CN111326725A - Lithium ion organic positive electrode material, preparation method and application - Google Patents
Lithium ion organic positive electrode material, preparation method and application Download PDFInfo
- Publication number
- CN111326725A CN111326725A CN202010148066.0A CN202010148066A CN111326725A CN 111326725 A CN111326725 A CN 111326725A CN 202010148066 A CN202010148066 A CN 202010148066A CN 111326725 A CN111326725 A CN 111326725A
- Authority
- CN
- China
- Prior art keywords
- lithium
- indigo
- disulfonate
- disulfonic acid
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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
- H01M4/362—Composites
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion battery anode materials, in particular to a lithium ion organic anode material, a preparation method and application. The invention not only prepares the indigo disulfonic acid lithium anode material for the first time, but also provides a preparation method of the indigo disulfonic acid lithium anode material, and prepares the indigo disulfonic acid lithium submicron particles by a reverse solvent method, and finally prepares the carbon-coated indigo disulfonic acid lithium anode material by a carbon coating method, and the carbon-coated indigo disulfonic acid lithium anode material has excellent conductivity and structural stability and can be applied to lithium ion batteries.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a lithium ion organic anode material, a preparation method and application.
Background
With the continuous and deep research of new energy materials, the research of organic cathode materials is paid more attention, the development of high-energy-density lithium ion batteries is the direction of key research, the performance of the lithium ion batteries is greatly influenced by different characteristics of the cathode materials, and compared with inorganic cathode materials, the organic cathode materials have the advantages of high theoretical specific capacity, rich raw materials, environmental friendliness, strong structure designability and system safety.
The anode material in the prior art can be partially dissolved in practical application, so that the percentage content of the organic anode material is changed, and along with the progress of charging and discharging, the appearance and the appearance inside the material can be continuously changed, so that various defects such as poor cycling stability and the like are caused, and therefore, the purpose of obtaining the organic anode material with high cycling stability and stable structure is continuously explored and sought by people.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a lithium ion organic positive electrode material, a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the lithium ion organic positive electrode material is an indigo disulfonic acid lithium positive electrode material, and the structure formula of the indigo disulfonic acid lithium is as follows:
preferably, the surface of the indigo disulfonic acid lithium cathode material is further coated with carbon.
The invention also provides a preparation method of the lithium ion organic anode material, and the indigo disulfonic acid lithium anode material is prepared by a sulfonation method or a synthesis method.
Preferably, the process for preparing the lithium indigo disulfonate cathode material by a sulfonation method comprises the following steps:
(1) preparation of indigo disulfonic acid: dropwise adding fuming sulfuric acid into the indigo at the speed of 2mL/min, and stirring for reacting for 30-50min to obtain indigo disulfonic acid;
wherein the mass fraction of sulfur trioxide in the oleum is 20%, and the ratio of the mass of the indigo to the volume of the oleum is 1: 0.5-2;
(2) diluting the indigo disulfonic acid prepared in the step (1) with deionized water, adding lithium carbonate, stirring for reaction until no bubbles are generated, continuing stirring for 10-15min, washing with ethanol, filtering, and drying to obtain indigo disulfonic acid lithium;
wherein the mass ratio of the fuming sulfuric acid to the lithium carbonate is 1: 0.75-1.
Preferably, the process for preparing the lithium indigo disulfonate cathode material by a sulfonation method comprises the following steps:
(1) preparation of indigo disulfonic acid: dropwise adding fuming sulfuric acid into the indigo at the speed of 2mL/min, and stirring for reacting for 30-50min to obtain indigo disulfonic acid;
wherein the mass fraction of sulfur trioxide in the oleum is 20%, and the ratio of the mass of the indigo to the volume of the oleum is 1: 0.5-2;
(2) adding a lithium hydroxide saturated solution into the indigo disulfonic acid prepared in the step (1), stirring and reacting for 10-20min, filtering, washing with water, and drying to obtain the indigo disulfonic acid lithium;
wherein the volume ratio of the indigo disulfonic acid to the lithium hydroxide saturated solution is 1: 3.5-4.
Preferably, the process for preparing the lithium indigo disulfonate cathode material by using a synthesis method comprises the following steps:
(1) preparation of sulfophenyl glycine: reacting sulfanilic acid and chloroacetic acid at 60-105 ℃ for 2-8h to obtain sulfophenyl glycine;
wherein the mass ratio of chloroacetic acid to sulfanilic acid is 1: 1.50-1.84;
(2) adding lithium amide and mixed alkali into the sulfophenyl glycine prepared in the step (1), reacting for 2-3h at the temperature of 220-250 ℃, then cooling to room temperature, adding water for dilution, and introducing air at room temperature for oxidation for 2.5-3h to obtain an indigo disulfonate mixture;
wherein the mixed alkali comprises dry lithium hydroxide and dry potassium hydroxide or dry lithium hydroxide and dry sodium hydroxide, the mass ratio of the lithium hydroxide to the potassium hydroxide or the sodium hydroxide is 1.5-2:1, and the ratio of sulfophenyl glycine: mixing alkali: the mass ratio of the lithium amide is 12-16:2-3: 1;
(3) and (3) completely dissolving the indigo disulfonate mixture prepared in the step (2) in water, then loading a lithium type cation exchange resin into a column, carrying out ion exchange reaction on the indigo disulfonate mixture at the flow rate of 0.1-0.6BV/h, and then concentrating, crystallizing and drying to obtain the indigo disulfonic acid lithium.
