Patent Application
20250210706
This application claims priority to European Patent Application No. 23219803.6 filed Dec. 22, 2023, the entire contents of which are incorporated herein by reference.
The present invention relates to a polymer electrolyte, in particular a solid state electrolyte. The present invention further relates to battery cells comprising the polymer electrolyte and to methods of producing the polymer electrolyte.
The importance of batteries and other energy storage devices is growing rapidly. The rise of e-mobility, in particular electronically driven automobiles and e-scooters, requires batteries with high capacity and a reasonable weight.
Current research in battery technology evolves around new materials to improve the safety of batteries as well as increasing and optimizing the volumetric energy density and the gravimetric energy density.
Conventional liquid electrolytes, such as for lithium batteries, are based on mixture of organic solvents and lithium salts. These electrolytes have high ionic conductivity and are electrochemically stable inside the voltage window of the battery. However, such liquid electrolytes are highly flammable, volatile and can leak outside the battery casing. These disadvantages can lead to a critical failure of the battery, fire and explosions.
Recently, in order to improve the safety of alkali metal batteries and alkaline earth metal batteries, solid electrolytes, polymer electrolytes (e.g. gel (polymer) electrolytes) and ionic liquid electrolytes, have been developed.
Gel polymer electrolytes are systems in which a liquid electrolyte is encapsulated and impregnated in a, typically chemically, cross-linked polymer structure. This type of electrolytes provides a relatively high ion conductivity at a reasonable price, and also have a high structural, thermal, and mechanical stability over time. However, the ion conductivity is still lower than that of liquid electrolytes, because the cross-linked polymer structure tends to hinder the movement of the metal ions, e.g. lithium ions for lithium ion batteries.
WO2022/055307 discloses a gel polymer electrolyte for lithium secondary batteries, obtained from a precursor composition comprising two cross-linking agents, one thereof comprising at least two thiol functional groups, a lithium salt and a small amount of an organic solvent.
US2023096123 discloses a solid polymer electrolyte comprising a cross-linked polymer network. The cross-linked polymer network comprises cross-linked groups, such as difunctional polyether groups and/or difunctional ionic groups, and cross-linked multifunctional crosslinker groups, and at least one cross-linking group comprising a thioether group. For the solid polymer electrolyte to be conductive, it must further comprise a dual-ion conductive salt (e.g. a metal salt), tethered ionic groups, and/or a liquid electrolyte.
A disadvantage of the foregoing electrolyte is that the polyether groups are unstable at a high voltage (e.g. 4 V and above). A further disadvantage is the risk of polarization in the battery cell comprising these electrolytes, due to the use of a dual-ion conducting salt and ascribed to a low lithium transference number of the electrolyte. Polarization, as is known, reduces the power density of the battery cell, thereby limiting the current value that can be used for charging and discharging the battery cell. In other words, polarization in a battery cell leads to battery cells having a performance that decreases rapidly with each charging and discharging cycle.
It is an aim of the present invention to overcome one or more of the foregoing drawbacks. It is an aim of the present invention to provide a polymer electrolyte having a high ionic conductivity, in particular to lithium ions. A further aim is to provide a polymer electrolyte having a high structural, electrochemical, thermal and mechanical stability over time. A further aim is to provide a polymer electrolyte which is substantially free from any processing solvent. A further aim is to provide a polymer electrolyte for a battery cell which reduces the risk of polarizations in the battery cell, thereby improving the current value that can be used with the battery cell, as well as providing a battery cell having a longer lifetime at high performance (i.e. the reduction of performance is significantly reduced to even avoided), in particular upon repeated charging/discharging cycles.
It is a further aim to provide methods of producing such a polymer electrolyte with high ionic conductivity, high voltage stability up to at least 4 V, and thermal and mechanical stability.
According to a first aspect of the present disclosure, there is provided a polymer electrolyte for a battery cell as set out in the appended claims. The polymer electrolyte comprises or substantially consists of a first polymaleimide polymer and a second polymaleimide polymer. The first polymaleimide polymer comprises or substantially consists of first polymaleimide repeat units. The second polymaleimide polymer comprises or substantially consists of second polymaleimide repeat units.
