CN110627031A - Preparation method of molybdenum-doped cobalt phosphide-carbon coral sheet composite material - Google Patents

Preparation method of molybdenum-doped cobalt phosphide-carbon coral sheet composite material Download PDF

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CN110627031A
CN110627031A CN201910910982.0A CN201910910982A CN110627031A CN 110627031 A CN110627031 A CN 110627031A CN 201910910982 A CN201910910982 A CN 201910910982A CN 110627031 A CN110627031 A CN 110627031A
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molybdenum
composite material
carbon
sheet composite
phosphide
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陶石
孙硕
谢天欢
钱斌
吴大军
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Changshu Institute of Technology
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00Phosphorus; Compounds thereof
    • C01B25/08Other phosphides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/5805Phosphides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
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    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
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    • C01INORGANIC CHEMISTRY
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    • C01P2004/04Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
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    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a preparation method of a molybdenum-doped cobalt phosphide-carbon coral sheet composite material. The method has simple steps and mild conditions, is convenient for industrial large-scale production, and the prepared nano coral sheet has high structural stability and electronic conductivity, is applied to lithium ion battery electrodes, and has excellent rate capability and cycle performance.

Description

Preparation method of molybdenum-doped cobalt phosphide-carbon coral sheet composite material
Technical Field
The invention relates to a preparation method of a cobalt carbon phosphide composite material in the field of lithium ion battery materials, in particular to a preparation method of a molybdenum-doped cobalt carbon phosphide coral sheet composite material.
Background
Lithium ion batteries have received more and more attention in the world today, and have become one of the most promising chemical energy sources in the 21 st century, and lithium ion batteries are widely used in hybrid vehicles and portable electronic devices due to their characteristics of high energy density, long cycle life, high safety, no pollution, high power, and the like. The negative electrode material of the lithium ion battery is an important component of the lithium ion battery, and affects one of the main bottlenecks of the electrochemical performance. However, the negative electrode material of the lithium ion battery which is commercialized at present is graphite material, and the theoretical capacity is only 372mAh g-1And the serious safety problem exists in the process of high-rate charge and discharge, and the ever-increasing requirements of people cannot be met, particularly in a new energy automobile power battery. Therefore, research and development of new anode materials are of great importance.
The transition metal phosphide material has the characteristics of high theoretical reversible specific capacity, rich resources, good conductivity and the like, and thus becomes one of the research hotspots in the field of energy and chemical engineering in recent years. Among them, cobalt phosphide has high theoretical specific capacity, non-toxic constituent elements and low cost, and is widely studied as a negative electrode material of a lithium ion battery. However, the large volume change caused during the charge and discharge process causes poor cycle stability and low rate performance, limiting further development. The preparation of Mo-Li by doping with metals is considered to be an effective improvement, Wang et al (Electrochim acta, 2019,301,319-324)2ZnTi3O8The nano particles are embedded into the three-dimensional porous graphene composite material, and the current density is 2A g-1The current density also shows 210mAh g after circulating for 300 circles-1The reversible specific capacity of (a). Xia et al (Front Mater,2019,6,00001) synthesized Mo-TiO2The nano particles are coated on the one-dimensional carbon network composite material, and the current density is 850mA g-1Shows 449.2mAh g under the current density-1The reversible specific capacity of (a). Chinese patent with publication number CN105161700A discloses a preparation method of molybdenum trioxide coated molybdenum doped titanium dioxide nano-particles, which adopts one-step flame sprayingThe molybdenum trioxide-coated molybdenum-doped titanium dioxide nano composite particle material is prepared by a combustion technology in a rapid and continuous mode, and the molybdenum trioxide-coated molybdenum-doped titanium dioxide nano particle has low tap density and small specific surface area due to small nano scale, so that the molybdenum trioxide-coated molybdenum-doped titanium dioxide nano particle material has low capacity as a lithium ion battery cathode material. Chinese patent with publication number CN109148843A discloses a boron-doped negative electrode material with good high-temperature performance and a solid-phase preparation method thereof, wherein a boron-oxygen compound is used as a doping agent, the boron-oxygen compound is directly decomposed at high temperature by one step through solid-phase reaction to generate boron oxide, the boron oxide is controlled to react with the surface of the negative electrode material, and through surface modification, on one hand, the surface defects of the negative electrode material can be reduced through the catalytic action of boron, and the graphitization degree of the negative electrode material is improved; on the other hand, the surface defects of the cathode material can be reduced through the composite reaction of boron oxide and the surface of the cathode material, but the preparation method utilizes non-metal doping, and the modification difficulty is high, so that the material has no advantages when being used as the cathode material of the lithium ion battery, and the cycle stability and the rate capability are greatly limited.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of a molybdenum-doped cobalt phosphide-carbon coral sheet composite material, which is used for preparing a cobalt phosphide nanosheet with high tap density and large specific surface area. The lithium ion battery cathode material has excellent rate performance and cycle stability.
