WO2024197861A1 - 一种电池正极材料及其处理方法和电池 - Google Patents

一种电池正极材料及其处理方法和电池 Download PDF

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WO2024197861A1
WO2024197861A1 PCT/CN2023/085616 CN2023085616W WO2024197861A1 WO 2024197861 A1 WO2024197861 A1 WO 2024197861A1 CN 2023085616 W CN2023085616 W CN 2023085616W WO 2024197861 A1 WO2024197861 A1 WO 2024197861A1
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positive electrode
electrode material
battery
cold plasma
carbon layer
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French (fr)
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梁风
东鹏
张达
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Priority to CN202380008984.5A priority Critical patent/CN118974974A/zh
Priority to EP23761743.6A priority patent/EP4462515B1/en
Priority to PCT/CN2023/085616 priority patent/WO2024197861A1/zh
Priority to JP2023090284A priority patent/JP7515924B1/ja
Priority to US18/346,970 priority patent/US20240332495A1/en
Publication of WO2024197861A1 publication Critical patent/WO2024197861A1/zh
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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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the field of battery materials, and more particularly to a battery positive electrode material and a processing method thereof and a battery.
  • lithium-ion or sodium-ion batteries are generally considered to be one of the most promising candidate batteries for large-scale energy storage applications.
  • the currently known positive electrode materials all have the bottleneck of slow lithium/sodium ion diffusion rate, the energy and power density of lithium-ion or sodium-ion batteries are low, and high-performance positive electrode materials can improve the energy density, cycle life and rate capability of lithium-ion or sodium-ion batteries. Therefore, it is particularly important to develop high-performance positive electrode materials.
  • one of the purposes of the present invention is to solve one or more problems in the prior art.
  • one of the purposes of the present invention is to provide a treatment method that can enhance the surface energy of the positive electrode particles of the battery and improve the interfacial affinity between the positive electrode particles and the electrolyte.
  • one aspect of the present invention provides a method for processing battery positive electrode materials, which may include the following steps: subjecting the battery positive electrode material having a carbon layer on at least a portion of its surface to be treated to cold plasma treatment to dope the carbon layer with active particles, wherein the active particle doping amount is not less than 50 ppm (molar fraction or volume fraction, parts per billion, ppm).
  • the power of the cold plasma treatment may be 100W to 500W.
  • the voltage of the cold plasma treatment may be 50V to 150V, and the treatment current may be 0.4A to 2A.
  • the cold plasma treatment time may be 1 min to 60 min.
  • the discharge for generating cold plasma may be selected from one or a combination of radio frequency plasma discharge, corona discharge, dielectric barrier discharge and sliding arc discharge.
  • the doping may be oxygen doping, nitrogen doping or a combination thereof.
  • cold plasma treatment may include inputting one or a combination of precursor gases of oxygen and nitrogen into a cold plasma generator to generate active particles for doping the carbon layer, wherein the precursor gas flow rate may be 1 ml/s to 15 ml/s.
  • the positive electrode material of the battery may be a polyanionic compound, a layered oxide, a spinel compound, Prussian blue or a positive electrode material of a ternary lithium battery.
  • the positive electrode material of the battery may be sodium vanadium phosphate, lithium iron phosphate, sodium titanium phosphate, sodium fluoride phosphate, LiMO 2 , NaMO 2 , LiN 2 O 4 , lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminum oxide, wherein M may be Co, Ni, Mn, V or Fe, and N may be Co, Nix, Mn or V.
  • At least a portion of the surface of the positive electrode material of the battery after doping has a rod-like morphology.
  • the average length of the rod-like morphology may be 1.5 ⁇ m to 3 ⁇ m.
  • a NaF layer is formed on at least a portion of the surface of the cathode material of the battery after doping, and the average thickness of the NaF layer may be 6 nm to 10 nm.
  • the content of the NaF layer is not less than 500 ppm.
  • Another aspect of the present invention provides a battery positive electrode material, at least a portion of its surface contains a carbon layer and at least a portion of the surface has a rod-like morphology, wherein the carbon layer is a carbon layer doped with active particles after cold plasma treatment; the doping amount is not less than 50ppm.
  • the active particles may be oxygen, nitrogen or a combination thereof.
  • the average length of the rod-like morphology is 1.5 ⁇ m to 3 ⁇ m.
  • a positive electrode sheet which may include the positive electrode material processed by the above method for processing the battery positive electrode material or the above battery positive electrode material.
  • Another aspect of the present invention provides a battery, which may include the positive electrode sheet described above.
  • the beneficial effects of the present invention include at least one of the following:
  • the treatment method of the present invention can enhance the surface energy of the battery positive electrode material particles, improve their interfacial affinity with the electrolyte, and obtain a positive electrode material with uniform texture, low porosity, high ionic conductivity and electronic conductivity.
  • the positive electrode material of the present invention has high electronic conductivity, good interfacial compatibility with the electrolyte, and a "rod-like" surface morphology, which makes the interface contact between the battery positive electrode material and the current collector have good stability and can improve the rate of sodium ion transmission and electronic conductivity.
  • the treatment method of the present invention can produce a NaF layer on the surface of the battery positive electrode material.
  • the layer has ultra-high sodium ion conductivity, limits the occurrence of side reactions between the positive electrode material and the electrolyte, and increases the transmission rate of sodium ions at the solid-liquid interface.
  • the lithium-ion batteries and sodium-ion batteries prepared using the battery positive electrode materials treated by the present invention have high energy density, cycle life and rate capability.
  • the treatment method of the present invention has a simple process flow, low energy consumption, small equipment investment, no generation of "three wastes", is environmentally friendly, and is suitable for large-scale production applications.
  • FIG. 1 shows a comparison diagram of XRD (X-ray diffraction, XRD) of the sodium vanadium phosphate positive electrode material before and after treatment in Example 1.
  • Figure 2 shows a comparison chart of the XPS (X-ray photoelectron spectroscopy, XPS) of the sodium vanadium phosphate positive electrode material before and after treatment in Example 1.
  • XPS X-ray photoelectron spectroscopy
  • Figure 3 shows the SEM (scanning electron microscope, SEM) image of the untreated sodium vanadium phosphate positive electrode material in Example 2.
  • FIG. 4 shows a SEM image of the sodium vanadium phosphate positive electrode material after treatment in Example 2.
  • FIG. 5 shows a voltage-capacity graph of the battery in Example 2.
  • FIG. 6 shows the contact angle of the untreated sodium vanadium phosphate positive electrode material to the electrolyte in Example 3.
  • FIG. 7 shows the contact angle of the sodium vanadium phosphate positive electrode material after treatment in Example 3 to the electrolyte.
  • FIG. 8 shows the EIS (Electrochemical Impedance Spectroscopy, EIS) graph of the sodium vanadium phosphate positive electrode material after treatment in Example 3.
  • EIS Electrochemical Impedance Spectroscopy
  • FIG. 9 shows the XPS of the untreated sodium vanadium phosphate positive electrode material in Example 4.
  • FIG. 10 shows the XPS of the sodium vanadium phosphate positive electrode material after treatment in Example 4.
  • FIG. 12 shows a long cycle diagram of sodium vanadium phosphate after treatment in Example 6.
  • FIG. 13 shows a voltage-capacity graph of the battery in Example 8.
  • FIG. 14 shows a long cycle diagram of lithium iron phosphate after treatment in Example 8.
  • FIG. 15 shows EIS graphs of lithium iron phosphate before and after treatment in Example 9.
  • One aspect of the present invention provides a method for processing a positive electrode material of a battery, which may include the following steps: subjecting a positive electrode material of a battery having a carbon layer on at least a portion of its surface to be processed to cold plasma treatment to dope the carbon layer, wherein the doping amount is not less than 50 ppm.
  • the positive electrode material of the battery is doped with highly active particles generated by cold plasma on the carbon layer attached to or coated on the surface of the positive electrode material, which can form more defects on the surface of the carbon layer, improve the stability of the interface contact between the positive electrode material and the current collector, thereby increasing the rate of sodium ion or lithium ion transmission and electronic conductivity.
