CN115132992A - Composite electrode material, preparation method thereof and battery - Google Patents

Composite electrode material, preparation method thereof and battery Download PDF

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Publication number
CN115132992A
CN115132992A CN202210802079.4A CN202210802079A CN115132992A CN 115132992 A CN115132992 A CN 115132992A CN 202210802079 A CN202210802079 A CN 202210802079A CN 115132992 A CN115132992 A CN 115132992A
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electrode material
composite electrode
carbon paper
precursor
carbon
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宋佃凤
钟可君
吴立群
徐汝义
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Shandong Renfeng Speical Materials Co ltd
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Shandong Renfeng Speical Materials 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
    • H01M4/362—Composites
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/133—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/583—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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes

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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a composite electrode material, a preparation method thereof and a battery, relates to the technical field of batteries and aims to solve the problems that the sodium storage capacity of a negative electrode material of a sodium battery is not ideal enough and the cost is high. A method of making a composite electrode material, comprising: providing a carbon paper precursor through wet forming; dipping the carbon paper precursor into tungsten disulfide precursor dispersion liquid to obtain a carbon paper precursor dip; carrying out hot-pressing curing and carbonization operations on the carbon paper precursor impregnation to obtain a composite electrode material semi-finished product; and vulcanizing the semi-finished product of the composite electrode material to obtain the composite electrode material containing tungsten disulfide. The composite electrode material is prepared by a preparation method of the composite electrode material; the battery includes a composite electrode material. The invention discloses a composite electrode material, a preparation method thereof and a battery for preparing the composite electrode material.

Description

Composite electrode material, preparation method thereof and battery
Technical Field
The invention relates to the technical field of batteries, in particular to a composite electrode material, a preparation method thereof and a battery.
Background
The sodium ion battery is a potential substitute of the lithium ion battery due to sufficient resource storage and low extraction cost, and sodium and lithium are located in the same main group and have similar physicochemical properties. However, the radius of sodium ions is much larger than that of lithium ions, so that the sodium ions are difficult to be extracted from the electrode material, and even if the sodium ions are successfully extracted from the electrode material, the carbon skeleton is deformed, so that the mechanical performance of the battery is reduced.
To overcome this drawback, the most commonly used anode material at the present stage is a hard carbon anode material. However, the hard carbon anode material has a less than ideal sodium storage capacity and is relatively high in cost. Therefore, the preparation of the electrode material with high sodium storage capacity and low cost is very key.
Disclosure of Invention
The invention aims to provide a composite electrode material, a preparation method thereof and a battery, so as to ensure high sodium storage capacity and low cost of the composite electrode material.
In order to achieve the above object, the present invention provides a method for preparing a composite electrode material, comprising:
providing a wet-formed carbon paper precursor;
dipping the carbon paper precursor into tungsten disulfide precursor dispersion liquid to obtain a carbon paper precursor dip;
carrying out hot-pressing curing and carbonization operations on the carbon paper precursor impregnation to obtain a composite electrode material semi-finished product;
and vulcanizing the semi-finished product of the composite electrode material to obtain the composite electrode material containing tungsten disulfide.
Compared with the prior art, in the preparation method of the composite electrode material, the carbon paper precursor is soaked in the tungsten disulfide precursor dispersion liquid, and hot pressing solidification is carried out on the carbon paper precursor soaked matter before carbonization operation, so that the tungsten disulfide precursor can be fully contacted with fibers in the carbon paper precursor under the action of hot pressing before the carbon paper precursor is not converted into carbon paper. Based on the method, after hot-pressing solidification, carbonization operation and vulcanization are carried out on the carbon paper precursor impregnation object, and the carbon fiber and tungsten disulfide in the formed composite electrode material can be ensured to have good composite effect. In addition, before the carbon paper is formed, the carbon paper precursor is soaked in the tungsten disulfide precursor dispersion liquid, and then hot pressing curing, carbonization operation and vulcanization are carried out, so that the compounding process of the carbon paper and the tungsten disulfide is synchronously carried out along with the manufacturing process of the carbon paper, the problem of complicated steps caused by coating the tungsten disulfide after the carbon paper is formed is solved, and the production cost is reduced. In addition, the wet forming can be used for mass production of the carbon paper, so that the production cost is further reduced.