The technical scheme of the invention is as follows: a preparation method of a molybdenum-doped cobalt phosphide-carbon coral sheet composite material comprises the following steps:
step 1, quickly pouring an aqueous solution containing 2-methylimidazole into an aqueous solution of cobalt nitrate, stirring, standing for reaction, taking out a precipitate, washing with deionized water, and performing vacuum drying at 60-80 ℃ to obtain an MOF-Co material;
step 2, adding an MOF-Co material into an ethanol/deionized water mixed solution containing ammonium molybdate, stirring, placing the solution in a bath kettle at 80-85 ℃ for reaction, centrifuging to obtain a precipitate, cleaning, and performing vacuum drying at 60-80 ℃ to obtain a precursor, wherein the mass ratio of the MOF-Co material to the ammonium molybdate is 2: 1-1: 2;
and 3, putting the precursor prepared in the step 2 into the tail end of a corundum boat, putting sodium hypophosphite into the front end of the corundum boat, then putting the corundum boat into a tubular furnace, heating to 350-400 ℃ at the speed of 1.5-2 ℃/min under the nitrogen atmosphere, and preserving the heat for 2-2.5 hours to obtain the molybdenum-doped cobalt phosphide-carbon coral sheet composite material.
Further, the mass ratio of the precursor to the sodium hypophosphite in the step 3 is 1: 15-1: 25.
Furthermore, the concentration of the 2-methylimidazole aqueous solution is 0.3-0.4M, and the concentration of the cobalt nitrate aqueous solution is 0.04-0.05M.
Further, the ratio of ethanol to deionized water in the step 2 is 1: 3-1: 4.
Further, the standing reaction time in the step 1 is not less than 4 hours, and the reaction time in the bath kettle in the step 2 is not less than 1 hour.
The technical scheme provided by the invention has the beneficial effects that the molybdenum ion modified cobalt-based metal organic compound is adopted as a precursor, and the formation of the molybdenum-doped cobalt phosphide nano coral sheet is realized by a low-temperature phosphating method. The 2-methylimidazole is used as an organic ligand and combined with cobalt ions to form a metal organic compound precursor, and in the phosphating process, the 2-methylimidazole can be pyrolyzed in situ to form nitrogen-doped carbon, so that the structural stability and the electronic conductivity of the composite material can be greatly improved. The nano coral pieces synthesized by the method are uniformly distributed and show excellent electrochemical performance. The preparation method has simple steps and mild conditions, and is convenient for industrial large-scale production.
Drawings
FIG. 1 is an SEM image of a molybdenum-doped cobalt phosphide-carbon coral plate composite material of example 1.
FIG. 2 is an XRD pattern of the molybdenum-doped cobalt phosphide-carbon coral plate composite material of example 1.
FIG. 3 is a TEM image of the molybdenum-doped cobalt phosphide-carbon coral plate composite of example 1.
FIG. 4 is a graph of the rate capability of the molybdenum-doped cobalt phosphide-carbon coral sheet composite material of example 1.
FIG. 5 is a graph of the cycle performance of the molybdenum-doped cobalt phosphide-carbon coral sheet composite material of example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto.
Example 1
1.3136g of 2-methylimidazole were dissolved in 40ml of deionized water to give a solution A, 0.582g of cobalt nitrate hexahydrate was dissolved in 40ml of deionized water to give a solution B, and the solution A was poured into the solution B rapidly with stirring. Stirring for 10 minutes at room temperature, standing for reaction for 4 hours, taking out the precipitate, washing for three to four times by using deionized water, and then putting into a vacuum drying oven at 60-80 ℃ for drying to obtain the MOF-Co material.
