，空气的流量为18～22L/min，还可以选择18.5L/min、19L/min、19.5L/min、20L/min、20.5L/min或21L/min。
在一种实施方式中，加热至温度为800～950℃过程中的升温速率为2～4℃/min。
在一种实施方式中，升温速率为2～4℃/min，还可以选择2.2℃/min、2.5℃/min、2.7℃/min、3℃/min、3.2℃/min、3.5℃/min或3.7℃/min。
本公开采用适宜的第一煅烧温度、升温速率、保温的时间和空气流量相配合，进而使得到的镍锰酸锂杂相含量少，有利于提高电池材料的循环性能。
在一种实施方式中，锰源、镍源、锂源和钴源的混合物先进行搅拌处理，再进行第一煅烧处理。
本公开将锰源、镍源、锂源先进行混匀，再与钴源混匀。
在一种实施方式中，搅拌处理的转速为1800～2200rpm，搅拌处理的时间为15～25min。在一种实施方式中，搅拌处理的转速为1800～2200rpm，还可以选择1850rpm、1870rpm、1900rpm、1920rpm、1950rpm或1970rpm；搅拌处理的时间还可以选择16min、17min、18min、19min、20min、21min、22min、23min或24min。
在一种实施方式中，第二煅烧处理包括以下步骤：
钴掺杂的镍锰酸锂与二氧化硅的混合物加热升温至500～700℃，并与500～700℃条件下进行保温处理。
在一种实施方式中，钴掺杂的镍锰酸锂与二氧化硅的混合物加热升温至500～700℃，还可以选择510℃、520℃、530℃、540℃、550℃、560℃、570℃、580℃、590℃、600℃、610℃、620℃、630℃、640℃、650℃、660℃、670℃、680℃或690℃。
在一种实施方式中，保温处理的时间为10～12h。
在一种实施方式中，保温时间还可以选择10.5h、11h或11.5h。
在一种实施方式中，第二煅烧处理于空气的气氛下进行，空气的流量为18～22L/min。
在一种实施方式中，空气的流量还可以选择18.2L/min、18.5L/min、18.7L/min、19L/min、19.2L/min、19.5L/min或19.7L/min。
在一种实施方式中，加热至温度为500～700℃过程中的升温速率为2～4℃/min。
在一种实施方式中，升温速率为2～4℃/min，还可以选择2.2℃/min、2.5℃/min、2.7℃/min、3℃/min、3.2℃/min、3.5℃/min或3.7℃/min。
在一种实施方式中，钴掺杂的镍锰酸锂与二氧化硅的混合物先进行搅拌处理，再进行第二煅烧处理。
在一种实施方式中，搅拌处理的转速为1800～2200rpm，搅拌处理的时间为 15～25min。在一种实施方式中，搅拌处理的转速为1800～2200rpm，还可以选择1850rpm、1870rpm、1900rpm、1920rpm、1950rpm或1970rpm；搅拌处理的时间还可以选择16min、17min、18min、19min、20min、21min、22min、23min或24min。
本公开还涉及如上的复合材料的制备方法得到的复合材料。
本公开的镍锰酸锂复合材料不仅具有超强的循环稳定性，而且能够进行超大倍率下充放电。
本公开还涉及一种锂离子电池正极材料，主要由如上的复合材料制备得到。
本公开的离子电池正极材料可更好地改善锂离子电池的循环稳定性和导电性。
以下为本公开典型但非限制性实施例：
图1中的(a)和图1中的(b)均为实施例1中得到复合材料的扫描电镜图。
图2为复合材料制备得到的电池的循环性能测试结果图；其中，图2中的(c)为容量保持率和循环圈数的关系图；图2中的(d)为放电比容量与循环圈数的关系图。
图3为复合材料制备得到的电池的恒电流充入比例与放电电流的关系图。
图4为复合材料制备得到的电池的放电容量保持率与放电电流的关系图。图4中，对比例1和实施例1在不同放电电流下的放电容量保持率的具体数值参见表2的倍率性能。
实施例1
一种复合材料的制备方法，包括以下步骤：
