CN111384403A - Preparation method of temperature-resistant transition metal fluoride battery positive electrode material - Google Patents

Preparation method of temperature-resistant transition metal fluoride battery positive electrode material Download PDF

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CN111384403A
CN111384403A CN202010282399.2A CN202010282399A CN111384403A CN 111384403 A CN111384403 A CN 111384403A CN 202010282399 A CN202010282399 A CN 202010282399A CN 111384403 A CN111384403 A CN 111384403A
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transition metal
temperature
metal fluoride
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positive electrode
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不公告发明人
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Jinhua Quick View Technology Development Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to the field of new energy, in particular to a preparation method of a temperature-resistant transition metal fluoride battery anode material; the method comprises the following steps: 65-85 parts of positive active material, 4-8 parts of binder and 2-7 parts of conductivity enhancer; the transition metal fluoride battery anode material prepared by the preparation method of the temperature-resistant transition metal fluoride battery anode material has higher energy storage capacity and better cycling stability, and a membrane with uniformly covered surface is formed due to the fact that the outer layer of the prepared transition metal fluoride nanoparticle hybrid carbon nanotube is coated by hyperbranched modified polyethylene glycol monomethyl ether; the polyethylene glycol-based high polymer material is used for a dielectric medium of a battery, has a very good lithium ion conduction characteristic, and can ensure that the transition metal fluoride nano particles are stable in shape and can conduct lithium ions freely, so that performance attenuation caused by falling of an energy storage material is avoided.

Description

Preparation method of temperature-resistant transition metal fluoride battery positive electrode material
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a preparation method of a temperature-resistant transition metal fluoride battery positive electrode material.
Background
The development of batteries has been over two hundred years, and the batteries are diversified, and generally classified into non-rechargeable primary batteries, fuel cells, reserve batteries, and rechargeable secondary batteries, etc., depending on the nature of operation and the manner of energy storage. The energy density of various batteries is far from the requirement of human use nowadays, and the positive electrode material is always a key factor for limiting the battery capacity.
201910340099.2A battery anode material, a battery anode plate using the battery anode material and a lithium battery using the battery anode plate, the battery anode material includes lithium cobaltate powder and ternary material powder, the lithium cobaltate powder and ternary material powder are mixed according to a preset proportion, before mixing, the lithium cobaltate powder and ternary material powder are both coated with an inorganic coating layer in advance, the inorganic coating layer is any one of metal oxide, metal phosphate, metal fluoride or metal sulfide. According to the invention, the lithium cobaltate powder and the ternary material powder are respectively coated with the inorganic coating layer in advance, so that the high-voltage resistance and the capacity of the anode material can be effectively improved, and the high-temperature flatulence of the anode material can be reduced. By matching the proper large-particle-size lithium cobalt oxide and the small-particle-size ternary material, high compaction density can be realized, the material cost of using pure lithium cobalt oxide is greatly reduced, and the cycle life of the composite anode is prolonged.
201811181608.3 discloses a positive electrode material for lithium battery, which comprises positive active material, binder, conductive agent, conductivity enhancer, dispersant, and slurry mixing solvent; the weight percentage of each component is as follows: 62-80% of positive electrode active substance, 5-10% of binder, 5-12% of conductive agent, 3-6% of conductive reinforcing agent, 0.2-1% of dispersing agent, 1-3% of auxiliary agent and 2-6% of slurry mixing solvent, wherein the slurry mixing solvent is a mixed solvent formed by mixing N, N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, trimethyl phosphate, dimethylformamide and water. The lithium battery provided by the invention has the advantages of excellent high-temperature performance, high capacity retention rate, good cycle performance and long service life.
201510422483.9 relates to a positive electrode material, which comprises a sulfur-containing positive electrode active material, a conductive agent and a positive electrode binder, wherein the positive electrode binder is a polymer obtained by polymerization reaction of diamine monomers and dianhydride monomers. The sulfur-containing positive electrode active material is elemental sulfur or a sulfur-based conductive polymer. The invention also relates to a lithium-sulfur battery which comprises a positive electrode, a negative electrode and an electrolyte. The positive electrode comprises the positive electrode material.
