CN111584852A - High-performance cathode material of lithium battery and preparation method and application thereof - Google Patents

High-performance cathode material of lithium battery and preparation method and application thereof Download PDF

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CN111584852A
CN111584852A CN202010466207.3A CN202010466207A CN111584852A CN 111584852 A CN111584852 A CN 111584852A CN 202010466207 A CN202010466207 A CN 202010466207A CN 111584852 A CN111584852 A CN 111584852A
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cathode material
citric acid
lithium battery
ethyl orthosilicate
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袁峰
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Xiwang New Energy Technology Kunshan 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
    • H01M10/052—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
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    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • H01M4/625—Carbon or graphite
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a high-performance cathode material of a lithium battery, which is prepared from the following raw materials: graphene oxide, carbon fluoride, tetraethyl titanate, ethyl orthosilicate, manganese acetate, carbon black, citric acid and a silane coupling agent. The invention provides a toolWith high energy density materials such as CF combined with graphene oxide/SiO2The electrochemical performance and the service life of the/Ti-Mn composite material-based electrode are simple, the preparation method is simple, the environment-friendly chemical synthesis is realized, and manganese and titanium can be combined to form a mixed oxide electrode with increased capacity and a required discharge curve, so that the mixed oxide electrode can be applied to a quick-charging lithium ion battery.

Description

High-performance cathode material of lithium battery and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a high-performance cathode material of a lithium battery, and a preparation method and application thereof.
Background
Lithium electrochemical cells, more commonly referred to as batteries (packs), are widely used in a variety of military and commercial products. Many of these products use high energy and high power batteries. Due in part to the miniaturization of portable electronic devices, it is desirable to develop smaller lithium batteries with increased power capacity and service life. One approach to developing smaller batteries with increased power capacity is to develop higher energy cathode materials.
One example of a high energy cathode material is fluorinated carbon (i.e., CF). CF is often used with lithium anodes in non-rechargeable (primary) batteries for military equipment and implantable medical devices, among others. CF (where x ═ 1.0) has a specific energy of about 860 mAh/g. Other examples of high energy cathode materials include silver vanadium oxide and manganese dioxide, which have specific energies of about 315 and 308mAh/g, respectively.
The cathode of a rechargeable (secondary) battery, such as a lithium ion battery, typically has a lower energy storage capacity than the cathode of the primary battery. However, secondary batteries are typically rechargeable hundreds of times, which significantly reduces life costs and battery handling costs. Examples of the secondary battery cathode for a lithium ion battery include lithium cobalt oxide, lithium iron phosphate, and lithium nickel cobalt oxide.
To meet the demand for longer-lasting and/or smaller batteries, there is still a need for cathodes exhibiting as much higher energy as primary batteries, having a partially or fully chargeable capacity as secondary batteries, thereby extending battery life and effectively reducing overall cost. Hybrid cathode materials have been proposed as one possible way to achieve such improved primary and/or secondary batteries. Other advantages of the hybrid cathode materials include improved rate capability and/or stability of the cathode while maintaining energy density per unit weight and/or volume. Methods to achieve these advantages typically include mixing cathode materials having high rate capability with cathode materials having high energy densities.
U.S. patent No.7,476,467 discloses a cathode material for a secondary lithium battery. The cathode active material includes a mixture of (A) a lithium manganese-metal composite oxide having a spinel structure and (B) a lithium nickel-manganese-cobalt composite oxide having a layered structure. The cathode active material is said to have superior safety and long-term service life at both room temperature and high temperature due to improved properties of lithium and metal oxides.
As known to those skilled in the art, the use includesComposite cathodes of fluorinated carbon and certain metal oxides provide batteries with reduced voltage delay, improved rate capability and low temperature performance. For example, U.S. patent No.5,667,916 describes a battery having a cathode mix of CF with other materials or mixtures of other materials, including, for example, copper oxide. Similarly, U.S. patent No.5,180,642 discloses an electrochemical cell or battery having a cathode mixture comprising manganese dioxide (MnO)2) Carbon monofluoride (CF, where x ═ 1), or a mixture of the two, and other additives selected from vanadium oxide, silver vanadate, bismuth fluoride, and titanium sulfide.
