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

Secondary battery cell for electromobiles, containing solid amorphous glass materials and nano/micro materials Download PDF

Info

Publication number
WO2019129316A1
WO2019129316A1 PCT/CZ2018/000061 CZ2018000061W WO2019129316A1 WO 2019129316 A1 WO2019129316 A1 WO 2019129316A1 CZ 2018000061 W CZ2018000061 W CZ 2018000061W WO 2019129316 A1 WO2019129316 A1 WO 2019129316A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
battery cell
secondary battery
oxidation
cathode
Prior art date
Application number
PCT/CZ2018/000061
Other languages
English (en)
French (fr)
Inventor
Martin ΜίΚΑ
Lukas SATURA
Florian WEYMAR
Ivana LUSTICKA
Original Assignee
Skoda Auto A.S.
Vysoka Skola Chemicko-Technologicka V Praze
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Skoda Auto A.S., Vysoka Skola Chemicko-Technologicka V Praze filed Critical Skoda Auto A.S.
Publication of WO2019129316A1 publication Critical patent/WO2019129316A1/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/62—Heating or cooling; Temperature control specially adapted for specific applications
    • H01M10/625—Vehicles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides

Definitions

  • 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.
  • 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.
  • 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.
  • 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 (uMh 2 q , ⁇ Mh 1 5 N ⁇ o , 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 d uuve.
  • 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 features glass transformation.
  • Glass electrolyte features claimed conductivity at least 13 mScnrf 1 at 25°C for a lithium ion and at least 17 mScnrT 1 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.
  • 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.
  • 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.
  • 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, Si0 2 or SiO x .
  • Method of production of this composite material 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
  • 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.
  • 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.
  • 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).
  • NCA nickel, cobalt and aluminium
  • NMC nickel, manganese, cobalt
  • LMO manganese oxides with a spinel structure
  • LTO titanates
  • FFP iron phosphate
  • 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.
  • 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
  • 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 d uu uibLn di gmg 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.
  • 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 10 4 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 10 3 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 10 6 S.m 1 .
  • GMC Glass Mixed Conductor
  • GFIC Glass Fast Ion-Conductor
  • 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 10 3 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 10 6 S.m 1 at 25°C.
  • 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.
  • 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-Li 2 0-MdO-Mm K O L -Mp K O L and/or NaX-Na 2 0- MdO-Mm K 0 L -Mp K O 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
  • the GFIC (Glass Fast Ion-conductor) glass with high ionic conductivity and very low electron conductivity is multi-component glass with the composition: LiX-Li 2 0-MdO-Mm k O L and/or NaX-Na 2 0-MdO-Mm K 0 L
  • 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
  • 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)
  • 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.
  • 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.
  • 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
  • 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.
  • Solid glass materials are used at this new secondary battery for construction of electrodes, anodes A and cathode K and electrolyte E.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
PCT/CZ2018/000061 2017-12-29 2018-12-27 Secondary battery cell for electromobiles, containing solid amorphous glass materials and nano/micro materials WO2019129316A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CZ2017859A CZ309338B6 (cs) 2017-12-29 2017-12-29 Sekundární bateriový článek pro elektromobily, obsahující pevné amorfní skelné materiály a nano/mikro materiály
CZPV2017-859 2017-12-29

Publications (1)

Publication Number Publication Date
WO2019129316A1 true WO2019129316A1 (en) 2019-07-04

Family

ID=65576083

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CZ2018/000061 WO2019129316A1 (en) 2017-12-29 2018-12-27 Secondary battery cell for electromobiles, containing solid amorphous glass materials and nano/micro materials

Country Status (3)

Country Link
CZ (1) CZ309338B6 (cs)
SK (1) SK9275Y1 (cs)
WO (1) WO2019129316A1 (cs)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021089066A1 (en) * 2019-11-05 2021-05-14 ŠKODA AUTO a.s. Secondary battery cell for electromobiles, cointaining amorphous glass materials and micro- and nano materials, and method of its production
US11658306B2 (en) 2020-02-04 2023-05-23 Samsung Electronics Co., Ltd. Cathode, lithium-air battery comprising the same, and method of preparing the cathode
US11764364B2 (en) 2020-02-04 2023-09-19 Samsung Electronics Co., Ltd. Cathode, lithium-air battery comprising the same, and method of preparing the cathode
CZ309795B6 (cs) * 2020-11-04 2023-10-18 ŠKODA AUTO a.s Sekundární bateriový článek pro elektromobily, obsahující amorfní skelné materiály a mikro a nano materiály a způsob jeho výroby