Preferably, the preparation process of the carbon-coated lithium indigo disulfonate cathode material is as follows:
(1) preparation of microcrystalline particles of lithium indigo disulfonate: adding a saturated solution of lithium indigo disulfonate into an alcohol solvent, crystallizing for 10-20min at the rotation speed of 1000-4000r/min and the system temperature of 25-35 ℃, and performing suction filtration, ethanol washing and drying to obtain lithium indigo disulfonate microcrystal particles;
wherein the alcohol solvent is ethanol or methanol, and the volume ratio of the indigo disulfonic acid lithium saturated solution to the alcohol solvent is 1: 10-20 parts of;
(2) preparing a carbon-coated lithium indigo disulfonate positive electrode material: adding the lithium indigo disulfonate microcrystalline particles prepared in the step (1) into a glucose saturated solution, stirring and mixing uniformly, then placing the mixture into a reaction kettle, performing hydrothermal carbonization at the temperature of 150-250 ℃ for 8-12h, naturally cooling, performing centrifugal separation, washing with distilled water and ethanol, and drying to obtain a carbon-coated lithium indigo disulfonate positive electrode material;
wherein the mass ratio of the glucose to the lithium indigo disulfonate particles is 1: 2-4.
The invention also provides a lithium ion battery which comprises the lithium ion organic anode material.
Preferably, the preparation method of the lithium ion battery comprises the following specific steps:
mixing and grinding the lithium ion organic positive electrode material, the conductive additive and the binder to obtain slurry;
coating the slurry on an aluminum foil, drying and tabletting to prepare an electrode plate;
and matching the electrode plate with a diaphragm and electrolyte to prepare the lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention prepares the lithium indigo disulfonate by a synthesis method or a sulfonation method for the first time, and synthesizes the carbon-coated lithium indigo disulfonate with excellent conductivity and stability by a carbon coating method.
2. According to the carbon-coated lithium indigo disulfonate positive electrode material prepared by the method, the conductivity of the lithium indigo disulfonate is enhanced by a carbon coating method, the particle size of an electrode material is improved, and the carbon coating can enable the lithium indigo disulfonate active material to have larger exertion capacity, so that the problem of energy density reduction caused by volume change is solved;
the specific capacity of the lithium indigo disulfonate is 124mAh/g, the cycle life is long, the high-temperature stability is good, the price is low, the environment is friendly, the discharge platform is matched with the currently used electrolyte, however, the conductivity of the pure lithium indigo disulfonate is poor, and the conductivity is about 5.1 × 10-9S·cm-1(LiCoO2:10-3S·cm-1，LiMn2O4:10-5S·cm-1) The invention improves the electrochemical performance of the electrode material by a carbon coating method, and the carbon coating of the lithium indigo disulfonate can enhance the conductivity of the lithium indigo disulfonate, inhibit the growth and agglomeration of crystal grains and reduce the electrode materialThe material has polarization effect, and provides a lithium ion channel for the indigo disulfonic acid lithium, so that the lithium ion is easier to be deintercalated.
3. According to the invention, the lithium indigo disulfonate is prepared by a synthesis method and a sulfonation method, then glucose coating is carried out on the prepared lithium indigo disulfonate by a carbon coating method, and the lithium indigo disulfonate with good conductivity is obtained after hydrothermal carbonization reaction. Meanwhile, due to the carbonization effect of glucose on the surface of the lithium indigo disulfonate, the solubility of the lithium indigo disulfonate in the organic electrolyte is reduced, the cycle stability of the lithium indigo disulfonate is enhanced, the lithium indigo disulfonate with good conductivity is synthesized by a carbon coating method, the using amount of a conductive agent SuperP can be reduced when a lithium ion battery positive plate is prepared, and the conductive efficiency of the plate is improved.
