WO2021089066A1 - Secondary battery cell for electromobiles, cointaining amorphous glass materials and micro- and nano materials, and method of its production - Google Patents

Secondary battery cell for electromobiles, cointaining amorphous glass materials and micro- and nano materials, and method of its production Download PDF

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Publication number
WO2021089066A1
WO2021089066A1 PCT/CZ2020/000047 CZ2020000047W WO2021089066A1 WO 2021089066 A1 WO2021089066 A1 WO 2021089066A1 CZ 2020000047 W CZ2020000047 W CZ 2020000047W WO 2021089066 A1 WO2021089066 A1 WO 2021089066A1
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WIPO (PCT)
Prior art keywords
glass
anode
cathode
electrolyte
layers
Prior art date
Application number
PCT/CZ2020/000047
Other languages
French (fr)
Inventor
Martin Míka
Florian WEYMAR
Ivana REA
Tomáš HÉGR
František Lahodný
Václav Procházka
Original Assignee
ŠKODA AUTO a.s.
Vysoká škola chemicko-technologická v Praze
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Publication date
Priority claimed from CZ2020-599A external-priority patent/CZ309795B6/en
Application filed by ŠKODA AUTO a.s., Vysoká škola chemicko-technologická v Praze filed Critical ŠKODA AUTO a.s.
Priority to EP20829790.3A priority Critical patent/EP4082054A1/en
Publication of WO2021089066A1 publication Critical patent/WO2021089066A1/en

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    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • Secondary battery cell for electromobiles containing amorphous glass materials and micro- and nano materials, and method of its production
  • the invention concerns a secondary battery cell for electromobiles, containing amorphous glass materials and micro- and nanomaterials.
  • the battery cell is manufactured on a glass basis. And it includes end metallic electron-conductive current collectors, between which there are arranged electron-conductive electrodes, i.e. a cathode and an anode, which are separated by an ion-conductive electrolyte.
  • the cathode, electrolyte and anode contain multi-component solid amorphous glass materials, preferably lithium or sodium multi-component glass for the cathode and for the anode with combined ion and electron conductivity, and multi-component glass for the electrolyte with high ion conductivity and very low electron conductivity.
  • the cathode glass with an admixture of the electrolyte glass is situated in the cathode in the collector vicinity and on the side facing this collector.
  • the anode glass with an admixture of the electrolyte glass is situated in the anode and on the side facing this collector.
  • the electrolyte glass with an admixture of both the electrodes, anode and cathode, is situated immediately within or in the vicinity of the electrolyte.
  • the battery cell contains solid amorphous multi-component glass and micro- and nanofibres and micro- and nanoparticles with a medium diameter from 1 nm to 100 ⁇ m;
  • Silica glass for glass fibres containing titanium dioxide and zirconium dioxide and oxides of alkali metals, and advantageously also aluminium oxide, calcium oxide and lithium oxide features a difference between the low drawing temperature and liquidus 91°C and more.
  • the glass may contain 300 to 500 pm particles and withstands immersion in 100 ml of 10% sodium hydroxide solution at a temperature of 80°C for 16 hours.
  • the method of production of fibres consists in continual drawing of fibres from a perforated bowl, when the drawing temperature is 90 and more degrees higher than the liquidus temperature.
  • a disadvantage is the fact that glass fibres do not contain any polyvalent elements, and therefore they cannot fully operate as electrochemically active redox centres in the electrode material of the battery.
  • the fibre obtained by means of this way of drawing will have a thickness at least in units of several microns, which means that the ratio of the surface area of fibres to their volume will not be suitable from the viewpoint of high ion conductivity and high electrochemical activity.
  • US 2015 266769 A1 published on 24 September 2016 describes a composition of glass for glass fibres and a method of production of glass fibres.
  • the patent states the composition of the glass materials for production of fibres featuring excellent corrosion resistance to alkalis, acids and water. They are a useful reinforcement of composite materials for plates or separators in batteries.
  • the fibres feature a relatively low drawing temperature and liquidus, and thanks to these properties they are very suitable for easy production.
  • the specified fibres have, according to the described composition and characteristics, a very high electric resistance. This fact rather limits the use of this type of fibres as an active component in batteries.
  • the described production technology does not enable creation of nanofibres either.
  • the method of production of the electrodes for the battery includes reduction of the fibrous silicon dioxide (silica) and at the same time etching of the surface of fibres of reduced silicon dioxide, so that a porous structure can be created, together with simultaneous creation of a conductive coating on the surface of the porous silica fibres.
  • Reduction of the structure of silicon dioxide fibers is carried out thermically with the help of metallic magnesium, during which fibrous silicon dioxide is reduced.
  • silicon dioxide fibre is selectively etched in the places of presence of magnesium oxide, arising as a product of magnesium-thermal reduction.
  • the conductive coating is created through a pyrolysis of the amorphous carbon coating on the surface of porous silicon.
  • the TEOS solution is used for creation of silicon dioxide fibres by electrospinning.
  • the resulting product consists of silicon nanofibres with a porous conductive surface.
  • Creation of silicon fibres directly by magnesium-thermal reduction through metallic magnesium is rather time demanding and is difficult to check from the viewpoint of reproducibility, including obvious creation of non-homogeneous materials with presupposed contamination of magnesium oxide.
  • the surface of nanofibres contains carbon, which can oxidise during the use of the battery and during a thermal load, which is accompanied by creation of toxic carbon monoxide and unbreathable carbon dioxide. There may arise a danger of explosion in consequence of large changes in volume during the arising of these gases.
  • CN 1394670 A published on 5 February 2003 concerns preparation of nano-powders CaCO 3 or TiO 2 or ZrO 2 -Y 2 O 3 , which are obtained in steps, and an important step among them is spraying of a homogeneous mixture of a water-based solution of urea in excess of NH 4 OH (ammonium hydroxide) at presence of precursors, such as Ca(OH) 2 at presence of CO 2 , or TiCI 4 or ZrOCl 2 .8H 2 O and YCI 3 . Spraying can be carried out at the compound boiling temperatures from 80 to 100°C or more. It is stated in the invention that nano- powder with an even grain size will be obtained.
  • NH 4 OH ammonium hydroxide
  • a disadvantage is the use of organic urea polymers with a high content of ammonium-based substances, i.e. substances with a high content of carbon, which is unsuitable for electric batteries for automobiles, because at a higher work load of batteries, when the temperature rises, there is a threat of release of a large volume of CO2 and NH3, which may lead to destruction of the battery.
  • CN 107034586 A published on 11 August 2017 concerns preparation of composite conductive membranes, where the composite is polyhydroxybutyrate.
  • Preparation consists of the mixing of the composite with dopant in a ratio of 1:1 to 1:6.
  • the resulting mixture is sprayed at a rate of 0.05 to 0.3 ml/hour at a distance of 10 to 20 cm from electrodes, in an electric field with a voltage of 10 - 30 kV.
  • This electrospinning makes it possible to obtain an electrically conductive membrane of nanofibres, with a diameter of 2000 to 500 nm.
  • a disadvantage is the obtaining of the membrane of nanofibres on the basis of organic polymers.
  • WO 97/18 431 A states the methods during which processing is made for applied powder nanoparticles, liquid suspensions of nanoparticles and organo-metallic liquids in conventional thermal spraying into a mould of nano-structured coatings.
  • the nano-structure batches consist of spherical agglomerates, produced again by processing of synthetised nano-structure powders.
  • a fine dispersion of nanoparticles is directly sprayed/inserted into the combustion flame or into a plasma thermal equipment with the arising of nano structure coatings.
  • liquid organic chemical precursors are directly injected into the combustion flame of the equipment for plasma thermal spraying, when the synthesis of nanoparticles, melting and tempering is carried out in one operation.
  • These methods use ultrasound for disintegration of agglomerates of synthetised particles, for dispersion of nanoparticles in a liquid medium and for atomisation of a liquid precursor.
  • the independent claims include a definition of the range of input nanoparticles with a size of 3 to 30 nm with the use of ultrasound for creation of a liquid dispersion.
  • One independent claim includes a definition of creation of one nano-structured coating and another independent claim describes creation of two nano-structured coatings on each other.
  • Ultrasound with a frequency of 20 kHz and power output of 300 to 400 W is used in one design example for dispersion of nano-structured WC/Co for creation of low- viscosity sludge.
  • JPH 10302776 A published on 13 November 1998 describes a secondary lithium battery with solid electrolyte, providing high voltage, high energy density and excellent cyclability.
  • the battery consists of a negative electrode, where the first electrode has electron conductivity and is able to create a layer of metallic lithium or to ensure dissolution of metallic lithium, during recharging or discharging of the battery.
  • the first electrode has electron conductivity and is able to create a layer of metallic lithium or to ensure dissolution of metallic lithium, during recharging or discharging of the battery.
  • it has another electrode, featuring electron mixed conductivity and also anisotropy for ion conductivity - through-pass of ions.
  • This second electrode with mixed electron ion conductivity is placed on the first electrode, for the purpose of removal of concentration differences during migration of ions.
  • a secondary lithium battery with a solid electrolyte may have another electrode containing a lithium-nitride composite, or a lithium-nitride- silica composite with a transition metal.
  • the solid secondary lithium battery with a solid electrolyte need not contain elements of transition metals.
  • a battery can have a positive electrode containing a lithium compound of an oxide of the transition metal.
  • composition of solid electrolytes which do not contain transition metals on the basis of sulphide or oxide-sulphide glass materials, in such systems as Lil-Li 2 S-SiS 2 , Lil-Li 2 S-P 2 S 5 , sulphide glass materials as Lil-Li 2 S-B 2 S 3 or Li 3 PO 4 -Li 2 S- SiS 2 , and also sulphide glass materials, such as Li 2 O-Li 2 S-SiS 2 .
  • the procedure is based on rapid cooling of melted lithium phosphate, lithium sulphide and silicon sulphide.
  • JP 2011 187 370 A published on 22 September 2011 describes a battery with a solid electrolyte resolving the issue of the increase in electric resistance on the interface between an active material and solid electrolyte.
  • the described battery contains a layer of the electrode active material and a layer of the first solid electrolyte placed on it, and this electrolyte has a different anion component from the active material and it is a monophase mixed electron and ion conductor.
  • This layer furthermore forms a contact with the layer of the second solid electrolyte, which has the same anion component as the first solid electrolyte.
  • a disadvantage is the presence of high concentrations of sulphide sulphur in the battery materials.
  • the secondary battery cell has end metallic electron-conductive current collectors, between which there are arranged electron-conductive electrodes which contain, as carriers of ion conductivity charges, migrating cations of lithium and/or sodium for migration from the anode through the electrolyte to the cathode during discharging and recharging.
  • Anode and cathode are separated by an ion-conductive electrolyte which is basically electron-nonconductive.
  • Electrodes, anode, as well as cathode have mixed conductivity, are electron-conductive and ion-conductive; contain solid amorphous multi-component glass composite material, also glass and/or metallic fibres and glass and/or crystalline particles with a medium diameter in nano/micrometres in the range from 1 nm to 100 ⁇ m. Both the electrodes have a surface of a composite material, fibres as well as particles, which material is micro- and nano-structural with mean roughness in the range from 1 nm to 100 ⁇ m.
  • the composite material of the electrodes contains active oxidation-reduction centres based on metallic silicon and/or oxides of silicon and/or glass materials containing electropositive polyvalent elements M p .
  • the electrolyte contains solid amorphous multi-component glass composite material, which is isotropic, with carriers of charges of the ion conductivity by a lithium cation and/or sodium cation with ion conductivity in all the directions with the same value.
  • the composite material of electrodes contains two types of multi-component glass.
  • One type of glass has mixed ion and electron conductivity; and the other type of glass has high ion conductivity and very low electron conductivity.
  • the secondary battery cell on the basis of glass contains at least one composite layer of the cathode, electrolyte and anode.
  • These composite layers are in a mixture on the basis of micro- and nanofibres and micro- and nanoparticles of glass materials with the first additives and with the second additives on the surface.
  • Each of these composite layers contains 0.1 to 10.0 volume % of the first additive for an increase in the electrochemical oxidation-reduction activity of these composite layers; 0.1 to 10.0 volume % of the second additive on the surface of micro- and nanofibres and micro- and nanoparticles for increasing adhesion of these composite layers; and 80 to 99.8 volume % of selected glass.
  • Each of these composite layers of the cathode, electrolyte and anode states a slow change of the functional-gradient concentration of immobile components of composite layers in the direction from the cathode to the anode depending on the distance between the cathode collector and the opposite anode collector and in the opposite direction.
  • the mobile component in these glass materials is either the lithium cation Li + or sodium cation Na + .
  • the main advantage of the invention is a battery cell based on inorganic glass and therefore non-combustible.
  • the content of amorphous glass enables exact setting of characteristics and functional-gradient concentration. Glass materials easily create fibrous structures. Immobile parts of the multi-component glass have large free space around them, enabling easy transport of lithium and sodium ions in all directions.
  • Micro- and nanofibres and micro- and nanoparticles enable creation of flexible composite layers also from these purely inorganic glass materials and therefore non-combustible materials. These composite layers make it possible to obtain a function-concentration gradient. It is possible to easily select various thickness of layers and thus also the energy density in the battery cell and its capacity.
  • the gradual change of the function-gradient concentration of immobile components of composite layers in the direction from the cathode to the anode in the secondary battery cell and vice versa ensures its positive function.
  • a function-gradient concentration is created in the given direction in such a way that the properties monitored can be changed in this direction as continuously as possible.
  • the given direction is determined by the movement of ions, especially lithium ion Li + , possibly sodium ions Na + during recharging and discharging of the secondary battery cell.
  • composite layers of the cathode, composite layers of the electrolyte and composite layers of the anode are arranged in a mutually parallel way and closely behind each other, which ensures compatibility of the cathode, electrolyte and anode of the secondary battery cell on the one hand, and at the same time it ensures also the required and adjustable change of the function-gradient concentration.
  • the cathode and anode layers state a greater width than the width of the electrolyte layers.
  • Individual layers of the cathode and anode can have e.g., a width in the range from 0.9 to 2.8 mm and individual electrolyte layers can have e.g., a width in the range from 0.1 to 0.4 mm. This way it is therefore possible to achieve a sufficiently high capacity of the secondary battery cell and the associated high value of the energy density and battery cell capacity.
  • the secondary battery cell can be basically flat, with a total height of 90 mm, with a total length of 60 mm and a total width of 6 mm, and with a total weight in the range from 33 to 38 g. These parameters can be changed according to requirements of the use.
  • the first additive for the cathode, the first additive for the electrolyte and the first additive for the anode are crystalline additives, such as metallic copper Cu, metallic iron Fe, metallic silicon Si, metallic nickel Ni and metallic aluminium Al, metallic Mn, metallic Co, metallic V, metallic Mo, metallic W, their amorphous compounds, such as metallic glass materials or their oxides, silicon carbide SiC, lithium chloride LiCI, sodium chloride NaCI and such elements as Mn, Fe, Co, Ni, V,
  • the first additives increase especially electron conductivity and effectiveness of transfer of electric charge and the rate of oxidation-reduction reactions.
  • the second additive for the cathode, the second additive for the electrolyte and the second additive for the anode are at least one compound from the group including LiPO 3 , NaPO 3 , Li 3 BO 3 , Na 3 BO 3 , Al 2 O 3; where the second additive represents crystalline or glass particles.
  • the second additives contribute to adhesion of individual composite layers of the electrodes and of the electrolyte and facilitate transition of materials across the interface between individual composite layers.
  • the invention concerns also the method of production of the secondary battery cell for electromobiles, containing amorphous glass materials and micro- and nanomaterials, whose substance consists in the fact that the method contains three fundamental technological blocks.
  • the second technological block for preparation of the layered cathode, layered electrolyte and layered anode by pressing these layers is a first technological block for preparation of the layered cathode, layered electrolyte and layered anode by pressing these layers.
  • the first technological block includes, with an advantage, preparation of individual composite layers of the cathode, electrolyte and anode, containing the following technological steps, in a chronological order:
  • the first additive for the cathode; the first additive for the electrolyte; and the first additive for the anode where the first additives are from the group including Cu, Fe, Si, Al, Mn, Fe, Co, Ni, V, Mo, W, their amorphous alloys such as metallic glass materials, or oxides, such as SiC, LiCI, NaCI, and elements Mn, Fe, Co, Ni, V, Mo, W, 0 in the form of compounds forming solid solutions with a spinel structure in such a quantity that the resulting composite layer of the cathode or electrolyte or anode can contain 80 to 99.8% (vol.) of the selected glass and 0.1 to 10% (vol.) of these first additives.
  • the first additives are from the group including Cu, Fe, Si, Al, Mn, Fe, Co, Ni, V, Mo, W, their amorphous alloys such as metallic glass materials, or oxides, such as SiC, LiCI, NaCI, and elements Mn, Fe, Co, Ni, V
  • the second technological block represents, with an advantage, preparation of the cathode, electrolyte and anode and includes the following technological steps, ordered chronologically:
  • the third technological block represents, with an advantage, the assembly of the battery cell and includes the following technological steps, ordered chronologically:
  • the main advantage of this method is an easy and reproducible production at controlled spinning and controlled obtaining of the function-gradient concentration of layers of the cathode, electrolyte and anode in the required direction.
  • the first additives are newly added to amorphous glass materials, and micro- and nanofibres are created from this mixture by spinning. Besides, their surface is newly covered with the second additives.
  • These additives markedly contribute to the required electrochemical and mechanical functionality of the created function-concentration gradient of the composite layers prepared. They influence, for example, electron and ion conductivity in these layers and also mechanical cohesion and electric contact of composite layers at volume changes in the layers during the battery cell activity, which has a large impact, for example, on the value of internal resistance of the cell and on its efficiency.
  • the actual creation of the function-gradient concentration of composite layers of the cell is described below in the examples of implementation.
  • the secondary battery cell can, moreover, be advantageously assembled of a combination of several composite layers, which may further increase the positive influence of the function-gradient concentration, leading to an increase in energy density in the cells, their cyclability and rate of recharging or discharging.
  • a number of selected technological steps can be used for preparation of individual preforms or intermediate products which can be manufactured, stored and used when required, or they can be used in parallel manufacturing processes. For example, it is possible to prepare glass materials, mixtures of the first or the second additives, their dry mixtures and especially individual composites and even composite layers to stock.
  • the technological procedure according to this invention leads to the obtaining of the assemblies of function-gradient composite layers of the cathode, electrolyte and anode, which are optimised in such a way that they form a solid secondary battery cell with a solid electrolyte (all-solid-state-battery), i.e. not containing organic liquid electrolyte, which is a necessary fundamental component in the existing secondary batteries, referred to in the patent literature.
  • the currently normally used electrolyte based on organic liquids can be a very weak point of the existing secondary battery cells in electromobiles, because it is combustible and easily subject to decomposition into toxic gaseous products, for example through the effects of a locally increased temperature or the effects of increased voltage.
  • a secondary battery cell according to this invention is non-combustible because it is based on inorganic glass.
  • the initial inorganic glass used is, with its amorphous nature, similar to the amorphous nature of liquids, and therefore it can be a very prospective substitution for liquid electrolytes.
  • this cell contains amorphous glass with a large free volume in the structure, this cell is able to achieve even better characteristics in comparison to the cells with a combustible liquid organic electrolyte.
  • a disadvantage of fragility of low flexibility of glass is just resolved in the invention in an innovative way by way of flexible composite layers.
  • the mixture of the carrier polymer contains a mixture of TEOS, PVP, ethanol and water, namely TEOS in a quantity from 0.01 to 10.37% (molar); PVP in a quantity from 0.03 to 0.05% (molar); ethanol in a quantity from 68.85 to 99.92% (molar); and water in a quantity from 0.02 to 20.75% (molar).
  • Figure 1.1 A secondary battery cell in an axonometric view with one layer of the cathode, anode and electrolyte;
  • Figure 1.2 A secondary battery cell in an axonometric view with two layers of the cathode, anode and electrolyte;
  • Figure 1.3 A secondary battery cell in an axonometric view with three layers of the cathode, anode and electrolyte;
  • Figure 1.4 An axonometric view of a secondary battery cell with one layer of the cathode, electrolyte and anode, with indicated roughness between them;
  • Figure 1.5 A view of the front side of a secondary battery cell from Fig. 4 with a detailed illustration of roughness between the cathode, electrolyte and anode.
  • Figure 2.8 Schematic illustration of the spinning equipment - electrospinning.
  • FIG. 3.1 View of the front side of the secondary battery cell from Fig. 1 with one layer of the cathode, anode and electrolyte, with schematic illustration at discharging and recharging of the secondary battery cell;
  • Figure 3.2 Charging curve for a secondary battery cell with two layers of the cathode, anode and electrolyte, illustrating voltage dependence of this cell on time during its recharging;
  • Figure 3.3 Charging and discharging curves for s secondary battery cell with two layers of the cathode, anode and electrolyte, illustrating dependence of the charging/discharging current on the recharging and discharging times;
  • Figure 3.4 Impedance spectrum of a battery cell with two layers of the cathode, anode and electrolyte.
  • Figure 4.1 Shot of one layer of fibres of the GMCK glass of the cathode from an optical microscope
  • Figure 4.2 Shot of one layer of fibres of the GFIC glass of the electrolyte from an optical microscope
  • Figure 4.4 Shot of one layer of fibres of the GMCA glass of the anode from an optical microscope.
  • Figure 5.1 View of a secondary battery cell from the cathode side
  • Figure 5.2 View of a secondary battery cell from the anode side.
  • FIGs 1.1, 1.2, 1.3 illustrate schematically particular possibilities of a solution of secondary battery cells B1 (Fig. 1.1), B2 (Fig.1.2) and B3 (Fig. 1.3).
  • Every secondary battery cell consists of three essential parts, namely cathode K and anode A, between which the electrolyte E is placed.
  • the collector KK is always placed from the external side of the cathode K, and the collector KA is placed from the external side of the anode A.
  • the secondary battery cells B1, B2, B3 have, in the example design, the shape of a rectangular parallelepiped and also the anode A, cathode K and electrolyte E have the shape of a rectangular parallelepiped as well.
  • Every secondary battery cell B1, B2, B3 has the height h, length I and width w. (Fig. 1.1, 1.2,
  • the secondary battery cell B1 (Fig. 1.1), secondary battery cell_B2 (Fig. 1.2) and secondary battery cell B3 (Fig. 1.3) in the example implementation have e.g., total height h_90 mm, total length J_60 mm and total width w 6 mm.
  • Figures 1.1, 1.2, 1.3 are schematic, in fact the cells are, with regard to the width dimension w, always basically flat secondary battery cells B1, B2, B3.
  • the different weight of the battery cells B1, B2, B3 is given by the number of layers of the cathode K, anode A and electrolyte E.
  • Figure 1.1 illustrates the assembly of the secondary battery cell B1, which consists of the cathode anode A1 and electrolyte E1.
  • Cathode K1 consists of one layer K1.1.
  • Electrolyte E1 consists of one layer E1.1.
  • Anode A1 consists of one layer A1.1.
  • Secondary battery cell B1 in the particular example implementation features e.g.: total height h 90 mm, total length I 60 mm and total width w 6mm.
  • Secondary battery cell B1 in the particular example implementation features e.g.: width W K1.1 of one layer K1.1 of the cathode K1 corresponding to 2.8 mm; width W E1.1 of one layer E1.1 of the electrolyte E1 corresponding to 0.4 mm; and width w A1.1 of one layer A1.1 of the anode A1 corresponding to 2.8 mm.
  • the height h and length I of the cathode K1.1, anode A1.1 and electrolyte E1.1 correspond to total dimensions of the secondary battery cell B1.
  • the edge layers K1.1 of the cathode K1 and A1.1 of the anode A1 are greater in comparison to the central layer E1.1 of the electrolyte E1 so that it can be possible to achieve sufficiently high capacity of the secondary battery cell B1
  • Roughness R a between these layers K1.1, E1.1 and A1.1 is in the range from 50 to 100 microns, with an advantage from 60 to 90 microns, with an advantage from 70 to 80 microns, with an advantage 60 microns.
  • This roughness R a helps to achieve a better mutual interconnection of the interface between the layers K1.1, E1.1 and A1.1 and better cohesion between them with the use of a "zip" effect.
  • the weight of this battery cell B1 is approx. 33 g.
  • Figure 1.2 illustrates an assembly of the secondary battery cell B2, which consists of the cathode K2, electrolyte E2 and anode A2
  • Cathode K2 consists of two layers K2.1, K2.2.
  • Electrolyte E2 consists of two layers E2.1, E2.2.
  • Anode A2 consists of two layers A2.1, A2.2.
  • the secondary battery cell B2 has, in the sequential order (Fig. 1.2): cathode K2, which has the first layer K2.1 and the second layer K2.2; electrolyte E2 with the first layer E2.1 and the second layer E2.2; and anode A2 with the first layer A2.1 and the second layer A2.2
  • the secondary battery cell B2 in the particular example implementation has a total height h of 90 mm, total length I of 60 mm and total width w of 6 mm.
  • the total height h and the total length I, together of all the layers K2.1, K2.2 of the cathode K2, all the layers A2.1, A2.2 of the anode A2 and all the layers E2.1, E2.2 of the electrolyte E2, are identical with the total height h and with the total length I, respectively, of the secondary battery cell B2.
  • the secondary battery cell B2 has width W K2.1 of the first layer K2.1 of the cathode K2 corresponding to 1.4 mm and width W K 2.2 of the second layer K2.2 of the cathode K2 also 1.4 mm; width W E2.1 of the first layer E2.1 of the electrolyte E2 corresponding to 0.2 mm and width w E2.e of the second layer E2.2 of the electrolyte E2 also 0.2 mm; and width W A2.1 of the first layer A2.1 of the anode A2 corresponding to 1.4 mm and width W A2.2 of the second layer A2.2 of the anode A2 also 1.4 mm.
  • the edge layers of the cathode K1 and anode A1 feature a greater width, in comparison to the electrolyte E2 placed between them, so that it can be possible to achieve sufficiently high capacity of the secondary battery cell B2.
  • Roughness R a _ between these layers K2.1, K2.2; E2.1, E2.2; and A2.1, A2.2; and also between the interfaces between the cathode K2 and the electrolyte E2; and between the electrolyte E2 and the anode A2; is in the range from 30 to 80 microns, with an advantage 40 to 70 microns, and with an advantage 50 to 60 microns and with an advantage about 55 microns.
  • This roughness R a helps to achieve a positive mutual interconnection of individual interfaces and better cohesion between them with the use of a "zip" effect.
  • the weight of this battery cell B2 is about 38 g.
  • Figure 1.3 shows the assembly of the secondary battery cell J33, which contains the cathode K3, anode A3 and electrolyte E3.
  • Cathode K3 consists of three layers K3.1, K3.2, K3.3.
  • Electrolyte E3 consists of three layers E3.1, E3.2, E3.3.
  • Anode A3 consists of three layers A3.1, A3.2, A3.3.
  • the secondary battery cell B3 in the particular example design has a total height h 90 mm, total length I 60 mm and total width w 6 mm.
  • A3.2, A3.3 of the anode A3 and of all the layers E3.1, E3.2, E3.3 of the electrolyte E3, are identical with the total height h and with the total length j, respectively, of the secondary battery cell B3.
  • the secondary battery cell B3 has, however, a different width of individual layers, namely: width W K3 1 of the first layer K3.1 of the cathode K3 is 1.0 mm, width W K3.2 of the second layer K3.2 of the cathode K3 is 0.9 mm and width W K3.3 of the third layer K3.3 of the cathode K3 is 0.9 mm; width W E3.1 of the first layer E3.1 of the electrolyte E3 is 0.1 mm width W E3.2 of the second layer E3.2 of the electrolyte E3 is 0.2 mm and width W E3.3 of the third layer E3.3 of the electrolyte E3 is 0.1 mm; width W A3.1 of the first layer A3.1 of the anode A3 is 0.9 mm, width W A3.2 of the second layer A3.2 of the anode A3 is 0.9 mm and width W A3.3 of the third layer A3.3 of the anode A3 is 1.0 mm.
  • edge electrodes, cathode K3 and anode A3 have a greater width, in comparison to the electrolyte E3 placed between them, so that it can be possible to achieve sufficiently high capacity of the secondary battery cell
  • Roughness R a _ on the interface between these layers K3.1, K3.2. K3.3; E3.1, E3.2, E3.3; and A3.1, A3.2, A3.3; and also on the interfaces between the cathode K3 and the electrolyte E3; and between the electrolyte E3 and the anode A3; is in the range from 30 to 80 microns, with an advantage about 50 microns.
  • This roughness R a helps to achieve positive mutual interconnection of individual interfaces and better cohesion between them by means of the "zip" effect.
  • the weight of this battery cell B2 is about 38 g.
  • Figure 1.4 illustrates, schematically in an axonometric view, the secondary battery cell B1 with one layer K1.1 of the cathode K1, one layer A1.1 of the anode A1 and one layer
  • E1.1 of the electrolyte E1. It illustrates, in a simplified way and schematically, two interfaces, indicated by means of a waved line.
  • One interface is between the layer K1.1 of the cathode K1 and the layer E1.1 of the electrolyte E1.
  • the second interface is between the layer E1.1 of the electrolyte E1 and the interface A1.1 of the anode A1.
  • Both the interfaces represent, in a simplified manner, roughness of external contact surfaces between the cathode K1 and the electrolyte E1; and the roughness of external contact surfaces between the electrolyte E1 and the anode A1.
  • Figure 1.5 illustrates the front wall of the secondary battery cell B1 with the width w K1.1 of the cathode K1, width w AK1.1 of the anode A1 and width w E1.1 of the electrolyte E1 ; and roughness R a is illustrated between them in a magnified schematic scale.
  • Chemical composition for function-gradient layers of the secondary battery cell B is based on the state-of-the-art technology of both the applicants, CZ PV 2017 - 859, and includes multi-component glass materials for the cathode K, electrolyte E and anode A, which are marked in this invention by means of relationship marks GMCK, GMCA, and GMCE.
  • the marks GMCK and GMCA relate to glass materials for electrodes, cathode K and anode A
  • the mark GF1C relates to the glass for the electrolyte E.
  • the mark GMCK Glass Mixed Conductor Cathode identifies glass GMCK for the cathode K whose content is the highest in the cathode K.
  • the mark GMCA Glass Mixed Conductor Anode identifies glass for the anode A, whose content is the highest in the anode A.
  • Both of these multi-component glass materials GMCK and GMCA have mixed ion and electron conductivity, where specific ion conductivity is at 25°C at least 10 -4 S.m -1 and specific electron conductivity at 25°C is at least 10 -6 S.m -1 .
  • the mark GFIC Glass Fast Ion Conductor
  • Glass GFIC for the electrolyte E concerns multi- component glass with high ion conductivity and very low electron conductivity, whose ion conductivity at 25°C is at least 10 -3 S.m -1 and the electron conductivity at 25°C is at least 3 orders lower than its specific ion conductivity and corresponds to the value at least 10 -6 S.m -1 .
  • This glass GFIC for the electrolyte E is isotropic and has, basically, the same value in all the directions and the electron conductivity at least 3 orders lower than its specific ion conductivity.
  • These multi-component glass materials GMCK, GMCA and GFIC are present in the cathode K, in the anode A and in the electrolyte E in the form of glass micro- and nanofibres, glass particles and amorphous glass.
  • Individual components of these glass materials GMCK, GMCA and GFIC are selected in such a way that they can form function-gradient concentration.
  • Function-gradient concentration denotes a change in the concentration of immobile components of these glass materials depending on the distance between the collector KK of the cathode K and the opposite collector KA of the anode A.
  • the mobile component in these glass materials GMCK, GMCA and GFIC is either lithium cation Li + or sodium cation Na + .
  • An improved solution according to this invention consists in these multi-component glass materials GMCK for the cathode K, glass GMCA for the anode A and glass GFIC for the electrolyte E, completed (on the basis of possible selected production, described at a detailed level below) with additives, added to melted glass materials GMCK, GMCA and GFIC.
  • suitable first additives are added to them, namely the first additive A1K for the cathode K; the first additive A1A for the anode A; and the first additive A1E for the electrolyte E; mainly for an increase in conductivity and effectiveness of the transfer of electric charge and the rate of reduction- oxidation reactions.
  • second additives are further added to their surface, namely the second additive A2K for the cathode K, the second additive A2A for the anode and the second additive A2E for the electrolyte E, especially for an increase in cohesion and adhesion of layers and facilitation of material transition through the interface between individual layers.
  • This first additives A1K; A1A; A1E; and second additives A2K; A2A; A2E are added to glass materials GMCK; GFIC; GMCA in a magnitude of tenths or units of volume %.
  • the composite in this invention consists of a mixture of glass materials GMCK, GFIC and GMCA in a mixture with the first additives A1K, A1E, A1A, inorganic (mostly) glass or (possibly) metallic fibres and with second additives A2K, A23E, A2A.
