WO2019039952A1 - Accumulateur de charge électrique et son procédé de fabrication - Google Patents

Accumulateur de charge électrique et son procédé de fabrication Download PDF

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Publication number
WO2019039952A1
WO2019039952A1 PCT/RU2017/000612 RU2017000612W WO2019039952A1 WO 2019039952 A1 WO2019039952 A1 WO 2019039952A1 RU 2017000612 W RU2017000612 W RU 2017000612W WO 2019039952 A1 WO2019039952 A1 WO 2019039952A1
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WO
WIPO (PCT)
Prior art keywords
layer
active material
electric charge
nanoparticles
carbon
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Application number
PCT/RU2017/000612
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English (en)
Russian (ru)
Inventor
Александр Васильевич АТРАЩЕНКО
Сергей Александрович ГУРЕВИЧ
Владимир Михайлович КОЖЕВИН
Алексей Владимирович ПЛАТОНОВ
Денис Алексеевич ЯВСИН
Original Assignee
Общество С Ограниченной Ответственностью "Сиэсси"
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Application filed by Общество С Ограниченной Ответственностью "Сиэсси" filed Critical Общество С Ограниченной Ответственностью "Сиэсси"
Priority to PCT/RU2017/000612 priority Critical patent/WO2019039952A1/fr
Publication of WO2019039952A1 publication Critical patent/WO2019039952A1/fr

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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
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based