Drawings
FIG. 1 is a scanning electron microscope image of lithium indigo disulfonate particles prepared by the anti-solvent ethanol recrystallization method in step (1) of example 8 of the present invention;
FIG. 2 is a scanning electron microscope image of a carbon-coated lithium indigo disulfonate positive electrode material prepared by a hydrothermal method in step (2) of example 8 of the present invention;
FIG. 3 is a charge-discharge curve diagram of a pure lithium indigo disulfonate anode material prepared in example 2 of the present invention; in the figure, the number of charge and discharge is represented by 1st, 2nd, 3th and 4th, respectively, and 1st, 2nd, 3th and 4th represent charge and discharge 1 time, 2 times, 3 times and 4 times, respectively;
fig. 4 is a charge-discharge curve of the carbon-coated lithium indigo disulfonate cathode material prepared in example 8 of the present invention, wherein 1st, 2nd and 100th represent charge- discharge times 1, 2 and 100, respectively;
fig. 5 is a charge-discharge performance test chart of the carbon-coated lithium indigo disulfonate cathode material prepared in example 8 of the present invention.
Detailed Description
The following description will be made by reference to preferred embodiments 1 to 5 in conjunction with the embodiments of the present invention.
Example 1
The process for preparing the indigo disulfonic acid lithium anode material by adopting the sulfonation method comprises the following steps:
(1) preparation of indigo disulfonic acid: weighing 10g of indigo, and measuring SO with the mass fraction of 20%3Under the condition of continuous stirring, dropwise adding fuming sulfuric acid into the indigo at the speed of 2mL/min, and stirring for reacting for 30min to obtain indigo disulfonic acid;
(2) and (2) adding 10mL of water into the indigo disulfonic acid prepared in the step (1) for dilution, then adding 15g of lithium carbonate, stirring for reaction until no bubbles are generated, continuing stirring for 10min, washing for 3 times by using ethanol, filtering, and drying in vacuum to obtain the indigo disulfonic acid lithium.
Example 2
The process for preparing the indigo disulfonic acid lithium anode material by adopting the sulfonation method comprises the following steps:
(1) preparation of indigo disulfonic acid: weighing 10g of indigo, and measuring SO with the mass fraction of 20%3Under the condition of continuously stirring, dropwise adding fuming sulfuric acid into the indigo at the speed of 2mL/min, and stirring for reacting for 40min to obtain indigo disulfonic acid;
(2) and (2) adding 8mL of water into the indigo disulfonic acid prepared in the step (1) for dilution, then adding 8g of lithium carbonate, stirring for reaction until no bubbles are generated, continuing stirring for 10min, washing for 3 times by using ethanol, filtering, and drying in vacuum to obtain the lithium indigo disulfonate.
Example 3
The process for preparing the indigo disulfonic acid lithium anode material by adopting the sulfonation method comprises the following steps:
(1) preparation of indigo disulfonic acid: weighing 10g of indigo, and measuring SO with the mass fraction of 20%3Under the condition of continuous stirring, dropwise adding fuming sulfuric acid into the indigo at the speed of 2mL/min, and stirring for reacting for 50min to obtain indigo disulfonic acid;
(2) adding 6mL of water into the indigo disulfonic acid prepared in the step (1) for dilution, then adding 5g of lithium carbonate, stirring for reaction until no bubbles are generated, continuing stirring for 10min, washing for 3 times by using ethanol, filtering, and drying in vacuum to obtain the lithium indigo disulfonate.
Example 4
The process for preparing the indigo disulfonic acid lithium anode material by adopting the sulfonation method comprises the following steps:
the same preparation method as in step (1) of example 2 was carried out except that:
adding the indigo disulfonic acid prepared in the step (1) into 120g of lithium hydroxide saturated solution with the solubility of 12.8g, stirring for reaction for 15min, filtering, washing with water, and drying in vacuum to obtain the indigo disulfonic acid lithium.
Example 5
The process for preparing the indigo disulfonic acid lithium anode material by adopting the synthesis method is as follows:
(1) preparation of lithium indigo disulfonate: reacting 18.4g of sulfanilic acid with 10g of chloroacetic acid at 60 ℃ for 8 hours to prepare sulfophenyl glycine;
(2) adding lithium amide and mixed alkali into the sulfophenyl glycine prepared in the step (1), carrying out alkali fusion reaction for 3h at 220 ℃, then cooling to room temperature, adding 2 times of volume of deionized water, and introducing air to oxidize for 2.5h at room temperature to obtain an indigo disulfonate mixture;
(3) adding water into the indigo disulfonate mixture to form a saturated solution, filling a lithium type cation exchange resin into a column, filling 100kg of wet resin into the ion exchange column, filling the resin layer with the height of 2.2m, feeding the indigo disulfonate mixture saturated solution into the exchange column from the bottom, controlling the flow rate through a rotameter and a valve of a feeding pipe at the bottom of the exchange column, and controlling the flow rate to be 0.1BV/h (m is m3/h·m3Wet resin), and performing an ion exchange reaction to obtain a lithium indigo disulfonate solution. And then concentrating, crystallizing and drying the indigo disulfonic acid lithium solution to obtain the indigo disulfonic acid lithium.