In addition, in the composite material prepared by the preparation method provided by the invention, the carbon paper has a porous structure, can provide a sodium ion diffusion channel, improves the charge transfer efficiency, accommodates volume expansion in the charge-discharge process, and improves the safety.
In a second aspect, the invention also provides a composite electrode material, and the composite electrode material is prepared by the preparation method of the composite electrode material.
In a third aspect, the invention also provides a battery comprising the composite electrode material.
Compared with the prior art, the beneficial effects of the composite electrode material and the battery provided by the invention are the same as those of the preparation method of the composite electrode material in the first aspect, and the details are not repeated herein.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a flow chart for preparing a composite electrode material provided in the present example;
fig. 2 is a schematic structural diagram of a battery provided in an embodiment of the present invention.
Reference numerals:
200-battery, 201-separator, 202 a-positive current collector, 202 b-positive electrode material, 203 a-carbon paper, 203 b-negative electrode material.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise. The meaning of "a number" is one or more unless specifically limited otherwise.
At present, the radius of sodium ions is much larger than that of lithium ions, so that the sodium ions are difficult to be extracted from the electrode material, and even if the sodium ions are smoothly extracted from the electrode material, the carbon skeleton is deformed, so that the mechanical performance of the battery is reduced. In order to overcome the defects, hard carbon is usually adopted as a negative electrode material in the market, but the sodium storage capacity of the hard carbon is not ideal enough, and the cost is high.
In view of the above problems, the embodiment of the invention provides a preparation method of a composite electrode material, which can prepare a hard carbon composite electrode material with high sodium storage capacity and low cost. Fig. 1 shows a flow chart for preparing a composite electrode material provided by an embodiment of the present invention. As shown in fig. 1, the preparation method of the composite electrode material comprises the following steps:
step 101: providing a wet-formed carbon paper precursor.
Illustratively, the carbon paper precursor in the embodiment of the present invention is obtained by a wet forming technique. In the technical means, the carbon fibers and the paper-based fibers are stirred in a solution at a speed of 500-1000 rpm for more than 10min to fully disperse the fibers, then the fully dispersed fibers are made into paper to form a wet paper web, and finally the wet paper web is dried at 90-110 ℃ for 30-40 min to obtain the carbon paper precursor obtained in the embodiment of the invention. In order to achieve a more complete interlacing of the fibres, organic compounds are usually added, which contain binders (e.g. polyvinyl alcohol, polyimide) and cationic strengthening agents (e.g. surfactants).
Step 102: and dipping the carbon paper precursor into the tungsten disulfide precursor dispersion liquid to obtain the carbon paper precursor dipped material.
Illustratively, the tungsten disulfide precursor dispersion liquid contains tungsten powder and hydrogen peroxide solution, and the mass ratio of the tungsten powder to the hydrogen peroxide is 7: 3. Grinding tungsten powder at the temperature of 25-40 ℃ to obtain a mixture, wherein the mixture is prepared from (7-10): and (3) dissolving the tungsten powder into a hydrogen peroxide solution according to the proportion of (3-5), wherein the tungsten powder can be completely dissolved into the hydrogen peroxide solution to prepare a tungstic acid suspension. And then adding isopropanol serving as a stabilizer into the peroxytungstic acid suspension, stirring for 30-90 min by using a magnetic stirrer at the speed of 500-700 r/min, and finally obtaining the tungsten disulfide precursor dispersion after 1 h. And finally, dipping the carbon paper precursor in the prepared tungsten disulfide precursor dispersion liquid to obtain the carbon paper precursor dipped material. Wherein the isopropanol is analytically pure, and 10-20 mL of isopropanol is required to be added into each 30mL of the tungstic acid suspension.