Definitions

  • the invention relates to electrical engineering, in particular to the technique of devices for the accumulation and storage of electric charge, and can be used in the manufacture of capacitors and rechargeable batteries with the highest possible electrical characteristics.
  • Nickel-cadmium batteries are much lighter than lead batteries, however, the number of charge-discharge cycles in these devices before the onset of chemical degradation of the electrode material is inferior to lead ones and their service life is significantly lower compared to them.
  • a major technological breakthrough in the development of devices for the accumulation and storage of electric charge was the creation of lithium-ion and lithium-polymer batteries. They are widely used in mobile devices because possess high values of specific capacity per unit mass and per unit volume. At the same time, technological challenges require the development of new, even more power-consuming devices, and the capabilities of the known electrochemical technologies are almost exhausted.
  • low-resistance highly porous activated carbons are traditionally used, which are obtained by carbonizing natural or synthetic materials: coal, coconut shells, other biological objects, and resins.
  • the resulting carbon materials are activated by physical or chemical means.
  • the prior art electrode material supercapacitor (US patent N27625839 B2, "Activated carbon dioxide, based on December 1, 2009) based on activated carbon obtained from coconut shells by carbonization of the feedstock followed by steaming at temperatures ranging from 900 to 1,100 degrees Celsius. It is stated that the specific surface of the carbon material obtained is from 2000 m / g to 2500 m 2 / g, the average pore diameter is in the range from 1.95 nm to 2.2 nm, the specific volume capacity of the material is 13 F / cm.
  • An alternative to activated carbons are the electrode materials of supercapacitors based on nanoscale carbon particles — carbon nanotubes, fullerenes, and graphene.
  • a known electrode material of a super capacitor (US Patent N ° 8213157 B2, "Single-wall carbon nanotube supercapacitor", published on July 3, 2012) based on single-walled carbon nanotubes (SWCNT) obtained by chemical vapor deposition.
  • the process of forming the material includes annealing, processing of single-carbon nanotubes in acid, followed by washing in distilled water and drying.
  • films of single-walled carbon nanotubes have a sufficiently high conductivity and can be used as an electrode material without a binder and without a metal current collector electrode (foil).
  • the specific capacity of the material based on the single-walled carbon nanotube is about 30 F / g.
  • the disadvantage of this material is its relatively low specific capacity, as well as the complexity of the formation process and the high cost of the single-walled carbon nanotubes.
  • a known electrode material for supercapacitors based on graphene (US patent application No. 20120026643 A1, "Supercapacitor with a meso-porous nano graphene electrode", publ. 02.02.2012).
  • Single-layer (true) graphene has an extremely large specific surface, more than 2600 m / g, however, graphene particles tend to stick together and form graphite-like aggregates, which leads to a decrease in the active surface of the material.
  • a method has been proposed that allows one to obtain plates of curved graphene.
  • the procedure for obtaining curved graphene involves dispersing graphite powder in concentrated acids, obtaining thermally expanded graphite by rapidly heating the resulting dispersion (up to a temperature of 1100 degrees Celsius), redispersing in a mixture of sulfuric and nitric acids using ultrasound to form nanosec oxidized graphene, followed by spraying graphene solution and liquid removal.
  • the pore sizes are in the range from 2 nm to 25 nm.
  • the specific capacity of the material obtained reaches 100-150 F / g.
  • the lack of material consists in a rather complicated (and expensive) technology for its preparation, as well as in the need to use binding agents in the formation of electrodes, which leads to an increase in resistance to a decrease in the specific capacitance of the electrode.
  • a graphene-based supercapacitor electrode material is known (Zhiwei Peng, et. Al., Flexible and Stackable Laser-Induced Graphene Supercapacitors, ACS Applied Materials & Interfaces, 201, 7 (5), pp. 3414–3419), which is obtained by exposure to radiation CO 2 laser on the surface of the film of polyimide with the formation of the surface layer of porous graphene.
  • the specific surface capacity of such a material is about 9 mF / cm 2 at a current density of 0.02 mA / cm 2.
  • the advantage of such a material is that when forming on its basis Super capacitor electrode is not required binder.
  • the disadvantage is the need for current collection on the graphene film (since the polyimide film is an insulator), which limits the power of the supercapacitor.
  • Known supercapacitor with inorganic solid electrolyte and carbon electrodes including current leads and two electrodes separated by a solid electrolyte, and a solid electrolyte placed between the electrodes, made of a solid solution RbNO 3 and RbNO 2 with a molar ratio of components equal to 7: 3, the electrodes are made of a mixture of solid electrolyte of the above composition and carbon electrode material, taken in the ratio: solid electrolyte 70-90 weight. % carbon electrode material - the rest, while the carbon electrode material consists of a mixture of amorphous carbon and graphene, taken in the ratio: amorphous carbon 50-80 weight.
  • the main disadvantage of this invention is the high temperature of its optimal operation, which lies in the range from 150 to 180 degrees Celsius. This temperature is due to the properties of the selected solid electrolyte, which limits the use of the described supercapacitor in home appliances.
  • the closest in technical essence and adopted for the prototype is a device for storing electrical energy (US patent N ° 9343241, "Power storage device”, publ. 17.05.2016) including a positive electrode, made in the form of positive a collector and a layer of active material deposited on its surface, a negative electrode made in the form of a negative collector and a layer of active material deposited on its surface, and an electrolyte between the electrodes containing lithium, the active material deposited on the surface of both electrodes consisting solely of graphite nanoparticles of carbon black, which form graphite particles with a primary diameter of from 1 micron to 50 microns, packed in graphite layers, filled with each other electrolyte gaps, and the specific surface area of graphite particles ranges from 20 m 2 / g to 200 m 2 / g.
  • the main disadvantage of the prototype is low operational efficiency due to insufficiently high functional characteristics such as specific capacitance, maximum permissible discharge current, number of charge-discharge cycles before the onset of chemical degradation of the electrode material, a narrow range of temperatures at which it provides efficient performance, which is due to during the operation of the prototype, the chemical processes of intercolation and de-intercalation of lithium ions having a temperature dependence of the activation of chemical reactions.
  • the presence in the composition of the electrolyte lithium makes the prototype unsafe during operation and disposal.
  • the aim of the invention is to improve the characteristics of the drive electric charge, such as the specific energy capacity, the resistivity of the electrode material of the drive and an increase in the number of charge-discharge cycles.
  • the claimed technical result can be attributed to the possibility of replacing the electrolyte containing lithium, a safer, which leads to increased technical and environmental safety of use and recycling the proposed device.
  • solid electrolyte - the rejection of the separator in the design of the drive and the manufacture of its components in a single process.
  • the essence of the invention lies in the fact that in the electric charge accumulator, including the first electrode, made in the form of the first current collector and deposited on its surface a layer of the first active material, the second electrode, made in the form of a second current collector and deposited on its surface a layer of the second active material and an electrolyte between the electrodes, characterized in that the active material layer deposited on at least one of said current collectors includes carbon nanoparticles, the average size of which d satisfies the condition