Example 6
The process for preparing the indigo disulfonic acid lithium anode material by adopting the synthesis method is as follows:
(1) preparation of lithium indigo disulfonate: reacting 16.5g of sulfanilic acid with 10g of chloroacetic acid at 80 ℃ for 5 hours to prepare sulfophenyl glycine;
(2) adding lithium amide and mixed alkali into the sulfophenyl glycine prepared in the step (1), carrying out alkali fusion reaction for 2.5h at 235 ℃, then cooling to room temperature, adding 2 times of volume of deionized water, and introducing air to oxidize for 2.5h at room temperature to obtain an indigo disulfonate mixture;
(3) adding water into the indigo disulfonate mixture to form a saturated solution, filling a lithium type cation exchange resin into a column, filling 100kg of wet resin into the ion exchange column, filling the resin layer with the height of 2.2m, feeding the indigo disulfonate mixture saturated solution into the exchange column from the bottom, controlling the flow rate through a rotameter and a valve of a feeding pipe at the bottom of the exchange column, and controlling the flow rate to be 0.4BV/h (m is m3/h·m3Wet resin), and performing an ion exchange reaction to obtain a lithium indigo disulfonate solution. And then concentrating, crystallizing and drying the indigo disulfonic acid lithium solution to obtain the indigo disulfonic acid lithium.
Example 7
The process for preparing the indigo disulfonic acid lithium anode material by adopting the synthesis method is as follows:
(1) preparation of lithium indigo disulfonate: reacting 15g of sulfanilic acid with 10g of chloroacetic acid at 105 ℃ for 2h to prepare sulfophenyl glycine;
(2) adding lithium amide and mixed alkali into the sulfophenyl glycine prepared in the step (1), carrying out alkali fusion reaction for 2 hours at 250 ℃, cooling the product, adding deionized water with 2 times of volume, cooling to room temperature, and introducing air to oxidize for 3 hours at room temperature to obtain an indigo disulfonate mixture;
(3) adding water into the indigo disulfonate mixture to form a saturated solution, filling a lithium type cation exchange resin into a column, filling 100kg of wet resin into the ion exchange column, filling the resin layer with the height of 2.2m, feeding the indigo disulfonate mixture saturated solution into the exchange column from the bottom, controlling the flow rate through a rotameter and a valve of a feeding pipe at the bottom of the exchange column, and controlling the flow rate to be 0.6BV/h (m is m3/h·m3Wet resin), and performing an ion exchange reaction to obtain a lithium indigo disulfonate solution. And then concentrating, crystallizing and drying the indigo disulfonic acid lithium solution to obtain the indigo disulfonic acid lithium.
The lithium indigo disulfonate cathode material prepared in each of embodiments 1 to 3 of the present invention is, for example, the lithium indigo disulfonate cathode material prepared in embodiment 2 of the present invention, and the lithium indigo disulfonate cathode material prepared in embodiment 2 of the present invention is coated by a carbon coating method, which specifically includes:
example 8
The process of the carbon-coated lithium indigo disulfonate cathode material is as follows:
(1) preparation of microcrystalline particles of lithium indigo disulfonate: adding water into the lithium indigo disulfonate prepared in the embodiment 2 to prepare a saturated solution, then adding 8 times of ethanol into the saturated solution of the lithium indigo disulfonate, crystallizing for 15min at the rotation speed of 4000r/min and the system temperature of 30 ℃, and carrying out suction filtration, ethanol washing and drying on the obtained precipitate to obtain lithium indigo disulfonate microcrystal particles;
(2) preparing a carbon-coated lithium indigo disulfonate positive electrode material: dissolving glucose in water to prepare a saturated solution, adding the lithium indigo disulfonate microcrystal particles prepared in the step (1) into the saturated glucose solution, stirring and mixing uniformly, then placing into a reaction kettle, performing hydrothermal carbonization for 10 hours at 200 ℃, naturally cooling, performing centrifugal separation, washing with distilled water and ethanol, and drying to obtain the carbon-coated lithium indigo disulfonate cathode material.
Example 9
The process of the carbon-coated lithium indigo disulfonate cathode material is as follows:
the procedure was as in example 8 except that ethanol was replaced with methanol.
The technical characteristics of the lithium indigo disulfonate and the carbon-coated lithium indigo disulfonate prepared by the present invention are as follows, and the specific methods and results are as follows:
scanning the indigo disulfonic acid lithium microcrystal particles prepared in the step (1) in the embodiment 8 through an electron microscope, wherein the scanning structure is shown in fig. 1, fig. 1 is a morphology diagram of the indigo disulfonic acid lithium microcrystal particles prepared through an anti-solvent ethanol recrystallization method, and as can be seen from the morphology in fig. 1, the flaky indigo disulfonic acid lithium microcrystal particles with the size less than one micron are obtained through the preparation method, which indicates that the submicron indigo disulfonic acid lithium microcrystal particles are obtained through the anti-solvent recrystallization method.
