EP4533505A2 - Use of multilayered nano-dispersed crystalline boron - Google Patents

Use of multilayered nano-dispersed crystalline boron

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Publication number
EP4533505A2
EP4533505A2 EP23738936.6A EP23738936A EP4533505A2 EP 4533505 A2 EP4533505 A2 EP 4533505A2 EP 23738936 A EP23738936 A EP 23738936A EP 4533505 A2 EP4533505 A2 EP 4533505A2
Authority
EP
European Patent Office
Prior art keywords
nano
multilayered
dispersed
carbon
crystalline boron
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
EP23738936.6A
Other languages
German (de)
French (fr)
Inventor
Ahmet Eymen AKSENER
Yurdanur TURKER
Koray Bahadir DONMEZ
Fatma Seniha GUNER
Mert Umut Ozkaynak
Nilgun KARATEPE YAVUZ
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.)
Istanbul Teknik Universitesi Bilimsel Arastirma Projeleri Birimi
Sabanci Universitesi
Original Assignee
Istanbul Teknik Universitesi Bilimsel Arastirma Projeleri Birimi
Sabanci Universitesi
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.)
Filing date
Publication date
Application filed by Istanbul Teknik Universitesi Bilimsel Arastirma Projeleri Birimi, Sabanci Universitesi filed Critical Istanbul Teknik Universitesi Bilimsel Arastirma Projeleri Birimi
Priority claimed from PCT/TR2023/050475 external-priority patent/WO2023229565A2/en
Publication of EP4533505A2 publication Critical patent/EP4533505A2/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes

Definitions

  • a supercapacitor has two electrodes and an electrolyte between the electrodes as a separator; energy is stored between the electrodes and the electrolyte.
  • the patent no. US 11075381B2 is related to a graphene sheet having a boron-doped anode part and to a sodium-ion battery comprising it.
  • the boron used therein is in the form of a boron-carbon compound.
  • Supercapacitor active material may be selected from a carbonbased active material such as graphene, carbon black, graphite, a single wall carbon nano-tube, a multi wall carbon nano-tube, active carbon, carbon nano-fibers, carbon fibers or a transition metal oxide such as NiCo2O4, MnC .
  • a material made of a mixture of more than one active material is also suitable for use with the multilayered, nano-dispersed, crystalline boron.
  • the composition to be applied to the surfaces comprises 5-80% graphene, 1-25% binder, for example PVDF (polyvinylidenefluoride) and 2-30% multilayered, nano-dispersed, crystalline boron by weight.
  • binder for example PVDF (polyvinylidenefluoride)
  • multilayered, nano-dispersed, crystalline boron by weight for example
  • the invention is also related to increasing efficiency of lithium-ion batteries.
  • the anode material of lithium-ion batteries is doped with the multilayered, nano-dispersed, crystalline boron.
  • the lithium-ion active material used in the composition of multilayered, nano-dispersed, crystalline boron may be selected from a carbon-based active material such as graphene, carbon black, graphite, a single wall carbon nano-tube, a multi wall carbon nano-tube, active carbon, carbon nano-fibers, carbon fibers.
  • the composition to be applied to the anode material comprises 5-90% graphite, 1-20% binder, 1-30% carbon black and 1-30% multilayered, nano-dispersed, crystalline boron by weight.
  • Figure 2 A view showing that the material is crystalline and the distance between atoms
  • Figure 3 A TEM analysis view of a multilayered, nano-dispersed, crystalline boron.
  • Figure 4 Result of an XRD analysis of multilayered, nano-dispersed, crystalline boron used
  • Figure 5 Cyclic voltammograms of supercapacitor cells with and without multilayered, nano-dispersed, crystalline boron doped
  • Figure 6 Electrochemical impedance spectra in the range of 100.000-0.01 Hz of supercapacitor cells with and without multilayered, nano-dispersed, crystalline boron doped
  • Figure 7 Galvanostatic charge-discharge curves of supercapacitor cells with and without multilayered, nano-dispersed, crystalline boron doped
  • Figure 8 Cyclic voltammograms, taken for example at the scan rate of 1 mV.s-1, of supercapacitor cells with multilayered, nano-dispersed, crystalline boron doped
  • Figure 9 Charge-discharge capacities of 50 cycles of Li-Ion cells with and without multilayered, nano-dispersed, crystalline boron doped
  • the invention is related to the use of a multilayered, nano-dispersed and crystalline boron material in energy storage systems or smart textiles.
  • the boron material of the invention is formulated with suitable binders and active materials, and applied to the current collector surfaces in energy storage, or fibers.
