WO2023245890A1 - Positive electrode material, and preparation method therefor and use thereof - Google Patents

Positive electrode material, and preparation method therefor and use thereof Download PDF

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WO2023245890A1
WO2023245890A1 PCT/CN2022/119997 CN2022119997W WO2023245890A1 WO 2023245890 A1 WO2023245890 A1 WO 2023245890A1 CN 2022119997 W CN2022119997 W CN 2022119997W WO 2023245890 A1 WO2023245890 A1 WO 2023245890A1
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manganese
present
cathode material
copolymer
based material
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PCT/CN2022/119997
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French (fr)
Chinese (zh)
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侯远飞
李长东
毛林林
阮丁山
王苑
戴海桃
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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Publication of WO2023245890A1 publication Critical patent/WO2023245890A1/en

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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
    • 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
    • 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
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 technical field related to batteries, and in particular, to a cathode material and its preparation method and application.
  • Lithium-ion batteries are widely used due to their good cycle performance, high capacity, low price, easy use, safety and environmental protection. With the development of transportation equipment such as electric vehicles, higher and higher requirements are placed on the performance of lithium batteries. Lithium-rich manganese-based cathode materials have high specific capacity (the theoretical capacity of some materials is greater than 250mAh/g) and a wide operating voltage window (2V ⁇ 4.8V), and are most likely to become the next generation of high-performance lithium-ion battery materials. However, current lithium-rich manganese-based cathode materials have obvious defects such as low rate performance and poor cycle stability, which severely limits their use.
  • Lithium-rich manganese-based cathode materials are usually dry-coated with metal oxides, metal fluorides, phosphates, etc.
  • the coating layer formed on the surface is intermittent and discontinuous, resulting in no significant improvement in cycle performance.
  • the present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention provides a cathode material with good cycle performance.
  • the invention also provides a method for preparing the above-mentioned cathode material.
  • the present invention also provides applications of the above-mentioned cathode materials.
  • the first aspect of the present invention provides a cathode material, including a core, the surface of which is coated with an organic copolymer layer; the core is a manganese-based material;
  • the thickness of the organic copolymer layer is 1 nm to 10 nm.
  • the present invention coats the surface of the manganese-based material with an organic copolymer layer and utilizes the organic copolymer layer to protect the manganese-based material; thus the manganese-based material is protected from the erosion of the electrolyte; and at the same time, it can also inhibit the decomposition of the electrolyte, thereby Improve the structural stability and interface stability of the cathode material, and ultimately improve the cycle performance of the cathode material.
  • the thickness of the organic copolymer layer is too thin to resist the erosion of the electrolyte.
  • the organic copolymer layer that is too thick will hinder the transmission of lithium ions, thereby adversely affecting the cathode material.
  • y in Li 1+x Ni y Co z Mn 1-yz O 2 is between 0.3 and 0.4.
  • the preparation method of the manganese-based material consists of the following steps:
  • the mixture is then subjected to ion exchange reaction at 750°C to 1000°C in an oxygen atmosphere for 8h to 20h.
  • the above-mentioned organic copolymer polymer has a better coating effect, can inhibit the decomposition of the electrolyte under high pressure, and can evenly coat the surface of manganese-based materials, and can control the thickness of the coating layer, improving the cycle performance of manganese-based cathode materials. be better improved.
  • the above-mentioned organic copolymer layer will be partially dissolved in the slurry; the organic copolymer will be dissolved in the organic oily solvent due to similar compatibility, which can enable the above-mentioned organic copolymer to be evenly dispersed in the slurry.
  • the positive electrode material manganese-based material
  • the stirring rate during the first stage of drying is 50 rpm to 500 rpm.
  • the ball milling time is 0.5h to 5h.
  • the coating layer will become worse. At this time, the coating layer effect will decrease and the effect of electrolyte decomposition cannot be suppressed. If the temperature is too high, the coating agent may decompose, and the coating layer will fail and cannot be used. It protects the cathode material.
  • the annealing is performed under a protective atmosphere.
  • the preparation method of the positive electrode slurry includes the following steps: mixing the positive electrode material, the binder and the conductive agent.
  • the electrolyte includes lithium salt, solvent and additives.
  • the molar concentration of the lithium salt in the electrolyte is 1.0 mol/L to 1.5 mol/L.
  • Figure 3 is a cyclic discharge curve diagram of the cathode material (three sets of parallel samples) corresponding to Embodiment 3 of the present invention.
  • the calculation method for the thickness of the coating layer of the organic copolymer (coating agent) is:
  • the Dv50 of manganese-based materials is 4 ⁇ m and the specific surface area is 1.12 m 2 /g.
  • the ball-milling speed is 200 rpm; the ball-milling time is 1 hour; after the ball-milling is completed, pass it through a 300-mesh screen (the purpose of passing the screen is to remove large particles of material that are still agglomerated after ball-milling) If there are too many materials agglomerated together, the subsequent homogenization of the electrode material cannot be carried out smoothly);
  • the screened material into a tube furnace and perform annealing treatment in an inert gas (nitrogen atmosphere).
  • the annealing temperature is 140°C and the time is 3 hours; after the annealing is completed, the cathode material is obtained.
  • the material of the organic copolymer layer is vinylidene fluoride-trifluoroethylene copolymer; the thickness of the organic copolymer layer is 6.5 nm.
  • the mixture is heated at 900
  • the ion exchange reaction was carried out at °C and oxygen atmosphere for 15 hours to finally obtain manganese-based material powder; the Dv50 of the precursor was 3 ⁇ m and the specific surface area was 12.3m 2 /g.
  • the Dv50 of the manganese-based material was 4 ⁇ m.
  • the specific surface area is 1.12m 2 /g;
  • the ball-milling speed is 200 rpm; the ball-milling time is 1 hour; after the ball-milling is completed, pass it through a 300-mesh screen;
  • the screened material into a tube furnace and perform annealing treatment in an inert gas (nitrogen atmosphere).
  • the annealing temperature is 145°C and the time is 1 hour; after the annealing is completed, the cathode material is obtained.
  • This embodiment is a cathode material and a preparation method thereof.
  • the core of the positive electrode material is a manganese-based material (Li 1.2 Ni 0.35 Co 0.05 Mn 0.6 O 2 ); the surface of the manganese-based material is evenly coated with an organic copolymer layer.
  • the Dv50 of manganese-based materials is 4 ⁇ m and the specific surface area is 1.12 m 2 /g.
  • the material of the organic copolymer layer is vinylidene fluoride-trifluoroethylene copolymer; the thickness of the organic copolymer layer is 1 nm.
  • the manganese-based hydroxide precursor Ni 0.35 Co 0.05 Mn 0.6 (OH) 2
  • (Li 2 CO 3 ) are thoroughly mixed (the molar ratio of the precursor to the lithium salt is 1:0.6)
  • the mixture is heated at 750 Conduct an ion exchange reaction at ⁇ 1000°C and an oxygen atmosphere for 8 to 20 hours to finally obtain manganese-based material powder;
  • the Dv50 of the precursor is 3 ⁇ m and the specific surface area is 12.3m 2 /g.
  • the manganese-based material has a Dv50 is 4 ⁇ m, and the specific surface area is 1.12m 2 /g;
  • the ball-milling speed is 200 rpm; the ball-milling time is 1 hour; after the ball-milling is completed, pass it through a 300-mesh screen;
  • the core of the positive electrode material is a manganese-based material (Li 1.2 Ni 0.35 Co 0.05 Mn 0.6 O 2 ); the surface of the manganese-based material is evenly coated with an organic copolymer layer.
  • the Dv50 of manganese-based materials is 4 ⁇ m and the specific surface area is 1.12 m 2 /g.
  • the material of the organic copolymer layer is vinylidene fluoride-trifluoroethylene copolymer; the thickness of the organic copolymer layer is 10 nm.
  • the mixture is heated at 900
  • the ion exchange reaction was carried out at °C and oxygen atmosphere for 15 hours to finally obtain manganese-based material powder; the Dv50 of the precursor was 3 ⁇ m and the specific surface area was 12.3m 2 /g.
  • the Dv50 of the manganese-based material was 4 ⁇ m.
  • the specific surface area is 1.12m 2 /g;
  • the ball-milling speed is 200 rpm; the ball-milling time is 1 hour; after the ball-milling is completed, pass it through a 300-mesh screen (the purpose of passing the screen is to remove large particles of material that are still agglomerated after ball-milling) If there are too many materials agglomerated together, the subsequent homogenization of the electrode material cannot be carried out smoothly);
  • This embodiment is a cathode material and a preparation method thereof.
  • the core of the positive electrode material is a manganese-based material (Li 1.2 Ni 0.35 Co 0.05 Mn 0.6 O 2 ); the surface of the manganese-based material is evenly coated with an organic copolymer layer.
  • the Dv50 of manganese-based materials is 4 ⁇ m and the specific surface area is 1.12 m 2 /g.
  • the material of the organic copolymer layer is vinylidene fluoride copolymer; the thickness of the organic copolymer layer is 10 nm.
  • the mixture is heated at 900
  • the ion exchange reaction was carried out at °C and oxygen atmosphere for 15 hours to finally obtain manganese-based material powder; the Dv50 of the precursor was 3 ⁇ m and the specific surface area was 12.3m 2 /g.
  • the Dv50 of the manganese-based material was 4 ⁇ m.
  • the specific surface area is 1.12m 2 /g;
  • the ball-milling speed is 300 rpm; the ball-milling time is 0.5 h; after the ball-milling is completed, pass it through a 300-mesh screen (the purpose of the screen is to remove the large particle materials that are still agglomerated after ball-milling) Remove them. If there are too many materials that are agglomerated together, the subsequent homogenization of the electrode material will not be carried out smoothly);
  • This embodiment is a cathode material and a preparation method thereof.
  • Example 1 The difference between the positive electrode material in this embodiment and Example 1 is that the vinylidene fluoride-trifluoroethylene copolymer is replaced by the vinylidene fluoride-tetrafluoroethylene copolymer (the amount added is converted based on the thickness).
  • This embodiment is a cathode material and a preparation method thereof.
  • the difference between the positive electrode material of this embodiment and Example 1 is that the vinylidene fluoride-trifluoroethylene copolymer layer is replaced with a vinylidene fluoride-trifluoroethylene copolymer and a vinylidene fluoride copolymer mixed layer (ylidene fluoride The mass ratio of ethylene-trifluoroethylene copolymer and vinylidene fluoride copolymer is 1:1).
  • This comparative example is a cathode material, which is Li 1.2 Ni 0.35 Co 0.05 Mn 0.6 O 2 (D50 is 4 ⁇ m).
  • the preparation method of the cathode material in this comparative example is as follows:
  • the manganese-based hydroxide precursor and (Li 2 CO 3 ) are thoroughly mixed (the molar ratio of the precursor to the lithium salt is 1:0.6), the mixture is subjected to an ion exchange reaction at 900°C and an oxygen atmosphere for 15 hours. Finally, Manganese-based material powder is obtained; the Dv50 of the precursor is 3 ⁇ m and the specific surface area is 12.3m 2 /g. After lithium mixing and sintering, the Dv50 of the manganese-based material is 4 ⁇ m and the specific surface area is 1.12m 2 /g.
  • the cathode materials corresponding to Examples 1 to 4 of the present invention and Comparative Example 1 were subjected to electrode preparation and battery assembly to perform performance testing (the performance test of the corresponding battery in the embodiment of the present invention was repeated three times to obtain an average value).
  • the electrode preparation method in this test example consists of the following steps:
  • the battery assembly method in this test example consists of the following steps:
  • the cathode material corresponding to Example 1 of the present invention has an initial discharge specific capacity of 231.4mA/g, and still has a discharge ratio of 187.9mA/g after 50 cycles. capacity, its capacity retention rate is 81.2%.
  • the cathode material corresponding to Example 2 of the present invention has an initial discharge specific capacity of 230mAh/g under the test conditions of a voltage of 2.0V to 4.8V and a rate of 0.5C. After 50 cycles, the discharge specific capacity is still 185mAh/g. The capacity retention rate is 80.4%.
