EP4460855A1 - Composite material with biomimetic structure for cathodes of lithium-ion aqueous rechargeable batteries and method of its preparation - Google Patents

Composite material with biomimetic structure for cathodes of lithium-ion aqueous rechargeable batteries and method of its preparation

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Publication number
EP4460855A1
EP4460855A1 EP22859457.8A EP22859457A EP4460855A1 EP 4460855 A1 EP4460855 A1 EP 4460855A1 EP 22859457 A EP22859457 A EP 22859457A EP 4460855 A1 EP4460855 A1 EP 4460855A1
Authority
EP
European Patent Office
Prior art keywords
composite material
lmo
cnt
biomimetic structure
biomimetic
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
Application number
EP22859457.8A
Other languages
German (de)
French (fr)
Inventor
Constantin BUBULINCA
Irina SAPURINA
Natalia Kazantseva
Viera PECHANCOVÁ
Petr SÁHA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tomas Bata University in Zlín
Original Assignee
Tomas Bata University in Zlín
Priority date (The priority date 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 date listed.)
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Publication date
Application filed by Tomas Bata University in Zlín filed Critical Tomas Bata University in Zlín
Publication of EP4460855A1 publication Critical patent/EP4460855A1/en
Pending legal-status Critical Current

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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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

Definitions

  • the invention relates to a composite material with a biomimetic structure for cathodes of rechargeable lithium-ion aqueous batteries, based on spinel lithium manganese oxide LiMii2O4 (LMO) and carbon nanotubes (CNT). Furthermore, the invention includes a method of preparing this composite material with a biomimetic structure.
  • LMO spinel lithium manganese oxide
  • CNT carbon nanotubes
  • lithium-ion batteries in various designs, such as coins, cartridges, prismatic or cylindrical, have a leading position on the market. In general, they still require improvement of the main electrochemical parameters, especially the power density.
  • the cathodes of a battery can be conventionally produced by applying a paste based on an active material, a conductive carbon material, a binder and a solvent to a metal sheet. Electrodes of this type, however, have low flexibility due to their rigid construction.
  • LMO spinel lithium manganese oxide
  • LiMnzO4 spinel lithium manganese oxide
  • Mn 3+ the solubility of Mn 3+
  • structural degradation caused by the electrochemical reaction associated with low electronic conductivity which definitely limits the application of LMO in high-performance lithium batteries.
  • Various treatments have been developed in order to prevent Mn 3+ dissolution, such as surface coating, changing electrolytes, etc.
  • a number of approaches using organic and inorganic materials have been applied in the field of LMO surface coatings.
  • the coating of the LMO surface can be mentioned, using metal oxides such as AI2O3 and Z1O2, as well as the use of SiOs, AIF3 or AIPO4 salts and conductive polymers such as polyaniline (PAN! and polypyrrole (PPy), or doping using Ni-Co-Mn or Co- Mg-Ni in order to protect against exposure to electrolytes.
  • Aqueous battery technology represents an alternative to organic cells. However, there is not much interest in the research of these cells and in integration of the above-mentioned types of electrodes in them. Nevertheless, the most important advantages of aqueous batteries include low production costs, a better level of safety and also a higher ionic conductivity than within organic cells.
  • the composite material with a biomimetic structure for the cathodes of rechargeable lithium-ion aqueous batteries according to the invention considerably contributes to solving the problems indicated in the description of the current state of the art, i.e. in particular, finding suitable materials for the cathodes of aqueous lithium batteries. It is a material based on the aforementioned spinel lithium manganese oxide - LiMmCh (LMO) and carbon nanotubes (CNT).
  • LMO spinel lithium manganese oxide - LiMmCh
  • CNT carbon nanotubes
  • this composite material is formed by the LMO/CNT- Gr ternary “tectonic plate-island bridge” biomimetic structure, where the multilayered graphene (Gr) forms a “tectonic plate” substrate on which there are the “islands” of the LiMmO ⁇ active material interconnected by a “bridge network” of multi-walled carbon nanotubes.