  • the suitable binders may be for example PVDF, PTFE, carboxy methyl cellulose, poly aery lie acid, styrene butadiene rubber, PTFE, LA 132, LA 133.
  • the active material although may vary depending on the intended use, may be selected from a carbon-based active material such as graphene, carbon black, graphite, a single wall carbon nano-tube, a multi wall carbon nano-tube, active carbon, carbon nano-fibers, carbon fibers or a transition metal oxide such as NiCoiCL, MnCE.
  • the electrodes in a supercapacitor which is one of the energy storage systems, are prepared with a capacitor active material that is doped with a multilayered, nanodispersed and crystalline boron material of invention ( Figure- 1).
  • the anode material is doped with a multilayered, nanodispersed and crystalline boron of the invention.
  • the multilayered, nano-dispersed and crystalline boron is applied to the fibers/fabrics chosen for the intended use. With said application, it is intended to dope the fibers with the multilayered, nano-dispersed and crystalline boron.
  • the multilayered, nano- dispersed and crystalline boron prepared is applied to the fibers preferably by soaking.
  • the fibers are endowed with the qualities of conductivity and energy storage, and the use of products such as garments, shoes, blankets, beds, etc. to be produced with these fibers, enhances the thermal comfort/conduction to the maximum extent possible.
  • a smart garment which serves to monitor human body functions, to measure signals such as heart rate, blood pressure and fever, it must be able to conduct electric current.
  • Such systems should have detectors, sensors, a processor to process the data output by sensors, and fibers suitable for providing a connection therebetween.
  • the multilayered, nano-dispersed and crystalline boron of invention serves to perform this function in smart textile products.
  • the multilayered, nano-dispersed and crystalline boron is doped to the energy storage systems or textile products in a pure form, at 0,001% to 38%, preferably 5% to 20%, more preferably, 8% to 15% by weight. In the most preferable embodiment of invention, it is doped at 11%.
  • the material coated onto the graphite foam in the preparation of a supercapacitor comprises the multilayered, nano-dispersed and crystalline boron, PVDF, carbon black and graphene.
  • This mixture is dispersed in solvents such as for example N-Methyl-2-Pyrrolidone (NMP), acetone, ethanol or water and the surfaces are covered with this by a suitable method for example by dripping onto the foam surfaces or applying with a spray.
  • NMP N-Methyl-2-Pyrrolidone
  • acetone acetone
  • ethanol ethanol
  • a preferred solvent is NMP.
  • said foam surfaces are covered with an active material as doped in accordance with this invention, in an amount ranging between 0.10 to 100 mg, preferably 0.25 to 40 mg, more preferably 0.50 to 30 mg per 1 cm 2 of a foam surface. In the most preferred embodiment, this amount ranges between 0.75 to 5 mg.
  • the foam surface area in the examples of invention is 0.95 cm 2 and only 1 mg conductive material has been applied thereon.
  • Tests show that a prototype supercapacitor doped in accordance with this invention has a higher specific capacitance than its equivalents without doping. The results of the tests also show that the supercapacitors doped with the multilayered, nanodispersed and crystalline boron are charged faster and discharged slower than those without doping.
  • Cellulose acetate, polyethylene, polypropylene, polypropylene/polyethylene/polypropylene (PP/PE/PP) or ceramic may be used as a separator.
  • the dispersion of multilayered, nano-dispersed and crystalline boron used in the scope of the invention, is prepared by acoustic cavitation, for example sonication.
  • the composition to be used for a lithium-ion battery comprises 5-90% graphite, 1-20% binder, 1-30% carbon black and 1-30% multilayered, nano-dispersed, crystalline boron by weight.
  • the composition comprises 10-70%, preferably 15-60% graphite, 2-15% binder, 4- 25%, preferably 5-15% carbon black and 2-25%, preferably 5-20% multilayered, nano-dispersed, crystalline boron by weight. Cyclic voltammetry and galvanostatic charge-discharge tests were made comparatively on the formulations with and without doping and showed that the doped formulation has a clearly higher specific capacity and a higher specific capacitance by about 40% than a conventional lithium-ion half cell.
  • a multilayered, nano-dispersed and crystalline boron of invention can be used in the production of the beds configured to adjust body temperature of a patient who needs to stay in bed for a long time, of the garments configured to facilitate monitoring vital functions of a patient who needs care at home or hospital, the garments configured to protect a fireman who performs a highly risks task like fire-fighting.
  • the invention also provides a method of preparation of a multilayered, nanodispersed and crystalline boron.