Transition metal fluorides have long been used as positive electrode materials for batteries, which have a very high theoretical capacity, storing 2-3 times the energy per unit mass of transition metal fluoride as compared to conventional positive electrode materials. However, the transition metal fluoride expands/contracts in volume to a large extent during discharge/charge due to the low density and fluffy texture of LiF generated during discharge. After many charge-discharge cycles, the transition metal fluoride is powdered, so that the electricity storage capacity is attenuated. More importantly, the reaction rate increases and deepens with increasing temperature, so that the stability of the transition metal fluoride is extremely poor in the working temperature range (more than 40 ℃) slightly higher than room temperature.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a temperature-resistant transition metal fluoride battery positive electrode material.
A preparation method of a temperature-resistant transition metal fluoride battery positive electrode material comprises the following specific scheme:
according to the mass parts, the positive electrode material of the temperature-resistant transition metal fluoride battery comprises: 65-85 parts of positive active material, 4-8 parts of binder and 2-7 parts of conductivity enhancer; the preparation method of the positive active material is characterized by comprising the following steps: dispersing 5-10 parts of carbon nano tube in 50-100 parts of pure water, then adding 0.1-0.5 part of surfactant C14 tertiary alkylamine ethoxylation propoxylate, stirring and mixing uniformly, controlling the temperature to be 50-70 ℃, stirring for 30-60min, filtering, drying, immersing with 20-40 parts of hydrofluoric acid solution, then adding 0.7-4 parts of transition metal nitrate, stirring and dissolving, standing for 10-30h, then slowly stirring, heating to 55-75 ℃, volatilizing the solution completely, putting the rest materials into a vacuum drying oven, controlling the temperature to be 80-200 ℃, and drying for 5-10 h; after the preparation is finished, 40-65 parts of 0.1-0.5mol/L lithium salt acetonitrile solution and 15-25 parts of hyperbranched modified polyethylene glycol monomethyl ether are uniformly mixed and used for fully infiltrating the material, so that the material volatilizes acetonitrile at room temperature, and the positive active substance can be obtained.
The preparation method of the hyperbranched modified polyethylene glycol monomethyl ether comprises the following steps:
dissolving 0.4-2.2 parts by mass of 4, 4-methylenebis (2, 6-diethylphenylisocyanate) in 300 parts by mass of tetrahydrofuran, uniformly stirring and mixing, controlling the temperature to be minus 5-10 ℃, then dropwise adding 80-100 parts of tetrahydrofuran solution containing 10-20 parts of methoxypolyethylene glycol 1000 into a reaction kettle, controlling the temperature to be 30-60 ℃ after dropwise adding, stirring and reacting for 10-18h, then dissolving 4-15 parts of polyethylene glycol 600 and 0.01-0.2 part of di-n-butyltin dilaurate in 30-50 parts of tetrahydrofuran, dropwise adding into the reaction kettle, controlling the temperature to be 50-70 ℃, stirring and reacting for 20-30h, and evaporating the solvent after completing the reaction to obtain the hyperbranched modified methoxypolyethylene glycol.
The transition metal fluoride is ferric trifluoride, cobalt trifluoride or vanadium trifluoride.
The adhesive is polyvinylidene fluoride or polytetrafluoroethylene.
The conductive reinforcing agent is conductive carbon black or graphene or carbon fiber or carbon nano tube.
The hydrofluoric acid solution contains 100% -110% of the amount of hydrofluoric acid required to form the transition metal fluoride.
The lithium salt is lithium hexafluorophosphate or lithium perchlorate or trifluoromethyl sulfimide or lithium hexafluoroarsenate or lithium bis (oxalato) borate.
The positive active substance, the binder and the conductive reinforcing agent are weighed according to the proportion and then uniformly mixed, and then the mixture is pressed into the temperature-resistant transition metal fluoride battery positive material.