  • the core formed by the above-mentioned LMO/CNT-Gr ternary biomimetic structure can advantageously be provided with a shell based on polyaniline (PANI).
  • the nature of the method of preparing a composite material with a biomimetic structure according to the invention is that 7.5 to 8.5 parts by weight of LMO, 0.5 to 1.0 parts by weight of CNT and 0.1 to 0.5 parts by weight of Gr in powder form is dispersed in an aqueous solution with an assisted surfactant. Further, ultrasonic treatment is carried out for at least 30 min, followed by vacuum filtration, repeated washing with demineralized water and drying the composite material first in air and then in an oven at 90 to 120 °C for 4 to 12 h.
  • the prepared composite material with a biomimetic structure is preferably subsequently modified with polyaniline by in situ polymerization so that either the composite powder is dispersed in an aqueous medium, after which solutions of the monomer (aniline and o -phenylenediamine) in H2SO4 and ammonium persulfate also in H2SO4, or the self-standing cathode made of a composite material with a biomimetic structure is modified by short-term exposure - for at least 0.5 min. into a solution of monomer (aniline and o -phenylenediamine) in H2SO4 and ammonium persulfate also in H2SO4.
  • the precipitates of the powder materials are decanted onto a filter, washed with water and ethanol and air-dried, while the self- standing cathode made of a composite material with a biomimetic structure is rinsed with water and dried.
  • the main benefit of the composite material with a biomimetic structure for cathodes of rechargeable lithium-ion aqueous batteries and the method of its preparation according to the invention is the fact that it is a new low-cost cathode material composition based on low-cost raw materials and low-cost technology. This is a definite advantage compared to the known solutions.
  • the solution according to the invention is also interesting from the point of view of its useful properties.
  • Graphene combined with LMO and CNTs creates a so-called “tectonic bridge plate” that enables better ion kinetics by shortening and tunnelling the electron transfer pathways.
  • the PANI core-shell coating of this structure prepared by in situ polymerization creates a thin shield against Mn dissolution and a lower Jahn-Teller effect by decreasing the charge transfer resistance, thus improving the electrical conductivity and increasing the specific capacity due to an extended potential window.
  • the electrochemical measurements show that the composite electrode that contains PANI exhibits the best specific discharge capacity of approximately 136 mA h-g-1 compared to 111 mA h-g ⁇ l of LMO/CNT and good cycling stability up to 200 GCD cycles, thus making this structure a candidate for environmentally friendly cathode materials of rechargeable aqueous batteries.
  • FIG. 1 SEM images of the morphology of LMO/CNT and LMO/CNT-Gr biomimetic composites
  • the composite material with a biomimetic structure for the cathodes of rechargeable lithium-ion aqueous batteries in an exemplary embodiment based on spinel lithium manganese oxide LiMmCXi (LMO) and carbon nanotubes (CNT) is formed by the LMO/CNT- Gr ternary “tectonic plate-island bridge” biomimetic structure.
  • the multilayered graphene (Gr) forms a “tectonic plate” substrate on which there are “islands” of the LiMniCE active material interconnected by a “bridge network” of multi-walled carbon nanotubes.
  • Fig. 1 the morphology, i.e., the thickness and layered structure of the LMO/CNT and LMO/CNT-Gr biomimetic composites of self-standing binder-free biomimetic electrodes is shown using SEM images.
  • SEM images On the surface of the electrode, homogeneously dispersed micron and nano-sized LMO particles (Fig. la) interconnected by a supporting network of CNTs are visible at higher magnification (Fig. lb).
  • a cross-sectional SEM image of the LMO/CNT-Gr composite cathode shows a thickness of approximately 64 pm (Fig. 1c), which can be considered optimal for cathode materials.
  • Fig. 1c the SEM images
  • the cross- sectional geometry of the electrode consists of superimposed layers of a “tectonic-plate islandbridge” biomimetic structure. This arrangement provides fast kinetics and reduces the length of the ion path supported by the tunnelling effect created by the CNT matrix.