Adding 0.2g of MOF-Co into an ethanol/deionized water (1: 4, 100ml) mixed solution containing 0.2g of ammonium molybdate, stirring for ten minutes, then placing the solution in a bath kettle at 85 ℃ for reacting for 1 hour, centrifuging to obtain a precipitate, cleaning, and then drying in vacuum at 60-80 ℃ to obtain a precursor.
And (2) putting the precursor and sodium hypophosphite into two ends of the corundum boat according to the mass ratio of 1: 20, wherein the sodium hypophosphite is positioned at the upstream, the precursor is positioned at the downstream, heating to 350 ℃ at the speed of 1.5 ℃/min in nitrogen atmosphere, keeping for 2h, cooling, and collecting black powder to obtain the target product. The SEM, XRD and TEM are shown in figures 1, 2 and 3.
Example 2
1.3136g of 2-methylimidazole were dissolved in 40ml of deionized water to give a solution A, 0.582g of cobalt nitrate hexahydrate was dissolved in 40ml of deionized water to give a solution B, and the solution A was poured into the solution B rapidly with stirring. Stirring for 10 minutes at room temperature, standing for reaction for 4 hours, taking out the precipitate, washing for three to four times by using deionized water, and then putting into a vacuum drying oven at 60-80 ℃ for drying to obtain the MOF-Co material.
Adding 0.2g of MOF-Co into an ethanol/deionized water (1: 3, 100ml) mixed solution containing 0.4g of ammonium molybdate, stirring for ten minutes, then placing the solution in a bath kettle at 80 ℃ for reacting for 1 hour, centrifuging to obtain a precipitate, cleaning, and then drying in vacuum at 60-80 ℃ to obtain a precursor.
And (2) putting the precursor and sodium hypophosphite into two ends of the corundum boat according to the mass ratio of 1: 20, wherein the sodium hypophosphite is positioned at the upstream, the precursor is positioned at the downstream, heating to 350 ℃ at the speed of 2 ℃/min in a nitrogen atmosphere, keeping for 2.5h, cooling, and collecting black powder to obtain the target product.
Example 3
1.3136g of 2-methylimidazole were dissolved in 40ml of deionized water to give a solution A, 0.582g of cobalt nitrate hexahydrate was dissolved in 40ml of deionized water to give a solution B, and the solution A was poured into the solution B rapidly with stirring. Stirring for 10 minutes at room temperature, standing for reaction for 4 hours, taking out the precipitate, washing for three to four times by using deionized water, and then putting into a vacuum drying oven at 60-80 ℃ for drying to obtain the MOF-Co material.
Adding 0.2g of MOF-Co into an ethanol/deionized water (1: 4, 100ml) mixed solution containing 0.1g of ammonium molybdate, stirring for ten minutes, then placing the solution in a bath kettle at 80 ℃ for reacting for 1 hour, centrifuging to obtain a precipitate, cleaning, and then drying in vacuum at 60-80 ℃ to obtain a precursor.
And (2) putting the precursor and sodium hypophosphite into two ends of the corundum boat according to the mass ratio of 1: 15, wherein the sodium hypophosphite is positioned at the upstream, the precursor is positioned at the downstream, heating to 350 ℃ at the speed of 1.5 ℃/min in nitrogen atmosphere, keeping for 2.5h, cooling, and collecting black powder to obtain the target product.
Example 4
1.3136g of 2-methylimidazole were dissolved in 40ml of deionized water to give a solution A, 0.582g of cobalt nitrate hexahydrate was dissolved in 40ml of deionized water to give a solution B, and the solution A was poured into the solution B rapidly with stirring. Stirring for 10 minutes at room temperature, standing for reaction for 4 hours, taking out the precipitate, washing for three to four times by using deionized water, and then putting into a vacuum drying oven at 60-80 ℃ for drying to obtain the MOF-Co material.
Adding 0.2g of MOF-Co into an ethanol/deionized water (1: 3, 100ml) mixed solution containing 0.2g of ammonium molybdate, stirring for ten minutes, then placing the solution in a bath kettle at 85 ℃ for reacting for 1 hour, centrifuging to obtain a precipitate, cleaning, and then drying in vacuum at 60-80 ℃ to obtain a precursor.
