WO2016110108A1 - Method of preparing plasma spraying for nanoscale lithium-ion composite positive electrode - Google Patents

Method of preparing plasma spraying for nanoscale lithium-ion composite positive electrode Download PDF

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WO2016110108A1
WO2016110108A1 PCT/CN2015/087983 CN2015087983W WO2016110108A1 WO 2016110108 A1 WO2016110108 A1 WO 2016110108A1 CN 2015087983 W CN2015087983 W CN 2015087983W WO 2016110108 A1 WO2016110108 A1 WO 2016110108A1
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positive electrode
carbon
parts
nano
lithium ion
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PCT/CN2015/087983
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French (fr)
Chinese (zh)
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阮殿波
袁峻
傅冠生
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宁波南车新能源科技有限公司
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Publication of WO2016110108A1 publication Critical patent/WO2016110108A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0419—Methods of deposition of the material involving spraying
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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 invention relates to the technical field of lithium ion batteries, in particular to a plasma spray preparation method of a nanometer lithium ion composite cathode.
  • a lithium ion battery is a green secondary battery having a large energy density, a high average output voltage, a small self-discharge, and no toxic substances. After nearly two decades of development, lithium-ion batteries have been able to reach 100Wh/kg to 150Wh/kg, and the working voltage can reach up to 4V.
  • Supercapacitor is an energy storage device based on the principle of double-layer energy storage and high reversibility redox quasi-capacitor. It has the advantages of high power density, short charge and discharge time, long cycle life and wide operating temperature range. The energy density is relatively low and so on.
  • the difference in specific energy and specific power between lithium-ion battery and super-capacitor determines the difference between charge and discharge rates.
  • supercapacitors and lithium-ion batteries have their own outstanding advantages and limitations.
  • the combination of parallel or series capacitor batteries makes up for this gap.
  • the positive electrode is mixed with a certain amount of porous carbon material using a positive electrode material of a lithium ion battery, and the porous carbon material includes activated carbon, mesoporous carbon, carbon nanotubes, graphene, and the like.
  • the composite effect is not ideal, and uniform dispersion and nano-level mixing cannot be achieved.
  • lithium battery cathode materials are from layered structure of lithium cobaltate, spinel structure of lithium manganate, olivine structure of lithium phosphite to ternary material lithium nickel cobalt manganese.
  • Lithium cobaltate cathode material is the main material used in lithium batteries in traditional electronic products, mainly based on its large capacity and large voltage range. Lithium manganate has been widely used in electric bicycles, electric vehicles, etc. due to its low cost, stability, and good electrical conductivity, but it also has its capacity attenuation problem.
  • the plasma spraying method uses a plasma arc driven by a direct current as a heat source to heat a ceramic, an alloy, a metal or the like into a molten or semi-molten state, and sprays the surface of the pretreated workpiece at a high speed to form a firmly adhered surface layer.
  • the method uses a plasma arc, and the ion arc is a compression arc. Compared with the free arc, the arc column is thin, the current density is high, and the gas ionization degree is high, so the temperature is high, the energy is concentrated, and the arc stability is good.
  • the purpose of the invention is to solve the problem that the electrochemical performance of the positive electrode composite material of the lithium ion capacitor battery is limited due to the defects of dispersion, uniformity and particle size distribution in the preparation process, and a nanometer lithium ion composite positive electrode is provided.
  • the invention can produce lithium mixed uniformly on the nanometer size in a relatively economical way An electric positive electrode material and a porous carbon composite material were coated on an aluminum foil to obtain a composite electrode.
  • a plasma jet preparation method for a nano-scale lithium ion composite positive electrode comprising the following steps:
  • the lithium positive electrode material is LiCoO 2 , LiMn 2 O 4 , LiMnO 2 , LiNiO 2 , LiFePO 4 , LiMnPO 4 , LiNi 0.8 Co 0.2 O 2 or LiNi 1/3 Co 1/3 Mn 1/3 O 2 .
  • the porous carbon material is activated carbon, mesoporous carbon, carbon aerogel, carbon fiber, carbon nanotube, carbon black, hard carbon or graphene.
  • the current collector is a carbon coated aluminum foil, an aluminum foil, a perforated aluminum foil, a copper foil or a perforated copper foil.
  • the current collector has a thickness of 20 ⁇ m.
  • the conductive agent is conductive carbon black, graphene or carbon nanotubes.
  • the plasma spraying technology comprises: low temperature and low pressure plasma technology, high temperature and low pressure plasma technology, vacuum plasma technology, water stable plasma technology and gas stabilization plasma technology.
  • the plasma injection technique has process parameters of: argon gas pressure of 1.2-2.7 MPa, nitrogen pressure of 0.9-1.3 MPa, voltage of 5000-12000 V, current of 700-850 A, and spraying distance of 10-15 m.
  • step 3 the front current collector is subjected to a surface treatment process.
  • the surface treatment process comprises the following steps: collecting and cleaning the current collector after double-sided etching, and then immersing in the treatment liquid. After soaking, washing, drying and spraying the liquid on both sides with an inert gas.
  • the treatment liquid has a composition of: 20-25 parts by weight of sodium molybdate, 15-30 parts of fruit acid, 2-6 parts of thiourea, 3-10 parts of sodium phytate, and 10-15 parts of aspartic acid. 10-18 parts of benzotriazole, 2-6 parts of honey, 90-130 parts of water; the double-sided etching of the current collector means that the coating is performed at a coating speed of 15-25 m/min by a coater.
  • the acid surface treatment liquid is applied to the surface of the current collector for double-sided corrosion.
  • the composition of the chromic acid surface treatment liquid is 10-15 parts by weight of lithium chromate, 15-20 parts of water, 3-6 parts of sodium tungstate, and concentrated. 65-75 parts of sulfuric acid; the temperature of the current collector soaked in the treatment liquid is 70-85 ° C, soaking time 2-4 h; the current collector is dried at 60 ° C for 2 h and then heated to 80 ° C for 1.5 h, and finally 105 Dry at °C for 1 h; the gas flow rate of the double-sided jet of the current collector using an inert gas was 120-260 mL/min.
  • the surface area of the current collector is increased, the surface tension is decreased, and the adhesion of the electrode film can be improved.
  • the combined strength helps to reduce the internal resistance of the electrode and prolong the service life of the lithium ion battery; the treatment liquid can improve the corrosion resistance of the current collector, and can further improve the adhesion performance of the positive electrode material on the surface of the current collector, thereby reducing the internal resistance.
  • the activated carbon is activated carbon with coconut shell or needle coke as a precursor, and the activated carbon is used after surface modification treatment, and the surface modification treatment method is: coupling silane with a mass concentration of 5-10%.
  • the anhydrous ethanol solution is mixed with activated carbon for 30-50min, then added with a concentration of 8-15% aluminate coupling agent in absolute ethanol solution for 30-50min, filtered, and the filter is dried at 70-80 ° C. 4-5h, and then activated at 100 ° C -105 ° C for 1-2 h, the amount of silane coupling agent is 0.5-1% of the weight of activated carbon, and the amount of aluminate coupling agent is 1-1.5% of the weight of activated carbon.
  • the activated carbon having a coconut shell or needle coke as a precursor has a moderate pore size, and the performance for the positive electrode active material is better.
  • the first surface treatment of activated carbon is first carried out by using a silane coupling agent. After the silane coupling agent is mixed into the activated carbon, it can effectively penetrate into the gap between the activated carbon particles, so that the activated carbon particles are relatively isolated. It can effectively improve the dispersibility of activated carbon, and then the second surface treatment of the treated activated carbon by adding an aluminate coupling agent, which can effectively solve the problem of agglomeration of activated carbon and make the aluminate coupling agent effective.
  • the activated carbon is further prevented from agglomeration of the activated carbon. Due to the treatment of the coupling agent, the oleophilic group of the activated carbon is increased, and the components such as the binder are more uniformly mixed, and the obtained positive electrode material has a uniform distribution and stable performance.
  • the conductive agent is a modified carbon nanotube, and the steps of preparing the modified carbon nanotube are as follows:
  • the secondary modified carbon nanotubes and the perchloric acid having a mass concentration of 50-60% are uniformly mixed according to the ratio of material to liquid of 1g: 20-30mL, heated to 60-70 ° C for 24 hours, cooled, filtered, washed with water, After vacuum drying, the modified carbon nanotubes are obtained; wherein the acid solution is a mixture of concentrated nitric acid having a mass concentration of 70% and a concentrated sulfuric acid having a mass concentration of 98% in a volume ratio of 1-2:1; the chemical shear liquid A mixture of a sodium molybdate solution having a concentration of 0.5-0.8 mol/L and a silicomolybdic acid solution having a concentration of 0.3-0.5 mol/L in a volume ratio of 1:1.
  • Typical multi-walled carbon nanotubes generally have a diameter of a few nanometers to several tens of nanometers and a length of several to several tens of micrometers.
  • the prepared samples are mostly disorderly distributed, and the carbon nanotubes are intertwined and difficult to disperse, and the agglomerated carbon nanotubes need to be dispersed into individual carbon nanotubes to exert their special properties.
  • Step (1) mixing the carbon nanotubes with a dimethylformamide solution having a mass concentration of 30-50% and an acid solution, and simultaneously stirring to enlarge the contact surface of the carbon nanotubes with the liquid, so that the carbon nanotubes are uniformly dispersed.
  • the specific solvent combination system of the dimethylformamide solution and the acid solution with a mass concentration of 30-50% can make the carbon nanotubes disperse more uniformly in the system and effectively avoid the agglomeration of the carbon nanotubes.
  • Step (1) firstly dispersing the carbon nanotubes uniformly, which facilitates the shearing of the step (2), and hydrothermally reacts the uniformly dispersed carbon nanotubes of the step (1) with the specific chemical shear liquid of the present invention, thereby effectively cutting the carbon.
  • uniform carbon nanotubes having a relatively uniform length (about 100-150 nm in length) are obtained, and such carbon nanotubes can exhibit more excellent electrical and thermal conduction effects in a smaller amount when used for an electrode material.
  • Step (3) The homogenized carbon nanotube obtained in the step (2) is hydrothermally reacted in perchloric acid, and the perchloric acid molecule can intercalate and swell the carbon nanotube bundle, so that the carbon nanotubes are separated from each other and the surface thereof is highly reacted.
  • the activated carbonaceous by-products are exposed to achieve selective functionalization of carbonaceous by-products. Similar to surfactants, these functionalized carbon by-products have amphiphilic properties, which can improve the interaction between carbon nanotubes and binders, assist in the dispersion of carbon nanotubes, and greatly improve the preparation of positive and negative materials for carbon nanotubes. Uniform dispersion performance.
  • the invention has the following beneficial effects:
  • Lithium battery positive electrode material surface can be uniformly dispersed and coated with carbon source to make up for the low conductivity of lithium battery cathode material
  • the materials used in the examples of the present invention are all raw materials commonly used in the art, and the methods used in the examples are all conventional methods in the art.
  • the plasma injection technology has the following process parameters: argon pressure 1.2-2.7 Mpa, nitrogen pressure 0.9-1.3 Mpa, voltage 5000-12000 V, current 700-850 A, and spraying distance 10-15 m.
  • a plasma jet preparation method for a nano-scale lithium ion composite positive electrode is as follows:
  • Raw materials LiFePO 4 (Formine Plastic Park), activated carbon (South Korea PCT), conductive carbon black (TIMCAL), aluminum foil (20 ⁇ m from Korea).
  • LiFePO 4 , activated carbon, and conductive carbon black having a total mass of 500 g were uniformly mixed at a mass ratio of 20:65:10, and added to a powder feeder, and plasma spray coating was performed at a speed of 5 m/min.
  • a positive electrode having a thickness of 200 ⁇ m was obtained, and the electrode density was determined to be 0.93 g/cm 3 .
  • the obtained positive electrode tab and the graphite negative electrode tab were assembled, and the obtained capacitor battery was subjected to performance test, and charged to 3.7 V with 1 C, discharged to 2.0 V at 1 C, and the specific energy of the capacitor battery was 35.6 Wh/kg.
  • the power is 3800 W/kg, and after 15,000 charge and discharge cycles of 1 C, the capacity is maintained at 91.3%.
  • the obtained positive electrode sheet was observed by SEM scanning, and the activated carbon, conductive carbon black and lithium iron phosphate particles were uniformly mixed, the lithium iron phosphate particles were below 100 nm, and the surface of the lithium iron phosphate was coated with conductive carbon black and Activated carbon mixture.