Copper vanadium oxide electrodes are known for general use in lithium batteries. For example, U.S. patent No.4,310,609 discloses the use of an electrochemical cell having as the positive electrode a composite oxide substrate comprised of vanadium oxide chemically reacted with a group IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIIIB metal, such as copper oxide. U.S. patent No.5,670,276 describes a non-aqueous electrochemical cell having a copper silver vanadium oxide cathode wherein the copper silver vanadium oxide is made from vanadium oxide in combination with copper nitrate and silver oxide, or copper oxide and silver nitrate.
Although the energy density of the electrode materials described in U.S. Pat. Nos. 4,310,609 and 5,670,276 is improved compared to certain active materials such as manganese oxide, there is still a great need to improve the copper-vanadium oxide-based electrodes of lithium batteries and batteries, particularly graphene oxide/SiO in combination with materials having high energy density such as CF2The electrochemical performance and the service life of the/Ti-Mn composite material-based electrode. We have now found that manganese, titanium can be combined to form mixed oxide electrodes with increased capacity and desired discharge curves by using simple and environmentally friendly chemical synthesis.
Disclosure of Invention
The invention aims to provide a high-performance cathode material of a lithium battery, and a preparation method and application thereof, wherein a material with high energy density such as CF (carbon fiber) is combined with graphene oxide/SiO2The electrochemical performance and the service life of the/Ti-Mn composite material-based electrode.
The technical scheme of the invention is realized as follows:
the invention provides a high-performance cathode material of a lithium battery, which is prepared from the following raw materials: graphene oxide, carbon fluoride, tetraethyl titanate, ethyl orthosilicate, manganese acetate, carbon black, citric acid and a silane coupling agent.
Hydrolyzing tetraethyl titanate, ethyl orthosilicate and manganese acetate by a sol-gel method, and depositing a layer of silicon dioxide, titanium dioxide and manganese oxide compound on the surface of the graphene oxide to form graphene oxide/SiO2The dissolution can be inhibited and the electrochemical performance can be improved by blocking the direct contact of particles and electrolyte in the/Ti-Mn composite material, the Ti-Mn composite material is coated by the graphene oxide, a regular channel is formed in the charge and discharge process, and the Li is reduced+A barrier to migration, thereby enhancing the electrical conductivity of the material;
combining a material with high energy density such as CF, CF having a specific energy of about 860mAh/g, manganese oxide having a specific energy of 308mAh/g, with graphene oxide/SiO2the/Ti-Mn composite material-based electrode can obviously improve the electrochemical performance and the service life, and meets the requirements of longer-lasting and/or smaller batteries of lithium batteries.
Oxidizing graphene/SiO2Other advantages of the hybrid cathode material made by mixing the/Ti-Mn composite, carbon black and CF include improved rate capability and/or stability of the cathode while maintaining energy density per unit weight and/or volume.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 1-2 parts of graphene oxide, 3-5 parts of carbon fluoride, 5-12 parts of tetraethyl titanate, 3-10 parts of ethyl orthosilicate, 2-7 parts of manganese acetate, 30-70 parts of carbon black, 1-3 parts of citric acid and 0.5-1.5 parts of silane coupling agent.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 1.2-1.7 parts of graphene oxide, 3.5-4.5 parts of carbon fluoride, 7-10 parts of tetraethyl titanate, 4-8 parts of ethyl orthosilicate, 3-6 parts of manganese acetate, 40-60 parts of carbon black, 1.5-2.5 parts of citric acid and 0.8-1.4 parts of silane coupling agent.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 1.5 parts of graphene oxide, 4 parts of carbon fluoride, 8 parts of tetraethyl titanate, 6 parts of ethyl orthosilicate, 5 parts of manganese acetate, 55 parts of carbon black, 2 parts of citric acid and 1 part of a silane coupling agent.