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6020476A (ja) 1983-07-13 1985-02-01 Showa Denko Kk 二次電池
CN1177847A (zh) 1997-09-11 1998-04-01 周国君 高能动力电池
JPH10302776A (ja) * 1997-04-30 1998-11-13 Matsushita Electric Ind Co Ltd 全固体リチウム二次電池
CZ301387B6 (cs) 2008-09-19 2010-02-10 He3Da S.R.O. Lithiový akumulátor s prostorovým typem elektrod a zpusob jeho výroby
JP2011187370A (ja) * 2010-03-10 2011-09-22 Toyota Motor Corp 全固体電池
WO2015128834A1 (en) 2014-02-26 2015-09-03 Universidade Do Porto A solid electrolyte glass for lithium or sodium ions conduction
US20150266769A1 (en) * 2012-10-25 2015-09-24 Nippon Electric Glass Co., Ltd. Glass composition for glass fiber, glass fiber, and method for producing glass fiber
WO2016205064A1 (en) 2015-06-18 2016-12-22 Board Of Regents, The University Of Texas System Water solvated glass/amorphous solid ionic conductors
US9553303B2 (en) 2010-01-18 2017-01-24 Enevate Corporation Silicon particles for battery electrodes
US20170040598A1 (en) 2015-08-07 2017-02-09 Enevate Corporation Surface modification of silicon particles for electrochemical storage

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2489483Y (zh) * 2001-07-24 2002-05-01 江苏隆源双登电源有限公司 长寿命、高性能阀控密封铅酸蓄电池
CN1905264A (zh) * 2006-07-31 2007-01-31 长沙丰日电气集团有限公司 电动车用胶体蓄电池
CN203218295U (zh) * 2013-04-28 2013-09-25 中利腾晖光伏科技有限公司 一种晶硅电池轻质组件
CN104465833A (zh) * 2014-12-23 2015-03-25 常熟高嘉能源科技有限公司 一种多晶硅电池组件
CN205335328U (zh) * 2015-12-16 2016-06-22 河南超威电源有限公司 一种二氧化硅隔板

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6020476A (ja) 1983-07-13 1985-02-01 Showa Denko Kk 二次電池
JPH10302776A (ja) * 1997-04-30 1998-11-13 Matsushita Electric Ind Co Ltd 全固体リチウム二次電池
CN1177847A (zh) 1997-09-11 1998-04-01 周国君 高能动力电池
CZ301387B6 (cs) 2008-09-19 2010-02-10 He3Da S.R.O. Lithiový akumulátor s prostorovým typem elektrod a zpusob jeho výroby
CN102165628A (zh) 2008-09-19 2011-08-24 He3Da有限责任公司 锂蓄电池及其制备方法
RU2519935C2 (ru) 2008-09-19 2014-06-20 ХЕЗДА с.р.о. Литиевый аккумулятор и способ его изготовления
JP6085085B2 (ja) 2008-09-19 2017-02-22 ハーエー３デーアー エス．エル．オー． リチウム蓄電池及びその製造方法
AU2009295014B2 (en) 2008-09-19 2016-03-24 He3Da S.R.O. Lithium accumulator and the method of producing thereof
US9437855B2 (en) 2008-09-19 2016-09-06 He3Da S.R.O. Lithium accumulator and the method of producing thereof
US9553303B2 (en) 2010-01-18 2017-01-24 Enevate Corporation Silicon particles for battery electrodes
JP2011187370A (ja) * 2010-03-10 2011-09-22 Toyota Motor Corp 全固体電池
US20150266769A1 (en) * 2012-10-25 2015-09-24 Nippon Electric Glass Co., Ltd. Glass composition for glass fiber, glass fiber, and method for producing glass fiber
US9643881B2 (en) 2012-10-25 2017-05-09 Nippon Electric Glass Co., Ltd. Glass composition for glass fiber, glass fiber, and method for producing glass fiber
EP3111503A1 (en) 2014-02-26 2017-01-04 Universidade do Porto A solid electrolyte glass for lithium or sodium ions conduction
US20160365602A1 (en) 2014-02-26 2016-12-15 Universidade Do Porto A solid electrolyte glass for lithium or sodium ions conduction
WO2015128834A1 (en) 2014-02-26 2015-09-03 Universidade Do Porto A solid electrolyte glass for lithium or sodium ions conduction
WO2016205064A1 (en) 2015-06-18 2016-12-22 Board Of Regents, The University Of Texas System Water solvated glass/amorphous solid ionic conductors
US20170040598A1 (en) 2015-08-07 2017-02-09 Enevate Corporation Surface modification of silicon particles for electrochemical storage
WO2017027263A1 (en) 2015-08-07 2017-02-16 Enevate Corporation Surface modification of silicon particles for electrochemical storage

