WO2016110108A1 - Procédé de préparation par pulvérisation à plasma pour électrode positive composite lithium-ion nanométrique - Google Patents

Procédé de préparation par pulvérisation à plasma pour électrode positive composite lithium-ion nanométrique 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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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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    • 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

La présente invention concerne le domaine technique des batteries lithium-ion, et spécifiquement un procédé de préparation par pulvérisation à plasma pour une électrode positive composite lithium-ion nanométrique, le procédé comprenant les étapes suivantes : (1) obtention de matériaux sources conformément aux proportions suivantes : 15 à 20 % d'un matériau d'électrode positive de batterie à lithium, 5 à 20 % d'un agent conducteur et 60 à 80 % d'un matériau de carbone poreux, et mélange uniforme des matériaux source en un mélange ; (2) ensuite, ajout du mélange dans un dispositif d'alimentation de poudre ; et (3) revêtement du mélange sur un collecteur à une vitesse de 5 m/min par une technique de pulvérisation à plasma, le revêtement étant à double face, et le revêtement ayant une épaisseur de 50 à 100 µm.
PCT/CN2015/087983 2015-01-06 2015-08-25 Procédé de préparation par pulvérisation à plasma pour électrode positive composite lithium-ion nanométrique WO2016110108A1 (fr)

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