As a further improvement of the invention, the silane coupling agent is selected from one or a mixture of several of KH550, KH560, KH570, KH792, KH561 and KH 590.
The invention further provides a preparation method of the high-performance cathode material of the lithium battery, which comprises the following steps:
s1, dissolving graphene oxide in distilled water, adding a silane coupling agent, heating to 60-90 ℃, and reacting for 2-4 hours to obtain a solution A;
s2, weighing tetraethyl titanate, ethyl orthosilicate, manganese acetate and citric acid, dissolving the tetraethyl titanate, the ethyl orthosilicate, the manganese acetate and the citric acid in the solution A obtained in the step S1, stirring until the tetraethyl titanate, the ethyl orthosilicate, the manganese acetate and the citric acid are dissolved, slowly dropwise adding ammonia water to adjust the pH value, stirring and reacting at 70-80 ℃ to enable the solution to become gel, transferring the gel into a drying oven, heating and drying by distillation to obtain dried gel, transferring the dried gel into a muffle furnace, heating and roasting, cooling and grinding to obtain black powder;
and S3, respectively grinding the carbon black and the carbon fluoride to be below 200 meshes, uniformly mixing the carbon black and the carbon fluoride with the black powder obtained in the step S2, and tabletting to obtain the high-performance cathode material of the lithium battery.
As a further improvement of the invention, the mass fraction of the ammonia water is 25-55 wt%, and the pH value is adjusted to 8-9.
As a further improvement of the invention, the drying temperature of the oven is 100-.
As a further improvement of the invention, the heating and roasting temperature is 700-800 ℃, and the time is 10-12 h.
The invention further protects the application of the high-performance cathode material of the lithium battery in preparing the cathode of the quick-charging lithium battery.
The invention has the following beneficial effects: the invention adopts a sol-gel method combined with silane coupling agent for coupling to prepare graphene oxide/SiO2the/Ti-Mn composite material can realize the uniform atomic mixing of reactants and low synthesis temperature, so the prepared product has small (mostly nano-scale) particle size and is uniformGood performance, large specific surface area, and easy control of form and composition;
the graphene oxide/SiO prepared by the invention2the/Ti-Mn composite material has proper grain diameter, and if the crystal particles are too small, the contact area of a solid and a liquid electrolyte is too large, so that the dissolution speed of Mn and Ti ions is increased, and the surface structure of the crystal is damaged. According to the invention, the Ti-Mn composite material prepared by a sol-gel method is coated on the surface by graphene oxide, and direct contact between particles and electrolyte is prevented, so that dissolution can be inhibited, and the electrochemical performance is improved;
according to the invention, the Ti-Mn composite material is coated by the graphene oxide, and Li can be reduced by the regular channel in the charge and discharge process+The barrier to migration can enhance the electrical conductivity of the material;
the invention combines the materials with high energy density such as CF with graphene oxide/SiO2The electrochemical performance and the service life of the/Ti-Mn composite material-based electrode are simple, the preparation method is simple, the environment-friendly chemical synthesis is realized, and manganese and titanium can be combined to form a mixed oxide electrode with increased capacity and a required discharge curve, so that the mixed oxide electrode can be applied to a quick-charging lithium ion battery.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The preparation method of the graphene oxide comprises the following steps:
step one, weighing 10G of natural graphite powder (G), 4G of potassium persulfate and 10G of phosphorus pentoxide, adding the natural graphite powder (G), the potassium persulfate and the phosphorus pentoxide into a three-neck flask filled with 24mL of sulfuric acid under the condition of stirring, firstly reacting for 3h in a constant-temperature water bath at 60 ℃, then moving the three-neck flask into a constant-temperature water bath at 25 ℃ for reacting for 5h, performing suction filtration, washing the three-neck flask to be neutral by using ionized water, and drying the three-neck flask in the air to obtain pre-oxidized graphite (P-G);
step two, weighing 1g of pre-oxidized graphite, adding the pre-oxidized graphite into a three-neck flask filled with 25mL of sulfuric acid under the condition of stirring, putting the three-neck flask into an ice-water bath, adding 3g of potassium permanganate after the pre-oxidized graphite is completely dissolved, reacting for 2 hours, moving the three-neck flask into a constant-temperature water bath at 35 ℃ for reacting for 40 minutes, finally adding deionized water, continuing to react for 1 hour at 35 ℃, and finally dropwise adding 30% of H2O2So that the solution turned bright yellow until no more gas was formed. The mixture was filtered by centrifugation while hot and washed to neutrality with a large amount of 5% hydrochloric acid and deionized water. And (3) carrying out ultrasonic oscillation on the final precipitate for 1h, pouring the final precipitate into a culture dish, and drying the final precipitate for 24h at 90 ℃ to obtain Graphite Oxide (GO).