  • a layer of active material applied to at least one of the mentioned current collectors may additionally include metal oxide nanoparticles, the size of which r 0 satisfies the condition
  • the average volume fraction of metal oxides in the active material layer can be from 2% to 50%, including those with a gradient distribution of the active material layer across the thickness.
  • a layer of active material deposited on at least one of the mentioned current collectors may additionally include metal nanoparticles, the size of which G ⁇ satisfies the condition
  • a layer of active material applied to at least one of the mentioned current collectors may additionally include solid ionic conductor nanoparticles, the size of which r 2 satisfies the condition
  • the average volume fraction of the solid ionic conductor in the active material layer can be from 2% to 50%, including with a gradient distribution of the active material across the thickness.
  • the electrolyte can be used a layer of solid ionic conductor, the thickness of which is H, satisfies the condition
  • At least one of the current collectors can be made in the form of a conductive plate made of metal, semiconductor or carbon, on which conductive microwires are located in electrical contact with the plate with a minimum diameter of at least 10 nm and a length of at least 500 nm between which L satisfies the condition
  • one of the layers of active material can be made of metal that simultaneously performs the function of a current collector.
  • the proposed drive electric charge differs from the prototype an important feature that qualitatively changes its technical characteristics.
  • This feature is the form factor of carbon particles that form the basis of the active material in both the prototype and in the invention.
  • the layer of active material has a surface that is 10 times larger than the technical carbon used in the prototype as an active material.
  • nanoparticles with a size of not more than 5 nm have an amorphous structure, as evidenced by the type of Raman spectra and X-ray and electron diffraction patterns.
  • Such nanoparticles provide a large surface on which a double electric layer is formed with a large electrokinetic potential for the interaction of carbon with electrolyte.
  • the result of this is an increase in the specific volume and mass capacity of the electrode material.
  • the addition of metal oxide nanoparticles provides an additional contribution to the pseudocapacity in the active material.
  • reducing the size of carbon nanoparticles and increasing its porosity does not contribute to a decrease in specific resistance. To do this, it is necessary to introduce nanoparticles of a conductive material (metal, semiconductor, graphene or carbon nanotubes) into the active layer.
  • the dimensions of the nanoparticles of conductive material should be comparable to the size of carbon nanoparticles, and the volume content of the conductive material should be from 2% to 50%. It should be noted that an increase in the volume content of the conductive material in the active material inevitably leads to a certain decrease in the specific volume and mass capacity of the electrode layer as a whole. However, the high specific capacity of the active material in the form of amorphous carbon nanoparticles provides, in comparison with the prototype, an advantage in the value of the specific capacitance of the electrode, even with the addition of nanoparticles of conductive materials. As the electrolyte in the inventive device, you can use solid, liquid and semi-solid electrolytes.
  • a distinctive feature of the claimed invention in comparison with the prototype is that when using a solid electrolyte, the electrolyte layer having high ionic and low electronic conductivity simultaneously performs the function of a separator. Lack of construction a separate separator element improves the specific electrical characteristics of the drive, reduced to its mass.
  • Obtaining nanoparticles in this way involves dispersing the molten material, feeding the resulting liquid droplets of the material into the plasma formed in an inert gas at a pressure of 10 "4 -10 -1 Pa, cooling the liquid nanoparticles formed in the said plasma before solidification and applying the resulting solid nanoparticles to carrier, and the plasma parameters must satisfy the relations RD R d ⁇ R D + R d)
  • T e is the electron temperature of the plasma, eV
  • ⁇ ⁇ is the plasma lifetime, s
  • T t is the melting point of the conductive material, K
  • Metals, metal oxides, carbon or semiconductors can be used as a material for the production of nanoparticles.
  • the deposition of the resulting nanoparticles on the carrier can be conducted in an electric field, the intensity vector of which is directed at an angle to the direction of movement of the nanoparticles, for example, in a non-uniform electric field.
  • the invention proposes the following methods for applying to the surface at least one of the collectors a current of an active material layer by laser ablation of targets made of various materials with laser plasma parameters created by laser pulses satisfying the conditions: wavelength from 300 nm up to 2000 nm, power density not less than 1 GW / cm, pulse duration exceeds 20 ns:
  • a layer of solid electrolyte nanoparticles should be deposited by laser ablation of a target from a solid electrolyte material with laser plasma parameters created by laser pulses satisfying the conditions: wavelength from 300 nm to 2000 nm, power density at least 1 GW / cm 2 , pulse duration exceeding 20 not
  • Figure 1 of the drawings shows a general view of the inventive device
  • figure 2 presents an enlarged image of a portion of the active layer
  • figure fig.3 shows the test results of the proposed electric energy storage device with different volume content ⁇ of metal in the active material.
  • the numbers indicate: 1 - positive collector; 2 - negative collector; 3 - carbon nanoparticles; 4 - electrolyte; 5 - metal nanoparticles; 6 - the area of the positive electrode; 7 - area of the negative electrode; 8 - separator area.
  • Fig. 3 shows graphs of changes in specific electric capacity (solid curve), specific conductivity (dashed curve) and energy efficiency (dashed curve) as a function of the volume content ⁇ of metal (Cu) nanoparticles in the active layer of the storage ring.
  • the current collectors are made of metal foil of the minimum possible thickness.
  • On the surface of the foil contains a layer of active material with a thickness of 300 nm.
  • the storage capacity increases proportional to the thickness of the active material layer up to a thickness of about 300 nm, a significant excess of which leads to a decrease in the value of the specific capacitance, deterioration of the adhesion of the layer to the collector and degradation of the mechanical strength of the electrodes.
  • 300 nm can be considered the optimal value of the layer thickness, and 500 nm - the ultimate operational value.
  • the average volume fraction of conductive material in the active material of the claimed invention is from 2% to 50% for various materials, and for conductive material in the form of spherical copper nanoparticles, its optimal value is 30%.
  • Solid electrolyte RbAg 4 I 5 is proposed as the best electrolyte.
  • the best results of applying to the surface at least one of the current collectors a layer of active material are achieved by dispersing the materials and feeding the resulting liquid droplets into the plasma by laser ablation of the corresponding targets in an inert gas atmosphere at a pressure of 10 "4 Pa.
  • the claimed electric charge accumulator and methods for manufacturing its components contain a new set of features ensuring the achievement of a technical result — an increase in the specific energy capacity, a decrease in the specific resistance of the electrode material of the accumulator and an increase in the number of charge-discharge cycles.
  • the technical result can be attributed to the possibility of replacing the electrolyte containing lithium, a safer, including solid electrolyte, which leads to improving the technical and environmental safety of the use and disposal of the proposed device.
  • solid electrolyte the rejection of the separator in the design of the drive and the manufacture of its components in a single process.

