EP4046222A1 - Réseaux polymères semi-interpénétrants en tant que séparateurs destinés à être utilisés dans des batteries à métal alcalin - Google Patents

Réseaux polymères semi-interpénétrants en tant que séparateurs destinés à être utilisés dans des batteries à métal alcalin

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Publication number
EP4046222A1
EP4046222A1 EP20792348.3A EP20792348A EP4046222A1 EP 4046222 A1 EP4046222 A1 EP 4046222A1 EP 20792348 A EP20792348 A EP 20792348A EP 4046222 A1 EP4046222 A1 EP 4046222A1
Authority
EP
European Patent Office
Prior art keywords
solid electrolyte
equal
alkali metal
battery
weight
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP20792348.3A
Other languages
German (de)
English (en)
Inventor
Gerrit HOMANN
Johannes Kasnatscheew
Jijeesh Ravi Nair
Martin Winter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Forschungszentrum Juelich GmbH
Original Assignee
Forschungszentrum Juelich GmbH
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 Forschungszentrum Juelich GmbH filed Critical Forschungszentrum Juelich GmbH
Publication of EP4046222A1 publication Critical patent/EP4046222A1/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M2300/0082—Organic polymers
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a solvent-free solid electrolyte for an alkali metal solid battery comprising an alkali metal conductive salt and a semi-interpenetrating network (sIPN) made of a cross-linked and a non-cross-linked polymer, the semi-interpenetrating network being made of a non-cross-linked polymer selected from the group consisting of polyethylene oxide (PEO), polycarbonate (PC), polycaprolactone (PCL), chain-modified derivatives of these polymers or mixtures of at least two components thereof and the crosslinked polymer comprises polyethylene glycol dimethacrylate (PEG-dMA).
  • PEG-dMA polyethylene glycol dimethacrylate
  • the invention also relates to a method for producing a solid electrolyte and an alkali metal battery with the solid electrolyte according to the invention.
  • the patent literature also contains some examples of the design of alkali metal batteries with polymer-based solid electrolytes.
  • WO 2014 147 648 A1 discloses an electrolyte composition with high ionic conductivity.
  • the document discloses highly ionic conductivity electrolyte compositions of semi-interpenetrating polymer networks and their nanocomposites as a quasi-solid / solid electrolyte matrix for energy generation, storage and delivery devices, in particular for hybrid solar cells, accumulators, capacitors, electrochemical systems and flexible devices.
  • the binary or ternary component of a semi-interpenetrating polymer network electrolyte composition comprises: a) a poly- mernetzwerk with polyether backbone (component I); b) a linear, branched, hyperbranched polymer with a low molecular weight or any binary combination of such polymers with preferably non-reactive end groups (component II and / or component III to form a ternary semi-IPN system); c) an electrolyte salt and / or a redox couple and optionally d) a pure or surface-modified nanostructured material for forming a nanocomposite.
  • WO 2015 043 564 A1 discloses a method for producing at least one electrochemical cell of a solid-state battery, comprising a mixed conductivity anode, a mixed conductivity cathode, and an electrolyte layer arranged between anode and cathode, with the steps
  • the surface of at least one of the two electrodes is modified by an additional process step in such a way that the electronic conductivity perpendicular to the cell is lowered to less than 10 8 S / cm in a layer of the electrode close to the surface, and
  • the anode and the cathode are built together to form a solid-state battery in such a way that the surface-modified layer of at least one electrode is arranged as an electrolyte layer at the border between the anode and cathode, and the mischlei border electrodes are thereby electronically separated.
  • the object is achieved according to the invention by a solid electrolyte with the features of claim 1.
  • the object is also achieved according to the invention by a method with the features of claim 6 and a battery according to claim 9.
  • Preferred embodiments of the invention are in the subclaims , specified in the description or the figures, with further features described or shown in the dependent claims or in the description or the figures individually or in any combination may represent an object of the invention, as long as the context does not clearly indicate the opposite.