  • the method of preparing a composite material with a biomimetic structure consists in the fact that 8.5 parts by weight of LMO, 1.0 parts by weight of CNT and 0.5 parts by weight of Gr in powder form is dispersed in an aqueous solution (50 ml) with the poly(ethylene glycol) p- isooctyl-phenyl ether (Triton X-100) surfactant assisting for 30 min at a constant temperature of 20 °C.
  • Triton X-100 poly(ethylene glycol) p- isooctyl-phenyl ether
  • ultrasonic treatment is carried out for 30 min, and it is followed by vacuum filtration, repeated washing with 150 ml of demineralized water in order to remove the surfactant, and drying of the composite material, first in air and then in a drying oven at a temperature of 110 °C for 4 hours.
  • a composite material with a biomimetic structure for the cathodes of rechargeable lithium-ion aqueous batteries in an exemplary embodiment based on spinel lithium manganese oxide LiMmCU (LMO) and carbon nanotubes (CNT) is formed similarly to example 1 by a LMO/CNT-Gr ternary “tectonic plate-island bridge” biomimetic structure.
  • the multilayered graphene (Gr) forms a “tectonic plate” substrate on which there are “islands” of the LiMn2O4 active material interconnected by a “bridge network” of multi-walled carbon nanotubes.
  • the method of preparation of a composite material with a biomimetic structure consists in the fact that 7.5 parts by weight of LMO, 0.5 parts by weight of CNT and 0.3 parts by weight of Gr in powder form is dispersed in an aqueous solution (50 ml) with the poly(ethylene glycol) p-isooctyl-phenyl ether (Triton X- 100) surfactant assisting for 30 min at a constant temperature of 20 °C.
  • Triton X- 100 poly(ethylene glycol) p-isooctyl-phenyl ether
  • ultrasonic treatment is carried out for 30 min, and it is followed by vacuum filtration, repeated washing with 150 ml of demineralized water in order to remove the surfactant, and drying of the composite material, first in air and then in a drying oven at a temperature of 90 °C for 10 hours.
  • the composite material in powder form contains a core formed by a composite material with a LMO/CNT-Gr ternary biomimetic structure according to the example 1 or 2, which is provided with a shell based on polyaniline (PANI).
  • PANI polyaniline
  • the morphological structure of the seif-standing binder-free composite electrode based on LMO/CNT-Gr/PANI was investigated by SEM and HRTEM (see Fig. 3).
  • the SEM image of the PANI core-shell coated composite is depicted in Fig. 3a and shows the active structure of the LMO particles with different particle sizes, from hundreds of nanometers to several micrometers.
  • a semi-transparent waved PANI layer coating the entire surface of the composite electrode can be seen at the top of the structure.
  • the structure of the composite electrode was studied in more detail using HRTEM (Fig. 3), where it can be observed that the PANI layer has a variable thickness of several nanometers (see Fig. 3b).
  • Figure 3c shows the position of the graphene structure placed between two multi-layered carbon nanotubes that interconnect the LMO particles (Fig. 3d) to create the so-called “tectonic plate-island bridge” biomimetic structure.
  • the method of preparation of this material consists in the fact that the composite material with a biomimetic structure prepared according to example 1 or 2 is subsequently modified with polyaniline by in situ polymerization so that the composite powder (0.5 g) is dispersed into an aqueous medium.
  • the self- standing cathode is made of a core- shell composite material.
  • the core is made of a composite material with LMO/CNT-Gr ternary biomimetic structure according to example 1 or 2 and is provided with a shell based on polyaniline (PANI).
  • PANI polyaniline
  • the method of preparation of this material consists in the fact that the composite material with a biomimetic structure prepared according to example 1 is subsequently modified with polyaniline by in situ polymerization so that the self- standing cathode of the composite material with a biomimetic structure is modified by a short exposure - for a period of 0.5 min into the monomer solution - 0.01M aniline and 0.001M o-phenylenediamine in 20 mL of 1 M H2SO4 and subsequent addition of a 0.01M ammonium persulfate solution in 10 ml 1 M H2SO4. After the synthesis of polyaniline in the solution, the self- standing cathode made of a composite material with a biomimetic structure is rinsed off with water and dried.