  • the cathode material corresponding to Example 3 of the present invention has an initial discharge specific capacity of 230mAh/g under the test conditions of a voltage of 2.0V to 4.8V and a rate of 0.5C. After 50 cycles, the discharge specific capacity is still 177mAh/g. Capacity retention is 77%.
  • the cathode material corresponding to Example 4 of the present invention has an initial discharge specific capacity of 204.1mAh/g, and the discharge specific capacity is still 185mAh/g after 50 cycles. Its capacity retention rate is 83.7%.
  • the cathode material corresponding to Comparative Example 1 of the present invention has an initial discharge specific capacity of 231mAh/g under the test conditions of a voltage of 2.0V to 4.8V and a rate of 0.5C. After 50 cycles, the discharge specific capacity is still 172.3mAh/g. Its capacity retention rate is 74.6%.
  • the cyclic discharge curves of the cathode materials corresponding to Example 1, Example 3 and Comparative Example 1 of the present invention are shown in Figure 2.
  • Example 2 Example 3
  • Example 4 Comparative example 1 Coating layer thickness (nm) 6.4 6.5 1 10 0
  • Initial discharge specific capacity (mAh/g) 231.4 230 230 204.1 231
  • Discharge specific capacity after 50 cycles (mAh/g) 187.9 185 177 185 172.3
  • Capacity retention rate (after 50 cycles) 81.2% 80.4% 77% 83.7% 74.6%
  • Embodiment 1 and Embodiment 2 of the present invention are differences in coating thickness, annealing temperature and annealing time; from the data in Table 1, it can be known that under the coupling of appropriate annealing temperature and annealing time, performance can be obtained
  • the excellent coating layer improves the effect of inhibiting the decomposition of the electrolyte, further improving the cycle performance of the cathode material.
  • Embodiment 2 differs from Embodiment 3 of the present invention from Embodiment 3 of the present invention from Embodiment 3, the thickness of the coating layer is thin; the thickness of the organic copolymer layer is too thin to resist the erosion of the electrolyte, resulting in a decrease in the capacity retention rate.
  • Embodiment 4 The difference between Embodiment 2 and Embodiment 4 of the present invention is that in Embodiment 4, the thickness of the coating layer is thicker; an excessively thick organic copolymer layer will hinder the transmission of lithium ions, thereby affecting the initial discharge capacity.
  • Figure 3 is a cyclic discharge curve diagram of the battery (three sets of parallel samples) corresponding to the positive electrode material in Example 3 of the present invention. It can be seen from Figure 3 that the overlap of the parallel samples tested repeatedly in Example 3 is relatively high, and the cycles of the test batteries are consistent. The performance is also high. The cycle difference is indeed caused by the coating thickness, not the difference caused by the assembled battery test.
  • Figure 4 is a discharge median voltage diagram of the corresponding cathode materials of Example 1 and Comparative Example 1.
  • the initial discharge median voltage of Example 1 is 3.83V
  • the discharge median voltage after 50 cycles is 3.59V. After 50 cycles, it is 3.59V.
  • the discharge median voltage difference is 0.24V.
  • the initial discharge median voltage of Comparative Example 1 is 3.825V
  • the discharge median voltage after 50 cycles is 3.49V
  • the difference between the discharge median voltage after 50 cycles and the first cycle is 0.335V.
  • the organic copolymer layer in Example 5 of the present invention is a polyvinylidene fluoride layer. After testing, its implementation effect is similar to that of Example 4 (the performance in Example 4 is relatively better).
  • the organic copolymer layer in Example 6 of the present invention is a vinylidene fluoride-tetrafluoroethylene copolymer layer. After testing, its implementation effect is similar to that of Example 1 (the performance in Example 1 is relatively better).
  • the organic copolymer layer in Example 7 of the present invention is a uniform mixture layer formed of vinylidene fluoride-trifluoroethylene copolymer and polyvinylidene fluoride. After testing, its implementation effect is similar to that of Example 1 (the performance in Example 1 relatively better).
  • the performance of the vinylidene fluoride-trifluoroethylene copolymer layer is > the performance of the vinylidene fluoride-tetrafluoroethylene copolymer layer > the performance of the polyvinylidene fluoride layer.
  • the reason is: Vinylidene fluoride-trifluoroethylene copolymer has the best crystallization properties, vinylidene fluoride-tetrafluoroethylene copolymer has slightly worse crystallization properties, and polyvinylidene fluoride has the worst performance among the three, resulting in poor performance of its cathode material Relatively poor.
  • the preparation method in the embodiment of the present invention can form a uniform and dense coating layer with controllable thickness on the surface of the material; that is, the present invention coats the surface of the manganese-based material with a uniform layer of organic copolymer polymer, which is uniform and controllable.
  • the coating layer can protect the cathode material from the erosion of the electrolyte and inhibit the decomposition of the electrolyte, thus improving the structural stability and interface stability of the material.
  • the organic copolymer polymer in the embodiment of the present invention After the organic copolymer polymer in the embodiment of the present invention is annealed, it has excellent structural stability and stronger piezoelectricity after crystallization.
  • its functional group (-C-F) can attract more electrons, giving it a high degree of anode stability, thereby increasing the lithium ion content in the material and accelerating the diffusion and charge transfer process of lithium ions at the electrode/electrolyte interface. , improve the conductive properties of lithium-rich manganese-based cathode materials.
  • the preparation method of the present invention can form a coating layer with controllable thickness, uniformity and density on the surface of the material.
  • the coating can be evenly distributed on the cathode material; thereby producing a cathode material with excellent cycle performance.

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Abstract

The present invention relates to the technical field of batteries. Disclosed are a positive electrode material, and a preparation method therefor and a use thereof. In a first aspect, the present invention provides a positive electrode material, comprising an inner core. The surface of the inner core is coated with an organic copolymer layer; the inner core is a manganese-based material; the chemical formula of the manganese-based material is Li1+xNiyCozMn1-y-zO2, wherein 0<x≤1, 0≤y<1, 0≤z<1, and y+z<1. The organic copolymer layer has a thickness of 1-10 nm. According to the present invention, by coating the surface of the manganese-based material with the organic copolymer layer, the protection of the manganese-based material is realized by using the organic copolymer layer, so that the manganese-based material is avoided from being eroded by an electrolyte solution, and the decomposition of the electrolyte can also be inhibited, and thus, the structural stability and interface stability of the positive electrode material are improved, and the cycle performance of the positive electrode material is finally improved.

Description

一种正极材料及其制备方法与应用A kind of cathode material and its preparation method and application 技术领域Technical field
本发明涉及电池相关技术领域，尤其是涉及一种正极材料及其制备方法与应用。The present invention relates to the technical field related to batteries, and in particular, to a cathode material and its preparation method and application.
背景技术Background technique
锂离子电池因循环性能好、容量高、价格低廉、使用方便、安全和环保等优点而得到广泛应用。随着电动汽车等交通设备的发展，对于锂电池的使用性能提出越来越高的要求。富锂锰基正极材料具有高的比容量(部分材料的理论容量大于250mAh/g)和宽的工作电压窗口(2V～4.8V)，最有可能成为下一代高性能锂离子电池材料。但是目前富锂锰基正极材料由于存在倍率性能低、循环稳定性差等明显缺陷而严重限制了其使用。Lithium-ion batteries are widely used due to their good cycle performance, high capacity, low price, easy use, safety and environmental protection. With the development of transportation equipment such as electric vehicles, higher and higher requirements are placed on the performance of lithium batteries. Lithium-rich manganese-based cathode materials have high specific capacity (the theoretical capacity of some materials is greater than 250mAh/g) and a wide operating voltage window (2V ~ 4.8V), and are most likely to become the next generation of high-performance lithium-ion battery materials. However, current lithium-rich manganese-based cathode materials have obvious defects such as low rate performance and poor cycle stability, which severely limits their use.
在循环过程中，富锂锰基正极材料与电解液发生反应，会造成正极材料中的金属元素溶解(如Mn)、固体电解质界面膜的厚度增加(固体电解质界面膜厚度增加后会阻碍锂离子的传输，同时导致阻抗增加)等问题，从而导致电池的容量衰减，并导致安全性下降。因此，需要采用表面包覆等技术手段来改进富锂锰基正极材料的电化学性能。通常采用金属氧化物，金属氟化物，磷酸盐等对富锂锰基正极材料进行干法包覆来稳定颗粒的表面结构，从而改善常温和高温下富锂锰基正极材料的性能。但是利用上述材料对富锂锰基正极材料进行包覆，表面形成的包覆层间断、不连续，从而导致对循环性能并无显著的提升。During the cycle, the lithium-rich manganese-based cathode material reacts with the electrolyte, which will cause the metal elements in the cathode material to dissolve (such as Mn) and the thickness of the solid electrolyte interface film to increase (the increase in the thickness of the solid electrolyte interface film will hinder lithium ions transmission, and at the same time leads to problems such as increased impedance), which leads to battery capacity attenuation and reduced safety. Therefore, surface coating and other technical means are needed to improve the electrochemical performance of lithium-rich manganese-based cathode materials. Lithium-rich manganese-based cathode materials are usually dry-coated with metal oxides, metal fluorides, phosphates, etc. to stabilize the surface structure of the particles, thereby improving the performance of lithium-rich manganese-based cathode materials at normal and high temperatures. However, when the above-mentioned materials are used to coat lithium-rich manganese-based cathode materials, the coating layer formed on the surface is intermittent and discontinuous, resulting in no significant improvement in cycle performance.
综上，需要开发一种循环性能好的正极材料。In summary, it is necessary to develop a cathode material with good cycle performance.
发明内容Contents of the invention
本发明旨在至少解决现有技术中存在的技术问题之一。为此，本发明提供了一种正极材料，该正极材料的循环性能好。The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention provides a cathode material with good cycle performance.
本发明还提供了上述正极材料的制备方法。The invention also provides a method for preparing the above-mentioned cathode material.
本发明还提供了上述正极材料的应用。The present invention also provides applications of the above-mentioned cathode materials.
具体如下，本发明的第一方面提供了一种正极材料，包括内核，所述内核表面包覆有机共聚物层；所述内核为锰基材料；Specifically, the first aspect of the present invention provides a cathode material, including a core, the surface of which is coated with an organic copolymer layer; the core is a manganese-based material;
所述锰基材料的化学式为Li 1+xNi yCo zMn 1-y-zO 2；其中0＜x≤1，0≤y＜1，0≤z＜1，y+z＜1； The chemical formula of the manganese-based material is Li 1+x Ni y Co z Mn 1-yz O 2 ; where 0<x≤1, 0≤y<1, 0≤z<1, y+z<1;
所述有机共聚物层的厚度为1nm～10nm。The thickness of the organic copolymer layer is 1 nm to 10 nm.
根据本发明正极材料技术方案中的一种技术方案，至少具备如下有益效果：According to one of the cathode material technical solutions of the present invention, it at least has the following beneficial effects:
本发明通过在锰基材料表面包覆有机共聚物层，利用有机共聚物层实现对锰基材料的保护；从而使得锰基材料免于电解液的侵蚀；同时还能抑制电解液的分解，从而提升正极材料 的结构稳定性和界面稳定性，最终提升正极材料的循环性能。The present invention coats the surface of the manganese-based material with an organic copolymer layer and utilizes the organic copolymer layer to protect the manganese-based material; thus the manganese-based material is protected from the erosion of the electrolyte; and at the same time, it can also inhibit the decomposition of the electrolyte, thereby Improve the structural stability and interface stability of the cathode material, and ultimately improve the cycle performance of the cathode material.
有机共聚物层的厚度过薄不足以抵挡电解液的侵蚀，有机共聚物层过厚会阻碍锂离子的传输；从而对正极材料产生不利的影响。The thickness of the organic copolymer layer is too thin to resist the erosion of the electrolyte. The organic copolymer layer that is too thick will hinder the transmission of lithium ions, thereby adversely affecting the cathode material.