  • a plasma jet preparation method for a nano-scale lithium ion composite positive electrode is as follows:
  • Raw materials LiMnPO 4 (Ningbo Materials Institute), activated carbon (South Korea PCT), conductive carbon black (TIMCAL), carbon coated aluminum foil (20 ⁇ m from Korea), graphene (Yancheng Naxin), additive S (laboratory synthesis).
  • the total mass of 600 g of LiMnPO 4 , activated carbon, conductive carbon black, and graphene were uniformly mixed at a mass ratio of 15:70:9:1, and added to the powder feeder to coat the carbon coated aluminum foil at a speed of 5 m/min. Plasma spray coating.
  • a positive electrode having a thickness of 220 ⁇ m was obtained, and the electrode density was determined to be 0.86 g/cm 3 .
  • the obtained positive electrode tab and the hard carbon negative electrode tab were assembled, and the obtained capacitor battery was subjected to performance test after being charged and discharged by 0.02 C, and charged to 4.5 V with 1 C, discharged to 2.0 V at 1 C, and the specific energy of the capacitor battery was 52.3. Wh/kg, the specific power is 4250W/kg, and the capacity is maintained at 92.1% after 15000 charge and discharge cycles.
  • the obtained positive electrode piece was observed by SEM scanning, and the activated carbon, conductive carbon black, graphene and lithium manganese phosphate particles were uniformly mixed, and activated carbon, conductive carbon black and lithium manganese phosphate were uniformly distributed in the conduction of single-layer graphene. Structurally, the surface of the nano-sized lithium manganese phosphate is coated with conductive carbon black.
  • a plasma jet preparation method for a nano-scale lithium ion composite positive electrode is as follows:
  • Raw materials LiNi 1/3 Co 1/3 Mn 1/3 O 2 (Shenzhen Betray), activated carbon (South Korea PCT), hard carbon (EnerG2), conductive carbon black (TIMCAL), aluminum foil (produced in Korea 20 ⁇ m), Additive S (laboratory synthesis).
  • LiNi 1/3 Co 1/3 Mn 1/3 O 2 , activated carbon, hard carbon, and conductive carbon black having a total mass of 550 g are uniformly mixed at a mass ratio of 15:60:10:10, and added to the powder feeder.
  • the carbon coated aluminum foil was plasma spray coated at a speed of 5 m/min.
  • a positive electrode having a thickness of 200 ⁇ m was obtained, and the electrode density was measured to be 1.02 g/cm 3 .
  • the obtained positive electrode tab and the silicon carbon negative electrode tab were assembled, and the obtained capacitor battery was subjected to performance test after being charged and discharged by 0.02 C, and charged to 4.2 V with 1 C, discharged to 2.0 V at 1 C, and the specific energy of the capacitor battery was 55.4. Wh/kg, the specific power is 4560 W/kg, and the capacity is maintained at 89.2% after 15,000 charge and discharge cycles.
  • the obtained positive electrode tab was observed by SEM scanning, and the activated carbon, the hard carbon, the conductive carbon black and the ternary cobalt nickel manganese particles were uniformly mixed, and the surface of the cobalt nickel manganese was coated with conductive carbon black.
  • a plasma jet preparation method for a nano-scale lithium ion composite positive electrode is as follows:
  • Raw materials LiFePO 4 (Forminol Changyuan), activated carbon, modified carbon nanotubes, aluminum foil (20 ⁇ m from Korea).
  • Activated carbon is activated carbon with coconut shell or needle coke as precursor.
  • the activated carbon is used after surface modification treatment.
  • the surface modification treatment method is as follows: the silane coupling agent anhydrous ethanol solution with mass concentration of 5% and activated carbon After mixing for 30 min, then adding a solution of aluminate coupling agent in absolute ethanol with a concentration of 8% for 30 min, filtering, drying the filter at 70 ° C for 4 h, then activating at 100 ° C for 1 h, the amount of silane coupling agent
  • the amount of the aluminate coupling agent is 1% by weight of the activated carbon, which is 0.5% by weight of the activated carbon.
  • the secondary modified carbon nanotubes and the perchloric acid with a mass concentration of 50% are uniformly mixed according to the ratio of material to liquid of 1g: 20mL, heated to 60 ° C for 24 hours, cooled, filtered, washed with water, and modified after vacuum drying.
  • a carbon nanotube wherein the acid solution is a mixture of concentrated nitric acid having a mass concentration of 70% and a concentrated sulfuric acid having a mass concentration of 98% in a volume ratio of 1:1; the chemical shearing solution is a molybdenum having a concentration of 0.5 mol/L.
  • the current collecting process is performed before the plasma spraying, and the surface treatment process comprises the following steps: collecting and cleaning the collector, and then performing double-sided etching on the current collector, and coating the chromium with a coating machine at a coating speed of 15 m/min.
  • the acid surface treatment liquid is applied to the surface of the current collector for double-sided etching, and the composition of the chromic acid surface treatment liquid is: lithium chromate 10 parts, water 15 parts, sodium tungstate 3 parts, concentrated sulfuric acid 65 parts; Soaked in the treatment solution, the composition of the treatment liquid is: 20 parts of sodium molybdate, 15 parts of fruit acid, 2 parts of thiourea, 3 parts of sodium phytate, 10 parts of aspartic acid, benzotriazine 10 parts of azole, 2 parts of honey, 90 parts of water, soaking temperature is 70 ° C, soaking time 2h, after washing, washing with water, first drying at 60 ° C for 2h and then heating to 80 ° C for 1.5h, and finally drying at 105 ° C for 1h .
  • the collector was sprayed on both sides with an inert gas (either argon or nitrogen) at a gas flow rate of 120 mL/min.
  • LiFePO 4 , activated carbon, and carbon nanotubes having a total mass of 500 g were uniformly mixed at a mass ratio of 20:65:10, and added to a powder feeder for plasma spray coating at a speed of 5 m/min.
  • a positive electrode having a thickness of 200 ⁇ m was obtained, and the electrode density was determined to be 0.93 g/cm 3 .
  • the obtained positive electrode tab and the graphite negative electrode tab were assembled, and the obtained capacitor battery was subjected to performance test, and charged to 3.7 V with 1 C, discharged to 2.0 V at 1 C, and the specific energy of the capacitor battery was 35.6 Wh/kg.
  • the power is 3800 W/kg, and after 15,000 charge and discharge cycles of 1 C, the capacity is maintained at 91.3%.
  • the obtained positive electrode sheet was observed by SEM scanning, and the activated carbon, conductive carbon black and lithium iron phosphate particles were uniformly mixed, the lithium iron phosphate particles were below 100 nm, and the surface of the lithium iron phosphate was coated with conductive carbon black and Activated carbon mixture.
  • a plasma jet preparation method for a nano-scale lithium ion composite positive electrode is as follows:
  • Raw materials LiFePO 4 (Forminol Changyuan), activated carbon, carbon nanotubes, aluminum foil (20 ⁇ m from Korea).
  • the fluid collecting surface is subjected to a surface treatment process, and the surface treatment process comprises the following steps: collecting and cleaning the current collector after double-sided etching, and then immersing in the treatment liquid, immersing, washing, drying and using an inert gas to the liquid collecting surface.
  • the composition of the treatment liquid is: 22 parts of sodium molybdate, 18 parts of fruit acid, 5 parts of thiourea, 7 parts of sodium phytate, 12 parts of aspartic acid, and 15 parts of benzotriazole.
  • the double-sided etching of the current collector means that the surface treatment liquid of chromic acid is applied to the surface of the current collector by a coater at a coating speed of 20 m/min for double-sided corrosion, chromium
  • the composition of the acid surface treatment liquid is: 12 parts of lithium chromate, 17 parts of water, 5 parts of sodium tungstate, 70 parts of concentrated sulfuric acid; the temperature of the current collector in the treatment liquid is 75 ° C, and the soaking time is 3 hours; When the fluid was dried, it was first dried at 60 ° C for 2 h and then heated to 80 ° C for 1.5 h, and finally dried at 105 ° C for 1 h; the flow velocity of the double-sided jet of the collector using an inert gas was 180 mL / min.
  • Activated carbon is activated carbon with coconut shell or needle coke as precursor, and the activated carbon is used after surface modification treatment.
  • the surface modification treatment method is as follows: the silane coupling agent anhydrous ethanol solution with mass concentration of 8% and activated carbon Mix for 40 min, then add 10% by mass of aluminate coupling agent in absolute ethanol solution for 30-50 min, filter, filter at 75 ° C for 4.5 h, then at 102 ° C for 1.5 h, silane The coupling agent is used in an amount of 0.8% by weight of the activated carbon, and the amount of the aluminate coupling agent is 1.2% by weight of the activated carbon.
  • LiFePO 4 , activated carbon, and conductive carbon black having a total mass of 500 g were uniformly mixed at a mass ratio of 20:65:10, and added to a powder feeder, and plasma spray coating was performed at a speed of 5 m/min.
  • a positive electrode having a thickness of 200 ⁇ m was obtained, and the electrode density was determined to be 0.93 g/cm 3 .
  • the obtained positive electrode tab and the graphite negative electrode tab were assembled, and the obtained capacitor battery was subjected to performance test, and charged to 3.7 V with 1 C, discharged to 2.0 V at 1 C, and the specific energy of the capacitor battery was 35.6 Wh/kg.
  • the power is 3800 W/kg, and after 15,000 charge and discharge cycles of 1 C, the capacity is maintained at 91.3%.
  • the obtained positive electrode sheet was observed by SEM scanning, and the activated carbon, conductive carbon black and lithium iron phosphate particles were uniformly mixed, the lithium iron phosphate particles were below 100 nm, and the surface of the lithium iron phosphate was coated with conductive carbon black and Activated carbon mixture.
  • a plasma jet preparation method for a nano-scale lithium ion composite positive electrode is as follows:
  • Raw materials LiFePO 4 (Forminol Changyuan), activated carbon, modified carbon nanotubes, aluminum foil (20 ⁇ m from Korea).
  • the fluid collecting surface is subjected to a surface treatment process, and the surface treatment process comprises the following steps: collecting and cleaning the current collector after double-sided etching, and then immersing in the treatment liquid, immersing, washing, drying and using an inert gas to the liquid collecting surface.
  • the composition of the treatment liquid is: 25 parts of sodium molybdate, 30 parts of fruit acid, 6 parts of thiourea, 10 parts of sodium phytate, 15 parts of aspartic acid, and 18 parts of benzotriazole.
  • the double-sided etching of the current collector means that the surface treatment liquid of chromic acid is applied to the surface of the current collector by a coater at a coating speed of 25 m/min for double-sided corrosion, chromium
  • the composition of the acid surface treatment liquid is: 15 parts of lithium chromate, 20 parts of water, 6 parts of sodium tungstate, and 75 parts of concentrated sulfuric acid; the temperature of the current collector in the treatment liquid is 85 ° C, and the soaking time is 4 hours; When the fluid was dried, it was first dried at 60 ° C for 2 h and then heated to 80 ° C for 1.5 h, and finally dried at 105 ° C for 1 h; the flow rate of the double-sided jet of the collector using an inert gas was 260 mL / min.
  • the secondary modified carbon nanotubes and the perchloric acid with a mass concentration of 60% are uniformly mixed according to the ratio of material to liquid of 1g: 30mL, heated to 70 ° C for 24 hours, cooled, filtered, washed with water, and modified after vacuum drying.
  • a carbon nanotube wherein the acid solution is a mixture of concentrated nitric acid having a mass concentration of 70% and a concentrated sulfuric acid having a mass concentration of 98% in a volume ratio of 2:1; the chemical shearing solution is a molybdenum having a concentration of 0.8 mol/L.
  • LiFePO 4 , activated carbon, and modified carbon nanotubes having a total mass of 500 g were uniformly mixed at a mass ratio of 20:65:10, and added to a powder feeder for plasma spray coating at a speed of 5 m/min.
  • a positive electrode having a thickness of 200 ⁇ m was obtained, and the electrode density was determined to be 0.93 g/cm 3 .
  • the obtained positive electrode tab and the graphite negative electrode tab were assembled, and the obtained capacitor battery was subjected to performance test, and charged to 3.7 V with 1 C, discharged to 2.0 V at 1 C, and the specific energy of the capacitor battery was 35.6 Wh/kg.
