WO2019129316A1

WO2019129316A1 - Secondary battery cell for electromobiles, containing solid amorphous glass materials and nano/micro materials

Info

Publication number: WO2019129316A1
Application number: PCT/CZ2018/000061
Authority: WO
Inventors: Martin ΜίΚΑ; Lukas SATURA; Florian WEYMAR; Ivana LUSTICKA
Original assignee: Skoda Auto A.S.; Vysoka Skola Chemicko-Technologicka V Praze
Priority date: 2017-12-29
Filing date: 2018-12-27
Publication date: 2019-07-04
Also published as: CZ309338B6; SK9275Y1; CZ2017859A3; SK500742020U1

Abstract

The electrodes, anode (A) as well as cathode (K), are electronically and ionically conductive, contain solid amorphous glass composite material and also glass and/or metallic fibres and glass and/or crystalline particles with a mean diameter in nano/micrometres from 1 nm to 100 μm. Their surface is nano/micro-structural with mean roughness from 1 nm to 100 μm; and contains, as ionic charge carriers, migrating lithium and/or sodium cations for migration from the anode (A) through the electrolyte (E) to the cathode (K) during discharging of the secondary battery cell (B) and from the cathode (K) to the anode (A) during recharging of the secondary battery cell (B). The electrolyte (E) is ion-conducting, it contains solid amorphous glass composite material with lithium and/or sodium cations as the ionic charge carriers. The composition of the glass for the electrodes (A, K) as well as electrolyte (E) and their conductivity are claimed. The composite material of the electrodes (A, K) contains active oxidation-reduction centres based on metallic silicon and/or silicon oxides and/or glasses containing electropositive polyvalent elements Mp, where these oxidation-reduction centres have the ratio of the higher oxidation state to the lower oxidation state of polyvalent elements Mp from 0.1 to 10, and thus also create gradient nano/micro composite glass material of the electrodes (A, K) with mixed ionic and electron conductivity. The oxidation-reduction centres have polyvalent elements Mp which for the assurance of reversible oxidation- reduction reactions are able to,transfer their oxidation states.

Description

Secondary battery cell for electromobiles, containing so!iu «inurpiiuub gid b mdiendi* and nano/micro materials

Technical field

The invention concerns a secondary battery cell for electromobiles, containing solid amorphous glass materials and nano/micro materials. The secondary battery cell includes end metallic electron-conductive current collectors, between which there are arranged electron-conductive electrodes, separated by an ion-conductive electrolyte, which is basically electron-nonconductive.

Background of Invention

JPS 6020476, publ. on 1 Feb. 1985, describes a secondary battery containing a glass fibre fabric used as a separator. The high-molecular compound having a conjugated double bond in the primary chain or the high-molecular compound obtained by doping is used at least for one electrode. An aromatic nitrile-based compound is used as an organic solvent of the electrolyte. The glass fibre fabric is used as a separator of the secondary battery. A large quantity of individual glass fibres with a diameter of 9 to 22 pm is obtained by using the method of melting and the spinning of alkaline glass which features good resistance to acids, which cross each other and are attached in order to create a sheet. The glass fibres may feature a porosity of at least 30 % and more, their thickness does not exceed 1 cm.

A disadvantage may be the use of chemical dopants, such as fluorides and phosphates, also cyano-compounds. Besides, the battery uses a liquid electrolyte on the basis of a nitrogen-based organic solvent, which could lead to problems at a larger load of the battery when the electrolyte is locally heated, and this situation may lead to possible burning or even an explosion due to intensive development of toxic gases, on heating, it may be oxidized which leads to the releasing of unwanted carbon oxides.

CN 1177847 A, publ. on 1 April 1998, describes a high-energy battery. Its electrode uses a netting system made of metallic fibres containing glass fibres as well. During the manufacturing procedure, the metallic fibre obtained is woven into the netting, cut to the area size required, then it is coated with the coating of a special mixed colloid dye, it is laminated and assembled for the purpose of the obtaining of a bipolar structure of the battery. With an advantage they contain metallic fibres in weigm -/o. /u g bb nui«, ±.J sodium; 5 lead; 1 silver; 1.5 nickel; 10 lithium; 1.5 sulphur; 1 hydrogen; 1.5 cadmium; 1 samarium, 3 zinc; 3 rare earth metals.