根据本发明的一些实施方式，所述锰基材料的D50为1μm～15μm。According to some embodiments of the present invention, the D50 of the manganese-based material is 1 μm to 15 μm.
锰基材料的粒径越小，材料在循环过程中的放电比容量越高，其循环性能变差；粒径越大放电比容量越低，循环性能会有所优化。所以，控制锰基材料的颗粒粒径在一定范围内使其材料发挥出最佳的电化学性能。The smaller the particle size of the manganese-based material, the higher the discharge specific capacity of the material during the cycle, and its cycle performance becomes worse; the larger the particle size, the lower the discharge specific capacity, and the cycle performance will be optimized. Therefore, controlling the particle size of manganese-based materials within a certain range allows the materials to exhibit optimal electrochemical performance.
根据本发明的一些实施方式，所述锰基材料的D50为3μm～5μm。According to some embodiments of the present invention, the D50 of the manganese-based material is 3 μm to 5 μm.
根据本发明的一些实施方式，所述Li 1+xNi yCo zMn 1-y-zO 2中x在0.1～0.3之间。 According to some embodiments of the present invention, x in Li 1+x Ni y Co z Mn 1-yz O 2 is between 0.1 and 0.3.
根据本发明的一些实施方式，所述Li 1+xNi yCo zMn 1-y-zO 2中y在0.3～0.4之间。 According to some embodiments of the present invention, y in Li 1+x Ni y Co z Mn 1-yz O 2 is between 0.3 and 0.4.
根据本发明的一些实施方式，所述Li 1+xNi yCo zMn 1-y-zO 2中z在0.01～0.1之间。 According to some embodiments of the present invention, z in Li 1+x Ni y Co z Mn 1-yz O 2 is between 0.01 and 0.1.
根据本发明的一些实施方式，所述锰基材料的制备方法，由如下步骤组成：According to some embodiments of the present invention, the preparation method of the manganese-based material consists of the following steps:
将锰基氢氧化物前驱体与锂盐经过充分混合后，制得混合物；After thoroughly mixing the manganese-based hydroxide precursor and the lithium salt, a mixture is prepared;
再将混合物在750℃～1000℃和氧气氛围下进行离子交换反应8h～20h。The mixture is then subjected to ion exchange reaction at 750°C to 1000°C in an oxygen atmosphere for 8h to 20h.
根据本发明的一些实施方式，所述有机共聚物层为聚偏二氟乙烯层、偏二氟乙烯-三氟乙烯共聚物层、偏二氟乙烯-四氟乙烯共聚物层中的至少一种。According to some embodiments of the present invention, the organic copolymer layer is at least one of a polyvinylidene fluoride layer, a vinylidene fluoride-trifluoroethylene copolymer layer, and a vinylidene fluoride-tetrafluoroethylene copolymer layer. .
上述有机共聚物高分子的包覆效果更好，能够抑制高压下电解液的分解，并且能够均匀包覆在锰基材料表面，且能控制包覆层的厚度，使得锰基正极材料的循环性能得到较好地提高。The above-mentioned organic copolymer polymer has a better coating effect, can inhibit the decomposition of the electrolyte under high pressure, and can evenly coat the surface of manganese-based materials, and can control the thickness of the coating layer, improving the cycle performance of manganese-based cathode materials. be better improved.
同时在正极浆料制备的过程中，上述有机共聚物层会部分溶解在浆料中；有机共聚物会因相似相溶而溶于有机油性溶剂中，可以使上述有机共聚物能均匀地分散在正极材料(锰基材料)周围，从而提升了抑制电解液分解的效果，使得正极材料的循环性能得到进一步提升。At the same time, during the preparation process of the positive electrode slurry, the above-mentioned organic copolymer layer will be partially dissolved in the slurry; the organic copolymer will be dissolved in the organic oily solvent due to similar compatibility, which can enable the above-mentioned organic copolymer to be evenly dispersed in the slurry. around the positive electrode material (manganese-based material), thereby improving the effect of inhibiting the decomposition of the electrolyte, further improving the cycle performance of the positive electrode material.
根据本发明的一些实施方式，所述有机共聚物层的厚度为6nm～10nm。According to some embodiments of the present invention, the thickness of the organic copolymer layer is 6 nm to 10 nm.
根据本发明的一些实施方式，所述有机共聚物层的厚度为6nm～7nm。According to some embodiments of the present invention, the thickness of the organic copolymer layer is 6 nm to 7 nm.
本发明第二方面提供了上述正极材料的制备方法，包括以下步骤：将有机共聚物分散液和所述锰基材料混合后干燥、球磨后退火。A second aspect of the present invention provides a method for preparing the above-mentioned cathode material, which includes the following steps: mixing an organic copolymer dispersion liquid and the manganese-based material, drying, ball milling and then annealing.
根据本发明制备方法技术方案中的一种技术方案，至少具备如下有益效果：According to one of the technical solutions of the preparation method of the present invention, it at least has the following beneficial effects:
本发明的制备方法将锰基材料和有机共聚物充分混合后，使有机共聚物均匀包裹在锰基材料表面，提升了抑制电解液分解的效果，使得正极材料的循环性能得到进一步提升。The preparation method of the present invention fully mixes the manganese-based material and the organic copolymer, so that the organic copolymer is evenly wrapped on the surface of the manganese-based material, which improves the effect of inhibiting the decomposition of the electrolyte and further improves the cycle performance of the cathode material.
有机共聚物高分子经过退火处理后，其结晶后具有优异的结构稳定性和更强的压电性。另外其功能团组(-C-F)能够吸引更多电子，使之具有高度的阳极稳定性，从而提高正极材料中 锂离子的含量，能够加快锂离子在电极/电解液界面处的扩散和电荷转移过程，提高了正极材料的导电性能。After the organic copolymer polymer is annealed, it has excellent structural stability and stronger piezoelectricity after crystallization. In addition, its functional group (-C-F) can attract more electrons, giving it a high degree of anode stability, thus increasing the lithium ion content in the cathode material and accelerating the diffusion and charge transfer of lithium ions at the electrode/electrolyte interface. process, improving the conductive properties of the cathode material.
根据本发明的一些实施方式，所述有机共聚物分散液的制备原料为有机共聚物和溶剂。According to some embodiments of the present invention, the raw materials for preparing the organic copolymer dispersion are organic copolymers and solvents.
根据本发明的一些实施方式，所述溶剂为N-甲基吡咯烷酮、二甲基甲酰胺、丁酮中的至少一种。According to some embodiments of the present invention, the solvent is at least one of N-methylpyrrolidone, dimethylformamide, and butanone.
根据本发明的一些实施方式，所述有机共聚物分散液中所述有机共聚物的质量浓度为1g/L-25g/L。According to some embodiments of the present invention, the mass concentration of the organic copolymer in the organic copolymer dispersion is 1g/L-25g/L.
根据本发明的一些实施方式，所述混合的分散速率为50rpm～2000rpm。According to some embodiments of the present invention, the dispersion rate of the mixing is 50 rpm to 2000 rpm.
根据本发明的一些实施方式，所述干燥的温度为60℃～100℃。According to some embodiments of the present invention, the drying temperature is 60°C to 100°C.
干燥温度过低，会导致包覆层来不及附着在材料表面，可能会随着溶剂沉淀在材料底部，导致包覆层无法均匀地分散在正极材料周围，无法抑制电解液分解的效果；If the drying temperature is too low, the coating layer will not have time to adhere to the surface of the material, and may precipitate at the bottom of the material with the solvent, causing the coating layer to be unable to be evenly dispersed around the cathode material and unable to inhibit the decomposition of the electrolyte;
干燥温度过高，会使包覆层在未能附着在材料表面上时就提前结晶，结晶后的包覆层与正极材料之间的附着力下降，可能发生分离，分离的包覆层无法对正极材料起到保护作用。If the drying temperature is too high, the coating layer will crystallize in advance before it can adhere to the surface of the material. The adhesion between the crystallized coating layer and the cathode material will decrease, and separation may occur. The separated coating layer cannot be attached to the surface of the material. The cathode material plays a protective role.
根据本发明的一些实施方式，所述干燥由第一段干燥和第二段干燥组成。According to some embodiments of the present invention, the drying consists of a first stage of drying and a second stage of drying.
根据本发明的一些实施方式，所述第一段干燥的温度为60℃～90℃。According to some embodiments of the present invention, the temperature of the first stage of drying is 60°C to 90°C.
第一段干燥的目的为蒸干溶剂，故而第一段干燥需要进行搅拌。The purpose of the first stage of drying is to evaporate the solvent, so the first stage of drying requires stirring.
根据本发明的一些实施方式，所述第一段干燥过程中搅拌的速率为50rpm～500rpm。According to some embodiments of the present invention, the stirring rate during the first stage of drying is 50 rpm to 500 rpm.
根据本发明的一些实施方式，所述第二段干燥的温度为80℃～100℃。According to some embodiments of the present invention, the temperature of the second stage of drying is 80°C to 100°C.
根据本发明的一些实施方式，所述第二段干燥的时间为10h～24h。According to some embodiments of the present invention, the second drying period ranges from 10 hours to 24 hours.
根据本发明的一些实施方式，所述球磨的转速为200rpm～300rpm。According to some embodiments of the present invention, the rotation speed of the ball mill is 200 to 300 rpm.
球磨转速过高，会导致材料表面的包覆层被球磨珠之间的剪切力给打破打散，使表面的包覆层失去作用，无法均匀地分散在正极材料周围，无法抑制电解液分解的效果；球磨转速过低，会导致团聚在一起的材料无法分散，使表面的包覆层无法发挥作用，并且在后续退火中，团聚加剧，后续对电极材料的搅浆匀浆无法顺利进行。If the ball milling speed is too high, the coating layer on the surface of the material will be broken and scattered by the shear force between the ball milling beads, causing the surface coating layer to lose its function and cannot be evenly dispersed around the cathode material, and cannot inhibit the decomposition of the electrolyte. The effect; if the ball milling speed is too low, the agglomerated materials will not be dispersed, making the surface coating unable to function. In addition, during the subsequent annealing, the agglomeration will be intensified, and the subsequent homogenization of the electrode materials will not proceed smoothly.
根据本发明的一些实施方式，所述球磨的时间为0.5h～5h。According to some embodiments of the present invention, the ball milling time is 0.5h to 5h.
根据本发明的一些实施方式，所述退火的温度为135℃～155℃。According to some embodiments of the present invention, the annealing temperature ranges from 135°C to 155°C.
温度过低，包覆层的结晶性变差，此时的包覆层效果下降，无法抑制电解液分解的效果；温度过高，包覆剂可能发生分解，此时的包覆层失效，不能对正极材料起到保护的作用。If the temperature is too low, the crystallinity of the coating layer will become worse. At this time, the coating layer effect will decrease and the effect of electrolyte decomposition cannot be suppressed. If the temperature is too high, the coating agent may decompose, and the coating layer will fail and cannot be used. It protects the cathode material.
根据本发明的一些实施方式，所述退火在保护性气氛下进行。According to some embodiments of the invention, the annealing is performed under a protective atmosphere.
在保护性气氛下进行，防止有机共聚物在退火过程中被氧化。Carry out under a protective atmosphere to prevent the organic copolymer from being oxidized during the annealing process.
有机共聚物层经过退火后，其分子链发生了变化，已经结晶为晶体结构，具有晶体结构 的有机共聚物层只有部分会溶解在浆料中，溶解量在2％以下(室温25℃)。After the organic copolymer layer is annealed, its molecular chain has changed and has crystallized into a crystal structure. Only part of the organic copolymer layer with a crystal structure will be dissolved in the slurry, and the amount of dissolution is less than 2% (room temperature 25°C).
制备搅浆过程中温度越高，有机共聚物溶解的量会越多，若要完全溶解掉，需要达到有机共聚物的熔点附近。The higher the temperature during the pulp preparation process, the more the organic copolymer will be dissolved. To completely dissolve it, it needs to be near the melting point of the organic copolymer.
