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• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B32/00—Carbon; Compounds thereof
  • C01B32/15—Nano-sized carbon materials
  • C01B32/182—Graphene
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/381—Alkaline or alkaline earth metals elements
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/46—Alloys based on magnesium or aluminium
  • H01M4/463—Aluminium based
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/027—Negative electrodes
• • 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
  • H01M4/04—Processes of manufacture in general
  • H01M4/043—Processes of manufacture in general involving compressing or compaction
• • 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
  • H01M4/04—Processes of manufacture in general
  • H01M4/043—Processes of manufacture in general involving compressing or compaction
  • H01M4/0433—Molding
• • 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
  • H01M4/04—Processes of manufacture in general
  • H01M4/043—Processes of manufacture in general involving compressing or compaction
  • H01M4/0435—Rolling or calendering
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the invention relates to chemical power sources and may be used to create chemical power sources with high density of stored energy and short charge time, including the creation of aluminum-graphene batteries and supercapacitors.
• Patents describing aluminum-ion batteries are known in the art, for example, US9466853, 5/04/2012 patent, Gilbert M. Brown, Mariappan Parans Paranthaman, Sheng Dai, Nancy J. Dudney,“High energy density aluminum battery”, in which the battery contains an anode containing aluminum metal, a cathode containing spinel Al2Mn04, an electrolyte that is an ionic liquid with aluminum-containing ions.
• An ionic liquid is used as electrolytes in these batteries which is a eutectic mixture of a strong Lewis acid - aluminum halide (AlCl 3 ) and the main amide ligand (urea or acetamine) of Lewis.
• a strong Lewis acid - aluminum halide AlCl 3
• the main amide ligand urea or acetamine
• cathode materials - layered materials which, as in lithium-ion batteries, provide intercalation-deintercalation of aluminum-containing ions into the interlayer space. It can be various types of graphite - from natural to thermally expanded, graphene and its derivatives, as well as perovskite-like oxide materials - oxides of molybdenum, vanadium, manganese, as well as some sulfides, in particular nickel and molybdenum sulfide.
• High-purity aluminum is currently used as anodes in aluminum-ion batteries.
• the disadvantages of the known solutions are determined by the use of anode from chemically pure aluminum.
• the aluminum anode is oxidized to oxides and hydroxides even by trace amounts of oxygen and water, which inevitably remain in the ionic liquid after preparation, which shortens the life of the batteries.
• At all stages from the production of foil to sealing the finished battery is required to limit the contact of the surface of aluminum with water and oxygen.
• pure aluminum anodes are more susceptible to degradation in ionic liquids than lithium battery anodes.
• the objective of the invention is to increase the aluminum-ionic conductivity in chemical power sources and increase the resistance of the anode to the effects of an aggressive environment at all stages of production and use, including the effects of electrolytes of supercapacitors and aluminum-ion batteries.
• the technical result achieved with the use of the invention is reducing production costs, increasing the service life of finished products, as well as in increasing the specific electrical capacitance of finished products and charge and discharge currents. These benefits allow to expand the scope of application of chemical power sources and reduce environmental damage from products that are unsuitable for further use.
• the invention improves the electrochemical stability of the anode, increases the storage time of current sources without recharging, increases the number of recharge cycles and, accordingly, the service life of finished products.
• an anode of a chemical rechargeable power source is made of an aluminum-graphene composite material containing from 99 to 99.9 wt. % of aluminum containing not more than 0.1 wt. % impurities and graphene - the rest.
• the anode material may contain graphene in the form of flakes with a thickness, mainly, in 3 layers of graphene and with transverse dimensions ("length" and "width") from 2 pm to 50 pm, uniformly distributed throughout the material without forming continuous network of graphene in aluminum.
• the anode material can be made according to the technology described in the patent of the Russian Federation No.
• 2623410 dated 07/20/2015 for example, by melting aluminum in a melt of alkali metal halides containing 0.1-20 wt.% Carbon- containing additive, within 1-5 h. at a temperature of 700-750 °C with further slow cooling at a rate of not more than l°C /min, where the carbon-containing additive is chosen from the series, including metal or non-metal carbides or solid organic substances, such as hydrocarbons, or carbohydrates, or carboxylic acids.
• the anode can be made in the form of a foil produced by hot or cold rolling of the anode material.
• a chemical rechargeable power source contains, in cross section, alternating layers of a cathode, a separator and a flat anode, wherein the anode is made from an aluminum-graphene composite material containing from 99 to 99.9 wt. % aluminum containing, it turn, not more than 0.1 wt. % impurities and graphene - the rest, while the chemical power source contains an electrolyte that fills the free space between the anode and the cathode, and the cathode is made flat and contains a metal base, covered on both sides with layers of carbon, ensuring the mechanical strength of the coating.
• the anode can be performed by rolling a composite material, for example, by repeatedly rolling the anode material, the final stage of which is cold rolling, while at least one rolling stage preceding the final one can be hot rolling.