The first polymaleimide repeat units are according to R3(Q)μ. μ, individually, is at least 2, preferably between 2 and 4. Q, individually, is according to formula (I):
Advantageously, R2 is methyl, ethyl, propyl, n-butyl, iso-butyl, benzyl or styryl.
Advantageously, R4 is H, methyl, ethyl or propyl.
R3, individually, is C(H)h(CxH2x+1)i((CH2)ψ)j(CH2OC(O)(CH2)σ)k or a polyether, wherein i is between 0 and 2; j and k, individually, are between 0 and 4; h is 4-i-j-k; the sum of h and i is between 0 and 2; x is between 1 and 6; ψ is between 1 and 10; and σ is between 1 and 20.
Advantageously, when R3 is a polyether, the polyether is according to wherein ω is between 0 and 4,
is between 1 and 4, and α is between 1 and 10, preferably between 1 and 5.
Alternatively, yet advantageously, R3 is —(CH2)β—, wherein β is between 1 and 20 (i.e. h is 2, i is 0, j is 2, k is 0). Yet alternatively and advantageously, R3 is C(CH2CH3)(CH2OC(O)(CH2)σ)3— (i.e. h is 0, i is 1, j is 0 and k is 3). Yet alternatively and advantageously, R3 is C(CH2OC(O)(CH2)σ)4— (i.e. h is 0, i is 0, j is 0 and k is 4).
The second polymaleimide repeat units are according to formula (II):
Advantageously, R1 is H, methyl, ethyl or propyl.
Advantageously, X is CF3, CH3 or F.
Advantageously, the alkali metal is lithium, sodium or potassium, preferably lithium. In other words, the alkali metal ion advantageously is a lithium ion (Li+), a sodium ion (Na+), or a potassium ion (K+), preferably a lithium ion.
Advantageously, the molar ratio of the first polymaleimide polymer to the second polymaleimide polymer is between 5 and 95, preferably between 10 and 75, more preferably between 20 and 50, based on the total mol of each polymer in the polymer electrolyte. The inventors have discovered that when the molar ratio of the first polymaleimide polymer to the second polymaleimide polymer is between 5 and 95, the polymer electrolyte has an excellent ionic conductivity in combination with optimal mechanical properties.
The polymer electrolyte can further comprise a plasticizing agent. Advantageously, the polymer electrolyte comprises between 0% and 90% by weight of a plasticizing agent, preferably between 0% and 80%, based on the total weight of the polymer electrolyte. Advantageously, when the polymer electrolyte comprises a plasticizing agent, it comprises between 0.5% and 90% by weight of the plasticizing agent, such as between 5% and 85% by weight, preferably between 10% and 85% by weight, for example between 20% and 80% by weight, more preferably between 45% and 60% by weight, based on the total weight of the polymer electrolyte.
Advantageously, the plasticizing agent is selected from the group consisting of linear carbonates, cyclic carbonates, ethers, and nitriles. Preferably, the plasticizing agent is a linear carbonate or a cyclic carbonate. Particularly preferred examples of the plasticizing agent are propylene carbonate and ethylene carbonate. The polymer electrolyte can comprise two or more plasticizing agents, which are individually selected from the group consisting of linear carbonates, cyclic carbonates, ethers, and nitriles.
According to a second aspect of the present disclosure, there is provided a battery cell as set out in the appended claims.
The battery cell comprises the polymer electrolyte according to the first aspect of the present disclosure. Advantageously, the battery cell is a secondary battery cell. Advantageously, the battery cell is a lithium metal battery cell.
According to a third aspect of the present disclosure, there is provided a method for producing a polymer electrolyte for a battery cell as set out in the appended claims. The polymer electrolyte comprises or substantially consists of a first polymaleimide polymer and a second polymaleimide polymer. Advantageously, the polymer electrolyte produced by the methods of the third aspect of the present disclosure is a polymer electrolyte according to the first aspect of the present disclosure.
The method comprises a step of preparing a compound comprising a third polymaleimide polymer comprising or substantially consisting of third polymaleimide repeat units, a second polymaleimide polymer comprising or substantially consisting of second polymaleimide repeat units, a free radical initiator and a thiol-ene reaction agent.