And (2) putting the precursor and sodium hypophosphite into two ends of the corundum boat according to the mass ratio of 1: 25, wherein the sodium hypophosphite is positioned at the upstream, the precursor is positioned at the downstream, heating to 400 ℃ at the speed of 2 ℃/min in a nitrogen atmosphere, keeping for 2h, cooling, and collecting black powder to obtain the target product.
Example 5
0.984g of 2-methylimidazole is dissolved in 40ml of deionized water to obtain a solution A, 0.466g of cobalt nitrate hexahydrate is dissolved in 40ml of deionized water to obtain a solution B, and the solution A is quickly poured into the solution B under stirring. Stirring for 10 minutes at room temperature, standing for reaction for 4 hours, taking out the precipitate, washing for three to four times by using deionized water, and then putting into a vacuum drying oven at 60-80 ℃ for drying to obtain the MOF-Co material.
Adding 0.2g of MOF-Co into an ethanol/deionized water (1: 3, 100ml) mixed solution containing 0.4g of ammonium molybdate, stirring for ten minutes, then placing the solution in a bath kettle at 80 ℃ for reacting for 1 hour, centrifuging to obtain a precipitate, cleaning, and then drying in vacuum at 60-80 ℃ to obtain a precursor.
And (2) putting the precursor and sodium hypophosphite into two ends of the corundum boat according to the mass ratio of 1: 20, wherein the sodium hypophosphite is positioned at the upstream, the precursor is positioned at the downstream, heating to 350 ℃ at the speed of 2 ℃/min in a nitrogen atmosphere, keeping for 2.5h, cooling, and collecting black powder to obtain the target product.
Example 6
1.23g of 2-methylimidazole was dissolved in 40ml of deionized water to obtain a solution A, 0.524g of cobalt nitrate hexahydrate was dissolved in 40ml of deionized water to obtain a solution B, and the solution A was rapidly poured into the solution B with stirring. Stirring for 10 minutes at room temperature, standing for reaction for 4 hours, taking out the precipitate, washing for three to four times by using deionized water, and then putting into a vacuum drying oven at 60-80 ℃ for drying to obtain the MOF-Co material.
Adding 0.2g of MOF-Co into an ethanol/deionized water (1: 4, 100ml) mixed solution containing 0.1g of ammonium molybdate, stirring for ten minutes, then placing the solution in a bath kettle at 80 ℃ for reacting for 1 hour, centrifuging to obtain a precipitate, cleaning, and then drying in vacuum at 60-80 ℃ to obtain a precursor.
And (2) putting the obtained precursor and sodium hypophosphite at a mass ratio of 1: 15 into two ends of a corundum boat, wherein the precursor is positioned at the upstream, the sodium hypophosphite is positioned at the downstream, heating to 350 ℃ at a speed of 1.5 ℃/min in a nitrogen atmosphere, keeping for 2.5h, cooling, and collecting black powder to obtain the target product.
Example 7
0.655g of 2-methylimidazole was dissolved in 40ml of deionized water to give a solution A, 0.29g of cobalt nitrate hexahydrate was dissolved in 40ml of deionized water to give a solution B, and the solution A was poured into the solution B rapidly with stirring. Stirring for 10 minutes at room temperature, standing for reaction for 4 hours, taking out the precipitate, washing for three to four times by using deionized water, and then putting into a vacuum drying oven at 60-80 ℃ for drying to obtain the MOF-Co material.
Adding 0.2g of MOF-Co into an ethanol/deionized water (1: 3, 100ml) mixed solution containing 0.4g of ammonium molybdate, stirring for ten minutes, then placing the solution in a bath kettle at 80 ℃ for reacting for 1 hour, centrifuging to obtain a precipitate, cleaning, and then drying in vacuum at 60-80 ℃ to obtain a precursor.
And (2) putting the precursor and sodium hypophosphite into two ends of the corundum boat according to the mass ratio of 1: 20, wherein the sodium hypophosphite is positioned at the upstream, the precursor is positioned at the downstream, heating to 350 ℃ at the speed of 2 ℃/min in a nitrogen atmosphere, keeping for 2.5h, cooling, and collecting black powder to obtain the target product.