  • the power is 3800 W/kg, and after 15,000 charge and discharge cycles of 1 C, the capacity is maintained at 91.3%.
  • the obtained positive electrode sheet was observed by SEM scanning, and the activated carbon, conductive carbon black and lithium iron phosphate particles were uniformly mixed, the lithium iron phosphate particles were below 100 nm, and the surface of the lithium iron phosphate was coated with conductive carbon black and Activated carbon mixture.
  • a plasma jet preparation method for a nano-scale lithium ion composite positive electrode is as follows:
  • Raw materials LiFePO 4 (Forminol Changyuan), activated carbon, modified carbon nanotubes, aluminum foil (20 ⁇ m from Korea).
  • Activated carbon is activated carbon with coconut shell or needle coke as precursor, and the activated carbon is used after surface modification treatment.
  • the surface modification treatment method is as follows: a silane coupling agent anhydrous ethanol solution with a mass concentration of 10% and activated carbon Mix for 50min, then add 15% mass concentration of aluminate coupling agent in absolute ethanol solution for 50min, filter, filter at 80 ° C for 5h, then activate at 105 ° C for 2h, the amount of silane coupling agent
  • the amount of the aluminate coupling agent is 1.5% by weight of the activated carbon, which is 1% by weight of the activated carbon.
  • the secondary modified carbon nanotubes and the perchloric acid with a mass concentration of 55% are uniformly mixed according to the ratio of material to liquid of 1g: 25mL, heated to 65 ° C for 24 hours, cooled, filtered, washed with water, and modified after vacuum drying.
  • a carbon nanotube wherein the acid solution is a mixture of concentrated nitric acid having a mass concentration of 70% and a concentrated sulfuric acid having a mass concentration of 98% in a volume ratio of 1:1; the chemical shearing solution is a molybdenum having a concentration of 0.6 mol/L.
  • LiFePO 4 , activated carbon, and modified carbon nanotubes having a total mass of 500 g were uniformly mixed at a mass ratio of 20:65:10, and added to a powder feeder for plasma spray coating at a speed of 5 m/min.
  • a positive electrode having a thickness of 200 ⁇ m was obtained, and the electrode density was determined to be 0.93 g/cm 3 .
  • the obtained positive electrode tab and the graphite negative electrode tab were assembled, and the obtained capacitor battery was subjected to performance test, and charged to 3.7 V with 1 C, discharged to 2.0 V at 1 C, and the specific energy of the capacitor battery was 41.6 Wh/kg.
  • the power is 4200 W/kg, and after 15,000 charge and discharge cycles of 1 C, the capacity is maintained at 94.3%.
  • the obtained positive electrode sheet was observed by SEM scanning, and the activated carbon, conductive carbon black and lithium iron phosphate particles were uniformly mixed, the lithium iron phosphate particles were below 100 nm, and the surface of the lithium iron phosphate was coated with conductive carbon black and Activated carbon mixture.
  • the plasma spraying method can achieve nano-level mixing, so that the surface of the lithium-ion positive electrode material can uniformly coat the carbon source, and make up for the low conductivity of the lithium-ion positive electrode material.
  • the plasma jet method enables a dense electrode layer without the need for a rolling process to ensure electrode density.
  • the ratio of the lithium positive electrode material and the porous carbon material of the positive electrode composite electrode is related to the energy density, power density, cycle life, etc. of the finally assembled capacitor battery.
  • the voltage range used is related to the lithium battery cathode material used.

Abstract

The present invention relates to the technical field of lithium-ion batteries, and specifically to a method of preparing plasma spraying for a nanoscale lithium-ion composite positive electrode, the method comprising the following steps: (1) obtaining source materials according to the following proportions: 15-20% of a lithium battery positive electrode material, 5-20% of a conductive agent and 60-80% of a porous carbon material, and uniformly mixing the source materials into a mixture; (2) then adding the mixture into a powder feeder; and (3) coating the mixture onto a collector at a speed of 5 m/min by a plasma spraying technique, the coating being double-sided, and the coating having a thickness of 50-100 μm.

Description

一种纳米级锂离子复合正极的等离子喷射制备方法Plasma jet preparation method for nano-scale lithium ion composite cathode 技术领域Technical field
本发明涉及锂离子电池技术领域，具体涉及一种纳米级锂离子复合正极的等离子喷射制备方法。The invention relates to the technical field of lithium ion batteries, in particular to a plasma spray preparation method of a nanometer lithium ion composite cathode.
背景技术Background technique
锂离子电池是一种能量密度大，平均输出电压高，自放电小并且不含有毒物质的绿色二次电池。经过了将近二十年的发展，锂离子电池已经能达到100Wh/kg到150Wh/kg，工作电压最大可达4V。超级电容是基于双电层储能原理以及可逆性较高的氧化还原准电容原理的储能器件，具有功率密度高、充放电时间短、循环寿命长、工作温度范围宽等优点，同时也具有能量密度相对较低等劣势。A lithium ion battery is a green secondary battery having a large energy density, a high average output voltage, a small self-discharge, and no toxic substances. After nearly two decades of development, lithium-ion batteries have been able to reach 100Wh/kg to 150Wh/kg, and the working voltage can reach up to 4V. Supercapacitor is an energy storage device based on the principle of double-layer energy storage and high reversibility redox quasi-capacitor. It has the advantages of high power density, short charge and discharge time, long cycle life and wide operating temperature range. The energy density is relatively low and so on.
锂离子电池和超级电容在比能量和比功率上的差异决定了两者充放电速率的差异，而在实际的应用中，由于超级电容和锂离子电池具有各自突出的优点以及局限性，两者结合起来的并联式或者串联式电容电池的应用弥补了这一块的空白。正极采用锂离子电池的正极材料混合一定量的多孔碳材料，多孔碳材料包括活性炭、介孔碳、碳纳米管、石墨烯等。然而由于复合正极材料制备过程中受到工艺和成本的影响，复合效果并不理想，无法达到均匀分散以及纳米级别的混合。The difference in specific energy and specific power between lithium-ion battery and super-capacitor determines the difference between charge and discharge rates. In practical applications, supercapacitors and lithium-ion batteries have their own outstanding advantages and limitations. The combination of parallel or series capacitor batteries makes up for this gap. The positive electrode is mixed with a certain amount of porous carbon material using a positive electrode material of a lithium ion battery, and the porous carbon material includes activated carbon, mesoporous carbon, carbon nanotubes, graphene, and the like. However, due to the influence of process and cost in the preparation process of the composite positive electrode material, the composite effect is not ideal, and uniform dispersion and nano-level mixing cannot be achieved.
锂电正极材料的发展历程从层状结构的钴酸锂，尖晶石结构的锰酸锂，橄榄石结构的磷铁酸锂到三元材料锂镍钴锰。钴酸锂正极材料是目前传统电子产品中锂电的主要使用材料，主要是基于其容量大、电压范围大等优势。锰酸锂由于其低价、稳定、导电性能好等优点在电动自行车、电动汽车等领域广泛应用，但也存在其容量衰减问题。近年来随着使用清洁能源的公共交通的大力发展，橄榄石结构的磷酸铁锂正极材料和更为技术发展前沿的三元材料锂镍钴锰被广泛地应用到电动汽车及大规模储能器件。The development of lithium battery cathode materials is from layered structure of lithium cobaltate, spinel structure of lithium manganate, olivine structure of lithium phosphite to ternary material lithium nickel cobalt manganese. Lithium cobaltate cathode material is the main material used in lithium batteries in traditional electronic products, mainly based on its large capacity and large voltage range. Lithium manganate has been widely used in electric bicycles, electric vehicles, etc. due to its low cost, stability, and good electrical conductivity, but it also has its capacity attenuation problem. In recent years, with the development of public transportation using clean energy, the olivine-structured lithium iron phosphate cathode material and the more advanced development of the ternary material lithium nickel cobalt manganese have been widely applied to electric vehicles and large-scale energy storage devices. .
等离子喷射法是是采用由直流电驱动的等离子电弧作为热源，将陶瓷、合金、金属等材料加热到熔融或半熔融状态，并以高速喷向经过预处理的工件表面而形成附着牢固的表面层的方法。该方法利用等离子弧进行的，离子弧是压缩电弧，与自由电弧相比较，其弧柱细，电流密度大，气体电离度高，因此具有温度高，能量集中，弧稳定性好等特点。The plasma spraying method uses a plasma arc driven by a direct current as a heat source to heat a ceramic, an alloy, a metal or the like into a molten or semi-molten state, and sprays the surface of the pretreated workpiece at a high speed to form a firmly adhered surface layer. method. The method uses a plasma arc, and the ion arc is a compression arc. Compared with the free arc, the arc column is thin, the current density is high, and the gas ionization degree is high, so the temperature is high, the energy is concentrated, and the arc stability is good.
发明内容Summary of the invention
本发明的目的是为了解决锂离子电容电池正极复合材料在制备工艺上由于分散、性能均一以及粒径分布等方面的不足导致电化学性能受到限制的问题，提供一种纳米级锂离子复合正极的等离子喷射制备方法。本发明能够以较为经济的方法制得在纳米尺寸上混合均匀的锂 电正极材料和多孔碳复合材料，并且将其涂覆在铝箔上得到复合电极。The purpose of the invention is to solve the problem that the electrochemical performance of the positive electrode composite material of the lithium ion capacitor battery is limited due to the defects of dispersion, uniformity and particle size distribution in the preparation process, and a nanometer lithium ion composite positive electrode is provided. Plasma spray preparation method. The invention can produce lithium mixed uniformly on the nanometer size in a relatively economical way An electric positive electrode material and a porous carbon composite material were coated on an aluminum foil to obtain a composite electrode.
为了达到上述发明目的，本发明采用以下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种纳米级锂离子复合正极的等离子喷射制备方法，包括以下步骤：A plasma jet preparation method for a nano-scale lithium ion composite positive electrode, comprising the following steps:
(1)按比例取原料15-20％锂电正极材料、5-20％的导电剂和60-80％多孔碳材料混合均匀成混合物；(1) Proportionally taking 15-20% lithium battery positive electrode material, 5-20% conductive agent and 60-80% porous carbon material to form a mixture;
(2)然后将混合物加入到送粉器中；(2) then adding the mixture to the powder feeder;
(3)以5m/min的速度将混合物采用等离子喷射技术涂覆到集流体上，涂覆为双面涂覆，涂覆的厚度为50-100μm。(3) The mixture was applied to the current collector by a plasma jet technique at a speed of 5 m/min, and the coating was applied by double-sided coating to a thickness of 50 to 100 μm.
作为优选，锂电正极材料为LiCoO2、LiMn2O4、LiMnO2、LiNiO2、LiFePO4、LiMnPO4、LiNi0.8Co0.2O2或LiNi1/3Co1/3Mn1/3O2。Preferably, the lithium positive electrode material is LiCoO 2 , LiMn 2 O 4 , LiMnO 2 , LiNiO 2 , LiFePO 4 , LiMnPO 4 , LiNi 0.8 Co 0.2 O 2 or LiNi 1/3 Co 1/3 Mn 1/3 O 2 .
作为优选，多孔碳材料为活性炭、介孔碳、碳气凝胶、碳纤维、碳纳米管、炭黑、硬炭或石墨烯中。Preferably, the porous carbon material is activated carbon, mesoporous carbon, carbon aerogel, carbon fiber, carbon nanotube, carbon black, hard carbon or graphene.
作为优选，所述集流体为涂炭铝箔、铝箔、带孔铝箔、铜箔或带孔铜箔。Preferably, the current collector is a carbon coated aluminum foil, an aluminum foil, a perforated aluminum foil, a copper foil or a perforated copper foil.
作为优选，集流体的厚度为20μm。Preferably, the current collector has a thickness of 20 μm.
作为优选，所述导电剂为导电炭黑、石墨烯或碳纳米管。Preferably, the conductive agent is conductive carbon black, graphene or carbon nanotubes.
作为优选，所述等离子喷射技术包括：低温低压等离子技术、高温低压等离子技术、真空等离子技术、水稳等离子技术和气稳等离子技术。Preferably, the plasma spraying technology comprises: low temperature and low pressure plasma technology, high temperature and low pressure plasma technology, vacuum plasma technology, water stable plasma technology and gas stabilization plasma technology.