Illustratively, the carbon paper precursor has a basis weight of from 80 grams per square meter to 90 grams per square meter. Within the range, the lower cost can be ensured, the strength, the conductivity and the weight of the formed carbon paper can be ensured to meet the requirement of the sodium battery, and when the quantitative amount of the carbon paper precursor is 90 g/square meter, the carbon fiber with enough quantity is provided, so that the tungsten disulfide precursor can be fully contacted with the carbon paper precursor in the steps of dipping the tungsten disulfide precursor dispersion liquid and hot pressing and curing, and the tungsten disulfide precursor is fully loaded, thereby ensuring that the carbon fiber and the tungsten disulfide in the composite electrode material have good composite effect. More importantly, wet forming is the mainstream production technology of the carbon paper at the present stage, and can realize large-scale production of the composite electrode material provided by the embodiment of the invention, and the composite electrode material has good consistency and stability and low manufacturing cost.
Step 103: and carrying out hot-pressing curing and carbonization operations on the carbon paper precursor impregnated matter to obtain a semi-finished product of the composite electrode material.
For example, the dried carbon paper precursor impregnation is hot-pressed and cured before the carbonization operation, so that the tungsten disulfide precursor can be fully contacted with the fibers in the carbon paper precursor under the action of hot pressing before the carbon paper precursor is not converted into the carbon paper. Just so, the carbon paper precursor impregnation object after hot pressing and curing can obtain good composite effect of the carbon fiber and the tungsten disulfide precursor through carbonization.
Step 104: and vulcanizing the semi-finished product of the composite electrode material to obtain the composite electrode material formed by tungsten disulfide and carbon paper.
Illustratively, the obtained composite electrode material semi-finished product is immersed in thiourea, put into an alumina crucible, and sintered in a tubular atmosphere furnace filled with protective gas, so that the vulcanized composite electrode material semi-finished product is protected from the outside gas at high temperature. Through the steps, the carbon fiber and the tungsten disulfide in the composite electrode material have a good composite effect, so that the composite electrode material is ensured to have better conductivity and physical properties which can be applied to the field of fuel cells. Moreover, in the preparation method provided by the embodiment of the invention, the compounding process of the carbon paper and the tungsten disulfide is synchronously carried out along with the manufacturing process of the carbon paper, so that the problem of complicated steps caused by coating the tungsten disulfide after the carbon paper is formed is avoided, and the production cost is reduced.
In an alternative form, the carbon paper precursor includes carbon fiber feedstock, a binder, and ethylene oxide and a surfactant.
Illustratively, the carbon fiber feedstock is composed of carbon fibers and paper-based fibers, including at least one of viscose fibers, cellulose nanofibrils, and carbon fibers. The carbon fiber is at least one of polyacrylonitrile-based carbon fiber and asphalt-based carbon fiber, wherein the polyacrylonitrile-based carbon fiber has good structural and functional characteristics and high yield; although pitch-based carbon fibers are relatively small, they are a good choice of carbon fiber types because the carbon yield after carbonization exceeds 80%.
Illustratively, the mass ratio of the viscose fibers, the carbon fibers and the cellulose nanofibrils is (10-15): (83-88): (1-2). Adding proper amount of water, stirring at 500-1000 rpm for over 10min to disperse the carbon fiber material. When the carbon fiber raw material accounts for 0.1-0.15% of the mass of the mixture of the carbon fiber raw material and water, the carbon fiber raw material can be fully dispersed into single fibers, so that the phenomenon of fiber agglomeration is avoided. The carbon fiber has a length of 5mm to 6mm, and a resistivity of 0.001 to 0.1 Ω · cm. The length of the viscose fiber is 3 mm-5 mm. When the length of the viscose fiber is 3-4 mm, the filling effect is better, and the formed paper is more uniform.