As an advantage, the invention features high tensile strength and resistance to corrosion for metallic fibres, while for battery it is suitable to mention high density of energy, its fast recharging, maintenance-free and extensive application range at a low price. The invention is intended for electromobiles as a source of energy.

A disadvantage is the relatively high content of toxic heavy metals, such as lead and cadmium. Glass fibres are probably of common chemical composition and they obviously serve as mechanical filling of electrodes, and therefore they do not have any electrochemical function of the active material of electrodes.

The priority CZ 301 387 B6, publ. on 10 Feb. 2010, (corresponding AU 2009 295014 B2, CN 102165628B, JP 6085085 B2, RU 2519935 C2, US 9437855 B2) describes a lithium accumulator with a spatial type of the electrode and the method of its production. The electrodes of the lithium accumulator are separated with a separator, which contains a non-aqueous solution of lithium salt in an organic polar solvent. The thickness of the electrodes is 0.5 mm and one of them is formed of an electron-conductive component, containing an active material, which has morphology of hollow balls with the thickness of the wall of that ball not exceeding 10 pm or morphology of aggregates or agglomerates with a size up to 30 pm. The separator contains a pressed, highly porous and highly electrically non-conductive ceramic material with open pores and porosity of 30 to 95 %. Optimum structures are spinel structures into which lithium penetrates and is released in all crystalline orientations. With an advantage it is possible to use doped or non-doped spinels of the lithium-manganese oxide (uMh₂q ,ϋMh_{1 5}Nΐo_, q ) or lithium-titanium oxide (LUTisOiz)).

An advantage of the solution is given by the spatial structure of a rechargeable lithium accumulator in a combination with metallic lithium as a negative electrode. The declared advantage consists in simplified production of lithium accumulators, capacity increase, reduction of dimensions, weight and price and improvement of their safety. This type of the accumulator is suitable as replacement of lead accumulators especially in the automotive industry, for manual electrical tools and portable electrical and electronical instruments, e.g. it increases capacity of button accumulator cells. A disadvantage is the carbon content which was uibujb eu _duuve. Hnuuier disadvantage is the necessity of the use of a liquid polar organic solvent, which can leak in consequence of leakage from the accumulator in its liquid or gaseous state. Hollow balls of active material have a closed shape which can markedly slow down migration of lithium ions, and therefore also the accumulator effectiveness.

WO 2015/128 834 A1 (corresponding US 2016 365 602 A1 or EP 3 111 503 Al), publ. on 3 Sep. 2015, describes a solid glass electrolyte with charge carriers in the form of lithium or sodium ions. The glass electrolyte composition can be expressed with the formula "R3-_2xM_xHalO", where R is selected from the group consisting of lithium or sodium, M is selected from the group consisting of magnesium, calcium or strontium, Hal is selected from the group consisting of fluorine, chromium, bromine, iodine or their mixtures, X being the number of moles M, and 0 = x = 0.01. The glass electrolyte features glass transformation. Glass electrolyte features claimed conductivity at least 13 mScnrf¹ at 25°C for a lithium ion and at least 17 mScnrT¹ at 25°C for a sodium ion. Individual possible combinations of compounds, method of preparation and application of this glass in the battery are claimed as well.

Declared advantages refer to the facts that glass electrolytes for lithium-sodium batteries are inexpensive, recyclable, non-combustible and non-toxic and feature good thermal stability in the extent of the above mentioned applications at given temperatures.

A disadvantage of the chemical composition of the electrolyte is an easy phases separation and subsequent devitrification, leading to formation of crystals of lithium or sodium compounds, as it is clearly seen e.g. from the diffraction pattern provided for in Fig.1 of this invention, where it is possible to see a number of crystalline phases. Partial crystallisation can therefore easily occur during the recharging and discharging battery cycles, which may lead to a growth of the internal resistance of the battery and to a decrease in the battery capacity, with a significant reduction of the battery lifetime.