Carbon fluoride, CAS number: 51311-17-2.
Tetraethyl titanate, CAS No.: 3087-36-3.
Tetraethoxysilane, CAS No.: 78-10-4.
Manganese acetate, CAS No.: 19513-05-4.
Carbon black, CAS No.: 1333-86-4.
Citric acid, CAS No.: 77-92-9. Chemicals were purchased from the national pharmaceutical group.
Silane coupling agents are available from Guangzhou Lvwei plastics, Inc.
Example 1
The raw materials comprise the following components in parts by weight: 1 part of graphene oxide, 3 parts of carbon fluoride, 5 parts of tetraethyl titanate, 3 parts of ethyl orthosilicate, 2 parts of manganese acetate, 30 parts of carbon black, 1 part of citric acid and KH 5600.5 parts of a silane coupling agent.
The preparation method of the high-performance cathode material of the lithium battery comprises the following steps:
s1, dissolving graphene oxide in distilled water, adding a silane coupling agent KH560, heating to 60 ℃, and reacting for 2 hours to obtain a solution A;
s2, weighing tetraethyl titanate, ethyl orthosilicate, manganese acetate and citric acid, dissolving the tetraethyl titanate, the ethyl orthosilicate, the manganese acetate and the citric acid in the solution A obtained in the step S1, stirring until the tetraethyl titanate, the ethyl orthosilicate, the manganese acetate and the citric acid are dissolved, slowly dropwise adding 25 wt% ammonia water to adjust the pH value to 8, stirring and reacting at 70 ℃ to make the solution become gel, transferring the solution into an oven, heating and evaporating to dryness, wherein the oven heating and evaporating temperature is 100 ℃ for 3 hours to obtain dry gel, transferring the dry gel into a muffle furnace, heating and roasting at 700 ℃ for 10 hours, cooling and grinding to obtain black powder;
and S3, respectively grinding the carbon black and the carbon fluoride to be below 200 meshes, uniformly mixing the carbon black and the carbon fluoride with the black powder obtained in the step S2, and tabletting to obtain the high-performance cathode material of the lithium battery.
Example 2
The raw materials comprise the following components in parts by weight: 2 parts of graphene oxide, 5 parts of carbon fluoride, 12 parts of tetraethyl titanate, 10 parts of ethyl orthosilicate, 7 parts of manganese acetate, 70 parts of carbon black, 3 parts of citric acid and KH 5501.5 parts of a silane coupling agent.