The transition metal fluoride battery anode material prepared by the preparation method of the temperature-resistant transition metal fluoride battery anode material has higher energy storage capacity and better cycling stability, and a membrane with uniformly covered surface is formed due to the fact that the outer layer of the prepared transition metal fluoride nanoparticle hybrid carbon nanotube is coated by hyperbranched modified polyethylene glycol monomethyl ether; the polyethylene glycol-based high polymer material is used for a dielectric medium of a battery, has a very good lithium ion conduction characteristic, and can ensure that the transition metal fluoride nano particles are stable in shape and can conduct lithium ions freely, so that performance attenuation caused by falling of an energy storage material is avoided.
Detailed Description
The invention is further illustrated by the following specific examples:
assembling the prepared positive electrode material into a button battery by taking a lithium sheet as a counter electrode and taking lithium salt-containing POE as electrolyte, and measuring the capacity and the cycle performance of the battery; according to IEC619602000.11 standard, the battery is discharged to 3V at 0.2C, then the battery is charged to 4.2V at 1C, and the current is cut off to 20MA, and the battery is in a cycle with an interval of 60min between two cycles, a working temperature of 50 ℃ and a cycle number of 300.
Example 1
A preparation method of a temperature-resistant transition metal fluoride battery positive electrode material comprises the following specific scheme:
according to the mass parts, the positive electrode material of the temperature-resistant transition metal fluoride battery comprises: 65g of positive electrode active material, 4g of binder and 2g of conductivity enhancer; the preparation method of the positive active material is characterized by comprising the following steps: dispersing 5g of carbon nano tube in 50g of pure water, then adding 0.1g of surfactant C14 tertiary alkylamine ethoxylated propoxylate, stirring and mixing uniformly, controlling the temperature to be 50 ℃, stirring for 30min, filtering, drying, immersing with 20g of hydrofluoric acid solution, then adding 0.7g of transition metal nitrate, stirring and dissolving, standing for 10h, then slowly stirring, heating to 55 ℃, volatilizing the solution completely, putting the rest materials into a vacuum drying oven, controlling the temperature to be 80 ℃, and drying for 5 h; after the preparation, 40g of 0.1mol/L lithium salt acetonitrile solution and 15g of hyperbranched modified polyethylene glycol monomethyl ether are uniformly mixed and used for fully infiltrating the material, and the material is enabled to volatilize acetonitrile at room temperature, so that the positive active substance can be obtained.
The preparation method of the hyperbranched modified polyethylene glycol monomethyl ether comprises the following steps:
according to the mass portion, 0.4g of 4, 4-methylenebis (2, 6-diethylphenyl isocyanate) is dissolved in 100g of tetrahydrofuran, the mixture is stirred and mixed uniformly, the temperature is controlled to be minus 5 ℃, then 80 parts of tetrahydrofuran solution containing 10g of polyethylene glycol monomethyl ether 1000 is dripped into a reaction kettle, the temperature is controlled to be 30 ℃ after the dripping is finished, the stirring reaction is carried out for 10 hours, then 4g of polyethylene glycol 600 and 0.01g of di-n-butyltin dilaurate are dissolved in 30g of tetrahydrofuran, the dropwise addition is carried out in the reaction kettle, the temperature is controlled to be 50 ℃, the stirring reaction is carried out for 20 hours, and the solvent is evaporated after the reaction is finished, thus obtaining the hyperbranched modified polyethylene glycol monomethyl ether.
The transition metal fluoride is ferric trifluoride.
The adhesive is polyvinylidene fluoride.
The conductive reinforcing agent is conductive carbon black.
The hydrofluoric acid solution contains hydrofluoric acid in an amount of 100% of the amount required to form the transition metal fluoride.
The lithium salt is lithium hexafluorophosphate.
The positive active substance, the binder and the conductive reinforcing agent are weighed according to the proportion and then uniformly mixed, and then the mixture is pressed into the temperature-resistant transition metal fluoride battery positive material.