US 9,643,881 B2, publ. on 9 April 2015, describes a glass composition for glass fibres and a method of production of glass fibres, where the battery separator is mentioned as one of the applications. For silicate glass used for glass fibres containing titanium dioxide and zirconium dioxide and oxides of alkaline metals, and with an advantage also aluminium oxide, calcium dioxide and lithium monoxide, the

drawing temperature and liquidus is 91°C and more.

Glass fibres feature declared excellent resistance to alkaline substances as well as acids and good hydrolytic resistance. Glass may contain particles of 300 to 500 pm and withstands immersion in 100 ml of a 10% sodium hydroxide solution at a temperature of 80°C for the period of 16 hours.

A disadvantage is 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.

WO 2016/205 064 Al, publ. on 22 Dec. 2016, describes water-soluble glass/ amorphous solid ion-conductors. Electrochemical devices and products use a combination of ion and electron-conductors and internal electric dipoles. The claim consists in the method of preparation of this glass by dissolving in water and the composition of electrolytes, containing an ion of sodium or lithium, bonded to oxides, sulphides and halogenides, and it is also possible to use sulphates, phosphates or hydroxides with barium, potassium, rubidium or caesium ions for this purpose. A part of the claim is also the method of application of the electrolyte in the form of a paste or mash with the enabling of evaporation of organic and/or ion liquid and/or polymer. The application in batteries and fuel cells is claimed too.

An advantage stated in the invention is the fact that liquids are much better ion- conductors at a room temperature than most known solid substances, which is a reason for which liquids are commonly used as electrolytes in the equipment intended for a room temperature; but it admits that in some applications solid electrolytes may be heavily preferred.

A disadvantage of this electrolyte is its easy solubility in water, given by its chemical composition. This property means that the electrolyte will be also less resistant to air humidity, and therefore it will be hygroscopic and unsuitable for electromobile batteries because it cannot guarantee reliability at long-term use.

US 9,553,303 B2, granted on 24 Jan. 2017 (as a continuation priority application from 2010), states silicon nanoparticles for battery electrodes. The subject matter of the claim is the method of production of the composite material at which a side product of fluidised reactor is provided, where this composite material product contains more than 0 % and less than about 90 % (weight) of silicon particles with the size uciwccn m.ii i emu mii i and surface with the size of nanometres. Composite material contains also more than 0 % and less than about 90 % (weight) of one or more types of carbon phases, where at least one or more types of carbon phases is/are basically continual phase(s), containing solid carbon, which holds the composite material together.

As an advantage, the invention states that silicon particles can improve performance of electrochemically active materials, such as improvement in terms of capacity and/or cycling. Electrochemically active materials have such silicon particles that cannot significantly degrade in consequence of netting of the silicon particles. An advantage of the composed carbon mixture which uses a carbonised (carcoal)polymer may be e.g.: higher capacity, increased protection at overloading during recharging/discharging, lower non-returnable capacity in consequence of elimination (or minimisation) of collectors of current of the metallic foil and possible cost savings thanks to simpler production.

A disadvantage is the high content of carbon which has lower thermal resistance during frequent recharging/discharging cycles at an increased current density, which leads to an increase in the battery temperature. A consequence of this fact may be releasing of toxic carbon monoxide or irrespirable carbon dioxide.

WO 2017/027 263 (Al) publ. on 16 Feb. 2017, corresponding US 2017/0040598 A1 publ. on 9 Feb. 2017, describe treatment of silicon particles for electrochemical deposition, which may be used as electrode material for a battery. The claim is aimed at the film of a composite material, containing more than 0 % and less than about 90 % (weight) of silicon particles whose surface is coated with silicon carbides or a mixture of carbides and silicon carbides; more than 0 % and less than about 90 % (weight) of one or more types of carbon phases, which are basically continual phases. The size of silicon particles is about 0.1 pm to 30 pm. The surface of silicon particles may be formed of silicon oxides, such as SiO, Si0₂ or SiO_x. Method of production of this composite material is also claimed and described, including a mixture of the precursor and silicon particles, by means of precursor pyrolysis into one or more phases of carbon, and creation of silicon carbides on at least a part of the surface of silicon particles. Pyrolysis takes place at temperatures from about 750°C to about 1300°C. Films can be rolled or cut into pieces which are then layered into an assembly. Foils of the composite material may be self-containing. Active materials with a separator

electrochemically in an alternating way.

