CN113611840B - Amorphous MnO x Preparation method of/WS-P lithium ion battery cathode material - Google Patents

Amorphous MnO x Preparation method of/WS-P lithium ion battery cathode material Download PDF

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CN113611840B
CN113611840B CN202110887986.9A CN202110887986A CN113611840B CN 113611840 B CN113611840 B CN 113611840B CN 202110887986 A CN202110887986 A CN 202110887986A CN 113611840 B CN113611840 B CN 113611840B
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lithium ion
mno
ion battery
preparation
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CN113611840A (en
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徐桂英
刘渤
印瑞琳
徐子昂
张鹏
王坤
李建科
张殿浩
周卫民
张文武
孟祥安
王士戈
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Haicheng Shenhe Tech Co ltd
University of Science and Technology Liaoning USTL
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Haicheng Shenhe Tech Co ltd
University of Science and Technology Liaoning USTL
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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
    • H01M4/48—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
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to amorphous MnO x The preparation method of the/WS-P lithium ion battery cathode material comprises the following steps: 1) Dissolving water-soluble coal pitch and urea in deionized water, and dropwise adding a NaOH solution to obtain a solution A; 2) To KMnO 4 Slowly adding concentrated sulfuric acid into the solution to obtain a solution B; 3) Slowly adding the solution A into the solution B, stirring, transferring into a reaction kettle, and carrying out hydrothermal reaction at a constant temperature of 150-180 ℃; 4) Respectively centrifugally cleaning with deionized water and absolute ethyl alcohol to obtain black precipitates; drying; and finally, calcining the mixture in a nitrogen atmosphere to obtain a final product. The advantages are that: the cheap and easily obtained modified medium-temperature coal pitch is adopted, the process is simplified, and the large-scale production can be realized. The electrochemical performance of the material is improved.