  • Inorganic fibres arise by burning polymer nanofibres after the below-explained thermal treatment after electrostatic spinning, during which the organic component is eliminated at an increased temperature.
  • the finished composite layer denotes the pressed composite in this invention.
  • Cathode K contains a layer of the composite based on glass GMCK with an admixture of the composite based on glass GFIC. This admixture of glass GFIC is situated in the cathode K in the vicinity of the electrolyte E, on the side facing the collector KK.
  • Anode A contains a layer of the composite based on glass GMCA with an admixture of the composite based on glass GFIC. This admixture of glass GFIC is situated in the anode A in the vicinity of the electrolyte E, on the side facing the collector KA.
  • the percentage voluminous share of the layers of composites based on glass materials GMCK/GFIC in the cathode K and of the layers of composites based on glass materials GMCA/GFIC in the anode A corresponds to the values from 100 to 0.1; and with an advantage from 90 to 10; with an advantage from 60 to 40 and with an advantage around 50.
  • Tables 1, 2 and 3 provide for more detailed clarifications of possible example and proven creations of function-gradient concentrations in composite layers based on glass materials GMCK; GMCA; GFIC and suitable additives A1K, A1A, A1E; A2K, A2A, A2E.
  • the text and tables below use weight %, molar % and volume %.
  • the weight percentage is intended e.g., for the weighing of the glass batch for the selection of the glass GMCK, GFIC and GMCA.
  • the molar percentage is suitable and intended for assessment of the structure of compounds, chemical reactions, mutual ratios of the number of atoms and molecules arising from them, e.g., solid spinel solutions of NiFe 2 O 4 or Fe 3 O 4 .
  • volume percentage is intended for expression of the volume of solutions and their flow, e.g., during their mixing or extrusion from the spinning equipment. Also, in Tables 1, 2 and 3 these figures facilitate a well-arranged and clear description of the battery cells B with regard to the assessment of the important volumetric energy density.
  • Each layer of glass materials forms a sum of 100% (vol.), namely: the layer K1.1 containing the glass GMCK and GFIC with the first additive A1K and the second additive A2K; the layer E1.1 containing the glass GFIC and the first additive A1E and the second additive A2E ; and also the layer A1.1 containing the glass GFIC and GMCA and the first additive A1A and the second additive A2A.
  • the composite layer K1.1 contains mostly the amorphous glass GMCK with the additive A1K, A2K for the cathode K1.
  • This composite layer K1.1 performs a function of active substance and ensures a highly efficient transfer of the charge from the ions Li + or Na + in the cathode K1.
  • the composite layer K1.1 contains a very small quantity of the amorphous glass GFIC for the electrolyte E, which ensures good transport of the ions Li + or Na + and their intercalation into the entire volume of the cathode K1.
  • the voluminous ratio of the content of the glass materials GMCK/GFIC can be generally in the range from 0.1 to 100, in this particular case 30.7.
  • it contains crystalline metallic particles of the additives A1K, A2K, which increase electron conductivity of this composite, and thus they facilitate transport of electrons to the collector KK of the cathode K1.
  • the composite layer E1.1 of the electrolyte E1 has a function of a separator, separating the cathode K1 from the anode A1, and consists of the amorphous glass GFIC, whose high ion conductivity, together with a smaller quantity of crystalline metallic additives A1E, A2E, enables a rapid transport of charge carriers at simultaneously very low electron conductivity, and this way it successfully prevents the secondary battery cell B1 from self-discharging.
  • the composite layer A1.1 of the anode A1 contains mostly amorphous multi-component glass GMKA performing the function of active substance, ensuring a highly efficient transfer of charge and redox reaction of Li + or Na + ions. Besides, it contains a small quantity of the amorphous glass GFIC ensuring good transport of Li + or Na + ions and their intercalation into the entire volume of the anode A1. The ratio of the contents of the glass materials GMCA/GFIC is 18.0. And in smaller quantities too, it contains crystalline metallic particles of the additives A1A, A2A, which increase electron conductivity of this composite, and thus they facilitate transport of electrons to the collector KA of the anode A1.
  • E2,l, E2.2 based on the glass GFIC and additives A1E, A2E for the electrolyte E2;
  • each of these composite layers of given glass materials together with appropriate first and second additives gives a sum of 100% (vol.). This means 100% by volume for: composite layer K2.1 with the first additive A1A and the second additive A2K, composite layer K2.2 with the first additive A1A and the second additive A2K; composite layer E2.1 with the first additive A1E and the second additive A2E, composite layer E2.2 with the first additive A1E and the second additive A2E, composite layer A2.1 with the first additive A1A and the second additive A2A, composite layer A2.2 with the first additive A1A and the second additive A2A.
  • the layer K2.1 contains mostly amorphous glass GMCK for the cathode K2 performing the function of an active substance ensuring redox reactions for a highly efficient transfer of charge from Li + or Na + ions. Besides, it contains a small quantity of the amorphous glass GFIC for the anode A ensuring good transport of Li + or Na + ions and their intercalation to the entire cathode volume.
  • the ratio of the content of glass materials GMCK/GFIC is 47.0. It contains also crystalline metallic particles of suitable additives AIK, A2K, which increase electron conductivity of this composite, and thus they facilitate transport of electrons to the collector KK of the cathode K.
  • the ratio of the glass materials GMCK/GFIC changes to 3.3 and therefore the share of ion conductivity rises.
  • This layer K2.2 contains a small quantity of crystalline metallic particles of the additives A1K, A2K as well. Through this process, the layer K2.2 creates a desirable function-gradient transition of characteristics between the cathode K and the electrolyte E and ensures good mutual electrochemical and mechanical compatibility of the composite layers of the cathode and electrolyte.
  • the layer E2.1 of the electrolyte E consists of the amorphous glass GFIC, whose high ion conductivity enables rapid transport of charge carriers at simultaneously very low electron conductivity, and this way it successfully prevents the secondary battery cell B2 from selfdischarging.
  • the subsequent layer E2.2 of the electrolyte E contains mostly amorphous glass GFIC ensuring high ion conductivity and small quantity of the amorphous glass for the anode A2.1 with the additives A1E, A2E; at the ratio of the glass materials GMCA/GFIC corresponding to 0.05.
  • This layer E2.2 markedly improves compatibility of the electrolyte E and the anode A, and this way it markedly increases capacity of the secondary battery cell B2 and its long-term lifetime at a large number of cycling operations. These characteristics are supported at the anode A by the subsequent function-gradient layer A2.1 with the ratio of the glass materials GMCA/GFIC 2.6 and a small quantity of the additives A1E, A2E.
  • the subsequent layer A2.2 contains mostly amorphous glass GMCA performing the function of an active substance ensuring redox reactions for a highly efficient transfer of charge from Li + or Na + ions. Besides, it contains a small quantity of the amorphous glass GFIC ensuring good transport of Li + or Na + ions and their migration to the entire volume of the anode A. The ratio of the content of the glass materials GMCA/GFIC is 23.0.
  • the layer A2.2 contains also an increased content of crystalline metallic particles of the additives A1A, A2A, which increase its electron conductivity, and thus they facilitate transport of electrons to the collector KA of the anode A.
  • each of these composite layers of given glass materials together with appropriate first and second additives gives a sum of 100% (vol.). This means 100% by volume for: composite layer K3.1 with the first additive AIA and the second additive A2K, composite layer K3.2 with the first additive AIA and the second additive A2K, composite layer K3.3 with the first additive A1A and the second additive A2K, composite layer E3.1 with the first additive A1E and the second additive A2E, composite layer E3.2 with the first additive A1E and the second additive A2E, composite layer E3.2 with the first additive A1E and the second additive A2E, composite layer A3.1 with the first additive A1A and the second additive A2A, composite layer A3.2 with the first additive A1A and the second additive A2A, composite layer A3.3 with the first additive A1A and the second additive A2A.
  • the first additive A1K is added to powder mixture of the glass GMCK for the cathode K for an increase in the cathode material activity.
  • the second additive A2K is added onto the exfoliated micro- and nanofibres of layers for the cathode K for an increase in adhesion of layers of the cathode K.
  • the first additive A1E is added to powder mixture of the glass GFIC for the electrolyte E for an increase in ion conductivity of the electrolyte E.
  • the second additive A2E is added onto the exfoliated micro- and nanofibres of layers for the electrolyte E for an increase in adhesion of layers of the electrolyte E.
  • the first additive A1 is added to powder mixture of the glass GMCA for the anode A for an increase in the anode material activity.
  • the second additive A2A is added onto the exfoliated micro- and nanofibres of layers for the anode A for an increase in adhesion of layers of the anode A.
  • the layer K3.1 contains mostly amorphous glass GMCK performing the function of an active substance ensuring redox reactions for highly efficient transfer of charge from Li + or Na + ions during the cycles of recharging or discharging.
  • the added small quantity of amorphous glass GFIC ensures good transport of Li + or Na + ions and their effective intercalation to the entire volume of the cathode K.
  • the ratio of the content of GMCK/GFIC is 47.
  • this layer K3.1 contains crystalline metallic particles of the additives A1K, A2K which increase its electron conductivity, and thus they facilitate transport of electrons to the collector KK of the cathode K.
  • the ratio GMCK/GFIC decreases to 3.3. That is why the share of ion conductivity grows and the share of electron conductivity in the total conductivity decreases.
  • This composite contains also a small quantity of crystalline metallic particles of the additives A1K, A2K.
  • the next layer K3.3 features still a lower ratio GMCK/GFIC equal to 1.0, and therefore its ion conductivity still rises while the electron conductivity is decreasing.
  • the layers K3.2 and K3.3 therefore create a very gradual, and therefore highly effective function-gradient transition of electrochemical, thermal and mechanical characteristics between the cathode K3 and electrolyte E3 and ensure excellent mutual physical and chemical compatibility of composite layers of the cathode and of the electrolyte.
  • the electrolyte layer E3.1 contains amorphous glass GFIC as the main highly ion- conductive component. Together with a small quantity of amorphous glass GMCK for the cathode K at the ratio GMCK/GFIC being equal to 0.05, it forms an initial transition layer of the function-gradient concentration between the layer K3.3 of the cathode K and the layer E3.2 of the electrolyte E.
  • This layer E3.1 markedly improves compatibility of the layers of the electrolyte E and of the anode A of the secondary battery cell B3, and thus it markedly increases capacity of the secondary battery cell B3 and its long-term lifetime at a large number of cycles.
  • Another separator layer E3.2 of the electrolyte E is again formed of the amorphous glass GFIC featuring high ion conductivity and very low electron conductivity.
  • the neighbouring layer of the electrolyte E3.3 contains mostly amorphous glass GFIC for the electrolyte E ensuring high ion conductivity and small quantity of amorphous glass GMCA for the anode A at the ratio GMCA/GF1C being equal to 0.05.
  • This is an initial transition layer of function-gradient concentration between the layer E3.3 of the electrolyte E and the layer A3.1 of the anode A.
  • This layer E3.3 markedly improves compatibility of layers of the electrolyte E and anode A, and thus it markedly increases movability of charge carriers especially in the direction perpendicular to mutual contact areas of individual layers. This way, the electric resistance of the secondary battery cell B3 is markedly reduced, which is advantageous for the battery supplying a high electric power output. Simultaneously, the capacity of the battery markedly increases and the cyclability of the battery is extended.
  • the anode A is created by the layer A3.1 with the ratio GMCA/GFIC being equal to 1.0 with a very small quantity of the added crystalline metallic additive A1A, A2A; the following layer A3.2 with the ratio GMCA/GFIC being equal to 2.6 with a smaller quantity of the crystalline metallic additive A1A, A2A; and the end layer A3.3 with the ratio GMCA/GFIC being equal to 23.0 and with a larger quantity of the crystalline metallic additive A1A, A2A.
  • Percentage molar chemical composition of the amorphous multi-component glass GMCK-Li for: one layer K1.l of the cathode K1 of the secondary lithium battery cell B1; two layers K2.1, K2.2 of the cathode K2 of the secondary lithium battery cell B2; and three layers K3.1, K3.2, K3.3 of the cathode K3 of the secondary lithium battery cell B3.
  • Li 2 O in quantity from 8.2 to 8.9 (molar %) serves for creation of the mobile cation Li + .
  • Oxides selected according to their electronegativity serve as other components for creation of the glass GMCK-Li of the cathode K in such a way that it can be possible to create environment with optimum distribution of partial negative charge on oxygen atoms for achieving the required high mixed electric conductivity and rapid transfer of charge through rapid reduction-oxidation reactions.
  • the oxidised form of an oxide of polyvalent elements is its form at a higher oxidation state and the reduced form is its form at a lower oxidation state.
  • Percentage molar chemical composition of the amorphous multi-component glass GMCK-Na for: one layer K1.1 of the cathode K1 of the secondary sodium battery cell B1; two layers K2.1. K2.2 of the cathode K2, of the secondary sodium battery cell B2; and three layers K3.1, K3.2, K3.3 of the cathode K3 of the secondary sodium battery cell B3.
  • Na 2 O in quantity from 8.4 to 9.1 (molar %) serves for creation of the mobile cation Na + .
  • Oxides selected according to their electronegativity serve as other components for creation of the glass GMCK-Na of the cathode K in such a way that it can be possible to create environment with optimum distribution of partial negative charge on oxygen atoms for achieving the required high mixed electric conductivity and rapid transfer of charge through rapid reduction-oxidation reactions.
  • Percentage molar chemical composition of the amorphous multi-component glass GFIC-Li for: one layer E1.1 of the electrolyte E1 of the secondary lithium battery cell B1; two layers E2.1, E2.2 of the electrolyte E2 of the secondary lithium battery cell B2; and three layers E3.1, E3.2, E3.3 of the electrolyte E3 of the secondary lithium battery cell B3.
  • U 2 O in a quantity from 8.8 to 10.9 (molar %); LiCI in a quantity from 31.0 to 31.2 (molar %) and Lil in a quantity from 3.9 to 4.1 (molar %) serve for creation of the Li + mobile cation.
  • Oxides selected according to their electronegativity serve as other components for creation of the glass GFIC-Li of the electrolyte E in such a way that it can be possible to create environment with optimum distribution of partial negative charge on oxygen atoms for achieving the required high ion conductivity.
  • Percentage molar chemical composition of the amorphous multi-component glass GFIC-Na for: one layer E1.1 of the electrolyte E1 of the secondary sodium battery cell B1; two layers E2.1, E2.2 of the electrolyte E2, of the secondary sodium battery cell B2; and three layers E3.1, E3.2, E3.3 of the electrolyte AE3 of the secondary sodium battery cell B3.
  • Na 2 O in a quantity from 8.9 to 10.0 (molar %), NaCI in a quantity from 32.0 to 33.1 (molar %) and Nal in a quantity from 3.9 to 4.3 (molar %) serve for creation of the mobile cation Na + .
  • Oxides selected according to their electronegativity serve as other components for creation of the glass GFIC-Na of the electrolyte E in such a way that it can be possible to create environment with optimum distribution of partial negative charge on oxygen atoms for achieving the required high ion conductivity.
  • E.g., Cu, Fe, Si are used as the first additive A1E; e.g., NaPO 3 , Na 3 BO 3j Al 2 O 3 are used as the second additive A2E
  • Li 2 O in a quantity from 16.5 to 18.4 (molar %) serve for creation of the mobile cation Li + .
  • Oxides selected according to their electronegativity serve as other components for creation of the glass GMCA-Li of the anode A in such a way that it can be possible to create environment with optimum distribution of partial negative charge on oxygen atoms for achieving the required high mixed electric conductivity and rapid charge transfer through fast reduction-oxidation reactions.
  • Percentage molar chemical composition of the amorphous multi-component glass GMCA- Li for: one layer A1.1 of the anode A1 of the secondary sodium battery cell B1; two layers A2.1, A2.2 of the anode A2, of the secondary sodium battery cell B2; and three layers A3.1, A3.2, A3.3 of the anode A3 of the secondary sodium battery cell B3.
  • Percentage molar chemical composition of the second additive A2A of the composite layers A1.1; A2.1, A2.2; A3.1, A3.2, A3.3; of the anode A1; A2; A3; of the lithium secondary battery cell B1; B2; B3.
  • Percentage molar chemical composition of the amorphous multi-component glass GMCA-Na for: one layer All of the anode A1 of the secondary sodium battery cell B1; two layers A2.1, A2.2 of the anode A2 of the secondary sodium battery cell B2; and three layers A3.1, A3.2, A3.3 of the anode A3 of the secondary sodium battery cell B3.
  • Na 2 O in a quantity from 16.1 to 17.5 (molar %) serves for creation of mobile Na + cation.
  • Oxides selected according to their electronegativity serve as other components for creation of the glass GMCA-Na of the anode A in such a way that it can be possible to create environment with optimum distribution of partial negative charge on oxygen atoms for achieving the required high mixed electric conductivity and a rapid charge transfer through fast reduction-oxidation reactions.
  • Table 9a
  • Percentage molar chemical composition the first additive A1A of the composite layer A1.1, A2.1, A2.2; A3.1, A3.2, A3.3; of the anode A1; A2; A3; of the sodium secondary battery cell B1;
  • TEOS from the Germany-based company Merc Sigma-Aldrich, purity 99.95% (weight).
  • PVP from the Germany-based company Sigma- Aldrich, purity 99.98 % (weight).
  • the oxides, carbonates, metals used originated from the Germany-based companies Sigma-Aldrich, PuraLab, HiChem, Lachner (p.a. purity) or from Fischer Scientific.
  • composition of amorphous glass materials of the cathode K is stated in molar %, in Table 4 for the lithium secondary battery cells B1, B2, and B3; and for the sodium secondary battery cells B1, B2 and B3 in Table 5. Composition of these glass materials is developed in such a way that it can be possible to achieve creation of the function-gradient concentration in the composite of cathodes with highly continuous transition of characteristics.
  • the ratio of oxidised and reduced forms of polyvalent elements M p is optimised in this composite in such a way that the composite can state high electron and mixed electric conductivity, ensuring cooperative mechanism of charge transfer and migration of ion carriers of the charge to the entire volume of the cathode K, which leads to the very effective use of the volume of an active substance of this electrode as large as possible.
  • This makes it possible to achieve a high rate and reversibility of electrode reactions, which is necessary for the battery cells B1, B2, and B3 to be able to provide a high current and power density.
  • These composites are, therefore, suitable for construction of batteries for electromobiles, where electric sources of a high current and power density are required.
  • Table 4a states characteristics of the lithium glass materials for layers of the cathode K
  • Table 4b states composition of the first additives A1K
  • Table 4c provides for composition of the second additive A2K for these lithium glass materials.
  • Table 5a states characteristics of the sodium glass materials for layers of the cathode K
  • Table 5b states composition of the first additives A1K
  • Table 5c provides for composition of the second additive A2K for these sodium glass materials.
  • Chemical composition of amorphous glass materials for the electrolyte E is stated in molar %, for the lithium secondary battery cells B1, B2 and B3 in Table 6, containing Li + ions as highly mobile ion carriers of a charge; and the chemical composition of amorphous glass materials for the sodium secondary battery cells B1, B2, B3 is stated in Table 7, containing Na + ions as highly mobile ion carriers of a charge.
  • Chemical composition of the electrolytes E features, for both Li + ions and Na + ions, basicity of the glass matrix set up in a directed manner on the basis of an optimum ratio of concentrations of electropositive and electronegative elements.
  • Table 6a states characteristics of lithium glass materials for layers of the electrolyte E
  • Table 6b states composition of the first additives A1E
  • Table 6c states composition of the second additives A2E for these lithium glass materials.
  • Table 7a states characteristics of sodium glass materials for layers of the electrolyte E
  • Table 7b states composition of the first additive A1E
  • Table 7c states composition of the second additive A2E for these sodium glass materials.
  • amorphous glass materials of the anode A is stated in molar % for the lithium secondary battery cells B1, B2, and B3 in Table 8; and for the sodium battery cells B1, B2 and B3 it is provided for in Table 9.
  • These glass materials feature an optimised representation of the ratio of oxidised and reduced forms of the polyvalent elements Mp with suitable electronegativity and electron affinity in such a way that the resulting glass can state a gradual transition from mixed electric conductivity to prevailing high electron conductivity in the area of contacts with the collector KA. This ensures the necessary cooperative mechanism of the charge transfer and migration of ion carriers of a charge to the entire volume of the anode A, which leads to a very effective use of the maximum possible volume of an active substance of this electrode.
  • Table 9a states characteristics of sodium glass materials for layers of the cathode A
  • Table 9b states composition of the first additives A1A
  • Table 9c states composition of the second additives A2A for these sodium glass materials.
  • the above-mentioned function-gradient composite layers for the cathode K, electrolyte E and anode A are therefore suitable for construction of the secondary battery cells Bi for example for electromobiles where high-capacity electric sources with high energy, current and power densities are required.
  • Oxides and carbonates of both metals and non-metals and actual metals used for the melting of glass materials and as the first as well as second additives were selected in such a way that the corresponding substance can be stable, little hygroscopic and cost- efficient.
  • These raw materials were supplied in the p.a. purity by such companies as Sigma-Aldrich spol. s.r.o, Na Hfebenech II 1718/10, 140 00 Prague 4, Czech Republic; Puralab spol. s.r.o., Podnikatelska 552, 19011 Prague, Bechovice, Hichem spol. s.r.o., Novodvorska 994/138, Branik, 142 00 Prague; Lach-Ner spol. s.r.o., Tovarni 157, 27711 Neratovice; Fisher Scientific, spol. s r.o., Kosmonautu 324, 53009 Pardubice.
  • Figure 2.1 has the first continuation marked as 2.1a and the second continuation marked as 2.1b.
  • the continuations 2.2a; 2.2b and 2.3a; 2.3b are marked in a similar way.
  • the first technological block represents preparation of composite layers of the cathode K, electrolyte E and anode A, at a more detailed level described in following chapters 3.1- 3.1.16.
  • the second technological block represents (from these obtained layers in the first technological block) preparation of the cathode K, electrolyte and anode A, at a more detailed level described in following chapters 3.2 - 3.2.3.
  • the third technological block represents assembly of the secondary battery cells B1; B2; B3 according to Figure 2.7 and at a more detailed level described in subsequent chapter 3.3. 3.1 Procedure of production of individual layers
  • the illustrated procedure states certain common technological steps, marked on the left side of each Figure of the flow charts and referred to below.
  • the arrangement of individual technological steps is ordered chronologically.
  • Markings 101. 201, 301 correspond to the technological step of the selection and choice of suitable chemical composition of the glass GMCK for the cathode K or of the glass GFIC for the electrolyte E or of the glass GMCA for the anode A, then also of the selection and choice of composition of the first additive A1K for the cathode K or of the first additive A1E for the electrolyte E or of the first additive A1A for the anode A.
  • Marking 101 corresponds to the choice of chemical composition of the glass materials GMCK; GFIC and selected composition of the first additives A1K; A1E, all of this for preparation of layers of the cathode K according to Figure 2.1.
  • Marking 201 corresponds to the choice of chemical composition of the glass materials GMCK; GFIC; GMCA and also of suitable chemical compositions of the first additives A1K; A1E; A1A. all of this for preparation of layers of the electrolyte E according to Figure 2.2.
  • Marking 301 corresponds to the choice of chemical composition of the glass materials GMCA; GFIC and of the first additives A1A; A1E, for preparation of layers of the anode A according to Figure 2.3.
  • Markings 102, 202, 302 state a technological step consisting in the input of raw materials in the form of glass batches and the first additives, namely the batch for the selected glass materials GMCK; GFIC; GMCA and suitable selected first additives A1K; A1E; A1A.
  • Marking 102 states a technological step consisting in the input of batches for the glass materials GMCK; GFIC and then it states the input of the first additives A1K; A1E, all of this being for preparation of layers of the cathodes K1; K2; K3 according to Figure 2.1.
  • Marking 202 states the input of batches for the glass materials GMCK; GFIC; GMCA, and moreover it states the input of the first additives A1K; A1E; A1A, all of this being for preparation of layers of the electrolytes E1; E2; E3 according to Figure 2.2.
  • Marking 302 states the input of batches for the glass GMCA and the glass GFIC. and moreover it states the input of the first additives A1A; A1E, all of this being for preparation of the anodes A1; A2; A3 according to Figure 2.3.
  • Markings 103, 203, 303 concern the subsequent technological step consisting in the melting of glass melts, for glass materials GMCK; GFIC; GMCA. If it is not necessary to ensure the control of the oxidation-reduction (redox) state of the glass melt, the melting operation takes place in the air. Nevertheless, if the control of the redox state of the glass melt is necessary, then the melting of glass melts takes place in the controlled atmosphere.
  • redox oxidation-reduction
  • Marking 103 concerns the melting of the glass melt GMCK; GFIC according to the above-stated possibility of the choice of the melting method, always for preparation of layers of the cathodes K1; K2; K3 according to Figure 2.1.
  • Marking 203 concerns the melting of the glass melt GMCK; GFIC; and of the glass melt GMCA according to the above-mentioned possibility of the choice of the melting method, for preparation of layers of the electrolytes E1; E2; E3 according to Figure 2.2.
  • Marking 303 concerns the melting of the glass melt GMCA; GFIC according to the above-mentioned possibility of the choice of the melting method, for preparation of layers of the anodes A1; A2; A3 according to Figure 2.3.
  • Markings 104, 204 and 304 represent the technological step of the process of cooling of melted glass materials, namely the glass materials GMCK; GFIC; GMCA, in the air or in a protective atmosphere.
  • Marking 104 represents the process of cooling of the melted glass GMCK; GFIC in the air or in a protective atmosphere, for preparation of layers of the cathodes K1; K2; K3 according to Figure 2.1.
  • Marking 204 represents the process of cooling of the melted glass GMCK; GFIC; GMCA in the air or in a protective atmosphere, for preparation of layers of the electrolytes E1; E2; E3 according to Figure 2.2.
  • Marking 304 represents the process of cooling of the melted glass GMCA; GFIC in the air or in a protective atmosphere, for preparation of layers of the anodes A1; A2; A3 according to Figure 2.3.
  • Markings 105, 205, 305 represent a subsequent technological step consisting in the crushing of melted and cooled glass into cullet, namely of the glass materials GMCK; GFIC; and the glass GMCA.
  • Marking 105 represents the technological step of the crushing of the glass GMCK; GFIC into cullet, all for preparation of layers of the cathode K1; K2; K3 according to Figure 2.1.
  • Marking 205 represents the technological step of the crushing of the glass GMCK; GFIC; GMCA into cullet, all for preparation of layers of the electrolytes E1; E2; E3 according to Figure 2.2.
  • Marking 305 represents a subsequent technological step of crushing of the glass GMCA; GFIC, all for preparation of layers of the anodes A1; A2; A3 according to Figure 2.3.
  • Markings 106, 206, 306 concern the technological step of adding the first additive A1K or the first additive A1E or the first additive A1A to the cullet of the glass GMCK, or to the cullet of the glass GFIC, or to the cullet of the glass GMCA.
  • This first additives set up electron conductivity of these materials, and thus also the effectiveness of the transfer of electric charge with the help of rapid oxidation-reduction reactions.
  • Marking 106 concerns adding the first additive A1K to the cullet of the glass GMCK; adding the first additive A1E to the cullet of the glass GFIC; for preparation of layers of the cathodes K1; K2; K3 according to Figure 2.1.
  • Marking 206 concerns adding the first additive A1E to the cullet of the glass GFIC; adding the first additive A1K to the cullet of the glass GMCK; adding the first additive A1A to the cullet of the glass GMCA; all of this being for preparation of layers of the electrolytes E1; E2; E3 according to Figure 2.2.
  • Marking 306 concerns adding the first additive A1E to the cullet of the glass GFIC; adding the first additive A1A to the cullet of the glass GMCA; all for preparation of layers of the anodes A1; A2; A3 according to Figure 2.3.
  • Markings 106a, 206a and 306a concern the technological step of mixing the cullet with the first additives for the cathode K or anode A or electrolyte E, with a reference to Tables 10, 14, 18, 22, 26, 30, 34, 38 and 42.
  • Marking 106a identifies mutual mixing of the glass GMCK with the additive A1K; of the glass GFIC with the additive A1E; with a reference to Tables 10, 22 and 34 and Fig. 2.1, all of this being for preparation of layers of the cathodes K1; K2; K3.
  • Marking 206a identifies mutual mixing of the glass GMCK with the additive A1K with the glass GFIC with the additive A1E and also with the glass GMCA and with the additive A1A; with a reference to Tables 14, 26 and 38 and Fig. 2.2, all of this being for preparation of layers of the electrolytes E1; E2; E3.
  • Marking 306a identifies mutual mixing of the glass GMCA with the additive A1A with the glass GFIC with the additive A1E; with a reference to Tables 18, 30 and 42 and Fig.
  • Markings 107, 207, 307 identify the technological step of grinding the cullet with the first additives into micro- and nanoparticles, namely the grinding of cullet of the glass GMCK together with the first additive A1K or grinding of the glass GFIC with the first additive A1E or grinding of the glass GMCA with the first additive A1A, with a reference to related Tables 10, 14, 18, 22, 26, 30, 34, 38 and 42 and related Fig. 2.1a, 2.2a, 2.3a.
  • Marking 107 identifies the grinding of cullet of the glass GMCK with the first additive A1K or of the glass GFIC with the first additive A1E, into micro- and nanoparticles, with a reference to Tables 10, 14, 22, 26, 34, and 38, for preparation of layers of the cathode K1; K2; K3 according to Figure 2.1a.
  • Marking 207 identifies the grinding of cullet of the glass GFIC with the first additive A1E or the grinding of cullet of the glass GMCK with the first additive A1K or the grinding of cullet of the glass GMCA with the first additive A1A, into micro- and nanoparticles for the electrolyte E1; E2; E3, with a reference to Tables 10, 14, 18, 26, 30, 34, 38 and 42, according to Figure 2.2a.
  • Marking 307 identifies the grinding of cullet of the glass GMCA with the first additive A1A or the grinding of cullet of the glass GFIC with the first additive A1E into micro- and nanoparticles; with a reference to Tables 14, 18, 22, 26, 30, 34, 38 and 42; for preparation of layers of the anodes A1; A2; A3 according to Figure 2.3a.
  • Markings 108, 208 and 308 represent the technological step of admixing obtained micro- and nanoparticles into carrier polymer liquid mixtures, where the obtained micro- and nanoparticles contain the glass GFIC with the first additive A1E or the glass GMCK with the first additive A1K or the glass GMCA with the first additive A1A, and the carrier polymer mixtures help to create micro- or nanofibres in an electric field; with a reference to related Tables 11, 12, 15, 16, 19, 20, 23, 24, 27, 28, 31, 32, 35, 36, 39, 40, 43 and 44 and related Figures 2.1a, 2.2b and 2.3a.
  • Marking 108 represents admixing the obtained micro- and nanoparticles into the carrier polymer liquid mixtures, which help to create micro- or nanofibres in an electric field; with a reference to Tables 11, 12, 15, 16, 23, 24, 27, 28, 35, 36, 39 and 40; for preparation of layers of the cathodes K1; K2; K3 according to Figure 2.1a.
  • Marking 208 represents admixing the obtained micro- and nanoparticles for the electrolyte E into the carrier polymer liquid mixtures, which help to create micro- or nanofibres in an electric field; with a reference to Tables 11, 12, 15, 16, 19, 20, 23, 24, 27, 28, 31, 32, 35, 36, 39, 40, 43 and 44; for preparation of layers of the electrolytes E1; E2; E3 according to Figure 2.2a.
  • Marking 308 represents admixing the micro- and nanoparticles for the anode A into the carrier polymer liquid mixtures, which help to create micro- or nanofibres in an electric field; with a reference to Tables 15, 16, 19, 20, 23, 24, 27, 28, 31, 32, 35, 36, 39, 40, 43 and 44; for preparation of layers of the anodes A1; A2; A3 according to Figure 2.3a.
  • Markings 109, 209, 309 illustrate the technological step of the dosing of the obtained mixture into an electric spinner with a reference to Tables 13, 17, 21, 25, 29, 33, 37, 41 and 45; and Figures 2.1a, 2.2a and 2.3a.
  • Marking 109 illustrates the dosing of the obtained mixture into the spinning equipment (electric spinner); with a reference to Tables 13, 25, 37; for preparation of layers of the cathodes K1; K2; K3 according to Figure 2.1a.
  • Marking 209 illustrates the dosing of the obtained mixture for preparation of layers of the electrolyte E into the spinning equipment; with a reference to Tables 17, 29, 41; for preparation of layers of the electrolytes E1; E2; E3 according to Figure 2.2a.
  • Marking 309 illustrates the dosing of the obtained mixture into the spinning equipment; with a reference to Tables 21, 33, 45; for preparation of layers of the anodes A1; A2; A3 according to Figure 2.3a.
  • Markings 110, 210, 310 show the technology of the step of the drawing of micro- and nanofibres in an electric field; with a reference to Figures 2.1a, 2.2a, 2.3a and also Figure 2.8.
