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WO2018070969A2 - Électrode d'anode et source d'énergie produite à partir de celle-ci - Google Patents

Électrode d'anode et source d'énergie produite à partir de celle-ci Download PDF

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Publication number
WO2018070969A2
WO2018070969A2 PCT/TR2017/050425 TR2017050425W WO2018070969A2 WO 2018070969 A2 WO2018070969 A2 WO 2018070969A2 TR 2017050425 W TR2017050425 W TR 2017050425W WO 2018070969 A2 WO2018070969 A2 WO 2018070969A2
Authority
WO
WIPO (PCT)
Prior art keywords
anode
lead
carbon aerogel
power source
graphene
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.)
Ceased
Application number
PCT/TR2017/050425
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English (en)
Other versions
WO2018070969A3 (fr
Inventor
Ahmet ÖZKAN
Münevver Aslı DAI
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.)
Solena Enerji Ueretim Sanayi Ve Dis Ticaret Ltd Sirketi
Original Assignee
Solena Enerji Ueretim Sanayi Ve Dis Ticaret Ltd Sirketi
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 Solena Enerji Ueretim Sanayi Ve Dis Ticaret Ltd Sirketi filed Critical Solena Enerji Ueretim Sanayi Ve Dis Ticaret Ltd Sirketi
Publication of WO2018070969A2 publication Critical patent/WO2018070969A2/fr
Publication of WO2018070969A3 publication Critical patent/WO2018070969A3/fr
Anticipated expiration legal-status Critical
Ceased 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
    • H01M4/14—Electrodes for lead-acid accumulators
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • 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
    • H01M2004/027—Negative 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