  • a solid electrolyte for an alkali metal solid battery comprising at least one alkali metal conductive salt and a semi-interpenetrating network (sIPN) made of a crosslinked and a non-crosslinked polymer, the semi-interpenetrating network being greater than or equal to 50 % By weight and less than or equal to 80% by weight of a non-crosslinked polymer selected from the group consisting of polyethylene oxide (PEO), polycarbonate (PC), polycaprolactone (PCL), chain-modified derivatives of these polymers or mixtures of at least two components from it; and greater than or equal to 20% by weight and less than or equal to 50% by weight polyethylene glycol dimethacrylate (PEGdMA) as crosslinked polymer, the solid electrolyte being greater than or equal to 90% by weight and less than or equal to 100% by weight consists of the alkali conducting salt and the sIPN; and the solid electrolyte is solvent-free.
  • PEO polyethylene oxide
  • PC polycarbonate
  • the thermal working window of alkali metal batteries is thereby expanded and, in particular, shifted to lower temperatures, which can increase the ease of use.
  • Another advantage of these solid electrolytes is that even higher voltages and currents can be safely handled via the solid electrolyte, so that safe operation of alkali metal batteries can be guaranteed even under these difficult electrical conditions.
  • the polymer electrolyte according to the invention has both a highly amorphous alkali ion-conducting phase and increased mechanical stability. Both factors lead to higher operational reliability, more reproducible charging / discharging behavior and a larger temperature application window.
  • the solid electrolyte according to the invention is a solvent-free solid electrolyte for an alkali metal solid battery.
  • a solid electrolyte is also called a solid electrolyte, solid electrolyte or solid ion conductor.
  • the solid electrolyte has a coherent polymeric support structure and alkali metal ions embedded therein, which are mobile within the polymeric matrix of the solid electrolyte. An electric current can flow through the mobility of the ions in the solid electrolyte.
  • Solid electrolytes are electrically conductive, but have a rather low electronic conductivity compared to metals.
  • An alkali metal solid battery has at least two electrodes and a solid, in particular non-flowable electrolyte arranged between the electrodes.
  • a solid-state battery can also have further layers or layers.
  • a solid battery can have additional layers between the solid electrolyte and the electrodes.
  • the electrical properties of solid alkali metal batteries are based on the redox reaction of alkali metals, i.e. the metals from the 1st main group of the periodic system. In particular, lithium, sodium and potassium can be used as alkali metals.
  • the solid electrolyte comprises at least one alkali metal conductive salt and a semi-interpenetrating network (sIPN) made of a crosslinked and a non-crosslinked polymer.
  • the mechanical backbone of the solid electrolyte is formed by a network of two different polymers, which also gives it its strength.
  • a semi-interpenetrating network is a network that has two different polymer species.
  • One polymer can be crosslinked to form a three-dimensional network with the formation of covalent bonds between the monomers, whereas the other polymer, for lack of functional groups, is linked purely via ionic or van der Waals interactions. Both polymer components can, at least in principle, be separated from one another via a washout process.
  • the two components physically penetrate each other and together form the semi-interpenetrating network.
  • the further component of the solid electrolyte forms the alkali metal conductive salt, which is present “dissolved” within the network or bound to it, but is not regarded according to the invention as a component of the polymer network but as a component of the solid electrolyte.
  • the semi-interpenetrating network has greater than or equal to 50% by weight and less than or equal to 80% by weight of a non-crosslinked polymer selected from the group consisting of polyethylene oxide (PEO), polycarbonate (PC), polycaprolactone (PCL), chain-end-modified derivatives of these polymers or mixtures of at least two components thereof on.
  • a non-crosslinked polymer selected from the group consisting of polyethylene oxide (PEO), polycarbonate (PC), polycaprolactone (PCL), chain-end-modified derivatives of these polymers or mixtures of at least two components thereof on.
  • the semi-interpenetrating network made up of two polymeric components thus has PEO, PC, PCL or mixtures of these components as the main weight component.
  • the non-crosslinkable polymers can in each case be substituted at the chain ends.
  • PEO is understood to mean monomers with the following structural formula where the index n can expediently be chosen from 10 to 120,000.
  • the radicals R can each independently represent hydrogen, a substituted or unsubstituted alkyl or aryl radical.
  • the substituted or unsubstituted alkyl or aryl radicals can have a carbon number of Cl to C20 and further, non-crosslinkable functional substituents, such as halogen, ME, NO2.
  • Polycarbonates are understood to mean compounds with the following structural formula where the index n can expediently be chosen from 3 to 120,000.
  • the radicals R at the chain ends correspond to the definition given above.
  • the group R 1 stands for an aromatic or aliphatic CI -Cl 5 group.
  • Polycaprolactone is understood to mean compounds with the following structural formula where the index n can expediently be chosen from 3 to 120,000.