  • it will also increase the affinity between the positive electrode material and the electrolyte, alleviate the serious volume effect caused by the large radius of sodium ions or lithium ions, and make the active material have good structural stability during long cycles.
  • batteries using treated positive electrode materials have lower polarization voltage, lower interface impedance, more stable charge and discharge platform and higher specific capacity.
  • the battery positive electrode material to be processed indicates that at least a portion has a carbon layer to achieve doping of the carbon layer.
  • the carbon layer can be fully coated or partially coated on the surface of the positive electrode material to be processed. That is, the carbon layer described herein can form all or only a portion of the surface of the positive electrode material, and in some embodiments, the carbon layer can be one or more layers, for example, the carbon layer can be 2 layers, or 3 layers, or 4 layers, or more than 5 layers, or more than 6 layers. It should be understood that the surface of the positive electrode material may not only contain a carbon layer, but also contain other coating layers or adhesion layers on the surface of the positive electrode material that can improve the performance of the positive electrode material.
  • the doping amount may affect the electronic conductivity of the carbon layer on the surface of the positive electrode material. If the doping amount is less than 50 ppm, the electronic conductivity of the carbon layer on the surface of the positive electrode material is not significantly improved. Therefore, the doping amount may be not less than 50 ppm, not less than 70 ppm, not less than 85 ppm, not less than 105 ppm, Not less than 123ppm, not less than 152ppm, or 160ppm to 246ppmm, or 214ppm to 318ppmm, or 259ppm to 413ppmm, or 586ppm to 793ppmm, or 803ppm to 1050ppm. In addition, a doping amount greater than 600ppm may cause damage to the surface carbon layer and reduce the cycle stability of the active particles. Therefore, preferably, the doping amount is between 50ppm and 600ppm.
  • the thickness of the positive electrode material to be treated can be adjusted, as described herein, any thickness of the positive electrode material can be treated with the treatment method herein.
  • the thickness of the positive electrode material to be treated can be 30 ⁇ m to 100 ⁇ m, for example, the thickness can be less than 28 ⁇ m or greater than 110 ⁇ m, or 15 ⁇ m, or 45 ⁇ m, or 84 ⁇ m, or 141 ⁇ m.
  • the power of the cold plasma treatment can be 100W to 500W. In the range of 100W to 500W, doping can be achieved while ensuring the stability of the carbon layer on the surface of the positive electrode material. If the power is lower than 100W, the energy to break the carbon-carbon bond will not be reached, so that the active particles cannot be doped; if the energy is higher than 500W, the carbon layer structure on the surface of the positive electrode material will be destroyed, resulting in a decrease in its electrochemical performance. And within this power range, the positive electrode material can obtain a high surface energy and improve the affinity with the electrolyte interface.
  • the generation of cold plasma can be the active particles generated by transporting a gas source such as oxygen, nitrogen or a mixed gas to a cold plasma generator.
  • the power is the power directly acting on the precursor gas, that is, the power directly received by the gas source.
  • the power of the cold plasma treatment can be not less than 150W, or not less than 245W, or not less than 289W, or not less than 423W.
  • the voltage of the cold plasma treatment can be 50V to 150V, and the treatment current can be 0.4A to 2A. Applying the voltage and current within the above range can make the power of the cold plasma treatment reach 100W to 500W, which can break the carbon-carbon bond while ensuring the stability of the carbon layer on the surface of the positive electrode material. It should be understood in the art that the voltage and current here are the voltage and current applied to the cold plasma generator. In certain embodiments, the voltage of the cold plasma treatment can be not less than 60V, or not less than 72V, or not less than 83V, or not less than 114V, or not less than 127V, or not less than 142V or a combination of the above ranges.
  • the current of the cold plasma treatment can be 0.5A to 1.8A, 0.7A to 1.6A, 0.9A to 1.4A, 1.1A to 1.3A or a combination of the above ranges.
  • the surface of the positive electrode material can have a rod-like morphology (rod-like structure), so that the positive electrode material has the properties described herein.
  • the cold plasma treatment time can be 1 min to 60 min.
  • the treatment voltage and treatment current applied in coordination can ensure that the carbon layer on the surface of the positive electrode material is doped to a doping amount of more than 50 ppm.
  • the treatment time It can be not less than 2 minutes, not less than 15 minutes, not less than 23 minutes, not less than 38 minutes, not less than 47 minutes, not less than 52 minutes.
  • the treatment time of cold plasma can be greater than about 30 seconds, or greater than about 45 seconds. However, it should be understood that the treatment time can be adjusted arbitrarily while achieving the doping amount described herein.
  • the content of NaF produced will affect the electrochemical properties of the electrode surface. If the content of NaF is less than 50ppm, the ionic conductivity of the positive electrode material surface is not significantly improved. Therefore, the content of NaF is not less than 50ppm, not less than 70ppm, not less than 85ppm, not less than 105ppm, not less than 123ppm, not less than 152ppm, or 160ppm-246ppmm, or 214ppm-318ppmm, or 259ppm-413ppmm, or 586ppm-793ppmm, or 803ppm-1050ppm. In addition, a doping amount greater than 50ppm may cause damage to the electrode surface binder and reduce the bonding force between the active substances. Therefore, preferably, the doping amount is between 50ppm and 500ppm.
  • the discharge for generating cold plasma is selected from one or a combination of radio frequency plasma discharge (RF), corona discharge (CD), dielectric barrier discharge (DBD) and glide arc discharge (GAD).
  • RF radio frequency plasma discharge
  • CD corona discharge
  • DBD dielectric barrier discharge
  • GID glide arc discharge
  • the above-mentioned cold plasma equipment can discharge stably under high pressure, is simple to operate and can form a large area of plasma discharge area, so that the active particles in the discharge area have a larger range of action, which provides a basis for efficient doping treatment.
  • any other discharge suitable for generating cold plasma is also suitable for the treatment method described herein.
  • the doped active particles or doped active materials may be one or a combination of oxygen doping and nitrogen doping.
  • it may be independent oxygen doping, nitrogen doping or oxygen-nitrogen doping.
  • Doping the carbon layer with highly active particles generated by cold plasma can enable the positive electrode material to obtain better electrochemical properties.
  • the doping of the above-mentioned active particles may include inputting one or a combination of precursor gases of oxygen and nitrogen into a cold plasma generator to generate active particles and then doping the carbon layer on the surface of the positive electrode material.
  • the doping of active particles can also be achieved by other forms of cold plasma generators.
  • the flow rate of the precursor gas introduced into the cold plasma generator can be 1 ml/s to 15 ml/s.
  • the voltage and current applied in coordination can ensure the realization of carbon layer doping.
  • the positive electrode material to be treated can be placed in the cold plasma generator, and the precursor gas can be introduced at the rate described herein, and the cold plasma generator can be adjusted to The positive electrode material to be treated can be treated by the voltage and current described in this article.
  • oxygen doping when oxygen doping is achieved, oxygen doping needs to be completed in a short time under an oxygen atmosphere to ensure that little oxidation occurs while introducing oxygen-containing functional groups, and to avoid oxidation caused by too long a time or too high a power.
  • oxygen-containing mixed gases the oxidation effect can be ignored due to the low oxygen content.
  • the treated positive electrode material described herein has different morphological characteristics compared to the existing positive electrode material.
  • the positive electrode material By treating the positive electrode material, at least a portion of the surface of the positive electrode material has a rod-like morphology.
  • the sodium vanadium phosphate positive electrode material after being treated by the treatment method described herein, a large number of rod-like structures or rod-like structures or sheet-like structures will appear on its surface.