Among advantages, the invention states composite carbon mixtures, using carbonised polymer, they may concern e.g. higher capacity, increased protection from overloading, lower irreversible capacity in consequence of elimination or minimisation of collectors of the metallic foil current. The above mentioned electrodes may contain silicon particles which have coatings containing carbon and silicon carbide, and in consequence of this they may achieve a high energy density between approx. 500 mAh/g and 2500 mAh/g, thanks to e.g. the use of silicon or full or partial elimination of current from metallic collectors through the fact that they consist, partially or fully, of an efficient active electrode material.

A disadvantage is the composite with a content of carbon, whose disadvantages are discussed above.

At present, lithium-based (known as Li-ion) batteries are used in automobiles, which have (if compared to the previous battery generation based on nickel metal hydride (NiMH)) a higher energy density, they do not discharge spontaneously and do not suffer from a memory effect. Concerning use in the automotive industry, suitable batteries are those based on lithium and electrode materials containing e.g. nickel, cobalt and aluminium (NCA); nickel, manganese, cobalt (NMC); manganese oxides with a spinel structure (LMO); titanates (LTO); or iron phosphate (LFP). At present they are used also in electromobiles, e.g. by such companies as Mitsubishi in the iMiEV vehicles, Tesla in the Roadster vehicles or Nissan in the Leaf vehicles.

A disadvantage of these widely used solutions is the reserve in the values of volumetric and gravimetric capacity, a consequence of which consists of persisting problems of the existing electromobiles, e.g. insufficient driving range, or slow recharging and short lifetime of the battery of electromobiles. Possible use of the above mentioned lithium salts in an organic polar solvent at a larger current load may lead to decomposition processes of these salts and to the arising of even highly toxic products, containing fluorine or chlorine.

In general it is possible to state that with regard to current requirements for electromobiles, lithium-based batteries continue to have an insufficient capacity, which means also a small driving distance at a relatively large weight of the battery system; besides they feature long recharging times and safety risks

the existing possibility of local overheating, which may lead even to system destruction.

From the viewpoint of production of lithium batteries, there is a risk that lithium supplies are limited and the mass production of lithium batteries may be accompanied also by the lithium price growth. Another point of view consists in possible undesirable environmental impacts caused by its mining.

Summary of the Invention

The above mentioned disadvantages will be removed or essentially limited in the secondary battery cell for electromobiles, according to this invention, whose subject matter consists in the fact that electrodes, anode as well as cathode, have mixed conductivity, they are both electronically and ionically conductive. Both the anode and cathode contain a solid amorphous multi-component glass composite material, as well as glass and/or metallic fibres and glass and/or crystalline particles with a mean diameter in nano/ micrometres from 1 nm to 100 pm. The surface of the composite material, fibres as well as particles is nano/microstructural with mean roughness from 1 nm to 100 pm. The composite material of electrodes contains active oxidation-reduction centres based on metallic silicon and/or silicon oxides and/or glass containing electropositive polyvalent elements M_p. These oxidation-reduction centres have the ratio of the higher oxidation state to the lower oxidation state of polyvalent elements M_p from 0.1 to 10.