  • Marking 110 shows the technology of the step of the drawing of micro- and nanofibres in an electric field for the cathodes K1; K2; K3 according to Figure 2.1a and with a reference to Figure 2.8.
  • Marking 210 shows the technology of the step of the drawing of micro- and nanofibres in an electric field for the electrolytes E1; E2; E3 according to Figure 2.2a and with a reference to Figure 2.8.
  • Marking 310 shows the technology of the step of the drawing of micro- and nanofibres in an electric field for the anodes A1; A2; A3 according to Figure 2.3a and with a reference to Figure 2.8.
  • Markings 111, 211, 311 are a subsequent technological step of thermal processing of micro- and nanofibres at temperatures from 200 to 1200°C with a reference to Figures 4.1, 4.2, 4.4 and Figures 2.1a, 2.2a and 2.3a. This technological step enables creation of flexible layers even of these purely inorganic materials and therefore non-combustible materials.
  • Marking 111 represents the technological step of thermal processing of micro- and nanofibres for preparation of layers of the cathodes K1; K2; K3 at temperatures from 200 to 1200°C according to Figure 2.1a and with a reference to Figures 4.1 and 4.2.
  • Marking 211 is a subsequent technological step of thermal processing of micro- and nanofibres for preparation of layers of the electrolytes E1; E2; E3 at temperatures from 200 to 1200°C according to Figure 2.2a and with a reference to Figures 4.1, 4.2 and 4.4.
  • Marking 311 is a subsequent technological step of thermal processing of micro- and nanofibres for preparation of layers of the anodes A1; A2; A3 at temperatures from 200 to 1200°C according to Figure 2.3a and with a reference to Figures 4.1, and 4.2.
  • Markings 112, 212, 312 represent a technological step of exfoliation of micro- and nanofibres. Exfoliation concerns the opening of the surface of micro/nanofibres, which leads to a significant increase in the ratio of the fibre surface to the fibre volume.
  • Marking 112 represents exfoliation of micro- and nanofibres for preparation of layers of the cathodes K1; K2; K3. Exfoliation concerns the opening of the surface of micro/nanofibres, which leads to a significant increase in the ratio of the fibre surface to the fibre volume according to Figure 2.1a.
  • Marking 212 represents exfoliation of micro- and nanofibres for preparation of layers of the electrolytes E1; E2; E3. Exfoliation concerns the opening of the surface of micro/nanofibres, which leads to a significant increase in the ratio of the fibre surface to the fibre volume according to Figure 2.2a.
  • Marking 312 represents exfoliation of micro- and nanofibres for preparation of layers of the anodes A1; A2i A3. Exfoliation concerns the opening of the surface of micro/nanofibres, which leads to a significant increase in the ratio of the fibre surface to the fibre volume according to
  • Markings 113, 213, 313 correspond to the important technological step of application of the second additive, namely the second additive A2K for the cathode K, the second additive A2E for the electrolyte E and the second additive A2A for the anode A.
  • the second additive ensures positive cohesion of composite layers and their adhesion e.g., also to the collector KK of the cathode K and to the collector KA of the anode A.
  • Marking 113 corresponds to the important step applying the second additive, namely the second additive A2K for the cathodes K1; K2; K3 according to Figure 2.1a and with a reference to Tables 4c, 5c, 6c, and 7c.
  • the second A2K ensures positive cohesion of composite layers and their adhesion e.g., also to the collector KK of the cathode K.
  • Marking 213 corresponds to the important step applying the second additive, namely the second additive A2E for the electrolytes E1; E2; E3 according to Figure 2.2a and with a reference to Tables 6c and 7c.
  • the second additive A2E ensures positive cohesion of composite layers.
  • Marking 313 corresponds to the important step applying the second additive, namely the second additive A2A for the anodes A1; A2; A3 according to Figure 2.3a and with a reference to Tables 8c and 9c.
  • the second additive A2A ensures positive cohesion of composite layers and their adhesion e.g., also to the collector KA of the anode A.
  • Markings 114, 124 and 314 concern a subsequent technological step of the pressing of obtained composite layers for the cathode K, electrolyte E and anode A.
  • Marking 114 concerns subsequent pressing of obtained composite layers for preparation of layers of the cathode K according to Figure 2.1b.
  • Marking 214 concerns subsequent pressing of obtained composite layers for preparation of layers of the electrolyte E according to Figure 2.2b.
  • Marking 314 concerns subsequent pressing of obtained composite layers for preparation of layers of the anode A according to Figure 2.3b.
  • Markings 115, 215 and 315 represent a technological step of subsequent thermal processing of the pressed layer obtained this way, which is carried out by heating to a temperature from 100 to 500°C and subsequent sufficiently slow cooling, with an advantage in the same equipment, for the purpose of achieving the adhesion of the second additives A2K: A2E; A2A, with a reference to Figures 2.1a, 2.2b and 2.2c.
  • Marking 115 represents subsequent thermal processing of the pressed layer, which is carried out by heating to a temperature from 100 to 500°C with subsequent cooling for the purpose of achieving the adhesion of the second additive A2K for preparation of layers of the cathode K according to Figure 2.1b.
  • Marking 215 represents subsequent thermal processing of pressed layers, which is carried out by heating to a temperature from 100 to 500°C and subsequent cooling for the purpose of achieving the adhesion of the second additive A2E for preparation of layers of the electrolyte E according to Figure 2.2b.
  • Marking 315 represents subsequent thermal processing of pressed layers, which is carried out by heating to a temperature from 100 to 500°C and subsequent cooling for the purpose of achieving the adhesion of the second additive A2A for preparation of layers of the anode A according to Figure 2.3b.
  • Markings 116, 216, 316 are a final technological step consisting in obtaining individual finished composite layers with a reference to Figures 1.1, 1.2, 1.3 and 2.1a, 2.2b, 2.3b, namely: composite layers K1.1; K2.1, K2.2; or layers K3.1, K3.2, K3.3 of the cathode K; or composite layers E1.1, or E2.1, E2.2; or E3.1, E3.2. E3.3 of the electrolyte E; or composite layers A1.1 or A2.1. A2.2 or A3.1, A3.2, A3.3 of the anode A.
  • Marking 116 is a final step consisting in obtaining finished composite layers with a reference to Figures 1.1 to 1.3, namely: composite layers K1.1; or K2.1, K2.2; or layers K3.1, K3.2, K3.3 of the cathode K according to Figure 2.1b.
  • Marking 216 is a final step consisting in obtaining finished composite layers with a reference to Figures 1.1 to 1.3, namely: composite layers E1.1; or E2.1, E2.2; or layers E3.1. E3.2, E3.3 of the electrolyte E according to Figure 2.2b.
  • Marking 316 is a final step consisting in obtaining finished composite layers with a reference to Figures 1.1 to 1.3, namely: composite layers A1.1; or A2.1, A2.2; or layers A3.1. A3.2, A3.3 of the anode A according to Figure 2.3b.
  • the second technological block represents preparation of the cathode, electrolyte and anode, and is illustrated in Figures 2.4 to 2.5.
  • Preparation of the cathode K is illustrated in Figure 2.4, preparation of the electrolyte E in Figure 2.5 and preparation of the anode A in Figure 2.6.
  • the technological procedure has certain common features with a reference to Figures 1.1 to 1.3.
  • Markings 401, 501, 601 illustrate a technological step, namely the number of optional layers, for this example 1 to 3 layers of the cathode K (Fig. 2.4) or electrolyte E (Fig. 2.5) and anode A (Fig. 2.6).
  • Marking 401 illustrates the number of selected and manufactured layers of the cathode K for the cell B1 created in Example 1 by means of one layer K1.1, or for the cell B2 created in Example 2 by means of two layers K2.1; K2.2, or for the cell B3 created by means of three layers K3.1; K3.2; K3.3 according to Figure 2.4, possibly also with a reference to Figures 1.1, 1.2, 1.3.
  • Marking 501 illustrates the number of optional layers for the electrolyte E, for the cell B1 created in Example 1 by means of one layer E1.1, or for the cell B2 created in Example 2 by means of two layers E2.1; E2.2, or for the cell B3 created by means of three layers E3.1; E3.2; E3.3. according to Figure 2.5, possibly also with a reference to Figures 1.1, 1.2, 1.3.
  • Marking 601 illustrates the number of optional layers for the anode A for the cell B1 created in Example 1 by means of one layer A1.1. or for the cell B2 created in Example 2 by means of two layers A2.1; A2.2, or for the cell B3 created by means of three layers A3.1; A3.2; A3.3, according to Figure 2.6, possibly also with a reference to Figures 1.1,
  • Possibility of choice of a different number of layers for creation of the cathode K, electrolyte E and anode A flexibly ensures their optimum creation with regard to the ratio of the price and key electric parameters of the battery cells assembled of them, such as electrical output and energy density.
  • An economy variant is formed of cells with one layer for the cathode K, electrolyte E and anode A and also of the cells with two layers of a simplified chemical composition, having a lower output, lower energy density and shorter lifetime.
  • Markings 402, 502, 602 illustrate the technological step of pressing the individual composite layers of the cathode K, anode A and electrolyte E together.
  • Marking 402 illustrates the pressing of individual composite layers for the cathode K together, namely pressing of one layer or 2 layers or 3 layers, according to Figure 2.4, possibly also with a reference to Figures 1.1, 1.2, 1.3.
  • Marking 502 illustrates the pressing of individual composite layers for the electrolyte E together, namely pressing of one layer or 2 layers or 3 layers, according to Figure 2.5, possibly also with a reference to Figures 1.1, 1.2, 1.3.
  • Marking 602 illustrates the pressing of individual composite layers for the anode A together, namely pressing of one layer or 2 layers or 3 layers, according to Figure 2.6, possibly also with a reference to Figures 1.1, 1.2, 1.3.
  • Markings 403, 503, 603 represent a technological step of the final obtaining of composite layers of the cathode K, electrolyte E or anode A, according to Figures 2.4, 2.5, 2.6, possibly also with a reference to Figures 1.1, 1.2, 1.3.
  • Marking 403 represents final obtaining of pressed composite layers of the cathode K, namely of the 1-layer, 2-layer or 3-layer cathodes according to Figure 2.4.
  • Marking 503 represents final obtaining of pressed composite layers of the electrolyte
  • Marking 603 represents final obtaining of pressed composite layers of the anode A, namely of the 1-layer, 2-layer or 3-layer anodes according to Figure 2.6.
  • the third and last technological block, assembly of the secondary battery cells B1, B2, B3, is illustrated schematically in Figure 2.7 with a reference to Figure 5.1 and 5.2.
  • Marking 701 is based on the already finished prepared cathodes K1 or K2 or K3; electrolytes E1 or E2 or E3; and anodes A1 or A2 or A3.
  • the cathode K1 or electrolyte E1 or anode A1 consists of one layer.
  • the cathode K2, electrolyte E2 and anode A2 consists of two layers.
  • the cathode K3, electrolyte E3 and anode A3 consists of three layers.
  • Marking 701a represents attachment of electrodes to the electrolyte.
  • E1 is attached to the cathode K1 and the anode A1 is attached to that electrolyte; or the electrolyte E2 is attached to the cathode K2 and the anode A2 is attached to that electrolyte; or the electrolyte E3 is attached to the cathode K3 and the anode A3 is attached to that electrolyte.
  • Marking 702 represents connection of the collector KK to the cathode K1, or to the cathode K2, or to the cathode and of the collector KA to the anode A1, or to the anode A2, or to the anode A3. This way there will arise a non-pressed assembly of the secondary battery cell B1 or B2 or B3.
  • Marking 703 includes subsequent pressing of a non-pressed assembly into the final secondary battery cell B1 or B2 or B3, without an external package.
  • Marking 704 concerns vacuum sealing of the obtained pressed assembly into a plastic package.
  • Marking 705 illustrates finalisation and obtaining of the secondary battery cell B1 or
  • Figure 2.8 illustrates schematically the spinning equipment (electric spinner) at creation of the important technological step of spinning in the technological direction of two marked arrows (from the left to the right).
  • the spinning equipment includes the pump 1 with a solution, mouthing to the nozzle 2 of the Taylor cone 3 and collection areas 4. Between the end of the Taylor cone 3 and the collection areas 4, there is an area 5 of the spinning of micro- and nano fibres (transition between the glass melt and the solid state of glass fibres). In the area 5, of the spinning process, there is indicated a stream 6 of micro- and nano fibres arising in the spinning process, indicated illustratively in the form of flying waves of fibres (in the shape of the letter "V"), respectively in the shape of growing waveforms.
  • small acceleration takes place, while rapid acceleration takes place in the area 5 of the spinning process.
  • Spinning 110, 210, 310 takes place e.g. in such a way that the obtained powder mixture of micro- and nanoparticles of the composite is admixed into the liquid mixture with tetraethoxysilane (TEOS), while stirring, until the obtaining of a homogeneous dispersion liquid mixture with evenly dispersed solid micro- and nano particles of glass and of the first additive A1.
  • TEOS tetraethoxysilane
  • agitation is performed e.g. by a magnetic agitator for the time of 24 hours at temperatures from 20 to 25°C. It is possible to accelerate polymerisation of the carrier polymer with ultrasound.
  • the actual spinning equipment dispenses the content of individual storage tanks at various present rate of the outflow of the mixture into the electric field.
  • the inserted direct-current voltage is 30kV and the distance between the positive nozzle 2 and the collection area 4 in the function of a negative collector is 15 cm. This setting ensures the arising of required micro- and nanofibres.
  • the finished homogeneous dispersion liquid spinning mixtures are poured into at least two to seven individual storage tanks of the spinning equipment - electrospinning. From these storage tank, the spinning mixtures are pushed out, either with pistons or by means of peristaltic pumps, slowly and evenly into needle nozzles 2, which are connected to the positive pole of the direct-current high-voltage source. From individual nozzles 2, these mixtures are pushed out into an electrical field with a high intensity, in magnitudes of kV-m -1 , which is formed of the opposite collection area 4, in the particular example e.g., of an area-wide collector connected to the negative pole of the source 7.
  • Small drops of polymerous mixtures with a positive charge are transported by this direct-current electrical field fast in the stream 6 from the mouth of the nozzles 2 and during the flying motion in the area 5 of the spinning process they are formed in micro- and nano fibres, which fall onto the opposite collection area 4, i.e. in the function of the flat collector with a negative charge; and this way they create a continuous layer of non-woven fibres with a mean diameter from 1 nm to 100 ⁇ m.
  • the layer arising contains also mixtures of glass and/or crystalline particles, and these particles are situated especially inside and partly also on the surface of the micro- and nanofibres arising this way.
  • the actual spinning equipment has e.g., from one to seven storage tanks.
  • the spinning equipment has 7 storage tanks:
  • Fibre from the 1 st storage tank brings affecting mechanical characteristics of fibres into the composite
  • Fibre from the 4 th storage tank brings reduction-oxidation balance into the composite, Fibre from the 5 th storage tank contributes to mutual connection of other fibres,
  • Fibre from the 6 th storage tank brings thermal conductivity into the composite
  • Fibre from the 7 th storage tank brings another possible complementary characteristic (e.g., magnetic or optical characteristics) to the composite.
  • the spinning mixture is prepared by mixing the powder mixture of micro- and nanoparticles with the mixtures of carrier polymers.
  • the spinning mixture is in the form of a liquid dispersion.
  • the required powder mixture shall be prepared for each storage tank, e.g. according to Tables 10, 14, 18, 22, 26, 30, 34, 38, 42.
  • These powder glass mixtures of micro- and nanoparticles with the first additives A1K or A1A or A1E shall be mixed, during the continual stirring, advantageously into ethanol and then into polymer mixtures with addition of an ordinary dispersion agent, marked in an abbreviated form in Tables 10, 11, 15 as "dispersant"; according to the markings 108, 208, 308 and corresponding Figures 2.1a, 2.2a, 2.3a. Subsequently, they will be separated, e.g. with the help of ultrasound until the arising of dispersion of separated particles.
  • the mixture of the carrier polymer shall be prepared for every individual storage tank, e.g. according to Tables 11, 15, 19, 23, 27, 31, 35, 39, 43.
  • the mixture of the carrier polymer contains a mixture, e.g. consisting of TEOS, PVP, ethanol and water, expressed in molar %.
  • TEOS is in a quantity from 0.01 to 10.37% (molar)
  • PVP in a quantity from 0.03 to 0.05% (molar)
  • ethanol in a quantity from 68.85 to 99.92% (molar)
  • water in a quantity from 0.02 to 20.75% (molar).
  • a small quantity of an ordinary dispersion agent, marked in the tables for abbreviation purposes as "dispersant" shall still be added to this mixture of carrier polymers as an addition, in voluminous %, mostly in a quantity of 0.1 (vol. %).
  • a liquid dispersion shall be created of the glass powder mixture of micro- and nanoparticles with the first additives A1K; A1A; A1E and their mixing 108, 208, 308 into the mixtures of carrier organic polymers.
  • the obtained glass mixture of micro- and nanoparticles with the first additives A1K or A1A or A1E shall subsequently be mixed with organic substances as future carrier polymers - carriers (e.g., Tables 12, 16, 20, 24, 28, 32, 35, 40, 44) for the purpose of transformation of the mixture of micro- and nanoparticles with the first additives A1K or A1A or A1E to the form of micro- and nanofibres by spinning.
  • Spinning is carried out by drawing glass micro/nanofibres either preferentially by spinning in an electric field, known as electrospinning ( Figure 2.8), or possibly by spinning in an air stream.
  • the actual spinning equipment - electrospinning dispenses the content of individual storage tanks with various present rate of outflow of the mixture into the electric field.
  • the outflow rate in the example implementations oscillates, according to Tables 13, 17, 21, 25, 29, 33, 36, 41, 45, from 0.01 to 1.98 ml.h -1 .
  • the flow charts in Fig. 2.1-2.7 schematically depict the procedure of preparation of the secondary battery cell B of the pouch type (the so-called pouch cell) from its main components; i.e. the function-gradient concentration of the composite of the cathode K, anode A and electrolyte E.
  • These composites are assembled by assembling the fundamental amorphous glass materials GMCK. GMCA and GFIC, complemented with the crystalline first additives A1K, A1E, A1A and second additives A2K, A2E and A2A.
  • the fundamental morphology of these prepared elements consists especially in micro- and nanoparticles and micro- and nanofibres, featuring a very high surface-to-volume ratio.
  • GMCK, GMCA GMC- Glass Mixed Conductor
  • GFIC Glass Fast-Ion Conductor
  • Raw materials for glass batches are weighted with precision in thousands of grams. Subsequently, the mixture is mechanically homogenised in a grinding mortar in an agitating device for the time of at least 1 hour. After achievement of the homogeneous mixture, the mixture is dispensed, e.g. into fire-resistant cups of corundum (aluminium oxide - Al 2 O 3 ), porcelain or PtRh compound. For the purpose of obtaining appropriate glass materials, the raw materials are subsequently melted in the technological melting step 103, 203, 303 in an electric furnace either by means of a common way of the melting of the glass melt in the airy atmosphere or the melting of the glass melt in a controlled atmosphere, until the obtaining of the homogeneous glass melt.
  • the controlled atmosphere of the melting process features the setting of suitable partial pressure of oxygen (O2) for achievement of the necessary oxidation or reduction atmosphere during the melting process.
  • O2 partial pressure of oxygen
  • the melting temperature oscillates within the range from 300 to 1500°C for the time from 0.5 to 4 hours.
  • the obtained homogeneous melt is subsequently cooled at a sufficient rate in the technological step of the cooling 104, 204, 304 of melted glass materials, either by free cooling in the air, or by controlled cooling performed by pouring into a metallic mould, on a rapidly rotating cylinder or between two rapidly rotating cylinders, whereby homogeneous solid glass in the form of blocks or cullet is created.
  • the cooling rates oscillate from 100 °C.s -1 to 1000°C.s -1 Cooling takes place in the air or in a controlled atmosphere with the present suitable partial pressure of oxygen O 2 for achievement of the necessary oxidation or reduction atmosphere.
  • the solid glass obtained this way is then mechanically crushed in a mill in a common way into cullet in the form of small glass particles/glass powder in the technological step of crushing 105, 205, 305, for the time necessary for obtaining glass particles/glass powder with a size in a magnitude from millimetres to micrometres.
  • Appropriate first additive A1K: A1E: A1A is then added to the glass particles obtained this way, in the subsequent technological step 106, 206, 306, such an additive being e.g., Cu, Fe, Al, Si, Mn, Fe, Co, Ni, V, Mo, W, their amorphous compounds as metallic glass materials or their oxides, SiC, LiCI, NaCI and elements Mn, Fe, Co, Ni, V, Mo, W, O in the form of compounds forming solid solutions with the structure of a spinel with the medium size of particles in a magnitude from millimetres to micrometres.
  • an additive being e.g., Cu, Fe, Al, Si, Mn, Fe, Co, Ni, V, Mo, W, their amorphous compounds as metallic glass materials or their oxides, SiC, LiCI, NaCI and elements Mn, Fe, Co, Ni, V, Mo, W, O in the form of compounds forming solid solutions with the structure of a spinel with the medium size of particles in a magnitude
  • thermal processing 111, 211, 311 of the composite layers of micro/nanofibres is followed by the technological step of thermal processing 111, 211, 311 of the composite layers of micro/nanofibres.
  • Prepared composite layers are subsequently burnt out during a 24-hour cycle at a maximum temperature in the range from 200 - 1200°C, so that it can be possible to remove unnecessary carbon substances, such as function groups, ethoxy groups or ethanol residua.
  • the fibres of a given composition are subject to exfoliation 112, 212, 312 in hot water or in an autoclave in water steam environment.
  • suitable second additives A2K; A2E; A2A are applied onto the composite layer of micro/nanofibres by electric spraying, spraying with air, coating or soaking of suitable crystalline glass additives A2K; A2E; A2A, such as Si, SiC, LiCI, NaCI, (Mn, Fe, Co, Ni, V, Mo, W, O) spinel materials, Cu, Al, particles of low-viscosity phosphate glass.
  • the arising composite layer is subject to the pressing 114, 214, 314 of the layer of micro/nanofibres.
  • the pressed composite layer is subsequently subjected to thermal processing 115, 215, 315 at temperatures from 100 to 500°C and subsequent slow cooling which can take place directly in the furnace in order to eliminate cracking.
  • the result of this first technological block is the obtaining 116, 216, 316 of one final composite layer of the cathode K, electrolyte E or anode A based on glass micro/nanofibres and micro/nanoparticles, which are covered, after the thermal processing, on the surface with corresponding coatings/particles of the second additives A2K; A2E; A2A and interconnected through a connection matrix based on the glass.
  • Every individual mixture for each storage tank 1 to 7 represents concentration of related glass materials GMCK, GFIC.
  • GMCA and the first additives A1K, A1A in total of 100% of weight Table 11 Liquid polymer mixtures for preparation of carrier polymers, for liquid dispersion, dosed into the storage tanks 1 to 7, used for preparation of the composite layers K1.1 for the cathode K1
  • Every polymer mixture for every individual storage tank 1 to 7 contains 4 components in molar %, whose total is 100% (molar). Molar % values are stated here for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water. Besides, every individual mixture contains furthermore a dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume). Voluminous % is commonly applied at the use of a liquid polymer mixture for practical reasons because the polymer mixture is measured and dosed in volume % with the help of measuring vessels.
  • the carrier polymers are organic substances supporting the spinning of glass mixtures of microfibers/nanofibres, they represent a mixture of appropriate monomers, such as tetraethoxysilane (TEOS) or e.g., of oligomers, such as polyvinylpyrrolidone (PVP). These organic substances are formed in a form of mostly linear carrier polymers suitable for spinning. For final fibres they contain SiO 2 , then the carrier polymer is a polysiloxane polymer created by polymerisation of TEOS. If the final fibres are without SiO 2 , then the carrier polymer PVP is used. Table 12 Composition of liquid dispersion of a powder mixture of micro- and nano particles based on glass in the carrier polymer for storage tanks 1 to 7 used for preparation of the composite layer K1.1 for the cathode K1
  • Every liquid dispersion for an individual storage tank 1 to 7 contains (in % weight) a carrier polymer and a powder mixture of micro/nanoparticles based on glass whose total is 100% (by weight).
  • Every individual powder mixture of micro- and nano particles for a given storage tank contains given glass and suitable additive, in % of weight, whose total is 100% (by weight)
  • Every polymer mixture for every individual storage tank 1 to 7 contains 4 components in molar %, whose total is 100% (molar), which are stated for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water.
  • every individual mixture contains furthermore a dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume).
  • Voluminous % values are used because the liquid polymer mixture is measured and dosed in volume % with the help of measuring vessels for the storage tank in question.
  • Table 16 Composition of liquid dispersion of powders of micro- and nanoparticles based on glass in the carrier polymer for storage tanks 1 to 7 used for preparation of the composite layer
  • Every liquid dispersion (in % by weight) for an individual storage tank 1 to 7 contains a carrier polymer and a powder mixture of micro- and nanoparticles based on glass, whose total is 100% (by weight)
  • Table 18 Mixing of the mixtures of micro- and nano powders based on glass for storage tanks 1 to 7 for preparation of the composite layer A1.1 for the anode A1 Every individual powder mixture for a given storage tank contains given glass and a suitable first additive, whose total is 100% (by weight).
  • Every polymer mixture for every individual storage tank 1 to 7 contains 4 components in molar %, whose total is 100% (molar), for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water. Every individual mixture contains furthermore a dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume). Voluminous % values are used for measuring and dosing in volume % with the help of measuring vessels for the storage tank in question.
  • Table 20 Composition of liquid dispersion of powders of micro- and nanoparticles based on glass in the carrier polymer for storage tanks 1 to 7 used for preparation of the composite layer A1.1 for the anode A1
  • Every liquid dispersion for an individual storage tank 1 to 7 contains a carrier polymer mixture and powder mixture of micro- and nanoparticles of the glass composite whose total is 100% (by weight).
  • Table 21 Rates of outflow of liquid dispersion from the storage tanks 1 to 7 into nozzles of the electric spinner for creation of fibres of the composite layer A1.l for the anode A1
  • Every individual powder mixture of micro- and nanoparticles for a given storage tank contains given glass and suitable first additive in % by weight whose total is 100% by weight.
  • Table 23 Liquid polymer mixtures for preparation of carrier polymers for storage tanks 1o 7 used for preparation of the composite layers K2.1 and K2.2 for the cathode K2
  • Every liquid polymer mixture for every individual storage tank 1 to 7 contains 4 components in molar %, whose total is 100% (molar) for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water.
  • Each of these individual mixtures contains also dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume).
  • Voluminous % is used for measuring and dosing in volume % with the help of measuring vessels for a given storage tank.
  • Table 24 Composition of liquid dispersion of a powder mixture of micro- and nano particles based on glass in the carrier polymer for storage tanks 1 to 7used for preparation of the composite layers K2.1 and K2.2 for the cathode K2.
  • Every liquid dispersion for an individual storage tank 1 to 7 contains (in % weight) a carrier polymer mixture and a powder mixture of micro- and nanoparticles, whose total is 100% (by weight).
  • Table 26 Mixing of mixtures of micro- and nano powders based on glass for storage tanks 1 to 7 for preparation of the composite layers E2.1 and E2.2 for the electrolyte E2 Every individual powder mixture of micro- and nanoparticles of the glass composite for a given storage tank contains given glass and suitable first additive in % by weight whose total is 100% by weight.
  • Every polymer mixture for every individual storage tank 1 to 7 contains 4 components in molar %, whose total is 100% (molar), for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water. Every individual mixture contains furthermore a dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume). Voluminous % values are used for measuring and dosing in volume % with the help of measuring vessels for a given storage tank.
  • Table 28 Composition of liquid dispersion of powders based on glass in the carrier polymer for storage tanks 1 to 7 used for preparation of the composite layers E2.1 and
  • Every liquid dispersion for an individual storage tank 1 to 7 contains a carrier polymer and a powder mixture of micro- and nanoparticles of the composite whose total is 100% by weight.
  • Every individual powder mixture of micro- and nanoparticles of glass composite for a given storage tank contains given glass and a suitable first additive in % by weight whose total is 100% by weight.
  • Table 31 Liquid polymer mixtures for preparation of carrier polymers for storage tanks 1 to 7 used for preparation of the composite layers A2.1 and A2.2 for the anode A2 Polymer mixture for every individual storage tank 1 to 7 contains 4 components in molar %, whose total is 100% (molar), for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water. Every individual mixture contains furthermore a dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume). Voluminous % values are used for measuring and dosing in volume % with the help of measuring vessels for the storage tank in question.
  • Table 32 Composition of liquid dispersion of powders based on the glass in the carrier polymer for storage tanks 1 to 7 used for preparation of the composite layers A2.1 and A2.2 for the anode A2
  • Every liquid dispersion for an individual storage tank 1 to 7 contains a carrier polymer mixture and a powder mixture of micro- and nanoparticles of the glass composite whose total is 100% (by weight).
  • Table 33 Rates of outflow of liquid dispersion from the storage tanks 1 to 7 into nozzles of the electric spinner for creation of fibres of the composite layers A2.1 and A2.2 for the anode A2
  • Every individual powder mixture of micro- and nanoparticles of the composite for a given storage tank contains given glass and a suitable first additive in % by weight whose total is 100% by weight.
  • Table 35 Liquid polymer mixtures for preparation of carrier polymers for storage tanks 1o 7 used for preparation of the composite layers K3.1, K3.2 and K3.3 for the cathode K3
  • Every polymer mixture for every individual storage tank 1 to 7 contains 4 components in molar %, whose total is 100% (molar) for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water. Every individual mixture still contains, in addition, dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume). Voluminous % is used for measuring and dosing in volume % with the help of measuring vessels for a given storage tank.
  • Table 36 Composition of liquid dispersion of powders based on glass in the carrier polymer for storage tanks 1 to 7used for preparation of the composite layers K3.1, K3.2 and K3.3 for the cathode K3
  • Every liquid dispersion for an individual storage tank 1 to 7 contains a carrier polymer mixture and a powder mixture of micro- and nanoparticles of the glass composite whose total is 100% by weight.
  • Table 37 Rates of outflow of liquid dispersion from the storage tanks 1 to 7 into nozzles of the electric spinner for creation of fibres of the composite layers K3.1, K3.2 and K3.3 for the cathode K3
  • Every individual powder mixture for a given storage tank contains given glass in the form of a powder mixture of micro- and nanoparticles of the composite and a suitable first additive in % by weight whose total is 100% by weight.
  • Table 39 Liquid polymer mixtures for preparation of carrier polymers for storage tanks 1 to 7 used for preparation of the composite layers E3.1, E3.2 and E3.3 for the electrolyte E3
  • Every polymer mixture for every individual storage tank 1 to 7 contains 4 components in molar %, whose total is 100% (molar), for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water. Every individual mixture contains also a dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume). Voluminous % values are used for measuring and dosing in volume % with the help of measuring vessels for a given storage tank.
  • Table 40 Composition of liquid dispersion of powders based on glass in the carrier polymer for storage tanks 1 to 7 used for preparation of the composite layers E3.1, E3.2 and E3.3 for the cathode E3
  • Every liquid dispersion for an individual storage tank 1 to 7 contains a carrier polymer mixture and a powder mixture of micro- and nanoparticles of the composite whose total is 100% by weight.
  • Table 41 Rates of outflow of liquid dispersion from the storage tanks 1 to 7 into nozzles of the electric spinner for creation of fibres of the composite layers E3.1. E3.2 and E3.3 for the electrolyte E3
  • Every individual powder mixture for a given storage tank contains given glass in the powder mixture of micro- and nanoparticles of the glass composite and a suitable first additive whose total is 100% by weight.
  • Table 43 Liquid polymer mixtures for preparation of carrier polymers for storage tanks 1o 7 used for preparation of the composite layers A3.1. A3.2 and A3.3 for the anode A3
  • Every liquid polymer mixture for every storage tank 1 to 7 contains 4 components in molar % whose total is 100% molar for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water. Every individual mixture contains furthermore a dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume). Voluminous % values are used for measuring and dosing in volume % with the help of measuring vessels for the storage tank in question.
  • Table 44 Composition of liquid dispersion of powders based on the glass in the carrier polymer for storage tanks 1 to 7 used for preparation of the composite layers A3.1, A3.2 and A3.3 for the anode A3
  • Every liquid dispersion for an individual storage tank 1 to 7 contains a carrier polymer and a powder mixture of micro- and nanoparticles of the glass composite whose total is 100% by weight.
  • Table 45 Rates of outflow of liquid dispersion from the storage tanks 1 to 7 into nozzles of the electric spinner for creation of fibres of the layers A3.1, A3.2 and A3.3 for the anode A3
  • Figure 2.7 illustrates chronologically the technological steps for the assembly of the battery cells B1; B2; B3.