• the separator of a chemical power source can be made porous from a material that is chemically resistant to electrolyte, for example, from polyethylene or tetrafluoroethylene with an open pores diameter from 40 to 160 pm.
• the separator can be made pre-impregnated with electrolyte before assembling a chemical current source, for example, by keeping in the electrolyte for at least 1 and not more than 5 days or using vacuum impregnation technology.
• the anode of the chemical power source may contain graphene in the form of scales or flakes with a thickness, mainly, in 3 layers of graphene and transverse dimensions from 2 pm to 50 pm.
• the anode material can be made according to the technology described in the patent of the Russian Federation No. 2623410 dated 07/20/2015, including by melting aluminum in a melt of alkali metal halides containing 0.1-20 wt.% carbon-containing additive, within 1-5 h.
• a carbon-containing additive comprising at least one of the components belonging to metal carbides or non-metal carbides or to solid organic substances, as hard organic substances may be used together or separately hydrocarbons, carbohydrates and carboxylic acids.
• the electrolyte in a chemical power source a solution of aluminum salts in an organic polar solvent can be used, for example, the electrolyte can be made as a mixture of 1 -methyl-3 - ethylimidazolium chloride, and anhydrous aluminum trichloride in ratios from 1 : 0.4 to 1 : 2 by weight.
• metal foil can be used, made, for example, of the metal from the sixth group of the periodic table of elements or iron, or their alloy modified with maximum ductility, where tungsten and molybdenum may be used as elements of the sixth group, and a layer of carbon on the cathode can be formed in form of several layers of graphene, the layers of which can be applied by airbrushing with subsequent annealing of the deposited layers, where 3 to 10 layers of graphene can be applied.
• graphene layers can be applied by mechanically applying a suspension of graphene in an organic solvent on the substrate material, followed by rolling the solution on the substrate material and annealing.
• a layer of carbon on the cathode can be formed in form of several thin graphite layers, which can be formed by removing 10 pm thick layers from the graphite foil and applying the split layers to the substrate material and then rolling layers together with the substrate.
• the cathode of the chemical power source can be kept in the electrolyte before assembling the chemical power source, for example, for at least 1 and not more than 7 days, or the carbon layer of the cathode can be soaked with electrolyte before assembling the chemical power source using vacuum impregnation technology.
• the material used for the manufacture of the anode has improved anti-corrosion properties in comparison with electrodes made of pure aluminum.
• the mechanism of this property is not completely apprehensible, but can be explained by the "extrusion" of graphene to the surface, in the process of forming aluminum-graphene foil, with the formation of a thin and dense protective film.
• batteries with an anode in which the content of graphene is below 0.1 wt. % do not differ from batteries with anodes of pure aluminum, and the increase in the content of graphene in the anodes is more than 1 wt. % leads to an erosion of the anode during operation.
• the use of a separator in batteries with a pore size of 40 to 160 pm ensures an optimal combination of the separator strength and the minimum number of voids in the separator not filled with electrolyte.
• a graphene layer on the anode with a thickness of 3 to 7 graphene layers is optimal from the view of simplifying the production technology of a mechanically strong graphene layer and ensuring high electrical parameters of the battery, for example, thinning the thickness of the graphene layer does not lead to any positive changes in the battery and increase the thickness may lead to loss of functionality.
• the required parameters of graphene distributed in the anode material are achieved by using the proposed method of manufacturing the aluminum-graphene composite.
• the content of graphene flakes in the synthesized material, as well as their size can be regulated by the amount and type of carbon-containing precursor: metal carbides or non-metals, or organic precursors, temperature and synthesis time, as well as cooling and/or further heat treatment parameters in molten salts.
• the required compositions and parameters for the synthesis of graphene are now determined empirically.
• the average content of graphene in each metal layer after cooling is a constant value that does not vary with depth.
• graphene flakes are formed in a plane parallel to the horizontal surface.
• it is proposed to produce anode foil by rolling the source material in a plane parallel to the plane of formation of most graphene scales.
• the lower limit of the temperature range for the production of an aluminum-graphene composite material is 700 °C , and is determined on the basis of the melting point of aluminum 662 °C , and the melting point of the chloride-fluoride electrolyte so that the entire volume of the salt electrolyte, as well as metals and alloys, is melted the course of the experiment.
• the temperature rises above 750 °C a significant salinity is formed during the interaction by the reaction of aluminum trichloride, which affects the environmental friendliness and processability of the process.
• an increase in the reaction temperature is undesirable due to the increased risk of formation of aluminum carbide.
• the melting point of aluminum and salt electrolytes determines the optimal temperature range for the synthesis of aluminum-graphene composites.
• the time of the process of high-temperature interaction is selected based on the rate of interaction of carbon-containing components of the melt with liquid aluminum in order to forced interaction, allowing to achieve higher concentrations of carbon atoms in liquid aluminum.
• the time of solidification of molten aluminum is more critical, since in the process of extremely slow solidification of aluminum that carbon atoms in the aluminum matrix are combined into graphene scales.