  • the entire surface of the positive electrode material has a rod-like morphology, or at least 0.01% of the surface area coverage has a rod-like morphology, or at least 0.1% of the surface area has a rod-like morphology, or at least 5% of the surface area has a rod-like morphology, or at least 9.8% of the surface area has a rod-like morphology, or at least 15.3% of the surface area has a rod-like morphology, or at least 21.5% of the surface area has a rod-like morphology, or at least 35.4% of the surface area has a rod-like morphology, or at least 41.2% of the surface area has a rod-like morphology, or at least 49.8% of the surface area has a rod-like morphology, or at least 55.1% of the surface area has a rod-like morphology, or at least 61.5% of the surface area has a rod-like morphology, or at least 73.5% of the surface area has a
  • the stability of the positive electrode material and the current collector interface contact can be improved, thereby increasing the rate of sodium ion transmission and electronic conductivity.
  • the rod-like shape described herein refers to an elongated form or presents an elongated structure, and can also be described as a columnar shape, etc.
  • the rod-like morphology may have a specific length, that is, the average length of the rod-like morphology may be not less than 1.6 ⁇ m, not less than 2.1 ⁇ m, not less than 2.4 ⁇ m, not less than 2.6 ⁇ m, not less than 2.8 ⁇ m, not less than 2.9 ⁇ m.
  • the rod-like morphology may have a specific diameter (i.e., the radial diameter of the rod), that is, the average diameter of the rod-like morphology may be not less than 154 nm, not less than 167 nm, not less than 179 nm, not less than 189 nm, not less than 208 nm, not less than 238 nm, not less than 268 nm, not less than 294 nm, not less than 283 nm.
  • the average diameter of the rod-like morphology may be not less than 154 nm, not less than 167 nm, not less than 179 nm, not less than 189 nm, not less than 208 nm, not less than 238 nm, not less than 268 nm, not less than 294 nm, not less than 283 nm.
  • the mass ratio of the rod-shaped material to the positive electrode material can be specific.
  • the mass ratio of the rod-shaped material to the positive electrode material can be 2% to 10%.
  • the mass ratio of the rod-shaped material to the positive electrode material can be not less than 0.5%, or not less than 0.8%, or not less than 1.5%, or not less than 2.7%, or not less than 3.4%, or not less than 4.7%, or not less than 5.9%, or not less than 6.7%, or not less than 9.4%.
  • the mass proportion is not less than 15.8%, not less than 20.1%, not less than 30.5%, or not less than 36.8%.
  • the positive electrode material of the battery can be a polyanionic compound, a layered oxide, a spinel compound, Prussian blue or a ternary lithium battery positive electrode material.
  • the polyanionic compound can include sodium vanadium phosphate, lithium iron phosphate, sodium titanium phosphate and sodium fluoride phosphate.
  • the layered oxide can include LiMO 2 and NaMO 2 , wherein M can be Co, Ni, Mn, V or Fe.
  • the spinel compound can include LiN 2 O 4 , wherein N can be Co, Nix, Mn or V.
  • the positive electrode material of the ternary lithium battery can be lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminum oxide. It should be understood that the treatment method described herein can also treat some other positive electrode materials.
  • the positive electrode material can be obtained by the method for treating a positive electrode material for a battery described herein.
  • at least a portion of the surface of the positive electrode material contains a carbon layer and at least a portion of the surface has a rod-like morphology, wherein the carbon layer is a carbon layer doped with active particles after cold plasma treatment.
  • the doping level may be no less than 50 ppm.
  • the active species is one of oxygen, nitrogen, or a combination thereof.
  • the rod-like morphology may have an average length of 1.5 ⁇ m to 3 ⁇ m and an average diameter of 150 nm to 300 nm.
  • the mass ratio of the rod-shaped material may be specific.
  • the mass ratio of the rod-shaped material to the positive electrode material may be 2% to 10%.
  • a positive electrode sheet comprising a current collector and a positive electrode material layer disposed on the current collector, wherein the positive electrode material comprises a positive electrode material treated by the method for treating a positive electrode material of a battery as described above or comprises a positive electrode material as described above.
  • the positive electrode material layer may also include a conductive agent and a binder. The positive electrode material layer may be introduced into the positive electrode sheet by methods known in the art.
  • Another aspect of the present invention provides a battery, in particular a sodium ion battery, comprising the positive electrode sheet as described above. It should be understood that the battery also comprises some other essential components constituting the battery, and the assembly method of the battery is known in the art.
  • Step 1 preparation of sodium vanadium phosphate positive electrode material: using a conventional coating process, using aluminum foil to coat the cut pieces to obtain a sodium vanadium phosphate positive electrode material with a thickness of 80 ⁇ m.
  • Step 2 nitrogen DBD cold plasma activation treatment: first, coat the sodium vanadium phosphate positive electrode material in step (1) with one side having the active material, and perform nitrogen DBD cold plasma activation treatment for 1 min at a gas flow rate of 10 ml/s, a working current of 1 A, and a voltage of 150 V under nitrogen DBD cold plasma, and cool to room temperature to obtain the activated sodium vanadium phosphate positive electrode material.
  • Step 3 assembly of button cells: put the sodium vanadium phosphate positive electrode material after activation treatment in step (2) into the glove box, assemble the button cells, and test the cells after standing for 12 hours.
  • the sodium vanadium phosphate positive electrode material obtained after nitrogen DBD cold plasma activation treatment was physically characterized. It can be seen from the XRD diagram of the sodium vanadium phosphate positive electrode material in Figure 1 that the physical properties of the sodium vanadium phosphate positive electrode material after nitrogen DBD cold plasma activation treatment (DBD-1min in the figure) are not changed compared with those without treatment (DBD-0min in the figure), indicating that nitrogen DBD cold plasma treatment will not destroy the crystal structure of sodium vanadium phosphate. It can be seen from the XPS diagram of the sodium vanadium phosphate positive electrode material in Figure 2 that, compared with the electrode sheet that has not undergone nitrogen DBD-0min, a NaF layer will be produced after nitrogen DBD-1min treatment.
  • a method for processing a positive electrode material of a battery comprising the following steps:
  • Step 1 preparation of sodium vanadium phosphate positive electrode material: using a conventional coating process, using aluminum foil to coat the cut pieces to obtain a sodium vanadium phosphate positive electrode material with a thickness of 80 ⁇ m.
  • Step 2 nitrogen DBD cold plasma activation treatment: first, coat the sodium vanadium phosphate positive electrode material in step (1) with one side having the active material, and perform nitrogen DBD cold plasma activation treatment for 2 minutes at a gas flow rate of 10 ml/s, a working current of 1 A, and a voltage of 150 V under nitrogen DBD cold plasma, and cool to room temperature to obtain the activated sodium vanadium phosphate positive electrode material.
  • Step 3 assembly of button cells: Place the sodium vanadium phosphate positive electrode material after the activation treatment in step (2) into a glove box, assemble button cells, and conduct battery testing after standing for 12 hours.
  • a method for processing a positive electrode material of a battery comprising the following steps:
  • Step 1 preparation of sodium vanadium phosphate positive electrode material: using a conventional coating process, using aluminum foil to coat the cut pieces to obtain a sodium vanadium phosphate positive electrode material with a thickness of 80 ⁇ m.
  • Step 2 nitrogen DBD cold plasma activation treatment: first, coat the sodium vanadium phosphate positive electrode material in step (1) on one side with the active material, perform nitrogen DBD cold plasma activation treatment for 4 minutes at a gas flow rate of 10 ml/s, a working current of 1 A, and a voltage of 150 V under nitrogen DBD cold plasma, and cool to room temperature to obtain the activated sodium vanadium phosphate positive electrode material.
  • Step 3 assembly of button cells: placing the activated sodium vanadium phosphate positive electrode material into a glove box, assembling button cells, and conducting battery testing after standing for 12 hours.
  • a method for processing a positive electrode material of a battery comprising the following steps:
  • Step 1 preparation of sodium vanadium phosphate positive electrode material: using a conventional coating process, using aluminum foil to coat the cut pieces to obtain a sodium vanadium phosphate positive electrode material with a thickness of 80 ⁇ m.