  • the composite material according to the invention formed by the LMO/CNT- Gr ternary “tectonic plate-island bridge” biomimetic structure, is especially suitable for the cathodes of rechargeable lithium-ion aqueous batteries due to its unique properties.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The composite material with a biomimetic structure based on spinel lithium manganese oxide LiMn2CO4 (LMO) and carbon nanotubes (CNT) is formed by the LMO/CNT-Gr ternary "tectonic plate-island bridge" biomimetic structure, where the multilayered graphene (Gr) forms a "tectonic plate" substrate on which there are the "islands" of the LMO active material interconnected by a "bridge network" of multi- walled carbon nano tubes. In addition, the core formed by the LMO/CNT-Gr ternary biomimetic structure can be provided with a polyaniline (PANI)-based shell in the application for cathodes of the rechargeable lithium-ion aqueous batteries. Furthermore, the invention relates to a method of preparation of a composite material with biomimetic structure.

Description

COMPOSITE MATERIAL WITH BIOMIMETIC STRUCTURE FOR CATHODES OF
LITHIUM-ION AQUEOUS RECHARGEABLE BATTERIES AND METHOD OF ITS
PREPARATION
Field of technology
The invention relates to a composite material with a biomimetic structure for cathodes of rechargeable lithium-ion aqueous batteries, based on spinel lithium manganese oxide LiMii2O4 (LMO) and carbon nanotubes (CNT). Furthermore, the invention includes a method of preparing this composite material with a biomimetic structure.
State of the art
In recent decades, new types of smart electronics such as wearable devices and roll-up displays have emerged, placing demands on the adaptation of energy storage technology in terms of electrochemical properties and related requirements for a suitable cathode structure. Currently, lithium-ion batteries in various designs, such as coins, cartridges, prismatic or cylindrical, have a leading position on the market. In general, they still require improvement of the main electrochemical parameters, especially the power density.
It is known that the cathodes of a battery can be conventionally produced by applying a paste based on an active material, a conductive carbon material, a binder and a solvent to a metal sheet. Electrodes of this type, however, have low flexibility due to their rigid construction.
This problem can be overcome by flexible binder-free electrodes based on carbon nanotubes (CNT) and graphene networks.
One of the most popular active materials used is the spinel lithium manganese oxide LiMnzO4 (LMO) due to its abundance (availability), good electrochemical properties, low' price and the possibility to facilitate the intercalation of Li-ions. However, LMO also exhibits several disadvantages, among them the solubility of Mn3+ and the structural degradation caused by the electrochemical reaction associated with low electronic conductivity, which definitely limits the application of LMO in high-performance lithium batteries. Various treatments have been developed in order to prevent Mn 3+ dissolution, such as surface coating, changing electrolytes, etc. A number of approaches using organic and inorganic materials have been applied in the field of LMO surface coatings. The coating of the LMO surface can be mentioned, using metal oxides such as AI2O3 and Z1O2, as well as the use of SiOs, AIF3 or AIPO4 salts and conductive polymers such as polyaniline (PAN!) and polypyrrole (PPy), or doping using Ni-Co-Mn or Co- Mg-Ni in order to protect against exposure to electrolytes.
Aqueous battery technology represents an alternative to organic cells. However, there is not much interest in the research of these cells and in integration of the above-mentioned types of electrodes in them. Nevertheless, the most important advantages of aqueous batteries include low production costs, a better level of safety and also a higher ionic conductivity than within organic cells.
Nature of the invention
The composite material with a biomimetic structure for the cathodes of rechargeable lithium-ion aqueous batteries according to the invention considerably contributes to solving the problems indicated in the description of the current state of the art, i.e. in particular, finding suitable materials for the cathodes of aqueous lithium batteries. It is a material based on the aforementioned spinel lithium manganese oxide - LiMmCh (LMO) and carbon nanotubes (CNT).