Description

Amorphous MnO x Preparation method of/WS-P lithium ion battery cathode material
Technical Field
The invention relates to the field of lithium ion battery manufacturing, in particular to a method for preparing amorphous MnO x A preparation method of/WS-P (water-soluble coal tar pitch) lithium ion battery cathode material.
Background
Lithium Ion Batteries (LIBs) have a very promising development prospect in the field of sustainable energy as a very good energy storage and portable device. However, the theoretical capacity of the current commercial graphite electrode is relatively low (372 mAh/g), and the demand of the society on high-capacity and high-density batteries cannot be met, so that the further development of the high-capacity and high-density batteries is limited. Therefore, in order to meet the requirements of high capacity, long cycle life and cycle stability of next generation lithium ion batteries, it is important to develop new anode materials.
MnO x As transition metal oxide, the transition metal oxide has the advantages of high theoretical capacity, abundant natural reserves, low cost and the like. When MnO is present x When the material is used as a lithium ion battery cathode material, huge volume change is easily generated in the process of repeated charge and discharge, capacity attenuation is caused, the cycle stability is poor, and MnO is added x The conductivity is lower, and the rate capability is poor under high current density. At present, the most common method for improving the electrochemical performance of the metal oxide negative electrode material is to compound the metal oxide negative electrode material with a carbon material to enhance the conductivity and the structural stability, and further improve the lithium storage performance. However, most reports adopt graphene, carbon nanotubes, polyvinylpyrrolidone and the like as carbon sources in composite materials, but these materials are often expensive, complex in process and difficult to use on a large scale.
Coal tar pitch is an important coking byproduct, has the characteristics of low price, easy obtainment, high aromaticity, rich carbon content and the like, is often used as an excellent precursor for preparing carbon materials, and can be well applied to preparing composite materials. However, in the prior art, asphalt is difficult to dissolve in common reaction systems, such as aqueous solution, ethanol solution and the like, and further extension of coal asphalt downstream industries is hindered.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide amorphous MnO x A preparation method of a/WS-P lithium ion battery cathode material comprises the steps of converting medium-temperature asphalt into water-soluble coal asphalt which can be dissolved in alkali liquor and organic solvent after being treated by a mixed acid method, and preparing high-performance MnO by a hydrothermal method x the/WS-P (water-soluble coal tar pitch) lithium ion battery cathode material.
In order to realize the purpose, the invention is realized by the following technical scheme:
amorphous MnO x The preparation method of the/WS-P lithium ion battery cathode material comprises the following steps:
1) Dissolving water-soluble coal pitch and urea in deionized water according to the mass ratio of 3-5, and dropwise adding 1mol/L NaOH solution to obtain a solution A;
2) Preparing 0.1-0.3 mol/L KMnO 4 To KMnO 4 Slowly adding concentrated sulfuric acid with the mass fraction of 95%, the concentrated sulfuric acid and KMnO into the solution 4 The mass ratio is 1-2, and a solution B is obtained;
3) Slowly adding the solution A into the solution B, stirring for 20-30 min, transferring into a reaction kettle, and carrying out hydrothermal reaction at a constant temperature of 150-180 ℃ for 6-12 h;
4) Cooling the reaction kettle to room temperature, and respectively centrifugally cleaning with deionized water and absolute ethyl alcohol to obtain black precipitates; drying at 80-85 deg.c for 10-15 hr; finally, calcining for 4 to 5 hours at the temperature of 350 to 400 ℃ in the nitrogen atmosphere to obtain the final product MnO x the/WS-P composite electrode material.
The preparation method of the water-soluble coal pitch comprises the following steps:
1) Crushing, grinding and sieving the medium-temperature coal pitch by a 100-mesh sieve to obtain raw material pitch;
2) Adding raw material asphalt into a mixed acid solution, stirring in a constant temperature water bath, pouring a solid-liquid mixture into deionized water after the reaction is finished to terminate the reaction, performing heat filtration after the reaction is terminated, washing a filter cake with water until the pH value is 5-6, mixing the filter cake with 1mol/L NaOH solution until the pH value is more than 12, stirring in the constant temperature water bath, filtering and collecting filtrate, then adjusting the pH value to be less than 2 by using dilute hydrochloric acid, performing centrifugal separation to collect black-brown precipitate, drying at constant temperature and grinding into powder of 50-100 mu m.
The mixed acid solution is prepared by mixing the following components in a volume ratio of 7:3, mixed solution of concentrated sulfuric acid and concentrated nitric acid.
Compared with the prior art, the invention has the beneficial effects that:
the method adopts cheap and easily-obtained modified medium-temperature coal pitch, simplifies the process and can realize large-scale production. And MnO prepared x the/WS-P composite material effectively overcomes the defects, greatly improves the electrochemical performance of the material, expands the application of the coal tar pitch in the field of clean energy, and provides a new idea and idea for the preparation of other electrode materials.
Drawings
FIG. 1 is a flow chart of the production of water-soluble coal pitch.
FIG. 2 is an amorphous MnO x A production process route diagram of the/WS-P lithium ion composite material.
Fig. 3 is a flow chart of lithium ion battery assembly and testing.
FIG. 4 is an amorphous MnO x XRD pattern of/WS-P lithium ion battery cathode material.
In FIG. 4, (a) and (b) are SEM pictures of MC-0.3; (c) is an SEM image of MC-0.4; (d) is an SEM photograph of MC-0.5.
FIG. 5 shows amorphous MnO x SEM image of/WS-P lithium ion battery cathode material.
In FIG. 5, (a) is an EDS scan of MC-0.3; (b) is an EDS scan of MC-0.4; (c) EDS map of MC-0.5.
FIG. 6 is an amorphous MnO x EDS diagram of/WS-P lithium ion battery cathode material.
FIG. 7 shows amorphous MnO x A multiplying power performance diagram of the negative electrode material of the/WS-P lithium ion battery.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings, but it should be noted that the present invention is not limited to the following embodiments.
Example 1
Amorphous MnO x Preparing a negative electrode material of the/WS-P lithium ion battery:
1) The preparation of water-soluble coal tar pitch is shown in figure 1:
a. the medium temperature coal pitch is crushed, ground and sieved (100 meshes) to obtain the raw material pitch.
b. Slowly adding 5g of raw material asphalt into 100mL of mixed acid solution (mixed solution of 70mL of concentrated sulfuric acid and 30mL of concentrated nitric acid), stirring for 5 hours in a 40 ℃ constant-temperature water bath, pouring the solid-liquid mixture into 500mL of deionized water to stop the reaction after the reaction is finished, carrying out thermal filtration and washing a filter cake to adjust the pH value to 6 after the solid-liquid mixture is static, mixing the filter cake and 1mol/L of NaOH solution until the pH value is greater than 12, stirring for 1 hour in a 80 ℃ constant-temperature water bath, filtering and collecting filtrate after full dissolution, then adjusting the pH value to be less than 2 by using diluted concentrated hydrochloric acid, carrying out centrifugal separation to collect black-brown precipitate, drying for more than 8 hours at the constant temperature of 80 ℃, taking out and grinding into powder for later use.
2)MnO x Preparation of the/WS-P composite, see FIG. 2:
a. 0.3g of water-soluble coal tar pitch and 0.1g of urea are respectively weighed and dissolved in 20ml of deionized water, and after the mixture is fully stirred and stirred uniformly, 20-30 drops of 1mol/L NaOH solution are dripped in, and the mixture is stirred for 30min to obtain solution A.
b. Then 0.5g of KMnO was weighed out separately 4 And 0.5ml of 95% concentrated sulfuric acid, and mixing the obtained mixture with KMnO 4 Dissolving in 15ml of deionized water, fully stirring until the solution is completely dissolved, slowly adding 0.5ml of 95% concentrated sulfuric acid, and stirring for 30min to obtain a solution B.
c. Then, the solution A was slowly added to the solution B, and sufficiently stirred for 30min.
d. The mixed solution is transferred to a 100mL reaction kettle and is hydrothermally processed for 6h at a constant temperature of 150 ℃. And after the reaction kettle is cooled to room temperature, firstly using deionized water and then using absolute ethyl alcohol to centrifugally clean the reaction kettle to obtain black precipitate.
e.80 ℃ constant temperature drying for 12h.
f. Finally, under the atmosphere of nitrogen, calcining for 5 hours at the high temperature of 400 ℃ to obtain the final product MnO x The MnO is added into the/WS-P composite electrode material according to the addition amount of the water-soluble coal tar x the/WS-P composite electrode material is named as MC-0.3.
g. And selecting 0.4g of water-soluble coal pitch and 0.5g of potassium permanganate respectively, and preparing the composite electrode materials which are named as MC-0.4 and MC-0.5 respectively in the same way except for the operation.
The assembly of the lithium ion battery includes the preparation of electrode sheets and the process of assembling the lithium ion battery, as shown in fig. 3, specifically as follows:
(1) Dry grinding: the electrode material, the conductive agent (acetylene black, SP) and the binder (polyvinylidene fluoride, PVDF) are uniformly ground in an agate mortar according to the mass ratio of 8.
(2) Wet grinding and size mixing: nitrogen Methyl Pyrrolidone (NMP) is dripped into an agate mortar, and the mixture is continuously ground until the mixture becomes uniform and sticky slurry.
(3) Smearing: and wiping the copper foil to be used with absolute ethyl alcohol, drying, placing the ground slurry on the surface of the copper foil, and uniformly coating the slurry on the copper foil by using an automatic film coating device.
(4) And (3) drying: and (3) placing the electrode slice in the air, drying at 80 ℃ for 1h, and then transferring to a vacuum drying oven to dry at 120 ℃ for 12h.
(5) Cutting: the electrode sheet was cut into a circular piece having a diameter of 11mm using a sheet cutter.
After the electrode plate is prepared, a CR2032 button cell is adopted to assemble a lithium ion battery in a vacuum glove box (the water concentration is less than 0.1ppm, and the oxygen concentration is less than 0.1 ppm). The lithium ion battery counter electrode is a lithium sheet, the specific assembly sequence is a negative electrode shell, the lithium sheet, a diaphragm, 100ul of electrolyte, an electrode plate, a steel sheet, an elastic sheet and a positive electrode shell, and after the battery is assembled, the battery is kept stand for 12 hours and then is subjected to related electrochemical performance tests.
See FIG. 4, amorphous MnO with increasing WS-P addition x The shape of the/WS-P composite material is hugeA change in the position of the mobile terminal. The MC-0.3 composite material is in a pellet shape and is uniformly dispersed. The MC-0.4 and MC-0.5 composite materials all have irregular block structures.
See FIG. 5, mnO at different WS-P addition levels x Mn, C and O elements in the/WS-P composite material are uniformly distributed on the surface of the material.
See FIG. 6, no significant MnO was observed x So that MnO is considered x the/WS-P composite material is in an amorphous structure.
See FIG. 7, the rate performance of WS-P, mnOx/WS-P composites at current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1.0A/g, 2.0A/g, and 5.0A/g, where the MC-0.3 composites exhibit better rate performance than other materials. After circulating for ten circles under the current density of 0.1A/g, the discharge specific capacity is 605.66mAh/g, and the charge specific capacity is 613.69mAh/g. Even under the condition of 5A/g large current density, the MC-0.3 composite material still shows good lithium storage performance, the discharge specific capacity is as high as 129.46mAh/g, and the charge specific capacity is as high as 130.67mAh/g. When the current density returns to 0.1A/g again, the discharge specific capacity of the MC-0.3 composite material is 793.98mAh/g, the charge specific capacity is 809.31mAh/g, the MC-0.3 composite material is obviously higher than other materials, and the MC-0.3 composite material has good rate multiplying performance. And the lithium storage capacity and rate capability of other composite materials are also obviously superior to those of carbon materials prepared by pure water-soluble coal pitch.
Amorphous MnO x The composite structure of the/WS-P lithium ion battery cathode material can relieve the huge volume change in the lithiation process and effectively inhibit MnO x The aggregation and polarization phenomena of the material can be generated, and a stable SEI film can be formed at the same time, so that the integrity of the electrode is ensured, and the introduction of the non-activated carbon material greatly improves the conductivity of the material and the cycling stability and rate capability of the material as a lithium ion battery cathode.