The initial discharge capacity of the button cell assembled by the transition metal fluoride battery anode material prepared by the experiment is 623mAhg-1And the battery capacity after 300 cycles is 492 mAhg-1。
Example 2
A preparation method of a temperature-resistant transition metal fluoride battery positive electrode material comprises the following specific scheme:
according to the mass parts, the positive electrode material of the temperature-resistant transition metal fluoride battery comprises: 75g of positive electrode active material, 6g of binder and 5g of conductivity enhancer; the preparation method of the positive active material is characterized by comprising the following steps: dispersing 8g of carbon nanotubes in 80g of pure water, adding 0.3g of surfactant C14 tertiary alkylamine ethoxylated propoxylate, stirring and mixing uniformly, controlling the temperature to be 60 ℃, stirring for 45min, filtering, drying, immersing with 30g of hydrofluoric acid solution, adding 2g of transition metal nitrate, stirring and dissolving, standing for 20h, slowly stirring, heating to 65 ℃, volatilizing the solution completely, putting the rest materials into a vacuum drying oven, controlling the temperature to be 120 ℃, and drying for 8 h; after the preparation, 55g of 0.3mol/L lithium salt acetonitrile solution and 20g of hyperbranched modified polyethylene glycol monomethyl ether are uniformly mixed and used for fully infiltrating the material, so that the material volatilizes acetonitrile at room temperature, and the positive active substance can be obtained.
The preparation method of the hyperbranched modified polyethylene glycol monomethyl ether comprises the following steps:
dissolving 1.2g of 4, 4-methylenebis (2, 6-diethylphenylisocyanate) in 200g of tetrahydrofuran, uniformly stirring and mixing, controlling the temperature to be 8 ℃ below zero, then dropwise adding 90 parts of tetrahydrofuran solution containing 15g of polyethylene glycol monomethyl ether 1000 into a reaction kettle, controlling the temperature to be 40 ℃ after dropwise adding, stirring and reacting for 14h, then dissolving 8g of polyethylene glycol 600 and 0.1g of di-n-butyltin dilaurate in 40g of tetrahydrofuran, dropwise adding into the reaction kettle, controlling the temperature to be 60 ℃, stirring and reacting for 25h, and evaporating the solvent after the reaction is finished to obtain the hyperbranched modified polyethylene glycol monomethyl ether.
The transition metal fluoride is cobalt trifluoride.
The adhesive is polytetrafluoroethylene.
The conductive reinforcing agent is graphene.
The hydrofluoric acid solution contained hydrofluoric acid in an amount of 105% of the amount required to form the transition metal fluoride.
The lithium salt is lithium perchlorate.
The positive active substance, the binder and the conductive reinforcing agent are weighed according to the proportion and then uniformly mixed, and then the mixture is pressed into the temperature-resistant transition metal fluoride battery positive material.
The initial discharge capacity of the button cell assembled by the transition metal fluoride battery anode material prepared by the experiment is 648mAhg-1And the battery capacity after 300 cycles is 524 mAhg-1。
Example 3
A preparation method of a temperature-resistant transition metal fluoride battery positive electrode material comprises the following specific scheme:
according to the mass parts, the positive electrode material of the temperature-resistant transition metal fluoride battery comprises: 85g of positive electrode active material, 8g of binder and 7g of conductivity enhancer; the preparation method of the positive active material is characterized by comprising the following steps: dispersing 10g of carbon nano tube in 100g of pure water, then adding 0.5g of surfactant C14 tertiary alkylamine ethoxylated propoxylate, stirring and mixing uniformly, controlling the temperature to be 70 ℃, stirring for 60min, filtering, drying, immersing with 40g of hydrofluoric acid solution, then adding 4g of transition metal nitrate, stirring and dissolving, standing for 30h, then slowly stirring, heating to 75 ℃, volatilizing the solution completely, putting the rest materials into a vacuum drying oven, controlling the temperature to be 200 ℃, and drying for 10 h; after the preparation is finished, 65g of 0.5mol/L lithium salt acetonitrile solution and 25g of hyperbranched modified polyethylene glycol monomethyl ether are uniformly mixed and used for fully infiltrating the material, and acetonitrile is volatilized from the material at room temperature, so that the positive active substance can be obtained.