  • the radicals R at the chain ends correspond to the definition given above.
  • the semi-interpenetrating network has greater than or equal to 20% by weight and less than or equal to 50% by weight of polyethylene glycol dimethacrylate (PEGdMA) as the crosslinked polymer.
  • the weight data relate to the two polymeric components and in this respect the weight proportion of the PEGdMA in the polymer network is at most the same as the proportion of the non-crosslinkable component.
  • the weight fractions of the alkali metal conductive salt are not taken into account, since the formation of the semi-interpenetrating network is essentially determined by the polymeric components.
  • PEGdMA is understood to mean a monomer with the following structure where the index n can expediently assume values from 5 to 1000.
  • the monomer has two functional methacrylic groups, which are responsible for the crosslinking of different monomers.
  • the weight proportions of the crosslinked and uncrosslinked polymer in the sIPN can add up to 100% by weight.
  • the semi-interpenetrating network it is possible for the semi-interpenetrating network not to have any further monomer / polymer components in large amounts in addition to the polymer components mentioned. Larger amounts are, for example, amounts above 5% by weight based on the crosslinked and non-crosslinked polymers specified above.
  • no further monomers or polymers can be present in the structure of the solid electrolyte.
  • the solid electrolyte consists of greater than or equal to 90% by weight and less than or equal to 100% by weight of the alkali conducting salt and the sIPN.
  • the solid electrolyte has no other components in addition to the components of crosslinked polymer, uncrosslinked polymer and conductive salt.
  • the solid electrolyte can be free from solvents.
  • the solid electrolyte can be free of further constituents which are intended to increase the solubility of the alkali metal conductive salt or to give the semi-interpenetrating network further mechanical stability. This configuration can in particular contribute to maintaining the amorphous structure of the semi-interpenetrating network, which can also contribute to a conductivity that is as constant as possible, even at low temperatures.
  • the non-crosslinked polymer can be polyethylene oxide and the solid electrolyte can have a molar ratio of ethylene oxide units to alkali ions, expressed by the quotient EO / Li, of greater than or equal to 5 and less than or equal to 15 exhibit.
  • the ratio of ethylene oxide units to alkali ions in the solid electrolyte given above has proven to be particularly suitable. This relation enables a relatively high mobility of the ions and only slightly disrupts the mechanical structure of the semi-interpenetrating network, so that, in addition to the increased conductivity, a very reproducible charging / discharging process is obtained.
  • the EO units of the crosslinked and the EO units of the uncrosslinked polymer are considered.
  • the respective sizes can be determined using methods known to the person skilled in the art.
  • the ion concentration for example, via dissolution of the network and ICP.
  • the number of EO units can, if necessary after the covalent bonds of the crosslinked polymer have been broken, for example by HPLC or GC methods.
  • the ratio can preferably also be greater than or equal to 8 and less than or equal to 13, furthermore preferably greater than or equal to 9 and less than or equal to 12.
  • the solid electrolyte can have a thickness of greater than or equal to 20 ⁇ m and less than or equal to 60 ⁇ m. Surprisingly, it has been shown that the solid electrolyte according to the invention shows excellent mechanical stability even with very small layer thicknesses. These layer thicknesses are sufficient to provide very reproducible electrical behavior over many charge / discharge cycles. This means that very compact and long-lasting designs can be implemented. Overall, layer thicknesses of up to 250 ⁇ m, preferably up to 200 ⁇ m and more preferably up to 150 ⁇ m can be produced.
  • the weight ratio of non-crosslinked polymer P N and crosslinked polymer Pv in the sIPN, expressed by the quotient P N / PV, can be greater than or equal to 2 and less than or equal to 2.5.
  • This ratio of the weight proportions of non-crosslinked and crosslinked polymer have proven to be particularly mechanically stable and lead to preferred amorphous structures which enable the solid electrolyte to have sufficient conductivity even at low temperatures.
  • the PEGdMA can have an average molecular weight of greater than or equal to 300 g / mol and less than or equal to 1000 g / mol.
  • This range of chain lengths for the crosslinkable polymer have led to a preferred stability of the available semi-interpenetrating networks. Larger PEG-dMA chains can lead to a reduction in mechanical strength. Shorter chains can also reduce the mechanical strength, probably due to insufficient crosslinking of the relatively short chains.