作为优选，等离子喷射技术的工艺参数为：氩气压力1.2-2.7Mpa，氮气压力为0.9-1.3Mpa，电压5000-12000V，电流700-850A，喷涂距离10-15米。Preferably, the plasma injection technique has process parameters of: argon gas pressure of 1.2-2.7 MPa, nitrogen pressure of 0.9-1.3 MPa, voltage of 5000-12000 V, current of 700-850 A, and spraying distance of 10-15 m.
作为优选，步骤3)前集流体进行表面处理工艺。Preferably, step 3) the front current collector is subjected to a surface treatment process.
作为优选，所述表面处理工艺包括以下步骤：集流体清洗、干燥后对集流体进行双面腐蚀，然后放入处理液中浸泡，浸泡完后水洗、干燥并用惰性气体对集流体双面喷射。所述处理液按重量份计其组成为：钼酸钠20-25份、果酸15-30份、硫脲2-6份、植酸钠3-10份、天冬氨酸10-15份、苯并三氮唑10-18份、蜂蜜2-6份、水90-130份；所述对集流体进行双面腐蚀是指用涂布机经15-25m/min的涂布速度将铬酸表面处理液涂布到集流体表面进行双面腐蚀，铬酸表面处理液按重量份其组成为：铬酸锂10-15份、水15-20份、钨酸钠3-6份、浓硫酸65-75份；集流体在处理液中浸泡的温度为70-85℃，浸泡时间2-4h；集流体干燥时先在60℃下干燥2h然后升温至80℃干燥1.5h，最后再105℃干燥1h；使用惰性气体对集流体双面喷射的气流速度为120-260mL/min。Preferably, the surface treatment process comprises the following steps: collecting and cleaning the current collector after double-sided etching, and then immersing in the treatment liquid. After soaking, washing, drying and spraying the liquid on both sides with an inert gas. The treatment liquid has a composition of: 20-25 parts by weight of sodium molybdate, 15-30 parts of fruit acid, 2-6 parts of thiourea, 3-10 parts of sodium phytate, and 10-15 parts of aspartic acid. 10-18 parts of benzotriazole, 2-6 parts of honey, 90-130 parts of water; the double-sided etching of the current collector means that the coating is performed at a coating speed of 15-25 m/min by a coater. The acid surface treatment liquid is applied to the surface of the current collector for double-sided corrosion. The composition of the chromic acid surface treatment liquid is 10-15 parts by weight of lithium chromate, 15-20 parts of water, 3-6 parts of sodium tungstate, and concentrated. 65-75 parts of sulfuric acid; the temperature of the current collector soaked in the treatment liquid is 70-85 ° C, soaking time 2-4 h; the current collector is dried at 60 ° C for 2 h and then heated to 80 ° C for 1.5 h, and finally 105 Dry at °C for 1 h; the gas flow rate of the double-sided jet of the current collector using an inert gas was 120-260 mL/min.
在本技术方案中，对集流体表面处理后比表面积增大，表面张力减小，可提高电极薄膜的粘 合强度，有助于降低电极的内阻，延长锂离子电池的使用寿命；处理液可以提高集流体的耐腐蚀性，可以进一步提高正极材料在集流体表面的粘合性能，从而降低内阻。In the technical solution, the surface area of the current collector is increased, the surface tension is decreased, and the adhesion of the electrode film can be improved. The combined strength helps to reduce the internal resistance of the electrode and prolong the service life of the lithium ion battery; the treatment liquid can improve the corrosion resistance of the current collector, and can further improve the adhesion performance of the positive electrode material on the surface of the current collector, thereby reducing the internal resistance.
作为优选，所述活性炭是以椰壳或针状焦为前驱体的活性炭，所述活性炭表面改性处理后使用，表面改性处理的方法为：将质量浓度为5-10％的硅烷偶联剂无水乙醇溶液与活性炭混合30-50min，然后再加入质量浓度为8-15％的铝酸酯偶联剂无水乙醇溶液在混合30-50min，过滤，过滤物在70-80℃下干燥4-5h，再在100℃-105℃下活化1-2h，硅烷偶联剂用量为活性炭重量的0.5-1％，铝酸酯偶联剂用量为活性炭重量的1-1.5％。Preferably, the activated carbon is activated carbon with coconut shell or needle coke as a precursor, and the activated carbon is used after surface modification treatment, and the surface modification treatment method is: coupling silane with a mass concentration of 5-10%. The anhydrous ethanol solution is mixed with activated carbon for 30-50min, then added with a concentration of 8-15% aluminate coupling agent in absolute ethanol solution for 30-50min, filtered, and the filter is dried at 70-80 ° C. 4-5h, and then activated at 100 ° C -105 ° C for 1-2 h, the amount of silane coupling agent is 0.5-1% of the weight of activated carbon, and the amount of aluminate coupling agent is 1-1.5% of the weight of activated carbon.
在本技术方案中，以椰壳或针状焦为前驱体的活性炭，孔隙适中，用于正极活性物质的性能较佳。发明人通过长期的实验研究后发现，先通过使用硅烷偶联剂对活性炭进行第一次表面处理，硅烷偶联剂混入活性炭后，能有效渗入活性炭颗粒之间的间隙，使活性炭颗粒间相对隔离，能有效的提高活性炭的分散性，然后再通过添加铝酸酯偶联剂对处理过的活性炭进行第二次表面处理，这样能有效解决活性炭团聚的问题，使铝酸酯偶联剂有效的包裹活性炭，进一步的防止了活性炭的团聚，由于偶联剂的处理，活性炭亲油基团增加，与粘结剂等成分混合的更均匀，所得正极材料成分分布均匀，性能稳定。In the present technical solution, the activated carbon having a coconut shell or needle coke as a precursor has a moderate pore size, and the performance for the positive electrode active material is better. After long-term experimental research, the inventors discovered that the first surface treatment of activated carbon is first carried out by using a silane coupling agent. After the silane coupling agent is mixed into the activated carbon, it can effectively penetrate into the gap between the activated carbon particles, so that the activated carbon particles are relatively isolated. It can effectively improve the dispersibility of activated carbon, and then the second surface treatment of the treated activated carbon by adding an aluminate coupling agent, which can effectively solve the problem of agglomeration of activated carbon and make the aluminate coupling agent effective. The activated carbon is further prevented from agglomeration of the activated carbon. Due to the treatment of the coupling agent, the oleophilic group of the activated carbon is increased, and the components such as the binder are more uniformly mixed, and the obtained positive electrode material has a uniform distribution and stable performance.
作为优选，所述导电剂为改性碳纳米管，改性碳纳米管的制备方法步骤如下：Preferably, the conductive agent is a modified carbon nanotube, and the steps of preparing the modified carbon nanotube are as follows:
(1)将碳纳米管、质量浓度30-50％的二甲基甲酰胺溶液及酸溶液按照1g：10-20mL：5-15mL的料液比混合，控制温度35-45℃下搅拌混合30-50min，过滤，分别用水和无水乙醇洗涤，80-100℃下真空干燥30-60min得初级改性碳纳米管；(1) mixing carbon nanotubes, a concentration of 30-50% dimethylformamide solution and an acid solution according to a ratio of material to liquid of 1g: 10-20mL: 5-15mL, and mixing and controlling at a temperature of 35-45 ° C. -50min, filtration, washing with water and anhydrous ethanol, vacuum drying at 80-100 ° C for 30-60min to obtain primary modified carbon nanotubes;
(2)将初级改性碳纳米管与化学剪切液按照1g：30-50mL的料液比混合，加热至150-180℃，水热反应40-60h，冷却，水洗，得次级改性碳纳米管；(2) mixing the primary modified carbon nanotubes with the chemical shear liquid according to the ratio of material to liquid of 1g: 30-50mL, heating to 150-180 ° C, hydrothermal reaction for 40-60 hours, cooling, washing with water to obtain secondary modification. Carbon nanotubes;
(3)次级改性碳纳米管与质量浓度50-60％的高氯酸按照1g：20-30mL的料液比混合均匀，加热至60-70℃保持24小时，冷却，过滤，水洗，真空干燥后得改性碳纳米管；其中，所述酸溶液为质量浓度70％的浓硝酸与质量浓度98％的浓硫酸按照1-2:1的体积比的混合物；所述化学剪切液为浓度0.5-0.8moL/L的钼酸钠溶液与浓度0.3-0.5moL/L的硅钼酸溶液按照1:1的体积比的混合物。(3) The secondary modified carbon nanotubes and the perchloric acid having a mass concentration of 50-60% are uniformly mixed according to the ratio of material to liquid of 1g: 20-30mL, heated to 60-70 ° C for 24 hours, cooled, filtered, washed with water, After vacuum drying, the modified carbon nanotubes are obtained; wherein the acid solution is a mixture of concentrated nitric acid having a mass concentration of 70% and a concentrated sulfuric acid having a mass concentration of 98% in a volume ratio of 1-2:1; the chemical shear liquid A mixture of a sodium molybdate solution having a concentration of 0.5-0.8 mol/L and a silicomolybdic acid solution having a concentration of 0.3-0.5 mol/L in a volume ratio of 1:1.
在本技术方案中，研究表明：在包含碳纳米管的电极中，当碳纳米管的数量大到足以使碳纳米管能够彼此接触时，才能使电极不受碳纳米管自身的电阻影响，而主要受相互之间的接触电阻影响。因此在添加碳纳米管时需要的量就会较大。典型的多壁碳纳米管的直径一般为几纳米至几十纳米，长度为几至几十微米。制备的样品多呈杂乱分布，碳纳米管之间相互缠绕难以分散，成团状的碳纳米管需要被分散成单个的碳纳米管，才能发挥其特殊性能。In the present technical solution, studies have shown that in an electrode comprising carbon nanotubes, when the number of carbon nanotubes is large enough to allow the carbon nanotubes to contact each other, the electrode is not affected by the resistance of the carbon nanotube itself. Mainly affected by the contact resistance between each other. Therefore, the amount required for the addition of carbon nanotubes is large. Typical multi-walled carbon nanotubes generally have a diameter of a few nanometers to several tens of nanometers and a length of several to several tens of micrometers. The prepared samples are mostly disorderly distributed, and the carbon nanotubes are intertwined and difficult to disperse, and the agglomerated carbon nanotubes need to be dispersed into individual carbon nanotubes to exert their special properties.
步骤(1)将碳纳米管与质量浓度30-50％的二甲基甲酰胺溶液及酸溶液混合，同时辅以搅拌，以扩大碳纳米管与液体的接触面，使得碳纳米管分散均匀，质量浓度30-50％的二甲基甲酰胺溶液及酸溶液的特定溶剂组合体系，能够使得碳纳米管能在体系中分散更均匀，有效避免碳纳米管团聚。 Step (1) mixing the carbon nanotubes with a dimethylformamide solution having a mass concentration of 30-50% and an acid solution, and simultaneously stirring to enlarge the contact surface of the carbon nanotubes with the liquid, so that the carbon nanotubes are uniformly dispersed. The specific solvent combination system of the dimethylformamide solution and the acid solution with a mass concentration of 30-50% can make the carbon nanotubes disperse more uniformly in the system and effectively avoid the agglomeration of the carbon nanotubes.
步骤(1)先将碳纳米管分散均匀，这样利于步骤(2)的剪切，将步骤(1)分散均匀的碳纳米管与本发明特定的化学剪切液水热反应，能有效切断碳纳米管，获得长度较均一(长度大约在100-150nm)左右的均一化碳纳米管，这样的碳纳米管在用于电极材料时，可以用更少的量发挥更优异的导电导热效果。Step (1) firstly dispersing the carbon nanotubes uniformly, which facilitates the shearing of the step (2), and hydrothermally reacts the uniformly dispersed carbon nanotubes of the step (1) with the specific chemical shear liquid of the present invention, thereby effectively cutting the carbon. In the nanotubes, uniform carbon nanotubes having a relatively uniform length (about 100-150 nm in length) are obtained, and such carbon nanotubes can exhibit more excellent electrical and thermal conduction effects in a smaller amount when used for an electrode material.