The preparation method of the high-performance cathode material of the lithium battery comprises the following steps:
s1, dissolving graphene oxide in distilled water, adding a silane coupling agent KH550, heating to 90 ℃, and reacting for 4 hours to obtain a solution A;
s2, weighing tetraethyl titanate, ethyl orthosilicate, manganese acetate and citric acid, dissolving the tetraethyl titanate, the ethyl orthosilicate, the manganese acetate and the citric acid in the solution A obtained in the step S1, stirring until the tetraethyl titanate, the ethyl orthosilicate, the manganese acetate and the citric acid are dissolved, slowly dropwise adding 55 wt% of ammonia water to adjust the pH value to 9, stirring and reacting at 80 ℃ to make the solution become gel, transferring the gel into an oven, heating and evaporating to dryness at the temperature of 110 ℃ for 5 hours to obtain dry gel, transferring the dry gel into a muffle furnace, heating and roasting at the temperature of 800 ℃ for 12 hours, cooling and grinding to obtain black powder;
and S3, respectively grinding the carbon black and the carbon fluoride to be below 200 meshes, uniformly mixing the carbon black and the carbon fluoride with the black powder obtained in the step S2, and tabletting to obtain the high-performance cathode material of the lithium battery.
Example 3
The raw materials comprise the following components in parts by weight: 1.2 parts of graphene oxide, 3.5 parts of carbon fluoride, 7 parts of tetraethyl titanate, 4 parts of ethyl orthosilicate, 3 parts of manganese acetate, 40 parts of carbon black, 1.5 parts of citric acid and KH 5610.8 parts of a silane coupling agent.
The preparation method of the high-performance cathode material of the lithium battery comprises the following steps:
s1, dissolving graphene oxide in distilled water, adding a silane coupling agent KH561, heating to 65 ℃, and reacting for 3 hours to obtain a solution A;
s2, weighing tetraethyl titanate, ethyl orthosilicate, manganese acetate and citric acid, dissolving the tetraethyl titanate, the ethyl orthosilicate, the manganese acetate and the citric acid in the solution A obtained in the step S1, stirring until the tetraethyl titanate, the ethyl orthosilicate, the manganese acetate and the citric acid are dissolved, slowly dropwise adding 35 wt% ammonia water to adjust the pH value to 8.2, stirring and reacting at 72 ℃ to make the solution become gel, transferring the gel into an oven, heating and evaporating to dryness at the oven heating and evaporating temperature of 102 ℃ for 3.5h to obtain dried gel, transferring the dried gel into a muffle furnace, heating and roasting at the heating and roasting temperature of 720 ℃ for 11h, cooling and grinding to obtain black powder;
and S3, respectively grinding the carbon black and the carbon fluoride to be below 200 meshes, uniformly mixing the carbon black and the carbon fluoride with the black powder obtained in the step S2, and tabletting to obtain the high-performance cathode material of the lithium battery.
Example 4
The raw materials comprise the following components in parts by weight: 1.7 parts of graphene oxide, 4.5 parts of carbon fluoride, 10 parts of tetraethyl titanate, 8 parts of ethyl orthosilicate, 6 parts of manganese acetate, 60 parts of carbon black, 2.5 parts of citric acid and KH 5701.4 parts of a silane coupling agent.
The preparation method of the high-performance cathode material of the lithium battery comprises the following steps:
s1, dissolving graphene oxide in distilled water, adding a silane coupling agent KH570, heating to 80 ℃, and reacting for 3 hours to obtain a solution A;
s2, weighing tetraethyl titanate, ethyl orthosilicate, manganese acetate and citric acid, dissolving the tetraethyl titanate, the ethyl orthosilicate, the manganese acetate and the citric acid in the solution A obtained in the step S1, stirring until the tetraethyl titanate, the ethyl orthosilicate, the manganese acetate and the citric acid are dissolved, slowly dropwise adding 45 wt% ammonia water to adjust the pH value to 8.9, stirring and reacting at 78 ℃ to make the solution become gel, transferring the gel into an oven, heating and evaporating to dryness at the temperature of 108 ℃ for 4 hours to obtain dried gel, transferring the dried gel into a muffle furnace, heating and roasting at the temperature of 780 ℃ for 11 hours, cooling and grinding to obtain black powder;
and S3, respectively grinding the carbon black and the carbon fluoride to be below 200 meshes, uniformly mixing the carbon black and the carbon fluoride with the black powder obtained in the step S2, and tabletting to obtain the high-performance cathode material of the lithium battery.