FIG. 2 is a scanning electron microscope image of a carbon-coated lithium indigo disulfonate positive electrode material prepared in step (2) of example 8 of the present invention; in comparison with fig. 1, carbon coating of lithium indigo disulfonate effectively inhibits the growth and agglomeration of crystal grains, and illustrates that the present invention effectively carbon-coats submicron lithium indigo disulfonate crystallite particles.
FIG. 3 is a charge-discharge curve of a pure lithium indigo disulfonate cathode material prepared in example 2; the 1st, 2nd, 3th and 4th represent the first, second, third and fourth charge and discharge experiments respectively, and it can be seen that the first discharge of the lithium indigo disulfonate is only 60mAh/g, and the capacity is rapidly attenuated along with the increase of the charge and discharge times, and only 35mAh/g is left until the fourth charge and discharge, which indicates that the capacity of the material cannot be fully exerted, and meanwhile, the cycle is unstable, the capacity is rapidly attenuated, which is also a common problem of organic electrode materials, and further modification is needed.
Fig. 4 is a charge-discharge curve of the carbon-coated lithium indigo disulfonate cathode material prepared in example 8, where 1th, 2nd, and 100th in fig. 4 represent the first, second, and 100th charge-discharge experiments, respectively, and the first discharge capacity and the last discharge capacity of the carbon-coated lithium indigo disulfonate cathode material are greater than 60mAh/g, as can be seen from comparison between fig. 3 and fig. 4, after 100 charge-discharge experiments, the charge-discharge performance of the carbon-coated lithium indigo disulfonate cathode material in fig. 4 is greatly improved, the specific capacity of the battery is improved, and the cycle stability is improved.
The conductivity of the powdery organic crystal material is tested by adopting a four-probe method, related analysis data are obtained, the conductivity of the pure lithium indigo disulfonate prepared in the example 2 is poor, and the conductivity is about 5.1 × 10-9S·cm-1After carbon coating, the conductivity is greatly improved and reaches a value of 4.9 × 10-7S·cm-1The description explains that the carbon-coated indigo disulfonic acid lithium positive electrode materialThe conductivity of the material is greatly improved, and the conductivity is more excellent.
The invention also assembles the button cell by the carbon-coated lithium indigo disulfonate anode material, and the concrete method comprises the following steps:
① preparation of working electrode
Mixing the coated lithium indigo disulfonate, the conductive carbon black and the binder (PVDF) according to the mass ratio of 7:2:1, fully stirring and grinding, adjusting the thickness to 8 mu m by using a film coating device, uniformly coating the slurry on an aluminum foil current collector, drying at 85 ℃ for 12h in vacuum drying, tabletting under the pressure of 8Mpa, and slicing for later use.
② Assembly of Battery
With LiPF61mol LiPF prepared from EC + DMC mixed solvent (volume ratio of 1:1) as electrolyte salt6And (EC: DMC) is electrolyte, and the diaphragm adopts glass fiber (Whatman, Grade GF/D) to be packaged into the CR2032 type button cell.
Fig. 5 is a performance test of charging and discharging the carbon-coated lithium indigo disulfonate prepared in example 8 after being prepared into an electrode and assembled into a button cell, after 100 charging and discharging cycles with a current density of 0.1C, the stable capacity can reach 100mAh/g, and after the cycle number reaches 10, the cycle tends to be stable, so the cycle stability of the lithium indigo disulfonate is greatly improved after carbon coating, which indicates that the feasibility of the carbon coating method is extremely high. And in the positive electrode material: conductive agent: the mass ratio of the binder is 7-8:1-2:1, the coating method is used for synthesizing the indigo disulfonic acid lithium with good conductivity as the anode material, the using amount of the conductive agent Super P can be reduced to 5%, and the indigo disulfonic acid lithium still has good high rate performance.
In conclusion, the indigo disulfonic acid lithium positive electrode material is prepared, and the pure indigo disulfonic acid lithium positive electrode material is poor in conductivity and cycle performance, on the basis, the carbon-coated indigo disulfonic acid lithium is subjected to carbon coating, so that the carbon-coated indigo disulfonic acid lithium positive electrode material is prepared, and the carbon-coated indigo disulfonic acid lithium positive electrode material is compared with the indigo disulfonic acid lithium, so that the conductivity and the charge-discharge cycle stability of the prepared carbon-coated indigo disulfonic acid lithium positive electrode material are greatly improved, and the conductivity and the cycle stability of the indigo disulfonic acid lithium positive electrode material are improved by a carbon coating method.