  • the PEGdMA can have an average molecular weight of greater than or equal to 4,500 g / mol and less than or equal to 900 g / mol, furthermore greater than or equal to 600 g / mol and less than or equal to 850 g / mol.
  • the solid electrolyte can be a solid electrolyte for a Li solid battery and the alkali metal conductive salt can be a mixture of at least two different lithium salts.
  • the use of a mixture of different conductive salts can lead to improved electrical properties in the solid electrolytes according to the invention.
  • Suitable combinations for a Li structure can be selected, for example, from LiTFSI + LiFTFSI, LiTFSI + LiFSI, LiTFSI + LiBF 4 , LiTFSI + LiBOB, LiTFSI + LiDFOB, LiDFOB + L1BF 4 or suitable combinations with one another.
  • the solid electrolyte can have further additives, such as fluorinated additives, which may suppress the aluminum dissolution of further constituents of a battery, or SEI additives which can be used to stabilize the anode boundary layer.
  • a method for solvent-free production of an alkali metal battery solid electrolyte having a semi-interpenetrating polymer network comprising the method steps: a) producing a homogeneous solution from an alkali metal electrolyte, a polymerization initiator and a crosslinkable polymer having at least two crosslinkable groups; b) mixing the solution obtained from step a) with a non-crosslinkable polymer to obtain a homogeneous mixture; and c) pressing the homogeneous mixture obtained from process step b) with the formation of an uncrosslinked, flat membrane; d) crosslinking of the membrane obtained in process step c) to obtain a solid electrolyte.
  • Process step a) comprises the production of a homogeneous solution of alkali conducting salt, polymerization initiator and crosslinkable polymer.
  • the homogeneous solution can be formed by purely mechanical mixing or stirring of the three components.
  • the definitions for the possible electrolyte salts and the crosslinkable polymers have already been given above.
  • the chemical substances known to the person skilled in the art are suitable as polymerization initiators, which are able, by means of a change in an environmental variable, to break down into radicals, for example, and thus to crosslink the crosslinkable polymer.
  • Possible environmental variables are, for example, the temperature or an energy input via irradiation with light of different wavelengths.
  • Possible initiators are therefore compounds which decompose into radicals either through heat or irradiation.
  • This process step a) is carried out in such a way that the initiator does not yet react.
  • Process step b) comprises mixing the solution obtained from step a) with a non-crosslinkable polymer.
  • This process step can also be carried out, for example, by purely mechanical mixing or kneading of the mixture.
  • the usual times until a homogeneous mixture is obtained can be, for example, in the range from 1 hour to 2 hours.
  • Process step c) comprises compressing the mixture obtained from process step b).
  • the pressing can take place by means of a press, it being possible for the pressing to take place, for example, in a pressure range of 0.1-200 MPa over a period of 30 minutes to 3 hours.
  • the thickness of the mixture can usually be reduced by a factor of 10% -100%, preferably 20% -80%, via the pressing process. About this thickness reduction tion, mechanically very stable but nevertheless sufficiently porous networks can be provided after polymerization, which have very good mechanical and electrical properties. Without being bound by theory, this also seems to be attributable to the fact that the networks obtainable in this way do not show any traces of solvent. This can contribute to an increase in the reproducibility of the electrical charging / discharging processes.
  • Process step d) comprises the crosslinking of the membrane obtained in process step c) while obtaining a solid electrolyte.
  • the membrane can be crosslinked by changing the ambient conditions, which stimulate the initiator to form radials.
  • the membrane can be exposed to higher temperatures in a heating cabinet.
  • the crosslinked membrane can be dried by a further temperature treatment under normal pressure or in a vacuum in order to remove any traces of water.
  • the method according to the invention can contribute to the production of solid electrolytes for particularly long-lived batteries with reproducible charging / discharging kinetics.
  • the batteries show a larger temperature window in which particularly advantageous electrical properties can be achieved. In particular, this temperature window is shifted towards lower temperatures.
  • the polymerization initiator can be incorporated in process step b) instead of in process step a).
  • the polymerization initiator can also be incorporated into the mixture in process step b). This can lead to an undesirable reaction from the initia- counteract tors in process step a) and shift the temperature window of processing to higher temperatures.
  • a polymeric solid electrolyte which was produced according to the method according to the invention.