The main advantage of this invention is the fact that a large capacity and high gravimetric and volumetric density of energy of the secondary battery cell in values from 250 Ah. kg ¹ to 500 Ah. kg ¹ can be achieved. Solid amorphous glass multi-component composite materials are used at this new secondary battery for construction of the electrodes and electrolyte. A solid amorphous glass composite material preventing the formation and growth of dendrites of metals on electrodes is used for the electrolyte for separation of the cathode and anode of the secondary battery cell. Amorphous glass material is in a solid state from the mechanical point of view, but in terms of its disordered structure it is similar to the liquid state. The high capacity is ensured through a very high surface area of electrodes which have a nano/microstructure surface. The electrode structure based on fibres and/or glass particles ensures the necessary flexibility, and thanks to this fact the electrodes are not subject to long-term damage in consequence of volumetric changes during the recharging _duu uibLn_digmg prut,eb:>e:_>. Redox centres are formed of glass particles containing polyvalent elements, which are easy to transfer between their oxidation states, and this way they effectively ensure the necessary redox reactions. A functionally gradient composite material featuring a gradient chemical composition and structure is used there. The oxidation-reduction centres also create the gradient nano/micro composite glass material of electrodes, whereby they support the mixed ionic and electron conductivity.

The multi-component composite material of the glass electrolyte features the high ionic conductivity in all the directions with the same values, which is ensured with homogenous isotropic glass. This way the electrolyte ensures an uniform current distribution, which means that any spots of a very high current density do not form when the battery cell would be subject to overheating and its material could be subject to fast degrading.

For both the glass types the matter concerns a non-flammable material. These mixed materials are prepared by using the techniques of deposition, pressing, sintering and melting.

It is an advantage when the composite material of electrodes contains GMC (Glass Mixed Conductor) glass with mixed ionic and electron conductivity, where specific ionic conductivity is at 25°C at least 10⁴ S.m ¹ and specific electron conductivity is at 25°C at least 10^~6 S.m ¹; and furthermore it includes GFIC (Glass Fast Ion-Conductor) glass with high ionic conductivity and very low electron conductivity, where ionic conductivity is at 25°C at least 10³ S.m ¹ and electron conductivity at 25°C is minimal of 3 magnitudes lower than its specific ionic conductivity, and corresponds to the value of maximum 10⁶ S.m ¹.

It is also advantageous when the electrolyte contains GFIC (Glass Fast Ion

Conductor) glass, which is isotropic and features high ionic conductivity and very low electron conductivity, where the ionic conductivity is at 25°C at least 10³ S.m ¹ and has, basically in all the directions, the same value and electron conductivity at least 3 magnitudes lower than its specific ionic conductivity, and corresponds to the value of maximum 10⁶ S.m ¹ at 25°C.

It is also advantageous when the GMC1 cathode glass with an admixture of the GFIC glass is situated in the cathode near the collector and on the side oriented at this collector; the GMC2 anode glass with admixture of the GFIC giaas _{15 snudicu m} me cmuue in the collector vicinity and on the side oriented at this collector; and the GFIC glass with the GMC1 and GMC2 glass admixture is situated immediately at or in the vicinity of the electrolyte. The volume ratio of the GMC1/GFIC phases in the cathode and GMC2/GFIC in the anode is in the immediate vicinity of corresponding collectors from 100 to 0.1 and the volume ratio of the GFIC/GMC1 and GFIC/GMC2 phases in the electrodes in the immediate vicinity of the electrolyte is from 100 do 10.

Moreover, it is advantageous, when the GMC1 (Glass Mixed Conductor) cathode glass or the GMC2 anode glass with mixed ionic and electron conductivity is the multi- component glass with the composition: LiX-Li₂0-MdO-Mm_KO_L-Mp_KO_L and/or NaX-Na₂0- MdO-Mm_K0_L-Mp_KO_L; where the following applies: X is at least one halogen from the F, Cl, Br, I group; Md is at least one of the divalent elements of the group including Ba, Sr, Zn; Mm is at least one monovalent element from the group including B, Al, Y, La, Si, Ge, Ti, Zr, P, Nb; and Mp is at least one electropositive polyvalent element of the group consisting of Cu, Fe, Co, Ni, Mn, Nb, Sn, Si, Sb, V, Ta, Mo, W, Ti; K is a stechiometric coefficient with a value of K = 1, 2; and L is a stechiometric coefficient with a value of L = 1, 2, 3, 4, 5, 6, 7.