  • the method comprises the following steps. a) Powder boron is mixed with an organic solvent at a suitable temperature, speed and time. The temperature is preferably 22-36 °C, the speed is preferably a speed that can create a vortex, for example between 300 to 1200 rpm, and the time is preferably 60 to 120 minutes. As a result of this step, a homogeneous dispersion of boron is obtained. b) The resulting boron dispersion is heat-treated at a suitable temperature, preferably between 185 and 220°C, for 12 to 22 hours. c) The product of step b) is allowed to cool to the room temperature.
  • Powder boron and an organic solvent (acetone) is mixed in a ratio of 1 to 0,5 at 28 °C and at a speed to create vortex for 75 minutes and a homogeneous boron dispersion is formed.
  • the dispersion obtained is heat-treated at 195 °C for 16 hours and after that allowed to cool on its own.
  • the cooled dispersion is sonicated at 200 W for 6 hours (acoustic cavitation). Then the particles are allowed to precipitate overnight, supernatant is collected and then the dispersion is filtered.
  • the product obtained after filtration is heat-treated at a temperature of 180 °C for 12 hours. At the end of the process, a light yellow to dark brown product is obtained.
  • the graphics in Figure 6 show that the supercapacitors doped with the multilayered, nano-dispersed and crystalline boron are charged faster and discharged slower than those without doping.
  • PP/PE/PP was used as separator.
  • a lithium chip is selected as cathode to prepare batteries.
  • the formulation comprising 77% graphite, 10% PVDF and 10% carbon black, was doped with 3% multilayered, nano-dispersed and crystalline boron. Cyclic voltammetry and galvanostatic charge-discharge tests were made comparatively on the formulations with and without doping and the results were evaluated (Figure 8 and Figure 9).
  • FIGURE 1 A first figure.
  • N Specific current (mA g' 1 )

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention is related to the application of a multilayered, nano-dispersed and crystalline boron to the surfaces whose electrical and thermal qualities are desired to be improved, and to the compositions used for this purpose. Although principal use of this invention relates to the current collector surfaces within the supercapacitors and lithium-ion batteries, the materials of this invention are used for the applications that require an increase in thermal conductivity, for example as an additive for the textile fibers in smart textile applications.

Description

USE OF MULTILAYERED NANO-DISPERSED CRYSTALLINE BORON
Field of Invention
This invention is related to the use of multilayered, nano-dispersed crystalline boron in the energy storage systems (super-capacitors, lithium-ion batteries) and in those applications that require an increase in thermal conductivity, for example in the smart textile applications.
Background Art
As conventional energy sources such as natural gas and coal decrease, renewable energy sources are increasingly needed particularly during the last decades, which made energy storage one of the key technologies. Whether the energy obtained from natural and renewable sources like wind, sun and water, is utilized efficiently or not, depends on the ability to store it. Energy storage is important not only for the energy obtained from the renewable sources, but also for increasing the efficiency of the energy sources which are currently in use.
Today cells and batteries are the most commonly used energy storage units. In addition, capacitors and supercapacitors have gained interest increasingly due to their inherent advantages. Batteries ensure that the electric energy is stored in the form of a chemical energy and re-converted into electric energy when needed. Batteries like zinc-carbon or zinc-chloride can not be recharged, however batteries like lithium ion or nickel-cadmium are recharged and used repeatedly. Supercapacitors, the so-called ultracapacitors, are characterized in their ability to charge and discharge very fast. Also their energy storage capacity is much higher than the batteries. A supercapacitor has two electrodes and an electrolyte between the electrodes as a separator; energy is stored between the electrodes and the electrolyte.
The particular electrode active materials used have a great impact on the performance of a supercapacitor. Carbon-based materials (graphite, carbon black, graphene) are preferably used as active materials for the commercial supercapacitors. In the process of preparation of supercapacitor electrodes, the active material is treated with conventional binders selected and is coated onto the current collector surfaces.
In known state of art, the so-called boron-doped system comprises a structure where boron binds to carbon via a covalent bond.
The patent document no. CN113130878A is related to a method of making a negative electrode material for a lithium ion battery and to the technical field of use of solid waste sources, particularly to the preparation method and application of boron-doped silicon-based negative electrode material. In the preparation method of boron-doped silicon-based negative electrode material, the conductive agent may be selected from carbon black, graphene, carbon nano tubes, and the binder may be selected from PVDF, CMC, PAA, LA 133, sodium alginate, CMC + SBR. A so- called boron-doped system seemingly denotes a structure where boron binds to silicon via a covalent bond. Also it is mentioned that the boron used for formulation is mixed with carbon. The patent no. US 11075381B2 is related to a graphene sheet having a boron-doped anode part and to a sodium-ion battery comprising it. The boron used therein is in the form of a boron-carbon compound.