The preparation method of the hyperbranched modified polyethylene glycol monomethyl ether comprises the following steps:
dissolving 2.2g of 4, 4-methylenebis (2, 6-diethylphenylisocyanate) in 300g of tetrahydrofuran, uniformly stirring and mixing, controlling the temperature to be 10 ℃ below zero, then dropwise adding 100 parts of tetrahydrofuran solution containing 20g of polyethylene glycol monomethyl ether 1000 into a reaction kettle, controlling the temperature to be 60 ℃ after dropwise adding, stirring and reacting for 18 hours, then dissolving 15g of polyethylene glycol 600 and 0.2g of di-n-butyltin dilaurate in 50g of tetrahydrofuran, dropwise adding into the reaction kettle, controlling the temperature to be 70 ℃, stirring and reacting for 30 hours, and evaporating the solvent after the reaction is finished to obtain the hyperbranched modified polyethylene glycol monomethyl ether.
The transition metal fluoride is vanadium trifluoride.
The adhesive is polytetrafluoroethylene.
The conductive reinforcing agent is carbon nano-tubes.
The hydrofluoric acid solution contains hydrofluoric acid in an amount of 110% of the amount required to form the transition metal fluoride.
The lithium salt is lithium hexafluoroarsenate.
The positive active substance, the binder and the conductive reinforcing agent are weighed according to the proportion and then uniformly mixed, and then the mixture is pressed into the temperature-resistant transition metal fluoride battery positive material.
The initial discharge capacity of the button cell assembled by the transition metal fluoride battery anode material prepared by the experiment is 657mAhg-1And the battery capacity after 300 cycles is 537mAhg-1。
Comparative example 4
A preparation method of a temperature-resistant transition metal fluoride battery positive electrode material comprises the following specific scheme:
according to the mass parts, the positive electrode material of the temperature-resistant transition metal fluoride battery comprises: 65g of positive electrode active material, 4g of binder and 2g of conductivity enhancer; the preparation method of the positive active material is characterized by comprising the following steps: dispersing 8g of carbon nanotubes in 80g of pure water, adding 0.3g of surfactant C14 tertiary alkylamine ethoxylated propoxylate, stirring and mixing uniformly, controlling the temperature to be 60 ℃, stirring for 45min, filtering, drying, immersing with 30g of hydrofluoric acid solution, adding 2g of transition metal nitrate, stirring and dissolving, standing for 20h, slowly stirring, heating to 65 ℃, volatilizing the solution completely, putting the rest materials into a vacuum drying oven, controlling the temperature to be 120 ℃, and drying for 8 h; after the preparation, 55g of 0.3mol/L lithium salt acetonitrile solution and 20g of hyperbranched modified polyethylene glycol monomethyl ether are uniformly mixed and used for fully infiltrating the material, so that the material volatilizes acetonitrile at room temperature, and the positive active substance can be obtained.
The preparation method of the hyperbranched modified polyethylene glycol monomethyl ether comprises the following steps:
dissolving 2.2g of 4, 4-methylenebis (2, 6-diethylphenylisocyanate) in 300g of tetrahydrofuran, uniformly stirring and mixing, controlling the temperature to be 10 ℃ below zero, then dropwise adding 100 parts of tetrahydrofuran solution containing 20g of polyethylene glycol monomethyl ether 1000 into a reaction kettle, controlling the temperature to be 60 ℃ after dropwise adding, stirring and reacting for 18 hours, then dissolving 15g of polyethylene glycol 600 and 0.2g of di-n-butyltin dilaurate in 50g of tetrahydrofuran, dropwise adding into the reaction kettle, controlling the temperature to be 70 ℃, stirring and reacting for 30 hours, and evaporating the solvent after the reaction is finished to obtain the hyperbranched modified polyethylene glycol monomethyl ether.