  • a solvent-free manufacture can provide a modified proportion of amorphous areas, which can result in improved conductivity or a longer service life of the batteries equipped with the polymeric solid electrolyte according to the invention.
  • an alkali metal battery having an anode, a cathode and a solid electrolyte arranged between anode and cathode, the solid electrolyte being a solid electrolyte according to the invention.
  • the alkali metal batteries according to the invention reference is made explicitly to the advantages of the method according to the invention and the polymeric solid electrolyte according to the invention.
  • the batteries can generally also have other layers.
  • the electrode layer includes, for example, active materials such as LiNi x Mn y Co z 02 (NMC), LiCoCh (LCO), LiFeP04 (LFP) or LNi x Mn y 04 (LNMO).
  • active materials such as LiNi x Mn y Co z 02 (NMC), LiCoCh (LCO), LiFeP04 (LFP) or LNi x Mn y 04 (LNMO).
  • the positive electrode can also bind, electronically conductive material to increase the electronic conductivity, e.g. B.
  • acetylene black, carbon black, graphite, carbon fiber and carbon nanotubes, and electrolyte material, in particular a polymer or solid electrolyte, to increase the ionic conductivity, as well as other Ad ditives include.
  • Materials for an all-solid-state lithium battery can be used as the negative electrode of the alkali metal battery in an embodiment as a Li-metal battery.
  • the electrode layer can comprise an active material suitable for a negative electrode, for example a transition metal composite oxide, amorphous carbon or graphite.
  • the negative electrode can also contain binders, e.g. B.
  • PVDF polyvinylidene fluoride
  • PEG polyethylene glycol
  • alginates in conjunction with finely divided silicon, as well as electronically conductive material to increase the electronic conductivity, and electrolyte material, in particular a polymer or solid electrolyte, to increase the ionic conductivity, and other additives.
  • electrolyte material in particular a polymer or solid electrolyte, to increase the ionic conductivity, and other additives.
  • pure lithium for example in the form of a Li foil, or alloys of lithium with indium or gold, zinc, magnesium or aluminum can also be used as the negative electrode.
  • Further suitable negative electrodes for all-solid-state lithium-ion batteries are, for example, graphite electrodes, silicon-based electrodes, silicon-carbon composites, titanium oxides or lithium metal electrodes.
  • the battery can be a Li-metal battery and the battery can have at least one high-current or high-voltage electrode. Due to the improved mechanical and electrical properties of the solid electrolyte, the solid electrolytes according to the invention are particularly suitable for the above-mentioned electrically highly demanding applications.
  • High-current electrodes are electrodes which can provide a specific capacity of over 100 mAh g 1 with a charging time of less than or equal to 15 hours. High-voltage electrodes can provide an end-of-charge voltage of> 4V.
  • the solid electrolyte according to the invention can be used in electrochemical devices. In addition to primary and secondary batteries, electrochemical devices can also include fuel cells or capacitors. Furthermore, the solid electrolyte according to the invention can be used in electrochemical devices can be used as a layer to improve the electrical contact (“wetting”) of electrodes.
  • Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI, 0.878 g) is dissolved in aceto nitrile (6 g) together with PEGdMA (0.450 g) and the radical starter azoisobutyronitrile (AIBN, 0.047 g, 2% by weight).
  • the solution is added to a vessel with polyethylene oxide (PEO, 1 g, 300 kg / mol) and stirred for four hours at room temperature.
  • the mixture is applied to a Mylar plastic film using a doctor blade method.
  • the membrane is dried in a laboratory hood for at least half an hour.
  • the film is polymerized at 80 ° C. under a stream of nitrogen for 1 hour and then dried in vacuo for at least 12 hours.
  • a wet layer thickness of approximately 1.5 mm is necessary.
  • the conductive salt LiTFSI (0.878 g) is stirred together with PEGdMA (0.450 g) and the radical starter AIBN (0.047 g, 2% by weight) for 1 hour until a clear solution is formed.
  • the solution is distributed over the PEO powder (1 g, 300 kg / mol) and mixed by means of a magnetic stirrer at 1000 rpm for 10 min. The components clump together.
  • the mixture is placed between two Mylar foils with a 100 ⁇ m spacer and repeatedly pressed and folded together for half an hour using a laboratory press with a force of 25 kN. The mixture is then pressed to the desired film thickness and polymerized between Mylar films at 80 ° C under a stream of nitrogen for 1 hour.