根据本发明的一些实施方式，所述保护性气氛为氮气、氩气、氖气、氪气、氙气中的至少一种。According to some embodiments of the present invention, the protective atmosphere is at least one of nitrogen, argon, neon, krypton, and xenon.
根据本发明的一些实施方式，所述退火的时间为2h～6h。According to some embodiments of the present invention, the annealing time is 2h to 6h.
退火时间过短，材料的结晶度不高，此时的包覆层效果下降，无法抑制电解液分解的效果；时间过长，包覆剂可能发生分解，此时的包覆层失效，不能对正极材料起到保护的作用。The annealing time is too short, and the crystallinity of the material is not high. At this time, the coating effect is reduced and the effect of electrolyte decomposition cannot be suppressed. If the annealing time is too long, the coating agent may decompose, and the coating layer will fail at this time and cannot be used for annealing. The cathode material plays a protective role.
本发明第三方面提供了上述正极材料在制备锂离子电池中的应用。The third aspect of the present invention provides the application of the above-mentioned cathode material in preparing lithium-ion batteries.
根据本发明的一些实施方式，所述锂离子电池包括正极极片、负极极片、置于正极极片和负极极片之间的隔离膜以及电解液。According to some embodiments of the present invention, the lithium ion battery includes a positive electrode sheet, a negative electrode sheet, a separator film disposed between the positive electrode sheet and the negative electrode sheet, and an electrolyte.
根据本发明的一些实施方式，所述正极极片包含所述正极材料。According to some embodiments of the present invention, the positive electrode sheet includes the positive electrode material.
根据本发明的一些实施方式，所述负极极片包含能嵌入、脱出锂离子的负极活性材料。According to some embodiments of the present invention, the negative electrode sheet includes a negative electrode active material capable of inserting and extracting lithium ions.
根据本发明的一些实施方式，所述负极活性材料包括硬碳、天然石墨、人造石墨、软碳、炭黑、乙炔黑、碳纳米管、石墨烯、碳纳米纤维中的至少一种。According to some embodiments of the present invention, the negative active material includes at least one of hard carbon, natural graphite, artificial graphite, soft carbon, carbon black, acetylene black, carbon nanotubes, graphene, and carbon nanofibers.
根据本发明的一些实施方式，所述隔膜包括聚乙烯、聚丙烯、聚偏氟乙烯以及其多层复合膜中的一种。According to some embodiments of the present invention, the separator includes one of polyethylene, polypropylene, polyvinylidene fluoride and multi-layer composite films thereof.
根据本发明的一些实施方式，所述正极极片还包括粘结剂和导电剂。According to some embodiments of the present invention, the positive electrode sheet further includes a binder and a conductive agent.
根据本发明的一些实施方式，所述正极极片的制备方法，包括以下步骤：将包含有所述正极材料、粘结剂和导电剂的正极浆料涂覆在正极集流体上，待正极浆料干燥后获得正极片。According to some embodiments of the present invention, the preparation method of the positive electrode sheet includes the following steps: coating the positive electrode slurry containing the positive electrode material, the binder and the conductive agent on the positive electrode current collector, and waiting for the positive electrode slurry to After the material is dried, the positive electrode sheet is obtained.
根据本发明的一些实施方式，所述正极浆料的制备方法，包括以下步骤：将所述正极材料、所述粘结剂和所述导电剂混合。According to some embodiments of the present invention, the preparation method of the positive electrode slurry includes the following steps: mixing the positive electrode material, the binder and the conductive agent.
根据本发明的一些实施方式，所述混合的温度为15℃～25℃。According to some embodiments of the present invention, the mixing temperature is 15°C to 25°C.
根据本发明的一些实施方式，所述混合的速度为1800rpm～2200rmp。According to some embodiments of the present invention, the mixing speed is 1800 rpm to 2200 rpm.
根据本发明的一些实施方式，所述混合的时间为50min～100min。According to some embodiments of the present invention, the mixing time is 50 minutes to 100 minutes.
根据本发明的一些实施方式，所述负极极片还包括粘结剂和导电剂。According to some embodiments of the present invention, the negative electrode sheet further includes a binder and a conductive agent.
根据本发明的一些实施方式，所述负极极片的制备方法，包括以下步骤：将包含有负极活性材料、粘结剂和导电剂的负极浆料涂覆在负极集流体上，待负极浆料干燥后获得负极片。According to some embodiments of the present invention, the preparation method of the negative electrode sheet includes the following steps: coating the negative electrode slurry containing the negative electrode active material, the binder and the conductive agent on the negative electrode current collector, and waiting for the negative electrode slurry to After drying, the negative electrode sheet is obtained.
根据本发明的一些实施方式，所述电解液包括锂盐、溶剂和添加剂。According to some embodiments of the invention, the electrolyte includes lithium salt, solvent and additives.
根据本发明的一些实施方式，所述锂盐为LiPF 6、LiBOB、LiODFB、LiFSI、LiTFSI、LiPO 2F 2中的至少一种。 According to some embodiments of the present invention, the lithium salt is at least one of LiPF 6 , LiBOB, LiODFB, LiFSI, LiTFSI, and LiPO 2 F 2 .
根据本发明的一些实施方式，所述锂盐在所述电解液中的摩尔浓度为1.0mol/L～1.5mol/L。According to some embodiments of the present invention, the molar concentration of the lithium salt in the electrolyte is 1.0 mol/L to 1.5 mol/L.
根据本发明的一些实施方式，所述溶剂为碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)、乙酸乙酯(EA)、丙酸乙酯(EP)、丁酸甲酯(MB)、丁酸乙酯(EB)、甲酯(PA)中的至少一种。According to some embodiments of the present invention, the solvent is ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), At least one of ethyl acetate (EA), ethyl propionate (EP), methyl butyrate (MB), ethyl butyrate (EB), and methyl ester (PA).
根据本发明的一些实施方式，所述添加剂为碳酸亚乙烯酯(VC)、氟代碳酸乙烯酯(FEC)、1，3-丙烷磺酸内酯(PS)、硫酸乙烯酯(DTD)、碳酸二苯酯(DPC)、碳酸甲苯酯(MPC)、丁二酸酐(SA)、丁二腈(SN)、己二腈(AND)中的至少一种。According to some embodiments of the present invention, the additive is vinylene carbonate (VC), fluoroethylene carbonate (FEC), 1,3-propane sultone (PS), vinyl sulfate (DTD), carbonic acid At least one of diphenyl ester (DPC), toluene carbonate (MPC), succinic anhydride (SA), succinonitrile (SN), and adiponitrile (AND).
本发明的其它特征和优点将在随后的说明书中阐述，并且，部分地从说明书中变得显而易见，或者通过实施本发明而了解。Additional features and advantages of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the invention.
附图说明Description of the drawings
本发明的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：The above and/or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:
图1为本发明实施例1与对比例1中正极材料的XRD图谱。Figure 1 is the XRD pattern of the cathode material in Example 1 and Comparative Example 1 of the present invention.
图2为本发明实施例1、实施例3与对比例1对应的正极材料的循环放电曲线图。Figure 2 is a cyclic discharge curve diagram of the cathode material corresponding to Example 1, Example 3 and Comparative Example 1 of the present invention.
图3为本发明实施例3对应的正极材料(三组平行样)的循环放电曲线图。Figure 3 is a cyclic discharge curve diagram of the cathode material (three sets of parallel samples) corresponding to Embodiment 3 of the present invention.
图4为本发明实施例1与对比例1对应的正极材料在循环过程中放电中值电压对比图。Figure 4 is a comparison chart of the discharge median voltage of the cathode materials corresponding to Example 1 of the present invention and Comparative Example 1 during the cycle.
具体实施方式Detailed ways
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。The concept of the present invention and the technical effects produced will be clearly and completely described below with reference to the embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without exerting creative efforts are all protection scope of the present invention.
本发明的描述中，参考术语“一个实施例”、“一些实施例”、“示意性实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。In the description of the present invention, reference to the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples" is intended to be in conjunction with the description of the embodiment. or examples describe specific features, structures, materials, or characteristics that are included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。If the specific conditions are not specified in the examples, the conditions should be carried out according to the conventional conditions or the conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not indicated, they are all conventional products that can be purchased commercially.
本发明中“约”代表±2％，例如约100代表100±2，即98～102。In the present invention, "about" represents ±2%, for example, about 100 represents 100±2, that is, 98 to 102.
本发明实施方式中有机共聚物(包覆剂)包覆层厚度放入计算方法为In the embodiment of the present invention, the calculation method for the thickness of the coating layer of the organic copolymer (coating agent) is:
包覆厚度＝包覆剂质量/包覆剂密度/(锰基材料的比表面积*锰基材料的质量)。Coating thickness = coating agent mass / coating agent density / (specific surface area of manganese-based material * mass of manganese-based material).
例如：已知偏二氟乙烯-三氟乙烯的密度为1.78g/cm 3，锰基材料的比表面积为1.12m 2/g，通过计算可知； For example: it is known that the density of vinylidene fluoride-trifluoroethylene is 1.78g/cm 3 and the specific surface area of manganese-based material is 1.12m 2 /g. It can be known through calculation;
包覆厚度＝偏二氟乙烯-三氟乙烯质量/偏二氟乙烯-三氟乙烯密度/(富锂锰基正极材料的比表面积*富锂锰基正极材料的质量)。Coating thickness = mass of vinylidene fluoride-trifluoroethylene/density of vinylidene fluoride-trifluoroethylene/(specific surface area of lithium-rich manganese-based cathode material * mass of lithium-rich manganese-based cathode material).
包覆1.28g偏二氟乙烯-三氟乙烯到100g富锂锰基正极材料上，其包覆厚度为6.4nm。Coating 1.28g of vinylidene fluoride-trifluoroethylene onto 100g of lithium-rich manganese-based cathode material, the coating thickness is 6.4nm.
下面详细描述本发明的具体实施例。Specific embodiments of the present invention are described in detail below.
实施例1Example 1
本实施例为一种正极材料及其制备方法。This embodiment is a cathode material and a preparation method thereof.
本实施例中正极材料的内核为锰基材料(Li 1.2Ni 0.35Co 0.05Mn 0.6O 2)；锰基材料的表面均匀包覆有机共聚物层。 In this embodiment, the core of the positive electrode material is a manganese-based material (Li 1.2 Ni 0.35 Co 0.05 Mn 0.6 O 2 ); the surface of the manganese-based material is evenly coated with an organic copolymer layer.
锰基材料的Dv50为4μm，比表面积为1.12m 2/g。 The Dv50 of manganese-based materials is 4 μm and the specific surface area is 1.12 m 2 /g.
有机共聚物层的材质为偏二氟乙烯-三氟乙烯共聚物；有机共聚物层的厚度为6.4nm。The material of the organic copolymer layer is vinylidene fluoride-trifluoroethylene copolymer; the thickness of the organic copolymer layer is 6.4 nm.