  • the cathode IQ is made with the use of the preformed layer K1.1, the electrolyte E1 with the use of the layer E1.1 and the anode A1 with the use of the layer A1.1.
  • an assembly of layers of the cell B1 is created when the layer E1.1 is inserted between the layers K1.1 and A1.1, and then the collector KK of the cathode K is attached to the layer K1.l, and the collector KA is attached to the layer A1.1.
  • the above-mentioned layers and collectors are normally pressed to each other and inserted into a plastic package in which they are sealed in a vacuum manner into a form of an airtight pouch with two rising contacts.
  • the plastic package is cut off into a final shape and the battery cell B1 is marked with an identification heading.
  • the cathode K2 is made with the use of the preformed layers K2.1 and K2.2, the electrolyte E2 with the use of the layers E2.1 and E2.2, and the anode A2 with the use of the layers A2.1 and A2.2. Subsequently, an assembly of layers of the cell B2 is created, when the layers K2.1 and K2.2 are placed on each other for the cathode K2, then the layers E2.1 and E2.2 of the electrolyte E2 are gradually placed on them and then the layers A2.1 and A2.2 of the anode A2 are installed. Then the collector KK of the cathode K is attached to the layer K2.1, and the collector KA is attached to the layer A2.2 of the anode A.
  • the above-mentioned layers and collectors are normally pressed to each other and inserted into a plastic package in which they are sealed in a vacuum manner into a form of an airtight pouch with two rising contacts.
  • the plastic package is cut off into a final shape and the battery cell B2 is marked with an identification heading.
  • the cathode K3 is made with the use of the preformed layers K3.1, K3.2 and K3.3, the electrolyte E3 with the use of the layers E3.1. E3.2 and E3.3, and the anode A3 with the use of the layers A3.1, A3.2, A3.3. Subsequently, an assembly of layers of the cell B3 is created, when the layers K3.1, K3.2 and K3.3 are placed on each other for the cathode K3, then the layers E3.1, E3.2 and E3.3 of the electrolyte E3 are gradually placed on them and then the layers A3.1, A3.2 and A3.3 of the anode A3 are installed.
  • the collector KK of the cathode K3 is attached to the layer K3.1 and the collector KA of the anode A3 is attached to the layer A3.3.
  • the above-mentioned layers and collectors are normally pressed to each other and inserted into a plastic package in which they are sealed in a vacuum manner into a form of an airtight pouch with two rising contacts.
  • the plastic package is cut off into a final shape and the battery cell B3 is marked with an identification heading.
  • Figure 3.1 illustrates schematically the processes of recharging and discharging taking place in the secondary battery cell B2.
  • the ion carriers of the charge are Li + cations in this case, but very similar scenarios will basically take place in the case that Na + cations are ion carriers of the charge.
  • the collectors KK and KA are connected by means of the inlet contacts 20 and 40 to the external source of electrical energy in such a way that electrons exit from the cathode K through the collector KK ⁇ and on the other side of the cell they enter into the anode A through the collector KA.
  • the collectors KK, KA of the cell B2 are connected by means of the contacts 20, 40 to the electric energy consumer ("load") in such a manner that electrons enter, through the collector KK ⁇ into the cathode K and on the other side they exit from the anode A through the collector KA.
  • the shot was made by using an optical microscope "Nikon” in magnification 75-10 4 x.
  • the shot was made by using an optical microscope "Nikon” in magnification 75-10 4 x.
  • the shot was made by using an optical microscope "Nikon” in magnification 75 10 4 x.
  • Figure 5.1 on the left and Figure 5.2 on the right depict schematically the prepared secondary battery cell B1 in the shape of a flat pouch ("pouch cell”), e.g. with dimensions of 60x90x4 mm, which is sealed in a plastic foil.
  • Figure 5.1 shows the secondary battery cell B1 illustrated from the side of the cathode K, and it is possible to see there the area 10 of the end electron-conductive current aluminium collector KK with the inlet contact 20; and also it is possible to see, on the opposite side, the inlet contact 40 of the current copper collector KA.
  • Figure 5.2 shows the secondary battery cell B1 illustrated from the side of the anode A, and it is possible to see there the area 30 of the end electron- conductive current copper collector KA with the inlet contact 40; and it is also possible to see, in the lower part on the opposite side, the inlet contact 20 of the current aluminium collector KK.
  • Table 46 states selected electric characteristics of the secondary battery cell B1, B2 and B3 with Li + ions.
  • Related electrode substances and electrolyte are formed of function- gradient composite layers for the cathode K, electrolyte E and anode A whose composition was suitably optimised with the first additives A1K, A1E and A1A and with the second additives A2K, A2E, A2A.
  • These optimised composite layers for the cathode K, electrolyte E and anode A in their mutual combination ensure high energy and power density values and therefore they are suitable for construction of high-capacity batteries.
  • the secondary battery cell B is intended for electromobiles. Reference signs
  • FIGURE 1.1, 1.2, 1.3, 1.5 h total height h of the battery cell B I total length I of the battery cell B w total width w of the battery cell B KK collector KK of the cathode K KA collector KA of the anode A R a roughness
  • E1 electrolyte E1 with one layer E1.l K1.1 one layer K1.1 of the cathode K1 A1.1 one layer A1.1 of the anode A1
  • K2 cathode K2 with two layers K2.1, K2.2 K2.1 first layer K2.1 of the cathode K2 K2.2 second layer K2.2 of the cathode K2
  • 701 Selection of the finished cathode K, finished electrolyte E and finished anode A; 701a Attachment of electrodes of the cathode K and anode A to the electrolyte E;
  • AIK, A1E, A1A powders of micro- and nanoparticles

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Abstract

The secondary battery cell (B, B1, B2, B3) is based on glass. Every composite layer (K1.1; K2.1, K2.2; K3.1, K3.2, K3.3) of the cathode (K; K1; K2; K3) or (E1.1; E2.1, E2.2; E3.1, E.2, E3.3) of the electrolyte (E; E1; E2; E3) or (A1.1; A2.1, A2.2; A3.1, A3.2, A3.3) of the anode (A; A1; A2; A3) contains: 0.1 to 10.0% volume of the first additive (A1K; A 1E; A1A) for an increase in electrochemical oxidation-reduction activity of these composite layers; 0.1 to 10.0% volume of the second additive (A2K; A2E; A2A) on the surface of micro- and nanofibres and micro- and nanoparticles for an increase in adhesion of these composite layers; and 80 to 99.8% by volume of selected glass (GMCK; GFIC; GMCA). Each of these composite layers of the cathode (K; K1; K2; K3), electrolyte (E; E1; E2; E3) and anode (A; A1; A2; A3) states a gradual change in the function-gradient concentration of immobile components of composite layers in the direction from the cathode (K) to the anode (A), depending on the distance between the collector (KK) of the cathode (K) and the opposite collector (KA) of the anode (A), and in the inverse direction, and the mobile component in these glass materials (GMCK; GMCA; GFIC) is either the lithium cation Li+ or the sodium cation Na+. The claims cover also the method of production of the secondary battery cell (B, B1, B2, B3).

Description

Secondary battery cell for electromobiles, containing amorphous glass materials and micro- and nano materials, and method of its production
TECHNICAL FIELD
The invention concerns a secondary battery cell for electromobiles, containing amorphous glass materials and micro- and nanomaterials. The battery cell is manufactured on a glass basis. And it includes end metallic electron-conductive current collectors, between which there are arranged electron-conductive electrodes, i.e. a cathode and an anode, which are separated by an ion-conductive electrolyte. The cathode, electrolyte and anode contain multi-component solid amorphous glass materials, preferably lithium or sodium multi-component glass for the cathode and for the anode with combined ion and electron conductivity, and multi-component glass for the electrolyte with high ion conductivity and very low electron conductivity.
The cathode glass with an admixture of the electrolyte glass is situated in the cathode in the collector vicinity and on the side facing this collector.
The anode glass with an admixture of the electrolyte glass is situated in the anode and on the side facing this collector.
The electrolyte glass with an admixture of both the electrodes, anode and cathode, is situated immediately within or in the vicinity of the electrolyte.
The battery cell contains solid amorphous multi-component glass and micro- and nanofibres and micro- and nanoparticles with a medium diameter from 1 nm to 100 μm;
BACKGROUND OF THE INVENTION
US 2015 266769 A1 published on 24 September 2016, US 9,643,881 B2, publ. 9.4.2015, describes a glass composition for glass fibres and a method of production of glass fibres, and a battery separator is mentioned as one of possible applications. Silica glass for glass fibres containing titanium dioxide and zirconium dioxide and oxides of alkali metals, and advantageously also aluminium oxide, calcium oxide and lithium oxide features a difference between the low drawing temperature and liquidus 91°C and more. The glass may contain 300 to 500 pm particles and withstands immersion in 100 ml of 10% sodium hydroxide solution at a temperature of 80°C for 16 hours. The method of production of fibres consists in continual drawing of fibres from a perforated bowl, when the drawing temperature is 90 and more degrees higher than the liquidus temperature. A disadvantage is the fact that glass fibres do not contain any polyvalent elements, and therefore they cannot fully operate as electrochemically active redox centres in the electrode material of the battery. The fibre obtained by means of this way of drawing will have a thickness at least in units of several microns, which means that the ratio of the surface area of fibres to their volume will not be suitable from the viewpoint of high ion conductivity and high electrochemical activity.
US 2015 266769 A1 published on 24 September 2016 describes a composition of glass for glass fibres and a method of production of glass fibres. The patent states the composition of the glass materials for production of fibres featuring excellent corrosion resistance to alkalis, acids and water. They are a useful reinforcement of composite materials for plates or separators in batteries. The fibres feature a relatively low drawing temperature and liquidus, and thanks to these properties they are very suitable for easy production. The specified fibres have, according to the described composition and characteristics, a very high electric resistance. This fact rather limits the use of this type of fibres as an active component in batteries. The described production technology does not enable creation of nanofibres either.
US 10,211,449 B2, published on 19 February 2019, states a micro-structured material based on silicon (Si) and a method of its preparation. This material is used for the electrode in the battery, such as e.g., a lithium ion battery. It describes a synthesis of paper based on silica nanofibres with a carbon coating for separate electrodes with adjustable dimensions and without a binding agent for a lithium ion battery, which can markedly increase the total capacity of the battery cell. High electrochemical stability and easy modification of dimensions is used with an advantage.
The method of production of the electrodes for the battery includes reduction of the fibrous silicon dioxide (silica) and at the same time etching of the surface of fibres of reduced silicon dioxide, so that a porous structure can be created, together with simultaneous creation of a conductive coating on the surface of the porous silica fibres. Reduction of the structure of silicon dioxide fibers is carried out thermically with the help of metallic magnesium, during which fibrous silicon dioxide is reduced. Alternatively, silicon dioxide fibre is selectively etched in the places of presence of magnesium oxide, arising as a product of magnesium-thermal reduction. The conductive coating is created through a pyrolysis of the amorphous carbon coating on the surface of porous silicon. The TEOS solution is used for creation of silicon dioxide fibres by electrospinning.
The resulting product consists of silicon nanofibres with a porous conductive surface. Creation of silicon fibres directly by magnesium-thermal reduction through metallic magnesium is rather time demanding and is difficult to check from the viewpoint of reproducibility, including obvious creation of non-homogeneous materials with presupposed contamination of magnesium oxide. The surface of nanofibres contains carbon, which can oxidise during the use of the battery and during a thermal load, which is accompanied by creation of toxic carbon monoxide and unbreathable carbon dioxide. There may arise a danger of explosion in consequence of large changes in volume during the arising of these gases.
CN 1394670 A published on 5 February 2003 concerns preparation of nano-powders CaCO3 or TiO2 or ZrO2-Y2O3, which are obtained in steps, and an important step among them is spraying of a homogeneous mixture of a water-based solution of urea in excess of NH4OH (ammonium hydroxide) at presence of precursors, such as Ca(OH)2 at presence of CO2, or TiCI4 or ZrOCl2.8H2O and YCI3. Spraying can be carried out at the compound boiling temperatures from 80 to 100°C or more. It is stated in the invention that nano- powder with an even grain size will be obtained. A disadvantage is the use of organic urea polymers with a high content of ammonium-based substances, i.e. substances with a high content of carbon, which is unsuitable for electric batteries for automobiles, because at a higher work load of batteries, when the temperature rises, there is a threat of release of a large volume of CO2 and NH3, which may lead to destruction of the battery.
CN 107034586 A published on 11 August 2017 concerns preparation of composite conductive membranes, where the composite is polyhydroxybutyrate. Preparation consists of the mixing of the composite with dopant in a ratio of 1:1 to 1:6. The resulting mixture is sprayed at a rate of 0.05 to 0.3 ml/hour at a distance of 10 to 20 cm from electrodes, in an electric field with a voltage of 10 - 30 kV. This electrospinning makes it possible to obtain an electrically conductive membrane of nanofibres, with a diameter of 2000 to 500 nm. A disadvantage is the obtaining of the membrane of nanofibres on the basis of organic polymers.
US 6,759,573 B2 published on 17 June 2003, corresponding to WO 97/18 431 A1, to EP 0866885 A1, CN 195884 C and CA 2237 588 A1, concerns the method of obtaining of nano-structural coatings by thermal spraying. E.g., WO 97/18 431 A states the methods during which processing is made for applied powder nanoparticles, liquid suspensions of nanoparticles and organo-metallic liquids in conventional thermal spraying into a mould of nano-structured coatings. In one design, the nano-structure batches consist of spherical agglomerates, produced again by processing of synthetised nano-structure powders. In another design, a fine dispersion of nanoparticles is directly sprayed/inserted into the combustion flame or into a plasma thermal equipment with the arising of nano structure coatings. In another design, liquid organic chemical precursors are directly injected into the combustion flame of the equipment for plasma thermal spraying, when the synthesis of nanoparticles, melting and tempering is carried out in one operation. These methods use ultrasound for disintegration of agglomerates of synthetised particles, for dispersion of nanoparticles in a liquid medium and for atomisation of a liquid precursor. The independent claims include a definition of the range of input nanoparticles with a size of 3 to 30 nm with the use of ultrasound for creation of a liquid dispersion. One independent claim includes a definition of creation of one nano-structured coating and another independent claim describes creation of two nano-structured coatings on each other. Ultrasound with a frequency of 20 kHz and power output of 300 to 400 W is used in one design example for dispersion of nano-structured WC/Co for creation of low- viscosity sludge.
JPH 10302776 A published on 13 November 1998 describes a secondary lithium battery with solid electrolyte, providing high voltage, high energy density and excellent cyclability. The battery consists of a negative electrode, where the first electrode has electron conductivity and is able to create a layer of metallic lithium or to ensure dissolution of metallic lithium, during recharging or discharging of the battery. Besides, it has another electrode, featuring electron mixed conductivity and also anisotropy for ion conductivity - through-pass of ions. This second electrode with mixed electron ion conductivity is placed on the first electrode, for the purpose of removal of concentration differences during migration of ions. A secondary lithium battery with a solid electrolyte may have another electrode containing a lithium-nitride composite, or a lithium-nitride- silica composite with a transition metal. The solid secondary lithium battery with a solid electrolyte need not contain elements of transition metals. Or a battery can have a positive electrode containing a lithium compound of an oxide of the transition metal. The description (0016) suggests composition of solid electrolytes which do not contain transition metals, on the basis of sulphide or oxide-sulphide glass materials, in such systems as Lil-Li2S-SiS2, Lil-Li2S-P2S5, sulphide glass materials as Lil-Li2S-B2S3 or Li3PO4-Li2S- SiS2, and also sulphide glass materials, such as Li2O-Li2S-SiS2.
The description states several procedures for obtaining such a battery, and one design example of them uses a procedure of preparation of a solid electrolyte in the form of sulphide glass materials. The procedure is based on rapid cooling of melted lithium phosphate, lithium sulphide and silicon sulphide.
JP 2011 187 370 A published on 22 September 2011 describes a battery with a solid electrolyte resolving the issue of the increase in electric resistance on the interface between an active material and solid electrolyte. The described battery contains a layer of the electrode active material and a layer of the first solid electrolyte placed on it, and this electrolyte has a different anion component from the active material and it is a monophase mixed electron and ion conductor. This layer furthermore forms a contact with the layer of the second solid electrolyte, which has the same anion component as the first solid electrolyte. A disadvantage is the presence of high concentrations of sulphide sulphur in the battery materials. This sulphur can lead, when the battery temperature rises, to the arising of toxic gases, such as sulphur dioxide SO2 or sulphur trioxide SO3. The patent states a possibility of the use of a large share of crystalline materials which, however, have a disadvantage for the use in batteries, because their conductivity can depend very much on the random direction of orientation of crystal planes with regard to the main direction of the ion movement. Powder layers in the assembled battery cell are crystalline structures. Thermal processing up to 300°C is used for their transformation to a more advantageous amorphous structure. This method is, however, disadvantageous for the reason of difficult assurance of the arising of a fully amorphous structure, with regard to ongoing chemical reactions to increased temperatures and arising of a number of metastable intermediate products. Subsequent cooling can lead to differences in local cooling rates which are to result in the arising of partly crystalline materials with a different temperature history, and therefore with a different share of crystalline phases influencing electrochemical behaviour of these thermally processed materials. This fact will have a negative impact on reproducibility of production of these batteries. The nearest state of technology is CZ PV 2017 - 859 corresponding to WO 2019 129316 A1, published on 10 July 2019 entitled: "Secondary battery cell for electromobiles, containing solid amorphous glass materials and micro- and nano materials". The secondary battery cell has end metallic electron-conductive current collectors, between which there are arranged electron-conductive electrodes which contain, as carriers of ion conductivity charges, migrating cations of lithium and/or sodium for migration from the anode through the electrolyte to the cathode during discharging and recharging. Anode and cathode are separated by an ion-conductive electrolyte which is basically electron-nonconductive. Electrodes, anode, as well as cathode have mixed conductivity, are electron-conductive and ion-conductive; contain solid amorphous multi-component glass composite material, also glass and/or metallic fibres and glass and/or crystalline particles with a medium diameter in nano/micrometres in the range from 1 nm to 100 μm. Both the electrodes have a surface of a composite material, fibres as well as particles, which material is micro- and nano-structural with mean roughness in the range from 1 nm to 100 μm. The composite material of the electrodes contains active oxidation-reduction centres based on metallic silicon and/or oxides of silicon and/or glass materials containing electropositive polyvalent elements Mp. These oxidation-reduction centres have a ratio of the higher oxidation state to the lower oxidation state of polyvalent elements 0.1 to 10. The electrolyte contains solid amorphous multi-component glass composite material, which is isotropic, with carriers of charges of the ion conductivity by a lithium cation and/or sodium cation with ion conductivity in all the directions with the same value.
The composite material of electrodes contains two types of multi-component glass. One type of glass has mixed ion and electron conductivity; and the other type of glass has high ion conductivity and very low electron conductivity.
SUMMARY OF THE INVENTION
The above-mentioned disadvantages will be removed or substantially reduced according to the pre-feature of the 1st claim of this invention, whose substance consists in the fact that the secondary battery cell on the basis of glass contains at least one composite layer of the cathode, electrolyte and anode. These composite layers are in a mixture on the basis of micro- and nanofibres and micro- and nanoparticles of glass materials with the first additives and with the second additives on the surface. Each of these composite layers contains 0.1 to 10.0 volume % of the first additive for an increase in the electrochemical oxidation-reduction activity of these composite layers; 0.1 to 10.0 volume % of the second additive on the surface of micro- and nanofibres and micro- and nanoparticles for increasing adhesion of these composite layers; and 80 to 99.8 volume % of selected glass. Each of these composite layers of the cathode, electrolyte and anode states a slow change of the functional-gradient concentration of immobile components of composite layers in the direction from the cathode to the anode depending on the distance between the cathode collector and the opposite anode collector and in the opposite direction. The mobile component in these glass materials is either the lithium cation Li+ or sodium cation Na+.
The main advantage of the invention is a battery cell based on inorganic glass and therefore non-combustible. The content of amorphous glass enables exact setting of characteristics and functional-gradient concentration. Glass materials easily create fibrous structures. Immobile parts of the multi-component glass have large free space around them, enabling easy transport of lithium and sodium ions in all directions. Micro- and nanofibres and micro- and nanoparticles enable creation of flexible composite layers also from these purely inorganic glass materials and therefore non-combustible materials. These composite layers make it possible to obtain a function-concentration gradient. It is possible to easily select various thickness of layers and thus also the energy density in the battery cell and its capacity. The gradual change of the function-gradient concentration of immobile components of composite layers in the direction from the cathode to the anode in the secondary battery cell and vice versa ensures its positive function. A function-gradient concentration is created in the given direction in such a way that the properties monitored can be changed in this direction as continuously as possible. The given direction is determined by the movement of ions, especially lithium ion Li+, possibly sodium ions Na+ during recharging and discharging of the secondary battery cell.
It is advantageous when composite layers of the cathode, composite layers of the electrolyte and composite layers of the anode are arranged in a mutually parallel way and closely behind each other, which ensures compatibility of the cathode, electrolyte and anode of the secondary battery cell on the one hand, and at the same time it ensures also the required and adjustable change of the function-gradient concentration.
With an advantage, the cathode and anode layers state a greater width than the width of the electrolyte layers. Individual layers of the cathode and anode can have e.g., a width in the range from 0.9 to 2.8 mm and individual electrolyte layers can have e.g., a width in the range from 0.1 to 0.4 mm. This way it is therefore possible to achieve a sufficiently high capacity of the secondary battery cell and the associated high value of the energy density and battery cell capacity.
The secondary battery cell can be basically flat, with a total height of 90 mm, with a total length of 60 mm and a total width of 6 mm, and with a total weight in the range from 33 to 38 g. These parameters can be changed according to requirements of the use.
It is also advantageous when the first additive for the cathode, the first additive for the electrolyte and the first additive for the anode are crystalline additives, such as metallic copper Cu, metallic iron Fe, metallic silicon Si, metallic nickel Ni and metallic aluminium Al, metallic Mn, metallic Co, metallic V, metallic Mo, metallic W, their amorphous compounds, such as metallic glass materials or their oxides, silicon carbide SiC, lithium chloride LiCI, sodium chloride NaCI and such elements as Mn, Fe, Co, Ni, V,
Mo, W, O forming solid solutions with the structure of a spinel. The first additives increase especially electron conductivity and effectiveness of transfer of electric charge and the rate of oxidation-reduction reactions.
Besides, it is advantageous when the second additive for the cathode, the second additive for the electrolyte and the second additive for the anode are at least one compound from the group including LiPO3, NaPO3, Li3BO3, Na3BO3, Al2O3; where the second additive represents crystalline or glass particles. The second additives contribute to adhesion of individual composite layers of the electrodes and of the electrolyte and facilitate transition of materials across the interface between individual composite layers.
The invention concerns also the method of production of the secondary battery cell for electromobiles, containing amorphous glass materials and micro- and nanomaterials, whose substance consists in the fact that the method contains three fundamental technological blocks.
The first technological block for preparation of flexible inorganic composite layers with a function-gradient concentration for the cathode, electrolyte and anode, containing micro- and nanofibres and micro- and nanoparticles based on amorphous glass materials, the first additives and the second additives, technologies of electrostatic spinning - known as electrospinning.
The second technological block for preparation of the layered cathode, layered electrolyte and layered anode by pressing these layers.
The third technological block for the assembly of the secondary battery cell from the layered cathode, layered electrolyte and layered anode, including connection of collectors and subsequent vacuum sealing of the battery cell into a plastic package.
More detailed description.
The first technological block includes, with an advantage, preparation of individual composite layers of the cathode, electrolyte and anode, containing the following technological steps, in a chronological order:
• Selection of a suitable selected chemical composition of lithium or sodium multi- component glass and selection of suitable chemical composition of the first additive.
• Input of raw materials in the form of glass batches for selected glass materials and input of raw materials for the selected first additive so that this resulting composite layer can contain 0.1 to 10% of these first additives in terms of volume.
• Melting of the lithium or sodium multi-component glass for the cathode; multi- component glass for the electrolyte; and multi-component glass for the anode (A), without the first additive at a temperature in the range from 300 to 1500°C, depending on the type of glass materials.
• Cooling of melted glass materials in a controlled atmosphere or in the air for achieving the necessary oxidation or reduction atmosphere.
• Crushing of cooled glass materials into glass cullet and into smaller glass particles/glass powder with a size in a magnitude from millimetres to micrometres;
• Adding, to these glass cullet, the first additive for the cathode; the first additive for the electrolyte; and the first additive for the anode, where the first additives are from the group including Cu, Fe, Si, Al, Mn, Fe, Co, Ni, V, Mo, W, their amorphous alloys such as metallic glass materials, or oxides, such as SiC, LiCI, NaCI, and elements Mn, Fe, Co, Ni, V, Mo, W, 0 in the form of compounds forming solid solutions with a spinel structure in such a quantity that the resulting composite layer of the cathode or electrolyte or anode can contain 80 to 99.8% (vol.) of the selected glass and 0.1 to 10% (vol.) of these first additives.
• Mixing of appropriate glass materials and corresponding first additives into the mixtures for a given composite layer.
• Grinding of the mixture of glass materials obtained this way with corresponding first additives into powders of glass and/or crystalline particles in the form of micro- and nanoparticles with a medium diameter from 1 nm to 100 μm.
• Admixing of these obtained powder mixtures of micro- and nanoparticles into a liquid mixture of carrier polymers for improvement of the spinning for obtaining liquid dispersion mixtures.
• Dosing of these dispersion liquid mixtures into at least one storage tank of the spinning equipment - electric spinner.
• Electrostatic spinning and drawing of micro- and nanofibres from dispersion liquid mixtures in the spinning equipment, in which controlled spinning into micro- and nanofibres and into micro- and nanoparticles with a medium diameter from 1 nm to 100 μm takes place while obtaining a function-gradient concentration thanks to various compositions of the mixtures and also thanks to various rates of the flow of the mixture into the spinning equipment.
• Thermal processing of the obtained micro- and nanofibres at a temperature from 200 to 1200°C including their cooling to the ambient temperature.
• Exfoliation for increasing the surface of the obtained micro- and nanofibres, leading to a significant increase in the rate of their surface to volume and for increasing adhesion for subsequent pressing into composite layers.
• Applying, spraying, soaking or coating of the surface of micro- and nanofibres with the second additives for increasing adhesion, where the second additive is at least one compound from the group including LiPO3, NaPO3, Li3BO3, Na3BO3, Al2O3, which is added in such a quantity that the resulting composite layer of the cathode or electrolyte or anode can contain 0.1 to 10% (vol.) of these second additives. • Pressing of the composite obtained this way into composite layers of micro/nanofibres for the cathode or electrolyte or for the anode.
• Thermal processing of the composite layer, including cooling of the obtained composite layer at a temperature of 100 - 500°C.
• Obtaining of the final layered composite layer with a function-gradient concentration for creation of the assembly of the cathode, electrolyte and anode of the secondary battery cell.
The second technological block represents, with an advantage, preparation of the cathode, electrolyte and anode and includes the following technological steps, ordered chronologically:
• Selection of the number of optional composite layers for the cathode, for the electrolyte and for the anode.
• Pressing of the selected number of composite layers for the cathode, for the electrolyte and for the anode.
• Final obtaining of composite layers for the layered cathode, for the layered electrolyte and for the layered anode.
The third technological block represents, with an advantage, the assembly of the battery cell and includes the following technological steps, ordered chronologically:
• Selection of the final layered cathode, final layered electrolyte and final layered anode.
• Attachment of the electrode, cathode and anode to the electrolyte.
• Attachment of the collector to the cathode and of the collector to the anode.
• Pressing into the final secondary battery cell without the external package.
• Vacuum sealing of the obtained pressed assembly into a plastic package.
• Finalisation and obtaining (705) of the secondary battery cell B.
The main advantage of this method is an easy and reproducible production at controlled spinning and controlled obtaining of the function-gradient concentration of layers of the cathode, electrolyte and anode in the required direction. The first additives are newly added to amorphous glass materials, and micro- and nanofibres are created from this mixture by spinning. Besides, their surface is newly covered with the second additives. These additives markedly contribute to the required electrochemical and mechanical functionality of the created function-concentration gradient of the composite layers prepared. They influence, for example, electron and ion conductivity in these layers and also mechanical cohesion and electric contact of composite layers at volume changes in the layers during the battery cell activity, which has a large impact, for example, on the value of internal resistance of the cell and on its efficiency. In this regard, there were selected and tested large quantities of these glass materials and suitable mixtures of the first and second additives suitable for them, and their characteristics were measured. The actual creation of the function-gradient concentration of composite layers of the cell is described below in the examples of implementation.
Individual technological steps described at a more detailed level concern special spinning of micro- and nano particles of glass-based composites, optimum liquid polymer mixture, admixing into the dispersion liquid mixture for spinning in several storage tanks and looking for optimum rates of outflow of liquid dispersions from individual storage tanks. This is used for very flexible and variable control and regulation of creation of the function-gradient concentration of the resulting composite layers.
The secondary battery cell can, moreover, be advantageously assembled of a combination of several composite layers, which may further increase the positive influence of the function-gradient concentration, leading to an increase in energy density in the cells, their cyclability and rate of recharging or discharging.
A number of selected technological steps can be used for preparation of individual preforms or intermediate products which can be manufactured, stored and used when required, or they can be used in parallel manufacturing processes. For example, it is possible to prepare glass materials, mixtures of the first or the second additives, their dry mixtures and especially individual composites and even composite layers to stock.
The technological procedure according to this invention leads to the obtaining of the assemblies of function-gradient composite layers of the cathode, electrolyte and anode, which are optimised in such a way that they form a solid secondary battery cell with a solid electrolyte (all-solid-state-battery), i.e. not containing organic liquid electrolyte, which is a necessary fundamental component in the existing secondary batteries, referred to in the patent literature. The currently normally used electrolyte based on organic liquids can be a very weak point of the existing secondary battery cells in electromobiles, because it is combustible and easily subject to decomposition into toxic gaseous products, for example through the effects of a locally increased temperature or the effects of increased voltage. These critical situations may occur at unsuitable recharging of the cell or at an accident of the electromobile, when the battery integrity is corrupted. Secondary battery cells according to this invention with a solid electrolyte are currently considered as the most suitable technology for the upcoming new generation of safe batteries for electromobiles.
A secondary battery cell according to this invention is non-combustible because it is based on inorganic glass. The initial inorganic glass used is, with its amorphous nature, similar to the amorphous nature of liquids, and therefore it can be a very prospective substitution for liquid electrolytes. With regard to the fact that this cell contains amorphous glass with a large free volume in the structure, this cell is able to achieve even better characteristics in comparison to the cells with a combustible liquid organic electrolyte. A disadvantage of fragility of low flexibility of glass is just resolved in the invention in an innovative way by way of flexible composite layers.
It is also advantageous for facilitation of spinning, when the mixture of the carrier polymer contains a mixture of TEOS, PVP, ethanol and water, namely TEOS in a quantity from 0.01 to 10.37% (molar); PVP in a quantity from 0.03 to 0.05% (molar); ethanol in a quantity from 68.85 to 99.92% (molar); and water in a quantity from 0.02 to 20.75% (molar).
DETAILED DESCRIPTION OF THE DRAWINGS
The invention is described at a detailed level in the text below in the non-limiting examples of implementation, and for clarification purposes it is illustrated on the attached schematic drawings. A secondary battery cell is illustrated schematically in Figures 1.1 - 1.5, where the
Figures illustrate as follows:
Figure 1.1: A secondary battery cell in an axonometric view with one layer of the cathode, anode and electrolyte;
Figure 1.2: A secondary battery cell in an axonometric view with two layers of the cathode, anode and electrolyte;
Figure 1.3: A secondary battery cell in an axonometric view with three layers of the cathode, anode and electrolyte;
Figure 1.4: An axonometric view of a secondary battery cell with one layer of the cathode, electrolyte and anode, with indicated roughness between them; and
Figure 1.5: A view of the front side of a secondary battery cell from Fig. 4 with a detailed illustration of roughness between the cathode, electrolyte and anode.
Preparation of secondary battery cells is schematically clarified in attached Figures 2.1 - 2.8, where the Figures illustrate as follows:
Figure 2.1 (2.1a, 2.1b): Preparation of cathode layers;
Figure 2.2 (2.2a, 2.2b): Preparation of electrolyte layers;
Figure 2.3 (2.3a, 2.3b): Preparation of anode layers;
Figure 2.4: Preparation of a cathode;
Figure 2.5: Preparation of an electrolyte;
Figure 2.6: Preparation of an anode;
Figure 2.7: Preparation of a secondary battery cell; and
Figure 2.8: Schematic illustration of the spinning equipment - electrospinning.