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021089066A1 (en) * 2019-11-05 2021-05-14 ŠKODA AUTO a.s. Secondary battery cell for electromobiles, cointaining amorphous glass materials and micro- and nano materials, and method of its production
US11658306B2 (en) 2020-02-04 2023-05-23 Samsung Electronics Co., Ltd. Cathode, lithium-air battery comprising the same, and method of preparing the cathode
US11764364B2 (en) 2020-02-04 2023-09-19 Samsung Electronics Co., Ltd. Cathode, lithium-air battery comprising the same, and method of preparing the cathode
CZ309795B6 (cs) * 2020-11-04 2023-10-18 ŠKODA AUTO a.s Sekundární bateriový článek pro elektromobily, obsahující amorfní skelné materiály a mikro a nano materiály a způsob jeho výroby

Also Published As

Publication number Publication date
SK9275Y1 (sk) 2021-08-11
SK500742020U1 (sk) 2021-04-14
CZ2017859A3 (cs) 2019-07-10
CZ309338B6 (cs) 2022-09-07

Similar Documents

Publication Publication Date Title
EP3813161B1 (en) All-solid secondary battery and method of manufacturing all-solid secondary battery
Courtel et al. High capacity anode materials for Li-ion batteries based on spinel metal oxides AMn 2 O 4 (A= Co, Ni, and Zn)
US11404726B2 (en) All-solid-state sodium ion secondary battery
US12191444B2 (en) All-solid secondary battery and method of manufacturing the same
US12362397B2 (en) Bipolar all-solid-state sodium ion secondary battery
WO2013074772A1 (en) Aqueous electrolyte lithium sulfur batteries
CN113346088A (zh) 负极和包括其的固态二次电池
WO2019129316A1 (en) Secondary battery cell for electromobiles, containing solid amorphous glass materials and nano/micro materials
US11664529B2 (en) Buffered negative electrode-electrolyte assembly, battery, and method of manufacture thereof
US12218358B2 (en) All-solid-state secondary battery
JP2022041968A (ja) 全固体二次電池用硫化物系固体電解質、その製造方法及びそれを含む全固体二次電池
WO2022255002A1 (ja) 電池
JP7617255B2 (ja) 固体イオン伝導体化合物、それを含む固体電解質、それを含む電気化学セル、及びその製造方法
JP7387564B2 (ja) 二次電池、電池パック、車両及び定置用電源
JP2021150277A (ja) 二次電池、電池パック、車両及び定置用電源
US20240145767A1 (en) Solid-state electrolyte, lithium battery comprising solid-state electrolyte, and preparation method of solid-state electrolyte
WO2012094761A1 (en) Ion-exchange battery
KR20240031908A (ko) 전고체 이차전지
WO2022254975A1 (ja) 電池
CN117751471A (zh) 全固态电池用正极以及包含其的全固态电池
KR20220118279A (ko) 음극 활물질층 재료, 이를 포함하는 전고체 이차전지 및 그 충전 방법
KR102857427B1 (ko) 전고체 이차전지
JP7589116B2 (ja) 二次電池、電池パック及び車両
US20230116728A1 (en) Secondary battery, battery pack, vehicle, and stationary power supply
JP7391799B2 (ja) 二次電池、電池パック、車両及び定置用電源

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18852711

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18852711

Country of ref document: EP

Kind code of ref document: A1