  • Step 2 nitrogen DBD cold plasma activation treatment: first, coat the sodium vanadium phosphate positive electrode material in step (1) on one side with the active material, perform nitrogen DBD cold plasma activation treatment for 6 minutes at a gas flow rate of 10 ml/s, a working current of 1 A, and a voltage of 150 V under nitrogen DBD cold plasma, and cool to room temperature to obtain the activated sodium vanadium phosphate positive electrode material.
  • Step 3 assembly of button cells: Place the sodium vanadium phosphate positive electrode material after the activation treatment in step (2) into a glove box, assemble button cells, and conduct battery testing after standing for 12 hours.
  • a method for processing a positive electrode material of a battery comprising the following steps:
  • Step 1 preparation of sodium vanadium phosphate positive electrode material: using a conventional coating process, using aluminum foil to coat the cut pieces to obtain a sodium vanadium phosphate positive electrode material with a thickness of 80 ⁇ m.
  • Step 2 oxygen RF cold plasma activation treatment: first, coat the sodium vanadium phosphate positive electrode material in step (1) with one side having the active material, and perform oxygen RF cold plasma activation treatment for 6 minutes at a gas flow rate of 10 ml/s, a working current of 1 A, and a voltage of 100 V under oxygen RF cold plasma, and cool to room temperature to obtain the activated sodium vanadium phosphate positive electrode material.
  • Step 3 assembly of button cells: Place the activated sodium vanadium phosphate positive electrode material described in step (2) into a glove box, assemble button cells, and perform battery testing after standing for 12 hours.
  • a method for processing a positive electrode material of a battery comprising the following steps:
  • Step 1 preparation of sodium vanadium phosphate positive electrode material: using a conventional coating process, using aluminum foil to coat the cut pieces to obtain a sodium vanadium phosphate positive electrode material with a thickness of 80 ⁇ m.
  • Step 2 nitrogen-oxygen mixed gas CD cold plasma activation treatment: first, coat the sodium vanadium phosphate positive electrode material in step (1) with one side having the active material, and perform nitrogen-oxygen mixed gas CD cold plasma activation treatment for 4 minutes at a gas flow rate of 10 ml/s, a working current of 2 A, and a voltage of 100 V under nitrogen-oxygen mixed gas CD cold plasma, and cool to room temperature to obtain an activated sodium vanadium phosphate positive electrode material.
  • Step 3 assembly of button cells: Place the activated sodium vanadium phosphate positive electrode material described in step (2) into a glove box and assemble button cells. All batteries must be left to stand for 12 hours before testing.
  • a method for processing a positive electrode material of a battery comprising the following steps:
  • Step 1 preparation of sodium vanadium phosphate positive electrode material: using a conventional coating process, using aluminum foil to coat the cut pieces to obtain a sodium vanadium phosphate positive electrode material with a thickness of 80 ⁇ m.
  • Step 2 oxygen CD cold plasma activation treatment: first, coat the sodium vanadium phosphate positive electrode material in step (1) with one side having the active material, and perform oxygen CD cold plasma activation treatment for 4 minutes at a gas flow rate of 10 ml/s, a working current of 2 A, and a voltage of 100 V under oxygen CD cold plasma, and cool to room temperature to obtain an activated sodium vanadium phosphate positive electrode material.
  • Step 3 assembly of button cells: Place the activated sodium vanadium phosphate positive electrode material described in step (2) into a glove box and assemble button cells. All batteries must be left to stand for 12 hours before testing.