Battery cell characteristics, such as recharging or discharging and impedance are schematically illustrated in Figures 3.1- 3.4, where the Figures illustrate as follows: Figure 3.1: View of the front side of the secondary battery cell from Fig. 1 with one layer of the cathode, anode and electrolyte, with schematic illustration at discharging and recharging of the secondary battery cell;
Figure 3.2: Charging curve for a secondary battery cell with two layers of the cathode, anode and electrolyte, illustrating voltage dependence of this cell on time during its recharging;
Figure 3.3: Charging and discharging curves for s secondary battery cell with two layers of the cathode, anode and electrolyte, illustrating dependence of the charging/discharging current on the recharging and discharging times; and
Figure 3.4: Impedance spectrum of a battery cell with two layers of the cathode, anode and electrolyte.
Lavers of glass fibres of a secondary battery cell are illustrated e.g., by Figures 4.1 to 4.4, where the Figures illustrate as follows:
Figure 4.1: Shot of one layer of fibres of the GMCK glass of the cathode from an optical microscope;
Figure 4.2: Shot of one layer of fibres of the GFIC glass of the electrolyte from an optical microscope; and
Figure 4.3: Shot of one layer of fibres of the GFIC glass of the electrolyte from an electron microscope and
Figure 4.4: Shot of one layer of fibres of the GMCA glass of the anode from an optical microscope.
Secondary battery cells are illustrated by Figures 5.1 and 5.2, where the Figures illustrate as follows:
Figure 5.1: View of a secondary battery cell from the cathode side; and Figure 5.2: View of a secondary battery cell from the anode side.
Examples of Invention Implementation E x a m p l e 1
(Fig. 1.1, 1.2, 1.3, 1.4, 1.5)
1. Secondary battery cells B - layers
Figures 1.1, 1.2, 1.3 illustrate schematically particular possibilities of a solution of secondary battery cells B1 (Fig. 1.1), B2 (Fig.1.2) and B3 (Fig. 1.3). Every secondary battery cell consists of three essential parts, namely cathode K and anode A, between which the electrolyte E is placed. The collector KK is always placed from the external side of the cathode K, and the collector KA is placed from the external side of the anode A.
The secondary battery cells B1, B2, B3 have, in the example design, the shape of a rectangular parallelepiped and also the anode A, cathode K and electrolyte E have the shape of a rectangular parallelepiped as well.
Every secondary battery cell B1, B2, B3 has the height h, length I and width w. (Fig. 1.1, 1.2,
1.3).
The secondary battery cell B1 (Fig. 1.1), secondary battery cell_B2 (Fig. 1.2) and secondary battery cell B3 (Fig. 1.3) in the example implementation have e.g., total height h_90 mm, total length J_60 mm and total width w 6 mm.
Figures 1.1, 1.2, 1.3 are schematic, in fact the cells are, with regard to the width dimension w, always basically flat secondary battery cells B1, B2, B3. The different weight of the battery cells B1, B2, B3 is given by the number of layers of the cathode K, anode A and electrolyte E.
1.1 Secondary battery cell B1 with one layer of cathode K1, anode A1 and electrolyte E1
(Fig. 1.1)
Figure 1.1 illustrates the assembly of the secondary battery cell B1, which consists of the cathode
Figure imgf000018_0001
anode A1 and electrolyte E1.
Cathode K1 consists of one layer K1.1.
Electrolyte E1 consists of one layer E1.1.
Anode A1 consists of one layer A1.1.
Secondary battery cell B1 in the particular example implementation features e.g.: total height h 90 mm, total length I 60 mm and total width w 6mm.
Secondary battery cell B1 in the particular example implementation features e.g.: width WK1.1 of one layer K1.1 of the cathode K1 corresponding to 2.8 mm; width WE1.1 of one layer E1.1 of the electrolyte E1 corresponding to 0.4 mm; and width wA1.1 of one layer A1.1 of the anode A1 corresponding to 2.8 mm.
The height h and length I of the cathode K1.1, anode A1.1 and electrolyte E1.1 correspond to total dimensions of the secondary battery cell B1. The edge layers K1.1 of the cathode K1 and A1.1 of the anode A1 are greater in comparison to the central layer E1.1 of the electrolyte E1 so that it can be possible to achieve sufficiently high capacity of the secondary battery cell B1
Roughness Ra between these layers K1.1, E1.1 and A1.1 is in the range from 50 to 100 microns, with an advantage from 60 to 90 microns, with an advantage from 70 to 80 microns, with an advantage 60 microns. This roughness Ra helps to achieve a better mutual interconnection of the interface between the layers K1.1, E1.1 and A1.1 and better cohesion between them with the use of a "zip" effect.
The weight of this battery cell B1 is approx. 33 g.
1.2. Secondary battery cell B2 with two layers of the cathode K2, electrolyte E2 and anode A2
(Fig. 1.2)
Figure 1.2 illustrates an assembly of the secondary battery cell B2, which consists of the cathode K2, electrolyte E2 and anode A2 Cathode K2 consists of two layers K2.1, K2.2.
Electrolyte E2 consists of two layers E2.1, E2.2.
Anode A2 consists of two layers A2.1, A2.2.
In this configuration, the secondary battery cell B2 has, in the sequential order (Fig. 1.2): cathode K2, which has the first layer K2.1 and the second layer K2.2; electrolyte E2 with the first layer E2.1 and the second layer E2.2; and anode A2 with the first layer A2.1 and the second layer A2.2
The secondary battery cell B2 in the particular example implementation has a total height h of 90 mm, total length I of 60 mm and total width w of 6 mm. The total height h and the total length I, together of all the layers K2.1, K2.2 of the cathode K2, all the layers A2.1, A2.2 of the anode A2 and all the layers E2.1, E2.2 of the electrolyte E2, are identical with the total height h and with the total length I, respectively, of the secondary battery cell B2.
The secondary battery cell B2 has width WK2.1 of the first layer K2.1 of the cathode K2 corresponding to 1.4 mm and width WK2.2 of the second layer K2.2 of the cathode K2 also 1.4 mm; width WE2.1 of the first layer E2.1 of the electrolyte E2 corresponding to 0.2 mm and width wE2.e of the second layer E2.2 of the electrolyte E2 also 0.2 mm; and width WA2.1 of the first layer A2.1 of the anode A2 corresponding to 1.4 mm and width WA2.2 of the second layer A2.2 of the anode A2 also 1.4 mm.
The edge layers of the cathode K1 and anode A1 feature a greater width, in comparison to the electrolyte E2 placed between them, so that it can be possible to achieve sufficiently high capacity of the secondary battery cell B2.
Roughness Ra_ between these layers K2.1, K2.2; E2.1, E2.2; and A2.1, A2.2; and also between the interfaces between the cathode K2 and the electrolyte E2; and between the electrolyte E2 and the anode A2; is in the range from 30 to 80 microns, with an advantage 40 to 70 microns, and with an advantage 50 to 60 microns and with an advantage about 55 microns. This roughness Ra helps to achieve a positive mutual interconnection of individual interfaces and better cohesion between them with the use of a "zip" effect.
The weight of this battery cell B2 is about 38 g.
1.3. Secondary battery cell B3 with three layers of the cathode K3, anode A3 and electrolyte E3 (Fig. 1.3)
Figure 1.3 shows the assembly of the secondary battery cell J33, which contains the cathode K3, anode A3 and electrolyte E3.
Cathode K3 consists of three layers K3.1, K3.2, K3.3.
Electrolyte E3 consists of three layers E3.1, E3.2, E3.3.
Anode A3 consists of three layers A3.1, A3.2, A3.3.
In the direction of the sequence of placement, the following items are arranged in a parallel manner behind each other (Fig. 1.3): cathode K3 containing the first layer K3.1, the second layer K3.2 and the third layer K3.3; electrolyte E3 containing the first layer E3.1, the second layer E3.2 and the third layer E3.3; anode A3 containing the first layer A3.1, the second layer A3.2 and the third layer A3.3.
The secondary battery cell B3 in the particular example design has a total height h 90 mm, total length I 60 mm and total width w 6 mm. The total height h and the total length j, together of all the layers K3.1, K3.2,K3.3 of the cathode K3, of all the layers A3.1. A3.2, A3.3 of the anode A3 and of all the layers E3.1, E3.2, E3.3 of the electrolyte E3, are identical with the total height h and with the total length j, respectively, of the secondary battery cell B3. The secondary battery cell B3 has, however, a different width of individual layers, namely: width WK3 1 of the first layer K3.1 of the cathode K3 is 1.0 mm, width WK3.2 of the second layer K3.2 of the cathode K3 is 0.9 mm and width WK3.3 of the third layer K3.3 of the cathode K3 is 0.9 mm; width WE3.1 of the first layer E3.1 of the electrolyte E3 is 0.1 mm width WE3.2 of the second layer E3.2 of the electrolyte E3 is 0.2 mm and width WE3.3 of the third layer E3.3 of the electrolyte E3 is 0.1 mm; width WA3.1 of the first layer A3.1 of the anode A3 is 0.9 mm, width WA3.2 of the second layer A3.2 of the anode A3 is 0.9 mm and width WA3.3 of the third layer A3.3 of the anode A3 is 1.0 mm.
In total, the edge electrodes, cathode K3 and anode A3, have a greater width, in comparison to the electrolyte E3 placed between them, so that it can be possible to achieve sufficiently high capacity of the secondary battery cell
Figure imgf000021_0001
Roughness Ra_ on the interface between these layers K3.1, K3.2. K3.3; E3.1, E3.2, E3.3; and A3.1, A3.2, A3.3; and also on the interfaces between the cathode K3 and the electrolyte E3; and between the electrolyte E3 and the anode A3; is in the range from 30 to 80 microns, with an advantage about 50 microns. This roughness Ra helps to achieve positive mutual interconnection of individual interfaces and better cohesion between them by means of the "zip" effect.
The weight of this battery cell B2 is about 38 g.
1.4 Roughness between layers of the secondary battery cell B
(Fig. 1.4, 1.5)
Figure 1.4 illustrates, schematically in an axonometric view, the secondary battery cell B1 with one layer K1.1 of the cathode K1, one layer A1.1 of the anode A1 and one layer
E1.1 of the electrolyte E1. It illustrates, in a simplified way and schematically, two interfaces, indicated by means of a waved line. One interface is between the layer K1.1 of the cathode K1 and the layer E1.1 of the electrolyte E1. The second interface is between the layer E1.1 of the electrolyte E1 and the interface A1.1 of the anode A1. Both the interfaces represent, in a simplified manner, roughness of external contact surfaces between the cathode K1 and the electrolyte E1; and the roughness of external contact surfaces between the electrolyte E1 and the anode A1.
Figure 1.5 illustrates the front wall of the secondary battery cell B1 with the width wK1.1 of the cathode K1, width wAK1.1 of the anode A1 and width wE1.1 of the electrolyte E1; and roughness Ra is illustrated between them in a magnified schematic scale.
E x a m p l e 2
2. Creation of the function-gradient concentration of composite layers of the secondary battery cell B
Chemical composition for function-gradient layers of the secondary battery cell B is based on the state-of-the-art technology of both the applicants, CZ PV 2017 - 859, and includes multi-component glass materials for the cathode K, electrolyte E and anode A, which are marked in this invention by means of relationship marks GMCK, GMCA, and GMCE. The marks GMCK and GMCA relate to glass materials for electrodes, cathode K and anode A, the mark GF1C relates to the glass for the electrolyte E.
The mark GMCK (Glass Mixed Conductor Cathode) identifies glass GMCK for the cathode K whose content is the highest in the cathode K.
The mark GMCA (Glass Mixed Conductor Anode) identifies glass for the anode A, whose content is the highest in the anode A.
Both of these multi-component glass materials GMCK and GMCA have mixed ion and electron conductivity, where specific ion conductivity is at 25°C at least 10-4 S.m-1 and specific electron conductivity at 25°C is at least 10-6 S.m-1.
The mark GFIC (Glass Fast Ion Conductor) identifies glass GFIC for the electrolyte E, whose content is the highest in the electrolyte. Glass GFIC for the electrolyte E concerns multi- component glass with high ion conductivity and very low electron conductivity, whose ion conductivity at 25°C is at least 10-3 S.m-1 and the electron conductivity at 25°C is at least 3 orders lower than its specific ion conductivity and corresponds to the value at least 10-6 S.m-1. This glass GFIC for the electrolyte E is isotropic and has, basically, the same value in all the directions and the electron conductivity at least 3 orders lower than its specific ion conductivity.
These multi-component glass materials GMCK, GMCA and GFIC are present in the cathode K, in the anode A and in the electrolyte E in the form of glass micro- and nanofibres, glass particles and amorphous glass. Individual components of these glass materials GMCK, GMCA and GFIC are selected in such a way that they can form function-gradient concentration. Function-gradient concentration denotes a change in the concentration of immobile components of these glass materials depending on the distance between the collector KK of the cathode K and the opposite collector KA of the anode A. The mobile component in these glass materials GMCK, GMCA and GFIC is either lithium cation Li+ or sodium cation Na+.
An improved solution according to this invention consists in these multi-component glass materials GMCK for the cathode K, glass GMCA for the anode A and glass GFIC for the electrolyte E, completed (on the basis of possible selected production, described at a detailed level below) with additives, added to melted glass materials GMCK, GMCA and GFIC.
After the melting and cooling of the glass materials GMCK; GMCA; GFIC, suitable first additives are added to them, namely the first additive A1K for the cathode K; the first additive A1A for the anode A; and the first additive A1E for the electrolyte E; mainly for an increase in conductivity and effectiveness of the transfer of electric charge and the rate of reduction- oxidation reactions.
After burning of micro/nanofibres and their exfoliation, other suitable second additives are further added to their surface, namely the second additive A2K for the cathode K, the second additive A2A for the anode and the second additive A2E for the electrolyte E, especially for an increase in cohesion and adhesion of layers and facilitation of material transition through the interface between individual layers.
This first additives A1K; A1A; A1E; and second additives A2K; A2A; A2E are added to glass materials GMCK; GFIC; GMCA in a magnitude of tenths or units of volume %.
By adding suitable additives A1K, A1A, A1E; A2K, A2A, A2E to suitable multi-component glass materials GMCK; GMCA; GFIC there arise composites, and after the pressing of the composites there arise final composite layers based on these glass materials.
The composite in this invention consists of a mixture of glass materials GMCK, GFIC and GMCA in a mixture with the first additives A1K, A1E, A1A, inorganic (mostly) glass or (possibly) metallic fibres and with second additives A2K, A23E, A2A. Inorganic fibres arise by burning polymer nanofibres after the below-explained thermal treatment after electrostatic spinning, during which the organic component is eliminated at an increased temperature.
The finished composite layer denotes the pressed composite in this invention.
The following applies to distribution of composite layers on the basis of the glass materials GMCK for the cathode K, on the basis of the glass materials GMCA for the anode A and on the basis of the glass materials GFIC for the electrolyte E. Cathode K contains a layer of the composite based on glass GMCK with an admixture of the composite based on glass GFIC. This admixture of glass GFIC is situated in the cathode K in the vicinity of the electrolyte E, on the side facing the collector KK.
Anode A contains a layer of the composite based on glass GMCA with an admixture of the composite based on glass GFIC. This admixture of glass GFIC is situated in the anode A in the vicinity of the electrolyte E, on the side facing the collector KA.
The percentage voluminous share of the layers of composites based on glass materials GMCK/GFIC in the cathode K and of the layers of composites based on glass materials GMCA/GFIC in the anode A corresponds to the values from 100 to 0.1; and with an advantage from 90 to 10; with an advantage from 60 to 40 and with an advantage around 50.
The following Tables 1, 2 and 3 provide for more detailed clarifications of possible example and proven creations of function-gradient concentrations in composite layers based on glass materials GMCK; GMCA; GFIC and suitable additives A1K, A1A, A1E; A2K, A2A, A2E. The text and tables below use weight %, molar % and volume %.
The weight percentage is intended e.g., for the weighing of the glass batch for the selection of the glass GMCK, GFIC and GMCA.
The molar percentage is suitable and intended for assessment of the structure of compounds, chemical reactions, mutual ratios of the number of atoms and molecules arising from them, e.g., solid spinel solutions of NiFe2O4 or Fe3O4.
The volume percentage is intended for expression of the volume of solutions and their flow, e.g., during their mixing or extrusion from the spinning equipment. Also, in Tables 1, 2 and 3 these figures facilitate a well-arranged and clear description of the battery cells B with regard to the assessment of the important volumetric energy density.
2.1 Percentage volume composition of composite layers of the cathode K, anode A and electrolyte E for creation of the function-gradient concentration in composite layers of the secondary battery cell B
2.1.1 Percentage volume composition of composite layers of the cathode K1^ anode A1 and electrolyte E1 for creation of the function-gradient concentration of the secondary battery cell B1 Table 1
Percentage volume composition of one composite layer
K1.1 based on the glass GMCK and additives A1K, A2K for the cathode K1;
E1.1 based on the glass GFIC and additives A1E, A2E for the electrolyte E1; and A1.1 based on the glass GMCA and additives A1A, A2A for the anode A1; for the secondary battery cell B1.
Figure imgf000025_0001
Each layer of glass materials, together with appropriate additives, forms a sum of 100% (vol.), namely: the layer K1.1 containing the glass GMCK and GFIC with the first additive A1K and the second additive A2K; the layer E1.1 containing the glass GFIC and the first additive A1E and the second additive A2E ; and also the layer A1.1 containing the glass GFIC and GMCA and the first additive A1A and the second additive A2A.
In the secondary battery cell B1, the composite layer K1.1 contains mostly the amorphous glass GMCK with the additive A1K, A2K for the cathode K1. This composite layer K1.1 performs a function of active substance and ensures a highly efficient transfer of the charge from the ions Li+ or Na+ in the cathode K1. Besides, the composite layer K1.1 contains a very small quantity of the amorphous glass GFIC for the electrolyte E, which ensures good transport of the ions Li+ or Na+ and their intercalation into the entire volume of the cathode K1. The voluminous ratio of the content of the glass materials GMCK/GFIC can be generally in the range from 0.1 to 100, in this particular case 30.7. Also, in a smaller quantity it contains crystalline metallic particles of the additives A1K, A2K, which increase electron conductivity of this composite, and thus they facilitate transport of electrons to the collector KK of the cathode K1.
The composite layer E1.1 of the electrolyte E1 has a function of a separator, separating the cathode K1 from the anode A1, and consists of the amorphous glass GFIC, whose high ion conductivity, together with a smaller quantity of crystalline metallic additives A1E, A2E, enables a rapid transport of charge carriers at simultaneously very low electron conductivity, and this way it successfully prevents the secondary battery cell B1 from self-discharging.
The composite layer A1.1 of the anode A1 contains mostly amorphous multi-component glass GMKA performing the function of active substance, ensuring a highly efficient transfer of charge and redox reaction of Li+ or Na+ ions. Besides, it contains a small quantity of the amorphous glass GFIC ensuring good transport of Li+ or Na+ ions and their intercalation into the entire volume of the anode A1. The ratio of the contents of the glass materials GMCA/GFIC is 18.0. And in smaller quantities too, it contains crystalline metallic particles of the additives A1A, A2A, which increase electron conductivity of this composite, and thus they facilitate transport of electrons to the collector KA of the anode A1.
2.1.2 Percentage volume composition of composite layers of the cathode K2 anode A2 and electrolyte E2 for creation of function-gradient concentration of the secondary battery cell B2
Table 2
Percentage volume composition of two composite layers
K2.1, K2.2 based on the glass GMCK and additives A1K, A2K for the cathode K2;
E2,l, E2.2 based on the glass GFIC and additives A1E, A2E for the electrolyte E2; and
A2.1, A2.2 based on the glass GMCA and additives A1A, A2A for the anode A2;
Figure imgf000026_0001
Each of these composite layers of given glass materials together with appropriate first and second additives gives a sum of 100% (vol.). This means 100% by volume for: composite layer K2.1 with the first additive A1A and the second additive A2K, composite layer K2.2 with the first additive A1A and the second additive A2K; composite layer E2.1 with the first additive A1E and the second additive A2E, composite layer E2.2 with the first additive A1E and the second additive A2E, composite layer A2.1 with the first additive A1A and the second additive A2A, composite layer A2.2 with the first additive A1A and the second additive A2A.
In the secondary battery cell B2, the layer K2.1 contains mostly amorphous glass GMCK for the cathode K2 performing the function of an active substance ensuring redox reactions for a highly efficient transfer of charge from Li+ or Na+ ions. Besides, it contains a small quantity of the amorphous glass GFIC for the anode A ensuring good transport of Li+ or Na+ ions and their intercalation to the entire cathode volume. The ratio of the content of glass materials GMCK/GFIC is 47.0. It contains also crystalline metallic particles of suitable additives AIK, A2K, which increase electron conductivity of this composite, and thus they facilitate transport of electrons to the collector KK of the cathode K.
In the subsequent layer K2.2, the ratio of the glass materials GMCK/GFIC changes to 3.3 and therefore the share of ion conductivity rises. This layer K2.2 contains a small quantity of crystalline metallic particles of the additives A1K, A2K as well. Through this process, the layer K2.2 creates a desirable function-gradient transition of characteristics between the cathode K and the electrolyte E and ensures good mutual electrochemical and mechanical compatibility of the composite layers of the cathode and electrolyte.
The layer E2.1 of the electrolyte E, consists of the amorphous glass GFIC, whose high ion conductivity enables rapid transport of charge carriers at simultaneously very low electron conductivity, and this way it successfully prevents the secondary battery cell B2 from selfdischarging.
The subsequent layer E2.2 of the electrolyte E contains mostly amorphous glass GFIC ensuring high ion conductivity and small quantity of the amorphous glass for the
Figure imgf000027_0001
anode A2.1 with the additives A1E, A2E; at the ratio of the glass materials GMCA/GFIC corresponding to 0.05. This is the initial transition layer of the function-gradient concentration between the layer E2.1 of the electrolyte E and the layer A2.1 of the anode A. This layer E2.2 markedly improves compatibility of the electrolyte E and the anode A, and this way it markedly increases capacity of the secondary battery cell B2 and its long-term lifetime at a large number of cycling operations. These characteristics are supported at the anode A by the subsequent function-gradient layer A2.1 with the ratio of the glass materials GMCA/GFIC 2.6 and a small quantity of the additives A1E, A2E.
The subsequent layer A2.2 contains mostly amorphous glass GMCA performing the function of an active substance ensuring redox reactions for a highly efficient transfer of charge from Li+ or Na+ ions. Besides, it contains a small quantity of the amorphous glass GFIC ensuring good transport of Li+ or Na+ ions and their migration to the entire volume of the anode A. The ratio of the content of the glass materials GMCA/GFIC is 23.0. The layer A2.2 contains also an increased content of crystalline metallic particles of the additives A1A, A2A, which increase its electron conductivity, and thus they facilitate transport of electrons to the collector KA of the anode A.
2.1.3 Percentage volume composition of composite layers of the cathode K3 anode A3 and electrolyte E3 for creation of function-gradient concentration of the secondary battery cell B3
Table 3
Percentage volume composition of three composite layers
K3.1, K3.2, K3.3 based on the glass materials GMCK and additives A1K, A2K for the cathode K3; E3.1, E3.2, E3.3 based on the glass materials GFIC and additives A1E, A2E for the electrolyte E3; and A3.1, A3.2. A3.3 based on the glass GMCA and additives A1A, A2A for the anode A3; for the secondary battery cell B3.
Figure imgf000028_0001
Each of these composite layers of given glass materials together with appropriate first and second additives gives a sum of 100% (vol.). This means 100% by volume for: composite layer K3.1 with the first additive AIA and the second additive A2K, composite layer K3.2 with the first additive AIA and the second additive A2K, composite layer K3.3 with the first additive A1A and the second additive A2K, composite layer E3.1 with the first additive A1E and the second additive A2E, composite layer E3.2 with the first additive A1E and the second additive A2E, composite layer E3.2 with the first additive A1E and the second additive A2E, composite layer A3.1 with the first additive A1A and the second additive A2A, composite layer A3.2 with the first additive A1A and the second additive A2A, composite layer A3.3 with the first additive A1A and the second additive A2A.
The first additive A1K is added to powder mixture of the glass GMCK for the cathode K for an increase in the cathode material activity.
The second additive A2K is added onto the exfoliated micro- and nanofibres of layers for the cathode K for an increase in adhesion of layers of the cathode K.
The first additive A1E is added to powder mixture of the glass GFIC for the electrolyte E for an increase in ion conductivity of the electrolyte E.
The second additive A2E is added onto the exfoliated micro- and nanofibres of layers for the electrolyte E for an increase in adhesion of layers of the electrolyte E.
The first additive A1 is added to powder mixture of the glass GMCA for the anode A for an increase in the anode material activity.
The second additive A2A is added onto the exfoliated micro- and nanofibres of layers for the anode A for an increase in adhesion of layers of the anode A.
In the secondary battery cell B3, the layer K3.1 contains mostly amorphous glass GMCK performing the function of an active substance ensuring redox reactions for highly efficient transfer of charge from Li+ or Na+ ions during the cycles of recharging or discharging. The added small quantity of amorphous glass GFIC ensures good transport of Li+ or Na+ ions and their effective intercalation to the entire volume of the cathode K. The ratio of the content of GMCK/GFIC is 47. Besides, this layer K3.1 contains crystalline metallic particles of the additives A1K, A2K which increase its electron conductivity, and thus they facilitate transport of electrons to the collector KK of the cathode K.
At the subsequent layers K3.2, the ratio GMCK/GFIC decreases to 3.3. That is why the share of ion conductivity grows and the share of electron conductivity in the total conductivity decreases. This composite contains also a small quantity of crystalline metallic particles of the additives A1K, A2K.
The next layer K3.3 features still a lower ratio GMCK/GFIC equal to 1.0, and therefore its ion conductivity still rises while the electron conductivity is decreasing. The layers K3.2 and K3.3 therefore create a very gradual, and therefore highly effective function-gradient transition of electrochemical, thermal and mechanical characteristics between the cathode K3 and electrolyte E3 and ensure excellent mutual physical and chemical compatibility of composite layers of the cathode and of the electrolyte.
The electrolyte layer E3.1, contains amorphous glass GFIC as the main highly ion- conductive component. Together with a small quantity of amorphous glass GMCK for the cathode K at the ratio GMCK/GFIC being equal to 0.05, it forms an initial transition layer of the function-gradient concentration between the layer K3.3 of the cathode K and the layer E3.2 of the electrolyte E. This layer E3.1 markedly improves compatibility of the layers of the electrolyte E and of the anode A of the secondary battery cell B3, and thus it markedly increases capacity of the secondary battery cell B3 and its long-term lifetime at a large number of cycles.
Another separator layer E3.2 of the electrolyte E is again formed of the amorphous glass GFIC featuring high ion conductivity and very low electron conductivity.
The neighbouring layer of the electrolyte E3.3 contains mostly amorphous glass GFIC for the electrolyte E ensuring high ion conductivity and small quantity of amorphous glass GMCA for the anode A at the ratio GMCA/GF1C being equal to 0.05. This is an initial transition layer of function-gradient concentration between the layer E3.3 of the electrolyte E and the layer A3.1 of the anode A. This layer E3.3 markedly improves compatibility of layers of the electrolyte E and anode A, and thus it markedly increases movability of charge carriers especially in the direction perpendicular to mutual contact areas of individual layers. This way, the electric resistance of the secondary battery cell B3 is markedly reduced, which is advantageous for the battery supplying a high electric power output. Simultaneously, the capacity of the battery markedly increases and the cyclability of the battery is extended.
These advantageous characteristics are further supported by a function-gradient composite layer, creating this way the anode A with a gradual gradient of chemical and physical characteristics. The anode A is created by the layer A3.1 with the ratio GMCA/GFIC being equal to 1.0 with a very small quantity of the added crystalline metallic additive A1A, A2A; the following layer A3.2 with the ratio GMCA/GFIC being equal to 2.6 with a smaller quantity of the crystalline metallic additive A1A, A2A; and the end layer A3.3 with the ratio GMCA/GFIC being equal to 23.0 and with a larger quantity of the crystalline metallic additive A1A, A2A. 2.2 Chemical composition of glass materials for creation of function-gradient concentration in composite layers of the battery cells B
2.2.1 Multi-component amorphous glass GMCK-Li for the cathode K of the lithium battery cell B; its characteristics and additives A1K, A2K Table 4
Percentage molar chemical composition of the amorphous multi-component glass GMCK-Li for: one layer K1.l of the cathode K1 of the secondary lithium battery cell B1; two layers K2.1, K2.2 of the cathode K2 of the secondary lithium battery cell B2; and three layers K3.1, K3.2, K3.3 of the cathode K3 of the secondary lithium battery cell B3.
Figure imgf000031_0001
Li2O in quantity from 8.2 to 8.9 (molar %) serves for creation of the mobile cation Li+. Oxides selected according to their electronegativity serve as other components for creation of the glass GMCK-Li of the cathode K in such a way that it can be possible to create environment with optimum distribution of partial negative charge on oxygen atoms for achieving the required high mixed electric conductivity and rapid transfer of charge through rapid reduction-oxidation reactions.
The oxidised form of an oxide of polyvalent elements is its form at a higher oxidation state and the reduced form is its form at a lower oxidation state.
Table 4a
Characteristics of the amorphous glass GMCK-Li forming the layers K1.1; K2.1, K2.2; K3.1,
K3.2, K3.3; of the cathodes JK1; K2 K3; of the lithium secondary battery cells B1; B2; B3.
Figure imgf000032_0001
Table 4b
Percentage molar chemical composition of the first additive A1K for the layers K1.1; K2.1, K2.2;
K3.1. K3.2, K3.3 of the cathodes K1 K2; K3 of the lithium secondary battery cell B1; B2; B3.
Figure imgf000032_0002
Table 4c
Percentage molar chemical composition of the second additive A2K for the layers K1.1; K2.1,
K2.2; K3.1, K3.2, K3.3 of the cathode K1; K2; K3 of the lithium secondary battery cell B1; B2; B3.
Figure imgf000033_0001
Melting temperatures of the glass materials GMCK-Li for the cathode K1, K2, K3 oscillate from 950 to 1010°C; oxidised form content in molar % from 59.5 to 61.5; reduced form content from 29.3 to 33.6 molar %. Specific electron conductivity of these glass materials at 25°C oscillate from 5.03 to 8.2 [S.m-1]. E.g., Cu, Fe, Si is used as the first additive A1K; and e.g., LiPO3; Li3BO3; Al2O3 is used as the second additive A2K
2.2.2 Multi-component amorphous glass GMCK-Na for the cathode K of the sodium battery cell B; its characteristics and additives A1K, A2K
Table 5
Percentage molar chemical composition of the amorphous multi-component glass GMCK-Na for: one layer K1.1 of the cathode K1 of the secondary sodium battery cell B1; two layers K2.1. K2.2 of the cathode K2, of the secondary sodium battery cell B2; and three layers K3.1, K3.2, K3.3 of the cathode K3 of the secondary sodium battery cell B3.
Figure imgf000034_0001
Na2O in quantity from 8.4 to 9.1 (molar %) serves for creation of the mobile cation Na+. Oxides selected according to their electronegativity serve as other components for creation of the glass GMCK-Na of the cathode K in such a way that it can be possible to create environment with optimum distribution of partial negative charge on oxygen atoms for achieving the required high mixed electric conductivity and rapid transfer of charge through rapid reduction-oxidation reactions.
Table 5a
Characteristics of amorphous glass GMCK-Na forming the layers K1.1; K2.1, K2.2; K3.1,
K3.2, K3.3; of the cathodes K1; K2; K3; of the secondary sodium battery cell B1; B2; B3.
Figure imgf000035_0001
Table 5b
Percentage molar chemical composition of the first additive A1K of the layers K1.1; K2.1, K2.2; K3.1, K3.2, K3.3; of the cathode K1; K2; K3; of the sodium secondary battery cell B1; B2; B3.
Figure imgf000035_0002
Melting temperatures of the glass materials GMCK-Na for the cathode K oscillate from 990 to 1015°C, oxidised form content in molar % from 39.2 to 40.9, reduced form content from 51.3 to 53.5 mol.%. Specific electron conductivity of these glass materials at 25°C oscillates from 5.01 to 8.1 [S.m-1]. E.g., Cu, Fe, Si, is used as the first additive A1K; e.g., NaPO3; Na3BO3; Al2O3 is used as the second additive A2K Table 5c
Percentage molar chemical composition of the second additive A2K of the layers K1.1. K2.1,
K2.2; K3.1, K3.2, K3.3; of the cathode K1; K2; K3; of the sodium secondary battery cell B1; B2; B3.
Figure imgf000036_0001
2.2.3 Multi-component amorphous glass GFIC-Li for the electrolyte E of the lithium battery cell B1 its characteristics and additives A1E, A2E
Table 6
Percentage molar chemical composition of the amorphous multi-component glass GFIC-Li for: one layer E1.1 of the electrolyte E1 of the secondary lithium battery cell B1; two layers E2.1, E2.2 of the electrolyte E2 of the secondary lithium battery cell B2; and three layers E3.1, E3.2, E3.3 of the electrolyte E3 of the secondary lithium battery cell B3.