Illustratively, when the mass ratio of the polyethylene oxide to the surfactant to the polyvinyl alcohol is 3:1:3, the dispersant and the polyvinyl alcohol enable the carbon fiber raw materials to be interwoven more fully at the mass ratio, so that the composite electrode material formed in the subsequent steps has good mechanical properties and conductivity.
Illustratively, the surfactant is at least one of tween-80, turkey red oil, and glyceryl oleate. Since carbon fibers have hydrophobicity, and are easily agglomerated in water and difficult to disperse uniformly, a surfactant is added thereto as a dispersant for the carbon fibers to promote sufficient dispersion in water. In the step of dipping the carbon paper precursor into the tungsten disulfide precursor dispersion liquid, the carbon paper precursor can be fully contacted with the tungsten disulfide precursor in the dipping process due to the fact that the surfactant is used as the dispersing agent of the carbon fibers, and the phenomenon that only part of the carbon paper precursor is dipped into the tungsten disulfide precursor dispersion liquid due to carbon fiber agglomeration is avoided. Based on this, after hot pressing solidification, after carbonizing operation and vulcanization are carried out on the carbon paper precursor impregnation, the carbon fiber and tungsten disulfide in the formed composite electrode material can be ensured to have good composite effect, and the composite electrode material has good rate performance and sodium storage capacity. When the surfactant is Tween-80, the addition amount of the surfactant is 0.02-0.05% of the mass of the carbon paper precursor before drying, and the generated dispersion effect is the best.
Illustratively, the carbon paper precursor contains 10% by mass of polyvinyl alcohol for paper processing. Since carbon fiber is a fiber structure of an inorganic carbon material, the tensile strength and tensile modulus are high, but the carbon fiber is a brittle material and has poor toughness. Therefore, polyvinyl alcohol is needed, and the toughness of the carbon paper can be improved through better strong adhesion, so that the composite electrode material prepared in the subsequent steps is ensured to have better mechanical property, and the durability of the composite electrode material is also improved. When the polyvinyl alcohol with the molecular weight of 17-22 ten thousand is selected, and the addition amount is 0.1-0.15% of the mass of the carbon paper precursor before drying, the toughness improvement effect on the carbon paper is the best.
Illustratively, the carbon paper precursor contains polyethylene oxide with the molecular weight of 600-800 ten thousand, and the addition amount of the polyethylene oxide accounts for 0.1-0.2% of the mass of the carbon paper precursor before drying. The polyoxyethylene is a water-soluble resin, can be used as a dispersant and has a dispersing function together with a surfactant, so that the dispersing effect of the carbon paper precursor is improved. Polyethylene oxide, a surfactant and polyvinyl alcohol contained in the carbon paper precursor act synergistically, so that carbon fiber raw materials are interwoven more fully, and the composite electrode material formed in the subsequent steps is ensured to have good mechanical property and conductivity.
In an optional mode, the reaction temperature of hot-pressing curing is 130-150 ℃, the reaction pressure is 10-15 MPa, and the reaction time is 40-50 min; the reaction temperature of the carbonization is 1400-1500 ℃, the heating rate is 25-35 ℃/min, and the reaction time is 7-9 h.
Exemplarily, the carbon paper precursor impregnated matter is placed in a flat vulcanizing machine, and is hot-pressed for 40min to 50min under the conditions of 130 ℃ to 150 ℃ and 10MPa to 15MPa, so that gas impurities in the carbon fibers can be discharged in time, the impregnated tungsten disulfide precursor can be better contacted and filled in gaps of the carbon fibers, the density of the extruded composite electrode material semi-finished product can be remarkably improved, and the performance of the composite material can be further improved. And then, the carbon paper is subjected to heat treatment for 7 to 9 hours at 1400 to 1500 ℃ and 25 to 35 ℃/min by using a vacuum tube furnace under the condition of introducing a protective gas (such as nitrogen), so that the carbon content in the composite electrode material semi-finished product is remarkably improved, and the composite electrode material semi-finished product has better conductivity and mechanical property.