  • a method for treating a positive electrode material comprising the following steps:
  • Step 1 preparation of lithium iron phosphate positive electrode material: using a conventional coating process, aluminum foil is used to coat the cut pieces to obtain a lithium iron phosphate positive electrode material with a thickness of 80 ⁇ m.
  • Step 2 nitrogen DBD cold plasma activation treatment: first, coat the lithium iron phosphate positive electrode material in step (1) on one side with the active material, perform nitrogen DBD cold plasma activation treatment for 4 minutes at a gas flow rate of 10 ml/s, a working current of 4 A, and a voltage of 100 V under nitrogen DBD cold plasma, and cool to room temperature to obtain an activated lithium iron phosphate positive electrode material.
  • Step 3 assembly of button cells: Place the activated lithium iron phosphate positive electrode material described in step (2) into a glove box and assemble button cells. All batteries must be left to stand for 12 hours before testing.
  • a method for processing lithium iron phosphate positive electrode material comprises the following steps:
  • Step 1 preparation of lithium iron phosphate positive electrode material: using a conventional coating process, aluminum foil is used to coat the cut pieces to obtain a lithium iron phosphate positive electrode material with a thickness of 80 ⁇ m.
  • Step 2 nitrogen DBD cold plasma activation treatment: first, coat the lithium iron phosphate positive electrode material in step (1) with one side having the active material, and perform nitrogen DBD cold plasma activation treatment for 10 minutes at a gas flow rate of 10 ml/s, a working current of 4 A, and a voltage of 100 V under nitrogen DBD cold plasma, and cool to room temperature to obtain an activated lithium iron phosphate positive electrode material.
  • Step 3 assembly of button cells: Place the activated lithium iron phosphate positive electrode material described in step (2) into a glove box and assemble button cells. All batteries must be left to stand for 12 hours before testing.

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Abstract

本发明提供了一种电池正极材料及其处理方法和电池。电池正极材料处理方法包括：将待处理的表面至少一部分具有碳层的电池正极材料进行冷等离子体处理以对碳层进行掺杂，其中，掺杂量不小于50ppm。电池正极材料其表面的至少一部分含有碳层且表面至少一部分具有棒状形态，其中，碳层为经冷等离子体处理后掺杂活性粒子的碳层，且在正极材料的表面形成一层高钠离子电导的NaF层。该发明的处理方法可以增强电池正极材料颗粒表面能，改善其与电解液的界面亲和性，可以获得质地均匀、孔隙率低、高离子电导率和电子电导率的正极材料。

Description

一种电池正极材料及其处理方法和电池 技术领域
本发明涉及电池材料领域，更具体地讲，涉及一种电池正极材料及其处理方法和电池。
背景技术
近年来，可移动消费电子与电动汽车等产业发展迅速，迫切需要发展高能量密度与高安全稳定性的新能源电池，以提高这些设备的长续航与长期稳定运行的能力。因此，锂离子或钠离子电池被普遍认为是大规模储能应用中最有前景的候选电池之一。但是，由于目前已知的正极材料都存在锂/钠离子扩散速率迟缓的瓶颈，造成锂离子或钠离子电池能量和功率密度较低，而高性能的正极材料能够提高锂离子或钠离子电池能量密度、循环寿命和倍率性等，因此，开发高性能的正极材料显得尤为重要。
发明内容
针对现有技术中存在的不足，本发明的目的之一在于解决上述现有技术中存在的一个或多个问题。例如，本发明的目的之一在于提供一种可以增强电池正极颗粒表面能，改善其与电解液的界面亲和性的处理方法。
为了实现上述目的，本发明的一方面提供了一种处理电池正极材料的方法，可以包括以下步骤：将待处理的表面至少一部分具有碳层的电池正极材料进行冷等离子体处理以对碳层进行活性粒子掺杂，其中，活性粒子掺杂量不小于50ppm(摩尔分数或体积分数，parts per billion,ppm)。
在本发明处理电池正极材料的方法的一个示例性实施例中，冷等离子体处理的功率可以为100W～500W。
在本发明处理电池正极材料的方法的一个示例性实施例中，冷等离子体处理的电压可以为50V～150V，处理电流可以为0.4A～2A。
在本发明处理电池正极材料的方法的一个示例性实施例中，冷等离子体处理时间可以为1min～60min。
在本发明处理电池正极材料的方法的一个示例性实施例中，生成冷等离子体的放电可以选自射频等离子体放电、电晕放电、介质阻挡放电和滑动电弧放电中的一种或组合。
在本发明处理电池正极材料的方法的一个示例性实施例中，掺杂可以为氧掺杂、氮掺杂中的一种或组合。
在本发明处理电池正极材料的方法的一个示例性实施例中，冷等离子体处理可以包括将氧气、氮气中的一种或组合的前驱气体输入冷等离子体发生器中生成活性粒子对碳层进行掺杂，其中，前驱气体流速可以为1ml/s～15ml/s。
在本发明处理电池正极材料的方法的一个示例性实施例中，电池正极材料可以为聚阴离子型化合物、层状氧化物、尖晶石型化合物、普鲁士蓝或三元锂电池正极材料。例如，电池正极材料可以为磷酸钒钠、磷酸铁锂、磷酸钛钠、氟化磷酸钠、LiMO2、NaMO2、LiN2O4、镍钴锰酸锂或镍钴铝酸锂，其中，M可以为Co、Ni、Mn、V或Fe，N可以为Co、Nix、Mn或V。
在本发明处理电池正极材料的方法的一个示例性实施例中，掺杂后的电池正极材料表面至少一部分具有棒状形态。
在本发明处理电池正极材料的方法的一个示例性实施例中，棒状形态的平均长度可以为1.5μm～3μm。
在本发明处理电池正极材料的方法的一个示例性实施例中，掺杂后的电池正极材料表面至少一部分形成NaF层，NaF层平均厚度可以为6nm～10nm。
在本发明处理电池正极材料的方法的一个示例性实施例中，NaF层含量不小于500ppm。