Smart textile applications constitute another field which may be associated with energy storage.. Smart textile is a progressing technology which can be defined as textile products that can sense and respond to ambient changes. Ambient changes include, but not limited to, changes in heat, temperature, pressure, sound, movement, etc. Temperature control is a key factor in this technology. In order to produce a material for a garment or bed which senses the ambient temperature and any changes therein and adopts itself thereto to keep the user at the same temperature, thermal energy needs to be stored.
Consequently, there is an ongoing need to increase efficiency of energy storage systems, particularly supercapacitors and also to improve smart textile products.
Summary of the Invention
An object of this invention is to increase efficiency and effectiveness of the energy storage systems. In order to achieve this object, a novel material has been contemplated to be used in the preparation process of storage systems.
In the main embodiment of the invention, a multilayered, nano-dispersed and crystalline boron material is applied to those surfaces whose electrical and thermal qualities are desired to be improved. Although principal use of this invention relates to the current collector surfaces within the supercapacitors and lithium-ion batteries, it is also possible to use the materials of this invention for the purpose of applications that require an increase in thermal conductivity, for example as an additive for the textile fibers in smart textile applications. In an embodiment of this invention, the multilayered, nano-dispersed and crystalline boron is doped with a conventional supercapacitor active material to be used in supercapacitors. Supercapacitor active material may be selected from a carbonbased active material such as graphene, carbon black, graphite, a single wall carbon nano-tube, a multi wall carbon nano-tube, active carbon, carbon nano-fibers, carbon fibers or a transition metal oxide such as NiCo2O4, MnC . According to this invention, a material made of a mixture of more than one active material is also suitable for use with the multilayered, nano-dispersed, crystalline boron.
In a preferred embodiment of invention, said active material is graphene. In another preferred embodiment of invention, the active material is carbon black or a mixture thereof with graphene.
In a preferred embodiment of invention, the composition to be applied to the surfaces comprises 5-80% graphene, 1-25% binder, for example PVDF (polyvinylidenefluoride) and 2-30% multilayered, nano-dispersed, crystalline boron by weight.
In another preferred embodiment of invention, the composition to be applied to the surfaces comprises 1-30% carbon black, 5-70% graphene, 1-25% binder, for example PVDF and 2-30% multilayered, nano-dispersed, crystalline boron by weight.
The invention is also related to increasing efficiency of lithium-ion batteries. Accordingly, in one embodiment, the anode material of lithium-ion batteries is doped with the multilayered, nano-dispersed, crystalline boron. The lithium-ion active material used in the composition of multilayered, nano-dispersed, crystalline boron may be selected from a carbon-based active material such as graphene, carbon black, graphite, a single wall carbon nano-tube, a multi wall carbon nano-tube, active carbon, carbon nano-fibers, carbon fibers.
In a preferred embodiment, the composition to be applied to the anode material comprises 5-90% graphite, 1-20% binder, 1-30% carbon black and 1-30% multilayered, nano-dispersed, crystalline boron by weight.
Another embodiment of the invention is the smart textile applications. Here, the multilayered, nano-dispersed, crystalline boron is applied to the textile fibers to give the fibers and the fabrics to be made therefrom the energy storage or conduction qualities. Accordingly, a composition comprising the multilayered, nano-dispersed, crystalline boron is applied to the fiber or the fabric as required for the intended use, by impregnation preferably through soaking or by coating onto the surface.
Description of the Figures
The drawings which are necessary to provide a better understanding of the subject of the invention and descriptions thereof are as follows.
Figure 1 : A representative scheme of the supercapacitor prepared
Figure 2: A view showing that the material is crystalline and the distance between atoms
Figure 3: A TEM analysis view of a multilayered, nano-dispersed, crystalline boron. Figure 4: Result of an XRD analysis of multilayered, nano-dispersed, crystalline boron used
Figure 5: Cyclic voltammograms of supercapacitor cells with and without multilayered, nano-dispersed, crystalline boron doped Figure 6: Electrochemical impedance spectra in the range of 100.000-0.01 Hz of supercapacitor cells with and without multilayered, nano-dispersed, crystalline boron doped
Figure 7: Galvanostatic charge-discharge curves of supercapacitor cells with and without multilayered, nano-dispersed, crystalline boron doped
Figure 8: Cyclic voltammograms, taken for example at the scan rate of 1 mV.s-1, of supercapacitor cells with multilayered, nano-dispersed, crystalline boron doped Figure 9: Charge-discharge capacities of 50 cycles of Li-Ion cells with and without multilayered, nano-dispersed, crystalline boron doped
Figure 10: Change in Coulomb efficiency with the number of cycles, obtained as a result of galvanostatic charge-discharge tests
Detailed Description of the Invention
The invention is related to the use of a multilayered, nano-dispersed and crystalline boron material in energy storage systems or smart textiles. The boron material of the invention is formulated with suitable binders and active materials, and applied to the current collector surfaces in energy storage, or fibers.