本发明实施例中正极材料的制备方法，由以下步骤组成：The preparation method of the cathode material in the embodiment of the present invention consists of the following steps:
S1、制备锰基材料粉体Li 1.2Ni 0.35Co 0.05Mn 0.6O 2； S1. Preparation of manganese-based material powder Li 1.2 Ni 0.35 Co 0.05 Mn 0.6 O 2 ;
将锰基氢氧化物前驱体(Ni 0.35Co 0.05Mn 0.6(OH) 2)与锂盐(Li 2CO 3)经过充分混合后(前驱体和锂盐的摩尔比为1:0.6)，将混合物在900℃和氧气氛围下进行离子交换反应15h，最终得到锰基材料粉体；该前驱体Dv50为3μm，比表面积为12.3m 2/g，经过混锂及烧结后其锰基材料的Dv50为4μm，比表面积为1.12m 2/g； After the manganese-based hydroxide precursor (Ni 0.35 Co 0.05 Mn 0.6 (OH) 2 ) and the lithium salt (Li 2 CO 3 ) are thoroughly mixed (the molar ratio of the precursor to the lithium salt is 1:0.6), the mixture is Conduct an ion exchange reaction at 900°C and an oxygen atmosphere for 15 hours to finally obtain manganese-based material powder; the Dv50 of the precursor is 3 μm and the specific surface area is 12.3m 2 /g. After lithium mixing and sintering, the Dv50 of the manganese-based material is 4μm, specific surface area is 1.12m 2 /g;
S2、将偏二氟乙烯-三氟乙烯共聚物(生产厂家为：Piezotech FC20，分子式为(CH 2CF 2) n；1.28g)溶解在N-甲基吡咯烷酮中；制得共聚物分散液(共聚物的质量浓度为12.8g/L)； S2. Dissolve vinylidene fluoride-trifluoroethylene copolymer (manufacturer: Piezotech FC20, molecular formula: (CH 2 CF 2 ) n ; 1.28g) in N-methylpyrrolidone; prepare a copolymer dispersion ( The mass concentration of the copolymer is 12.8g/L);
S3、将S1制得的锰基材料粉体(100g)添加至步骤S2中所得的共聚物分散液中，持续搅拌，搅拌速度为1000rpm，直至粉体与溶剂混合均匀；制得正极材料共聚物分散液；S3. Add the manganese-based material powder (100g) prepared in S1 to the copolymer dispersion obtained in step S2, and continue stirring at a stirring speed of 1000 rpm until the powder and solvent are evenly mixed; a cathode material copolymer is obtained. Dispersions;
S4、将S3中所得的正极材料共聚物分散液放入80℃水浴锅中，持续搅拌，搅拌速度为300rpm直至N-甲基吡咯烷酮蒸发完毕，之后将蒸发后物料放入100℃真空烘箱中干燥12h；制得前驱体；S4. Put the cathode material copolymer dispersion obtained in S3 into an 80°C water bath and continue stirring at a stirring speed of 300 rpm until N-methylpyrrolidone evaporates. Then, place the evaporated material into a 100°C vacuum oven for drying. 12h; Preparation of precursor;
S5、将S4制得的前驱体进行球磨，球磨转速为200rpm；球磨的时间为1h；球磨完成后过300目筛网(过筛网的目的是将球磨后依然团聚在一起的大颗粒材料剔除掉，若团聚在一起的材料较多，后续电极材料搅浆匀浆无法顺利进行)；S5. Ball-mill the precursor prepared in S4. The ball-milling speed is 200 rpm; the ball-milling time is 1 hour; after the ball-milling is completed, pass it through a 300-mesh screen (the purpose of passing the screen is to remove large particles of material that are still agglomerated after ball-milling) If there are too many materials agglomerated together, the subsequent homogenization of the electrode material cannot be carried out smoothly);
将过筛后的物料放入管式炉中在惰性气体(氮气气氛)中进行退火处理，退火温度140℃，时间3h；退火完成后即得到正极材料。Put the screened material into a tube furnace and perform annealing treatment in an inert gas (nitrogen atmosphere). The annealing temperature is 140°C and the time is 3 hours; after the annealing is completed, the cathode material is obtained.
实施例2Example 2
本实施例为一种正极材料及其制备方法。This embodiment is a cathode material and a preparation method thereof.
本实施例中正极材料的内核为锰基材料(Li 1.2Ni 0.35Co 0.05Mn 0.6O 2)；锰基材料的表面均匀包覆有机共聚物层。 In this embodiment, the core of the positive electrode material is a manganese-based material (Li 1.2 Ni 0.35 Co 0.05 Mn 0.6 O 2 ); the surface of the manganese-based material is evenly coated with an organic copolymer layer.
锰基材料的Dv50为4μm，比表面积为1.22m 2/g。 The Dv50 of manganese-based materials is 4 μm and the specific surface area is 1.22 m 2 /g.
有机共聚物层的材质为偏二氟乙烯-三氟乙烯共聚物；有机共聚物层的厚度为6.5nm。The material of the organic copolymer layer is vinylidene fluoride-trifluoroethylene copolymer; the thickness of the organic copolymer layer is 6.5 nm.
本发明实施例中正极材料的制备方法，由以下步骤组成：The preparation method of the cathode material in the embodiment of the present invention consists of the following steps:
S1、制备锰基材料粉体Li 1.2Ni 0.35Co 0.05Mn 0.6O 2； S1. Preparation of manganese-based material powder Li 1.2 Ni 0.35 Co 0.05 Mn 0.6 O 2 ;
将锰基氢氧化物前驱体(Ni 0.35Co 0.05Mn 0.6(OH) 2)与(Li 2CO 3)经过充分混合后(前驱体和锂盐的摩尔比为1:0.6)，将混合物在900℃和氧气氛围下进行离子交换反应15h，最终得到锰基材料粉体；该前驱体Dv50为3μm，比表面积为12.3m 2/g，经过混锂及烧结后其锰基材料的Dv50为4μm，比表面积为1.12m 2/g； After the manganese-based hydroxide precursor (Ni 0.35 Co 0.05 Mn 0.6 (OH) 2 ) and (Li 2 CO 3 ) are thoroughly mixed (the molar ratio of the precursor to the lithium salt is 1:0.6), the mixture is heated at 900 The ion exchange reaction was carried out at ℃ and oxygen atmosphere for 15 hours to finally obtain manganese-based material powder; the Dv50 of the precursor was 3 μm and the specific surface area was 12.3m 2 /g. After lithium mixing and sintering, the Dv50 of the manganese-based material was 4 μm. The specific surface area is 1.12m 2 /g;
S2、将偏二氟乙烯-三氟乙烯共聚物(生产厂家为：Piezotech FC20，分子式为(CH 2CF 2) n，1.41g)溶解在N-甲基吡咯烷酮中；制得共聚物分散液(共聚物的质量浓度为14.1g/L)； S2. Dissolve vinylidene fluoride-trifluoroethylene copolymer (manufacturer: Piezotech FC20, molecular formula: (CH 2 CF 2 ) n , 1.41g) in N-methylpyrrolidone; prepare a copolymer dispersion ( The mass concentration of the copolymer is 14.1g/L);
S3、将S1制得的锰基材料粉体(100g)添加至步骤S2中所得的共聚物分散液中，持续搅拌，搅拌速度为1000rpm，直至粉体与溶剂混合均匀；制得正极材料共聚物分散液；S3. Add the manganese-based material powder (100g) prepared in S1 to the copolymer dispersion obtained in step S2, and continue stirring at a stirring speed of 1000 rpm until the powder and solvent are evenly mixed; a cathode material copolymer is obtained. Dispersions;
S4、将S3中所得的正极材料共聚物分散液放入80℃水浴锅中，持续搅拌，搅拌速度为300rpm直至N-甲基吡咯烷酮蒸发完毕，之后将蒸发后物料放入100℃真空烘箱中干燥10h；制得前驱体；S4. Put the cathode material copolymer dispersion obtained in S3 into an 80°C water bath and continue stirring at a stirring speed of 300 rpm until N-methylpyrrolidone evaporates. Then, place the evaporated material into a 100°C vacuum oven for drying. 10h; Preparation of precursor;
S5、将S4制得的前驱体进行球磨，球磨转速为200rpm；球磨的时间为1h；球磨完成后过300目筛网；S5. Ball-mill the precursor prepared in S4. The ball-milling speed is 200 rpm; the ball-milling time is 1 hour; after the ball-milling is completed, pass it through a 300-mesh screen;
将过筛后的物料放入管式炉中在惰性气体(氮气气氛)中进行退火处理，退火温度145℃，时间1h；退火完成后即得到正极材料。Put the screened material into a tube furnace and perform annealing treatment in an inert gas (nitrogen atmosphere). The annealing temperature is 145°C and the time is 1 hour; after the annealing is completed, the cathode material is obtained.
实施例3Example 3
本实施例为一种正极材料及其制备方法。This embodiment is a cathode material and a preparation method thereof.
本实施例中正极材料的内核为锰基材料(Li 1.2Ni 0.35Co 0.05Mn 0.6O 2)；锰基材料的表面均匀包覆有机共聚物层。 In this embodiment, the core of the positive electrode material is a manganese-based material (Li 1.2 Ni 0.35 Co 0.05 Mn 0.6 O 2 ); the surface of the manganese-based material is evenly coated with an organic copolymer layer.
锰基材料的Dv50为4μm，比表面积为1.12m 2/g。 The Dv50 of manganese-based materials is 4 μm and the specific surface area is 1.12 m 2 /g.
有机共聚物层的材质为偏二氟乙烯-三氟乙烯共聚物；有机共聚物层的厚度为1nm。The material of the organic copolymer layer is vinylidene fluoride-trifluoroethylene copolymer; the thickness of the organic copolymer layer is 1 nm.
本发明实施例中正极材料的制备方法，由以下步骤组成：The preparation method of the cathode material in the embodiment of the present invention consists of the following steps:
S1、制备锰基材料粉体Li 1.2Ni 0.35Co 0.05Mn 0.6O 2； S1. Preparation of manganese-based material powder Li 1.2 Ni 0.35 Co 0.05 Mn 0.6 O 2 ;
将锰基氢氧化物前驱体(Ni 0.35Co 0.05Mn 0.6(OH) 2)与(Li 2CO 3)经过充分混合后(前驱体和锂盐的摩尔比为1:0.6)，将混合物在750～1000℃和氧气氛围下进行离子交换反应8～20h，最终得到锰基材料粉体；该前驱体Dv50为3μm，比表面积为12.3m 2/g，经过混锂及烧结后其锰基材料的Dv50为4μm，比表面积为1.12m 2/g； After the manganese-based hydroxide precursor (Ni 0.35 Co 0.05 Mn 0.6 (OH) 2 ) and (Li 2 CO 3 ) are thoroughly mixed (the molar ratio of the precursor to the lithium salt is 1:0.6), the mixture is heated at 750 Conduct an ion exchange reaction at ~1000°C and an oxygen atmosphere for 8 to 20 hours to finally obtain manganese-based material powder; the Dv50 of the precursor is 3 μm and the specific surface area is 12.3m 2 /g. After lithium mixing and sintering, the manganese-based material has a Dv50 is 4μm, and the specific surface area is 1.12m 2 /g;
S2、将偏二氟乙烯-三氟乙烯共聚物(生产厂家为：Piezotech FC20，分子式为(CH 2CF 2) n，0.2g)溶解在N-甲基吡咯烷酮中；制得共聚物分散液(共聚物的浓度为2g/L)； S2. Dissolve vinylidene fluoride-trifluoroethylene copolymer (manufacturer: Piezotech FC20, molecular formula: (CH 2 CF 2 ) n , 0.2g) in N-methylpyrrolidone; prepare a copolymer dispersion ( The concentration of copolymer is 2g/L);
S3、将S1制得的锰基材料粉体(100g)添加至步骤S2中所得的共聚物分散液中，持续搅拌，搅拌速度为1000rpm，直至粉体与溶剂混合均匀；制得正极材料共聚物分散液；S3. Add the manganese-based material powder (100g) prepared in S1 to the copolymer dispersion obtained in step S2, and continue stirring at a stirring speed of 1000 rpm until the powder and solvent are evenly mixed; a cathode material copolymer is obtained. Dispersions;
S4、将S3中所得的正极材料共聚物分散液放入80℃水浴锅中，持续搅拌，搅拌速度为300rpm直至N-甲基吡咯烷酮蒸发完毕，之后将蒸发后物料放入100℃真空烘箱中干燥10h；制得前驱体；S4. Put the cathode material copolymer dispersion obtained in S3 into an 80°C water bath and continue stirring at a stirring speed of 300 rpm until N-methylpyrrolidone evaporates. Then, place the evaporated material into a 100°C vacuum oven for drying. 10h; Preparation of precursor;
S5、将S4制得的前驱体进行球磨，球磨转速为200rpm；球磨的时间为1h；球磨完成后过300目筛网；S5. Ball-mill the precursor prepared in S4. The ball-milling speed is 200 rpm; the ball-milling time is 1 hour; after the ball-milling is completed, pass it through a 300-mesh screen;
将过筛后的物料放入管式炉中在惰性气体(氮气气氛)中进行退火处理，退火温度145℃，时间1h；退火完成后即得到正极材料。Put the screened material into a tube furnace and perform annealing treatment in an inert gas (nitrogen atmosphere). The annealing temperature is 145°C and the time is 1 hour; after the annealing is completed, the cathode material is obtained.