Figure imgf000036_0002
U2O in a quantity from 8.8 to 10.9 (molar %); LiCI in a quantity from 31.0 to 31.2 (molar %) and Lil in a quantity from 3.9 to 4.1 (molar %) serve for creation of the Li+ mobile cation. Oxides selected according to their electronegativity serve as other components for creation of the glass GFIC-Li of the electrolyte E in such a way that it can be possible to create environment with optimum distribution of partial negative charge on oxygen atoms for achieving the required high ion conductivity.
Table 6a
Characteristics of the amorphous glass GFIC-Li forming the layers E1.1; E2.1, E2.2; E3.1,
E3.2, E3.3; of the electrolyte E1; E2; E3; of the lithium secondary battery cell B1; B2; B3.
Figure imgf000037_0001
Table 6b
Percentage molar chemical composition of the first additive A1E of the composite layers
E1.1; E2.1, E2.2; E3.1, E3.2, E3.3; of the electrolyte E1; E2; E3; of the lithium secondary battery cell B1; B2; B3.
Figure imgf000037_0002
Table 6c
Chemical composition of the second additive A2E of the composite layers E1.1. E2.1, E2.2, E3.1, E3.2, E3.3 of the electrolyte E1, E2, E3 of the lithium secondary battery cell B1. B2, B3
Figure imgf000037_0003
Melting temperatures of the glass materials GFIC-Li of the electrolyte E oscillate from 990 to 1015°C, oxidised form content (molar %) from 39.2 to 40.9, reduced form content from 51.3 to 53.5 (mol.%). Specific electron conductivity of these glass materials at 25 °C oscillates from 5.01 to 8.1 [S.m-1]. E.g., Cu, Fe, Si is used as the first additive A1E, e.g. LiPO3, Li3BO3j AI2O3 is used as the second additive A2E
2.2.4 Multi-component amorphous glass GFIC-Na for the electrolyte E of the sodium battery cell B; its characteristics and additives A1E, A2E
Table 7
Percentage molar chemical composition of the amorphous multi-component glass GFIC-Na for: one layer E1.1 of the electrolyte E1 of the secondary sodium battery cell B1; two layers E2.1, E2.2 of the electrolyte E2, of the secondary sodium battery cell B2; and three layers E3.1, E3.2, E3.3 of the electrolyte AE3 of the secondary sodium battery cell B3.
Figure imgf000038_0001
Na2O in a quantity from 8.9 to 10.0 (molar %), NaCI in a quantity from 32.0 to 33.1 (molar %) and Nal in a quantity from 3.9 to 4.3 (molar %) serve for creation of the mobile cation Na+. Oxides selected according to their electronegativity serve as other components for creation of the glass GFIC-Na of the electrolyte E in such a way that it can be possible to create environment with optimum distribution of partial negative charge on oxygen atoms for achieving the required high ion conductivity.
Table 7a
Characteristics of the amorphous glass GFIC-Na forming the layers E1.1; E2.1, E2.2; E3.1,
E3.2, E3.3; of the electrolyte E1; E2; E3 of the sodium secondary battery cell B1; B2; B3.
Figure imgf000039_0001
Table 7b
Percentage molar chemical composition of the first additive A1E of the composite layers
E1.1; E2.1, E2.2; E3.1. E3.2, E3.3; of the electrolyte E1; E2; E3 of the sodium secondary battery cell B1; B2; B3.
Figure imgf000039_0002
Table 7c
Percentage molar chemical composition of the second additive A2E of the composite layers E1.1; E2.1. E2.2; E3.1, E3.2. E3.3; of the electrolyte E1; E2; E3; of the sodium secondary battery cell B1; B2; B3.
Figure imgf000039_0003
Melting temperatures of the glass materials GFIC-Na of the electrolyte E oscillate from 960 to 1015°C. Specific ion conductivity at 25°C oscillates from 0.4 to 2.1 [S.m-1]. Specific electron conductivity of these glass materials at 25°C oscillates in a magnitude from 10-7 to 10-6 [S.m-1]. E.g., Cu, Fe, Si are used as the first additive A1E; e.g., NaPO3, Na3BO3j Al2O3 are used as the second additive A2E
2.2.5 Multi-component amorphous glass GMCA-Li for the anode A of the lithium battery cell B; its characteristics and additives A1A, A2A
Li2O in a quantity from 16.5 to 18.4 (molar %) serve for creation of the mobile cation Li+. Oxides selected according to their electronegativity serve as other components for creation of the glass GMCA-Li of the anode A in such a way that it can be possible to create environment with optimum distribution of partial negative charge on oxygen atoms for achieving the required high mixed electric conductivity and rapid charge transfer through fast reduction-oxidation reactions.
Table 8
Percentage molar chemical composition of the amorphous multi-component glass GMCA- Li for: one layer A1.1 of the anode A1 of the secondary sodium battery cell B1; two layers A2.1, A2.2 of the anode A2, of the secondary sodium battery cell B2; and three layers A3.1, A3.2, A3.3 of the anode A3 of the secondary sodium battery cell B3.
Figure imgf000041_0001
Table 8a
Characteristics of the amorphous glass GMCA-Li forming layers A1.1; A2.1, A2.2; A3.1, A3.2, A3.3
Figure imgf000041_0002
Table 8b
Percentage molar chemical composition of the first additive A1A of the layers All; A2.1, A2.2;
A3.1, A3.2, A3.3 of the anode A1; A2; A3; of the lithium secondary battery cell B1; B2; B3.
Figure imgf000042_0001
j Table 8c
Percentage molar chemical composition of the second additive A2A of the composite layers A1.1; A2.1, A2.2; A3.1, A3.2, A3.3; of the anode A1; A2; A3; of the lithium secondary battery cell B1; B2; B3.
Figure imgf000042_0002
Melting temperatures of the glass materials GMCA-Li for the anode A oscillate from 950 to 1010°C, oxidised form content (in molar %) from 16.4 to 20.4, reduced form content from 67.8 to 74.1 mol.%. Specific electron conductivity of these glass materials at 25°C oscillates from 2.1 to 9.4 [S.m- 1]. E.g., Cu, Fe, Si are used as the first additive A1A; e.g., LiPO3; Li3BO3, Al2O3 are used as the second additive A2A
2.2.6 Multi-component amorphous glass GMCA-Na for the anode A of the sodium battery cell B; its characteristics and additives A1A, A2A
Table 9
Percentage molar chemical composition of the amorphous multi-component glass GMCA-Na for: one layer All of the anode A1 of the secondary sodium battery cell B1; two layers A2.1, A2.2 of the anode A2 of the secondary sodium battery cell B2; and three layers A3.1, A3.2, A3.3 of the anode A3 of the secondary sodium battery cell B3.
Figure imgf000043_0001
Na2O in a quantity from 16.1 to 17.5 (molar %) serves for creation of mobile Na+ cation.
Oxides selected according to their electronegativity serve as other components for creation of the glass GMCA-Na of the anode A in such a way that it can be possible to create environment with optimum distribution of partial negative charge on oxygen atoms for achieving the required high mixed electric conductivity and a rapid charge transfer through fast reduction-oxidation reactions. Table 9a
Characteristics of the amorphous glass GMCA-Na forming the layers A1.1; A2.1, A2.2; A3.1,
A3.2. A3.3; of the anode A1; A2; A3; of the sodium secondary battery cell B1; B2; B3.
Figure imgf000044_0001
Table 9b
Percentage molar chemical composition the first additive A1A of the composite layer A1.1, A2.1, A2.2; A3.1, A3.2, A3.3; of the anode A1; A2; A3; of the sodium secondary battery cell B1;
B2; B3.
Figure imgf000044_0002
Table 9c
Percentage molar chemical composition of the second additive A2A of the layers A1.1; A2.1, A2.2; A3.1, A3.2, A3.3; of the anode A1; A2; A3; of the lithium secondary battery cell B1; B2; B3.
Figure imgf000044_0003
Melting temperatures of the glass materials GMCA-Na for the anode A oscillate from 970 to 1015°C, oxidised form content (molar %) from 26.7 to 35.3, reduced form content from 104.5 to 111.7 mol.%. Specific electron conductivity of these glass materials at 25°C oscillates from 2.5 to 9.9 [S.m-1]. E.g., Cu, Fe, Si is used as the first additive A1A; e.g.,NaPO3; Na3BO3j Al2O3 is used as the second additive A2A
Concerning the raw materials used: TEOS from the Germany-based company Merc Sigma-Aldrich, purity 99.95% (weight). PVP from the Germany-based company Sigma- Aldrich, purity 99.98 % (weight). The oxides, carbonates, metals used originated from the Germany-based companies Sigma-Aldrich, PuraLab, HiChem, Lachner (p.a. purity) or from Fischer Scientific.
Chemical composition of amorphous glass materials of the cathode K is stated in molar %, in Table 4 for the lithium secondary battery cells B1, B2, and B3; and for the sodium secondary battery cells B1, B2 and B3 in Table 5. Composition of these glass materials is developed in such a way that it can be possible to achieve creation of the function-gradient concentration in the composite of cathodes with highly continuous transition of characteristics. The ratio of oxidised and reduced forms of polyvalent elements Mp is optimised in this composite in such a way that the composite can state high electron and mixed electric conductivity, ensuring cooperative mechanism of charge transfer and migration of ion carriers of the charge to the entire volume of the cathode K, which leads to the very effective use of the volume of an active substance of this electrode as large as possible. This makes it possible to achieve a high rate and reversibility of electrode reactions, which is necessary for the battery cells B1, B2, and B3 to be able to provide a high current and power density. These composites are, therefore, suitable for construction of batteries for electromobiles, where electric sources of a high current and power density are required.
Table 4a states characteristics of the lithium glass materials for layers of the cathode K, and Table 4b states composition of the first additives A1K, and Table 4c provides for composition of the second additive A2K for these lithium glass materials.
Table 5a states characteristics of the sodium glass materials for layers of the cathode K, Table 5b states composition of the first additives A1K, and Table 5c provides for composition of the second additive A2K for these sodium glass materials.
Chemical composition of amorphous glass materials for the electrolyte E is stated in molar %, for the lithium secondary battery cells B1, B2 and B3 in Table 6, containing Li+ ions as highly mobile ion carriers of a charge; and the chemical composition of amorphous glass materials for the sodium secondary battery cells B1, B2, B3 is stated in Table 7, containing Na+ ions as highly mobile ion carriers of a charge. Chemical composition of the electrolytes E features, for both Li+ ions and Na+ ions, basicity of the glass matrix set up in a directed manner on the basis of an optimum ratio of concentrations of electropositive and electronegative elements. This optimised composition of the solid electrolyte E thus guarantees high stability and simultaneously the necessary concentration of ion carriers of a charge with high movability. That is why the electrolyte E achieves high ion conductivity at very low electron conductivity. For this reason, they are suitable for construction of high-capacity secondary batteries.
Table 6a states characteristics of lithium glass materials for layers of the electrolyte E, Table 6b states composition of the first additives A1E and Table 6c states composition of the second additives A2E for these lithium glass materials.
Table 7a states characteristics of sodium glass materials for layers of the electrolyte E, Table 7b states composition of the first additive A1E and Table 7c states composition of the second additive A2E for these sodium glass materials.
Chemical composition of amorphous glass materials of the anode A is stated in molar % for the lithium secondary battery cells B1, B2, and B3 in Table 8; and for the sodium battery cells B1, B2 and B3 it is provided for in Table 9. These glass materials feature an optimised representation of the ratio of oxidised and reduced forms of the polyvalent elements Mp with suitable electronegativity and electron affinity in such a way that the resulting glass can state a gradual transition from mixed electric conductivity to prevailing high electron conductivity in the area of contacts with the collector KA. This ensures the necessary cooperative mechanism of the charge transfer and migration of ion carriers of a charge to the entire volume of the anode A, which leads to a very effective use of the maximum possible volume of an active substance of this electrode. This is manifested during the recharging of secondary battery cells through the ability of such anode A to achieve storage of very high capacity of the charge. This characteristic is necessary for the secondary battery cells B1, B2, B3 capable of achieving high gravimetric and volumetric energy density. At the same time, the high rate and reversibility of the electrode reactions is maintained, which is necessary for the secondary battery cells B1, B2, B3 to be able to provide high current and power density. Table 8a states characteristics of lithium glass materials for layers of the anode A, Table 8b states composition of the first additive A1A, and Table 8c states composition of the second additive A2A for these lithium glass materials.
Table 9a states characteristics of sodium glass materials for layers of the cathode A, Table 9b states composition of the first additives A1A, and Table 9c states composition of the second additives A2A for these sodium glass materials.
The above-mentioned function-gradient composite layers for the cathode K, electrolyte E and anode A are therefore suitable for construction of the secondary battery cells Bi for example for electromobiles where high-capacity electric sources with high energy, current and power densities are required.
Oxides and carbonates of both metals and non-metals and actual metals used for the melting of glass materials and as the first as well as second additives were selected in such a way that the corresponding substance can be stable, little hygroscopic and cost- efficient. These raw materials were supplied in the p.a. purity by such companies as Sigma-Aldrich spol. s.r.o, Na Hfebenech II 1718/10, 140 00 Prague 4, Czech Republic; Puralab spol. s.r.o., Podnikatelska 552, 19011 Prague, Bechovice, Hichem spol. s.r.o., Novodvorska 994/138, Branik, 142 00 Prague; Lach-Ner spol. s.r.o., Tovarni 157, 27711 Neratovice; Fisher Scientific, spol. s r.o., Kosmonautu 324, 53009 Pardubice.
Example 3
3. Flow charts for the procedure of preparation of the secondary battery cell B
(Fig. 2.1 to 2.7)
This example implementation clarifies, at a detailed level with the help of attached Figures 2.1 to 2.7, preparation of the secondary battery cells B1, B2, B3 in the form of flow charts.
Each of these Figures 2.1 to 2.7 of the flow charts states, on the first line, briefly a cogent characteristic concerning production of the secondary battery cell B.
Individual technological steps are put together in a chronological order and are briefly described in blocks, where the processes logically following up to each other are marked with arrows. These individual technological steps are numerically marked on the left side of each Figure of the flow chart, which means that a three-digit number corresponds to each technological step.
The right side of each Figure of the flow chart states references to corresponding tables in the text or attached Figures.
Furthermore, some of the Figures, e.g., Fig. 2.1, 2.2 and 2.3 have continuation. E.g., Figure 2.1 has the first continuation marked as 2.1a and the second continuation marked as 2.1b. The continuations 2.2a; 2.2b and 2.3a; 2.3b are marked in a similar way.
Preparation of the secondary battery cells B1, B2, B3 according to example implementations can be divided basically into three fundamental technological blocks, as clearly implies from the examples of implementations and attached Figures.
The first technological block represents preparation of composite layers of the cathode K, electrolyte E and anode A, at a more detailed level described in following chapters 3.1- 3.1.16.
Preparation of composite layers of the cathode K1; K2; K3 corresponds to Figures 2.1, 2.1a, 2.1b; of the electrolyte E1; E2; E3 corresponds to Figures 2.2, 2.2a, 2.2b; and of the anode A1; A2 corresponds to Figures 2.3, 2.3a, 2.3b.
The second technological block represents (from these obtained layers in the first technological block) preparation of the cathode K, electrolyte and anode A, at a more detailed level described in following chapters 3.2 - 3.2.3. Preparation of the cathode K1; K2; K3 corresponds to Figure 2.4; of the electrolyte E1; E2; E3 corresponds to Figure 2.5; and of the anode A1; A2; A3 corresponds to Figure 2.6.
The third technological block represents assembly of the secondary battery cells B1; B2; B3 according to Figure 2.7 and at a more detailed level described in subsequent chapter 3.3. 3.1 Procedure of production of individual layers
The layers of the cathode K, electrolyte E and anode A are illustrated in attached Figures 2.1 - 2.3, where at a more detailed level
• Figures 2.1, 2.1a, 2.1b describe preparation of layers for the cathode K,
• Figures 2.2, 2.2a, 2.2b describe preparation of layers for the electrolyte E and
• Figures 2.3, 2.3a, 2.3b describe preparation of layers for the anode A.
The illustrated procedure states certain common technological steps, marked on the left side of each Figure of the flow charts and referred to below. The arrangement of individual technological steps is ordered chronologically.
3.1.1. Composition of glass materials and of first additives
Tables 4, 4b, 4c, 5, 5b, 5c, 6, 6b, 6c, 7, 7b, 7c, 8, 8b, 8c, 9, 9b, 9c.
Markings 101. 201, 301 correspond to the technological step of the selection and choice of suitable chemical composition of the glass GMCK for the cathode K or of the glass GFIC for the electrolyte E or of the glass GMCA for the anode A, then also of the selection and choice of composition of the first additive A1K for the cathode K or of the first additive A1E for the electrolyte E or of the first additive A1A for the anode A.
Marking 101 corresponds to the choice of chemical composition of the glass materials GMCK; GFIC and selected composition of the first additives A1K; A1E, all of this for preparation of layers of the cathode K according to Figure 2.1.
Marking 201 corresponds to the choice of chemical composition of the glass materials GMCK; GFIC; GMCA and also of suitable chemical compositions of the first additives A1K; A1E; A1A. all of this for preparation of layers of the electrolyte E according to Figure 2.2.
Marking 301 corresponds to the choice of chemical composition of the glass materials GMCA; GFIC and of the first additives A1A; A1E, for preparation of layers of the anode A according to Figure 2.3.
3.1.2. Batches for glass materials with the first additives
Markings 102, 202, 302 state a technological step consisting in the input of raw materials in the form of glass batches and the first additives, namely the batch for the selected glass materials GMCK; GFIC; GMCA and suitable selected first additives A1K; A1E; A1A. Marking 102 states a technological step consisting in the input of batches for the glass materials GMCK; GFIC and then it states the input of the first additives A1K; A1E, all of this being for preparation of layers of the cathodes K1; K2; K3 according to Figure 2.1.
Marking 202 states the input of batches for the glass materials GMCK; GFIC; GMCA, and moreover it states the input of the first additives A1K; A1E; A1A, all of this being for preparation of layers of the electrolytes E1; E2; E3 according to Figure 2.2.
Marking 302 states the input of batches for the glass GMCA and the glass GFIC. and moreover it states the input of the first additives A1A; A1E, all of this being for preparation of the anodes A1; A2; A3 according to Figure 2.3.
3.1.3 Melting of glass melts
Markings 103, 203, 303 concern the subsequent technological step consisting in the melting of glass melts, for glass materials GMCK; GFIC; GMCA. If it is not necessary to ensure the control of the oxidation-reduction (redox) state of the glass melt, the melting operation takes place in the air. Nevertheless, if the control of the redox state of the glass melt is necessary, then the melting of glass melts takes place in the controlled atmosphere.
Marking 103 concerns the melting of the glass melt GMCK; GFIC according to the above-stated possibility of the choice of the melting method, always for preparation of layers of the cathodes K1; K2; K3 according to Figure 2.1.
Marking 203 concerns the melting of the glass melt GMCK; GFIC; and of the glass melt GMCA according to the above-mentioned possibility of the choice of the melting method, for preparation of layers of the electrolytes E1; E2; E3 according to Figure 2.2.
Marking 303 concerns the melting of the glass melt GMCA; GFIC according to the above-mentioned possibility of the choice of the melting method, for preparation of layers of the anodes A1; A2; A3 according to Figure 2.3.
3.1.4 Cooling of glass materials
Markings 104, 204 and 304 represent the technological step of the process of cooling of melted glass materials, namely the glass materials GMCK; GFIC; GMCA, in the air or in a protective atmosphere. Marking 104 represents the process of cooling of the melted glass GMCK; GFIC in the air or in a protective atmosphere, for preparation of layers of the cathodes K1; K2; K3 according to Figure 2.1.
Marking 204 represents the process of cooling of the melted glass GMCK; GFIC; GMCA in the air or in a protective atmosphere, for preparation of layers of the electrolytes E1; E2; E3 according to Figure 2.2.
Marking 304 represents the process of cooling of the melted glass GMCA; GFIC in the air or in a protective atmosphere, for preparation of layers of the anodes A1; A2; A3 according to Figure 2.3.
3.1.5. Crushing of glass
Markings 105, 205, 305 represent a subsequent technological step consisting in the crushing of melted and cooled glass into cullet, namely of the glass materials GMCK; GFIC; and the glass GMCA.
Marking 105 represents the technological step of the crushing of the glass GMCK; GFIC into cullet, all for preparation of layers of the cathode K1; K2; K3 according to Figure 2.1.
Marking 205 represents the technological step of the crushing of the glass GMCK; GFIC; GMCA into cullet, all for preparation of layers of the electrolytes E1; E2; E3 according to Figure 2.2.
Marking 305 represents a subsequent technological step of crushing of the glass GMCA; GFIC, all for preparation of layers of the anodes A1; A2; A3 according to Figure 2.3.
3.1.6 Adding the first additive to the cullet
Markings 106, 206, 306 concern the technological step of adding the first additive A1K or the first additive A1E or the first additive A1A to the cullet of the glass GMCK, or to the cullet of the glass GFIC, or to the cullet of the glass GMCA. This first additives set up electron conductivity of these materials, and thus also the effectiveness of the transfer of electric charge with the help of rapid oxidation-reduction reactions. Marking 106 concerns adding the first additive A1K to the cullet of the glass GMCK; adding the first additive A1E to the cullet of the glass GFIC; for preparation of layers of the cathodes K1; K2; K3 according to Figure 2.1.
Marking 206 concerns adding the first additive A1E to the cullet of the glass GFIC; adding the first additive A1K to the cullet of the glass GMCK; adding the first additive A1A to the cullet of the glass GMCA; all of this being for preparation of layers of the electrolytes E1; E2; E3 according to Figure 2.2.
Marking 306 concerns adding the first additive A1E to the cullet of the glass GFIC; adding the first additive A1A to the cullet of the glass GMCA; all for preparation of layers of the anodes A1; A2; A3 according to Figure 2.3.
3.1.6a Mixing the cullet with the first additives
Markings 106a, 206a and 306a concern the technological step of mixing the cullet with the first additives for the cathode K or anode A or electrolyte E, with a reference to Tables 10, 14, 18, 22, 26, 30, 34, 38 and 42.
Marking 106a identifies mutual mixing of the glass GMCK with the additive A1K; of the glass GFIC with the additive A1E; with a reference to Tables 10, 22 and 34 and Fig. 2.1, all of this being for preparation of layers of the cathodes K1; K2; K3.
Marking 206a identifies mutual mixing of the glass GMCK with the additive A1K with the glass GFIC with the additive A1E and also with the glass GMCA and with the additive A1A; with a reference to Tables 14, 26 and 38 and Fig. 2.2, all of this being for preparation of layers of the electrolytes E1; E2; E3.
Marking 306a identifies mutual mixing of the glass GMCA with the additive A1A with the glass GFIC with the additive A1E; with a reference to Tables 18, 30 and 42 and Fig.
2.3; all of this being for preparation of layers of the anodes A1; A2; A3.
3.1.7 Grinding a mixture of cullet with the first additives into micro- and nano particles Markings 107, 207, 307 identify the technological step of grinding the cullet with the first additives into micro- and nanoparticles, namely the grinding of cullet of the glass GMCK together with the first additive A1K or grinding of the glass GFIC with the first additive A1E or grinding of the glass GMCA with the first additive A1A, with a reference to related Tables 10, 14, 18, 22, 26, 30, 34, 38 and 42 and related Fig. 2.1a, 2.2a, 2.3a. Marking 107 identifies the grinding of cullet of the glass GMCK with the first additive A1K or of the glass GFIC with the first additive A1E, into micro- and nanoparticles, with a reference to Tables 10, 14, 22, 26, 34, and 38, for preparation of layers of the cathode K1; K2; K3 according to Figure 2.1a.
Marking 207 identifies the grinding of cullet of the glass GFIC with the first additive A1E or the grinding of cullet of the glass GMCK with the first additive A1K or the grinding of cullet of the glass GMCA with the first additive A1A, into micro- and nanoparticles for the electrolyte E1; E2; E3, with a reference to Tables 10, 14, 18, 26, 30, 34, 38 and 42, according to Figure 2.2a.
Marking 307 identifies the grinding of cullet of the glass GMCA with the first additive A1A or the grinding of cullet of the glass GFIC with the first additive A1E into micro- and nanoparticles; with a reference to Tables 14, 18, 22, 26, 30, 34, 38 and 42; for preparation of layers of the anodes A1; A2; A3 according to Figure 2.3a.
3.1.8 Admixing micro- and nanoparticles into carrier polymer liquid mixtures
Markings 108, 208 and 308 represent the technological step of admixing obtained micro- and nanoparticles into carrier polymer liquid mixtures, where the obtained micro- and nanoparticles contain the glass GFIC with the first additive A1E or the glass GMCK with the first additive A1K or the glass GMCA with the first additive A1A, and the carrier polymer mixtures help to create micro- or nanofibres in an electric field; with a reference to related Tables 11, 12, 15, 16, 19, 20, 23, 24, 27, 28, 31, 32, 35, 36, 39, 40, 43 and 44 and related Figures 2.1a, 2.2b and 2.3a.
Marking 108 represents admixing the obtained micro- and nanoparticles into the carrier polymer liquid mixtures, which help to create micro- or nanofibres in an electric field; with a reference to Tables 11, 12, 15, 16, 23, 24, 27, 28, 35, 36, 39 and 40; for preparation of layers of the cathodes K1; K2; K3 according to Figure 2.1a.
Marking 208 represents admixing the obtained micro- and nanoparticles for the electrolyte E into the carrier polymer liquid mixtures, which help to create micro- or nanofibres in an electric field; with a reference to Tables 11, 12, 15, 16, 19, 20, 23, 24, 27, 28, 31, 32, 35, 36, 39, 40, 43 and 44; for preparation of layers of the electrolytes E1; E2; E3 according to Figure 2.2a. Marking 308 represents admixing the micro- and nanoparticles for the anode A into the carrier polymer liquid mixtures, which help to create micro- or nanofibres in an electric field; with a reference to Tables 15, 16, 19, 20, 23, 24, 27, 28, 31, 32, 35, 36, 39, 40, 43 and 44; for preparation of layers of the anodes A1; A2; A3 according to Figure 2.3a.
3.1.9 Dosing the obtained mixture into the spinning equipment - electric spinner
Markings 109, 209, 309 illustrate the technological step of the dosing of the obtained mixture into an electric spinner with a reference to Tables 13, 17, 21, 25, 29, 33, 37, 41 and 45; and Figures 2.1a, 2.2a and 2.3a.
Marking 109 illustrates the dosing of the obtained mixture into the spinning equipment (electric spinner); with a reference to Tables 13, 25, 37; for preparation of layers of the cathodes K1; K2; K3 according to Figure 2.1a.
Marking 209 illustrates the dosing of the obtained mixture for preparation of layers of the electrolyte E into the spinning equipment; with a reference to Tables 17, 29, 41; for preparation of layers of the electrolytes E1; E2; E3 according to Figure 2.2a.
Marking 309 illustrates the dosing of the obtained mixture into the spinning equipment; with a reference to Tables 21, 33, 45; for preparation of layers of the anodes A1; A2; A3 according to Figure 2.3a.
3.1.10 Drawing micro- and nano fibres in an electric field in the spinning equipment - electric spinner
Markings 110, 210, 310 show the technology of the step of the drawing of micro- and nanofibres in an electric field; with a reference to Figures 2.1a, 2.2a, 2.3a and also Figure 2.8.
Marking 110 shows the technology of the step of the drawing of micro- and nanofibres in an electric field for the cathodes K1; K2; K3 according to Figure 2.1a and with a reference to Figure 2.8.
Marking 210 shows the technology of the step of the drawing of micro- and nanofibres in an electric field for the electrolytes E1; E2; E3 according to Figure 2.2a and with a reference to Figure 2.8. Marking 310 shows the technology of the step of the drawing of micro- and nanofibres in an electric field for the anodes A1; A2; A3 according to Figure 2.3a and with a reference to Figure 2.8.
3.1.11 Thermal processing of micro- and nanof ibres
Markings 111, 211, 311 are a subsequent technological step of thermal processing of micro- and nanofibres at temperatures from 200 to 1200°C with a reference to Figures 4.1, 4.2, 4.4 and Figures 2.1a, 2.2a and 2.3a. This technological step enables creation of flexible layers even of these purely inorganic materials and therefore non-combustible materials.
Marking 111 represents the technological step of thermal processing of micro- and nanofibres for preparation of layers of the cathodes K1; K2; K3 at temperatures from 200 to 1200°C according to Figure 2.1a and with a reference to Figures 4.1 and 4.2.
Marking 211 is a subsequent technological step of thermal processing of micro- and nanofibres for preparation of layers of the electrolytes E1; E2; E3 at temperatures from 200 to 1200°C according to Figure 2.2a and with a reference to Figures 4.1, 4.2 and 4.4.
Marking 311 is a subsequent technological step of thermal processing of micro- and nanofibres for preparation of layers of the anodes A1; A2; A3 at temperatures from 200 to 1200°C according to Figure 2.3a and with a reference to Figures 4.1, and 4.2.
3.1.12 Exfoliation of micro- and nanofibres
Markings 112, 212, 312 represent a technological step of exfoliation of micro- and nanofibres. Exfoliation concerns the opening of the surface of micro/nanofibres, which leads to a significant increase in the ratio of the fibre surface to the fibre volume.
Marking 112 represents exfoliation of micro- and nanofibres for preparation of layers of the cathodes K1; K2; K3. Exfoliation concerns the opening of the surface of micro/nanofibres, which leads to a significant increase in the ratio of the fibre surface to the fibre volume according to Figure 2.1a.
Marking 212 represents exfoliation of micro- and nanofibres for preparation of layers of the electrolytes E1; E2; E3. Exfoliation concerns the opening of the surface of micro/nanofibres, which leads to a significant increase in the ratio of the fibre surface to the fibre volume according to Figure 2.2a. Marking 312 represents exfoliation of micro- and nanofibres for preparation of layers of the anodes A1; A2i A3. Exfoliation concerns the opening of the surface of micro/nanofibres, which leads to a significant increase in the ratio of the fibre surface to the fibre volume according to
Figure 2.3a.
3.1.13 Applying the second additive
Markings 113, 213, 313 correspond to the important technological step of application of the second additive, namely the second additive A2K for the cathode K, the second additive A2E for the electrolyte E and the second additive A2A for the anode A. With a reference to Tables 4c, 5c, 6c, 7c, 8c and 9c. The second additive ensures positive cohesion of composite layers and their adhesion e.g., also to the collector KK of the cathode K and to the collector KA of the anode A.
Marking 113 corresponds to the important step applying the second additive, namely the second additive A2K for the cathodes K1; K2; K3 according to Figure 2.1a and with a reference to Tables 4c, 5c, 6c, and 7c. The second A2K ensures positive cohesion of composite layers and their adhesion e.g., also to the collector KK of the cathode K.
Marking 213 corresponds to the important step applying the second additive, namely the second additive A2E for the electrolytes E1; E2; E3 according to Figure 2.2a and with a reference to Tables 6c and 7c. The second additive A2E ensures positive cohesion of composite layers.
Marking 313 corresponds to the important step applying the second additive, namely the second additive A2A for the anodes A1; A2; A3 according to Figure 2.3a and with a reference to Tables 8c and 9c. The second additive A2A ensures positive cohesion of composite layers and their adhesion e.g., also to the collector KA of the anode A.
3.1.14 Pressing composite layers
Markings 114, 124 and 314 concern a subsequent technological step of the pressing of obtained composite layers for the cathode K, electrolyte E and anode A.
Marking 114 concerns subsequent pressing of obtained composite layers for preparation of layers of the cathode K according to Figure 2.1b.
Marking 214 concerns subsequent pressing of obtained composite layers for preparation of layers of the electrolyte E according to Figure 2.2b. Marking 314 concerns subsequent pressing of obtained composite layers for preparation of layers of the anode A according to Figure 2.3b.
3.1.15 Thermal processing for adhesion of the second additive
Markings 115, 215 and 315 represent a technological step of subsequent thermal processing of the pressed layer obtained this way, which is carried out by heating to a temperature from 100 to 500°C and subsequent sufficiently slow cooling, with an advantage in the same equipment, for the purpose of achieving the adhesion of the second additives A2K: A2E; A2A, with a reference to Figures 2.1a, 2.2b and 2.2c.
Marking 115 represents subsequent thermal processing of the pressed layer, which is carried out by heating to a temperature from 100 to 500°C with subsequent cooling for the purpose of achieving the adhesion of the second additive A2K for preparation of layers of the cathode K according to Figure 2.1b.
Marking 215 represents subsequent thermal processing of pressed layers, which is carried out by heating to a temperature from 100 to 500°C and subsequent cooling for the purpose of achieving the adhesion of the second additive A2E for preparation of layers of the electrolyte E according to Figure 2.2b.