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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

L'invention se rapporte au domaine du génie électrique, notamment aux techniques des instruments d'accumulation et de stockage de charge électrique, et peut être utilisée lors de la fabrication de condensateurs et de batteries d'accumulateurs ayant des caractéristiques électrochimiques extrêmes. L'invention concerne un accumulateur de charge électrique comprenant une première électrode se présentant sous forme d'un premier collecteur de courant et d'une couche d'un premier matériau actif appliquée à sa surface, une seconde électrode se présentant sous forme d'un second collecteur de courant et d'une couche d'un second matériau actif appliquée à sa surface, et un électrolyte disposé entre les électrodes; la couche de matériau actif appliquée sur au moins un desdits collecteurs de courant comprend des nanoparticules de carbone dont la taille moyenne d satisfait la condition 1 nm < d < 5 nm, tandis que l'épaisseur h de cette couche satisfait la condition h > 10 nm. De plus, la couche de matériau actif appliquée sur au moins un desdits collecteurs de courant peut en outre comprendre des nanoparticules d'oxydes de métaux dont la dimension r0 satisfait la condition 1 nm < d < 5 nm, tandis que la part moyenne en volume des oxydes de métaux dans la couche de matériau actif peut aller de 2% à 50%, y compris avec un gradient de distribution dans l'épaisseur de la couche de matériau actif.
PCT/RU2017/000612 2017-08-24 2017-08-24 Accumulateur de charge électrique et son procédé de fabrication WO2019039952A1 (fr)

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PCT/RU2017/000612 WO2019039952A1 (fr) 2017-08-24 2017-08-24 Accumulateur de charge électrique et son procédé de fabrication

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PCT/RU2017/000612 WO2019039952A1 (fr) 2017-08-24 2017-08-24 Accumulateur de charge électrique et son procédé de fabrication

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2242532C1 (ru) * 2003-09-09 2004-12-20 Гуревич Сергей Александрович Способ получения наночастиц
RU2460180C2 (ru) * 2006-12-12 2012-08-27 Коммонвелт Сайентифик Энд Индастриал Рисерч Организейшн Усовершенствованное устройство аккумулирования энергии
RU2531558C2 (ru) * 2010-05-31 2014-10-20 Ниссан Мотор Ко., Лтд. Отрицательный электрод для аккумуляторной батареи и способ его изготовления
WO2016154197A1 (fr) * 2015-03-24 2016-09-29 3M Innovative Properties Company Électrodes poreuses, ensembles membranes-électrodes, ensembles électrodes, ainsi que cellules électrochimiques et batteries à écoulement de liquide produites à partir de ceux-ci
WO2016178957A1 (fr) * 2015-05-04 2016-11-10 Basf Corporation Électrodes de stockage d'hydrogène et cellules électrochimiques

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2242532C1 (ru) * 2003-09-09 2004-12-20 Гуревич Сергей Александрович Способ получения наночастиц
RU2460180C2 (ru) * 2006-12-12 2012-08-27 Коммонвелт Сайентифик Энд Индастриал Рисерч Организейшн Усовершенствованное устройство аккумулирования энергии
RU2531558C2 (ru) * 2010-05-31 2014-10-20 Ниссан Мотор Ко., Лтд. Отрицательный электрод для аккумуляторной батареи и способ его изготовления
WO2016154197A1 (fr) * 2015-03-24 2016-09-29 3M Innovative Properties Company Électrodes poreuses, ensembles membranes-électrodes, ensembles électrodes, ainsi que cellules électrochimiques et batteries à écoulement de liquide produites à partir de ceux-ci
WO2016178957A1 (fr) * 2015-05-04 2016-11-10 Basf Corporation Électrodes de stockage d'hydrogène et cellules électrochimiques

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