Example 5
The raw materials comprise the following components in parts by weight: 1.5 parts of graphene oxide, 4 parts of carbon fluoride, 8 parts of tetraethyl titanate, 6 parts of ethyl orthosilicate, 5 parts of manganese acetate, 55 parts of carbon black, 2 parts of citric acid and 7921 parts of a silane coupling agent KH.
The preparation method of the high-performance cathode material of the lithium battery comprises the following steps:
s1, dissolving graphene oxide in distilled water, adding a silane coupling agent KH792, heating to 75 ℃, and reacting for 3 hours to obtain a solution A;
s2, weighing tetraethyl titanate, ethyl orthosilicate, manganese acetate and citric acid, dissolving the tetraethyl titanate, the ethyl orthosilicate, the manganese acetate and the citric acid in the solution A obtained in the step S1, stirring until the tetraethyl titanate, the ethyl orthosilicate, the manganese acetate and the citric acid are dissolved, slowly dropwise adding 40 wt% ammonia water to adjust the pH value to 8.5, stirring and reacting at 75 ℃ to make the solution become gel, transferring the gel into an oven, heating and evaporating to dryness at 105 ℃ for 4 hours to obtain dried gel, transferring the dried gel into a muffle furnace, heating and roasting at 750 ℃ for 11 hours, cooling and grinding to obtain black powder;
and S3, respectively grinding the carbon black and the carbon fluoride to be below 200 meshes, uniformly mixing the carbon black and the carbon fluoride with the black powder obtained in the step S2, and tabletting to obtain the high-performance cathode material of the lithium battery.
Comparative example 1
In comparison with example 5, no tetraethyl titanate was added, and the other conditions were unchanged.
The raw materials comprise the following components in parts by weight: 1.5 parts of graphene oxide, 4 parts of carbon fluoride, 6 parts of ethyl orthosilicate, 13 parts of manganese acetate, 55 parts of carbon black, 2 parts of citric acid and 7921 parts of a silane coupling agent KH.
The preparation method of the high-performance cathode material of the lithium battery comprises the following steps:
s1, dissolving graphene oxide in distilled water, adding a silane coupling agent KH792, heating to 75 ℃, and reacting for 3 hours to obtain a solution A;
s2, weighing tetraethyl titanate, ethyl orthosilicate, manganese acetate and citric acid, dissolving the tetraethyl titanate, the ethyl orthosilicate, the manganese acetate and the citric acid in the solution A obtained in the step S1, stirring until the tetraethyl titanate, the ethyl orthosilicate, the manganese acetate and the citric acid are dissolved, slowly dropwise adding 40 wt% ammonia water to adjust the pH value to 8.5, stirring and reacting at 75 ℃ to make the solution become gel, transferring the gel into an oven, heating and evaporating to dryness at 105 ℃ for 4 hours to obtain dried gel, transferring the dried gel into a muffle furnace, heating and roasting at 750 ℃ for 11 hours, cooling and grinding to obtain black powder;
and S3, respectively grinding the carbon black and the carbon fluoride to be below 200 meshes, uniformly mixing the carbon black and the carbon fluoride with the black powder obtained in the step S2, and tabletting to obtain the high-performance cathode material of the lithium battery.
Comparative example 2
Compared with example 5, manganese acetate was not added, and other conditions were not changed.
The raw materials comprise the following components in parts by weight: 1.5 parts of graphene oxide, 4 parts of carbon fluoride, 13 parts of tetraethyl titanate, 6 parts of ethyl orthosilicate, 55 parts of carbon black, 2 parts of citric acid and 7921 parts of a silane coupling agent KH.