本发明的另一方面提供了一种电池正极材料，其表面的至少一部分含有碳层且表面至少一部分具有棒状形态，其中，碳层为经冷等离子体处理后掺杂活性粒子的碳层；掺杂量不小于50ppm。
在本发明一种电池正极材料的一个示例性实施例中，活性粒子可以为氧、氮中的一种或组合。
在本发明一种电池正极材料的一个示例性实施例中，棒状形态的平均长度为1.5μm～3μm。
本发明的再一方面提供了一种正极片，可以包含以上所述的处理电池正极材料的方法处理后的正极材料或者以上所述的电池正极材料。
本发明的再一方面提供了一种电池，可以包含以上所述的正极片。
与现有技术相比，本发明的有益效果包含如下中的至少一项：
(1)本发明的处理方法可以增强电池正极材料颗粒表面能，改善其与电解液的界面亲和性，获得质地均匀、孔隙率低、高离子电导率和电子电导率的正极材料。
(2)本发明的正极材料有高的电子电导率，与电解液界面相容性好，表面具有“棒状”形态，使电池正极材料与集流体界面接触有好的稳定性，可以提高钠离子传输的速率以及电子导电率。
(3)本发明的处理方法可以在电池正极材料的表面产生NaF层，该层具有超高的钠离子电导率，限制正极材料与电解液副反应的发生，且提高钠离子在固液界面处的传输速率。
(4)使用本发明处理后的电池正极材料所制备得到的锂离子电池和钠离子电池具有高的能量密度、循环寿命和倍率性。
(5)本发明的处理方法工艺流程简单，能耗低，设备投资少，没有“三废”的产生，环境友好，适用于大规模生产应用。
附图说明
通过下面结合附图进行的描述，本发明的上述和其他目的和特点将会变得更加清楚，其中：
图1示出了示例1中处理后与处理前的磷酸钒钠正极材料XRD(X射线衍射,Diffractionofx－rays,XRD)对比图。
图2示出了示例1中处理后与处理前的磷酸钒钠正极材料XPS(X射线光电子能谱,X-ray photoelectron spectroscopy,XPS)对比图。
图3示出了示例2中未经处理的磷酸钒钠正极材料SEM(扫描电子显微镜,scanning electron microscope,SEM)图。
图4示出了示例2中处理后的磷酸钒钠正极材料SEM图。
图5示出了示例2中电池的电压-容量图。
图6示出了示例3中未经处理的磷酸钒钠正极材料对电解液的接触角。
图7示出了示例3中处理后的磷酸钒钠正极材料对电解液的接触角。
图8示出了示例3中处理后的磷酸钒钠正极材料的EIS(电化学阻抗谱,Electrochemical Impedance Spectroscopy,EIS)图。
图9示出了示例4中未经处理的磷酸钒钠正极材料的XPS。
图10示出了示例4中处理后的磷酸钒钠正极材料的XPS。
图11示出了示例6中电池的电压-容量图。
图12示出了示例6中处理后磷酸钒钠的长循环图。
图13示出了示例8中电池的电压-容量图。
图14示出了示例8中处理后磷酸铁锂的长循环图。
图15示出了示例9中处理前后磷酸铁锂的EIS图。
具体实施方式
在下文中，将结合附图和示例性实施例详细地描述根据本发明的一种电池正极材料及其处理方法和电池。
本发明的一方面提供了一种处理电池正极材料的方法，可以包括以下步骤：将待处理的表面至少一部分具有碳层的电池正极材料进行冷等离子体处理以对碳层进行掺杂，其中，掺杂量不小于50ppm。
电池正极材料通过冷等离子体产生的高活性粒子对附着或包覆在正极材料表面的碳层进行掺杂，可以在碳层表面形成更多的缺陷，提高了正极材料与集流体界面接触的稳定性，进而提高了钠离子或锂离子传输的速率以及电子导电率，另外也会提高正极材料与电解液之间的亲和性，缓解了由于钠离子或锂离子半径较大带来的严重的体积效应，使得活性物质在长循环的过程中具有良好的结构稳定性。与未经处理的正极材料相比，使用处理后正极材料的电池具有更低的极化电压、更低的界面阻抗、更稳定的充放电平台以及更高的比容量。
在一些实施方案中，待处理的电池正极材料表明至少一部分具有碳层以实现对碳层进行掺杂。碳层可以全包覆或部分包覆在待处理正极材料表面。即本文所描述的碳层可形成正极材料表面的全部或仅一部分，并且在一些实施方案中，碳层可以为一层或多层，例如，碳层可以为2层、或3层、或4层、或大于5层、或大于6层。应当理解的是，正极材料表面可以不仅仅包含碳层，还可以在正极材料表面含有其他可以提高正极材料性能的包覆层或附着层。
在一些实施方案中，掺杂量会影响正极材料表面碳层的电子导电性能，若掺杂量小于50ppm，对正极材料表面碳层的电子导电性能提升不明显，因此，掺杂量可以不小于50ppm、不小于70ppm、不小于85ppm、不小于105ppm、 不小于123ppm、不小于152ppm、或者160ppm～246ppmm，或者214ppm～318ppmm，或者259ppm～413ppmm，或者586ppm～793ppmm，或者803ppm～1050ppm。另外，掺杂量大于600ppm可能会造成表面碳层的破坏，降低活性粒子的循环稳定性，因此，优选地，掺杂量在50ppm～600ppm之间。
在一些实施方案中，待处理的正极材料厚度是可以调整的，如本文所述，任何厚度的正极材料均可以用本文的处理方法进行处理。在某些实施方案中，待处理的正极材料的厚度可以为30μm～100μm，例如，厚度可以为小于28μm或者大于110μm，或者15μm，或者45μm，或者84μm，或者141μm。
在一些实施方案中，冷等离子体处理的功率可以为100W～500W。在100W～500W的范围内能够实现掺杂的同时确保正极材料表面碳层的稳定性。若功率低于100W，会达不到打断碳碳键的能量，从而使得活性粒子掺杂不进去；若能量高于500W，会破坏正极材料表面的碳层结构导致其电化学性能下降。并且在该功率范围内可以使正极材料获得高表面能以及提高与电解液界面的亲和性。例如，冷等离子体的产生可以是将氧气、氮气或混合气体等气源输送到冷等离子体发生器内生成的活性粒子。而对于上述施加的功率，需要说明的是，该功率为直接作用在前驱气体上的功率，即气源直接所受到的功率。在某些实施方案中，冷等离子体处理的功率可以为不小于150W，或者不小于245W，或者不小于289W，或者不小于423W。
在一些实施方案中，冷等离子体处理的电压可以为50V～150V，处理电流可以为0.4A～2A。施加上述范围内的电压和电流，能够使冷等离子体处理的功率达到100W～500W，能够打断碳碳键的同时，确保正极材料表面碳层的稳定性。本领域应当理解，此处的电压和电流是施加在冷等离子体发生器上的电压和电流。在某些实施方案中，冷等离子体处理的电压可以为不小于60V，或者不小于72V，或者不小于83V，或者不小于114V，或者不小于127V，或者不小于142V或者以上范围的组合。冷等离子体处理的电流可以为0.5A～1.8A、0.7A～1.6A、0.9A～1.4A、1.1A～1.3A或者以上范围的组合。在上述施加的电压、电流以及功率下，能够使正极材料的表面具有棒状形态(棒状结构)，使正极材料具有本文所描述的性能。
在一些实施方案中，冷等离子体处理的时间可以为1min～60min。在上述冷等离子体处理时间内，协同施加的处理电压和处理电流，可以确保对正极材料表面的碳层进行掺杂，使其掺杂量达到50ppm以上。例如，处理的时间 可以为不小于2min、不小于15min、不小于23min、不小于38min、不小于47min、不小于52min。在某些情况下，冷等离子体的处理时间可以大于约30s、或者大于约45s。然而，应当理解的是，在能够达到本文所描述的掺杂量下，处理时间可以任意调整。
在一些实施方案中，产生NaF的含量会影响电极表面的电化学性能，若NaF的含量小于50ppm，对正极材料表面的离子电导率提高不明显，因此，NaF的含量不小于50ppm、不小于70ppm、不小于85ppm、不小于105ppm、不小于123ppm、不小于152ppm、或者160ppm～246ppmm，或者214ppm～318ppmm，或者259ppm～413ppmm，或者586ppm～793ppmm，或者803ppm～1050ppm。另外，掺杂量大于50ppm可能会造成电极表面粘结剂的破坏，降低活性物质之间的粘结力，因此，优选地，掺杂量在50ppm～500ppm之间。
在一些实施方案中，生成冷等离子体的放电选自射频等离子体放电(Radio Frequency,RF)、电晕放电(corona discharge,CD)、介质阻挡放电(Dielectric Barrier Discharge,DBD)和滑动电弧放电(Glide Arc Discharge,GAD)中一种或组合。采用上述冷等离子体设备能在高气压下稳定的放电，操作简单且能够形成较大面积的等离子体放电区域，从而使得放电区域活性粒子的作用范围较大，为高效的掺杂处理提供了基础。当然，应当理解的是，任何其他适用于生成冷等离子体的放电也适用于本文所描述的处理方法。
在一些实施方案中，掺杂的活性粒子或者掺杂的活性物质可以为氧掺杂、氮掺杂中的一种或组合。例如，在某些实施方案中，可以是独立的氧掺杂、氮掺杂或者氧氮掺杂。通过冷等离子体产生的高活性粒子对碳层进行掺杂可以使正极材料获得更好的电化学性能。当然，对于本领域应当理解，实现上述活性粒子的掺杂可以是包括将氧气、氮气中的一种或组合的前驱气体输入冷等离子体发生器中生成活性粒子后对正极材料表面的碳层进行掺杂。然而，在特定的实施方案中，活性粒子的掺杂还可以通过冷等离子体发生器的其他形式实现。