It is also advantageous when the GFIC (Glass Fast Ion-conductor) glass with high ionic conductivity and very low electron conductivity is multi-component glass with the composition: LiX-Li₂0-MdO-Mm_kO_L and/or NaX-Na₂0-MdO-Mm_K0_L where the following applies: X is at least one halogen from the group of F, Cl, Br, 1; Md is at least one divalent element from the group consisting of Ba, Sr, Zn; Mm is at least one monovalent element from the group consisting of B, Al, Y, La, Si, Ge, Ti, Zr, P, Nb; K is stechiometric coefficient with a value of K = 1, 2; and L is a stechiometric coefficient with a value of L = 1, 2, 3, 4, 5, 6, 7.

With an advantage, in the GFIC glass or in the GMC1 glass or in the GMC2 glass or at silicon oxides in oxidation-reduction centres, a part of the oxides is replaced (up to 20 molar %) with sulphides.

Besides, it is advantageous when the oxidation-reduction centres contain polyvalent elements Mp, which transfer, for assurance of reversible oxidation-reduction reactions, between their oxidation states, namely: Cu (II)

Cu (I) and/or Cu(0); Fe (III)

Mo (VI) Mo (V); W (VI) <-> W (V).

The GFIC (Glass Fast Ion-Conductor) glass is glass with high ionic conductivity and very low electron conductivity. The GMC - (Glass Mixed Conductor) glass is glass with optimised mixed conductivity (ionic/electron conductivity). These are multi-component glass types featuring optimised compositions, with ensured required functionality, high glass formation ability and stability.

The electrolyte can have a width of 1 to 100 pm and cathode and anode can have a width of 100 to 1000 pm(each), which is determined on the basis of the glass composition and required capacity, energy distribution and conductivity.

Brief Description of Drawings

The invention is described at a detailed level on the below non-limiting examples of execution and for clarification the attached figure provides schematic illustration of a secondary battery cell in the longitudinal section in the structure of the battery cell.

Examples of the Invention Implementation

Secondary battery cell B for electromobiles, containing solid amorphous glass materials and nano/micro materials, includes end metallic electron-conductive Cl, C2 current collectors between which the electron-conductive electrodes A, K are arranged, separated with the ion-conductive electrolyte E, which is basically electron non- conductive.

Both the electrodes, anode A as well as cathode K feature mixed conductivity; they are electron-conductive and ionically-conductive at the same time. The electrodes A, K contain solid amorphous glass composite material and also glass and/or metallic fibres and glass and/or crystalline particles with a mean diameter in nano/micrometres from 1 nm to 100 pm; in the particular exemplary design e.g. 100 nm.

Both the anode A and cathode K have nano/microstructure surface with mean roughness from 1 nm to 100 pm.

Both the anode A and cathode K contain, as the charge carriers, ionic conductivity, migrating cations of lithium and/or sodium for migration from the anode A through the electrolyte E to the cathode K during the discharging of the ot u 1 1 a i y uo uu y a nu from the cathode K to the anode A during recharging of the secondary battery cell B.

The current collector Cl contains aluminium Al, the current collector C2 contains copper Cu. Both the cathode K and anode A contain glass of the GMC+GFIC type as a functionally gradient material; the electrolyte E contains glass of the GFIC material type.

The following Tables (3) include more detailed specifications of possible and non limiting particular design cases.

Table 1: GFIC glass composition of the electrolyte E

Table 1 provides for composition of the GFIC-L glass electrolyte for the battery cell B on the basis of Li⁺ ions and of the GFIC-N electrolyte for the battery cell on the basis of Na⁺ ions. Their composition has an optimum ratio of electropositive and electronegative elements, guaranteeing high stability of the electrolyte E and a sufficiently high value of ionic conductivity at very low electron conductivity. That is why they are suitable for construction of high-capacity batteries. Table 2: Composition of GMC components for electrodes A,K

Table 2 provides for composition of the GMC1-L, d ^-L.

the battery cell B, based on the Li⁺ ions, and of the GMC1-N, GMC2-N electrode materials for the battery cell B, based on the Na⁺ ions. Their composition features an optimum ratio of oxidised and reduced forms of polyvalent elements Mp, which guarantees high reversibility and rate of electrode reactions supported by sufficiently high electron conductivity ensuring cooperative mechanism of reactions on the electrodes A, K. Therefore, they are suitable for construction of high-capacity batteries.