The embodiment of the invention also provides a composite electrode material, which is prepared by the preparation method of the composite electrode material.
In addition, the carbon paper itself can also serve as a current collector to act on sodium ions, so that the cost of arranging the current collector in a sodium ion battery is reduced. In the tungsten disulfide, tungsten atoms and sulfur atoms are in strong chemical bond connection, sulfur atoms between layers are in weak molecular bond connection, and the bonding force between layers is still Van der Waals force, so that the tungsten disulfide has larger interlayer spacing compared with molybdenum disulfide. The carbon fiber paper base and the tungsten disulfide with a two-dimensional layered structure are compounded, so that higher rate performance and sodium storage capacity can be achieved.
The embodiment of the invention provides a battery, which can comprise the composite electrode material provided by the embodiment of the invention so as to ensure that the composite electrode material has high sodium storage capacity and low cost. It is to be understood that the electrode material may be defined as a negative electrode material in which carbon paper may serve as a current collector for the negative electrode of an ion battery. The ion battery may further include a positive electrode material, a positive electrode current collector, a separator, and an electrolyte. The separator may be defined to have opposing first and second surfaces, with a positive electrode material between the positive electrode current collector and the first surface, and a negative electrode material between the carbon paper and the second surface. Fig. 2 shows a schematic structural diagram of a battery 200 according to an embodiment of the present invention, and as shown in fig. 2, the battery 200 according to an embodiment of the present invention includes a separator 201, and a positive electrode current collector 202a, a positive electrode material 202b, a negative electrode material 203b, and a carbon paper 203a distributed on both sides of the separator 201.
The present invention will be further described with reference to the following examples.
Example one
The preparation method of the composite electrode material provided by the embodiment of the invention comprises the following steps:
step one, preparing a carbon paper precursor: weighing 10 parts by mass of viscose fibers with the length of 3mm, 2 parts by mass of cellulose nanofibrils, 88 parts by mass of polyacrylonitrile-based carbon fibers with the length of 6mm and the resistivity of 10m omega/cm, adding the carbon fiber raw materials into a dispersing barrel with a stirrer, adding 568 parts of water to ensure that the total mass fraction of the viscose fibers, the cellulose nanofibrils and the polyacrylonitrile-based carbon fibers is 0.15%, and starting stirring at the rotating speed of 700 rpm. Adding 0.04 wt% of Tween-80, adding 0.12 wt% of polyethylene oxide (molecular weight is 600 ten thousand), completely dispersing the carbon fiber raw material into single fibers, adding 0.12 wt% of polyvinyl alcohol solution (molecular weight is 22 ten thousand, concentration is 10%), mechanically stirring for 10min, preparing wet paper webs by wet forming equipment, drying in an oven for 30min at 110 ℃, and preparing the carbon paper precursor with the quantitative of 90 g/square meter.
Step two, preparing a carbon paper precursor impregnant: 1.5g of tungsten powder is ground and dissolved in 30mL of hydrogen peroxide solution with the mass fraction of 30 percent, the temperature is kept at 35 ℃, and a tungstic acid suspension is generated after 1h of reaction. Then 15ml of analytically pure isopropanol is added into the tungstic acid suspension, and a magnetic stirrer is used for stirring at the speed of 600 revolutions per minute for 60 minutes to obtain the tungsten disulfide precursor dispersion liquid. And finally, dipping the carbon paper precursor into the tungsten disulfide precursor dispersion liquid, using ultrasonic equipment to assist in ultrasonic treatment, dipping for 1min, taking out and drying to obtain the carbon paper precursor dipped material.