Definitions

  • This invention is related to an anode electrode developed by using carbon aerogel or graphene added carbon aerogel for being used in power sources such as battery, accumulator.
  • porous materials Because there are many superior properties of porous materials, they are preferred to be used in a wide variety of processes in the technology. Because of their wide usage area, new research are made day by day on porous materials. Carbon based materials are the most commonly used porous materials. They have high surface area.
  • the graphene has a meso-porous structure and has a substantially wide surface area. Because of this property, its ion holding feature is quite good and it shows capacitor property and it can store energy better. Also, because the ion conduction accelerates due to the conductivity of the graphene, the charging time of the power source reduces by using this structure in a power source.
  • carbon structured graphene material has many useful features such as high mechanical strength, very high electron mobility and high thermal conductivity. Besides all these, the graphene is used as electrode material in the production of long-life power sources (like lead- acid accumulator, lithium-ion accumulator). During the usage of lead-acid accumulators developed by using only graphene material, the efficiency of these accumulators decreases in time because their structures change. When only graphene is used as the anode material in the studies performed, the performance increases a little but this performance does not remain stable. Its reason is that the graphene does not show the property of sponge structure and so it is exposed to microcracks after 4-5 cycles in the ion inlet and outlet. These microcracks in the anode material in which only graphene is used are problem in terms of performance loss. Loss of performance of power resources over time is a big problem when the usage area of the power resources is considered.
  • the sulfation of the lead in the anode creates a significant problem.
  • Sulphate ions that accumulate on lead plaques cause sulphation and sulphate ions prevent the lead plaques to store energy.
  • the sulphate ions which cause the sulfation separate from the electrolyte medium and hold on to the surface of the lead plaque in the discharge process and that's why these accumulators are discharged by themselves.
  • This holding ends with charging of the accumulator and the same ions leave the lead materials and enter again into the electrolyte medium. This cyclic movement repeats as long as the accumulator is charged and discharged.
  • the main problems in the existing lead-acid accumulators are that the ion holding capacity is low, the discharging time after charging is short, the problem of sulphation and the accumulator is heavy. Besides all these, another problem is that the lead in the lead acid accumulator structure in the market damages the environment.
  • Aerogels are porous synthetic materials obtained by gas exchange of liquid component of gels. Aerogels which is an insulator material have more superior properties than other known insulating materials. In addition to these, aerogels have light transmitting structures. All these features make aerogels distinguish from existing materials.
  • the aim of this invention is to realize an anode electrode to remove the problem of reducing efficiency caused by sulphation in power sources and to increase their performance and lifetime.
  • the problem of efficiency reduce in power sources caused by anode sulphation is solved.
  • the anode is made of only carbon aerogel material or only graphene added carbon material so it is cleared of lead material in the invention.
  • anode is made such that it consists of two parts, therefore the amount of lead material in the anode is reduced.
  • the sponge structure in the anode remains stable by using carbon aerogel or graphene added carbon aerogel in the invention on the purpose of preventing the cracks formed by using only graphene in the anode and, thus it is aimed that cracks which may form are prevented and the amount of ions stored is increased via the sponge structure.
  • the anode produced from the graphene added carbon aerogel material obtained by using the sponge structured, insulator aerogel and graphene together remains stable, has long-life and the current passing through the anode does not lose efficiency.
  • the anode is also a super lightweight element with the materials produced.
  • the power source is very light with the graphene added aerogel used in lead-acid accumulators.
  • the amount of lead holding ions decreases due to the sulphate ions holding to the lead material used in the anode and thus the lead is sulphated over time. Therefore, the lead part of the anode becomes useless after some time.
  • the current trying to go to the sulphated lead material from the carbon aerogel or graphene added carbon aerogel material is cut by connecting a diode to the part in which the lead material is present so that the carbon aerogel or graphene added carbon aerogel materials do not feed the lead material in this time.
  • the anode consists of only graphene added carbon aerogel material to remove the efficiency reduction due to the sulphation in power sources and to enhance the performance of power sources.
  • the anode used in the power source consists of only graphene added carbon aerogel material in order to obtain a power source which is light, conductive, fast charged, and has high capacity and discharge time increased.
  • the anode in order to remove the efficiency reduction due to sulphation in power sources and to improve the performance of power sources, the anode comprises a first part and a second part and the first part is formed from graphene added carbon aerogel material and the second part is formed from lead material, such that these two parts are connected electrically parallel to each other.
  • the diode which the anode comprises is connected between the first and second parts and prevents the flow of the circuit current from the first part to the second part as a result of becoming useless of the lead with the sulphation of the lead material in the second part due to sulphate ions and provides unidirectional flow of the circuit current through the graphene added carbon aerogel element.