在一些实施方案中，通入冷等离子体发生器的前驱气体的流速可以为1ml/s～15ml/s。在上述前驱气体流速下，协同施加的电压和电流可以确保碳层掺杂的实现。在一组实施方案中，可以将待处理的正极材料放入冷等离子体发生器中，并按照本文所描述的速率通入前驱气体，将冷等离子体发生器调 至本文所描述的电压以及电流即可对待处理的正极材料进行处理。当然，应当理解的是，实现氧掺杂时，氧气气氛下需要在短时间内完成氧掺杂，确保引入含氧官能团的同时极少产生氧化作用，避免时间过长或功率过高产生氧化作用。对于含氧的混合气而言由于氧的含量较低，所以氧化作用时可以忽略的。
在一些实施方案中，本文所描述的处理后的正极材料相比于现有的正极材料具有不一样的形貌特征。通过对正极材料的处理，正极材料表面至少一部分具有棒状形态。例如，对于磷酸钒钠正极材料，经过本文所描述的处理方法处理后其表面会出现大量的棒状结构或者类棒状结构或者片状结构等。在某些实施方案中，正极材料表面全部具有棒状形态、或者至少0.01％表面积覆盖率具有棒状形态、或者至少0.1％表面积具有棒状形态、或者至少5％表面积具有棒状形态、或者至少9.8％表面积具有棒状形态、或者至少15.3％表面积具有棒状形态、或者至少21.5％表面积具有棒状形态、或者至少35.4％表面积具有棒状形态、或者至少41.2％表面积具有棒状形态、或者至少49.8％表面积具有棒状形态、或者至少55.1％表面积具有棒状形态、或者至少61.5％表面积具有棒状形态、或者至少73.5％表面积具有棒状形态、或者至少84.5％表面积具有棒状形态。通过使在正极材料的表面具有棒状形态，可以提高正极材料与集流体界面接触的稳定性，进而可以提高钠离子传输的速率以及电子导电率。然而，应当理解的是，本文所描述的棒状是指一种细长的形态或者呈现的是一种细长的结构，也可以描述为柱状等。
在一些实施方案中，棒状形态是可以具有特定的长度的，即棒状形态的平均长度可以为不小于1.6μm、不小于2.1μm、不小于2.4μm、不小于2.6μm、不小于2.8μm、不小于2.9μm。在某些实施方案中，棒状形态是可以具有特定直径(即棒的径向直径)的，即棒状形态的平均值径可以为不小于154nm、不小于167nm、不小于179nm、不小于189nm、不小于208nm、不小于238nm、不小于268nm、不小于294nm、不小于283nm。
在一些实施方案中，呈棒状形态物质质量占正极材料的质量比可以是特定的。例如，呈棒状形态物质所占正极材料的质量比可以为2％～10％。在一些实施方案中，呈棒状形态物质所占正极材料的质量比可以为不小于0.5％、或者不小于0.8％、或者不小于1.5％、或者不小于2.7％、或者不小于3.4％、或者不小于4.7％、或者不小于5.9％、或者不小于6.7％、或者不小于9.4％。 在一些特定实施方案中，质量占比或者为不小于15.8％、或者为不小于20.1％、或者为不小于30.5％、或者为不小于36.8％。
在一些实施方案中，电池正极材料可以为聚阴离子型化合物、层状氧化物、尖晶石型化合物、普鲁士蓝或三元锂电池正极材料。聚阴离子型化合物可以包括磷酸钒钠、磷酸铁锂、磷酸钛钠和氟化磷酸钠。层状氧化物可以包括LiMO2和NaMO2，其中，M可以为Co、Ni、Mn、V或Fe。尖晶石型化合物可以包括LiN2O4，其中，N可以为Co、Nix、Mn或V。三元锂电池正极材料可以为镍钴锰酸锂和镍钴铝酸锂。应当理解的是，本文所描述的处理方法还可以处理其他一些正极材料。
在一些实施方案中，应当理解的是，其他一些可以增强本文所描述正极材料电化学性能的物质也可以引入。
本发明的另一方面提供了一种正极材料。在本发明的正极材料的一个示例性实施例中，正极材料可以由本文所描述的处理电池正极材料的方法处理后得到。在一些实施方案中，正极材料表面的至少一部分含有碳层且表面至少一部分具有棒状形态，其中，碳层为经冷等离子体处理后掺杂活性粒子的碳层。
在一些实施方案中，如本文所描述的，掺杂量可以不小于50ppm。
在一些实施方案中，如本文所描述的，活性粒子为氧、氮中的一种或组合。
在一些实施方案中，如本文所描述的，棒状形态的平均长度可以为1.5μm～3μm，平均直径可以为150nm～300nm。
在一些实施方案中，如本文所描述的，呈棒状形态物质所占质量比可以是特定的。例如，呈棒状形态物质所占正极材料的质量比可以为2％～10％。
本发明的再一方面提供了一种正极片，包含集流体和设置在集流体上的正极材料层，正极材料包含本文如上所述的处理电池正极材料的方法处理后的正极材料或者包含本文如上所述的正极材料。所述正极材料层除包括上述正极材料外，还可以包括导电剂和粘结剂。正极材料层可以通过本领域已知的方法引入正极片。
本发明的再一方面提供了一种电池，尤其是一种钠离子电池，包含如上所述的正极片。应当理解的是，电池还包含一些其他组成电池的必不可少的构件，电池的装配方法是本领域已知的。
在一些实施方案中，电池可以为纽扣电池。对于纽扣电池的装配可以是本领域已知的。例如，可以将正极片放入手套箱中，进行纽扣电池的装配。
为了更好地理解本发明的上述示例性实施例，下面结合具体示例对其进行进一步说明。
示例1
处理电池正极材料的方法，包括以下步骤：
步骤1，磷酸钒钠正极材料的制备：利用传统涂布工艺，使用铝箔进行涂布裁片，得到厚度为80μm的磷酸钒钠正极材料。
步骤2，氮气DBD冷等离子体活化处理：先把步骤(1)中的磷酸钒钠正极材料涂覆有活性物质的一面，在氮气DBD冷等离子体下气体流速为10ml/s，工作电流为1A，电压为150V，进行氮气DBD冷等离子体活化处理1min，冷却至室温，得到活化处理后的磷酸钒钠正极材料。
步骤3，纽扣电池的装配：将步骤(2)中的活化处理后的磷酸钒钠正极材料放入手套箱备中，进行纽扣电池的装配，静置12h后进行电池测试。
对氮气DBD冷等离子体活化处理后得到的磷酸钒钠正极材料进行物理表征，通过图1的磷酸钒钠正极材料XRD图可以看出，氮气DBD冷等离子体活化处理后的磷酸钒钠正极材料物理性质(图中的DBD-1min)与未经处理(图中的DBD-0min)相比未发生改变，表明氮气DBD冷等离子体处理不会对磷酸钒钠的晶体结构产生破坏，且通过图2的磷酸钒钠正极材料的XPS图可以看出，相比较于未经过氮气DBD-0min的电极片，经过氮气DBD-1min处理后会产生NaF层。
示例2
处理电池正极材料的方法，包括以下步骤：
步骤1，磷酸钒钠正极材料的制备：利用传统涂布工艺，使用铝箔进行涂布裁片，得到厚度为80μm的磷酸钒钠正极材料。
步骤2，氮气DBD冷等离子体活化处理：先把步骤(1)中的磷酸钒钠正极材料涂覆有活性物质的一面，在氮气DBD冷等离子体下气体流速为10ml/s，工作电流为1A，电压为150V，进行氮气DBD冷等离子体活化处理2min，冷却至室温，得到活化处理后的磷酸钒钠正极材料。
步骤3，纽扣电池的装配：将步骤(2)所述活化处理后的磷酸钒钠正极材料放入手套箱中，进行纽扣电池的装配，静置12h后进行电池测试。
对氮气DBD冷等离子体活化处理得到的磷酸钒钠的正极材料进行形貌表征和物理及电化学测试，氮掺杂在碳层中的含量为159ppm。通过图3和4中的SEM图可知，与未进行氮气DBD冷等离子体处理的磷酸钒钠正极材料相比(如图2)，处理后的磷酸钒钠正极材料(如图3)表面产生棒状形态(棒状结构、细长结构)，可以提高磷酸钒钠正极材料与电解液的界面接触。如图5的电压-容量图所示，电池的极化从0.04V降到0.03V以内，且充放电平台更加稳定且具有较高的比容量。
示例3
处理电池正极材料的方法，包括以下步骤：
步骤1，磷酸钒钠正极材料的制备：利用传统涂布工艺，使用铝箔进行涂布裁片，得到厚度为80μm的磷酸钒钠正极材料。
步骤2，氮气DBD冷等离子体活化处理：先把步骤(1)中的磷酸钒钠正极材料涂覆有活性物质的一面，在氮气DBD冷等离子体下气体流速为10ml/s，工作电流为1A，电压为150V，进行氮气DBD冷等离子体活化处理4min，冷却至室温，得到活化处理后的磷酸钒钠正极材料。
步骤3，纽扣电池的装配：将所述活化的磷酸钒钠正极材料放入手套箱中，进行纽扣电池的装配，静置12h后进行电池测试。
对氮气DBD冷等离子体活化处理后得到的磷酸钒钠正极材料进行物理及电化学测试，氮掺杂在碳层中的含量为87ppm，未进行处理的磷酸钒钠正极材料对电解液的接触角如图6，处理过后的磷酸钒钠正极材料对电解液的接触角如图7，其对电解液的接触角从14.15°减小到12.4°，证明经处理过后磷酸钒钠正极材料对电解液的浸润性变好。同时，如图8中的EIS(电化学阻抗谱)所示，与未处理相比，且界面阻抗从3200Ω降低到2500Ω。
示例4
处理电池正极材料的方法，包括以下步骤：
步骤1，磷酸钒钠正极材料的制备：利用传统涂布工艺，使用铝箔进行涂布裁片，得到厚度为80μm的磷酸钒钠正极材料。