• the cooling rate should not exceed l°C /min, since at higher cooling rates, the solidification of a metal droplet occurs more rapidly and as a result of the synthesis inside of aluminum, not all graphene can be formed, but other allotropic modifications of carbon— graphite, diamond, lonsdaleite. Depending on the carbon content and synthesis temperature, cooling may take from 8 to 20 hours.
• the carbon-containing additive in the claimed method is a source of atomic carbon, which, when it is supersaturated in aluminum and further cooled, forms graphene scales (flakes) in the metal matrix.
• a carbon-containing additive carbides of metals or non-metals or solid organic substances belonging to the classes of hydrocarbons, or carbohydrates or carboxylic acids are used.
• These can be saturated hydrocarbons - paraffins or ceresins with the general formula C l0 and higher, dibasic carboxylic acids - oxalic acid, succinic acid, hydroxy acids - tartaric acid, lactic acid, malic acid, citric acid, quinic acid - products of partial oxidation of sugars, carbohydrates - glucose, fructose, sucrose, maltose, as well as polysaccharides, such as starch and a number of others in the form of powders with a particle size of from 0.5 to 200 microns.
• the concentration of carbon-containing additives is from 0.1 to 20 wt.%, relative to the weight of the salt sample, and depends on the type of carbon precursor and the synthesis temperature. There were no significant differences in the conditions of the synthesis of graphene using different precursors belonging to the same class of organic or inorganic substances.
• the primary processing of the anode billet can be performed by hot rolling, but it is desirable to perform the finishing operations by cold rolling, in which, usually, the sheet temperature does not rise above 70 - 80 °C.
• the separator of a chemical power source is made pre-impregnated with electrolyte; it can be made porous from a material that is chemically resistant to electrolyte, for example, from polyethylene or tetrafluoroethylene with an open pores diameter of 40 to 160 pm.
• the separator may be made pre-impregnated with electrolyte as well.
• a solution of aluminum salts in an organic polar solvent may be used as an electrolyte in a chemical current source, for example, the electrolyte can be made as a mixture of 1 -methyl-3 -ethylimidazolium chloride, and anhydrous aluminum trichloride in ratios from 1 : 0.4 to 1 : 2 by weight.
• anhydrous electrolyte disclosed in US Pat. No. 5,554,458 of September 10, 1996 can also be used as electrolyte.
• the use of this electrolyte may also characterize the invention, and the cathode may contain iron (II) sulfide as it described in the above mentioned patent.
• An electrochemical cell was tested, in which a cold-rolled aluminum-graphene composite material containing 99.5 wt. % aluminum and 0.5 wt. % graphene.
• Electrolytes 141, 142, 143 Mixtures of 1 -methyl-3 -ethylimidazolium chloride with anhydrous aluminum trichloride in ratios of 1 : 1.3 (Electrolyte 141) were used as electrolytes.
• the cathode was made by the method of cold carbon deposition of a rough molybdenum substrate followed by annealing with the formation of a graphene layer 1 mm thick.
• Table 1 shows a comparison of the results of electrochemical measurements of electrochemical cells with aluminum-composite anodes with different graphene contents with electrochemical cells with an anode of pure aluminum (99.95%) in Electrolytes 141, 142, 143.
• the electrolyte used is 1 -methyl-3 -ethylimidazolium chloride mixed with anhydrous aluminum trichloride in a ratio of 1 : 1.3.
• the cathode was fabricated by the cold threefold deposition of graphene on a molybdenum substrate, followed by annealing. Electrochemical cycling was performed in 100 cycles with an interval of several days. Table 2 shows the results of electrochemical measurements. It is shown that the battery successfully operates for 400 charge/discharge cycles.
• An electrochemical cell was cycled, where a cold-rolled foil of an aluminum-graphene composite material containing 99.57 wt.% of aluminum and 0.43 wt. % graphene was used as the anode.
• the cycling was carried out in a discontinuous mode by the galvanostatic method at a current density of 0.26 mA/cm2. Cycling was performed in the following sequence: the cell was subjected to 100 charge/discharge cycles, then it was stored for 2 weeks, then it was subjected to 100 cycles and left for storage for 1 week, then 100 cycles and one week, after which it was subjected to 700 charge/cycles discharge.
• Porous open-cell polyethylene was used as a separator; 1 -methyl-3 -ethylimidazolium chloride mixed with anhydrous aluminum trichloride in a 1 : 1.3 ratio was used as an electrolyte.
• the cathode was made by the method of double cold deposition of graphene, followed by annealing on a rough tungsten substrate. This cell worked in the presented mode for 3100 cycles without loss of capacity. Then, the same cell was subjected to 100 charge/discharge cycles in an asymmetrical mode, namely, at a high charge rate and low discharge rate in the voltage range 1.5 - 2.3 V.
• Example 4 confirms the high efficiency of cells with the anode of the proposed design.

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