步骤(3)将步骤(2)得到的均一化碳纳米管在高氯酸中水热反应，高氯酸分子能够插层、溶胀碳纳米管束，使碳纳米管彼此分开并将其表面高反应活性的碳质副产物暴露出来，从而实现选择性功能化碳质副产物。与表面活性剂类似，这些功能化的碳质副产物具有两亲性，可改善碳纳米管与粘结剂的相互作用，协助碳纳米管分散，从而大大提高碳纳米管在制备正负极材料时的均匀分散性能。Step (3) The homogenized carbon nanotube obtained in the step (2) is hydrothermally reacted in perchloric acid, and the perchloric acid molecule can intercalate and swell the carbon nanotube bundle, so that the carbon nanotubes are separated from each other and the surface thereof is highly reacted. The activated carbonaceous by-products are exposed to achieve selective functionalization of carbonaceous by-products. Similar to surfactants, these functionalized carbon by-products have amphiphilic properties, which can improve the interaction between carbon nanotubes and binders, assist in the dispersion of carbon nanotubes, and greatly improve the preparation of positive and negative materials for carbon nanotubes. Uniform dispersion performance.
本发明与现有技术相比，有益效果是：Compared with the prior art, the invention has the following beneficial effects:
1锂电正极材料表面能均匀分散包覆碳源，弥补锂电正极材料存在的导电率低等问题1 Lithium battery positive electrode material surface can be uniformly dispersed and coated with carbon source to make up for the low conductivity of lithium battery cathode material
2等离子喷射法能够实现致密的电极层，无需经过碾压工序，保证电极密度，2 plasma spray method can achieve a dense electrode layer without the need of a rolling process to ensure electrode density,
具体实施方式detailed description
下面通过具体实施例对本发明的技术方案作进一步描述说明。The technical solutions of the present invention are further described below through specific embodiments.
如果无特殊说明，本发明的实施例中所采用的原料均为本领域常用的原料，实施例中所采用的方法，均为本领域的常规方法。Unless otherwise specified, the materials used in the examples of the present invention are all raw materials commonly used in the art, and the methods used in the examples are all conventional methods in the art.
本发明中，等离子喷射技术的工艺参数为：氩气压力1.2-2.7Mpa，氮气压力为0.9-1.3Mpa，电压5000-12000V，电流700-850A，喷涂距离10-15米。In the present invention, the plasma injection technology has the following process parameters: argon pressure 1.2-2.7 Mpa, nitrogen pressure 0.9-1.3 Mpa, voltage 5000-12000 V, current 700-850 A, and spraying distance 10-15 m.
实施例1：Example 1:
一种纳米级锂离子复合正极的等离子喷射制备方法，制备过程如下：A plasma jet preparation method for a nano-scale lithium ion composite positive electrode, the preparation process is as follows:
磷酸铁锂/活性炭复合电极的制备过程Preparation process of lithium iron phosphate/activated carbon composite electrode
原材料：LiFePO4(台塑长园)、活性炭(韩国PCT)、导电炭黑(TIMCAL)、铝箔(韩国产20μm)。Raw materials: LiFePO 4 (Formine Plastic Park), activated carbon (South Korea PCT), conductive carbon black (TIMCAL), aluminum foil (20 μm from Korea).
将总质量为500g的LiFePO4、活性炭、导电炭黑按照质量比为20:65:10的比例混合均匀，加入到送粉器中，用5m/min的速度进行等离子喷射涂覆。LiFePO 4 , activated carbon, and conductive carbon black having a total mass of 500 g were uniformly mixed at a mass ratio of 20:65:10, and added to a powder feeder, and plasma spray coating was performed at a speed of 5 m/min.
经过冷却干燥和双面涂覆后，得到厚度为200μm的正极，经测定，该电极密度为0.93g/cm3。将得到的正极极片与石墨负极极片进行组装，得到的电容电池经过化成后进行性能测试，用1C充电至3.7V，1C放电至2.0V，电容电池的比能量为35.6Wh/kg,比功率为3800W/kg，经过1C充放电循环15000次后，容量保持在91.3％。 After cooling and drying and double-sided coating, a positive electrode having a thickness of 200 μm was obtained, and the electrode density was determined to be 0.93 g/cm 3 . The obtained positive electrode tab and the graphite negative electrode tab were assembled, and the obtained capacitor battery was subjected to performance test, and charged to 3.7 V with 1 C, discharged to 2.0 V at 1 C, and the specific energy of the capacitor battery was 35.6 Wh/kg. The power is 3800 W/kg, and after 15,000 charge and discharge cycles of 1 C, the capacity is maintained at 91.3%.
将得到的正极极片经过SEM扫描得到的图片看出，活性炭、导电炭黑和磷酸铁锂颗粒混合均匀，磷酸铁锂颗粒在100nm以下，并且在磷酸铁锂表面均包覆有导电炭黑和活性炭混合物。The obtained positive electrode sheet was observed by SEM scanning, and the activated carbon, conductive carbon black and lithium iron phosphate particles were uniformly mixed, the lithium iron phosphate particles were below 100 nm, and the surface of the lithium iron phosphate was coated with conductive carbon black and Activated carbon mixture.
实施例2：Example 2:
一种纳米级锂离子复合正极的等离子喷射制备方法，制备过程如下：A plasma jet preparation method for a nano-scale lithium ion composite positive electrode, the preparation process is as follows:
磷酸锰锂/活性炭/石墨烯复合电极制备过程：Preparation process of lithium manganese phosphate/activated carbon/graphene composite electrode:
原材料：LiMnPO4(宁波材料所)、活性炭(韩国PCT)、导电炭黑(TIMCAL)、涂炭铝箔(韩国产20μm)、石墨烯(盐城纳新)、添加剂S(实验室合成)。Raw materials: LiMnPO 4 (Ningbo Materials Institute), activated carbon (South Korea PCT), conductive carbon black (TIMCAL), carbon coated aluminum foil (20 μm from Korea), graphene (Yancheng Naxin), additive S (laboratory synthesis).
将总质量为600g的LiMnPO4、活性炭、导电炭黑、石墨烯按照质量比为15:70:9:1的比例混合均匀，加入到送粉器中，用5m/min的速度对涂炭铝箔进行等离子喷射涂覆。The total mass of 600 g of LiMnPO 4 , activated carbon, conductive carbon black, and graphene were uniformly mixed at a mass ratio of 15:70:9:1, and added to the powder feeder to coat the carbon coated aluminum foil at a speed of 5 m/min. Plasma spray coating.
经过冷却干燥和双面涂覆后，得到厚度为220μm的正极，经测定，该电极密度为0.86g/cm3。将得到的正极极片与硬炭负极极片进行组装，得到的电容电池经过0.02C化成充放电后进行性能测试，用1C充电至4.5V，1C放电至2.0V，电容电池的比能量为52.3Wh/kg,比功率为4250W/kg，经过1C充放电循环15000次后，容量保持在92.1％。After cooling and drying and double-sided coating, a positive electrode having a thickness of 220 μm was obtained, and the electrode density was determined to be 0.86 g/cm 3 . The obtained positive electrode tab and the hard carbon negative electrode tab were assembled, and the obtained capacitor battery was subjected to performance test after being charged and discharged by 0.02 C, and charged to 4.5 V with 1 C, discharged to 2.0 V at 1 C, and the specific energy of the capacitor battery was 52.3. Wh/kg, the specific power is 4250W/kg, and the capacity is maintained at 92.1% after 15000 charge and discharge cycles.
将得到的正极极片经过SEM扫描得到的图片看出，活性炭、导电炭黑、石墨烯和磷酸锰锂颗粒混合均匀，活性炭、导电炭黑、磷酸锰锂均匀得分布在单层石墨烯的导电结构上，其中纳米级的磷酸锰锂表面还有导电炭黑的包覆。The obtained positive electrode piece was observed by SEM scanning, and the activated carbon, conductive carbon black, graphene and lithium manganese phosphate particles were uniformly mixed, and activated carbon, conductive carbon black and lithium manganese phosphate were uniformly distributed in the conduction of single-layer graphene. Structurally, the surface of the nano-sized lithium manganese phosphate is coated with conductive carbon black.
实施例3：Example 3:
一种纳米级锂离子复合正极的等离子喷射制备方法，制备过程如下：A plasma jet preparation method for a nano-scale lithium ion composite positive electrode, the preparation process is as follows:
三元钴镍锰/活性炭/硬炭复合电极制备过程：Preparation process of ternary cobalt nickel manganese/activated carbon/hard carbon composite electrode:
原材料：LiNi1/3Co1/3Mn1/3O2(深圳贝特瑞)、活性炭(韩国PCT)、硬炭(EnerG2)、导电炭黑(TIMCAL)、铝箔(韩国产20μm)、、添加剂S(实验室合成)。Raw materials: LiNi 1/3 Co 1/3 Mn 1/3 O 2 (Shenzhen Betray), activated carbon (South Korea PCT), hard carbon (EnerG2), conductive carbon black (TIMCAL), aluminum foil (produced in Korea 20 μm), Additive S (laboratory synthesis).
将总质量为550g的LiNi1/3Co1/3Mn1/3O2、活性炭、硬炭、导电炭黑按照质量比为15:60:10:10的比例混合均匀，加入到送粉器中，用5m/min的速度对涂炭铝箔进行等离子喷射涂覆。LiNi 1/3 Co 1/3 Mn 1/3 O 2 , activated carbon, hard carbon, and conductive carbon black having a total mass of 550 g are uniformly mixed at a mass ratio of 15:60:10:10, and added to the powder feeder. The carbon coated aluminum foil was plasma spray coated at a speed of 5 m/min.
经过冷却干燥和双面涂覆后，得到厚度为200μm的正极，经测定，该电极密度为1.02g/cm3。将得到的正极极片与硅碳负极极片进行组装，得到的电容电池经过0.02C化成充放电后进行性能测试，用1C充电至4.2V，1C放电至2.0V，电容电池的比能量为55.4Wh/kg,比功率为4560W/kg，经过1C充放电循环15000次后，容量保持在89.2％。After cooling and drying and double-sided coating, a positive electrode having a thickness of 200 μm was obtained, and the electrode density was measured to be 1.02 g/cm 3 . The obtained positive electrode tab and the silicon carbon negative electrode tab were assembled, and the obtained capacitor battery was subjected to performance test after being charged and discharged by 0.02 C, and charged to 4.2 V with 1 C, discharged to 2.0 V at 1 C, and the specific energy of the capacitor battery was 55.4. Wh/kg, the specific power is 4560 W/kg, and the capacity is maintained at 89.2% after 15,000 charge and discharge cycles.
将得到的正极极片经过SEM扫描得到的图片看出，活性炭、硬炭、导电炭黑和三元钴镍锰颗粒混合均匀，其中钴镍锰表面还有导电炭黑的包覆。The obtained positive electrode tab was observed by SEM scanning, and the activated carbon, the hard carbon, the conductive carbon black and the ternary cobalt nickel manganese particles were uniformly mixed, and the surface of the cobalt nickel manganese was coated with conductive carbon black.
实施例4 Example 4
一种纳米级锂离子复合正极的等离子喷射制备方法，制备过程如下：A plasma jet preparation method for a nano-scale lithium ion composite positive electrode, the preparation process is as follows:
磷酸铁锂/活性炭复合电极的制备过程Preparation process of lithium iron phosphate/activated carbon composite electrode
原材料：LiFePO4(台塑长园)、活性炭、改性纳米碳管、铝箔(韩国产20μm)。Raw materials: LiFePO 4 (Forminol Changyuan), activated carbon, modified carbon nanotubes, aluminum foil (20μm from Korea).
活性炭是以椰壳或针状焦为前驱体的活性炭，所述活性炭表面改性处理后使用，表面改性处理的方法为：将质量浓度为5％的硅烷偶联剂无水乙醇溶液与活性炭混合30min，然后再加入质量浓度为8％的铝酸酯偶联剂无水乙醇溶液在混合30min，过滤，过滤物在70℃下干燥4h，再在100℃下活化1h，硅烷偶联剂用量为活性炭重量的0.5％，铝酸酯偶联剂用量为活性炭重量的1％。Activated carbon is activated carbon with coconut shell or needle coke as precursor. The activated carbon is used after surface modification treatment. The surface modification treatment method is as follows: the silane coupling agent anhydrous ethanol solution with mass concentration of 5% and activated carbon After mixing for 30 min, then adding a solution of aluminate coupling agent in absolute ethanol with a concentration of 8% for 30 min, filtering, drying the filter at 70 ° C for 4 h, then activating at 100 ° C for 1 h, the amount of silane coupling agent The amount of the aluminate coupling agent is 1% by weight of the activated carbon, which is 0.5% by weight of the activated carbon.