Marking 315 represents subsequent thermal processing of pressed layers, which is carried out by heating to a temperature from 100 to 500°C and subsequent cooling for the purpose of achieving the adhesion of the second additive A2A for preparation of layers of the anode A according to Figure 2.3b.
3.1.16 Obtaining finished composite layers
Markings 116, 216, 316 are a final technological step consisting in obtaining individual finished composite layers with a reference to Figures 1.1, 1.2, 1.3 and 2.1a, 2.2b, 2.3b, namely: composite layers K1.1; K2.1, K2.2; or layers K3.1, K3.2, K3.3 of the cathode K; or composite layers E1.1, or E2.1, E2.2; or E3.1, E3.2. E3.3 of the electrolyte E; or composite layers A1.1 or A2.1. A2.2 or A3.1, A3.2, A3.3 of the anode A.
Marking 116 is a final step consisting in obtaining finished composite layers with a reference to Figures 1.1 to 1.3, namely: composite layers K1.1; or K2.1, K2.2; or layers K3.1, K3.2, K3.3 of the cathode K according to Figure 2.1b. Marking 216 is a final step consisting in obtaining finished composite layers with a reference to Figures 1.1 to 1.3, namely: composite layers E1.1; or E2.1, E2.2; or layers E3.1. E3.2, E3.3 of the electrolyte E according to Figure 2.2b.
Marking 316 is a final step consisting in obtaining finished composite layers with a reference to Figures 1.1 to 1.3, namely: composite layers A1.1; or A2.1, A2.2; or layers A3.1. A3.2, A3.3 of the anode A according to Figure 2.3b.
3.2 Preparation of electrodes of the cathode K and anode A and electrolyte E
The second technological block represents preparation of the cathode, electrolyte and anode, and is illustrated in Figures 2.4 to 2.5. Preparation of the cathode K is illustrated in Figure 2.4, preparation of the electrolyte E in Figure 2.5 and preparation of the anode A in Figure 2.6. The technological procedure has certain common features with a reference to Figures 1.1 to 1.3.
3.2.1 Selection of the number of optional layers of the cathode K, anode A and electrolyte E
Markings 401, 501, 601 illustrate a technological step, namely the number of optional layers, for this example 1 to 3 layers of the cathode K (Fig. 2.4) or electrolyte E (Fig. 2.5) and anode A (Fig. 2.6).
Marking 401 illustrates the number of selected and manufactured layers of the cathode K for the cell B1 created in Example 1 by means of one layer K1.1, or for the cell B2 created in Example 2 by means of two layers K2.1; K2.2, or for the cell B3 created by means of three layers K3.1; K3.2; K3.3 according to Figure 2.4, possibly also with a reference to Figures 1.1, 1.2, 1.3.
Marking 501 illustrates the number of optional layers for the electrolyte E, for the cell B1 created in Example 1 by means of one layer E1.1, or for the cell B2 created in Example 2 by means of two layers E2.1; E2.2, or for the cell B3 created by means of three layers E3.1; E3.2; E3.3. according to Figure 2.5, possibly also with a reference to Figures 1.1, 1.2, 1.3.
Marking 601 illustrates the number of optional layers for the anode A for the cell B1 created in Example 1 by means of one layer A1.1. or for the cell B2 created in Example 2 by means of two layers A2.1; A2.2, or for the cell B3 created by means of three layers A3.1; A3.2; A3.3, according to Figure 2.6, possibly also with a reference to Figures 1.1,
1.2, 1.3.
Possibility of choice of a different number of layers for creation of the cathode K, electrolyte E and anode A flexibly ensures their optimum creation with regard to the ratio of the price and key electric parameters of the battery cells assembled of them, such as electrical output and energy density. An economy variant is formed of cells with one layer for the cathode K, electrolyte E and anode A and also of the cells with two layers of a simplified chemical composition, having a lower output, lower energy density and shorter lifetime. On the high end, there are more expensive cells with three layers and optimised chemical composition for the cathode K, electrolyte E and anode A* achieving a higher output, energy density and a longer lifetime.
3.2.2 Pressing individual composite layers of the cathode K, anode A and electrolyte E together
Markings 402, 502, 602 illustrate the technological step of pressing the individual composite layers of the cathode K, anode A and electrolyte E together.
Marking 402 illustrates the pressing of individual composite layers for the cathode K together, namely pressing of one layer or 2 layers or 3 layers, according to Figure 2.4, possibly also with a reference to Figures 1.1, 1.2, 1.3.
Marking 502 illustrates the pressing of individual composite layers for the electrolyte E together, namely pressing of one layer or 2 layers or 3 layers, according to Figure 2.5, possibly also with a reference to Figures 1.1, 1.2, 1.3.
Marking 602 illustrates the pressing of individual composite layers for the anode A together, namely pressing of one layer or 2 layers or 3 layers, according to Figure 2.6, possibly also with a reference to Figures 1.1, 1.2, 1.3.
3.2.3 Final obtaining of layers of the cathode K, electrolyte E or anode A
Markings 403, 503, 603 represent a technological step of the final obtaining of composite layers of the cathode K, electrolyte E or anode A, according to Figures 2.4, 2.5, 2.6, possibly also with a reference to Figures 1.1, 1.2, 1.3.
Marking 403 represents final obtaining of pressed composite layers of the cathode K, namely of the 1-layer, 2-layer or 3-layer cathodes according to Figure 2.4. Marking 503 represents final obtaining of pressed composite layers of the electrolyte
E, namely of the 1-layer, 2-layer or 3-layer electrolytes according to Figure 2.5.
Marking 603 represents final obtaining of pressed composite layers of the anode A, namely of the 1-layer, 2-layer or 3-layer anodes according to Figure 2.6.
3.3 Assembly of the secondary battery cells B1, B2, B3
The third and last technological block, assembly of the secondary battery cells B1, B2, B3, is illustrated schematically in Figure 2.7 with a reference to Figure 5.1 and 5.2.
Marking 701 is based on the already finished prepared cathodes K1 or K2 or K3; electrolytes E1 or E2 or E3; and anodes A1 or A2 or A3. The cathode K1 or electrolyte E1 or anode A1 consists of one layer. The cathode K2, electrolyte E2 and anode A2 consists of two layers. The cathode K3, electrolyte E3 and anode A3 consists of three layers.
Marking 701a represents attachment of electrodes to the electrolyte. The electrolyte
E1 is attached to the cathode K1 and the anode A1 is attached to that electrolyte; or the electrolyte E2 is attached to the cathode K2 and the anode A2 is attached to that electrolyte; or the electrolyte E3 is attached to the cathode K3 and the anode A3 is attached to that electrolyte.
Marking 702 represents connection of the collector KK to the cathode K1, or to the cathode K2, or to the cathode
Figure imgf000060_0001
and of the collector KA to the anode A1, or to the anode A2, or to the anode A3. This way there will arise a non-pressed assembly of the secondary battery cell B1 or B2 or B3.
Marking 703 includes subsequent pressing of a non-pressed assembly into the final secondary battery cell B1 or B2 or B3, without an external package.
Marking 704 concerns vacuum sealing of the obtained pressed assembly into a plastic package.
Marking 705 illustrates finalisation and obtaining of the secondary battery cell B1 or
B2 or B3, e.g., to a final standard shape. 3.3.1 Spinning - electrospinning at a more detailed level
(Figure 2.8)
Figure 2.8 illustrates schematically the spinning equipment (electric spinner) at creation of the important technological step of spinning in the technological direction of two marked arrows (from the left to the right).
The spinning equipment includes the pump 1 with a solution, mouthing to the nozzle 2 of the Taylor cone 3 and collection areas 4. Between the end of the Taylor cone 3 and the collection areas 4, there is an area 5 of the spinning of micro- and nano fibres (transition between the glass melt and the solid state of glass fibres). In the area 5, of the spinning process, there is indicated a stream 6 of micro- and nano fibres arising in the spinning process, indicated illustratively in the form of flying waves of fibres (in the shape of the letter "V"), respectively in the shape of growing waveforms. In the area of the pump 1 and Taylor cone 3 with the nozzle 2, small acceleration takes place, while rapid acceleration takes place in the area 5 of the spinning process.
Spinning 110, 210, 310 takes place e.g. in such a way that the obtained powder mixture of micro- and nanoparticles of the composite is admixed into the liquid mixture with tetraethoxysilane (TEOS), while stirring, until the obtaining of a homogeneous dispersion liquid mixture with evenly dispersed solid micro- and nano particles of glass and of the first additive A1. For achievement of a perfectly homogeneous liquid dispersion mixture, agitation is performed e.g. by a magnetic agitator for the time of 24 hours at temperatures from 20 to 25°C. It is possible to accelerate polymerisation of the carrier polymer with ultrasound.
The actual spinning equipment dispenses the content of individual storage tanks at various present rate of the outflow of the mixture into the electric field. The inserted direct-current voltage is 30kV and the distance between the positive nozzle 2 and the collection area 4 in the function of a negative collector is 15 cm. This setting ensures the arising of required micro- and nanofibres.
The finished homogeneous dispersion liquid spinning mixtures are poured into at least two to seven individual storage tanks of the spinning equipment - electrospinning. From these storage tank, the spinning mixtures are pushed out, either with pistons or by means of peristaltic pumps, slowly and evenly into needle nozzles 2, which are connected to the positive pole of the direct-current high-voltage source. From individual nozzles 2, these mixtures are pushed out into an electrical field with a high intensity, in magnitudes of kV-m-1, which is formed of the opposite collection area 4, in the particular example e.g., of an area-wide collector connected to the negative pole of the source 7. Small drops of polymerous mixtures with a positive charge are transported by this direct-current electrical field fast in the stream 6 from the mouth of the nozzles 2 and during the flying motion in the area 5 of the spinning process they are formed in micro- and nano fibres, which fall onto the opposite collection area 4, i.e. in the function of the flat collector with a negative charge; and this way they create a continuous layer of non-woven fibres with a mean diameter from 1 nm to 100 μm. The layer arising contains also mixtures of glass and/or crystalline particles, and these particles are situated especially inside and partly also on the surface of the micro- and nanofibres arising this way.
The actual spinning equipment has e.g., from one to seven storage tanks. E.g., in Example 3 of the implementation of this invention, the spinning equipment has 7 storage tanks:
Fibre from the 1st storage tank brings affecting mechanical characteristics of fibres into the composite,
Fibre from the 2nd storage tank brings ion conductivity into the composite,
Fibre from the 3rd storage tank brings electron conductivity into the composite,
Fibre from the 4th storage tank brings reduction-oxidation balance into the composite, Fibre from the 5th storage tank contributes to mutual connection of other fibres,
Fibre from the 6th storage tank brings thermal conductivity into the composite, and Fibre from the 7th storage tank brings another possible complementary characteristic (e.g., magnetic or optical characteristics) to the composite.
The spinning mixture is prepared by mixing the powder mixture of micro- and nanoparticles with the mixtures of carrier polymers. The spinning mixture is in the form of a liquid dispersion.
The required powder mixture shall be prepared for each storage tank, e.g. according to Tables 10, 14, 18, 22, 26, 30, 34, 38, 42. These powder glass mixtures of micro- and nanoparticles with the first additives A1K or A1A or A1E shall be mixed, during the continual stirring, advantageously into ethanol and then into polymer mixtures with addition of an ordinary dispersion agent, marked in an abbreviated form in Tables 10, 11, 15 as "dispersant"; according to the markings 108, 208, 308 and corresponding Figures 2.1a, 2.2a, 2.3a. Subsequently, they will be separated, e.g. with the help of ultrasound until the arising of dispersion of separated particles.
The mixture of the carrier polymer shall be prepared for every individual storage tank, e.g. according to Tables 11, 15, 19, 23, 27, 31, 35, 39, 43. The mixture of the carrier polymer contains a mixture, e.g. consisting of TEOS, PVP, ethanol and water, expressed in molar %. For example, in the example implementations, TEOS is in a quantity from 0.01 to 10.37% (molar), PVP in a quantity from 0.03 to 0.05% (molar), ethanol in a quantity from 68.85 to 99.92% (molar) and water in a quantity from 0.02 to 20.75% (molar). A small quantity of an ordinary dispersion agent, marked in the tables for abbreviation purposes as "dispersant" shall still be added to this mixture of carrier polymers as an addition, in voluminous %, mostly in a quantity of 0.1 (vol. %).
For every individual storage tank, a liquid dispersion shall be created of the glass powder mixture of micro- and nanoparticles with the first additives A1K; A1A; A1E and their mixing 108, 208, 308 into the mixtures of carrier organic polymers. The obtained glass mixture of micro- and nanoparticles with the first additives A1K or A1A or A1E shall subsequently be mixed with organic substances as future carrier polymers - carriers (e.g., Tables 12, 16, 20, 24, 28, 32, 35, 40, 44) for the purpose of transformation of the mixture of micro- and nanoparticles with the first additives A1K or A1A or A1E to the form of micro- and nanofibres by spinning.
Spinning is carried out by drawing glass micro/nanofibres either preferentially by spinning in an electric field, known as electrospinning (Figure 2.8), or possibly by spinning in an air stream. The actual spinning equipment - electrospinning dispenses the content of individual storage tanks with various present rate of outflow of the mixture into the electric field. The outflow rate in the example implementations oscillates, according to Tables 13, 17, 21, 25, 29, 33, 36, 41, 45, from 0.01 to 1.98 ml.h-1.
By using this procedure, fibres featuring various chemical compositions, where the composition differences are controlled, gradually create a composite layer with a controlled chemical gradient of composition, which makes it possible to achieve the necessary function gradient of characteristics or functions, and this leads to the arising of the basis of the function- gradient concentration inside the composite for the composite layer of the cathode K or anode A or electrolyte E. 3.4 Detailed description of technological steps of preparation of individual layers of the battery cells B
(Figures 2.1 - 2.7)
The flow charts in Fig. 2.1-2.7 schematically depict the procedure of preparation of the secondary battery cell B of the pouch type (the so-called pouch cell) from its main components; i.e. the function-gradient concentration of the composite of the cathode K, anode A and electrolyte E. These composites are assembled by assembling the fundamental amorphous glass materials GMCK. GMCA and GFIC, complemented with the crystalline first additives A1K, A1E, A1A and second additives A2K, A2E and A2A. The fundamental morphology of these prepared elements consists especially in micro- and nanoparticles and micro- and nanofibres, featuring a very high surface-to-volume ratio.
The procedures schematically described by these flow charts are expressed by way of the flow charts in Fig. 2.1 - 2.7 which depict the sequences of individual important steps of the technology of preparation of these micro- and nanostructures for the cathode K, electrolyte E and anode A for the secondary battery cells B1, B2, B3, described above in chapter 3.
On the basis of the selected composition 101, 201, 301 of the amorphous glass materials GMCK, GMCA (GMC- Glass Mixed Conductor) with optimised mixed ion and electron/hole conductivity and on the basis of the type of the amorphous glass GFIC (Glass Fast-Ion Conductor) with optimised high ion conductivity and very low electron conductivity (Tables 4-9c), appropriate raw materials shall be selected and the calculation of composition of appropriate mixtures of raw materials (i.e. glass batches 102, 202, 302) will be made.
Raw materials for glass batches are weighted with precision in thousands of grams. Subsequently, the mixture is mechanically homogenised in a grinding mortar in an agitating device for the time of at least 1 hour. After achievement of the homogeneous mixture, the mixture is dispensed, e.g. into fire-resistant cups of corundum (aluminium oxide - Al2O3), porcelain or PtRh compound. For the purpose of obtaining appropriate glass materials, the raw materials are subsequently melted in the technological melting step 103, 203, 303 in an electric furnace either by means of a common way of the melting of the glass melt in the airy atmosphere or the melting of the glass melt in a controlled atmosphere, until the obtaining of the homogeneous glass melt. The controlled atmosphere of the melting process features the setting of suitable partial pressure of oxygen (O2) for achievement of the necessary oxidation or reduction atmosphere during the melting process. Depending on composition of the type of glass materials, the melting temperature oscillates within the range from 300 to 1500°C for the time from 0.5 to 4 hours.
The obtained homogeneous melt is subsequently cooled at a sufficient rate in the technological step of the cooling 104, 204, 304 of melted glass materials, either by free cooling in the air, or by controlled cooling performed by pouring into a metallic mould, on a rapidly rotating cylinder or between two rapidly rotating cylinders, whereby homogeneous solid glass in the form of blocks or cullet is created. In case of very fast cooling, the cooling rates oscillate from 100 °C.s-1 to 1000°C.s-1 Cooling takes place in the air or in a controlled atmosphere with the present suitable partial pressure of oxygen O2 for achievement of the necessary oxidation or reduction atmosphere.
The solid glass obtained this way is then mechanically crushed in a mill in a common way into cullet in the form of small glass particles/glass powder in the technological step of crushing 105, 205, 305, for the time necessary for obtaining glass particles/glass powder with a size in a magnitude from millimetres to micrometres.
Appropriate first additive A1K: A1E: A1A is then added to the glass particles obtained this way, in the subsequent technological step 106, 206, 306, such an additive being e.g., Cu, Fe, Al, Si, Mn, Fe, Co, Ni, V, Mo, W, their amorphous compounds as metallic glass materials or their oxides, SiC, LiCI, NaCI and elements Mn, Fe, Co, Ni, V, Mo, W, O in the form of compounds forming solid solutions with the structure of a spinel with the medium size of particles in a magnitude from millimetres to micrometres.
This is followed by the technological step of mixing 106a, 206a, 306a of the ground glass with suitable first additives A1K; A1E; A1A and their subsequent grinding 107, 207, 307 into micro- and nanoparticles. Grinding 107, 207, 307 in a magnitude into micrometres is carried out at first in a disk mill and subsequently in a vibration or ball mill, in a dry grinding process or in a liquid by using wet grinding for the time necessary for achievement of a homogeneous mixture with the required medium size of particles in a magnitude from micrometres to nanometres, with the necessary distribution curve with a width in the middle of the height in a magnitude of appropriate units of micrometres or nanometres. Possibly wet mixture is dried in a dryer at temperature around 120 °C ± 15 °C for the time approx. 20h±4h until achievement of a constant weight.
This is followed by technological steps which are described in subsequent chapters at a more detailed level. These are: mixing 108, 208, 308 of the obtained powder mixtures of selected glass materials GMCK; GMCA; GMCE with suitable first additives A1; A1K: A1E to carrier polymer dispersion liquid mixtures, subsequent dosing 109, 209, 309 of the dispersions obtained this way into the spinning equipment and subsequent spinning 110, 210, 310 into micro- and nanofibres in the spinning equipment, in which function- gradient concentration of composite layers of micro/nanofibres is created together with micro/nanoparticles.
This is followed by the technological step of thermal processing 111, 211, 311 of the composite layers of micro/nanofibres. Prepared composite layers are subsequently burnt out during a 24-hour cycle at a maximum temperature in the range from 200 - 1200°C, so that it can be possible to remove unnecessary carbon substances, such as function groups, ethoxy groups or ethanol residua.
For an increase of the effective surface of micro/nanofibres after the burning out, the fibres of a given composition are subject to exfoliation 112, 212, 312 in hot water or in an autoclave in water steam environment.
This is followed by application 113, 213. 313 of suitable second additives A2K; A2E; A2A. They are applied onto the composite layer of micro/nanofibres by electric spraying, spraying with air, coating or soaking of suitable crystalline glass additives A2K; A2E; A2A, such as Si, SiC, LiCI, NaCI, (Mn, Fe, Co, Ni, V, Mo, W, O) spinel materials, Cu, Al, particles of low-viscosity phosphate glass.
The arising composite layer is subject to the pressing 114, 214, 314 of the layer of micro/nanofibres. The pressed composite layer is subsequently subjected to thermal processing 115, 215, 315 at temperatures from 100 to 500°C and subsequent slow cooling which can take place directly in the furnace in order to eliminate cracking.
The result of this first technological block is the obtaining 116, 216, 316 of one final composite layer of the cathode K, electrolyte E or anode A based on glass micro/nanofibres and micro/nanoparticles, which are covered, after the thermal processing, on the surface with corresponding coatings/particles of the second additives A2K; A2E; A2A and interconnected through a connection matrix based on the glass. 3.5. Creation of function-gradient concentration of composite layers
Creation of function-gradient concentration of composite layers for the cathode K, electrolyte E and anode A is described and quantified at a detailed level by the following Tables 10 to 45 and the following chapter 3.6 for the 1-layer secondary battery cell B1, chapter 3.7 for the 2-layer secondary battery cell B2 and chapter 3.8 for the 3-layer secondary battery cell B3.
3.6 Secondary battery 1-layer cell B1
3.6.1 Creation of an active substance for the composite layer K1.l of the cathode K1 - one layer
Table 10 Mixing of the mixtures of micro- and nano powders based on the glass for dosing into storage tanks 1 to 7, for preparation of the composite layer K1.1 of the cathode K1
Figure imgf000067_0001
Every individual mixture for each storage tank 1 to 7 represents concentration of related glass materials GMCK, GFIC. GMCA and the first additives A1K, A1A in total of 100% of weight Table 11 Liquid polymer mixtures for preparation of carrier polymers, for liquid dispersion, dosed into the storage tanks 1 to 7, used for preparation of the composite layers K1.1 for the cathode K1
Figure imgf000068_0001
Every polymer mixture for every individual storage tank 1 to 7 contains 4 components in molar %, whose total is 100% (molar). Molar % values are stated here for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water. Besides, every individual mixture contains furthermore a dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume). Voluminous % is commonly applied at the use of a liquid polymer mixture for practical reasons because the polymer mixture is measured and dosed in volume % with the help of measuring vessels.
The carrier polymers are organic substances supporting the spinning of glass mixtures of microfibers/nanofibres, they represent a mixture of appropriate monomers, such as tetraethoxysilane (TEOS) or e.g., of oligomers, such as polyvinylpyrrolidone (PVP). These organic substances are formed in a form of mostly linear carrier polymers suitable for spinning. For final fibres they contain SiO2, then the carrier polymer is a polysiloxane polymer created by polymerisation of TEOS. If the final fibres are without SiO2, then the carrier polymer PVP is used. Table 12 Composition of liquid dispersion of a powder mixture of micro- and nano particles based on glass in the carrier polymer for storage tanks 1 to 7 used for preparation of the composite layer K1.1 for the cathode K1
Figure imgf000069_0001
Every liquid dispersion for an individual storage tank 1 to 7 contains (in % weight) a carrier polymer and a powder mixture of micro/nanoparticles based on glass whose total is 100% (by weight).
Table 13 Rates of outflow of liquid dispersion from the storage tanks 1 to 7 into nozzles of the electric spinner for creation of fibres of the composite layer K1.1 for the cathode K1
Figure imgf000069_0002
3.6.2 Creation of an active substance for the composite layer E1.l of the electrolyte E1_- one layer
Table 14 Mixing of mixtures of micro- and nano powders based on glass for storage tanks 1 to 7 for preparation of the composite layer E1.1 for the electrolyte E1
Figure imgf000070_0001
Every individual powder mixture of micro- and nano particles for a given storage tank contains given glass and suitable additive, in % of weight, whose total is 100% (by weight)
Table 15 Liquid polymer mixtures for preparation of carrier polymers for storage tanks 1 to 7 used for preparation of the composite layer E1.1 for the electrolyte E1
Figure imgf000070_0002
Every polymer mixture for every individual storage tank 1 to 7 contains 4 components in molar %, whose total is 100% (molar), which are stated for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water. Besides, every individual mixture contains furthermore a dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume). Voluminous % values are used because the liquid polymer mixture is measured and dosed in volume % with the help of measuring vessels for the storage tank in question. Table 16 Composition of liquid dispersion of powders of micro- and nanoparticles based on glass in the carrier polymer for storage tanks 1 to 7 used for preparation of the composite layer
E1.1 for the electrolyte E1.
Figure imgf000071_0001
Every liquid dispersion (in % by weight) for an individual storage tank 1 to 7 contains a carrier polymer and a powder mixture of micro- and nanoparticles based on glass, whose total is 100% (by weight)
Table 17 Rates of outflow of liquid dispersion from the storage tanks 1 to 7 into nozzles of the electric spinner for creation of fibres of the composite layer E1.l for the electrolyte E1
Figure imgf000071_0002
3.6.3 Creation of an active substance for the composite layer A1.l anode A1 - 1 layer
Table 18 Mixing of the mixtures of micro- and nano powders based on glass for storage tanks 1 to 7 for preparation of the composite layer A1.1 for the anode A1
Figure imgf000071_0003
Every individual powder mixture for a given storage tank contains given glass and a suitable first additive, whose total is 100% (by weight).
Table 19 Liquid polymer mixtures for preparation of carrier polymers for storage tanks 1 to 7 used for preparation of the composite layer A1.1 for the anode A1
Figure imgf000072_0001
Every polymer mixture for every individual storage tank 1 to 7 contains 4 components in molar %, whose total is 100% (molar), for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water. Every individual mixture contains furthermore a dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume). Voluminous % values are used for measuring and dosing in volume % with the help of measuring vessels for the storage tank in question.
Table 20 Composition of liquid dispersion of powders of micro- and nanoparticles based on glass in the carrier polymer for storage tanks 1 to 7 used for preparation of the composite layer A1.1 for the anode A1
Figure imgf000072_0002
Every liquid dispersion for an individual storage tank 1 to 7 contains a carrier polymer mixture and powder mixture of micro- and nanoparticles of the glass composite whose total is 100% (by weight). Table 21 Rates of outflow of liquid dispersion from the storage tanks 1 to 7 into nozzles of the electric spinner for creation of fibres of the composite layer A1.l for the anode A1
Figure imgf000073_0001
3.7 Secondary battery 2-layer cell B2
3.7.1 Creation of an active substance for the composite layers K2.1 and K2.2 of the cathode K2 - 2 layers
Table 22 Mixing of the mixtures of micro- and nano powders based on glass for storage tanks 1 to 7 for preparation of the composite layers K2.1 and K2.2 for the cathode K2
Figure imgf000073_0002
Every individual powder mixture of micro- and nanoparticles for a given storage tank contains given glass and suitable first additive in % by weight whose total is 100% by weight. Table 23 Liquid polymer mixtures for preparation of carrier polymers for storage tanks 1o 7 used for preparation of the composite layers K2.1 and K2.2 for the cathode K2
Figure imgf000074_0001
Every liquid polymer mixture for every individual storage tank 1 to 7 contains 4 components in molar %, whose total is 100% (molar) for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water. Each of these individual mixtures contains also dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume). Voluminous % is used for measuring and dosing in volume % with the help of measuring vessels for a given storage tank.
Table 24 Composition of liquid dispersion of a powder mixture of micro- and nano particles based on glass in the carrier polymer for storage tanks 1 to 7used for preparation of the composite layers K2.1 and K2.2 for the cathode K2.
Figure imgf000075_0001
Every liquid dispersion for an individual storage tank 1 to 7 contains (in % weight) a carrier polymer mixture and a powder mixture of micro- and nanoparticles, whose total is 100% (by weight).
Table 25 Rates of outflow of liquid dispersion from the storage tanks 1 to 7 into nozzles of the electric spinner for creation of fibres of the composite layers K2.1 and K2.2 for the cathode K2
Figure imgf000076_0001
3.7.2 Creation of an active substance of the composite layers E2.1 and E2.2 of the electrolyte E2 2 layers
Table 26 Mixing of mixtures of micro- and nano powders based on glass for storage tanks 1 to 7 for preparation of the composite layers E2.1 and E2.2 for the electrolyte E2
Figure imgf000076_0002
Every individual powder mixture of micro- and nanoparticles of the glass composite for a given storage tank contains given glass and suitable first additive in % by weight whose total is 100% by weight.
Table 27 Liquid polymer mixtures for preparation of carrier polymers for storage tanks 1 to 7 used for preparation of the composite layers E2.1 and E2.2 for the electrolyte E2
Figure imgf000077_0001
Every polymer mixture for every individual storage tank 1 to 7 contains 4 components in molar %, whose total is 100% (molar), for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water. Every individual mixture contains furthermore a dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume). Voluminous % values are used for measuring and dosing in volume % with the help of measuring vessels for a given storage tank. Table 28 Composition of liquid dispersion of powders based on glass in the carrier polymer for storage tanks 1 to 7 used for preparation of the composite layers E2.1 and
E2.2 for the electrolyte E2
Figure imgf000078_0001
Every liquid dispersion for an individual storage tank 1 to 7 contains a carrier polymer and a powder mixture of micro- and nanoparticles of the composite whose total is 100% by weight.
Table 29 Rates of outflow of liquid dispersion from the storage tanks 1 to 7 into nozzles of the electric spinner for creation of fibres of the composite layers E2.1 and E2.2 for the electrolyte E2
Figure imgf000078_0002
3.7.3 Creation of an active substance for the composite layers A2.1 and A2.2 of the anode A2 - 2 layers
Table 30 Mixing of the mixtures of micro- and nano powders based on glass for storage tanks 1 to 7 for preparation of the composite layer A2.1 and A2.2 for the anode A2
Figure imgf000079_0001
Every individual powder mixture of micro- and nanoparticles of glass composite for a given storage tank contains given glass and a suitable first additive in % by weight whose total is 100% by weight.
Table 31 Liquid polymer mixtures for preparation of carrier polymers for storage tanks 1 to 7 used for preparation of the composite layers A2.1 and A2.2 for the anode A2
Figure imgf000079_0002
Polymer mixture for every individual storage tank 1 to 7 contains 4 components in molar %, whose total is 100% (molar), for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water. Every individual mixture contains furthermore a dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume). Voluminous % values are used for measuring and dosing in volume % with the help of measuring vessels for the storage tank in question.
Table 32 Composition of liquid dispersion of powders based on the glass in the carrier polymer for storage tanks 1 to 7 used for preparation of the composite layers A2.1 and A2.2 for the anode A2
Figure imgf000080_0001
Every liquid dispersion for an individual storage tank 1 to 7 contains a carrier polymer mixture and a powder mixture of micro- and nanoparticles of the glass composite whose total is 100% (by weight). Table 33 Rates of outflow of liquid dispersion from the storage tanks 1 to 7 into nozzles of the electric spinner for creation of fibres of the composite layers A2.1 and A2.2 for the anode A2
Figure imgf000081_0001
3.8 Secondary battery 3-layer cell B3
3.8.1 Creation of an active substance for composite layers K3.1, K3.2 and K3.3 of the cathode K3 3 layers
Table 34 Mixing of the mixtures of micro- and nano powders based on glass for storage tanks 1 to 7 for preparation of the composite layers K3.1, K3.2 and K3.3 for the cathode K3
Figure imgf000082_0001
Every individual powder mixture of micro- and nanoparticles of the composite for a given storage tank contains given glass and a suitable first additive in % by weight whose total is 100% by weight. Table 35 Liquid polymer mixtures for preparation of carrier polymers for storage tanks 1o 7 used for preparation of the composite layers K3.1, K3.2 and K3.3 for the cathode K3
Figure imgf000083_0001
Every polymer mixture for every individual storage tank 1 to 7 contains 4 components in molar %, whose total is 100% (molar) for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water. Every individual mixture still contains, in addition, dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume). Voluminous % is used for measuring and dosing in volume % with the help of measuring vessels for a given storage tank. Table 36 Composition of liquid dispersion of powders based on glass in the carrier polymer for storage tanks 1 to 7used for preparation of the composite layers K3.1, K3.2 and K3.3 for the cathode K3
Figure imgf000084_0001
Every liquid dispersion for an individual storage tank 1 to 7 contains a carrier polymer mixture and a powder mixture of micro- and nanoparticles of the glass composite whose total is 100% by weight. Table 37 Rates of outflow of liquid dispersion from the storage tanks 1 to 7 into nozzles of the electric spinner for creation of fibres of the composite layers K3.1, K3.2 and K3.3 for the cathode K3
Figure imgf000085_0001
3.8.2 Creation of an active substance for the composite layers E3.1, E3.2 and E3.3 of the electrolyte E3 - 3 layers
Table 38 Mixing of mixtures of micro- and nano powders based on glass for storage tanks 1 to 7 for preparation of the composite layers E3.1, E3.2 and E3.3 for the electrolyte E3
Figure imgf000086_0001
Every individual powder mixture for a given storage tank contains given glass in the form of a powder mixture of micro- and nanoparticles of the composite and a suitable first additive in % by weight whose total is 100% by weight. Table 39 Liquid polymer mixtures for preparation of carrier polymers for storage tanks 1 to 7 used for preparation of the composite layers E3.1, E3.2 and E3.3 for the electrolyte E3
Figure imgf000087_0001
Every polymer mixture for every individual storage tank 1 to 7 contains 4 components in molar %, whose total is 100% (molar), for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water. Every individual mixture contains also a dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume). Voluminous % values are used for measuring and dosing in volume % with the help of measuring vessels for a given storage tank. Table 40 Composition of liquid dispersion of powders based on glass in the carrier polymer for storage tanks 1 to 7 used for preparation of the composite layers E3.1, E3.2 and E3.3 for the cathode E3
Figure imgf000088_0001
Every liquid dispersion for an individual storage tank 1 to 7 contains a carrier polymer mixture and a powder mixture of micro- and nanoparticles of the composite whose total is 100% by weight. Table 41 Rates of outflow of liquid dispersion from the storage tanks 1 to 7 into nozzles of the electric spinner for creation of fibres of the composite layers E3.1. E3.2 and E3.3 for the electrolyte E3
Figure imgf000089_0001
3.8.3 Creation of an active substance for the composite layers A3.1. A3.2 and A3.3 of the anode A3 - 3 layers
Table 42 Mixing of the mixtures of micro- and nano powders based on glass for storage tanks 1 to 7 for preparation of the composite layer A3.1, A3.2 and A3.3 for the anode A3
Figure imgf000090_0001
Every individual powder mixture for a given storage tank contains given glass in the powder mixture of micro- and nanoparticles of the glass composite and a suitable first additive whose total is 100% by weight. Table 43 Liquid polymer mixtures for preparation of carrier polymers for storage tanks 1o 7 used for preparation of the composite layers A3.1. A3.2 and A3.3 for the anode A3
Figure imgf000091_0001
Every liquid polymer mixture for every storage tank 1 to 7 contains 4 components in molar % whose total is 100% molar for the reason of a clear ratio between the number of molecules of TEOS, PVC, ethanol and water. Every individual mixture contains furthermore a dispersant in such a quantity that there is used a polymer mixture forming 99.9% (by volume), completed with the quantity of 0.1% of dispersant (by volume). Voluminous % values are used for measuring and dosing in volume % with the help of measuring vessels for the storage tank in question. Table 44 Composition of liquid dispersion of powders based on the glass in the carrier polymer for storage tanks 1 to 7 used for preparation of the composite layers A3.1, A3.2 and A3.3 for the anode A3
Figure imgf000092_0001
Every liquid dispersion for an individual storage tank 1 to 7 contains a carrier polymer and a powder mixture of micro- and nanoparticles of the glass composite whose total is 100% by weight. Table 45 Rates of outflow of liquid dispersion from the storage tanks 1 to 7 into nozzles of the electric spinner for creation of fibres of the layers A3.1, A3.2 and A3.3 for the anode A3
Figure imgf000093_0001
3.9 Detailed description of the assembly of the battery cell_B
(Figures 2.7, 5.1., 5.2)
Figure 2.7 illustrates chronologically the technological steps for the assembly of the battery cells B1; B2; B3. Selection 701 of individual cathodes K1; K2; K3, electrolytes E1; E2; E3 and anodes A1; A2; A3. This is followed by the attachment 701a of these electrodes to the electrolyte, then the attachment 702 of the collector KK to these cathodes and the collector KA to these anodes.