Step three, preparing a composite electrode material semi-finished product: and (3) placing the carbon paper precursor impregnated matter in a flat vulcanizing machine, carrying out hot pressing for 45min under the conditions of 140 ℃ and 10MPa, and carrying out heat treatment on the carbon paper precursor impregnated matter for 8h at the speed of 30 ℃/min at 1500 ℃ by using a vacuum tube furnace under the protection of introduced nitrogen, thus obtaining a semi-finished product of the composite electrode material.
Fourthly, preparing a composite electrode material: and immersing the semi-finished product of the composite electrode material in thiourea, putting the semi-finished product into an alumina crucible, and sintering in a tubular atmosphere furnace under the protection of argon to obtain the composite electrode material.
Example two
The preparation method of the composite electrode material provided by the embodiment of the invention comprises the following steps:
step one, preparing a carbon paper precursor: weighing 15 parts by mass of viscose fiber with the length of 3mm and 1 part by mass of cellulose nanofibril, 84 parts by mass of polyacrylonitrile-based carbon fiber with the length of 6mm and the resistivity of 10m omega/cm, adding 570 parts by mass of water into a dispersion barrel with a stirrer to ensure that the total mass fraction of the viscose fiber, the cellulose nanofibril and the polyacrylonitrile-based carbon fiber is 0.15%, starting stirring at the rotating speed of 700rpm, adding 0.04 wt% of tween-80, then 0.10 wt% of polyethylene oxide (molecular weight of 600 ten thousand), adding 0.10 wt% of polyvinyl alcohol solution (molecular weight of 20 ten thousand and concentration of 10%) after the carbon fiber raw material is completely dispersed into single fibers, mechanically stirring for 10min, preparing a wet paper web by a wet forming device, drying the wet paper web by an oven for 40min at 90 ℃, the carbon paper precursor with the quantitative rate of 90 g/square meter is prepared.
Step two, preparing carbon paper precursor impregnant: 2.0g of tungsten powder is ground and dissolved in 30ml of hydrogen peroxide solution with the mass fraction of 30 percent, the temperature is kept at 35 ℃, and a tungstic acid suspension is generated after 1h of reaction. Then 10ml of analytically pure isopropanol is added into the tungstic acid suspension, and the mixture is stirred for 60min by a magnetic stirrer at the speed of 600 revolutions per minute to obtain the tungsten disulfide precursor dispersion liquid. And finally, dipping the carbon paper precursor into the tungsten disulfide precursor dispersion liquid, using ultrasonic equipment to assist in ultrasonic treatment, dipping for 1min, taking out and drying to obtain the carbon paper precursor dipped material.
Thirdly, preparing a semi-finished product of the composite electrode material: and (3) placing the carbon paper precursor impregnated matter in a flat vulcanizing machine, carrying out hot pressing for 40min under the conditions of 150 ℃ and 15MPa, and carrying out heat treatment on the carbon paper precursor impregnated matter for 8h at the speed of 35 ℃/min at 1500 ℃ by using a vacuum tube furnace under the protection of introduced nitrogen, thus obtaining a semi-finished product of the composite electrode material.
Fourthly, preparing a composite electrode material: and immersing the semi-finished product of the composite electrode material in thiourea, putting the semi-finished product into an alumina crucible, and sintering in a tubular atmosphere furnace under the protection of argon to obtain the composite electrode material.
EXAMPLE III
The preparation method of the composite electrode material provided by the embodiment of the invention comprises the following steps:
step one, preparing a carbon paper precursor: weighing 10 parts by mass of viscose fibers with the length of 3mm, 2 parts by mass of cellulose nanofibrils, 88 parts by mass of pitch-based carbon fibers with the length of 6mm and the resistivity of 6m omega/cm, adding 600 parts by mass of water to ensure that the total mass fraction of the viscose fibers, the cellulose nanofibrils and the polyacrylonitrile-based carbon fibers is 0.10%, starting stirring at a rotation speed of 700rpm, adding 0.05 wt% of Turkey red oil, then 0.20 wt% of polyethylene oxide (molecular weight of 700 ten thousand), adding 0.15 wt% of polyvinyl alcohol solution (molecular weight of 22 ten thousand) after the carbon fiber raw materials are completely dispersed into single fibers, mechanically stirring for 10min, preparing a wet paper web by a wet forming device, drying for 40min by an oven at 90 ℃, the carbon paper precursor with the quantitative rate of 80 g/square meter is prepared.