The nature of the invention is that this composite material is formed by the LMO/CNT- Gr ternary “tectonic plate-island bridge” biomimetic structure, where the multilayered graphene (Gr) forms a “tectonic plate” substrate on which there are the “islands” of the LiMmO ■ active material interconnected by a “bridge network” of multi-walled carbon nanotubes.
The core formed by the above-mentioned LMO/CNT-Gr ternary biomimetic structure can advantageously be provided with a shell based on polyaniline (PANI).
The nature of the method of preparing a composite material with a biomimetic structure according to the invention is that 7.5 to 8.5 parts by weight of LMO, 0.5 to 1.0 parts by weight of CNT and 0.1 to 0.5 parts by weight of Gr in powder form is dispersed in an aqueous solution with an assisted surfactant. Further, ultrasonic treatment is carried out for at least 30 min, followed by vacuum filtration, repeated washing with demineralized water and drying the composite material first in air and then in an oven at 90 to 120 °C for 4 to 12 h.
The prepared composite material with a biomimetic structure is preferably subsequently modified with polyaniline by in situ polymerization so that either the composite powder is dispersed in an aqueous medium, after which solutions of the monomer (aniline and o -phenylenediamine) in H2SO4 and ammonium persulfate also in H2SO4, or the self-standing cathode made of a composite material with a biomimetic structure is modified by short-term exposure - for at least 0.5 min. into a solution of monomer (aniline and o -phenylenediamine) in H2SO4 and ammonium persulfate also in H2SO4. After the synthesis of polyaniline in solution, the precipitates of the powder materials are decanted onto a filter, washed with water and ethanol and air-dried, while the self- standing cathode made of a composite material with a biomimetic structure is rinsed with water and dried.
The main benefit of the composite material with a biomimetic structure for cathodes of rechargeable lithium-ion aqueous batteries and the method of its preparation according to the invention is the fact that it is a new low-cost cathode material composition based on low-cost raw materials and low-cost technology. This is a definite advantage compared to the known solutions.
In addition, considering the context of the known solutions, the solution according to the invention is also interesting from the point of view of its useful properties. The effect of Gr and PANI, as assessed by the dielectric spectra, shows a significant improvement in electrical conductivity from 0.005 to 0.025.1 mnS/ciir. Graphene combined with LMO and CNTs creates a so-called “tectonic bridge plate” that enables better ion kinetics by shortening and tunnelling the electron transfer pathways.
Moreover, the PANI core-shell coating of this structure prepared by in situ polymerization creates a thin shield against Mn dissolution and a lower Jahn-Teller effect by decreasing the charge transfer resistance, thus improving the electrical conductivity and increasing the specific capacity due to an extended potential window. The electrochemical measurements show that the composite electrode that contains PANI exhibits the best specific discharge capacity of approximately 136 mA h-g-1 compared to 111 mA h-g~ l of LMO/CNT and good cycling stability up to 200 GCD cycles, thus making this structure a candidate for environmentally friendly cathode materials of rechargeable aqueous batteries.
Brief description of drawings
The drawings attached to describe the nature of the invention in more detail include: Fig. 1 - SEM images of the morphology of LMO/CNT and LMO/CNT-Gr biomimetic composites,
Fig. 2 - ED AX spectra and structure of the LMO/CNT composite,
Fig. 3 - SEM images of the morphology of LMO/CNT -Gr/PANI biomimetic composites. Examples
Example 1
The composite material with a biomimetic structure for the cathodes of rechargeable lithium-ion aqueous batteries in an exemplary embodiment based on spinel lithium manganese oxide LiMmCXi (LMO) and carbon nanotubes (CNT) is formed by the LMO/CNT- Gr ternary “tectonic plate-island bridge” biomimetic structure. The multilayered graphene (Gr) forms a “tectonic plate” substrate on which there are “islands” of the LiMniCE active material interconnected by a “bridge network” of multi-walled carbon nanotubes.