As used herein, the suitable binders may be for example PVDF, PTFE, carboxy methyl cellulose, poly aery lie acid, styrene butadiene rubber, PTFE, LA 132, LA 133.
The active material, although may vary depending on the intended use, may be selected from a carbon-based active material such as graphene, carbon black, graphite, a single wall carbon nano-tube, a multi wall carbon nano-tube, active carbon, carbon nano-fibers, carbon fibers or a transition metal oxide such as NiCoiCL, MnCE. The electrodes in a supercapacitor which is one of the energy storage systems, are prepared with a capacitor active material that is doped with a multilayered, nanodispersed and crystalline boron material of invention (Figure- 1). In the case of lithium-ion batteries, the anode material is doped with a multilayered, nanodispersed and crystalline boron of the invention.
The supercapacitors and lithium-ion batteries produced with an active material doped with a multilayered, nano-dispersed and crystalline boron material of invention, give a higher Coulomb efficiency, a higher specific capacitance and an increased energy density than the conventional active materials used as a reference material.
In terms of smart textile applications, which is another embodiment of invention, the multilayered, nano-dispersed and crystalline boron is applied to the fibers/fabrics chosen for the intended use. With said application, it is intended to dope the fibers with the multilayered, nano-dispersed and crystalline boron. The multilayered, nano- dispersed and crystalline boron prepared is applied to the fibers preferably by soaking.
Thereby the fibers are endowed with the qualities of conductivity and energy storage, and the use of products such as garments, shoes, blankets, beds, etc. to be produced with these fibers, enhances the thermal comfort/conduction to the maximum extent possible.
Further in the field of medicine, for a smart garment which serves to monitor human body functions, to measure signals such as heart rate, blood pressure and fever, it must be able to conduct electric current. Such systems should have detectors, sensors, a processor to process the data output by sensors, and fibers suitable for providing a connection therebetween. The multilayered, nano-dispersed and crystalline boron of invention serves to perform this function in smart textile products.
Notably, the multilayered, nano-dispersed and crystalline boron material of this invention has all of three qualities mentioned hereabove. In other words, what makes the material of invention a special one, is that it has a multilayered structure, is nanodispersed (distribution of nano-sized particles) and has a crystalline structure. In terms of practical use, when a dispersion of nano-sized boron and a solvent, preferably acetone, DMF, IPA, ethylene or methylene, is mixed with powder materials, for example carbon black and/or graphene, the liquid component of the dispersion brings with it the nano-particles to everywhere it reaches and can be mixed uniformly with the powder materials, which facilitate the application thereof to the surfaces.
In an embodiment of invention, the multilayered, nano-dispersed and crystalline boron is doped to the energy storage systems or textile products in a pure form, at 0,001% to 38%, preferably 5% to 20%, more preferably, 8% to 15% by weight. In the most preferable embodiment of invention, it is doped at 11%.
In an embodiment of invention, the material coated onto the graphite foam in the preparation of a supercapacitor, comprises the multilayered, nano-dispersed and crystalline boron, PVDF, carbon black and graphene. This mixture is dispersed in solvents such as for example N-Methyl-2-Pyrrolidone (NMP), acetone, ethanol or water and the surfaces are covered with this by a suitable method for example by dripping onto the foam surfaces or applying with a spray. A preferred solvent is NMP.
In a preferred embodiment, said foam surfaces are covered with an active material as doped in accordance with this invention, in an amount ranging between 0.10 to 100 mg, preferably 0.25 to 40 mg, more preferably 0.50 to 30 mg per 1 cm2 of a foam surface. In the most preferred embodiment, this amount ranges between 0.75 to 5 mg. The foam surface area in the examples of invention is 0.95 cm2 and only 1 mg conductive material has been applied thereon.
In some embodiments of invention, PVDF is used as a binder and carbon black is used as a filler that bridges between the active elements during the preparation of an electrode. NMP is used to disperse the prepared mixture. Also water or any other solvent which may create a dispersion of materials involved, may be used instead of NMP. Graphene is used as an active material of electrode. Graphite foam and acid electrolyte are used to prepare supercapacitor cells. The multilayered, nanodispersed and crystalline boron is used as an additive to enhance the activity of the electrode active material.