Table 3: Exemplary designs of the assembly of the secondary battery cell B

Table 3 provides for exemplary designs of the battery cell 1 with Li⁺ ions and battery Cell 2 with Na⁺ ions. The corresponding electrode materials are formed of functionally gradient materials consisting of a mixture of corresponding GMC and GFIC materials. These electrode materials in a combination with the optimised glass electrolyte E_ensure high values of energy density and power, and therefore they are suitable for construction of high-capacity batteries.

Industrial Applicability

Solid glass materials are used at this new secondary battery for construction of electrodes, anodes A and cathode K and electrolyte E.

Claims

PATENT CLAIMS

1. Secondary battery cell for electromobiles, containing solid amorphous glass materials and nano/micro materials, which includes

the end metallic electronically conductive current collectors (Cl, C2) between which electronically conductive electrodes (A, K) are arranged, containing as ionic charge carriers the migrating cations of lithium and/or sodium for the migration from the anode (A) through the electrolyte (E) to the cathode (K) during the discharging of the secondary battery cell (B) and from the cathode (K) to the anode (A) during the recharging of the secondary battery cell (B);

where the anode (A) and cathode (K) are separated with the ion-conductive electrolyte (E) which is basically electron non-conductive,

characterised by the fact that

(a) the electrodes, anode (A) and cathode (K)

• feature mixed conductivity, are electronically as well as ionically conductive;

• contain solid amorphous multi-component glass composite material, also glass and/or metallic fibres and glass and/or crystalline particles with the mean diameter in nano/micrometres from 1 nm to 100 pm;

• have a surface of the composite material, fibres as well as particles is nano/micro-structural with mean roughness from 1 nm to 100 pm; where

the composite material of electrodes (A, K) contains active oxidation- reduction centres, based on metallic silicon and/or silicon oxides and/or glasses containing electropositive polyvalent elements M_p and

these oxidation-reduction centres have the ratio of higher oxidation state to lower oxidation state of polyvalent elements M_p from 0.1 to 10; and b) electrolyte (E)

• contains solid amorphous multi-component glass composite material, which is isotropic, with ionic charge carriers of conductivity of a lithium cation and/or sodium cation with .

the same value in all the directions.

2. Secondary battery cell for electromobiles according to claim 1, characterised by the fact that

the composite material of electrodes (A, K) contains multi-component glass

• GMC (Glass Mixed Conductor) with mixed ionic and electron conductivity,

where specific ionic conductivity is at 25°C at least 10⁴ S.m ¹ and specific electron conductivity is at 25°C at least 10⁶ S.m ¹; and

• GFIC (Glass Fast Ion-conductor) with high ionic conductivity and very low electron conductivity, where

ionic conductivity is at 25°C at least 10 ³ S.m ¹ and

electron conductivity is at 25°C at least 3 magnitudes lower than its specific ionic conductivity and corresponds to the maximum value of 10⁶ S.m ¹.

3. Secondary battery cell for electromobiles according to claim 1,

characterised by the fact that

the electrolyte (E) contains multi-component glass

• GFIC (Glass Fast Ion-Conductor), which is isotropic and has high ionic conductivity and very low electron conductivity, where

ionic conductivity is at 25°C at least 10³ S.m ¹ and has basically the same value in all the directions and

electron conductivity is at least 3 magnitudes lower than its specific ionic conductivity, and corresponds at 25°C to the maximum value of

10 ⁶ S.m ¹.