  • the membrane can then be dried in vacuo for 12 hours.
  • the conductive salt LiTFSI (0.878 g) is placed in a mortar together with PEO powder (1 g, 300 kg / mol) and homogenized for 10 min.
  • the resulting chewing gum-like material is shrink-wrapped in a pouch bag and stored at 60 ° C. for two days.
  • a solution of PEGdMA (0.450 g) and the radical starter AIBN (0.047 g, 2% by weight) is prepared with stirring for 1 hour.
  • the solution is vacuum-welded together with the previously produced PEO-LiTFSI material in a pouch bag and stored for 24 hours.
  • the mixture is placed between two Mylar foils with a 100 ⁇ m spacer and repeatedly pressed and folded using a laboratory press for half an hour.
  • the mixture is then pressed to the desired film thickness and polymerized between Mylar films at 80 ° C. under a stream of nitrogen for 1 hour.
  • the membrane can then be dried in vacuo for 12 hours.
  • the conductive salt LiTFSI (0.878 g) is placed in a mortar together with PEO powder (1 g, 300 kg / mol) and homogenized for 10 min.
  • the solution is also placed in the mortar and homogenized for at least 10 minutes.
  • the mixture is placed between two Mylar films with a 100 ⁇ m spacer and repeatedly pressed and folded using a laboratory press for half an hour. The mixture is then pressed to the desired film thickness and polymerized between Mylar films at 80 ° C. under a stream of nitrogen for 1 hour.
  • the measurements on battery types according to the invention were carried out on solid electrolytes which were produced by means of a solvent process.
  • the electrical properties of solid electrolytes according to the invention, which were produced by a solvent-free process, can have higher amorphous proportions.
  • a round piece of polymer film with a layer thickness of 100 ⁇ m is punched out and, like a separator, inserted between a lithium metal electrode and a positive electrode.
  • the electrical properties of lithium metal battery cells produced in this way were tested at different temperatures (60 ° C, 40 ° C).
  • FIGS. 1 and 2 show the normalized specific capacity of lithium metal battery cells according to the invention and not according to the invention as a function of the charge / discharge cycles. The normalization takes place on a theoretical capacity of 176 mAh / g.
  • the battery structure is as follows: positive electrode: NMC622; Negative electrode: Li; Charging current (3x each): 7.5 mA g 1 , 15 mA g 1 , 30 mA g 1 , 75 mA g 1 , 150 mA g 1 , 300 mA g 1 , 750 mA g 1 , 7.5 mA g voltage range 3 , 0-4.3 V, solid electrolyte as indicated with an EO: Li ratio of 15: 1; Temperature 60 ° C.
  • Figure 1 gives the mean capacity and the standard deviation of batteries with a pure PEO solid electrolyte and Figure 2 shows the mean capacity and the standard deviations of batteries with a PEO / PEGdMA solid electrolyte (PEGdMA 45 wt .-% based on PEO) again. They are the mean values and the standard deviation of Measurements on 5 different battery cells shown.
  • FIGS. 1 and 2 it becomes clear that the standard deviations for the specific capacity of the batteries according to the invention are significantly smaller compared to the batteries with pure PEO solid electrolytes. This suggests a more reproducible charging / discharging process for the batteries according to the invention.
  • the mechanical structure of the solid electrolytes according to the invention are probably less disturbed by the storage / removal processes of the metal ions than the structure of pure PEO solid electrolytes.
  • the increased electrical stability of the solid electrolytes according to the invention can be attributed to a reduced dendrite growth during the charging / discharging processes in the mechanically stabilized solid electrolytes according to the invention.
  • FIG. 3 shows the normalized specific capacity of a solid electrolyte according to the invention (PEO / PEGdMA) and a solid electrolyte not according to the invention (PEO).
  • the specifications of the experimental setup are as follows: Cell type: 2032 button cell, electrode: NMC 622 (Targray) Li (Albemarle); Electrolytes as indicated; EO: Li ratio: 15: 1; Test procedure: lx C / 20, 100x C / 10; Voltage range: 3.0 - 4.3 V; Temperature: 60 ° C; Active mass ⁇ 4 mg.
  • FIG. 4 shows the normalized specific capacity of a battery with a solid electrolyte according to the invention at 40 ° C. (triangles) and 60 ° C. (circles) as a function of the charge / discharge cycles. It can be seen from the course of the specific capacitance that the solid electrolyte according to the invention has a very good stability, especially at low temperatures, and the capacitance only drops to a very small extent.