In addition to foregoing and in a preferred embodiment of invention, carbon black may be used as an active material, alone or together with any other active materials. However, a combined use of graphene and carbon black gives the highest performance. The invention achieves its objectives also when each of the active materials mentioned above is used alone.
Tests show that a prototype supercapacitor doped in accordance with this invention has a higher specific capacitance than its equivalents without doping. The results of the tests also show that the supercapacitors doped with the multilayered, nanodispersed and crystalline boron are charged faster and discharged slower than those without doping.
An active material comprising 11% carbon black, 11% PVDF and 67% graphene and doped with the multilayered, nano-dispersed and crystalline boron at 11 % by mass, displayed the highest performance for the purpose of this invention. For the tests, the supercapacitor electrodes without doping were prepared with an NMP dispersion comprising 11% PVDF, 11% carbon black and 78% graphene by mass. Graphite foam and acid electrolyte are used to prepare supercapacitor cells. Graphite foam surface is covered with graphene and a filter paper is disposed between two foams as a separator before the cell is closed. Cellulose acetate, polyethylene, polypropylene, polypropylene/polyethylene/polypropylene (PP/PE/PP) or ceramic may be used as a separator. The dispersion of multilayered, nano-dispersed and crystalline boron used in the scope of the invention, is prepared by acoustic cavitation, for example sonication.
Results of a scaled TEM analysis give information about the sizes and the structure made of more than one layer. Figure-2 shows that the material has a crystal structure and distance between atoms is 0,39nm and Figure-3 shows that the structure is made of layers and is 4-7 layered regionally.
The commercial graphite chosen as an anode material for preparation of lithium-ion batteries of invention, is doped with the multilayered, nano-dispersed and crystalline boron. Other commercial anode materials such as MCMB, AGP-2/S360, 518/918, LTO, Si-C may be used instead of graphite. Here lithium, for example lithium hexafluorophosphate may be used as electrolyte. To prepare the batteries, for example a lithium chip is selected as a cathode. Other cathode materials such as NMC, LCO, LMO, LFPP, NCA may be used instead of the lithium chip.
In an embodiment of invention, the composition to be used for a lithium-ion battery comprises 5-90% graphite, 1-20% binder, 1-30% carbon black and 1-30% multilayered, nano-dispersed, crystalline boron by weight. In another embodiment, the composition comprises 10-70%, preferably 15-60% graphite, 2-15% binder, 4- 25%, preferably 5-15% carbon black and 2-25%, preferably 5-20% multilayered, nano-dispersed, crystalline boron by weight. Cyclic voltammetry and galvanostatic charge-discharge tests were made comparatively on the formulations with and without doping and showed that the doped formulation has a clearly higher specific capacity and a higher specific capacitance by about 40% than a conventional lithium-ion half cell.
In the smart textile applications of invention, the fabric or fiber as desired, comprises the multilayered, nano-dispersed and crystalline boron composition. Here, the composition of multilayered, nano-dispersed, crystalline boron, may comprise as an active material a carbon-based active material such as for example graphene, carbon black, graphite, a single wall carbon nano-tube, a multi wall carbon nano-tube, active carbon, carbon nano-fibers, carbon fibers or a transition metal oxide. The composition of invention which is most preferred for textile application, comprises 1-60% graphene, 1-25% binder, for example PVDF and 0.25-40% multilayered, nano-dispersed, crystalline boron by weight. Here in the mixture, the ratio of graphene is preferably between 5 and 30%, the ratio of binder is preferably between 2 and 15% and the ratio of the multilayered, nano-dispersed and crystalline boron is preferably between 4 and 25%.
Said compositions of multilayered, nano-dispersed and crystalline boron are applied to the fabric or fibers by soaking.
In an embodiment of invention, the fibers to be used may be one of the vegetable fibers (such as cotton, linen, bamboo), animal fibers (such as wool, angora, silk) or artificial fibers (such as carbon fiber, glass fiber, viscose, acetate, polyamide, polyester, polyolefin, polyvinyl fibers).
Use of the invention in smart textile applications is quite versatile. For example a multilayered, nano-dispersed and crystalline boron of invention can be used in the production of the beds configured to adjust body temperature of a patient who needs to stay in bed for a long time, of the garments configured to facilitate monitoring vital functions of a patient who needs care at home or hospital, the garments configured to protect a fireman who performs a highly risks task like fire-fighting.