Step two, preparing a carbon paper precursor impregnant: 2.5g of tungsten powder is ground and dissolved in 30ml of hydrogen peroxide solution with the mass fraction of 30 percent, the temperature is kept at 35 ℃, and the tungstic acid suspension is generated after 1 hour of reaction. Then 20ml of analytically pure isopropanol is added into the tungstic acid suspension, and the mixture is stirred for 40min by a magnetic stirrer at the speed of 700 r/min to obtain the tungsten disulfide precursor dispersion liquid. And finally, dipping the carbon paper precursor into the tungsten disulfide precursor dispersion liquid, using ultrasonic equipment to assist in ultrasonic treatment, dipping for 1min, taking out and drying to obtain the carbon paper precursor dipped material.
Step three, preparing a composite electrode material semi-finished product: and (3) placing the carbon paper precursor impregnated matter in a flat vulcanizing machine, carrying out hot pressing for 50min under the conditions of 130 ℃ and 10MPa, and carrying out heat treatment on the carbon paper precursor impregnated matter for 9h at the speed of 1400 ℃ and 35 ℃/min by using a vacuum tube furnace under the protection of nitrogen, thereby obtaining a semi-finished product of the composite electrode material.
Fourthly, preparing a composite electrode material: and immersing the semi-finished product of the composite electrode material in thiourea, putting the semi-finished product into an alumina crucible, and sintering in a tubular atmosphere furnace under the protection of argon to obtain the composite electrode material.
Example four
The preparation method of the composite electrode material provided by the embodiment of the invention comprises the following steps:
step one, preparing a carbon paper precursor: weighing 15 parts by mass of viscose fiber with the length of 3mm, 2 parts by mass of cellulose nanofibrils, 44 parts by mass of pitch-based carbon fiber with the length of 6mm and the resistivity of 6m omega/cm and 44 parts by mass of polyacrylonitrile-based carbon fiber with the length of 6mm and the resistivity of 6m omega/cm, adding the carbon fiber raw materials into a dispersing barrel with a stirrer, adding 800 parts of water to enable the total mass fraction of the viscose fiber, the cellulose nanofibrils and the polyacrylonitrile-based carbon fiber to be 0.15%, starting stirring at the rotating speed of 700rpm, firstly adding 0.02 wt% of glyceryl oleate, then adding 0.12 wt% of polyethylene oxide (molecular weight of 800 ten thousand), after the carbon fiber raw materials are completely dispersed into single fibers, adding 0.15 wt% of polyvinyl alcohol solution (molecular weight of 17 ten thousand and concentration of 10%), mechanically stirring for 10min, making wet paper web by wet forming equipment, drying in oven at 100 deg.C for 35min, and making carbon paper precursor with quantitative ratio of 85 g/square meter.
Step two, preparing a carbon paper precursor impregnant: 3.0g of tungsten powder is taken and dissolved in 30ml of hydrogen peroxide solution with the mass fraction of 30 percent after being ground, the temperature is kept at 35 ℃, and the tungstic acid suspension is generated after 1 hour of reaction. Then 20ml of analytically pure isopropanol is added into the tungstic acid suspension, and the mixture is stirred for 40min by a magnetic stirrer at the speed of 700 r/min to obtain the tungsten disulfide precursor dispersion liquid. And finally, dipping the carbon paper precursor into the tungsten disulfide precursor dispersion liquid, using ultrasonic equipment to assist in ultrasonic treatment, dipping for 1min, taking out and drying to obtain the carbon paper precursor dipped material.