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, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. The lithium ion organic positive electrode material is characterized by being a lithium indigo disulfonate positive electrode material, wherein the structural formula of the lithium indigo disulfonate is as follows:
2. the lithium ion organic cathode material according to claim 1, wherein the surface of the lithium indigo disulfonate cathode material is further coated with carbon.
3. The method for preparing a lithium ion organic cathode material according to claim 1 or 2, wherein the lithium indigo disulfonate cathode material is prepared by a sulfonation method or a synthesis method.
4. The preparation method of the lithium ion organic cathode material according to claim 3, wherein the process for preparing the lithium indigo disulfonate cathode material by a sulfonation method comprises the following steps:
(1) preparation of indigo disulfonic acid: dropwise adding fuming sulfuric acid into the indigo at the speed of 2mL/min, and stirring for reacting for 30-50min to obtain indigo disulfonic acid;
wherein the mass fraction of sulfur trioxide in the oleum is 20%, and the ratio of the mass of the indigo to the volume of the oleum is 1: 0.5-2;
(2) diluting the indigo disulfonic acid prepared in the step (1) with deionized water, adding lithium carbonate, stirring for reaction until no bubbles are generated, continuing stirring for 10-15min, washing with ethanol, filtering, and drying to obtain indigo disulfonic acid lithium;
wherein the mass ratio of the volume of the fuming sulfuric acid to the lithium carbonate is 1: 0.75-1.
5. The preparation method of the lithium ion organic cathode material according to claim 3, wherein the process for preparing the lithium indigo disulfonate cathode material by a sulfonation method comprises the following steps:
(1) preparation of indigo disulfonic acid: dropwise adding fuming sulfuric acid into the indigo at the speed of 2mL/min, and stirring for reacting for 30-50min to obtain indigo disulfonic acid;
wherein the mass fraction of sulfur trioxide in the oleum is 20%, and the ratio of the mass of the indigo to the volume of the oleum is 1: 0.5-2;
(2) adding a lithium hydroxide saturated solution into the indigo disulfonic acid prepared in the step (1), stirring and reacting for 10-20min, filtering, washing with water, and drying to obtain the indigo disulfonic acid lithium;
wherein the volume ratio of the indigo disulfonic acid to the lithium hydroxide saturated solution is 1: 3.5-4.
6. The preparation method of the lithium ion organic cathode material according to claim 3, wherein the process for preparing the lithium indigo disulfonate cathode material by adopting a synthesis method is as follows:
(1) preparation of sulfophenyl glycine: reacting sulfanilic acid and chloroacetic acid at 60-105 ℃ for 2-8h to obtain sulfophenyl glycine;
wherein the mass ratio of chloroacetic acid to sulfanilic acid is 1: 1.50-1.84;
(2) adding lithium amide and mixed alkali into the sulfophenyl glycine prepared in the step (1), reacting for 2-3h at the temperature of 220-250 ℃, then cooling to room temperature, adding water for dilution, and introducing air at room temperature for oxidation for 2.5-3h to obtain an indigo disulfonate mixture;
wherein the mixed alkali comprises dry lithium hydroxide and dry potassium hydroxide or dry lithium hydroxide and dry sodium hydroxide, the mass ratio of the lithium hydroxide to the potassium hydroxide or the sodium hydroxide is 1.5-2:1, and the ratio of sulfophenyl glycine: mixing alkali: the mass ratio of the lithium amide is 12-16:2-3: 1;
(3) and (3) completely dissolving the indigo disulfonate mixture prepared in the step (2) in water, then loading a lithium type cation exchange resin into a column, carrying out ion exchange reaction on the indigo disulfonate mixture at the flow rate of 0.1-0.6BV/h, and then concentrating, crystallizing and drying to obtain the indigo disulfonic acid lithium.
7. The preparation method of the lithium ion organic cathode material according to claim 2, wherein the preparation process of the carbon-coated lithium indigo disulfonate cathode material is as follows:
(1) preparation of microcrystalline particles of lithium indigo disulfonate: adding a saturated solution of lithium indigo disulfonate into an alcohol solvent, crystallizing for 10-20min at the rotation speed of 1000-4000r/min and the system temperature of 25-35 ℃, and performing suction filtration, ethanol washing and drying to obtain lithium indigo disulfonate microcrystal particles;
wherein the alcohol solvent is ethanol or methanol, and the volume ratio of the indigo disulfonic acid lithium saturated solution to the alcohol solvent is 1: 10-20 parts of;
(2) preparing a carbon-coated lithium indigo disulfonate positive electrode material: adding the lithium indigo disulfonate microcrystal particles prepared in the step (1) into a glucose saturated solution, stirring and mixing uniformly, then placing into a reaction kettle, performing hydrothermal carbonization at the temperature of 150-250 ℃ for 12-8h, naturally cooling, performing centrifugal separation, washing with distilled water and ethanol, and drying to obtain a carbon-coated lithium indigo disulfonate anode material;
wherein the mass ratio of the glucose to the lithium indigo disulfonate particles is 1: 2-4.