The transition metal fluoride is vanadium trifluoride.
The adhesive is polytetrafluoroethylene.
The conductive reinforcing agent is carbon nano-tubes.
The hydrofluoric acid solution contained an amount of hydrofluoric acid of 107% of the amount required to form the transition metal fluoride.
The lithium salt is trifluoromethyl sulfimide lithium.
The positive active substance, the binder and the conductive reinforcing agent are weighed according to the proportion and then uniformly mixed, and then the mixture is pressed into the temperature-resistant transition metal fluoride battery positive material.
The initial discharge capacity of the button cell assembled by the transition metal fluoride battery anode material prepared by the experiment is 639mAhg-1And the battery capacity after 300 cycles is 506 mAhg-1。
Comparative example 1
A preparation method of a temperature-resistant transition metal fluoride battery positive electrode material comprises the following specific scheme:
according to the mass parts, the positive electrode material of the temperature-resistant transition metal fluoride battery comprises: 65g of positive electrode active material, 4g of binder and 2g of conductivity enhancer; the preparation method of the positive active material is characterized by comprising the following steps: dispersing 5g of carbon nanotubes in 50g of pure water, uniformly stirring and mixing, controlling the temperature to be 50 ℃, stirring for 30min, filtering, drying, immersing with 20g of hydrofluoric acid solution, adding 0.7g of transition metal nitrate, stirring for dissolving, standing for 10h, slowly stirring, heating to 55 ℃, volatilizing the solution completely, putting the rest materials into a vacuum drying oven, controlling the temperature to be 80 ℃, and drying for 5 h; after the preparation, 40g of 0.1mol/L lithium salt acetonitrile solution and 15g of hyperbranched modified polyethylene glycol monomethyl ether are uniformly mixed and used for fully infiltrating the material, and the material is enabled to volatilize acetonitrile at room temperature, so that the positive active substance can be obtained.
The preparation method of the hyperbranched modified polyethylene glycol monomethyl ether comprises the following steps:
according to the mass portion, 0.4g of 4, 4-methylenebis (2, 6-diethylphenyl isocyanate) is dissolved in 100g of tetrahydrofuran, the mixture is stirred and mixed uniformly, the temperature is controlled to be minus 5 ℃, then 80 parts of tetrahydrofuran solution containing 10g of polyethylene glycol monomethyl ether 1000 is dripped into a reaction kettle, the temperature is controlled to be 30 ℃ after the dripping is finished, the stirring reaction is carried out for 10 hours, then 4g of polyethylene glycol 600 and 0.01g of di-n-butyltin dilaurate are dissolved in 30g of tetrahydrofuran, the dropwise addition is carried out in the reaction kettle, the temperature is controlled to be 50 ℃, the stirring reaction is carried out for 20 hours, and the solvent is evaporated after the reaction is finished, thus obtaining the hyperbranched modified polyethylene glycol monomethyl ether.
The transition metal fluoride is ferric trifluoride.
The adhesive is polyvinylidene fluoride.
The conductive reinforcing agent is conductive carbon black.
The hydrofluoric acid solution contains hydrofluoric acid in an amount of 100% of the amount required to form the transition metal fluoride.
The lithium salt is lithium hexafluorophosphate.
The positive active substance, the binder and the conductive reinforcing agent are weighed according to the proportion and then uniformly mixed, and then the mixture is pressed into the temperature-resistant transition metal fluoride battery positive material.