4. Secondary battery cell for electromobiles according to claim 1,

characterised by the fact that • GMC1 glass of the cathode (K) with

situated in the cathode (K) in the vicinity of the collector (Cl) and on the site oriented towards this collector (Cl),

• GMC2 glass of the anode (A) with admixture of the GFIC glass is situated in the anode (A) in the vicinity of the collector (C2) and on the site oriented towards this collector (C2), and

• GFIC glass with admixture of the GMC1 and GMC2 glass is situated immediately at or in the vicinity of the electrolyte (E);

and at the same time;

• the volume ratio of the GMC1/GFIC phases in the cathode (K) and

GMC2/GFIC in the anode (A) is in the immediate vicinity of the corresponding collectors (Cl, C2) from 100 to 0.1 and

• the volume ratio of the GFIC/GMC1 and GFIC/GMC2 phases in the electrodes (A, K) in the immediate vicinity of the electrolyte (E) is from 100 to 10.

5. Secondary battery cell for electromobiles according to claim 1,

characterised by the fact that

• the GMC1 (Glass Mixed Conductor) glass of the cathode (K) or the GMC2 glass of the anode (A) with mixed ionic and electron conductivity is the multi-component glass with the following composition:

LiX-Li20-Md0-Mm_K0_L-Mp_K0_L and/or

NaX-Na₂0-MdO-Mm_KO_L-Mp_KO_L,

where:

X is at least one halogen from the group F, Cl, Br, I;

Md is at least one divalent element from the group Ba, Sr, Zn;

Mm is at least one monovalent element from the group B, Al, Y, La, Si, Ge, Ti, Zr,

P, Nb; and

Mp is at least one electropositive polyvalent element from the group Cu, Fe, Co,

Ni, Mn, Nb, Sn, Si, Sb, V, Ta, Mo, W, Ti;

K is stechiometric coefficient with the value K = 1, 2; and

L is stechiometric coefficient with the value L = 1, 2, 3, 4, 5, 6, 7.

6. Secondary battery cell for electromobiles according to claim 1,

characterised by the fact that

• the GFIC (Glass Fast Ion Conductor) glass with high ionic conductivity and very low electron conductivity is multi-component glass with the composition:

UX-Li₂0-Md0-Mm_K0_L and/or

NaX-Na₂0-Md0-Mm_K0_L

where:

X is at least one halogen from the group F, Cl, Br, I;

Md is at least one divalent element from the group Ba, Sr, Zn;

Mm is at least one monovalent element from the group B, Al, Y, La, Si, Ge, Ti, Zr, P, Nb;

K is stechiometric coefficient with the value K = 1, 2; and

L is stechiometric coefficient with the value L = 1, 2, 3, 4, 5, 6, 7.

7. Secondary battery cell for electromobiles according to claim 1,

characterised by the fact that

the composite material of the electrodes (A, K) contains

• active oxidation-reduction centres

based on metallic silicon and/or oxides of silicon and/or glass containing electropositive polyvalent elements M_p, where:

• these oxidation-reduction centres have the ratio of the higher oxidation state to the lower oxidation state of polyvalent elements M_p from 0.1 to 10, whereby they create gradient nano/micro composite glass material of the electrodes (A, K) with mixed ionic and electron conductivity.

8. Secondary battery cell for electromobiles according to claim 1

characterised by the fact that

in the GFIC glass or in the GMC1 glass or in the GMC2 glass or in silicon oxide in the oxidation-reduction centres a part of the oxides is replaced with sulphides up to 20 % molar.

9. Secondary battery cell for electromobiles according to claim 1,

characterised by the fact that

the oxidation-reduction centres contain polyvalent elements Mp which for the assurance of reversible oxidation-reduction reactions transfer between their oxidation states, namely:

Cu (II) <-> Cu (I) and/or Cu(0);

Fe (III) Fe (II) and/or Fe (0);

Co (III) Co (II);

Si (IV) Si (0);

Ti (IV) <- Ti (III);

Mn (IV) Mn (III) and/or Mn (II); nd/or V (III);

and /or Nb (II);

W (VI) <® W (V).

10. Secondary battery cell for electromobiles according to any of the claims 1 to 9 characterised by the fact that

the electrolyte (E) features a width from 1 to 100 pm and

each of the cathode (K) and anode (A) have the width from 100 to 1000 pm.