The preparation method of the high-performance cathode material of the lithium battery comprises the following steps:
s1, dissolving graphene oxide in distilled water, adding a silane coupling agent KH792, heating to 75 ℃, and reacting for 3 hours to obtain a solution A;
s2, weighing tetraethyl titanate, ethyl orthosilicate and citric acid, dissolving the tetraethyl titanate, ethyl orthosilicate and citric acid in the solution A obtained in the step S1, stirring until the tetraethyl titanate, the ethyl orthosilicate and the citric acid are dissolved, slowly dropwise adding 40 wt% of ammonia water to adjust the pH value to 8.5, stirring and reacting at 75 ℃ to make the solution become gel, transferring the solution into an oven, heating and evaporating to dryness, wherein the oven heating and evaporating temperature is 105 ℃ and the time is 4 hours to obtain dried gel, transferring the dried gel into a muffle furnace, heating and roasting at 750 ℃ and the time is 11 hours, cooling and grinding to obtain black powder;
and S3, respectively grinding the carbon black and the carbon fluoride to be below 200 meshes, uniformly mixing the carbon black and the carbon fluoride with the black powder obtained in the step S2, and tabletting to obtain the high-performance cathode material of the lithium battery.
Test example 1
In order to confirm the effect of the heat treatment in the present invention, the high performance cathode materials for lithium batteries prepared in examples 1 to 5 and comparative examples 1 and 2, and the electrochemical properties of a commercially available cathode material for lithium batteries (available from electronics technologies, Inc., star, Dongguan) were measured. The results are shown in Table 1.
TABLE 1
Figure BDA0002512736700000121
As can be seen from the results of table 1, the high performance cathode material for lithium batteries prepared according to the present invention showed high cycle stability at high voltage, whereas comparative examples 1 and 2 and the commercially available cathode material were insufficient to achieve high cycle stability at high voltage.
Test example 2
High-performance cathode materials for lithium batteries prepared in examples 1 to 5 and comparative examples 1 and 2, and a commercially available cathode material for lithium batteries (available from electronics technologies, Inc. of Star of Dongguan) were used to prepare cathodes. Coin cells (with Li metal as anode) were then prepared and tested at 4.4V and 4.5V and at 25 ℃ and 50 ℃.
The results are shown in Table 2.
TABLE 2
Figure BDA0002512736700000122
Figure BDA0002512736700000131
As can be seen from the results shown in table 2, the high performance cathode material for lithium batteries prepared according to the present invention has improved cycle performance at high voltage, which is significantly superior to comparative examples 1 to 4 and the commercially available cathode material.
The cathode material prepared by the method is remarkably reduced in cycle performance under high pressure because tetraethyl titanate or manganese acetate is not added in a comparative example 1 and a comparative example 2 respectively, and the Ti-Mn composite material prepared by a sol-gel method is coated on the surface of the cathode material by graphene oxide, so that the dissolution can be inhibited and the electrochemical performance can be improved by preventing direct contact of particles and electrolyte, and therefore, the addition of tetraethyl titanate and manganese acetate has a synergistic effect. The formed Ti-Mn composite material has regular channels in the charge and discharge process to reduce Li+The barrier to migration can enhance the electrical conductivity of the material
Compared with the prior art, the graphene oxide/SiO prepared by combining the sol-gel method with the coupling of the silane coupling agent2the/Ti-Mn composite material can realize the uniform atomic mixing of reactants and low synthesis temperature, so the prepared product has small particle size (mostly nano-scale), good uniformity, large specific surface area and easy control of form and composition;
the graphene oxide/SiO prepared by the invention2the/Ti-Mn composite material has proper grain diameter, and if the crystal particles are too small, the contact area of a solid and a liquid electrolyte is too large, so that the dissolution speed of Mn and Ti ions is increased, and the surface structure of the crystal is damaged. According to the invention, the Ti-Mn composite material prepared by a sol-gel method is coated on the surface by graphene oxide, and direct contact between particles and electrolyte is prevented, so that dissolution can be inhibited, and the electrochemical performance is improved;
according to the invention, the Ti-Mn composite material is coated by the graphene oxide, and Li can be reduced by the regular channel in the charge and discharge process+The barrier to migration can enhance the electrical conductivity of the material;
the invention combines the materials with high energy density such as CF with graphene oxide/SiO2The electrochemical performance and the service life of the/Ti-Mn composite material-based electrode are simple, the preparation method is simple, the environment-friendly chemical synthesis is realized, and manganese and titanium can be combined to form a mixed oxide electrode with increased capacity and a required discharge curve, so that the mixed oxide electrode can be applied to a quick-charging lithium ion battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The high-performance cathode material for the lithium battery is characterized by being prepared from the following raw materials: graphene oxide, carbon fluoride, tetraethyl titanate, ethyl orthosilicate, manganese acetate, carbon black, citric acid and a silane coupling agent.