(a)将NiO配成固含量为30％的悬浊液，使用砂磨机进行砂磨，砂磨至D50＝500nm为止，收集NiO进行-30℃冷冻干燥，真空度8帕，直至完全干燥，收集纳米NiO粉料；
(b)对Li 2CO 3、NiO、Mn 3O 4按照Li：Ni：Mn原子摩尔比为1.05:0.4:1.6进行混合，其中，Mn 3O 4的粒径D50＝3μm，Li 2CO 3的粒径D50＝9μm；另外按照Ni：Co原子摩尔比为1：0.06添加Co(OH) 2，使用混合搅拌器2000转/min搅拌20min；将上述 混合搅拌好的料进行煅烧，煅烧方法包括：在空气气氛下20L/min气流量，4℃/min升温速率，升温至950℃，保温12h，自然降温，进行收料；
(c)将收集的镍锰酸锂与纳米SiO 2按照质量比为1:2％进行混合，SiO 2的粒度为20nm，使用混合搅拌器2000转搅拌20min，将混合好的物料，在空气气氛下20L/min气流量，4℃/min升温速率，升温至700℃，保温10h，自然降温，进行收料。
实施例2
一种复合材料的制备方法，包括以下步骤：
(a)将NiO配成固含量为30％的悬浊液，使用砂磨机进行砂磨，砂磨至D50＝300nm为止，收集NiO进行-20℃冷冻干燥，真空度3帕，直至完全干燥，收集纳米NiO粉料；
(b)对Li 2CO 3、NiO、Mn 3O 4按照Li：Ni：Mn原子摩尔比为1.05:0.4:1.6进行混合，其中，Mn 3O 4的粒径D50＝3μm，Li 2CO 3的粒径D50＝9μm；另外按照Ni：Co原子摩尔比为1：0.04添加Co(OH) 2，使用混合搅拌器2000转/min搅拌20min；将上述混合搅拌好的料进行煅烧，煅烧方法包括：在空气气氛下20L/min气流量，2℃/min升温速率，升温至800℃，保温10h，自然降温，进行收料；
(c)将收集的镍锰酸锂与纳米SiO 2按照质量比为1:0.5％进行混合，SiO 2的粒度为10nm，使用混合搅拌器2000转搅拌20min，将混合好的物料，在空气气氛下20L/min气流量，2℃/min升温速率，升温至500℃，保温10h，自然降温，进行收料。
实施例3
一种复合材料的制备方法，包括以下步骤：
(a)将NiO配成固含量为30％的悬浊液，使用砂磨机进行砂磨，砂磨至D50＝800nm为止，收集NiO进行-40℃冷冻干燥，真空度10帕，直至完全干燥，收集纳米NiO粉料；
(b)对Li 2CO 3、NiO、Mn 3O 4按照Li：Ni：Mn原子摩尔比为1.05:0.4:1.6进行混合，其中，Mn 3O 4的粒径D50＝3μm，Li 2CO 3的粒径D50＝9μm；另外按照Ni：Co原子摩尔比为1：0.05添加Co(OH) 2，使用混合搅拌器2000转/min搅拌20min；将上述 混合搅拌好的料进行煅烧，煅烧方法包括：在空气气氛下20L/min气流量，3℃/min升温速率，升温至900℃，保温11h，自然降温，进行收料；
(c)将收集的镍锰酸锂与纳米SiO 2按照质量比为1:2％进行混合，SiO 2的粒度为20nm，使用混合搅拌器2000转搅拌20min，将混合好的物料，在空气气氛下20L/min气流量，3℃/min升温速率，升温至600℃，保温11h，自然降温，进行收料。
对比例1
(a)将NiO配成固含量为30％的悬浊液，使用砂磨机进行砂磨，砂磨至D50＝500nm为止，收集NiO进行-30℃冷冻干燥，真空度8帕，直至完全干燥，收集纳米NiO粉料；
(b)对Li 2CO 3、NiO、Mn 3O 4按照Li：Ni：Mn原子摩尔比为1.05:0.4:1.6进行混合，其中，Mn 3O 4的粒径D50＝3μm，Li 2CO 3的粒径D50＝9μm；另外按照Ni：Co原子摩尔比为1：0.06添加Co(OH) 2，使用混合搅拌器2000转/min搅拌20min；将上述混合搅拌好的料进行煅烧，煅烧方法包括：在空气气氛下20L/min气流量，4℃/min升温速率，升温至950℃，保温12h，自然降温，进行收料。
对比例2
(a)将NiO配成固含量为30％的悬浊液，使用砂磨机进行砂磨，砂磨至D50＝500nm为止，收集NiO进行-30℃冷冻干燥，真空度8帕，直至完全干燥，收集纳米NiO粉料；