The initial discharge capacity of the button cell assembled by the transition metal fluoride battery anode material prepared by the experiment is 572mAhg-1And the battery capacity after 300 cycles is 437 mAhg-1。
Comparative example 2
A preparation method of a temperature-resistant transition metal fluoride battery positive electrode material comprises the following specific scheme:
according to the mass parts, the positive electrode material of the temperature-resistant transition metal fluoride battery comprises: 65g of positive electrode active material, 4g of binder and 2g of conductivity enhancer; the preparation method of the positive active material is characterized by comprising the following steps: dispersing 5g of carbon nano tube in 50g of pure water, then adding 0.1g of surfactant C14 tertiary alkylamine ethoxylated propoxylate, stirring and mixing uniformly, controlling the temperature to be 50 ℃, stirring for 30min, filtering, drying, immersing with 20g of hydrofluoric acid solution, then adding 0.7g of transition metal nitrate, stirring and dissolving, standing for 10h, then slowly stirring, heating to 55 ℃, volatilizing the solution completely, putting the rest materials into a vacuum drying oven, controlling the temperature to be 80 ℃, and drying for 5 h; after the preparation is finished, 40g of 0.1mol/L lithium salt acetonitrile solution and 15g of polyethylene glycol monomethyl ether 1000 are uniformly mixed and used for fully infiltrating the material, and the material volatilizes acetonitrile at room temperature to obtain the anode active substance.
The transition metal fluoride is ferric trifluoride.
The adhesive is polyvinylidene fluoride.
The conductive reinforcing agent is conductive carbon black.
The hydrofluoric acid solution contains hydrofluoric acid in an amount of 100% of the amount required to form the transition metal fluoride.
The lithium salt is lithium hexafluorophosphate.
The positive active substance, the binder and the conductive reinforcing agent are weighed according to the proportion and then uniformly mixed, and then the mixture is pressed into the temperature-resistant transition metal fluoride battery positive material.
The initial discharge capacity of the button cell assembled by the transition metal fluoride battery anode material prepared by the experiment is 618mAhg-1And the battery capacity after 300 cycles is 427mAhg-1。
Comparative example 3
A preparation method of a temperature-resistant transition metal fluoride battery positive electrode material comprises the following specific scheme:
according to the mass parts, the positive electrode material of the temperature-resistant transition metal fluoride battery comprises: 65g of positive electrode active material, 4g of binder and 2g of conductivity enhancer; the preparation method of the positive active material is characterized by comprising the following steps: dispersing 5g of carbon nano tube in 50g of pure water, adding 0.1g of surfactant C14 tertiary alkylamine ethoxylated propoxylate, stirring and mixing uniformly, controlling the temperature to be 50 ℃, stirring for 30min, filtering, drying, immersing with 20g of hydrofluoric acid solution, adding 0.7g of transition metal nitrate, stirring and dissolving, standing for 10h, slowly stirring, heating to 55 ℃, volatilizing the solution completely, putting the rest materials into a vacuum drying oven, controlling the temperature to be 80 ℃, and drying for 5 h.
The transition metal fluoride is ferric trifluoride.
The adhesive is polyvinylidene fluoride.
The conductive reinforcing agent is conductive carbon black.
The hydrofluoric acid solution contains hydrofluoric acid in an amount of 100% of the amount required to form the transition metal fluoride.
The lithium salt is lithium hexafluorophosphate.
The positive active substance, the binder and the conductive reinforcing agent are weighed according to the proportion and then uniformly mixed, and then the mixture is pressed into the temperature-resistant transition metal fluoride battery positive material.
The initial discharge capacity of the button cell assembled by the transition metal fluoride battery anode material prepared by the experiment is 606mAhg-1And the energy storage function of the battery is basically lost after the battery is cycled for 200 times.