In Fig. 1, the morphology, i.e., the thickness and layered structure of the LMO/CNT and LMO/CNT-Gr biomimetic composites of self-standing binder-free biomimetic electrodes is shown using SEM images. On the surface of the electrode, homogeneously dispersed micron and nano-sized LMO particles (Fig. la) interconnected by a supporting network of CNTs are visible at higher magnification (Fig. lb). A cross-sectional SEM image of the LMO/CNT-Gr composite cathode shows a thickness of approximately 64 pm (Fig. 1c), which can be considered optimal for cathode materials. According to the SEM images (Fig. Id), the cross- sectional geometry of the electrode consists of superimposed layers of a “tectonic-plate islandbridge” biomimetic structure. This arrangement provides fast kinetics and reduces the length of the ion path supported by the tunnelling effect created by the CNT matrix.
The method of preparing a composite material with a biomimetic structure consists in the fact that 8.5 parts by weight of LMO, 1.0 parts by weight of CNT and 0.5 parts by weight of Gr in powder form is dispersed in an aqueous solution (50 ml) with the poly(ethylene glycol) p- isooctyl-phenyl ether (Triton X-100) surfactant assisting for 30 min at a constant temperature of 20 °C. Further, ultrasonic treatment is carried out for 30 min, and it is followed by vacuum filtration, repeated washing with 150 ml of demineralized water in order to remove the surfactant, and drying of the composite material, first in air and then in a drying oven at a temperature of 110 °C for 4 hours.
To analyse the dispersion efficiency and homogeneity of particles in the basic structure of LMO/CNT, an energy dispersive X-ray measurement was performed (see Fig. 2). Ultrasonic treatment in an aqueous solution by a surfactant helps to create a uniform structure where the elements were well-dispersed - as shown by the elemental mapping in Fig. 2. In addition, the ED AX spectra contain peaks corresponding to the chemical elements of CNT (C peak), O and Mn comprised in the LMO/CNT sample without any contamination. Example 2
A composite material with a biomimetic structure for the cathodes of rechargeable lithium-ion aqueous batteries in an exemplary embodiment based on spinel lithium manganese oxide LiMmCU (LMO) and carbon nanotubes (CNT) is formed similarly to example 1 by a LMO/CNT-Gr ternary “tectonic plate-island bridge” biomimetic structure. The multilayered graphene (Gr) forms a “tectonic plate” substrate on which there are “islands” of the LiMn2O4 active material interconnected by a “bridge network” of multi-walled carbon nanotubes.
The method of preparation of a composite material with a biomimetic structure consists in the fact that 7.5 parts by weight of LMO, 0.5 parts by weight of CNT and 0.3 parts by weight of Gr in powder form is dispersed in an aqueous solution (50 ml) with the poly(ethylene glycol) p-isooctyl-phenyl ether (Triton X- 100) surfactant assisting for 30 min at a constant temperature of 20 °C. Further, ultrasonic treatment is carried out for 30 min, and it is followed by vacuum filtration, repeated washing with 150 ml of demineralized water in order to remove the surfactant, and drying of the composite material, first in air and then in a drying oven at a temperature of 90 °C for 10 hours.
Example 3
The composite material in powder form contains a core formed by a composite material with a LMO/CNT-Gr ternary biomimetic structure according to the example 1 or 2, which is provided with a shell based on polyaniline (PANI).