  • the anode used in the power source comprises a first part and a second part and the first part is formed from graphene added carbon aerogel material and the second part is formed from lead material such that these two parts are connected electrically parallel to each other.
  • the diode which the anode comprises is connected between the first and second parts and prevents the flow of the circuit current from the first part to the second part as a result of becoming useless of the lead with the sulphation of the lead material in the second part due to sulphate ions and provides unidirectional flow of the circuit current through the graphene added carbon aerogel element.
  • the anode consists of only carbon aerogel material in order to remove the efficiency reduction due to sulphation in power sources and to enhance the performance of the power sources.
  • the anode used in the power source consists of only carbon aerogel material in order to obtain a power source which is light, conductive, fast charged and which has high capacity and discharge time increased.
  • the anode in order to remove the efficiency reduction due to sulphation in power sources and to improve the performance of power sources, the anode comprises a first part and a second part and the first part is formed from carbon aerogel material and the second part is formed from lead material, such that these two parts are connected electrically parallel to each other.
  • the diode which the anode comprises is connected between the first and second parts and prevents the flow of the circuit current from the first part to the second part as a result of becoming useless of the lead with the sulphation of the lead material in the second part due to sulphate ions and provides unidirectional flow of the circuit current through the carbon aerogel element.
  • the anode used in the power source comprises a first part and a second part and the first part is formed from carbon aerogel material and the second part is formed from lead material such that these two parts are connected electrically parallel to each other.
  • the diode which the anode comprises is connected between the first and second parts and prevents the flow of the circuit current from the first part to the second part as a result of becoming useless of the lead with the sulphation of the lead material in the second part due to sulphate ions and provides unidirectional flow of the circuit current through the carbon aerogel element.
  • the anode obtained with the invention is produced especially for use in lead-acid accumulators and in embodiments wherein the power source is the lead-acid accumulator.
  • the anode consists of graphene material and/or graphene oxide material and/or graphene added carbon aerogel material and/or carbon aerogel material.
  • the anode formed is carbon nanotube structured.
  • Figure 1 It is a symbolic view of a battery structure used in the prior art.
  • Figure 2 It is a symbolic view of a battery structure in which the anode in the graphene- added carbon aerogel structure is used.
  • Figure 3 It is a symbolic view of a battery structure in which the anode in the hybrid graphene - added carbon aerogel-lead structure and the diode connected with this anode are used.
  • Figure 4 It is a symbolic view of a battery structure in which the anode in the carbon aerogel structure is used.
  • Figure 5 It is a symbolic view of a battery structure in which the anode in the hybrid carbon aerogel-lead structure and the diode connected with this anode are used.
  • Figure 6 It is a symbolic view of a battery structure in the electrolyte medium in which the anode in the hybrid graphene- added carbon aerogel-lead structure and the diode connected with this anode are used.
  • Figure 7 It is a symbolic view of a battery structure in the electrolyte medium in which the anode in the hybrid carbon aerogel-lead structure and the diode connected with this anode are used. Description of the references in the figures:
  • the power source(l) comprises an anode(10), a cathode(20) and a separator(30) between the anode(10) and the cathode(20) which separates them.
  • the anode(10) is an element which may be in a plaque form or in another shape or structure.
  • the anode(10) consists of only graphene added carbon aerogel material(lOl).
  • the anode(10) comprises a first part and a second part.
  • the first part and the second part are connected electrically parallel to each other.
  • the first part comprises a graphene added carbon aerogel element and the second part comprises a lead element.
  • the graphene added carbon aerogel element consists of the graphene added carbon aerogel material(lOl).
  • a schematic power source(l) structure is seen for this embodiment of the invention.
  • the cathode(20) consists of the lead oxide material(200).
  • the lead material(lOO) in the second part is sulphated during operation of the power source(l) after some time and then becomes unusable. Therefore, the lifetime of the lead material(lOO) ends.
  • the circuit current tries to flow from the first part to the second part.
  • the anode(lO) comprises a diode(40) connected between the first and second part, which prevents the flow of the circuit current from the first part to the second part in this alternative.
  • the diode(40) provides circuit current to flow through the graphene added carbon aerogel element in one direction.
  • the circuit current flows only through the graphene added carbon aerogel material(lOl). That's why, the power source(l) is provided to be a longer-lasting energy source by preventing leakage currents.
  • parallel connected materials form a hybrid structure.
  • the anode(lO) consists of only carbon aerogel material(102).
  • a power source(l) structure in which the anode(lO) is carbon aerogel material(102) and the cathode(20) is lead oxide material(200) is seen.
  • the carbon aerogel material(102) does not comprise the lead material(lOO).
  • the anode(lO) comprises a first part and a second part.
  • the first part and the second part are connected parallel to each other.
  • the first part comprises a carbon aerogel element and the second part comprises a lead element.
  • the carbon aerogel element is formed from the carbon aerogel material(102).
  • a schematic power source(l) structure is seen for this embodiment of the invention.