步骤2，氮气DBD冷等离子体活化处理：先把步骤(1)中的磷酸钒钠正极材料涂覆有活性物质的一面，在氮气DBD冷等离子体下气体流速为10ml/s，工作电流为1A，电压为150V，进行氮气DBD冷等离子体活化处理6min，冷却至室温，得到活化处理后的磷酸钒钠正极材料。
步骤3，纽扣电池的装配：将步骤(2)所述活化处理后的磷酸钒钠正极材料放入手套箱中，进行纽扣电池的装配，静置12h后进行电池测试。
对氮气DBD冷等离子体活化处理得到的磷酸钒钠正极材料进行物理及电化学测试，氮掺杂在碳层中的含量为308ppm，未进行处理的磷酸钒钠正极材料的XPS如图9所示，处理过后的磷酸钒钠正极材料的XPS如图10所示，其中吡啶氮、吡咯氮、石墨化氮的含量提高(这里的吡啶氮、吡咯氮、石墨化氮是氮粒子掺杂进碳层的三种不同的存在形式)，从而使得碳层的缺陷增多，这有助于提高磷酸钒钠的电子电导率和离子电导率。
示例5
处理电池正极材料的方法，包括以下步骤：
步骤1，磷酸钒钠正极材料的制备：利用传统涂布工艺，使用铝箔进行涂布裁片，得到厚度为80μm的磷酸钒钠正极材料。
步骤2，氧气RF冷等离子体活化处理：先把步骤(1)中的磷酸钒钠正极材料涂覆有活性物质的一面，在氧气RF冷等离子体下气体流速为10ml/s，工作电流为1A，电压为100V，进行氧气RF冷等离子体活化处理6min，冷却至室温，得到活化处理后的磷酸钒钠正极材料。
步骤3，纽扣电池的装配：将步骤(2)所述活化的磷酸钒钠正极材料放入手套箱中，进行纽扣电池的装配，静置12h后进行电池测试。
对氧气RF冷等离子体活化处理得到的磷酸钒钠的正极材料进行物理及电化学测试，氩掺杂在碳层中的含量为287ppm。与未处理的极片相比，具有较低的极化和阻抗，其中极化降低了43％，阻抗降低了18％。
示例6
处理电池正极材料的方法，包括以下步骤：
步骤1，磷酸钒钠正极材料的制备：利用传统涂布工艺，使用铝箔进行涂布裁片，得到厚度为80μm的磷酸钒钠正极材料。
步骤2，氮氧混合气CD冷等离子体活化处理：先把步骤(1)中的磷酸钒钠正极材料涂覆有活性物质的一面，在氮氧混合气CD冷等离子体下气体流速为10ml/s，工作电流为2A，电压为100V，进行氮氧混合气CD冷等离子体活化处理4min，冷却至室温，得到活化磷酸钒钠的正极材料。
步骤3，纽扣电池的装配：将步骤(2)所述活化的磷酸钒钠正极材料放入手套箱中，进行纽扣电池的装配，所有电池测试前需静置12h。
对氮氧混合气CD冷等离子体活化处理得到的磷酸钒钠的正极材料进行物理及电化学测试，氮氧掺杂在碳层中的含量为378ppm，与未处理的极片相比，具有较低的极化和阻抗。5C条件下磷酸钒钠的电压容量如图11所示，处理过后电池的容量在原来的基础上提高了13.6％，电池的极化降低了大约45％。5C条件下磷酸钒钠的长循环图如图12所示，处理过后电池的容量保持率在原来的基础上提高了14％。
示例7
处理电池正极材料的方法，包括以下步骤：
步骤1，磷酸钒钠正极材料的制备：利用传统涂布工艺，使用铝箔进行涂布裁片，得到厚度为80μm的磷酸钒钠正极材料。
步骤2，氧气CD冷等离子体活化处理：先把步骤(1)中的磷酸钒钠正极材料涂覆有活性物质的一面，在氧气CD冷等离子体下气体流速为10ml/s，工作电流为2A，电压为100V，进行氧气CD冷等离子体活化处理4min，冷却至室温，得到活化磷酸钒钠的正极材料。
步骤3，纽扣电池的装配：将步骤(2)所述活化的磷酸钒钠正极材料放入手套箱中，进行纽扣电池的装配，所有电池测试前需静置12h。
对氧气CD冷等离子体活化处理得到的磷酸钒钠的正极材料进行物理及电化学测试，氧掺杂在碳层中的含量为587ppm，与未处理的极片相比，具有较低的极化和阻抗，其中极化降低了45％，阻抗降低了20％。
示例8
处理正极材料的方法，包括以下步骤：
步骤1，磷酸铁锂正极材料的制备：利用传统涂布工艺，使用铝箔进行涂布裁片，得到厚度为80μm的磷酸铁锂正极材料。
步骤2，氮气DBD冷等离子体活化处理：先把步骤(1)中的磷酸铁锂正极材料涂覆有活性物质的一面，在氮气DBD冷等离子体下气体流速为10ml/s，工作电流为4A，电压为100V，进行氮气DBD冷等离子体活化处理4min，冷却至室温，得到活化磷酸铁锂的正极材料。
步骤3，纽扣电池的装配：将步骤(2)所述活化的磷酸铁锂正极材料放入手套箱中，进行纽扣电池的装配，所有电池测试前需静置12h。
对氮气DBD冷等离子体活化处理得到的磷酸铁锂的正极材料进行物理及电化学测试，氮掺杂在碳层中的含量为600ppm，与未处理的极片相比，具 有较低的极化、较高的容量以及较高的容量保持率。5C条件下处理后的磷酸铁锂的电压容量如图13所示，在处理过后的电池极化降低了大约86％，容量在原来的基础上提高了42.7％。5C条件下处理后的磷酸铁锂的长循环图如图14所示，容量保持率在原来的基础上提高了69.7％。
示例9
处理磷酸铁锂正极材料的方法，包括以下步骤：
步骤1，磷酸铁锂正极材料的制备：利用传统涂布工艺，使用铝箔进行涂布裁片，得到厚度为80μm的磷酸铁锂正极材料。
步骤2，氮气DBD冷等离子体活化处理：先把步骤(1)中的磷酸铁锂正极材料涂覆有活性物质的一面，在氮气DBD冷等离子体下气体流速为10ml/s，工作电流为4A，电压为100V，进行氮气DBD冷等离子体活化处理10min，冷却至室温，得到活化磷酸铁锂的正极材料。
步骤3，纽扣电池的装配：将步骤(2)所述活化的磷酸铁锂正极材料放入手套箱中，进行纽扣电池的装配，所有电池测试前需静置12h。
对氮气DBD冷等离子体活化处理得到的磷酸铁锂的正极材料进行物理及电化学测试，氮掺杂在碳层中的含量为700ppm，与未处理的极片相比，具有较低的阻抗。处理前后磷酸铁锂的EIS图如图15所示，处理后电池阻抗从126.3Ω减小到27.2Ω。
尽管上面已经通过结合示例性实施例描述了本发明，但是本领域技术人员应该清楚，在不脱离权利要求所限定的精神和范围的情况下，可对本发明的示例性实施例进行各种修改和改变。

Claims (17)

  1. 一种处理电池正极材料的方法，其特征在于，包括以下步骤：
    将待处理的表面至少一部分具有碳层的电池正极材料进行冷等离子体处理以对碳层进行活性粒子掺杂，其中，活性粒子掺杂量不小于50ppm。
  2. 根据权利要求1所述的处理电池正极材料的方法，其特征在于，冷等离子体处理的功率为100W～500W。
  3. 根据权利要求1或2所述的处理电池正极材料的方法，其特征在于，冷等离子体处理的电压为50V～150V，处理电流为0.4A～2A。
  4. 根据权利要求1或2所述的处理电池正极材料的方法，其特征在于，冷等离子体处理时间为1min～60min。
  5. 根据权利要求1或2所述的处理电池正极材料的方法，其特征在于，生成冷等离子体的放电选自射频等离子体放电、电晕放电、介质阻挡放电和滑动电弧放电中的一种或组合。
  6. 根据权利要求1或2所述的处理电池正极材料的方法，其特征在于，活性粒子掺杂为氧掺杂、氮掺杂中的一种或组合。
  7. 根据权利要求1或2所述的处理电池正极材料的方法，其特征在于，冷等离子体处理包括将氧气、氮气中的一种或组合的前驱气体输入冷等离子体发生器中生成活性粒子对碳层进行掺杂，其中，前驱气体流速为1ml/s～15ml/s。
  8. 根据权利要求1或2所述的处理电池正极材料的方法，其特征在于，电池正极材料为聚阴离子型化合物、层状氧化物、尖晶石型化合物、普鲁士蓝或三元锂电池正极材料。
  9. 根据权利要求8所述的处理电池正极材料的方法，其特征在于，电池正极材料为磷酸钒钠、磷酸铁锂、磷酸钛钠、氟化磷酸钠、LiMO2、NaMO2、LiN2O4、镍钴锰酸锂或镍钴铝酸锂，其中，M为Co、Ni、Mn、V或Fe，N为Co、Nix、Mn或V。
  10. 根据权利要求1、2或8所述的处理电池正极材料的方法，其特征在于，掺杂后的电池正极材料表面至少一部分具有棒状形态。
  11. 根据权利要求10所述的处理电池正极材料的方法，其特征在于，棒状形态的平均长度为1.5μm～3μm，平均直径为150nm～300nm。
  12. 一种电池正极材料，其特征在于，其表面的至少一部分含有碳层且表面至少一部分具有棒状形态和形成NaF层，其中，碳层为经冷等离子体处理后掺杂活性粒子的碳层，掺杂量不小于50ppm。
  13. 根据权利要求12所述的电池正极材料，其特征在于，活性粒子为氧、氮中的一种或组合。
  14. 根据权利要求12或13所述的电池正极材料，其特征在于，棒状形态的平均长度为1.5μm～3μm，平均直径为150nm～300nm。
  15. 根据权利要求12或13所述的电池正极材料，其特征在于，NaF层平均厚度为6nm～10nm，NaF的含量不小于500ppm。
  16. 一种正极片，其特征在于，包含集流体和设置在集流体上的正极材料层，正极材料层包括如权利要求1至11中任一项所述的处理电池正极材料的方法处理后的电池正极材料或者包含如权利要求12至14任一项所述的电池正极材料。
  17. 一种电池，其特征在于，包含如权利要求16所述的正极片。
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