(b)对Li 2CO 3、NiO、Mn 3O 4按照Li：Ni：Mn原子摩尔比为1.05:0.4:1.6进行混合，其中，Mn 3O 4的粒径D50＝3μm，Li 2CO 3的粒径D50＝9μm；使用混合搅拌器2000转/min搅拌20min；将上述混合搅拌好的料进行煅烧，煅烧方法包括：在空气气氛下20L/min气流量，4℃/min升温速率，升温至950℃，保温12h，自然降温，进行收料；
(c)将收集的镍锰酸锂与纳米SiO 2按照质量比为1:2％进行混合，SiO 2的粒度为20nm，使用混合搅拌器2000转搅拌20min，将混合好的物料，在空气气氛下20L/min气流量，4℃/min升温速率，升温至700℃，保温10h，自然降温，进行收料。
实验例
将上述实施例和对比例中制备得到的正极复合材料与导电炭黑SP和聚偏氟乙烯(PVDF)按照90:5:5的比例进行匀浆制备电极极片，最后制备成纽扣CR2032型电池，分别进行循环性能测试和倍率性能测试，循环性能测试的步骤和倍率性能测试的步骤包括：
(1)1C循环性能
使用蓝电测试仪对实施例1、对比例1、对比例2中材料所制备的纽扣电池进行测试，电压范围为3.5V-5V，0.1C充放电活化一圈，然后以0.5C恒流恒压充电，截止电流为0.05C，以1C电流进行恒流放电，循环50圈，得到首次放电容量、首次库伦效率、第100圈放电容量和第100圈容量保持率等参数的相关数据。
(2)倍率放电性能
使用蓝电测试仪对实施例1、对比例1、对比例2中的无钴厚电极所制备的纽扣电池进行测试，电压范围为3.5V-5V，以0.5C的电流进行恒流恒压充电，充电截止电流为0.05C；分别以0.5C、1C、2C、5C、10C、20C、40C、80C、0.5C电流进行恒流放电，放电截止电压为3.5V。
测试结果如表1和表2所示：
表1循环性能
1C循环性能 首次放电容量 首次库伦效率 第100圈放电容量 第100圈容量保持率
对比例1 125.5mAh/g 88.7％ 73.7mAh/g 58.73％
对比例2 120.9mAh/g 89.2％ 100.6mAh/g 83.21％
实施例1 133.8mAh/g 94.8％ 131.3mAh/g 98.13％
表2倍率性能
Figure PCTCN2022116295-appb-000001
Figure PCTCN2022116295-appb-000002
由表1可知，对比例1的首次放电容量为125.5mAh/g，对比例2的首次放电容量为120.9mAh/g，而实施例1的方法制备得到的小粒径镍锰酸锂复合材料的比容量能够提升到133.8mAh/g；首效提高到94.8％，同时本公开的小粒径镍锰酸锂复合材料能够将100圈循环之后容量保持率提升到98.13％。
由表2可知，在倍率性能测试中，对比例1中的复合材料在80C倍率放电性能的容量保持率为64.1％，对比例2中的复合材料在80C倍率放电性能的容量保持率为46.2％，实施例1的复合材料在80C倍率放电性能的容量保持率提升到81.8％，且80C的恒流充入比例提升到79.2％。由此可见，本公开的方法制备的镍锰酸锂复合材料，不仅能够提高电池的循环性能，而且为锂离子和电子提供更多的传输通道，大大改善电池的倍率性能，80C电流密度下能够电充电约80％，意味着电动汽车将在不到1min的时间内充电到80％，非常具有竞争优势。
工业实用性
综上所述，本公开提供了一种复合材料及其制备方法和锂离子电池正极材料。本公开的方法通过结合Co掺杂来提高材料稳定性和电子导电性，纳米NiO制备的小粒径镍锰酸锂保证容量的充分发挥，SiO 2作为包覆剂以提高材料的离子导电性和防止HF腐蚀，形成稳定界面；该方法有助于镍氧化物的嵌入，形成杂相较少的镍锰酸锂复合材料，能够有效地提高镍锰酸锂复合材料的容量和倍率性能；本公开的复合材料不仅具有超强的循环稳定性，而且能够进行超大倍率下充放电。

Claims (13)

  1. 一种复合材料的制备方法，其特征在于，包括以下步骤：
    将锰源、镍源、锂源和钴源的混合物进行第一煅烧处理，得到钴掺杂的镍锰酸锂；将所述钴掺杂的镍锰酸锂与二氧化硅的混合物进行第二煅烧处理。