  • the cathode(20) is formed from the lead oxide material(200).
  • the lead material(lOO) in the second part is sulphated during operation of the power source(l) after some time and becomes unusable after some time. Therefore, the lifetime of the lead material(lOO) ends.
  • the anode(10) comprises a diode(40) connected between the first and second part, which prevents the flow of the current from the first part to the second part in this alternative.
  • the diode(40) provides the circuit current to flow through the carbon aerogel material(102) in one direction.
  • the circuit current passes only through the graphene added carbon aerogel material(lOl). That's why, the power source(l) is provided to be a longer-lasting energy source by preventing leakage currents.
  • the parallel connected materials form the hybrid structure.
  • the problem caused by the sulphation of the lead material(lOO) used in the anode(10) over time and by becoming unusable of the lead material(lOO) after a while is solved by the invention.
  • the graphene added carbon aerogel material(lOl) for use in the anode(lO) is synthesized by using the pyrolysis and sol-gel(Sol-Gel) methods in the same process. Firstly, the graphene added carbon aerogel synthesis is carried out by using graphene oxide during the aerogel synthesis. A solution comprising resorcinol, formaldehyde and sodium carbonate as catalyst is prepared.
  • graphene oxide added R-F aerogel is obtained by performing the sol-gel process. Then the pyrolysis process is applied. While the graphene oxide is being transformed into graphene with the pyrolysis process, the R-F aerogel transforms into carbon aerogel. CO2 is used for drying in supercritical conditions. Thus, carbon aerogel is formed at critical temperature and mesoporous structured graphene is provided to be obtained.
  • the final graphene added carbon aerogel material(lOl) which has low density is obtained by increasing the surface area of the pores with the supercritical drying process. Thus, obtaining graphene added carbon aerogel for use in the anode(lO) is carried out.
  • the conductivity of the anode(lO) obtained from the graphene added carbon-aerogel material(lOl) obtained in this method is more than that obtained from the carbon-aerogel material(102).
  • the carbon aerogel material(102) for use in the anode(lO) is synthesized by using pyrolysis and sol-gel(Sol-Gel) methods in the same process.
  • aerogel synthesis is carried out with the sol-gel method.
  • R-F (Resorcinol-Formaldehyde) aerogels are synthesized with the sol-gel method by using resorcinol (i.e: solution material required for aerogel production), formaldehyde (i.e: solution material required for aerogel production) and catalyst (i.e: Sodium Carbonate - material exhibiting catalyst effect during the aerogel synthesis).
  • the source of carbon in aerogel structure comes from resornicol- formaldehyde structure.
  • the R-F aerogels are dried by means of organic solvent (such as acetone, ethanol) and CO2 used for atmosphere control.
  • organic solvent such as acetone, ethanol
  • CO2 used for atmosphere control.
  • the water is removed from the medium during the washing process with the organic solvent.
  • the organic solvent is also removed from the structure by carbondioxide drying.
  • the pore structure of the aerogel material is protected.
  • pyrolysis process namely, combustion process is applied to the aerogels at high temperatures under a controlled atmosphere by using a tube furnace.
  • the carbon aerogel material(102) is produced for use as the anode(10) by the pyrolysis method.
  • the drying temperature is increased and the material is split into a few equal parts and the drying process is continued.
  • graphene oxide is used during the aerogel synthesis
  • the sintering temperature is increased in a controlled manner and the sintering time is extended in order to remove the oxide from the system during sintering. Since the graphene and carbon network structure are synthesized in the same solution, the structure becomes homogeneous and stable. Thus, the circuit current is equally distributed everywhere.
  • the carbon aerogel material(102) and the graphene added carbon-aerogel material(lOl) obtained in the invention are used as anode(lO) in power sources(l) such as battery, accumulator.
  • the common features of the carbon aerogel material(102) and the graphene added carbon aerogel material(lOl) obtained in the invention are that the surface areas are very wide, the anodes(lO) produced therefrom are light and conductive, have low density and small pore structures.
  • a super capacitor having sponge structured carbon aerogel material(102) and graphene added carbon aerogel material(lOl) is obtained by using graphene which is known to have good conductivity and sponge structured carbon aerogel together.
  • the amount of ions stored is increased by ions holding in this sponge structure.
  • the usage time of power sources(l) such as accumulators used nowadays is provided to be increased.
  • the charging time of the power sources(l) is reduced because the ion transmission becomes faster due to the conductivity of the graphene.
  • the anode(10) electrode obtained by the invention is used in the lead acid power source(l) in the preferred embodiment. However, it may be used also in other power sources such as Li-ion.
  • the power source(l) may be a device such as accumulator, battery or cell.
  • an anode(10) which is lighter and has high ion exchange rate is produced as a result of using aerogel which is a holding material and has a large surface area, a low density and porous structure together with graphene. Also with this anode(10), a power source(l) is realized which is light, has a high energy storage capacity, is charged quickly and discharges in a longer time after charging.
  • an environment friendly accumulator is provided with the invention because less lead is used than the amount of lead used in lead-acid accumulators today.
  • the invention is used in every kind of power source(l) where electrical energy is used and stored. All electronic devices charging with the power source(l) work for a longer time and these devices continue operating with high performance.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inert Electrodes (AREA)
  • Hybrid Cells (AREA)