This is followed by their pressing 703 into an assembly of the secondary battery cell B, having, in edge areas, the connected collectors KK and KA with connected metallic inlets on both the sides of the secondary battery cell B. This assembly for the secondary battery cell B is sealed at the end in a vacuum and airtight manner by the sealing 704 into a plastic package and thus the finalisation 705 is completed and the finished product of the secondary battery cell B is created this way. The finished secondary battery cell is illustrated in Figures 5.1 and 5.2.
In case of the battery cell B1, the cathode IQ is made with the use of the preformed layer K1.1, the electrolyte E1 with the use of the layer E1.1 and the anode A1 with the use of the layer A1.1. Subsequently, an assembly of layers of the cell B1 is created when the layer E1.1 is inserted between the layers K1.1 and A1.1, and then the collector KK of the cathode K is attached to the layer K1.l, and the collector KA is attached to the layer A1.1. In the next step, the above-mentioned layers and collectors are normally pressed to each other and inserted into a plastic package in which they are sealed in a vacuum manner into a form of an airtight pouch with two rising contacts. In a final step, the plastic package is cut off into a final shape and the battery cell B1 is marked with an identification heading.
In case of the battery cell B2, the cathode K2 is made with the use of the preformed layers K2.1 and K2.2, the electrolyte E2 with the use of the layers E2.1 and E2.2, and the anode A2 with the use of the layers A2.1 and A2.2. Subsequently, an assembly of layers of the cell B2 is created, when the layers K2.1 and K2.2 are placed on each other for the cathode K2, then the layers E2.1 and E2.2 of the electrolyte E2 are gradually placed on them and then the layers A2.1 and A2.2 of the anode A2 are installed. Then the collector KK of the cathode K is attached to the layer K2.1, and the collector KA is attached to the layer A2.2 of the anode A. In the next step, the above-mentioned layers and collectors are normally pressed to each other and inserted into a plastic package in which they are sealed in a vacuum manner into a form of an airtight pouch with two rising contacts. In a final step, the plastic package is cut off into a final shape and the battery cell B2 is marked with an identification heading.
In case of the battery cell B^, the cathode K3 is made with the use of the preformed layers K3.1, K3.2 and K3.3, the electrolyte E3 with the use of the layers E3.1. E3.2 and E3.3, and the anode A3 with the use of the layers A3.1, A3.2, A3.3. Subsequently, an assembly of layers of the cell B3 is created, when the layers K3.1, K3.2 and K3.3 are placed on each other for the cathode K3, then the layers E3.1, E3.2 and E3.3 of the electrolyte E3 are gradually placed on them and then the layers A3.1, A3.2 and A3.3 of the anode A3 are installed. Then the collector KK of the cathode K3 is attached to the layer K3.1 and the collector KA of the anode A3 is attached to the layer A3.3. In the next step, the above-mentioned layers and collectors are normally pressed to each other and inserted into a plastic package in which they are sealed in a vacuum manner into a form of an airtight pouch with two rising contacts. In a final step, the plastic package is cut off into a final shape and the battery cell B3 is marked with an identification heading.
3.10 Characteristics and properties of the secondary battery cell
(Figures 3.1, 3.2, 3.3, 4.1, 4.2, 4.3, 4.4, 5.1, 5.2)
Figure 3.1 illustrates schematically the processes of recharging and discharging taking place in the secondary battery cell B2. The ion carriers of the charge are Li+ cations in this case, but very similar scenarios will basically take place in the case that Na+ cations are ion carriers of the charge. During the recharging of the cell
Figure imgf000095_0001
its collectors KK and KA are connected by means of the inlet contacts 20 and 40 to the external source of electrical energy in such a way that electrons exit from the cathode K through the collector KK^ and on the other side of the cell they enter into the anode A through the collector KA. This means that during the recharging process, the Li+ cations move in the direction from the left to the right, i.e. they rise up from the function-gradient composite cathode substance of the cathode K and migrate through the composite function-gradient substance of the electrolyte E until they settle in the anode substance of the anode A. This scenario usually continues until the battery cell is recharged to its full capacity characterised with the maximum achievable voltage U0cv = 4.3 V. During the discharging phase, the collectors KK, KA of the cell B2 are connected by means of the contacts 20, 40 to the electric energy consumer ("load") in such a manner that electrons enter, through the collector KK^ into the cathode K and on the other side they exit from the anode A through the collector KA. This means that during the discharging phase the Li+ cations move in the direction from the right to the left, i.e. they rise from the composite function-gradient anode substance of the anode A and migrate through the composite function-gradient substance of the electrolyte E until they settle in the composite function-gradient cathode substance of the cathode K. This scenario usually continues until the voltage of the cell drops typically below the value = 3.0 V. Figure 3.2 shows a curve indicating the time course of the recharging of the secondary battery cell B1 as voltage dependence on time with a constant current of 10 mA. The initial rapid growth of voltage, when the voltage of 5.5 V was achieved in 15 minutes, confirms high mobility of ion carriers of the charge and a rapid electrode reaction.
The high stability of the electrode substances as well as of the electrolyte E is confirmed by the long-term testing of functionality of the secondary battery cell B1^ which is depicted in Figure 3.3 illustrating the curves of cyclic recharging and discharging. There were carried out 100 charging/discharging cycles, and the curves indicate the courses of current depending on the time during the charging/discharging cycles. The curves feature very similar courses, which indicates the long-term stability of the function-gradient layers used in this secondary battery cell B1.
Dependence of the impedance of the secondary battery cell B2 on frequency of the alternating-current electric field is provided for in Figure 3.4, which illustrates the dependence of the imaginary component of the impedance on the real component of the impedance. From the shape of the curve and its intersection with the real axis at high frequencies of the electric field it is possible to conclude that this secondary battery cell B1 features a low internal resistance and is suitable for construction of the battery sources with a high capacity.
Figure 4.1 illustrates a simple layer of glass nanofibres of the glass GMCK-Li with a medium radius r = 450 nm for the layer K1.1 of the cathode K1 of the cell B1. The shot was made by using an optical microscope "Nikon" in magnification 75-104x.
Figure 4.2 illustrates a simple layer of glass nanofibres of the glass GFIC-Li with a medium radius r = 400 nm for the layer E1.1 of the electrolyte E1 of the cell B1. The shot was made by using an optical microscope "Nikon" in magnification 75-104x.
Figure 4.3 is a SEM shot of glass nanofibres for GFIC-Li with a medium radius r = 300 nm. The shot was made by using an electron microscope "Tescan" in magnification 7-106X.
Figure 4.4 illustrates a simple layer of glass nanofibres of the glass G MCA- Li with a medium radius r = 500 nm for the layer A1.1 of the anode A1 of the cell B1. The shot was made by using an optical microscope "Nikon" in magnification 75 104x. Figure 5.1 on the left and Figure 5.2 on the right depict schematically the prepared secondary battery cell B1 in the shape of a flat pouch ("pouch cell"), e.g. with dimensions of 60x90x4 mm, which is sealed in a plastic foil. Figure 5.1 shows the secondary battery cell B1 illustrated from the side of the cathode K, and it is possible to see there the area 10 of the end electron-conductive current aluminium collector KK with the inlet contact 20; and also it is possible to see, on the opposite side, the inlet contact 40 of the current copper collector KA. Figure 5.2 shows the secondary battery cell B1 illustrated from the side of the anode A, and it is possible to see there the area 30 of the end electron- conductive current copper collector KA with the inlet contact 40; and it is also possible to see, in the lower part on the opposite side, the inlet contact 20 of the current aluminium collector KK.
Table 46
Electrical characteristics of example implementations of assemblies of the secondary battery cells B1, B2 and B3
Figure imgf000097_0001
Table 46 states selected electric characteristics of the secondary battery cell B1, B2 and B3 with Li+ ions. Related electrode substances and electrolyte are formed of function- gradient composite layers for the cathode K, electrolyte E and anode A whose composition was suitably optimised with the first additives A1K, A1E and A1A and with the second additives A2K, A2E, A2A. These optimised composite layers for the cathode K, electrolyte E and anode A in their mutual combination ensure high energy and power density values and therefore they are suitable for construction of high-capacity batteries.
INDUSTRIAL APPLICABILITY
The secondary battery cell B is intended for electromobiles. Reference signs
B secondary battery cell K cathode E electrolyte A anode
GLASS
GMCK glass GMCK for the cathode K with mixed ion and electron conductivity (Glass Mixed Conductor Cathode)
GMCK-Na glass GMCK-Na for the cathode K with Na cation GMCK-Li glass GMCK-Li for the cathode K with Li cation
GMCA glass GMCA for the anode A with mixed ion and electron conductivity, and (Glass Mixed Conductor Anode)
GMCA-Na glass GMCA-Na for the anode A with Na cation GMCA-Li glass GMCA-Li for the anode A with Li cation
GFIC glass GFIC for the electrolyte E with high ion conductivity and very low electron conductivity (Glass Fast Ion Conductor)
ADDITIVES A1 First additive A1 A2 Second additive A2
AIK First additive A1K for the cathode K A2K Second additive A2K for the cathode K A1E First additive A1E for the electrolyte E A2E Second additive A2E for the electrolyte E A1A First additive A1 for the anode A A2A Second additive A2A for the anode A
FIGURE 1.1, 1.2, 1.3, 1.5 h total height h of the battery cell B I total length I of the battery cell B w total width w of the battery cell B KK collector KK of the cathode K KA collector KA of the anode A Ra roughness
Figure 2.8 SPINNING EQUIPMENT
1 Pump 1 with a solution
2 Nozzle
3 Taylor cone
4 Collective area 4
5 Area 5 of the spinning of micro- and nanofibres
6 Stream 6 of arising glass micro- and nanofibres
7 Source 7 of high direct-current voltage Figures 5.1 and 5.2 FINISHED BATTERY CELL
10 Area 10 of the collector KK of the cathode K 20 Inlet contact 20 of the cathode K 30 Area 30 of the anode A
40 Inlet contact 40 of the collector KA of the anode A
FIGURE 1.1
B1 battery cell B1 with one layer of the cathode K1, anode A1, electrolyte A1
K1 cathode K1 with one layer K1.l A1 anode A1 with one layer A1.l
E1 electrolyte E1 with one layer E1.l K1.1 one layer K1.1 of the cathode K1 A1.1 one layer A1.1 of the anode A1
E1.1 one layer E1.1 of the electrolyte E1
WK1.1 width W K1.1 of one layer K1.l of the cathode K1 WE1.1 1 width W E1.1 of one layer E1.l of the electrolyte E1 W A1.1 width W A1.1 of one layer A1.l of the anode A1
FIGURE 1.2
B2 battery cell B2 with two layers of the cathode K2, anode A2, electrolyte A2
K2 cathode K2 with two layers K2.1, K2.2 K2.1 first layer K2.1 of the cathode K2 K2.2 second layer K2.2 of the cathode K2
E2 electrode E2 with two layers of the electrolyte E2.1, E2.2 E2.2 first layer E2.1 of the electrolyte E2 E2.2 second layer E2.2 of the electrolyte E2
A2 anode A2 with two layers A2.1, A2.2 A2.2 first layer A2.1 of the anode A2 A2.2 second layer A2.2 of the anode A2
WK2.1 width WK2.1 of the first layer K2.1 of the cathode K2
WK2.2 width WK2.2 of the second layer K2.2 of the cathode K2
WE2.1 width WE2.1 of the first layer E2.1 of the electrolyte E2
WE2.2 width WE2.2 of the second layer E2.2 of the electrolyte E2
WA2.1 width WA2.1 of the first layer A2.1 of the anode A2
WA2.2 width WA2.2 of the second layer A2.2 of the anode A2 FIGURE 1.3
B3 battery cell B3 with three layers of the cathode K3, anode A3, electrolyte A3
K3 cathode K3 with three layers K3.1, K3.2, K3.3 A3 anode A2 with three layers A3.1, A3.2, A3.3 E3 electrolyte E3 with three layers E3.1, E3.2, E3.3
K3.1 first layer K3.1 of the cathode K3 K3.2 second layer K3.2 of the cathode K3 K3.3 third layer K3.3 of the cathode K3
E3.1 first layer E3.1 of the electrolyte E3 E3.2 second layer E3.2 of the electrolyte E3 E3.3 third layer E3.3 of the electrolyte E3
A3.1 first layer A3.1 of the anode A3 A3.2 second layer A3.2 of the anode A3 A3.3 third layer A3.3 of the anode A3 WK3.1 width W K3.1of the first layer K3.1 of the cathode K3 WK3.2 width WK3.2 of the second layer K3.2 of the cathode K3
Figure imgf000100_0001
layer K3.3 of the cathode K3
WE3.1 width f the first layer E3.1 of the electrolyte E3
WE3.2 width
Figure imgf000100_0002
WE3.2 the second layer E3.2 of the electrolyte E3
WE3.3 width WE3.3 of the third layer E3.3 of the electrolyte E3
WA3.1 width WA3.1 of the first layer A3.1 of the anode A3
WA3.2 width WA3.2 of the second layer A3.2 of the anode A3 WA3.3 width WA3.3 of the third layer A3.3 of the anode A3
Figures 2.4, 2.5, 2.6 PREPARATION OF THE CATHODE; ELECTROLYTE; ANODE
401, 501, 601 Selection of the number of finished composite layers,
401 for the cathode K, 501 for the electrolyte E, 601 for the anode A;
402, 502, 602 Pressing of individual composite layers,
402 for the cathode K, 502 for the electrolyte E, 602 for the anode A;
403, 503, 603 Final obtaining of composite layers,
403 for the cathode K, 503 for the electrolyte E, 603 for the anode A.
Figure 2.7 ASSEMBLY OF THE BATTERY CELL
701 Selection of the finished cathode K, finished electrolyte E and finished anode A; 701a Attachment of electrodes of the cathode K and anode A to the electrolyte E;
702 Connection of the collector KK to the cathode K and collector KA to the anode A;
703 Pressing to the final secondary battery cell B without an external package;
704 Vacuum sealing of the pressed assembly into a plastic package;
705 Finalisation and obtaining of the secondary battery cell B. Figures 2.1, 2.1a, 2.1b; 2.2, 2.2a, 2.2b; 2.3, 2.3a, 2.3b
PREPARATION OF THE CATHODE; ELECTROLYTE; ANODE
101, 201, 301 Selection of composition of the glass materials GMCK; GFIC; GMCA and the first additives AIK; A1E; A1A,
101 for the cathode K, 201 for the electrolyte E, 301 for the anode A;
102, 202, 302 Batches for the glass materials GMCK, GFIC, GMCA,
102 for the cathode K, 202 for the electrolyte E, 302 for the anode A;
103, 203, 303 Melting of the glass materials GMCK; GFIC; GMCA,
103 for the cathode K, 203 for the electrolyte E, 303 for the anode A
104, 204, 304 Cooling of the glass materials GMCK; GFIC; GMCA,
104 for the cathode K, 204 for the electrolyte E, 304 for the anode A;
105, 205, 305 Crushing of the glass materials GMCK; GFIC; GMCA into cullet,
105 for the cathode K, 205 for the electrolyte E, 305 for the anode A;
106, 206, 306 Adding of suitable first additives AIK, A1E, A1A to the glass materials GMCK, GFIC, GMCA
106 for the cathode K, 206 for the electrolyte E, 306 for the anode A;
106a, 206a, 306a Mixing of suitable mixtures of the glass materials GMCK, GFIC, GMCA with suitable first additive AIK, A1E, A1A,
106a for the cathode K; 206a for the electrolyte E, 306a for the anode A;
107, 207, 307 Grinding of mixtures of these glass materials GMCK, GFIC, GMCA with the first additives
AIK, A1E, A1A powders of micro- and nanoparticles,
107 for the cathode K, 207 for the electrolyte E, 307 for the anode A;
108, 208, 308 Admixing of powders of micro- and nanoparticles to the mixtures of carrier polymers for obtaining liquid dispersion mixtures,
108 for the cathode K, 208 for the electrolyte E, 308 for the anode A;
109, 209, 309 Dosing of liquid dispersion mixtures into the spinning equipment
109 for the cathode K, 209 for the electrolyte E, 309 for the anode A;
110, 210, 310 Spinning of dispersion mixtures into micro- and nanofibres,
110 for the cathode K, 210 for the electrolyte E, 310 for the anode A;
111, 211, 311 Thermal processing of micro- and nanofibres at 200-1200°C
111 for the cathode K, 211 for the electrolyte E, 311 for the anode A;
112, 212, 312 Exfoliation of micro- and nanofibres,
112 for the cathode K, 212 for the electrolyte E, 312 for the anode A;
113, 213, 313 Application of the second additives A2K, A2E, A2A onto micro- and nanofibres
113 for the cathode K, 213 for the electrolyte E, 313 for the anode A;
114, 214, 314 Pressing of the composite layer of the cathode K, electrolyte E, anode A,
114 for the cathode K, 214 for the electrolyte E, 314 for the anode A;
115, 215, 315 Thermal processing of the layer at temperatures 100 - 500°C and cooling,
115 for the cathode K, 215 for the electrolyte E, 315 for the anode A;
116, 216, 316 Obtaining the finished composite layer
116 for the cathode K, 216 for the electrolyte E, 316 for the anode A.

Claims

PATENT CLAIMS
1. Secondary battery cell for electromobiles, containing amorphous glass materials and micro- and nanomaterials, the battery cell (B) based on glass includes end metallic electron-conductive current collectors (KK, KA), between which electron- and ion- conductive electrodes are arranged, namely cathode (K) and anode (A), which are separated by an ion-conductive electrolyte (E), when the cathode, electrolyte and anode contain multi-component solid amorphous glass, preferentially lithium or sodium multi- component glass (GMCK) for the cathode (K) and glass (GMCA) for the anode (A) with ion and electron mixed conductivity and multi-component glass (GFIC) for the electrolyte (E) with high ion conductivity and very low electron conductivity, where the glass (GMCK) of the cathode (K) with an admixture of the glass (GFIC) of the electrolyte (E) is in the cathode (K) situated in the vicinity of the collector (KK) and on the side facing this collector (KK), the glass (GMCA) of the anode (A) with an admixture of the glass (GFIC) of the electrolyte (E) is in the anode (A) situated in the vicinity of the collector (KA) and on the side facing this collector (KA) and
- the glass (GFIC) of the electrolyte with an admixture of the glass (GMCK; GMCA) of both the electrodes is situated immediately in or near the electrolyte (E), and the battery cell (B) contains solid amorphous multi-component glass and micro- and nanofibers and micro- and nanoparticles with a medium diameter from 1 nm to 100 μm; characterized in that the secondary battery cell (B, B1, B2, B3) contains at least one composite layer (K1.l; K2.1, K2.2; K3.1, K3.2, K3.3) of the cathode (K; K1; K2; K3),
(E1.l; E2.1, E2.2; E3.1, E3.2, E3.3) of the electrolyte (E; E1; E2; E3) and
(A1.l; A2.1, A2.2; A3.1, A3.2, A3.3) of the anode (A; A1; A2; A3), and these composite layers are in a mixture on the basis of micro- and nanofibers and micro- and nanoparticles of the glass materials (GMCK; GMCA; GFIC) with the first additives
(AIK; A1E; A1A) and the second additives (A2K; A2E; A2A) on the surface, where each of these composite layers contains
0.1 to 10.0 volume % of the first additive (AIK; A1E; A1A) for an increase in electrochemical oxidation-reduction activity of these composite layers,
0.1 to 10.0 volume % of the second additive (A2K; A2E; A2A) on the surface of micro- and nanofibres and micro- and nanoparticles for an increase in adhesion of these composite layers,
80 to 99.8 volume % of the selected glass (GMCK; GFIC; GMCA), where each of these composite layers of the cathode (K; K1; K2; K3), electrolyte (E; E1; E2; E3) and anode (A; A1; A2; A3) states a gradual change in the function- gradient concentration of immobile components of composite layers in the direction from the cathode (K) to the anode (A), depending on the distance between the collector (KK) of the cathode (K) and the opposite collector (KA) of the anode (A) and in the reversed direction, and the mobile component in these glass materials (GMCK; GMCA; GFIC) is either the lithium cation Li+ or the sodium cation Na+.
2.Secondary battery cell for electromobiles according to claim 1, characterized in that the composite layers (K1.1; K2.1, K2.2; K3.1, K3.2, K3.3) of the cathode (K; K1; K2; K3), the composite layers (E1.1; E2.1, E2.2; E3.1, E3.2, E3.3) of the electrolyte (E; E1; E2; E3) and the composite layers (A1.1; A; 2.1, A2.2; A3.1, A3.2, A3.3) of the anode (A; A1; A2; A3) are arranged in a mutually parallel manner and closely behind each other, and the layers of the cathode (K) and of the anode (A) have a width (wi<; wa) greater than the width (we) of the layers of the electrolyte (E), where, with an advantage individual layers of the cathode (K) and of the anode (A) have a width (wk ; wa) in the range from 0.9 to 2.8 mm and individual layers of the electrolyte (E) have a width (we) in the range from 0.1 to 0.4 mm.
3. Secondary battery cell for electromobiles according to claim 1, characterized in that it is basically flat, its total height (h) is 90 mm, total length (I) is 60 mm and total width (w) is 6 mm, and its total weight is in the range from 33 to 38 g.
4.Secondary battery cell for electromobiles according to any of the previous claims 1 to 3, characterized in that the first additive (AIK) for the cathode (K), the first additive (A1E) for the electrolyte (E) and the first additive (A1A) for the anode (A) is a crystalline additive, such as metallic copper Cu, metallic iron Fe, metallic silicon Si, metallic nickel Ni and metallic aluminium Al, metallic Mn, metallic Co, metallic V, metallic Mo, metallic W, their amorphous alloys as metallic glasses or their oxides, silicon carbide SiC, lithium chloride LiCl, sodium chloride NaCI, and elements Mn, Fe, Co, Ni, V, Mo, W, 0 in the form of compounds forming solid solutions with a spinel structure.
5. Secondary battery cell for electromobiles according to any of the previous claims 1 to 4, characterized in that the second additive (A2K) for the cathode (K), the second additive (A2E) for the electrolyte (E) and the second additive (A2A) for the anode (A) is at least one compound from the group including LiPO3, NaPO3, Li3BO3, Na3BO3, Al2O3, and the second additive represents crystalline or glass particles.
6. Method of production of a secondary battery cell for electromobiles, containing amorphous glass materials and micro- and nanomaterials, according to claims 1 to 5, characterized in that the method contains three fundamental technological blocks, including:
• the first technological block for preparation of flexible inorganic composite layers with function-gradient concentration for the cathode (K), electrolyte (E) and anode (A) which contain micro- and nanofibres and micro- and nanoparticles on the basis of the amorphous glass materials (GMCK, GFIC, GMCA), the first additives (A1) and the second additives (A2), by using the technology of electrostatic spinning - electrospinning (110, 210, 310) ;
• the second technological block for preparation of the layered cathode (K), layered electrolyte (E) and layered anode (A) by the pressing (402) of these layers;
• the third technological block for assembly of the secondary battery cell (B) of the layered cathode (K), layered electrolyte (E) and layered anode (A), including connection (702) of the collectors (KK; KA) and subsequent vacuum sealing (704) of the battery cell (B) into a plastic package.
7. Method of production of a secondary battery cell for electromobiles according to claim
6, characterized in that the first technological block includes preparation of individual composite layers of the cathode (K), electrolyte (E) and anode (A), containing the following technological steps, ordered chronologically:
• selection (101; 201; 301) of a suitable selected chemical composition of the lithium or sodium multi-component glass (GMCK; GFIC; GMCA) and selection of a suitable chemical composition of the first additive (AIK; A1E, A1A),
• input (102, 202, 302) of raw materials in the form of glass batches for selected glass materials (GMCK; GFIC; GMCA), and input of raw materials for selected first additives (AIK; A1E; A1A) so that this resulting composite layer can contain 0.1 to 10% of volume of these first additives;
• melting (103, 203, 303) of lithium or sodium multi-component glass (GMCK) for the cathode (K); multi-component glass (GFIC) for the electrolyte (E); and multi- component glass (GMCA) for the anode (A), without the first additives at a temperature in the range from 300 to 1500°C, depending on the type of glass materials;
• cooling (103, 203, 303) of melted glass materials (GMCK; GFIC; GMCA) in a controlled atmosphere or in the air for achievement of the necessary oxidation or reduction atmosphere;
• crushing (105, 205, 305) of cooled glass materials (GMCK; GFIC; GMCA) into glass cullet, in smaller glass particles/glass powder with a size in a magnitude of millimetres to micrometres;
• adding (106, 206, 306), to this cullet of the glass (GMCK; GFIC; GMCAJ, of the first additive (AIK) for the cathode (K); the first additive (A1E) for the electrolyte ; and the first additive (A1A) for the anode (A), where the first additives (AIK; A1E; A1A) are from the group including Cu, Fe, Si, Ni, Al, Mn, Co, Ni, V, Mo, W, their amorphous alloys, such as metallic glasses, or their oxides, SiC, LiCI, NaCI, and elements Mn, Fe, Co, Ni, V, Mo, W, O in the form of compounds forming solid solutions with a spinel structure in such a quantity that the resulting composite layer
(K1.l; K2.1, K2.2; K3.1, K3.2, K3.3) of the cathode (K; K1; K2; K3) or (E1.1; E2.1, E2.2; E3.1, E.2, E3.3) of the electrolyte (E; E1; E2; E3) or
(A1.1; A2.1, A2.2; A3.1, A3.2, A3.3) of the anode (A; A1; A2; A3) can contain 80 to 99.8% volume of the selected glass (GMCK; GFIC; GMCA) and
0.1 to 10% volume of these first additives;
• mixing (106a, 206a, 306a) of appropriate glass materials (GMCK; GFIC; GMCA) and corresponding first additives (A1; AIK; A1E) to the mixtures for a given composite layer;
• grinding (107, 207, 307) of the mixture of glass materials (GMCK; GFIC; GMCA) obtained this way with the corresponding first additives (AIK; A1E; A1A) into powders of glass and/or crystalline particles in the form of micro- and nanoparticles with a medium diameter from 1 nm to 100 μm;
• mixing (108, 208, 308) of these obtained powder mixtures of micro- and nanoparticles to the liquid mixture of carrier polymers for improvement of spinning in order to obtain liquid dispersion mixtures;
• dosing (109, 209, 309) of these dispersion liquid mixtures into at least one storage tank of the spinning equipment-electrospinner;
• electrostatic spinning (110, 210, 310) and drawing of micro- and nanofibres of dispersion liquid mixtures in the spinning equipment, in which controlled spinning into micro- and nanofibres and micro- and nanoparticles with a medium diameter from 1 nm to 100 μm takes place, with the simultaneous obtaining of a function- gradient concentration thanks to different compositions of the mixtures and also thanks to different flow rates of the mixture into the spinning equipment;
• thermal processing (111, 211, 311) of the obtained micro- and nanofibres at a temperature from 200 to 1200°C, including their cooling to the ambient temperature;
• exfoliation (112, 212, 312) for enlargement of the surface of the obtained micro- and nanofibres, leading to a significant increase in the ratio of their surface to the volume and for an increase in adhesion for subsequent pressing to composite layers;
• applying (113, 213, 313), spraying, soaking or coating of the surface of micro- and nanofibres with the second additives (A2K, A2E, A2A) for an increase in adhesion, where the second additive (A2K; A2E; A2A) is at least one compound of the group including LiPO3; NaPO3, Li3BO3, Na3BO3, AI2O3, which is added in such a quantity that the resulting composite layer
(K1.1; K2.1, K2.2; K3.1, K3.2, K3.3) of the cathode (K; K1; K2; K3) or (E1.1; E2.1, E2.2; E3.1, E.2, E3.3) of the electrolyte (E; E1; E2; E3) or (A1.1; A2.1, A2.2; A3.1, A3.2, A3.3) of the anode (A; A1; A2; A3) can contain 0.1 to 10% volume of these second additives;
• pressing (114, 214, 314) of the composite obtained this way into composite layers of micro/nanofibres for the cathode (K) or the electrolyte (E) or for the anode (A);
• thermal processing (115, 215, 315) of the composite layer, including cooling of the obtained composite layer at a temperature 100 - 500°C;
• obtaining (116, 216, 316) of the finished layered composite layer with a function- gradient concentration for creation of the assembly of the cathode (K), electrolyte (E) and anode (A) of the secondary battery cell (B).
8. Method of production of a secondary battery cell for electromobiles according to claim 6 or 7, characterized in that the second technological block represents preparation of the cathode (K), electrolyte (E) and anode (A) and includes the following technological steps, ordered chronologically:
• selection (401, 501, 601) of the number of optional composite layers for the cathode (K) for the electrolyte (E) and for the anode (A);
• pressing (402, 502, 602) of the selected number of composite layers for the cathode (K), for the electrolyte (E) and for the anode (A);
• final obtaining (403, 503, 603) of composite layers for the layered cathode (K), for the layered electrolyte (E) and for the layered anode (A).
9. Method of production of a secondary battery cell for electromobiles according to claim 6 er-7-or to 8, characterized in that the third technological block represents assembly of the battery cell (B) and includes the following technological steps, ordered chronologically:
• selection (701) of the finished layered cathode (K), finished layered electrolyte (E) and finished layered anode (A); • attachment (701a) of electrodes, i.e. cathode (K) and anode (A), to the electrolyte
(E)
• attachment (702) of the collector (KK) to the cathode (K) and of the collector (KA) to the anode (A);
• pressing (703) to the final secondary battery cell (B) without an external package;
• vacuum sealing (704) of the obtained pressed assembly into a plastic package;
• finalisation and obtaining (705) of the secondary battery cell B.
10. Method of production of a secondary battery cell for electromobiles according to claim 6 , characterized in that the mixture of the carrier polymer contains the mixture of TEOS, PVP, ethanol and water, namely
TEOS in a quantity from 0.01 to 10.37% molar,
PVP in a quantity from 0.03 to 0.05% molar, ethanol in a quantity from 68.85 to 99.92% molar and water in a quantity from 0.02 to 20.75% molar.
PCT/CZ2020/000047 2019-11-05 2020-11-05 Secondary battery cell for electromobiles, cointaining amorphous glass materials and micro- and nano materials, and method of its production WO2021089066A1 (en)

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