2. The high-performance cathode material for the lithium battery as claimed in claim 1, which is prepared from the following raw materials in parts by weight: 1-2 parts of graphene oxide, 3-5 parts of carbon fluoride, 5-12 parts of tetraethyl titanate, 3-10 parts of ethyl orthosilicate, 2-7 parts of manganese acetate, 30-70 parts of carbon black, 1-3 parts of citric acid and 0.5-1.5 parts of silane coupling agent.
3. The high-performance cathode material for the lithium battery as claimed in claim 2, which is prepared from the following raw materials in parts by weight: 1.2-1.7 parts of graphene oxide, 3.5-4.5 parts of carbon fluoride, 7-10 parts of tetraethyl titanate, 4-8 parts of ethyl orthosilicate, 3-6 parts of manganese acetate, 40-60 parts of carbon black, 1.5-2.5 parts of citric acid and 0.8-1.4 parts of silane coupling agent.
4. The high-performance cathode material for the lithium battery as claimed in claim 3, which is prepared from the following raw materials in parts by weight: 1.5 parts of graphene oxide, 4 parts of carbon fluoride, 8 parts of tetraethyl titanate, 6 parts of ethyl orthosilicate, 5 parts of manganese acetate, 55 parts of carbon black, 2 parts of citric acid and 1 part of a silane coupling agent.
5. The high-performance cathode material for lithium batteries according to claim 1, wherein said silane coupling agent is selected from one or more of KH550, KH560, KH570, KH792, KH561 and KH 590.
6. A method for preparing a high performance cathode material for a lithium battery as claimed in any one of claims 1 to 5, comprising the steps of:
s1, dissolving graphene oxide in distilled water, adding a silane coupling agent, heating to 60-90 ℃, and reacting for 2-4 hours to obtain a solution A;
s2, weighing tetraethyl titanate, ethyl orthosilicate, manganese acetate and citric acid, dissolving the tetraethyl titanate, the ethyl orthosilicate, the manganese acetate and the citric acid in the solution A obtained in the step S1, stirring until the tetraethyl titanate, the ethyl orthosilicate, the manganese acetate and the citric acid are dissolved, slowly dropwise adding ammonia water to adjust the pH value, stirring and reacting at 70-80 ℃ to enable the solution to become gel, transferring the gel into a drying oven, heating and drying by distillation to obtain dried gel, transferring the dried gel into a muffle furnace, heating and roasting, cooling and grinding to obtain black powder;
and S3, respectively grinding the carbon black and the carbon fluoride to be below 200 meshes, uniformly mixing the carbon black and the carbon fluoride with the black powder obtained in the step S2, and tabletting to obtain the high-performance cathode material of the lithium battery.
7. The method according to claim 6, wherein the aqueous ammonia has a mass fraction of 25 to 55 wt% and the pH is adjusted to 8 to 9.
8. The method as claimed in claim 6, wherein the drying temperature of the oven is 100 ℃ and 110 ℃ for 3-5 h.
9. The method as claimed in claim 6, wherein the heating and baking temperature is 700-800 ℃ and the time is 10-12 h.
10. Use of a high performance cathode material for a lithium battery as claimed in any one of claims 1 to 5 for the preparation of a cathode for a fast-charging lithium battery.
CN202010466207.3A 2020-05-28 2020-05-28 High-performance cathode material of lithium battery and preparation method and application thereof Withdrawn CN111584852A (en)

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