实施例4Example 4
本实施例为一种正极材料及其制备方法。This embodiment is a cathode material and a preparation method thereof.
本实施例中正极材料的内核为锰基材料(Li 1.2Ni 0.35Co 0.05Mn 0.6O 2)；锰基材料的表面均匀包覆有机共聚物层。 In this embodiment, the core of the positive electrode material is a manganese-based material (Li 1.2 Ni 0.35 Co 0.05 Mn 0.6 O 2 ); the surface of the manganese-based material is evenly coated with an organic copolymer layer.
锰基材料的Dv50为4μm，比表面积为1.12m 2/g。 The Dv50 of manganese-based materials is 4 μm and the specific surface area is 1.12 m 2 /g.
有机共聚物层的材质为偏二氟乙烯-三氟乙烯共聚物；有机共聚物层的厚度为10nm。The material of the organic copolymer layer is vinylidene fluoride-trifluoroethylene copolymer; the thickness of the organic copolymer layer is 10 nm.
本发明实施例中正极材料的制备方法，由以下步骤组成：The preparation method of the cathode material in the embodiment of the present invention consists of the following steps:
S1、制备锰基材料粉体Li 1.2Ni 0.35Co 0.05Mn 0.6O 2； S1. Preparation of manganese-based material powder Li 1.2 Ni 0.35 Co 0.05 Mn 0.6 O 2 ;
将锰基氢氧化物前驱体(Ni 0.35Co 0.05Mn 0.6(OH) 2)与(Li 2CO 3)经过充分混合后(前驱体和锂盐的摩尔比为1:0.6)，将混合物在900℃和氧气氛围下进行离子交换反应15h，最终得到锰基材料粉体；该前驱体Dv50为3μm，比表面积为12.3m 2/g，经过混锂及烧结后其锰基材料的Dv50为4μm，比表面积为1.12m 2/g； After the manganese-based hydroxide precursor (Ni 0.35 Co 0.05 Mn 0.6 (OH) 2 ) and (Li 2 CO 3 ) are thoroughly mixed (the molar ratio of the precursor to the lithium salt is 1:0.6), the mixture is heated at 900 The ion exchange reaction was carried out at ℃ and oxygen atmosphere for 15 hours to finally obtain manganese-based material powder; the Dv50 of the precursor was 3 μm and the specific surface area was 12.3m 2 /g. After lithium mixing and sintering, the Dv50 of the manganese-based material was 4 μm. The specific surface area is 1.12m 2 /g;
S2、将偏二氟乙烯-三氟乙烯共聚物(生产厂家为：Piezotech FC20，分子式为(CH 2CF 2) n，2g)溶解在N-甲基吡咯烷酮中；制得共聚物分散液(共聚物的质量浓度为20g/L)； S2. Dissolve vinylidene fluoride-trifluoroethylene copolymer (manufacturer: Piezotech FC20, molecular formula: (CH 2 CF 2 ) n , 2g) in N-methylpyrrolidone; prepare a copolymer dispersion (copolymer The mass concentration of the substance is 20g/L);
S3、将S1制得的锰基材料粉体(100g)添加至步骤S2中所得的共聚物分散液中，持续搅拌，搅拌速度为1000rpm，直至粉体与溶剂混合均匀；制得正极材料共聚物分散液；S3. Add the manganese-based material powder (100g) prepared in S1 to the copolymer dispersion obtained in step S2, and continue stirring at a stirring speed of 1000 rpm until the powder and solvent are evenly mixed; a cathode material copolymer is obtained. Dispersions;
S4、将S3中所得的正极材料共聚物分散液放入80℃水浴锅中，持续搅拌，搅拌速度为300rpm直至N-甲基吡咯烷酮蒸发完毕，之后将蒸发后物料放入100℃真空烘箱中干燥10h；制得前驱体；S4. Put the cathode material copolymer dispersion obtained in S3 into an 80°C water bath and continue stirring at a stirring speed of 300 rpm until N-methylpyrrolidone evaporates. Then, place the evaporated material into a 100°C vacuum oven for drying. 10h; Preparation of precursor;
S5、将S4制得的前驱体进行球磨，球磨转速为200rpm；球磨的时间为1h；球磨完成后过300目筛网(过筛网的目的是将球磨后依然团聚在一起的大颗粒材料剔除掉，若团聚在一起的材料较多，后续电极材料搅浆匀浆无法顺利进行)；S5. Ball-mill the precursor prepared in S4. The ball-milling speed is 200 rpm; the ball-milling time is 1 hour; after the ball-milling is completed, pass it through a 300-mesh screen (the purpose of passing the screen is to remove large particles of material that are still agglomerated after ball-milling) If there are too many materials agglomerated together, the subsequent homogenization of the electrode material cannot be carried out smoothly);
将过筛后的物料放入管式炉中在惰性气体(氮气气氛)中进行退火处理，退火温度145℃，时间1h；退火完成后即得到正极材料。Put the screened material into a tube furnace and perform annealing treatment in an inert gas (nitrogen atmosphere). The annealing temperature is 145°C and the time is 1 hour; after the annealing is completed, the cathode material is obtained.
实施例5Example 5
本实施例为一种正极材料及其制备方法。This embodiment is a cathode material and a preparation method thereof.
本实施例中正极材料的内核为锰基材料(Li 1.2Ni 0.35Co 0.05Mn 0.6O 2)；锰基材料的表面均匀包覆有机共聚物层。 In this embodiment, the core of the positive electrode material is a manganese-based material (Li 1.2 Ni 0.35 Co 0.05 Mn 0.6 O 2 ); the surface of the manganese-based material is evenly coated with an organic copolymer layer.
锰基材料的Dv50为4μm，比表面积为1.12m 2/g。 The Dv50 of manganese-based materials is 4 μm and the specific surface area is 1.12 m 2 /g.
有机共聚物层的材质为偏二氟乙烯共聚物；有机共聚物层的厚度为10nm。The material of the organic copolymer layer is vinylidene fluoride copolymer; the thickness of the organic copolymer layer is 10 nm.
本发明实施例中正极材料的制备方法，由以下步骤组成：The preparation method of the cathode material in the embodiment of the present invention consists of the following steps:
S1、制备锰基材料粉体Li 1.2Ni 0.35Co 0.05Mn 0.6O 2； S1. Preparation of manganese-based material powder Li 1.2 Ni 0.35 Co 0.05 Mn 0.6 O 2 ;
将锰基氢氧化物前驱体(Ni 0.35Co 0.05Mn 0.6(OH) 2)与(Li 2CO 3)经过充分混合后(前驱体和锂盐的摩尔比为1:0.6)，将混合物在900℃和氧气氛围下进行离子交换反应15h，最终得到锰基材料粉体；该前驱体Dv50为3μm，比表面积为12.3m 2/g，经过混锂及烧结后其锰基材料的Dv50为4μm，比表面积为1.12m 2/g； After the manganese-based hydroxide precursor (Ni 0.35 Co 0.05 Mn 0.6 (OH) 2 ) and (Li 2 CO 3 ) are thoroughly mixed (the molar ratio of the precursor to the lithium salt is 1:0.6), the mixture is heated at 900 The ion exchange reaction was carried out at ℃ and oxygen atmosphere for 15 hours to finally obtain manganese-based material powder; the Dv50 of the precursor was 3 μm and the specific surface area was 12.3m 2 /g. After lithium mixing and sintering, the Dv50 of the manganese-based material was 4 μm. The specific surface area is 1.12m 2 /g;
S2、将聚偏二氟乙烯(生产厂家为：麦克林，分子式为(CH 2CF 2) n，CAS号为： S2. Polyvinylidene fluoride (manufacturer: McLean, molecular formula: (CH 2 CF 2 ) n , CAS number:
24937-79-9；产品型号为：P822261；Mw约为534,000；2g)溶解在N-甲基吡咯烷酮中；制得共聚物分散液(共聚物的质量浓度为20g/L)；24937-79-9; Product model: P822261; Mw is about 534,000; 2g) is dissolved in N-methylpyrrolidone; a copolymer dispersion is prepared (the mass concentration of the copolymer is 20g/L);
S3、将S1制得的锰基材料粉体(100g)添加至步骤S2中所得的共聚物分散液中，持续搅拌，搅拌速度为2000rpm，直至粉体与溶剂混合均匀；制得正极材料共聚物分散液；S3. Add the manganese-based material powder (100g) prepared in S1 to the copolymer dispersion obtained in step S2, and continue stirring at a stirring speed of 2000 rpm until the powder and solvent are evenly mixed; a cathode material copolymer is obtained. Dispersions;
S4、将S3中所得的正极材料共聚物分散液放入80℃水浴锅中，持续搅拌，搅拌速度为500rpm直至N-甲基吡咯烷酮蒸发完毕，之后将蒸发后物料放入100℃真空烘箱中干燥10h；制得前驱体；S4. Put the cathode material copolymer dispersion obtained in S3 into an 80°C water bath and continue stirring at a stirring speed of 500 rpm until N-methylpyrrolidone is evaporated. Then, place the evaporated material into a 100°C vacuum oven for drying. 10h; Preparation of precursor;
S5、将S4制得的前驱体进行球磨，球磨转速为300rpm；球磨的时间为0.5h；球磨完成后过300目筛网(过筛网的目的是将球磨后依然团聚在一起的大颗粒材料剔除掉，若团聚在一起的材料较多，后续电极材料搅浆匀浆无法顺利进行)；S5. Ball-mill the precursor prepared in S4. The ball-milling speed is 300 rpm; the ball-milling time is 0.5 h; after the ball-milling is completed, pass it through a 300-mesh screen (the purpose of the screen is to remove the large particle materials that are still agglomerated after ball-milling) Remove them. If there are too many materials that are agglomerated together, the subsequent homogenization of the electrode material will not be carried out smoothly);
将过筛后的物料放入管式炉中在惰性气体(氮气气氛)中进行退火处理，退火温度135℃，时间1h；退火完成后即得到正极材料。Put the screened material into a tube furnace and perform annealing treatment in an inert gas (nitrogen atmosphere). The annealing temperature is 135°C and the time is 1 hour; after the annealing is completed, the cathode material is obtained.
实施例6Example 6
本实施例为一种正极材料及其制备方法。This embodiment is a cathode material and a preparation method thereof.
本实施例正极材料与实施例1的差异在于：将偏二氟乙烯-三氟乙烯共聚物层替换为偏二氟乙烯-四氟乙烯共聚物层。The difference between the positive electrode material of this embodiment and Embodiment 1 is that the vinylidene fluoride-trifluoroethylene copolymer layer is replaced by a vinylidene fluoride-tetrafluoroethylene copolymer layer.
本实施例正极材料与实施例1的差异在于：将偏二氟乙烯-三氟乙烯共聚物替换为偏二氟乙烯-四氟乙烯共聚物(添加量依据厚度进行折算)。The difference between the positive electrode material in this embodiment and Example 1 is that the vinylidene fluoride-trifluoroethylene copolymer is replaced by the vinylidene fluoride-tetrafluoroethylene copolymer (the amount added is converted based on the thickness).
实施例7Example 7
本实施例为一种正极材料及其制备方法。This embodiment is a cathode material and a preparation method thereof.
本实施例正极材料与实施例1的差异在于：将偏二氟乙烯-三氟乙烯共聚物层替换为偏二氟乙烯-三氟乙烯共聚物和偏二氟乙烯共聚物混合层(偏二氟乙烯-三氟乙烯共聚物和偏二氟乙烯共聚物的质量比为1:1)。The difference between the positive electrode material of this embodiment and Example 1 is that the vinylidene fluoride-trifluoroethylene copolymer layer is replaced with a vinylidene fluoride-trifluoroethylene copolymer and a vinylidene fluoride copolymer mixed layer (ylidene fluoride The mass ratio of ethylene-trifluoroethylene copolymer and vinylidene fluoride copolymer is 1:1).