The morphological structure of the seif-standing binder-free composite electrode based on LMO/CNT-Gr/PANI was investigated by SEM and HRTEM (see Fig. 3). The SEM image of the PANI core-shell coated composite is depicted in Fig. 3a and shows the active structure of the LMO particles with different particle sizes, from hundreds of nanometers to several micrometers. Moreover, a semi-transparent waved PANI layer coating the entire surface of the composite electrode can be seen at the top of the structure. The structure of the composite electrode was studied in more detail using HRTEM (Fig. 3), where it can be observed that the PANI layer has a variable thickness of several nanometers (see Fig. 3b). Figure 3c shows the position of the graphene structure placed between two multi-layered carbon nanotubes that interconnect the LMO particles (Fig. 3d) to create the so-called “tectonic plate-island bridge” biomimetic structure. The method of preparation of this material consists in the fact that the composite material with a biomimetic structure prepared according to example 1 or 2 is subsequently modified with polyaniline by in situ polymerization so that the composite powder (0.5 g) is dispersed into an aqueous medium. Then, into the suspension, with stirring, aqueous solutions of the monomer - aniline 0.01 M + o-phenylenediamine 0.001 M in 20 mL 1 M H2SO4 and ammonium persulfate 0.01 M in 10 ml 1 M tkSCU were added. After the completion of the synthesis of polyaniline in solution, the precipitates of the powder materials are decanted onto a filter, washed with water and ethanol, and dried in air.
Example 4
The self- standing cathode is made of a core- shell composite material. The core is made of a composite material with LMO/CNT-Gr ternary biomimetic structure according to example 1 or 2 and is provided with a shell based on polyaniline (PANI).
The method of preparation of this material consists in the fact that the composite material with a biomimetic structure prepared according to example 1 is subsequently modified with polyaniline by in situ polymerization so that the self- standing cathode of the composite material with a biomimetic structure is modified by a short exposure - for a period of 0.5 min into the monomer solution - 0.01M aniline and 0.001M o-phenylenediamine in 20 mL of 1 M H2SO4 and subsequent addition of a 0.01M ammonium persulfate solution in 10 ml 1 M H2SO4. After the synthesis of polyaniline in the solution, the self- standing cathode made of a composite material with a biomimetic structure is rinsed off with water and dried.
Industrial applicability
The composite material according to the invention, formed by the LMO/CNT- Gr ternary “tectonic plate-island bridge” biomimetic structure, is especially suitable for the cathodes of rechargeable lithium-ion aqueous batteries due to its unique properties.

Claims

C L A I M S Composite material with a biomimetic structure for the cathodes of lithium-ion aqueous rechargeable batteries, based on spinel lithium manganese oxide LiMmCC (LMO) and carbon nanotubes (CNT), characterized in that it is formed by LMO/CNT-Gr ternary “tectonic plate-island bridge” biomimetic structure, where the multilayered graphene (Gr) forms a “tectonic plate” substrate on which there are the “islands” of the LMO active material interconnected by a “bridge network” of multi-walled carbon nanotubes. Composite material according to claim 1, characterized in that the core formed by the LMO/CNT-Gr ternary biomimetic structure is provided with a shell based on polyaniline (PANI). he method of preparation of a composite material with a biomimetic structure according to claim 1, characterized in that 7.5 to 8.5 parts by weight of LMO, 0.5 to 1.0 parts by weight of CNT and 0.1 to 0.5 parts by weight of Gr in powder form is dispersed in an aqueous solution with an assisted surfactant, further, ultrasonic treatment is carried out for at least 30 min, followed by vacuum filtration, repeated washing with demineralized water and drying the composite material first in air and then in an oven at 90 to 120 °C for 4 to 12 h. he method according to claim 3, characterized in that the prepared composite material with a biomimetic structure is subsequently modified with polyaniline by in situ polymerization so that either the composite powder is dispersed in an aqueous medium, after which solutions of the monomer (aniline and o -phenylenediamine) in H2SO4 and ammonium persulfate also in H2SO4 or the self-supporting cathode made of a composite material with a biomimetic structure is modified by short-term exposure - for at least 0.5 min. into a solution of monomer - aniline and o -phenylenediamine in H2SO4 and ammonium persulfate also in H2SO4, after the synthesis of polyaniline in the solution, the precipitates of the powder materials are decanted onto a filter, washed with water and ethanol and air-dried, while the self- standing cathode made of a composite material with a biomimetic structure is rinsed with water and dried.
7
EP22859457.8A 2022-01-04 2022-12-31 Composite material with biomimetic structure for cathodes of lithium-ion aqueous rechargeable batteries and method of its preparation Pending EP4460855A1 (en)

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