改性碳纳米管的制备方法步骤如下：The steps for preparing the modified carbon nanotubes are as follows:
(1)将碳纳米管、质量浓度30％的二甲基甲酰胺溶液及酸溶液按照1g：10mL：5mL的料液比混合，控制温度35℃下搅拌混合30min，过滤，分别用水和无水乙醇洗涤，80℃下真空干燥30min得初级改性碳纳米管；(1) Mixing carbon nanotubes, 30% by mass dimethylformamide solution and acid solution according to the ratio of material to liquid of 1g: 10mL: 5mL, stirring and mixing at a controlled temperature of 35 ° C for 30 min, filtering, respectively, with water and anhydrous Ethanol washing, vacuum drying at 80 ° C for 30 min to obtain primary modified carbon nanotubes;
(2)将初级改性碳纳米管与化学剪切液按照1g：30mL的料液比混合，加热至150℃，水热反应40h，冷却，水洗，得次级改性碳纳米管；(2) mixing the primary modified carbon nanotubes with the chemical shear liquid according to a ratio of 1 g: 30 mL of the liquid to liquid, heating to 150 ° C, hydrothermal reaction for 40 h, cooling, washing with water to obtain secondary modified carbon nanotubes;
(3)次级改性碳纳米管与质量浓度50％的高氯酸按照1g：20mL的料液比混合均匀，加热至60℃保持24小时，冷却，过滤，水洗，真空干燥后得改性碳纳米管；其中，所述酸溶液为质量浓度70％的浓硝酸与质量浓度98％的浓硫酸按照1:1的体积比的混合物；所述化学剪切液为浓度0.5moL/L的钼酸钠溶液与浓度0.3moL/L的硅钼酸溶液按照1:1的体积比的混合物。(3) The secondary modified carbon nanotubes and the perchloric acid with a mass concentration of 50% are uniformly mixed according to the ratio of material to liquid of 1g: 20mL, heated to 60 ° C for 24 hours, cooled, filtered, washed with water, and modified after vacuum drying. a carbon nanotube; wherein the acid solution is a mixture of concentrated nitric acid having a mass concentration of 70% and a concentrated sulfuric acid having a mass concentration of 98% in a volume ratio of 1:1; the chemical shearing solution is a molybdenum having a concentration of 0.5 mol/L. A mixture of sodium solution and a concentration of 0.3 mol/L of silicomolybdic acid solution in a volume ratio of 1:1.
集流体在进行等离子喷射前先进行表面处理工艺，所述表面处理工艺包括以下步骤：集流体清洗、干燥后对集流体进行双面腐蚀，用涂布机经15m/min的涂布速度将铬酸表面处理液涂布到集流体表面进行双面腐蚀，铬酸表面处理液按重量份其组成为：铬酸锂10份、水15份、钨酸钠3份、浓硫酸65份；然后放入处理液中浸泡，处理液按重量份计其组成为：钼酸钠20份、果酸15份、硫脲2-份、植酸钠3份、天冬氨酸10份、苯并三氮唑10份、蜂蜜2份、水90份，浸泡的温度为70℃，浸泡时间2h，浸泡完后水洗、先在60℃下干燥2h然后升温至80℃干燥1.5h，最后再105℃干燥1h。并用惰性气体(可以用氩气，也可以用氮气)对集流体双面喷射，气流速度为120mL/min。The current collecting process is performed before the plasma spraying, and the surface treatment process comprises the following steps: collecting and cleaning the collector, and then performing double-sided etching on the current collector, and coating the chromium with a coating machine at a coating speed of 15 m/min. The acid surface treatment liquid is applied to the surface of the current collector for double-sided etching, and the composition of the chromic acid surface treatment liquid is: lithium chromate 10 parts, water 15 parts, sodium tungstate 3 parts, concentrated sulfuric acid 65 parts; Soaked in the treatment solution, the composition of the treatment liquid is: 20 parts of sodium molybdate, 15 parts of fruit acid, 2 parts of thiourea, 3 parts of sodium phytate, 10 parts of aspartic acid, benzotriazine 10 parts of azole, 2 parts of honey, 90 parts of water, soaking temperature is 70 ° C, soaking time 2h, after washing, washing with water, first drying at 60 ° C for 2h and then heating to 80 ° C for 1.5h, and finally drying at 105 ° C for 1h . The collector was sprayed on both sides with an inert gas (either argon or nitrogen) at a gas flow rate of 120 mL/min.
将总质量为500g的LiFePO4、活性炭、纳米碳管按照质量比为20:65:10的比例混合均匀，加入到送粉器中，用5m/min的速度进行等离子喷射涂覆。LiFePO 4 , activated carbon, and carbon nanotubes having a total mass of 500 g were uniformly mixed at a mass ratio of 20:65:10, and added to a powder feeder for plasma spray coating at a speed of 5 m/min.
经过冷却干燥和双面涂覆后，得到厚度为200μm的正极，经测定，该电极密度为0.93g/cm3。将得到的正极极片与石墨负极极片进行组装，得到的电容电池经过化成后进行性能测试，用 1C充电至3.7V，1C放电至2.0V，电容电池的比能量为35.6Wh/kg,比功率为3800W/kg，经过1C充放电循环15000次后，容量保持在91.3％。After cooling and drying and double-sided coating, a positive electrode having a thickness of 200 μm was obtained, and the electrode density was determined to be 0.93 g/cm 3 . The obtained positive electrode tab and the graphite negative electrode tab were assembled, and the obtained capacitor battery was subjected to performance test, and charged to 3.7 V with 1 C, discharged to 2.0 V at 1 C, and the specific energy of the capacitor battery was 35.6 Wh/kg. The power is 3800 W/kg, and after 15,000 charge and discharge cycles of 1 C, the capacity is maintained at 91.3%.
将得到的正极极片经过SEM扫描得到的图片看出，活性炭、导电炭黑和磷酸铁锂颗粒混合均匀，磷酸铁锂颗粒在100nm以下，并且在磷酸铁锂表面均包覆有导电炭黑和活性炭混合物。The obtained positive electrode sheet was observed by SEM scanning, and the activated carbon, conductive carbon black and lithium iron phosphate particles were uniformly mixed, the lithium iron phosphate particles were below 100 nm, and the surface of the lithium iron phosphate was coated with conductive carbon black and Activated carbon mixture.
实施例5Example 5
一种纳米级锂离子复合正极的等离子喷射制备方法，制备过程如下：A plasma jet preparation method for a nano-scale lithium ion composite positive electrode, the preparation process is as follows:
磷酸铁锂/活性炭复合电极的制备过程Preparation process of lithium iron phosphate/activated carbon composite electrode
原材料：LiFePO4(台塑长园)、活性炭、纳米碳管、铝箔(韩国产20μm)。Raw materials: LiFePO 4 (Forminol Changyuan), activated carbon, carbon nanotubes, aluminum foil (20μm from Korea).
集流体进行表面处理工艺，表面处理工艺包括以下步骤：集流体清洗、干燥后对集流体进行双面腐蚀，然后放入处理液中浸泡，浸泡完后水洗、干燥并用惰性气体对集流体双面喷射；所述处理液按重量份计其组成为：钼酸钠22份、果酸18份、硫脲5份、植酸钠7份、天冬氨酸12份、苯并三氮唑15份、蜂蜜4份、水100份；所述对集流体进行双面腐蚀是指用涂布机经20m/min的涂布速度将铬酸表面处理液涂布到集流体表面进行双面腐蚀，铬酸表面处理液按重量份其组成为：铬酸锂12份、水17份、钨酸钠5份、浓硫酸70份；集流体在处理液中浸泡的温度为75℃，浸泡时间3h；集流体干燥时先在60℃下干燥2h然后升温至80℃干燥1.5h，最后再105℃干燥1h；使用惰性气体对集流体双面喷射的气流速度为180mL/min。The fluid collecting surface is subjected to a surface treatment process, and the surface treatment process comprises the following steps: collecting and cleaning the current collector after double-sided etching, and then immersing in the treatment liquid, immersing, washing, drying and using an inert gas to the liquid collecting surface. The composition of the treatment liquid is: 22 parts of sodium molybdate, 18 parts of fruit acid, 5 parts of thiourea, 7 parts of sodium phytate, 12 parts of aspartic acid, and 15 parts of benzotriazole. 4 parts of honey and 100 parts of water; the double-sided etching of the current collector means that the surface treatment liquid of chromic acid is applied to the surface of the current collector by a coater at a coating speed of 20 m/min for double-sided corrosion, chromium The composition of the acid surface treatment liquid is: 12 parts of lithium chromate, 17 parts of water, 5 parts of sodium tungstate, 70 parts of concentrated sulfuric acid; the temperature of the current collector in the treatment liquid is 75 ° C, and the soaking time is 3 hours; When the fluid was dried, it was first dried at 60 ° C for 2 h and then heated to 80 ° C for 1.5 h, and finally dried at 105 ° C for 1 h; the flow velocity of the double-sided jet of the collector using an inert gas was 180 mL / min.
活性炭是以椰壳或针状焦为前驱体的活性炭，所述活性炭表面改性处理后使用，表面改性处理的方法为：将质量浓度为8％的硅烷偶联剂无水乙醇溶液与活性炭混合40min，然后再加入质量浓度为10％的铝酸酯偶联剂无水乙醇溶液在混合30-50min，过滤，过滤物在75℃下干燥4.5h，再在102℃下活化1.5h，硅烷偶联剂用量为活性炭重量的0.8％，铝酸酯偶联剂用量为活性炭重量的1.2％。Activated carbon is activated carbon with coconut shell or needle coke as precursor, and the activated carbon is used after surface modification treatment. The surface modification treatment method is as follows: the silane coupling agent anhydrous ethanol solution with mass concentration of 8% and activated carbon Mix for 40 min, then add 10% by mass of aluminate coupling agent in absolute ethanol solution for 30-50 min, filter, filter at 75 ° C for 4.5 h, then at 102 ° C for 1.5 h, silane The coupling agent is used in an amount of 0.8% by weight of the activated carbon, and the amount of the aluminate coupling agent is 1.2% by weight of the activated carbon.
将总质量为500g的LiFePO4、活性炭、导电炭黑按照质量比为20:65:10的比例混合均匀，加入到送粉器中，用5m/min的速度进行等离子喷射涂覆。LiFePO 4 , activated carbon, and conductive carbon black having a total mass of 500 g were uniformly mixed at a mass ratio of 20:65:10, and added to a powder feeder, and plasma spray coating was performed at a speed of 5 m/min.
经过冷却干燥和双面涂覆后，得到厚度为200μm的正极，经测定，该电极密度为0.93g/cm3。将得到的正极极片与石墨负极极片进行组装，得到的电容电池经过化成后进行性能测试，用1C充电至3.7V，1C放电至2.0V，电容电池的比能量为35.6Wh/kg,比功率为3800W/kg，经过1C充放电循环15000次后，容量保持在91.3％。After cooling and drying and double-sided coating, a positive electrode having a thickness of 200 μm was obtained, and the electrode density was determined to be 0.93 g/cm 3 . The obtained positive electrode tab and the graphite negative electrode tab were assembled, and the obtained capacitor battery was subjected to performance test, and charged to 3.7 V with 1 C, discharged to 2.0 V at 1 C, and the specific energy of the capacitor battery was 35.6 Wh/kg. The power is 3800 W/kg, and after 15,000 charge and discharge cycles of 1 C, the capacity is maintained at 91.3%.
将得到的正极极片经过SEM扫描得到的图片看出，活性炭、导电炭黑和磷酸铁锂颗粒混合均匀，磷酸铁锂颗粒在100nm以下，并且在磷酸铁锂表面均包覆有导电炭黑和活性炭混合物。The obtained positive electrode sheet was observed by SEM scanning, and the activated carbon, conductive carbon black and lithium iron phosphate particles were uniformly mixed, the lithium iron phosphate particles were below 100 nm, and the surface of the lithium iron phosphate was coated with conductive carbon black and Activated carbon mixture.
实施例6 Example 6
一种纳米级锂离子复合正极的等离子喷射制备方法，制备过程如下：A plasma jet preparation method for a nano-scale lithium ion composite positive electrode, the preparation process is as follows:
磷酸铁锂/活性炭复合电极的制备过程Preparation process of lithium iron phosphate/activated carbon composite electrode
原材料：LiFePO4(台塑长园)、活性炭、改性纳米碳管、铝箔(韩国产20μm)。Raw materials: LiFePO 4 (Forminol Changyuan), activated carbon, modified carbon nanotubes, aluminum foil (20μm from Korea).