The above examples were tested as follows:
the synthesized sample (active material), acetylene black (conductive agent) and PVDF (binder) were mixed uniformly in NMP at a mass ratio of 7:2:1, then coated on a copper foil, and placed in a vacuum drying oven to be dried at 100 ℃ for 10 hours. After removal, the electrode discs were cut to 12mm diameter. The lithium ion battery is used as a negative plate, a metal lithium plate is used as a counter electrode, a polypropylene microporous membrane Celgard2400 is used as a diaphragm, foam nickel is used as a filler, and an electrolyte is 1M LiPF6the/EC + DMC (volume ratio 1:1), CR2016 type coin cell was assembled in a glove box filled with argon protection. The testing is carried out by adopting a LAND CT2001A (Wuhan blue electricity) multi-channel battery testing system, the voltage range is between 0.01 and 3.0V, and the temperature is room temperature. The rate performance profile obtained for the electrode made from the product of example 1 is shown in fig. 4, and the cycle performance profile is shown in fig. 5. Rate capability and cycling performance such as that obtained for electrodes made from the products of examples 1 to 5The following table shows.

Claims (5)

1. A preparation method of a molybdenum-doped cobalt phosphide-carbon coral sheet composite material is characterized by comprising the following steps:
step 1, quickly pouring an aqueous solution containing 2-methylimidazole into an aqueous solution of cobalt nitrate, stirring, standing for reaction, taking out a precipitate, washing with deionized water, and performing vacuum drying at 60-80 ℃ to obtain an MOF-Co material;
step 2, adding an MOF-Co material into an ethanol/deionized water mixed solution containing ammonium molybdate, stirring, placing the solution in a bath kettle at 80-85 ℃ for reaction, centrifuging to obtain a precipitate, cleaning, and performing vacuum drying at 60-80 ℃ to obtain a precursor, wherein the mass ratio of the MOF-Co material to the ammonium molybdate is 2: 1-1: 2;
and 3, putting the precursor prepared in the step 2 into the tail end of a corundum boat, putting sodium hypophosphite into the front end of the corundum boat, then putting the corundum boat into a tubular furnace, heating to 350-400 ℃ at the speed of 1.5-2 ℃/min under the nitrogen atmosphere, and preserving the heat for 2-2.5 hours to obtain the molybdenum-doped cobalt phosphide-carbon coral sheet composite material.
2. The preparation method of the molybdenum-doped cobalt carbon phosphide coral sheet composite material as claimed in claim 1, wherein the mass ratio of the precursor to the sodium hypophosphite in step 3 is 1: 15-1: 25.
3. The method for preparing the molybdenum-doped cobalt carbon phosphide coral sheet composite material as claimed in claim 1, wherein the concentration of the aqueous solution of 2-methylimidazole is 0.3-0.4M, and the concentration of the aqueous solution of cobalt nitrate is 0.04-0.05M.
4. The method for preparing the molybdenum-doped cobalt carbon phosphide coral sheet composite material as claimed in claim 1, wherein the ratio of ethanol to deionized water in the step 2 is 1: 3 to 1: 4.
5. The method for preparing the molybdenum-doped cobalt carbon phosphide coral sheet composite material as claimed in claim 1, wherein the standing reaction time in the step 1 is not less than 4 hours, and the reaction time in the water bath kettle in the step 2 is not less than 1 hour.
CN201910910982.0A 2019-09-25 2019-09-25 Preparation method of molybdenum-doped cobalt phosphide-carbon coral sheet composite material Pending CN110627031A (en)

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CN111710860A (en) * 2020-06-29 2020-09-25 山东大学 Nitrogen-phosphorus co-doped carbon composite material modified by cobalt-molybdenum phosphide particles and preparation method and application thereof
CN112072094A (en) * 2020-09-23 2020-12-11 中南大学 Molybdenum-doped nickel phosphide/carbon negative electrode material with microsphere structure and preparation method thereof
CN114744191A (en) * 2022-03-24 2022-07-12 河北科技大学 Cobalt phosphide cathode material and preparation method and application thereof
CN115440504A (en) * 2021-06-02 2022-12-06 重庆三峡学院 Mo-CoP @ Ni-Fe LDH core-shell hierarchical nanosheet and preparation method and application thereof

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Application publication date: 20191231