本实施例正极材料与实施例1的差异在于：将步骤S2中偏二氟乙烯-三氟乙烯共聚物等量替换为偏二氟乙烯-三氟乙烯共聚物和偏二氟乙烯共聚物混合物(偏二氟乙烯-三氟乙烯共聚物和偏二氟乙烯共聚物的质量比为1:1)。The difference between the positive electrode material of this embodiment and Example 1 is that the vinylidene fluoride-trifluoroethylene copolymer in step S2 is replaced by equal amounts of a vinylidene fluoride-trifluoroethylene copolymer and a mixture of vinylidene fluoride copolymer ( The mass ratio of vinylidene fluoride-trifluoroethylene copolymer and vinylidene fluoride copolymer is 1:1).
对比例1Comparative example 1
本对比例为一种正极材料，该正极材料为Li 1.2Ni 0.35Co 0.05Mn 0.6O 2(D50为4μm)。 This comparative example is a cathode material, which is Li 1.2 Ni 0.35 Co 0.05 Mn 0.6 O 2 (D50 is 4 μm).
本对比例中正极材料的制备方法如下：The preparation method of the cathode material in this comparative example is as follows:
将锰基氢氧化物前驱体与(Li 2CO 3)经过充分混合后(前驱体和锂盐的摩尔比为1:0.6)，将混合物在900℃和氧气氛围下进行离子交换反应15h，最终得到锰基材料粉体；该前驱体Dv50为3μm，比表面积为12.3m 2/g，经过混锂及烧结后其锰基材料的Dv50为4μm，比表面积为1.12m 2/g。 After the manganese-based hydroxide precursor and (Li 2 CO 3 ) are thoroughly mixed (the molar ratio of the precursor to the lithium salt is 1:0.6), the mixture is subjected to an ion exchange reaction at 900°C and an oxygen atmosphere for 15 hours. Finally, Manganese-based material powder is obtained; the Dv50 of the precursor is 3 μm and the specific surface area is 12.3m 2 /g. After lithium mixing and sintering, the Dv50 of the manganese-based material is 4 μm and the specific surface area is 1.12m 2 /g.
测试例test case
将本发明实施例1～4和对比例1对应的正极材料进行电极制备及电池组装，从而进行性能测试(本发明实施方式中对应电池的性能测试重复3次取平均值)。The cathode materials corresponding to Examples 1 to 4 of the present invention and Comparative Example 1 were subjected to electrode preparation and battery assembly to perform performance testing (the performance test of the corresponding battery in the embodiment of the present invention was repeated three times to obtain an average value).
本测试例中电极制备的方法，由以下步骤组成：The electrode preparation method in this test example consists of the following steps:
将正极材料与超级炭黑(上海海逸科贸有限公司，特密高||型号：SUPER P Li)、聚偏氟乙烯(PVDF)按质量比为9:0.5:0.5的比例称取并充分混合(温度为20℃，混合速度为2000rpm,时间80min)，涂于铝箔上(涂覆厚度为200μm)，并放入100℃真空干燥5h，取出之后放入辊压机上滚压几次之后切出圆片，制得正极极片。Weigh the positive electrode material, super carbon black (Shanghai Haiyi Technology and Trade Co., Ltd., Special High || Model: SUPER P Li) and polyvinylidene fluoride (PVDF) in a mass ratio of 9:0.5:0.5 and fully Mix (temperature is 20℃, mixing speed is 2000rpm, time is 80min), apply on aluminum foil (coating thickness is 200μm), and put into 100℃ vacuum drying for 5h, take it out and put it into a roller press for several times. Cut out discs to prepare positive electrode sheets.
本测试例中电池的组装方法，由以下步骤组成：The battery assembly method in this test example consists of the following steps:
以金属锂片作为负极，聚丙烯微孔膜为隔膜，1mol/L的LiPF 6+EC/DMC/EMC为电解液和上述正极极片；在充满氩气、水分含量低于0.1ppm的手套箱内完成CR2430不锈钢扣式电池的组装；静置10h后测试其充放电性能。 Use metal lithium sheet as the negative electrode, polypropylene microporous membrane as the separator, 1mol/L LiPF 6 +EC/DMC/EMC as the electrolyte and the above-mentioned positive electrode sheet; in a glove box filled with argon and with a moisture content of less than 0.1ppm Complete the assembly of the CR2430 stainless steel button battery; test its charge and discharge performance after leaving it for 10 hours.
本实施例1制得的正极材料与对比例1对应的正极材料的XRD图如图1所示(01-085-1981对应(Li 0.65Ni 0.05)NiO 2的PDF卡片；01-084-1634对应Li 2MnO 3的PDF卡片) 。从图1中得知包覆前后的衍射峰几乎全部重合在一起，证明正极材料的晶体结构并没有发生明显改变。 The XRD patterns of the cathode material prepared in Example 1 and the cathode material corresponding to Comparative Example 1 are shown in Figure 1 (01-085-1981 corresponds to the PDF card of (Li 0.65 Ni 0.05 ) NiO 2 ; 01-084-1634 corresponds PDF card for Li 2 MnO 3 ) . It can be seen from Figure 1 that the diffraction peaks before and after coating almost all overlap, proving that the crystal structure of the cathode material has not changed significantly.
本发明实施例1对应的正极材料在电压为2.0V～4.8V和倍率为0.5C测试条件下，其初始放电比容量为231.4mA/g，循环50圈后仍有187.9mA/g的放电比容量，其容量保持率为81.2％。Under the test conditions of a voltage of 2.0V to 4.8V and a rate of 0.5C, the cathode material corresponding to Example 1 of the present invention has an initial discharge specific capacity of 231.4mA/g, and still has a discharge ratio of 187.9mA/g after 50 cycles. capacity, its capacity retention rate is 81.2%.
本发明实施例2对应的正极材料在电压为2.0V～4.8V和倍率为0.5C测试条件下，其初始放电比容量为230mAh/g，循环50圈之后放电比容量仍有185mAh/g，其容量保持率为80.4％。The cathode material corresponding to Example 2 of the present invention has an initial discharge specific capacity of 230mAh/g under the test conditions of a voltage of 2.0V to 4.8V and a rate of 0.5C. After 50 cycles, the discharge specific capacity is still 185mAh/g. The capacity retention rate is 80.4%.
本发明实施例3对应的正极材料在电压为2.0V～4.8V和倍率为0.5C测试条件下，其初始放电比容量为230mAh/g，循环50圈之后放电比容量仍有177mAh/g，其容量保持率为77％。The cathode material corresponding to Example 3 of the present invention has an initial discharge specific capacity of 230mAh/g under the test conditions of a voltage of 2.0V to 4.8V and a rate of 0.5C. After 50 cycles, the discharge specific capacity is still 177mAh/g. Capacity retention is 77%.
本发明实施例4对应的正极材料在电压为2.0V～4.8V和倍率为0.5C测试条件下，其初始放电比容量为204.1mAh/g，循环50圈之后放电比容量仍有185mAh/g，其容量保持率为83.7％。Under the test conditions of a voltage of 2.0V to 4.8V and a rate of 0.5C, the cathode material corresponding to Example 4 of the present invention has an initial discharge specific capacity of 204.1mAh/g, and the discharge specific capacity is still 185mAh/g after 50 cycles. Its capacity retention rate is 83.7%.
本发明对比例1对应的正极材料在电压为2.0V～4.8V和倍率为0.5C测试条件下，其初始放电比容量为231mAh/g，循环50圈之后放电比容量仍有172.3mAh/g，其容量保持率为74.6％。本发明实施例1、实施例3与对比例1对应的正极材料的循环放电曲线见图2。The cathode material corresponding to Comparative Example 1 of the present invention has an initial discharge specific capacity of 231mAh/g under the test conditions of a voltage of 2.0V to 4.8V and a rate of 0.5C. After 50 cycles, the discharge specific capacity is still 172.3mAh/g. Its capacity retention rate is 74.6%. The cyclic discharge curves of the cathode materials corresponding to Example 1, Example 3 and Comparative Example 1 of the present invention are shown in Figure 2.
表1本发明实施例1～4和对比例1对应的正极材料的性能对比结果Table 1 Performance comparison results of the cathode materials corresponding to Examples 1 to 4 of the present invention and Comparative Example 1
-- 实施例1Example 1 实施例2Example 2 实施例3Example 3 实施例4Example 4 对比例1Comparative example 1
包覆层厚度(nm)Coating layer thickness (nm) 6.46.4 6.56.5 11 1010 00
起始放电比容量(mAh/g)Initial discharge specific capacity (mAh/g) 231.4231.4 230230 230230 204.1204.1 231231
50圈循环后放电比容量(mAh/g)Discharge specific capacity after 50 cycles (mAh/g) 187.9187.9 185185 177177 185185 172.3172.3
容量保持率(50圈循环后)Capacity retention rate (after 50 cycles) 81.2％81.2% 80.4％80.4% 77％77% 83.7％83.7% 74.6％74.6%
本发明实施例1与实施例2的差异在于：包覆厚度、退火温度和退火时间存在差异；由表1中数据得知：在经过合适的退火温度及退火时间的耦合下，均能得到性能优异的包覆层，从而提升了抑制电解液分解的效果，使得正极材料的循环性能得到进一步提升。The difference between Embodiment 1 and Embodiment 2 of the present invention is that there are differences in coating thickness, annealing temperature and annealing time; from the data in Table 1, it can be known that under the coupling of appropriate annealing temperature and annealing time, performance can be obtained The excellent coating layer improves the effect of inhibiting the decomposition of the electrolyte, further improving the cycle performance of the cathode material.
本发明实施例2与实施例3的差异在于：实施例3中包覆层的厚度较薄；有机共聚物层 的厚度过薄不足以抵挡电解液的侵蚀，从而导致容量保持率出现下降。The difference between Embodiment 2 and Embodiment 3 of the present invention is that: in Embodiment 3, the thickness of the coating layer is thin; the thickness of the organic copolymer layer is too thin to resist the erosion of the electrolyte, resulting in a decrease in the capacity retention rate.
本发明实施例2与实施例4的差异在于：实施例4中包覆层的厚度较厚；有机共聚物层过厚会阻碍锂离子的传输；从而影响到初始放电容量。The difference between Embodiment 2 and Embodiment 4 of the present invention is that in Embodiment 4, the thickness of the coating layer is thicker; an excessively thick organic copolymer layer will hinder the transmission of lithium ions, thereby affecting the initial discharge capacity.
图3为本发明实施例3正极材料对应的电池(三组平行样)的循环放电曲线图，由图3得知：实施例3重复测试的平行样品重合度较高，且测试电池的循环一致性也较高，循环差异的确是涂层厚度带来的，并不是组装电池测试带来的差异。Figure 3 is a cyclic discharge curve diagram of the battery (three sets of parallel samples) corresponding to the positive electrode material in Example 3 of the present invention. It can be seen from Figure 3 that the overlap of the parallel samples tested repeatedly in Example 3 is relatively high, and the cycles of the test batteries are consistent. The performance is also high. The cycle difference is indeed caused by the coating thickness, not the difference caused by the assembled battery test.