The invention also provides a method of preparation of a multilayered, nanodispersed and crystalline boron. The method comprises the following steps. a) Powder boron is mixed with an organic solvent at a suitable temperature, speed and time. The temperature is preferably 22-36 °C, the speed is preferably a speed that can create a vortex, for example between 300 to 1200 rpm, and the time is preferably 60 to 120 minutes. As a result of this step, a homogeneous dispersion of boron is obtained. b) The resulting boron dispersion is heat-treated at a suitable temperature, preferably between 185 and 220°C, for 12 to 22 hours. c) The product of step b) is allowed to cool to the room temperature. d) The cooled dispersion is sonicated in the range of 150 to 455 W, preferably for 2 to 6 hours. e) Then the particles are allowed to precipitate overnight. f) Supernatant is collected. g) Dispersion is filtered. h) The product obtained after filtration is heat-treated at a temperature of 160 to 190 °C, for a suitable time, preferably 12 hours.
The XRD results of multilayered, nano-dispersed and crystalline boron of invention are given in Figure 4. Examples
Preparation of multilayered, nano-dispersed and crystalline boron of invention:
Powder boron and an organic solvent (acetone) is mixed in a ratio of 1 to 0,5 at 28 °C and at a speed to create vortex for 75 minutes and a homogeneous boron dispersion is formed. The dispersion obtained is heat-treated at 195 °C for 16 hours and after that allowed to cool on its own. The cooled dispersion is sonicated at 200 W for 6 hours (acoustic cavitation). Then the particles are allowed to precipitate overnight, supernatant is collected and then the dispersion is filtered. The product obtained after filtration is heat-treated at a temperature of 180 °C for 12 hours. At the end of the process, a light yellow to dark brown product is obtained.
Preparation of supercapacitors and tests:
As a conventional supercapacitor active material, PVDF, carbon black and graphene, are doped with multilayered, nano-dispersed and crystalline boron prepared according to invention. The mixture is prepared so as to comprise 11% multilayered, nano-dispersed and crystalline boron, 11 % carbon black, 11 % PVDF and 67% graphene by mass. The prepared mixture is dispersed in NMP. A commercially available foam material is cut in pieces with a surface area of 0.95 cm2, then each piece of foam is coated with the conductive material by dripping only 1 mg conductive material per one surface. A cellulose acetate filter paper is disposed between two pieces of foam coated as a separator to create a supercapacitor cell.
The supercapacitors were subjected comparatively to the cyclic voltammetry, electrochemical impedance spectroscopy and cyclic charge-discharge performance tests. For the comparison, the supercapacitor electrodes without doping were used. The comparative electrodes were prepared with an NMP dispersion comprising 11% PVDF, 11% carbon black and 78% graphene by mass.
The cyclic voltammograms as shown in Figure 5 reveal that the prototype supercapacitor with doping has a higher specific capacitance than the one without doping.
The graphics in Figure 6 show that the supercapacitors doped with the multilayered, nano-dispersed and crystalline boron are charged faster and discharged slower than those without doping.
The impedance spectra as shown in Figure 7 show that the charge transfer resistance is lower in the electrodes with doping than those without doping. This suggests that the electron transfer takes place more easily in the supercapacitors with doping than the conventional ones.
Preparation of lithium-ion batteries and tests:
A commercially available graphite which is selected as an anode material for a lithium-ion battery, was doped with the multilayered, nano-dispersed and crystalline boron of invention and 1 M of lithium hexafluorophosphate was used as electrolyte. In the preparation of batteries, PP/PE/PP was used as separator. A lithium chip is selected as cathode to prepare batteries. The formulation comprising 77% graphite, 10% PVDF and 10% carbon black, was doped with 3% multilayered, nano-dispersed and crystalline boron. Cyclic voltammetry and galvanostatic charge-discharge tests were made comparatively on the formulations with and without doping and the results were evaluated (Figure 8 and Figure 9). The values obtained from the galvanostatic charge-discharge tests show that the specific capacity is about 150 mA h/g for the conventional lithium-ion half cell and about 210 mA h/g for the doped half cell, so the latter provides an about 40% higher specific capacitance than the conventional half cell without doping (Figure 9/25. Based on cyclic values).