  • FIG. 5 shows a DSC thermogram (temperature range -100 ° C.-100 ° C., 10 K / min) on solid electrolytes according to the invention (45% by weight PEGdMA) with different EO: Li ratios.
  • the crystalline content of the solid electrolyte can be suppressed by increasing the Li salt concentration to 10: 1 in the solid electrolyte. Accordingly, a highly amorphous solid electrolyte with improved electrical properties is obtained.
  • FIG. 6 shows the conductivity of solid electrolytes according to the invention (45% by weight PEGd MA) as a function of the EO: Li ratio and as a function of temperature.
  • the equipment structure is as follows: EIS; Frequency range: 1 MHz - 1 Hz; Temperature range 0 ° C - 70 ° C; Cell: 2032 button cell; Sample height: 100 pm; Sample diameter: 15 mm (circle); Blocking electrodes: stainless steel.
  • the batteries according to the invention with the solid electrolytes according to the invention have an ionic conductivity comparable to 60 ° C. at 40.degree. C. and an EO: Li ratio of 1:10.
  • the low-temperature behavior of the solid electrolytes according to the invention is thus significantly better than the electrical behavior of pure PEO solid electrolytes. Ulf. Use of two different Li-conductive salts
  • Figure 7 shows the voltage behavior of a battery with solid electrolytes according to the invention (45 wt .-% PEGdMA) over time as a function of the number of different Li conductive salts in an arrangement of NMC622 // PEO + PEGdMA // Li at 60 ° C with a specific charging current of 15 mA g 1 . It can be seen from the figure that the use of two Li salts (LiTFSI with LiFTFSI) results in an improved voltage increase over time compared to solid electrolytes with only one conductive salt (LiTFSI).
  • FIG. 8 shows the battery voltage using different anodes as a function of time.
  • An arrangement made of NMC622 // PEO + PEGdMA // graphite was used in FIG. 8 and an arrangement made of NMC622 // PEO + PEGdMA // LTO was used in FIG. It can be seen from the plots that error-free operation of cells is possible using NMC622 and a negative electrode other than metallic lithium.
  • FIGS. 10 and 11 show the electrical properties of batteries with a sIPN made from polycaprolactone and PEGdMA (45% by weight based on PCL) in an arrangement made from NMC622 // polycaprolactone + PEGdMA // Li at 60.degree.
  • FIG. 10 shows the voltage as a function of the specific capacity
  • FIG. 11 shows the voltage profile as a function of time at a specific charging current of 15 mA g 1 . It can be seen from the figures that stable and electrically suitable solid electrolytes, which are suitable for use in batteries, also result with PCL as a component of the sIPN.

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Abstract

La présente invention concerne un électrolyte solide sans solvant pour une batterie solide à métal alcalin comprenant un sel conducteur de métal alcalin et un réseau semi-interpénétrant (sIPN) consistant en un polymère réticulé et un polymère non réticulé, le réseau semi-interpénétrant étant constitué d'un polymère non réticulé choisi dans le groupe constitué d'oxyde de polyéthylène (PEO), de polycarbonate (PC), de polycaprolactone (PCL), de dérivés modifiés en bout de chaîne desdits polymères ou de mélanges d'au moins deux composants de ceux-ci et le polymère réticulé comprenant du diméthacrylate de polyéthylène glycol (PEG-dMA). L'invention concerne en outre un procédé de fabrication d'un électrolyte solide et une batterie à métal alcalin comprenant l'électrolyte solide selon l'invention.
EP20792348.3A 2019-10-14 2020-10-12 Réseaux polymères semi-interpénétrants en tant que séparateurs destinés à être utilisés dans des batteries à métal alcalin Pending EP4046222A1 (fr)

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DE102019127616.0A DE102019127616A1 (de) 2019-10-14 2019-10-14 Semi-interpenetrierende Polymernetzwerke als Separatoren für den Einsatz in Alkali-Metall-Batterien
PCT/EP2020/078606 WO2021074074A1 (fr) 2019-10-14 2020-10-12 Réseaux polymères semi-interpénétrants en tant que séparateurs destinés à être utilisés dans des batteries à métal alcalin

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JP2023502319A (ja) 2023-01-24
DE102019127616A1 (de) 2021-04-15

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