集流体进行表面处理工艺，表面处理工艺包括以下步骤：集流体清洗、干燥后对集流体进行双面腐蚀，然后放入处理液中浸泡，浸泡完后水洗、干燥并用惰性气体对集流体双面喷射；所述处理液按重量份计其组成为：钼酸钠25份、果酸30份、硫脲6份、植酸钠10份、天冬氨酸15份、苯并三氮唑18份、蜂蜜6份、水130份；所述对集流体进行双面腐蚀是指用涂布机经25m/min的涂布速度将铬酸表面处理液涂布到集流体表面进行双面腐蚀，铬酸表面处理液按重量份其组成为：铬酸锂15份、水20份、钨酸钠6份、浓硫酸75份；集流体在处理液中浸泡的温度为85℃，浸泡时间4h；集流体干燥时先在60℃下干燥2h然后升温至80℃干燥1.5h，最后再105℃干燥1h；使用惰性气体对集流体双面喷射的气流速度为260mL/min。The fluid collecting surface is subjected to a surface treatment process, and the surface treatment process comprises the following steps: collecting and cleaning the current collector after double-sided etching, and then immersing in the treatment liquid, immersing, washing, drying and using an inert gas to the liquid collecting surface. The composition of the treatment liquid is: 25 parts of sodium molybdate, 30 parts of fruit acid, 6 parts of thiourea, 10 parts of sodium phytate, 15 parts of aspartic acid, and 18 parts of benzotriazole. 6 parts of honey and 130 parts of water; the double-sided etching of the current collector means that the surface treatment liquid of chromic acid is applied to the surface of the current collector by a coater at a coating speed of 25 m/min for double-sided corrosion, chromium The composition of the acid surface treatment liquid is: 15 parts of lithium chromate, 20 parts of water, 6 parts of sodium tungstate, and 75 parts of concentrated sulfuric acid; the temperature of the current collector in the treatment liquid is 85 ° C, and the soaking time is 4 hours; When the fluid was dried, it was first dried at 60 ° C for 2 h and then heated to 80 ° C for 1.5 h, and finally dried at 105 ° C for 1 h; the flow rate of the double-sided jet of the collector using an inert gas was 260 mL / min.
改性碳纳米管的制备方法步骤如下：The steps for preparing the modified carbon nanotubes are as follows:
(1)将碳纳米管、质量浓度50％的二甲基甲酰胺溶液及酸溶液按照1g：20mL：15mL的料液比混合，控制温度45℃下搅拌混合50min，过滤，分别用水和无水乙醇洗涤，100℃下真空干燥60min得初级改性碳纳米管；(1) Mixing carbon nanotubes, 50% by mass dimethylformamide solution and acid solution according to the ratio of material to liquid of 1g: 20mL: 15mL, stirring and mixing at a controlled temperature of 45 ° C for 50 min, filtering, respectively, using water and anhydrous Ethanol washing, vacuum drying at 100 ° C for 60 min to obtain primary modified carbon nanotubes;
(2)将初级改性碳纳米管与化学剪切液按照1g：50mL的料液比混合，加热至180℃，水热反应60h，冷却，水洗，得次级改性碳纳米管；(2) mixing the primary modified carbon nanotubes with the chemical shear liquid according to a ratio of 1 g: 50 mL of the liquid to the liquid, heating to 180 ° C, hydrothermal reaction for 60 h, cooling, washing with water to obtain secondary modified carbon nanotubes;
(3)次级改性碳纳米管与质量浓度60％的高氯酸按照1g：30mL的料液比混合均匀，加热至70℃保持24小时，冷却，过滤，水洗，真空干燥后得改性碳纳米管；其中，所述酸溶液为质量浓度70％的浓硝酸与质量浓度98％的浓硫酸按照2:1的体积比的混合物；所述化学剪切液为浓度0.8moL/L的钼酸钠溶液与浓度0.5moL/L的硅钼酸溶液按照1:1的体积比的混合物。(3) The secondary modified carbon nanotubes and the perchloric acid with a mass concentration of 60% are uniformly mixed according to the ratio of material to liquid of 1g: 30mL, heated to 70 ° C for 24 hours, cooled, filtered, washed with water, and modified after vacuum drying. a carbon nanotube; wherein the acid solution is a mixture of concentrated nitric acid having a mass concentration of 70% and a concentrated sulfuric acid having a mass concentration of 98% in a volume ratio of 2:1; the chemical shearing solution is a molybdenum having a concentration of 0.8 mol/L. A mixture of sodium solution and a concentration of 0.5 moL/L of silicomolybdic acid solution in a volume ratio of 1:1.
将总质量为500g的LiFePO4、活性炭、改性纳米碳管按照质量比为20:65:10的比例混合均匀，加入到送粉器中，用5m/min的速度进行等离子喷射涂覆。LiFePO 4 , activated carbon, and modified carbon nanotubes having a total mass of 500 g were uniformly mixed at a mass ratio of 20:65:10, and added to a powder feeder for plasma spray coating at a speed of 5 m/min.
经过冷却干燥和双面涂覆后，得到厚度为200μm的正极，经测定，该电极密度为0.93g/cm3。将得到的正极极片与石墨负极极片进行组装，得到的电容电池经过化成后进行性能测试，用1C充电至3.7V，1C放电至2.0V，电容电池的比能量为35.6Wh/kg,比功率为3800W/kg，经过1C充放电循环15000次后，容量保持在91.3％。After cooling and drying and double-sided coating, a positive electrode having a thickness of 200 μm was obtained, and the electrode density was determined to be 0.93 g/cm 3 . The obtained positive electrode tab and the graphite negative electrode tab were assembled, and the obtained capacitor battery was subjected to performance test, and charged to 3.7 V with 1 C, discharged to 2.0 V at 1 C, and the specific energy of the capacitor battery was 35.6 Wh/kg. The power is 3800 W/kg, and after 15,000 charge and discharge cycles of 1 C, the capacity is maintained at 91.3%.
将得到的正极极片经过SEM扫描得到的图片看出，活性炭、导电炭黑和磷酸铁锂颗粒混合均匀，磷酸铁锂颗粒在100nm以下，并且在磷酸铁锂表面均包覆有导电炭黑和活性炭混合物。The obtained positive electrode sheet was observed by SEM scanning, and the activated carbon, conductive carbon black and lithium iron phosphate particles were uniformly mixed, the lithium iron phosphate particles were below 100 nm, and the surface of the lithium iron phosphate was coated with conductive carbon black and Activated carbon mixture.
实施例7 Example 7
一种纳米级锂离子复合正极的等离子喷射制备方法，制备过程如下：A plasma jet preparation method for a nano-scale lithium ion composite positive electrode, the preparation process is as follows:
磷酸铁锂/活性炭复合电极的制备过程Preparation process of lithium iron phosphate/activated carbon composite electrode
原材料：LiFePO4(台塑长园)、活性炭、改性纳米碳管、铝箔(韩国产20μm)。Raw materials: LiFePO 4 (Forminol Changyuan), activated carbon, modified carbon nanotubes, aluminum foil (20μm from Korea).
活性炭是以椰壳或针状焦为前驱体的活性炭，所述活性炭表面改性处理后使用，表面改性处理的方法为：将质量浓度为10％的硅烷偶联剂无水乙醇溶液与活性炭混合50min，然后再加入质量浓度为15％的铝酸酯偶联剂无水乙醇溶液在混合50min，过滤，过滤物在80℃下干燥5h，再在105℃下活化2h，硅烷偶联剂用量为活性炭重量的1％，铝酸酯偶联剂用量为活性炭重量的1.5％。Activated carbon is activated carbon with coconut shell or needle coke as precursor, and the activated carbon is used after surface modification treatment. The surface modification treatment method is as follows: a silane coupling agent anhydrous ethanol solution with a mass concentration of 10% and activated carbon Mix for 50min, then add 15% mass concentration of aluminate coupling agent in absolute ethanol solution for 50min, filter, filter at 80 ° C for 5h, then activate at 105 ° C for 2h, the amount of silane coupling agent The amount of the aluminate coupling agent is 1.5% by weight of the activated carbon, which is 1% by weight of the activated carbon.
改性碳纳米管的制备方法步骤如下：The steps for preparing the modified carbon nanotubes are as follows:
(1)将碳纳米管、质量浓度40％的二甲基甲酰胺溶液及酸溶液按照1g：15mL：10mL的料液比混合，控制温度40℃下搅拌混合40min，过滤，分别用水和无水乙醇洗涤，90℃下真空干燥45min得初级改性碳纳米管；(1) Mixing carbon nanotubes, 40% by mass dimethylformamide solution and acid solution according to the ratio of material to liquid of 1g: 15mL: 10mL, stirring and mixing at 40 ° C for 40 min, filtering, respectively, using water and anhydrous Ethanol washing, vacuum drying at 90 ° C for 45 min to obtain primary modified carbon nanotubes;
(2)将初级改性碳纳米管与化学剪切液按照1g：40mL的料液比混合，加热至170℃，水热反应50h，冷却，水洗，得次级改性碳纳米管；(2) mixing the primary modified carbon nanotubes with the chemical shear liquid according to the ratio of material to liquid of 1g: 40mL, heating to 170 ° C, hydrothermal reaction for 50 hours, cooling, washing with water to obtain secondary modified carbon nanotubes;
(3)次级改性碳纳米管与质量浓度55％的高氯酸按照1g：25mL的料液比混合均匀，加热至65℃保持24小时，冷却，过滤，水洗，真空干燥后得改性碳纳米管；其中，所述酸溶液为质量浓度70％的浓硝酸与质量浓度98％的浓硫酸按照1:1的体积比的混合物；所述化学剪切液为浓度0.6moL/L的钼酸钠溶液与浓度0.4moL/L的硅钼酸溶液按照1:1的体积比的混合物。(3) The secondary modified carbon nanotubes and the perchloric acid with a mass concentration of 55% are uniformly mixed according to the ratio of material to liquid of 1g: 25mL, heated to 65 ° C for 24 hours, cooled, filtered, washed with water, and modified after vacuum drying. a carbon nanotube; wherein the acid solution is a mixture of concentrated nitric acid having a mass concentration of 70% and a concentrated sulfuric acid having a mass concentration of 98% in a volume ratio of 1:1; the chemical shearing solution is a molybdenum having a concentration of 0.6 mol/L. A mixture of sodium solution and a concentration of 0.4 moL/L of silicomolybdic acid solution in a volume ratio of 1:1.
将总质量为500g的LiFePO4、活性炭、改性纳米碳管按照质量比为20:65:10的比例混合均匀，加入到送粉器中，用5m/min的速度进行等离子喷射涂覆。LiFePO 4 , activated carbon, and modified carbon nanotubes having a total mass of 500 g were uniformly mixed at a mass ratio of 20:65:10, and added to a powder feeder for plasma spray coating at a speed of 5 m/min.
经过冷却干燥和双面涂覆后，得到厚度为200μm的正极，经测定，该电极密度为0.93g/cm3。将得到的正极极片与石墨负极极片进行组装，得到的电容电池经过化成后进行性能测试，用1C充电至3.7V，1C放电至2.0V，电容电池的比能量为41.6Wh/kg,比功率为4200W/kg，经过1C充放电循环15000次后，容量保持在94.3％。After cooling and drying and double-sided coating, a positive electrode having a thickness of 200 μm was obtained, and the electrode density was determined to be 0.93 g/cm 3 . The obtained positive electrode tab and the graphite negative electrode tab were assembled, and the obtained capacitor battery was subjected to performance test, and charged to 3.7 V with 1 C, discharged to 2.0 V at 1 C, and the specific energy of the capacitor battery was 41.6 Wh/kg. The power is 4200 W/kg, and after 15,000 charge and discharge cycles of 1 C, the capacity is maintained at 94.3%.
将得到的正极极片经过SEM扫描得到的图片看出，活性炭、导电炭黑和磷酸铁锂颗粒混合均匀，磷酸铁锂颗粒在100nm以下，并且在磷酸铁锂表面均包覆有导电炭黑和活性炭混合物。The obtained positive electrode sheet was observed by SEM scanning, and the activated carbon, conductive carbon black and lithium iron phosphate particles were uniformly mixed, the lithium iron phosphate particles were below 100 nm, and the surface of the lithium iron phosphate was coated with conductive carbon black and Activated carbon mixture.