图4为本实施例1与对比例1的对应正极材料的放电中值电压图。在电压为2.0V～4.8V和倍率为0.5C测试条件下，本实施例1的初始放电中值电压为3.83V，循环50圈后的放电中值电压为3.59V，50圈后与首圈的放电中值电压差0.24V。而对比例1的初始放电中值电压为3.825V，循环50圈后的放电中值电压为3.49V，50圈后与首圈的放电中值电压差0.335V。说明经过包覆的样品的平均放电中值电压下降程度减缓(一般认为该过程为层状结构想尖晶石型结构转化而导致)。故而，放电中值电压的数据从侧面证明了本发明实施例1通过包覆层，使得正极材料的层状结构向尖晶石结构转变的过程减缓。Figure 4 is a discharge median voltage diagram of the corresponding cathode materials of Example 1 and Comparative Example 1. Under the test conditions of a voltage of 2.0V to 4.8V and a rate of 0.5C, the initial discharge median voltage of Example 1 is 3.83V, and the discharge median voltage after 50 cycles is 3.59V. After 50 cycles, it is 3.59V. The discharge median voltage difference is 0.24V. The initial discharge median voltage of Comparative Example 1 is 3.825V, the discharge median voltage after 50 cycles is 3.49V, and the difference between the discharge median voltage after 50 cycles and the first cycle is 0.335V. This shows that the decrease in the average discharge median voltage of the coated sample slows down (it is generally believed that this process is caused by the transformation of the layered structure into a spinel-type structure). Therefore, the data of the discharge median voltage proves from the side that the coating layer in Example 1 of the present invention slows down the transformation process of the layered structure of the cathode material into a spinel structure.
本发明实施例5中有机共聚物层为聚偏二氟乙层烯层，经测试，其实施效果与实施例4相近(实施例4中性能相对较优)。The organic copolymer layer in Example 5 of the present invention is a polyvinylidene fluoride layer. After testing, its implementation effect is similar to that of Example 4 (the performance in Example 4 is relatively better).
本发明实施例6中有机共聚物层为偏二氟乙烯-四氟乙烯共聚物层，经测试，其实施效果与实施例1相近(实施例1中性能相对较优)。The organic copolymer layer in Example 6 of the present invention is a vinylidene fluoride-tetrafluoroethylene copolymer layer. After testing, its implementation effect is similar to that of Example 1 (the performance in Example 1 is relatively better).
本发明实施例7中有机共聚物层为偏二氟乙烯-三氟乙烯共聚物和聚偏二氟乙烯形成的均一混合物层，经测试，其实施效果与实施例1相近(实施例1中性能相对较优)。The organic copolymer layer in Example 7 of the present invention is a uniform mixture layer formed of vinylidene fluoride-trifluoroethylene copolymer and polyvinylidene fluoride. After testing, its implementation effect is similar to that of Example 1 (the performance in Example 1 relatively better).
在包覆相同厚度的情况下，偏二氟乙烯-三氟乙烯共聚物层的性能>偏二氟乙烯-四氟乙烯共聚物层>聚偏二氟乙烯层的性能，其原因在于：偏二氟乙烯-三氟乙烯共聚物的结晶性能最优，偏二氟乙烯-四氟乙烯共聚物的结晶性能略差，聚偏二氟乙烯在三者中性能最差，从而导致其正极材料的性能相对较差。In the case of coating with the same thickness, the performance of the vinylidene fluoride-trifluoroethylene copolymer layer is > the performance of the vinylidene fluoride-tetrafluoroethylene copolymer layer > the performance of the polyvinylidene fluoride layer. The reason is: Vinylidene fluoride-trifluoroethylene copolymer has the best crystallization properties, vinylidene fluoride-tetrafluoroethylene copolymer has slightly worse crystallization properties, and polyvinylidene fluoride has the worst performance among the three, resulting in poor performance of its cathode material Relatively poor.
本发明实施方式中的制备方法能够在材料表面形成厚度可控、均匀致密的包覆层；即本发明通过在锰基材料表面包覆一层均匀的有机共聚物高分子，这种均匀可控的包覆层能够使正极材料免于电解液的侵蚀，抑制电解液的分解，从而提升材料的结构稳定性和界面稳定性。The preparation method in the embodiment of the present invention can form a uniform and dense coating layer with controllable thickness on the surface of the material; that is, the present invention coats the surface of the manganese-based material with a uniform layer of organic copolymer polymer, which is uniform and controllable. The coating layer can protect the cathode material from the erosion of the electrolyte and inhibit the decomposition of the electrolyte, thus improving the structural stability and interface stability of the material.
本发明实施方式中有机共聚物高分子经过退火处理后，其结晶后具有优异的结构稳定性和更强的压电性。另外其功能团组(-C-F)能够吸引更多电子，使之具有高度的阳极稳定性，从而提高材料中锂离子的含量，能够加快锂离子在电极/电解液界面处的扩散和电荷转移过程，提高富锂锰基正极材料的导电性能。After the organic copolymer polymer in the embodiment of the present invention is annealed, it has excellent structural stability and stronger piezoelectricity after crystallization. In addition, its functional group (-C-F) can attract more electrons, giving it a high degree of anode stability, thereby increasing the lithium ion content in the material and accelerating the diffusion and charge transfer process of lithium ions at the electrode/electrolyte interface. , improve the conductive properties of lithium-rich manganese-based cathode materials.
本发明实施方式中还设计了一种低成本，易实现的改性方法，能够显著提升锰基材料的 电化学性能，具有良好的应用前景。综上所述，本发明的制备方法能够在材料表面形成厚度可控、均匀致密的包覆层。通过将有机共聚物包覆物溶解在溶剂中，混合均匀后去除溶剂，从而使得包覆物能够均匀分布在正极材料上面；从而制得循环性能优异的正极材料。In the embodiment of the present invention, a low-cost and easy-to-implement modification method is also designed, which can significantly improve the electrochemical performance of manganese-based materials and has good application prospects. In summary, the preparation method of the present invention can form a coating layer with controllable thickness, uniformity and density on the surface of the material. By dissolving the organic copolymer coating in a solvent, mixing it evenly, and then removing the solvent, the coating can be evenly distributed on the cathode material; thereby producing a cathode material with excellent cycle performance.
上面结合具体实施方式对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。The embodiments of the present invention have been described in detail above in conjunction with specific implementation modes. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those of ordinary skill in the art, various modifications can be made without departing from the purpose of the present invention. kind of change. In addition, the embodiments of the present invention and the features in the embodiments may be combined with each other without conflict.

Claims (10)

  1. 一种正极材料，其特征在于：包括内核，所述内核表面包覆有机共聚物层；所述内核为锰基材料；A cathode material, characterized by: including a core, the surface of which is coated with an organic copolymer layer; the core is a manganese-based material;
    所述锰基材料的化学式为Li 1+xNi yCo zMn 1-y-zO 2；其中0＜x≤1，0≤y＜1，0≤z＜1，y+z＜1； The chemical formula of the manganese-based material is Li 1+x Ni y Co z Mn 1-yz O 2 ; where 0<x≤1, 0≤y<1, 0≤z<1, y+z<1;
    所述有机共聚物层的厚度为1nm～10nm。The thickness of the organic copolymer layer is 1 nm to 10 nm.
  2. 根据权利要求1所述的正极材料，其特征在于：所述锰基材料的D50为1μm～15μm。The cathode material according to claim 1, wherein the D50 of the manganese-based material is 1 μm to 15 μm.
  3. 根据权利要求1所述的正极材料，其特征在于：所述有机共聚物层为聚偏二氟乙烯层、偏二氟乙烯-三氟乙烯共聚物层、偏二氟乙烯-四氟乙烯共聚物层中的至少一种。The cathode material according to claim 1, characterized in that: the organic copolymer layer is a polyvinylidene fluoride layer, a vinylidene fluoride-trifluoroethylene copolymer layer, or a vinylidene fluoride-tetrafluoroethylene copolymer. at least one of the layers.
  4. 一种制备如权利要求1至3中任一项所述的正极材料的方法，其特征在于：包括以下步骤：将有机共聚物分散液和所述锰基材料混合后干燥、球磨后退火。A method for preparing the cathode material according to any one of claims 1 to 3, characterized by comprising the following steps: mixing the organic copolymer dispersion and the manganese-based material, drying, ball milling and then annealing.
  5. 根据权利要求4所述的方法，其特征在于：所述干燥的温度为60℃～100℃。The method according to claim 4, characterized in that: the drying temperature is 60°C to 100°C.
  6. 根据权利要求4所述的方法，其特征在于：所述球磨的转速为200rpm～300rpm。The method according to claim 4, characterized in that: the rotation speed of the ball mill is 200rpm to 300rpm.
  7. 根据权利要求4所述的方法，其特征在于：所述退火的温度为135℃～155℃。The method according to claim 4, characterized in that the annealing temperature is 135°C to 155°C.
  8. 根据权利要求4至7中任一项所述的方法，其特征在于：所述退火在保护性气氛下进行。The method according to any one of claims 4 to 7, characterized in that the annealing is performed under a protective atmosphere.
  9. 根据权利要求8所述的方法，其特征在于：所述退火的时间为2h～6h。The method according to claim 8, characterized in that: the annealing time is 2h to 6h.
  10. 权利要求1至3中任一项所述的正极材料在制备锂离子电池中的应用。Application of the cathode material according to any one of claims 1 to 3 in the preparation of lithium ion batteries.
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Publication number Priority date Publication date Assignee Title
CN115036500A (en) * 2022-06-24 2022-09-09 广东邦普循环科技有限公司 Cathode material and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1290047A (en) * 1999-09-25 2001-04-04 默克专利股份有限公司 Lithium coated mixed oxide paticles and use thereof
JP2013143304A (en) * 2012-01-11 2013-07-22 Toyota Motor Corp Method of manufacturing electrode for battery and electrode for battery
CN106058192A (en) * 2016-07-20 2016-10-26 南京航空航天大学 Coated modified lithium ion battery layered cathode material and preparation method thereof
CN106848241A (en) * 2017-02-27 2017-06-13 苏州大学 A kind of preparation method of polymer overmold lithium ion battery electrode material
CN112820873A (en) * 2020-12-31 2021-05-18 深圳市德方纳米科技股份有限公司 Polymer-coated lithium battery positive electrode material and preparation method thereof
CN115036500A (en) * 2022-06-24 2022-09-09 广东邦普循环科技有限公司 Cathode material and preparation method and application thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103219506B (en) * 2012-01-18 2015-09-02 比亚迪股份有限公司 A kind of anode material for lithium-ion batteries and preparation method thereof and a kind of lithium ion battery
CN108649186B (en) * 2018-05-04 2021-06-22 苏州清陶新能源科技有限公司 Preparation method and application of composite positive plate rich in lithium-rich manganese base
CN109286013A (en) * 2018-11-16 2019-01-29 华南师范大学 A kind of lithium ion battery high pressure lithium-rich manganese-based anode material and its coating modification methods and applications coating polyamide organic matter layer

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1290047A (en) * 1999-09-25 2001-04-04 默克专利股份有限公司 Lithium coated mixed oxide paticles and use thereof
JP2013143304A (en) * 2012-01-11 2013-07-22 Toyota Motor Corp Method of manufacturing electrode for battery and electrode for battery
CN106058192A (en) * 2016-07-20 2016-10-26 南京航空航天大学 Coated modified lithium ion battery layered cathode material and preparation method thereof
CN106848241A (en) * 2017-02-27 2017-06-13 苏州大学 A kind of preparation method of polymer overmold lithium ion battery electrode material
CN112820873A (en) * 2020-12-31 2021-05-18 深圳市德方纳米科技股份有限公司 Polymer-coated lithium battery positive electrode material and preparation method thereof
CN115036500A (en) * 2022-06-24 2022-09-09 广东邦普循环科技有限公司 Cathode material and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KONG JI-ZHOU; XU LI-PENG; WANG CHUN-LEI; JIANG YOU-XUAN; CAO YAN-QIANG; ZHOU FEI: "Facile coating of conductive poly(vinylidene fluoride-trifluoroethylene) copolymer on Li1.2Mn0.54Ni0.13Co0.13O2as a high electrochemical performance cathode for Li-ion battery", JOURNAL OF ALLOYS AND COMPOUNDS, ELSEVIER SEQUOIA, LAUSANNE., CH, vol. 719, 20 May 2017 (2017-05-20), CH , pages 401 - 410, XP085067014, ISSN: 0925-8388, DOI: 10.1016/j.jallcom.2017.05.184 *

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