Claims (8)

1. A preparation method of a temperature-resistant transition metal fluoride battery positive electrode material comprises the following specific scheme:
according to the mass parts, the positive electrode material of the temperature-resistant transition metal fluoride battery comprises: 65-85 parts of positive active material, 4-8 parts of binder and 2-7 parts of conductivity enhancer; the preparation method of the positive active material is characterized by comprising the following steps: dispersing 5-10 parts of carbon nano tube in 50-100 parts of pure water, then adding 0.1-0.5 part of surfactant C14 tertiary alkylamine ethoxylation propoxylate, stirring and mixing uniformly, controlling the temperature to be 50-70 ℃, stirring for 30-60min, filtering, drying, immersing with 20-40 parts of hydrofluoric acid solution, then adding 0.7-4 parts of transition metal nitrate, stirring and dissolving, standing for 10-30h, then slowly stirring, heating to 55-75 ℃, volatilizing the solution completely, putting the rest materials into a vacuum drying oven, controlling the temperature to be 80-200 ℃, and drying for 5-10 h; after the preparation is finished, 40-65 parts of 0.1-0.5mol/L lithium salt acetonitrile solution and 15-25 parts of hyperbranched modified polyethylene glycol monomethyl ether are uniformly mixed and used for fully infiltrating the material, so that the material volatilizes acetonitrile at room temperature, and the positive active substance can be obtained.
2. The method for preparing the temperature-resistant transition metal fluoride battery positive electrode material according to claim 1, which is characterized by comprising the following steps: the preparation method of the hyperbranched modified polyethylene glycol monomethyl ether comprises the following steps:
dissolving 0.4-2.2 parts by mass of 4, 4-methylenebis (2, 6-diethylphenylisocyanate) in 300 parts by mass of tetrahydrofuran, uniformly stirring and mixing, controlling the temperature to be minus 5-10 ℃, then dropwise adding 80-100 parts of tetrahydrofuran solution containing 10-20 parts of methoxypolyethylene glycol 1000 into a reaction kettle, controlling the temperature to be 30-60 ℃ after dropwise adding, stirring and reacting for 10-18h, then dissolving 4-15 parts of polyethylene glycol 600 and 0.01-0.2 part of di-n-butyltin dilaurate in 30-50 parts of tetrahydrofuran, dropwise adding into the reaction kettle, controlling the temperature to be 50-70 ℃, stirring and reacting for 20-30h, and evaporating the solvent after completing the reaction to obtain the hyperbranched modified methoxypolyethylene glycol.
3. The method for preparing the temperature-resistant transition metal fluoride battery positive electrode material according to claim 1, which is characterized by comprising the following steps: the transition metal fluoride is ferric trifluoride, cobalt trifluoride or vanadium trifluoride.
4. The method for preparing the temperature-resistant transition metal fluoride battery positive electrode material according to claim 1, which is characterized by comprising the following steps: the adhesive is polyvinylidene fluoride or polytetrafluoroethylene.
5. The method for preparing the temperature-resistant transition metal fluoride battery positive electrode material according to claim 1, which is characterized by comprising the following steps: the conductive reinforcing agent is conductive carbon black or graphene or carbon fiber or carbon nano tube.
6. The method for preparing the temperature-resistant transition metal fluoride battery positive electrode material according to claim 1, which is characterized by comprising the following steps: the hydrofluoric acid solution contains 100% -110% of the amount of hydrofluoric acid required to form the transition metal fluoride.
7. The method for preparing the temperature-resistant transition metal fluoride battery positive electrode material according to claim 1, which is characterized by comprising the following steps: the lithium salt is lithium hexafluorophosphate or lithium perchlorate or trifluoromethyl sulfimide or lithium hexafluoroarsenate or lithium bis (oxalato) borate.
8. The method for preparing the temperature-resistant transition metal fluoride battery positive electrode material according to claim 1, which is characterized by comprising the following steps: the positive active substance, the binder and the conductive reinforcing agent are weighed according to the proportion and then uniformly mixed, and then the mixture is pressed into the temperature-resistant transition metal fluoride battery positive material.
CN202010282399.2A 2020-04-12 2020-04-12 Preparation method of temperature-resistant transition metal fluoride battery positive electrode material Withdrawn CN111384403A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112615007A (en) * 2020-12-23 2021-04-06 西北工业大学 Ion/electron double-conduction material for modified positive electrode of solid-state battery and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112615007A (en) * 2020-12-23 2021-04-06 西北工业大学 Ion/electron double-conduction material for modified positive electrode of solid-state battery and preparation method thereof

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Application publication date: 20200707