Step three, preparing a composite electrode material semi-finished product: and (3) placing the carbon paper precursor impregnated matter in a flat vulcanizing machine, carrying out hot pressing for 50min under the conditions of 140 ℃ and 10MPa, and carrying out heat treatment on the carbon paper precursor impregnated matter for 7h at the speed of 30 ℃/min and 1500 ℃ by using a vacuum tube furnace under the protection of nitrogen, thereby obtaining a semi-finished product of the composite electrode material.
Fourthly, preparing a composite electrode material: and immersing the semi-finished product of the composite electrode material in thiourea, putting the semi-finished product into an alumina crucible, and sintering in a tubular atmosphere furnace under the protection of argon to obtain the composite electrode material.
While the foregoing is directed to embodiments of the present invention, it will be apparent that various modifications and combinations can be made without departing from the spirit and scope of the invention. Accordingly, the specification and figures are merely exemplary of the invention as defined in the appended claims and are intended to cover any and all modifications, variations, combinations, or equivalents within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Any person skilled in the art can easily conceive of changes or substitutions within the technical scope of the present disclosure, and all such changes or substitutions are included in the scope of the present disclosure. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (10)

1. A method for preparing a composite electrode material, comprising:
providing a wet-formed carbon paper precursor;
dipping the carbon paper precursor into tungsten disulfide precursor dispersion liquid to obtain a carbon paper precursor dipped material;
carrying out hot-pressing curing and carbonizing operation on the carbon paper precursor impregnated matter to obtain a semi-finished product of the composite electrode material;
and vulcanizing the semi-finished product of the composite electrode material to obtain the composite electrode material formed by tungsten disulfide and carbon paper.
2. The method of preparing a composite electrode material according to claim 1, wherein the carbon paper precursor comprises a carbon fiber raw material, a binder, polyethylene oxide, and a surfactant.
3. The method of manufacturing a composite electrode material according to claim 2, wherein the fiber raw material includes at least one of viscose, cellulose nanofibrils and carbon fibers.
4. The method for preparing the composite electrode material according to claim 3, wherein the carbon fiber is at least one of polyacrylonitrile-based carbon fiber and pitch-based carbon fiber, the length of the carbon fiber is 5mm to 6mm, and the length of the viscose fiber is 3mm to 5 mm.
5. The method for preparing the composite electrode material according to claim 3, wherein the mass ratio of the viscose fibers, the carbon fibers and the cellulose nanofibrils is (10-15): (83-88): (1-2).
6. The method for preparing the composite electrode material according to claim 2, wherein the binder is polyvinyl alcohol, and the mass ratio of the polyethylene oxide to the surfactant to the polyvinyl alcohol is (2-3): (0.8-1): 2-3).
7. The method for preparing a composite electrode material according to claim 6, wherein the surfactant is at least one of Tween-80, Turkey red oil and glyceryl oleate.
8. The method for preparing the composite electrode material according to any one of claims 1 to 7, wherein the carbon paper precursor has a quantitative content of 80 to 90 grams per square meter; and/or the presence of a gas in the gas,
the tungsten disulfide precursor dispersion liquid contains tungsten powder and hydrogen peroxide solution, and the mass ratio of the tungsten powder to the hydrogen peroxide is (7-10): (3-5); and/or the presence of a gas in the atmosphere,
the reaction temperature of the hot-pressing solidification is 130-150 ℃, the reaction pressure is 10-15 MPa, and the reaction time is 40-50 min; the reaction temperature of carbonization is 1400-1500 ℃, the heating rate is 25-35 ℃/min, and the reaction time is 7-9 h.
9. A composite electrode material, characterized in that the composite electrode material is prepared by the preparation method of the composite electrode material according to any one of claims 1 to 8.
10. A battery comprising the composite electrode material of claim 9.
CN202210802079.4A 2022-07-07 2022-07-07 Composite electrode material, preparation method thereof and battery Pending CN115132992A (en)

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