从上述实例可以看出，采用等离子喷射法可以实现纳米级别的混合，使得锂电正极材料表面能均匀包覆碳源，弥补锂电正极材料存在的导电率低等问题。此外，等离子喷射法能够实现致密的电极层，无需经过碾压工序，保证电极密度。其中，正极复合电极的锂电正极材料和多孔碳材料的比例和最终组装而成的电容电池的能量密度、功率密度、循环寿命等有关 系，所使用的电压范围和采用的锂电正极材料有关。 It can be seen from the above examples that the plasma spraying method can achieve nano-level mixing, so that the surface of the lithium-ion positive electrode material can uniformly coat the carbon source, and make up for the low conductivity of the lithium-ion positive electrode material. In addition, the plasma jet method enables a dense electrode layer without the need for a rolling process to ensure electrode density. Among them, the ratio of the lithium positive electrode material and the porous carbon material of the positive electrode composite electrode is related to the energy density, power density, cycle life, etc. of the finally assembled capacitor battery. The voltage range used is related to the lithium battery cathode material used.

Claims (12)

  1. 一种纳米级锂离子复合正极的等离子喷射制备方法，其特征在于，包括以下步骤：A plasma jet preparation method for a nano-scale lithium ion composite positive electrode, comprising the steps of:
    (1)按比例取原料15-20％锂电正极材料、5-20％的导电剂和60-80％多孔碳材料混合均匀成混合物；(1) Proportionally taking 15-20% lithium battery positive electrode material, 5-20% conductive agent and 60-80% porous carbon material to form a mixture;
    (2)然后将混合物加入到送粉器中；(2) then adding the mixture to the powder feeder;
    (3)以5m/min的速度将混合物采用等离子喷射技术涂覆到集流体上，涂覆为双面涂覆，涂覆的厚度为50-100μm。(3) The mixture was applied to the current collector by a plasma jet technique at a speed of 5 m/min, and the coating was applied by double-sided coating to a thickness of 50 to 100 μm.
  2. 根据权利要求1所述的一种纳米级锂离子复合正极的等离子喷射制备方法，其特征在于，锂电正极材料为LiCoO2、LiMn2O4、LiMnO2、LiNiO2、LiFePO4、LiMnPO4、LiNi0.8Co0.2O2或LiNi1/3Co1/3Mn1/3O2。The plasma jet preparation method of a nano-scale lithium ion composite positive electrode according to claim 1, wherein the lithium positive electrode material is LiCoO 2 , LiMn 2 O 4 , LiMnO 2 , LiNiO 2 , LiFePO 4 , LiMnPO 4 , LiNi 0.8 Co 0.2 O 2 or LiNi 1/3 Co 1/3 Mn 1/3 O 2 .
  3. 根据权利要求1所述的一种纳米级锂离子复合正极的等离子喷射制备方法，其特征在于，多孔碳材料为活性炭、介孔碳、碳气凝胶、碳纤维、碳纳米管、炭黑、硬炭或石墨烯中。The plasma jet preparation method of a nano-scale lithium ion composite positive electrode according to claim 1, wherein the porous carbon material is activated carbon, mesoporous carbon, carbon aerogel, carbon fiber, carbon nanotube, carbon black, hard In charcoal or graphene.
  4. 根据权利要求1所述的一种纳米级锂离子复合正极的等离子喷射制备方法，其特征在于，所述集流体为涂炭铝箔、铝箔、带孔铝箔、铜箔或带孔铜箔。The plasma jet preparation method of a nano-scale lithium ion composite positive electrode according to claim 1, wherein the current collector is a carbon coated aluminum foil, an aluminum foil, a perforated aluminum foil, a copper foil or a perforated copper foil.
  5. 根据权利要求1所述的一种纳米级锂离子复合正极的等离子喷射制备方法，其特征在于，集流体的厚度为20μm。The plasma jet preparation method of a nano-scale lithium ion composite positive electrode according to claim 1, wherein the current collector has a thickness of 20 μm.
  6. 根据权利要求1所述的一种纳米级锂离子复合正极的等离子喷射制备方法，其特征在于，所述导电剂为导电炭黑、石墨烯或碳纳米管。The plasma jet preparation method of a nano-scale lithium ion composite positive electrode according to claim 1, wherein the conductive agent is conductive carbon black, graphene or carbon nanotube.
  7. 根据权利要求1所述的一种纳米级锂离子复合正极的等离子喷射制备方法，其特征在于，所述等离子喷射技术为低温低压等离子技术、高温低压等离子技术、真空等离子技术、水稳等离子技术或气稳等离子技术。The plasma jet preparation method of a nano-scale lithium ion composite positive electrode according to claim 1, wherein the plasma spray technology is a low temperature low pressure plasma technology, a high temperature low pressure plasma technology, a vacuum plasma technology, a water stabilization plasma technology or Gas-stable plasma technology.
  8. 根据权利要求1所述的一种纳米级锂离子复合正极的等离子喷射制备方法，其特征在于，等离子喷射技术的工艺参数为：氩气压力1.2-2.7Mpa，氮气压力为0.9-1.3Mpa，电压5000-12000V，电流700-850A，喷涂距离10-15米。The plasma jet preparation method of a nano-scale lithium ion composite positive electrode according to claim 1, wherein the plasma injection technology has the following process parameters: an argon pressure of 1.2-2.7 MPa, a nitrogen pressure of 0.9-1.3 MPa, and a voltage. 5000-12000V, current 700-850A, spraying distance 10-15 meters.
  9. 根据权利要求1所述的一种纳米级锂离子复合正极的等离子喷射制备方法，其特征在于，步骤3)前集流体进行表面处理工艺。The plasma jet preparation method of a nano-scale lithium ion composite positive electrode according to claim 1, wherein the step 3) front surface current is subjected to a surface treatment process.
  10. 根据权利要求9所述的一种纳米级锂离子复合正极的等离子喷射制备方法，其特征在于，所述表面处理工艺包括以下步骤：集流体清洗、干燥后对集流体进行双面腐蚀，然后放入处理液中浸泡，浸泡完后水洗、干燥并用惰性气体对集流体双面喷射；所述处理液按重量份计其组成为：钼酸钠20-25份、果酸15-30份、硫脲2-6份、植酸钠3-10份、天冬氨酸10-15份、苯并三氮唑10-18份、蜂蜜2-6份、水90-130份；所述对集流体进行双面腐蚀是指用涂 布机经15-25m/min的涂布速度将铬酸表面处理液涂布到集流体表面进行双面腐蚀，铬酸表面处理液按重量份其组成为：铬酸锂10-15份、水15-20份、钨酸钠3-6份、浓硫酸65-75份；集流体在处理液中浸泡的温度为70-85℃，浸泡时间2-4h；集流体干燥时先在60℃下干燥2h然后升温至80℃干燥1.5h，最后再105℃干燥1h；使用惰性气体对集流体双面喷射的气流速度为120-260mL/min。The method for preparing a plasma spray of a nano-scale lithium ion composite positive electrode according to claim 9, wherein the surface treatment process comprises the following steps: cleaning and drying the current collector, and then performing double-sided corrosion on the current collector, and then placing Soaked into the treatment liquid, washed, dried, and sprayed on both sides of the current collector with an inert gas; the composition of the treatment liquid is 20-25 parts by weight of sodium molybdate, 15-30 parts of fruit acid, sulfur 2-6 parts of urea, 3-10 parts of sodium phytate, 10-15 parts of aspartic acid, 10-18 parts of benzotriazole, 2-6 parts of honey, 90-130 parts of water; Double-sided corrosion means coating The chromic acid surface treatment liquid is applied to the surface of the current collector for double-sided corrosion by a coating speed of 15-25 m/min, and the composition of the chromic acid surface treatment liquid is 10-15 parts by weight of lithium chromate. 15-20 parts, 3-6 parts of sodium tungstate, 65-75 parts of concentrated sulfuric acid; the temperature of the current collector in the treatment liquid is 70-85 ° C, the soaking time is 2-4 h; the current collector is dried at 60 ° C first. It was dried for 2 h and then heated to 80 ° C for 1.5 h, and finally dried at 105 ° C for 1 h; the gas flow rate of the double-sided jet of the collector using an inert gas was 120-260 mL/min.
  11. 根据权利要求3所述的一种纳米级锂离子复合正极的等离子喷射制备方法，其特征在于，所述活性炭是以椰壳或针状焦为前驱体的活性炭，所述活性炭表面改性处理后使用，表面改性处理的方法为：将质量浓度为5-10％的硅烷偶联剂无水乙醇溶液与活性炭混合30-50min，然后再加入质量浓度为8-15％的铝酸酯偶联剂无水乙醇溶液在混合30-50min，过滤，过滤物在70-80℃下干燥4-5h，再在100℃-105℃下活化1-2h，硅烷偶联剂用量为活性炭重量的0.5-1％，铝酸酯偶联剂用量为活性炭重量的1-1.5％。The method for preparing a nano-sized lithium ion composite positive electrode according to claim 3, wherein the activated carbon is activated carbon having a coconut shell or a needle coke as a precursor, and the activated carbon is surface-modified. The surface modification treatment method is: mixing a silane coupling agent anhydrous ethanol solution having a mass concentration of 5-10% with activated carbon for 30-50 min, and then adding an aluminate coupling having a mass concentration of 8-15%. The anhydrous ethanol solution is mixed for 30-50min, filtered, the filtrate is dried at 70-80 ° C for 4-5h, and then activated at 100 ° C-105 ° C for 1-2h, the amount of silane coupling agent is 0.5-weight of activated carbon. 1%, the amount of the aluminate coupling agent is 1-1.5% by weight of the activated carbon.
  12. 根据权利要求1所述的一种纳米级锂离子复合正极的等离子喷射制备方法，其特征在于，所述导电剂为改性碳纳米管，改性碳纳米管的制备方法步骤如下：The method of preparing a nano-sized lithium ion composite positive electrode according to claim 1 , wherein the conductive agent is a modified carbon nanotube, and the method for preparing the modified carbon nanotube is as follows:
    (1)将碳纳米管、质量浓度30-50％的二甲基甲酰胺溶液及酸溶液按照1g：10-20mL：5-15mL的料液比混合，控制温度35-45℃下搅拌混合30-50min，过滤，分别用水和无水乙醇洗涤，80-100℃下真空干燥30-60min得初级改性碳纳米管；(1) mixing carbon nanotubes, a concentration of 30-50% dimethylformamide solution and an acid solution according to a ratio of material to liquid of 1g: 10-20mL: 5-15mL, and mixing and controlling at a temperature of 35-45 ° C. -50min, filtration, washing with water and anhydrous ethanol, vacuum drying at 80-100 ° C for 30-60min to obtain primary modified carbon nanotubes;
    (2)将初级改性碳纳米管与化学剪切液按照1g：30-50mL的料液比混合，加热至150-180℃，水热反应40-60h，冷却，水洗，得次级改性碳纳米管；(2) mixing the primary modified carbon nanotubes with the chemical shear liquid according to the ratio of material to liquid of 1g: 30-50mL, heating to 150-180 ° C, hydrothermal reaction for 40-60 hours, cooling, washing with water to obtain secondary modification. Carbon nanotubes;
    (3)次级改性碳纳米管与质量浓度50-60％的高氯酸按照1g：20-30mL的料液比混合均匀，加热至60-70℃保持24小时，冷却，过滤，水洗，真空干燥后得改性碳纳米管；其中，所述酸溶液为质量浓度70％的浓硝酸与质量浓度98％的浓硫酸按照1-2:1的体积比的混合物；所述化学剪切液为浓度0.5-0.8moL/L的钼酸钠溶液与浓度0.3-0.5moL/L的硅钼酸溶液按照1:1的体积比的混合物。 (3) The secondary modified carbon nanotubes and the perchloric acid having a mass concentration of 50-60% are uniformly mixed according to the ratio of material to liquid of 1g: 20-30mL, heated to 60-70 ° C for 24 hours, cooled, filtered, washed with water, After vacuum drying, the modified carbon nanotubes are obtained; wherein the acid solution is a mixture of concentrated nitric acid having a mass concentration of 70% and a concentrated sulfuric acid having a mass concentration of 98% in a volume ratio of 1-2:1; the chemical shear liquid A mixture of a sodium molybdate solution having a concentration of 0.5-0.8 mol/L and a silicomolybdic acid solution having a concentration of 0.3-0.5 mol/L in a volume ratio of 1:1.
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