Abstract

L'invention concerne une électrode d'anode (10) développée uniquement au moyen de matériau d'aérogel de carbone ajouté au graphène (101) ou uniquement au moyen d'un matériau d'aérogel de carbone (102) qui élimine complètement la sulfatation provoquée par le matériau conducteur (100) des sources d'énergie (1), notamment par un accumulateur d'acide conducteur et par une source d'énergie (1) dans laquelle cette électrode est utilisée. Cette invention concerne une anode (10) développée, de sorte qu'il y a deux parties séparées connectées électriquement et en parallèle entre elles dans l'anode (10), au moyen de matériau d'aérogel de carbone ajouté au graphène (101) dans la première parte dans un mode de réalisation ou au moyen d'un matériau d'aérogel de carbone (102) dans la première partie d'un autre mode de réalisation et au moyen de matériau conducteur (100) dans une seconde partie et relié à une source d'énergie (1) dans laquelle cette anode (10) est utilisée pour éliminer également complètement la sulfatation causée par le matériau conducteur (100) dans les sources d'énergie.
PCT/TR2017/050425 2016-09-10 2017-09-11 Électrode d'anode et source d'énergie produite à partir de celle-ci Ceased WO2018070969A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2016/12957A TR201612957A2 (tr) 2016-09-10 2016-09-10 BİR ANOT ELEKTROT ve BU ELEKTROTTAN ÜRETİLMİŞ BİR GÜÇ KAYNAĞI
TR2016/12957 2016-09-10

Publications (2)

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WO2018070969A2 true WO2018070969A2 (fr) 2018-04-19
WO2018070969A3 WO2018070969A3 (fr) 2018-06-07

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110071286A (zh) * 2019-04-19 2019-07-30 肇庆理士电源技术有限公司 可再生能源储存用高性能蓄电池负极铅膏及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010088186A2 (fr) 2009-01-27 2010-08-05 Applied Materials, Inc. Supercondensateur à base de carbone
WO2012167117A2 (fr) 2011-06-03 2012-12-06 Energ2 Technologies, Inc. Mélanges carbone-plomb pour l'utilisation dans des dispositifs de stockage d'énergie hybrides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010088186A2 (fr) 2009-01-27 2010-08-05 Applied Materials, Inc. Supercondensateur à base de carbone
WO2012167117A2 (fr) 2011-06-03 2012-12-06 Energ2 Technologies, Inc. Mélanges carbone-plomb pour l'utilisation dans des dispositifs de stockage d'énergie hybrides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110071286A (zh) * 2019-04-19 2019-07-30 肇庆理士电源技术有限公司 可再生能源储存用高性能蓄电池负极铅膏及其制备方法

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WO2018070969A3 (fr) 2018-06-07
TR201612957A2 (tr) 2018-03-21

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