Claims (3)

1. Amorphous MnO x The preparation method of the negative electrode material of the/WS-P lithium ion battery is characterized by comprising the following steps of:
1) Dissolving water-soluble coal pitch and urea in deionized water according to the mass ratio of 3-5, and dropwise adding 1mol/L NaOH solution to obtain a solution A;
2) Preparing 0.1-0.3 mol/L KMnO 4 To KMnO 4 Slowly adding concentrated sulfuric acid with the mass fraction of 95%, the concentrated sulfuric acid and KMnO into the solution 4 The mass ratio is 1-2, and a solution B is obtained;
3) Slowly adding the solution A into the solution B, stirring for 20-30 min, transferring into a reaction kettle, and carrying out hydrothermal reaction at the constant temperature of 150-180 ℃ for 6-12 h;
4) Cooling the reaction kettle to room temperature, and respectively centrifugally cleaning with deionized water and absolute ethyl alcohol to obtain black precipitates; drying at 80-85 deg.c for 10-15 hr; finally, calcining for 4-5 h at the temperature of 350-400 ℃ in the nitrogen atmosphere to obtain the final product MnO x Composite electrode material of/WS-P, mnO x the/WS-P composite electrode material is in an amorphous structure.
2. An amorphous MnO according to claim 1 x The preparation method of the/WS-P lithium ion battery cathode material is characterized in that the preparation method of the water-soluble coal tar pitch comprises the following steps:
1) Crushing, grinding and sieving the medium-temperature coal pitch by a 100-mesh sieve to obtain raw material pitch;
2) Adding raw material asphalt into a mixed acid solution, stirring in a constant temperature water bath, pouring a solid-liquid mixture into deionized water after the reaction is finished to terminate the reaction, performing heat filtration after the reaction is terminated, washing a filter cake with water until the pH value is 5-6, mixing the filter cake with 1mol/L NaOH solution until the pH value is more than 12, stirring in the constant temperature water bath, filtering and collecting filtrate, then adjusting the pH value to be less than 2 by using dilute hydrochloric acid, performing centrifugal separation to collect black-brown precipitate, drying at constant temperature and grinding into powder of 50-100 mu m.
3. An amorphous MnO according to claim 2 x The preparation method of the/WS-P lithium ion battery cathode material is characterized in that the mixed acid solution is prepared by mixing the following components in a volume ratio of 7:3 of concentrated sulfuric acid and concentrated nitric acid.
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CN114715936B (en) * 2022-04-18 2023-10-03 鸡西市唯大新材料科技有限公司 Negative electrode NaSbS of lithium or sodium ion battery 2 Preparation method of @ C composite material

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CN110429289A (en) * 2019-08-19 2019-11-08 北京林业大学 A kind of preparation method of the catalyst for direct lignin alkaline fuel cell anode

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