8. A lithium ion battery comprising the lithium ion organic positive electrode material according to claim 1 or 2.
9. The preparation method of the lithium ion battery according to claim 8, comprising the following steps:
mixing and grinding the lithium ion organic positive electrode material, the conductive additive and the binder to obtain slurry;
coating the slurry on an aluminum foil, drying and tabletting to prepare an electrode plate;
and matching the electrode plate with a diaphragm and electrolyte to prepare the lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010148066.0A CN111326725A (en) | 2020-03-05 | 2020-03-05 | Lithium ion organic positive electrode material, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010148066.0A CN111326725A (en) | 2020-03-05 | 2020-03-05 | Lithium ion organic positive electrode material, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111326725A true CN111326725A (en) | 2020-06-23 |
Family
ID=71165831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010148066.0A Pending CN111326725A (en) | 2020-03-05 | 2020-03-05 | Lithium ion organic positive electrode material, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111326725A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109331043A (en) * | 2018-11-19 | 2019-02-15 | 青海民族大学 | A kind of pharmaceutical composition and preparation method thereof for treating ulcer malignant boil furuncle |
| CN114150164A (en) * | 2021-12-21 | 2022-03-08 | 苏州中科百奥科技发展有限公司 | Method for separating lithium ions from mixed solution |
| CN117393870A (en) * | 2023-12-11 | 2024-01-12 | 大连理工大学 | Zinc ion battery energy storage device |
| CN117936759A (en) * | 2024-03-22 | 2024-04-26 | 河南湛拓新能源科技有限公司 | High-capacity sodium battery positive electrode material and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004079276A (en) * | 2002-08-13 | 2004-03-11 | Sony Corp | Positive electrode activator and its manufacturing method |
| CN101894943A (en) * | 2010-04-20 | 2010-11-24 | 华南师范大学 | Method for coating lithium ion battery anode material with carbon |
| JP2011103260A (en) * | 2009-11-12 | 2011-05-26 | National Institute Of Advanced Industrial Science & Technology | Positive electrode active material for nonaqueous secondary battery |
| WO2012045211A1 (en) * | 2010-10-09 | 2012-04-12 | 河南环宇集团有限公司 | Production method of lithium-ferrous phosphate double-salt positive-electrode material and positive-electrode material obtained |
| CN102569792A (en) * | 2011-11-07 | 2012-07-11 | 四川大学 | Preparation method for one-step synthesis of high-rate-performance carbon-coated lithium iron phosphate cathode material by in-situ hydrothermal carbonization |
| CN102760879A (en) * | 2012-08-01 | 2012-10-31 | 东北师范大学 | Method for preparing nanometer lithium iron phosphate/carbon compound with stable low temperature performance |
| CN103035899A (en) * | 2013-01-14 | 2013-04-10 | 山东天润丰新能源科技有限公司 | Method for performing carbon coating modification on nano-powder by adopting water-soluble polymer |
| EP2876709A1 (en) * | 2013-11-22 | 2015-05-27 | Funai Electric Co., Ltd. | Lithium ion capacitor |
| CN110291668A (en) * | 2017-02-15 | 2019-09-27 | 魁北克电力公司 | Electrode material and preparation method thereof |
-
2020
- 2020-03-05 CN CN202010148066.0A patent/CN111326725A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004079276A (en) * | 2002-08-13 | 2004-03-11 | Sony Corp | Positive electrode activator and its manufacturing method |
| JP2011103260A (en) * | 2009-11-12 | 2011-05-26 | National Institute Of Advanced Industrial Science & Technology | Positive electrode active material for nonaqueous secondary battery |
| CN101894943A (en) * | 2010-04-20 | 2010-11-24 | 华南师范大学 | Method for coating lithium ion battery anode material with carbon |
| WO2012045211A1 (en) * | 2010-10-09 | 2012-04-12 | 河南环宇集团有限公司 | Production method of lithium-ferrous phosphate double-salt positive-electrode material and positive-electrode material obtained |
| CN102569792A (en) * | 2011-11-07 | 2012-07-11 | 四川大学 | Preparation method for one-step synthesis of high-rate-performance carbon-coated lithium iron phosphate cathode material by in-situ hydrothermal carbonization |
| CN102760879A (en) * | 2012-08-01 | 2012-10-31 | 东北师范大学 | Method for preparing nanometer lithium iron phosphate/carbon compound with stable low temperature performance |
| CN103035899A (en) * | 2013-01-14 | 2013-04-10 | 山东天润丰新能源科技有限公司 | Method for performing carbon coating modification on nano-powder by adopting water-soluble polymer |
| EP2876709A1 (en) * | 2013-11-22 | 2015-05-27 | Funai Electric Co., Ltd. | Lithium ion capacitor |