  2. 根据权利要求1所述的复合材料的制备方法，其特征在于，包含以下特征(1)至(2)中的至少一种：
    (1)所述锰源包括四氧化三锰；
    (2)所述锰源的粒径D50为2～4μm。
  3. 根据权利要求1所述的复合材料的制备方法，其特征在于，包含以下特征(1)至(2)中的至少一种：
    (1)所述镍源包括氧化镍；
    (2)所述镍源的粒径D50为8～10μm。
  4. 根据权利要求1所述的复合材料的制备方法，其特征在于，包含以下特征(1)至(2)中的至少一种：
    (1)所述锂源包括碳酸锂；
    (2)所述锂源的粒径D50为8～10μm。
  5. 根据权利要求1所述的复合材料的制备方法，其特征在于，所述钴源包括氢氧化钴和/或氧化钴。
  6. 根据权利要求1～5中任一项所述的复合材料的制备方法，其特征在于，包含以下特征(1)至(2)中的至少一种：
    (1)所述锂源、镍源和锰源分别以Li、Ni和Mn计的原子摩尔比为(1.01～1.05):(0.4～0.475):(1.525～1.6)；
    (2)所述钴源和镍源分别以Co和Ni计的原子摩尔比为(0.03～0.06):1。
  7. 根据权利要求1～5中任一项所述的复合材料的制备方法，其特征在于，包含以下特征(1)至(3)中的至少一种：
    (1)所述氧化镍的制备方法包括以下步骤：
    将氧化镍的悬浊液研磨至粒径D50为300～800nm后进行冷冻干燥；
    (2)所述氧化镍的悬浊液中，氧化镍的固含量为25％～35％；
    (3)所述冷冻干燥的温度为-20～-40℃，所述冷冻干燥的真空度为3～10Pa。
  8. 根据权利要求1所述的复合材料的制备方法，其特征在于，包含以下特征(1)至(2)中的至少一种：
    (1)所述钴掺杂的镍锰酸锂和所述二氧化硅的质量比为1：(0.005～0.02)；
    (2)所述二氧化硅的粒径为10～20nm。
  9. 根据权利要求1～8中任一项所述的复合材料的制备方法，其特征在于，包含以下特征(1)至(4)中的至少一种：
    (1)所述第一煅烧处理包括以下步骤：
    所述锰源、镍源、锂源和钴源的混合物加热至温度为800～950℃，并于800～950℃条件下进行保温；
    (2)所述保温的时间为10～12h；
    (3)所述第一煅烧处理于空气的气氛下进行，所述空气的流量为18～22L/min；
    (4)所述加热至温度为800～950℃过程中的升温速率为2～4℃/min。
  10. 根据权利要求1～8中任一项所述的复合材料的制备方法，其特征在于，包含以下特征(1)至(2)中的至少一种：
    (1)所述锰源、镍源、锂源和钴源的混合物先进行搅拌处理，再进行所述第一煅烧处理；
    (2)所述搅拌处理的转速为1800～2200rpm，所述搅拌处理的时间为15～25min。
  11. 根据权利要求1～8中任一项所述的复合材料的制备方法，其特征在于，包含以下特征(1)至(6)中的至少一种：
    (1)所述第二煅烧处理包括以下步骤：
    所述钴掺杂的镍锰酸锂与二氧化硅的混合物加热升温至500～700℃，并与500～700℃条件下进行保温处理；
    (2)所述保温处理的时间为10～12h；
    (3)所述第二煅烧处理于空气的气氛下进行，所述空气的流量为18～22L/min；
    (4)所述加热至温度为500～700℃过程中的升温速率为2～4℃/min；
    (5)所述钴掺杂的镍锰酸锂与二氧化硅的混合物先进行搅拌处理，再进行所述第二煅烧处理；
    (6)所述搅拌处理的转速为1800～2200rpm，所述搅拌处理的时间为15～25min。
  12. 权利要求1～11中任一项所述的复合材料的制备方法制备得到的复合材料。
  13. 一种锂离子电池正极材料，其特征在于，主要由权利要求12所述的复合材料制备得到。
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