The Coulomb efficiency value is 98% for the conventional cell while it increased to 99,8% in the doped cell (Figure-10)
NOMENCLATURE FOR FIGURES
FIGURE 1
A= Positive Electrode
B= Negative Electrode
C= Current Collector
D= Electrode Material + Active Material
E= Separator / Electrolyte
FIGURE 4
F= Numbers
G= Diffraction angles (2 teta) (Coupled TwoTheta/Theta) WL= 1.54060
FIGURE 5
H= Current (A/g)
1= Voltage
FIGURE 6
J= Zim (ohm)
K= Zre (ohm)
FIGURE 7
L= Charge and discharge
M= Time (h)
FIGURE 8
N= Specific current (mA g'1)
0= Cycle
P= Li/Li+ against potential (V) FIGURE 9
R= Specific capacity (mAh/g)
S= Control sample - Lithiation
T= Control sample - Delithiation
U= Sample X - Lithiation
V= Sample X - Delithiation
Y= Number of cycles
FIGURE 10
Z= Coulomb efficiency (%)
A l = Control sample
B 1= Sample X

Claims

1. A composition of multilayered, nano-dispersed and crystalline boron, comprising as an active material a carbon-based active material such as graphene, carbon black, graphite, a single wall carbon nano-tube, a multi wall carbon nano-tube, active carbon, carbon nano-fibers, carbon fibers or a transition metal oxide such as NiCoiC , MnOi.
2. A composition according to Claim 1, comprising graphene or carbon black or a combination thereof as an active material.
3. A composition according to Claim 1, comprising graphite as an active material.
4. A composition according to any one of Claims 1 to 3, further comprising a binder.
5. A composition according to Claim 4, wherein the binder is selected from PVDF, PTFE, carboxy methyl cellulose and polyacrylic acid.
6. A composition according to any one of Claims 1 to 5, comprising 0,001% to 38% multilayered, nano-dispersed, crystalline boron by weight.
7. A composition according to any one of Claims 4 to 6, comprising 1-30% carbon black, 5-70% graphene, 1-25% binder, 2-30% multilayered, nano- dispersed, crystalline boron by weight.
8. A composition according to any one of Claims 4 to 6, comprising 5-90% graphite, 1-20% binder, 1-30% carbon black and 1-30% multilayered, nano- dispersed, crystalline boron by weight.
9. Use of the multilayered, nano-dispersed, crystalline boron in energy storage systems.
10. Use according to Claim 9, wherein the energy storage system is a supercapacitor.
11. Use according to Claim 9 or 10, wherein said composition of multilayered, nanodispersed, crystalline boron is a composition as claimed in Claims 1 to 8.
12. Use according to Claim 9, wherein the energy storage system is a lithium-ion battery.
13. Use according to Claim 12, wherein said composition of multilayered, nanodispersed, crystalline boron comprises a carbon-based active material such as graphene, carbon black, graphite, a single wall carbon nano-tube, a multi wall carbon nano-tube, active carbon, carbon nano-fibers, carbon fibers as an active material.
14. A flexible electrode comprising the multilayered, nano-dispersed, crystalline boron.
15. A flexible electrode according to Claim 14, wherein said composition of multilayered, nano-dispersed, crystalline boron is a composition as claimed in Claims 1 to 8.
16. Use of a flexible electrode according to Claim 14 or 15 in the energy storage systems or smart textile applications.
17. A supercapacitor, characterized in that; a positive electrode ( 1 ) and a negative electrode (2) wherein its surfaces facing each other are coated with a composition of multilayered, nano-dispersed, crystalline boron, an electrolyte (4) provided between the positive electrode ( 1 ) and the negative electrode (2), one or more separators (3) that separate positive electrode (1) and negative electrode (2) physically.
18. A lithium-ion battery, characterized in that it comprises; an electrode coated with a composition of multilayered, nano-dispersed, crystalline boron, an electrolyte provided between the positive and the negative electrode, one or more separators that separate positive and negative electrode physically.
19. A fabric, characterized in that it comprises the composition of multilayered, nano-dispersed, crystalline boron.
20. A fabric according to Claim 19, wherein the composition of multilayered, nano- dispersed, crystalline boron comprises an active material.
21. A fabric according to Claim 20, wherein said active material comprises a carbon-based active material such as graphene, carbon black, graphite, a single wall carbon nano-tube, a multi wall carbon nano-tube, active carbon, carbon nano-fibers, carbon fibers or a transition metal oxide such as NiCoiC , MnC .
22. A method of producing the multilayered, nano-dispersed, crystalline boron, comprising the following steps: a) Powder boron is mixed with an organic solvent at a suitable temperature, speed and time, b) Resulting boron dispersion is heat-treated at a suitable temperature, c) Product of step b) is allowed to cool to the room temperature, d) Cooled dispersion is sonicated, e) Sonicated dispersion is left untreated overnight to allow particles to precipitate, f) Supernatant is collected, g) Dispersion is filtered.
EP23738936.6A 2022-05-26 2023-05-25 Use of multilayered nano-dispersed crystalline boron Pending EP4533505A2 (en)

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PCT/TR2023/050475 WO2023229565A2 (en) 2022-05-26 2023-05-25 Use of multilayered nano-dispersed crystalline boron

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