| CN110291668A (en) * | 2017-02-15 | 2019-09-27 | 魁北克电力公司 | Electrode material and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| GUANGCHUAN LIANG 等: "《Lithium iron phosphate with high-rate capability synthesized through hydrothermal reaction in glucose solution》", 《JOURNAL OF POWER SOURCES》 * |
| 刘学军主编: "《食品添加剂》", 31 December 2004, 长春：吉林科学技术出版社 * |
| 张权: "《食品着色剂靛蓝中间体靛红的合成新工艺》", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 朱洪法等主编: "《无机化工产品手册》", 31 December 2008, 北京：金盾出版社 * |
| 杭州大学化学系分析化学教研室编: "《分析化学手册 第1分册 基础知识与安全知识》", 31 January 1997, 北京：化学出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109331043A (en) * | 2018-11-19 | 2019-02-15 | 青海民族大学 | A kind of pharmaceutical composition and preparation method thereof for treating ulcer malignant boil furuncle |
| CN114150164A (en) * | 2021-12-21 | 2022-03-08 | 苏州中科百奥科技发展有限公司 | Method for separating lithium ions from mixed solution |
| CN117393870A (en) * | 2023-12-11 | 2024-01-12 | 大连理工大学 | Zinc ion battery energy storage device |
| CN117393870B (en) * | 2023-12-11 | 2024-02-13 | 大连理工大学 | Zinc ion battery energy storage device |
| CN117936759A (en) * | 2024-03-22 | 2024-04-26 | 河南湛拓新能源科技有限公司 | High-capacity sodium battery positive electrode material and preparation method thereof |
| CN117936759B (en) * | 2024-03-22 | 2024-06-07 | 河南湛拓新能源科技有限公司 | High-capacity sodium battery positive electrode material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111326725A (en) | Lithium ion organic positive electrode material, preparation method and application | |
| CN102655231B (en) | A kind of method preparing high power performance anode material for lithium-ion batteries LiMn2O4 | |
| CN103280570B (en) | Preparation method of micron-order single-crystal nickel lithium manganate anode material | |
| CN103236518A (en) | Lithium ion battery negative nanometer material SnO2/MCMB (Mesophase Carbon Micro Beads) shell, and preparation method and application thereof | |
| CN112290022B (en) | Lithium ion battery anode lithium supplement additive and preparation method and application thereof | |
| WO2024055516A1 (en) | Method for preparing lithium manganese iron phosphate positive electrode material by means of spray combustion and use thereof | |
| CN111146429A (en) | Preparation method of graphene oxide/sulfur microcapsule composite material, lithium-sulfur battery positive electrode and lithium-sulfur battery | |
| CN113428912A (en) | Quaternary positive electrode material and preparation method and application thereof | |
| CN113772718B (en) | SnS-SnS 2 @ GO heterostructure composite material and preparation method and application thereof | |
| CN114039051A (en) | MXene/SnO with three-dimensional structure2/C negative electrode composite material and preparation method thereof | |
| FR3141159A1 (en) | METHOD FOR PREPARING LITHIUM-MANGANESE-IRON PHOSPHATE POSITIVE ELECTRODE MATERIAL BY CO-PRECIPITATION AND USE THEREOF | |
| CN115611773B (en) | Lithium supplementing compound, preparation method thereof and lithium ion battery | |
| CN116404108A (en) | Positive plate and preparation method thereof, electrode assembly, energy storage device and electric equipment | |
| CN116314739A (en) | Manganese-based layered oxide positive electrode material and preparation method and application thereof | |
| CN113328077B (en) | Cathode material, preparation method and application thereof | |
| CN111354942B (en) | Micron-sized rod-shaped lithium manganate and preparation method and application thereof | |
| CN113809419A (en) | Formation method and formed lithium ion battery | |
| CN113488641A (en) | Rapid preparation method of lithium ion battery anode material vanadium pentoxide nanosheet | |
| CN107394177B (en) | Nickel bicarbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof | |
| CN112271342A (en) | Preparation method of zinc ion battery ZIB based on vanadium oxide positive electrode material | |
| CN111261866A (en) | Preparation method of ZnO/C nano composite microsphere material with capsule structure | |
| WO2023060992A1 (en) | Method for synthesizing high-safety positive electrode material by recycling positive electrode leftover materials, and application | |
| CN113745475B (en) | Graphene/iron diselenide composite material for lithium ion battery cathode material and preparation method thereof | |
| CN110143619B (en) | Preparation method of lithium-rich manganese-based cathode material with special-morphology micro-nano structure | |
| CN103137958B (en) | A kind of modification vanadic oxide positive electrode and methods for making and using same thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200623 |
|
| RJ01 | Rejection of invention patent application after publication |