The third polymaleimide repeat units are according to formula (III):
The second polymaleimide repeat units are according to formula (II).
The thiol-ene reaction agent comprises thiol groups. The number of thiol groups, q, is at least two, such as two, three, four or more.
With a “thiol group” is meant in the present disclosure a functional group —SH, i.e. a sulphur atom covalently bond to a hydrogen atom.
The number of third polymaleimide repeating units, n, the number of thiol groups, q, and the number of thiol-ene reaction agent molecules, a, are selected so that
preferably
more preferably
such as about 1.
Optionally, the compound further comprises a processing solvent. The term “processing solvent” is used in the present disclosure for solvents that are used during the manufacturing of the polymer electrolyte but are not present therein. Advantageously, the optional processing solvent comprises or substantially consists of acetone, dimethylformamide, dimethyl sulfoxide, N-Methyl-2-pyrrolidone, or a combination of two or more thereof.
The inventors have surprisingly discovered that the compound allows handling thereof, such as application to a substrate, without the need for a processing solvent to obtain a favourable viscosity and handling characteristics, thereby rendering the presence of a processing solvent in the compound surprisingly optional.
Optionally, the compound further comprises a plasticizing agent. The optional plasticizing agent is as described hereinabove. Advantageously, the compound comprises between 0.5% and 90% by weight of the plasticizing agent, such as between 5% and 85% by weight, between 10% and 85% by weight, preferably between 20% and 80% by weight, such as between 45% and 60% by weight, based on the total weight of the compound minus the weight of the optional processing solvent.
In the present disclosure, the term “the total weight of the compound minus the weight of the optional processing solvent” is used for the weight of the compound as such when the compound does not comprise a processing solvent, and for the weight of the compound without taking into account the weight of the processing solvent when the compound comprises a processing solvent.
Advantageously, the free radical initiator is capable of initiating a thiol-ene reaction between the third polymaleimide repeat units and the thiol-ene reaction agent. Advantageously, upon initiation, sulphur-carbon covalent bonds are formed between the third polymaleimide repeat unit and the thiol-ene reaction agent, leading to a thio-ether linkage.
Advantageously, the compound comprises between 0.05% and 1.5% by weight of the free radical initiator, preferably between 0.075% and 1.4% by weight, more preferably between 0.1% and 1.25% by weight, based on the total weight of the compound minus the weight of the optional processing solvent.
Advantageously, the compound comprises between 0% and 95% by weight of the processing solvent, such as between 1% and 95% by weight, between 5% and 92.5% by weight, preferably between 10% and 90% by weight, more preferably between 20% and 90% by weight, such as between 50% and 90% by weight, based on the total weight of the compound including the weight of the processing solvent.
In the present disclosure, the term “total weight of the compound including the weight of the processing solvent” is used for the weight of the compound as such when the compound does not comprise a processing solvent (0% by weight of processing solvent in the compound), and for the weight of all components of the compound, including the processing solvent, when the compound comprises a processing solvent.
Advantageously, the compound comprises between 3% and 45% by weight of the third polymaleimide polymer and the thiol-ene reaction agent combined, preferably between 10% and 40% by weight, based on the total weight of the compound minus the weight of the optional processing solvent.
Advantageously, the compound comprises between 5% and 95% by weight of the second polymaleimide polymer, preferably between 40% and 90% by weight, based on the total weight of the compound minus the weight of the optional processing solvent.
Advantageously, when the compound comprises a plasticizing agent, it comprises between 30% and 80% by weight of plasticizing agent, between 3% and 45% by weight of the third polymaleimide polymer and the thiol-ene reaction agent combined, between 1% and 45% by weight of the second polymaleimide polymer, between 0.05% and 1.5% by weight of the free radical initiator, based on the total weight of the compound minus the weight of the optional processing solvent.
More preferably, when the compound comprises a plasticizing agent, it comprises between 45% and 75% by weight of plasticizing agent, between 5% and 40% by weight of the third polymaleimide polymer and the thiol-ene reaction agent combined, between 2% and 40% by weight of the second polymaleimide polymer, between 0.1% and 1.25% by weight of the free radical initiator, based on the total weight of the compound minus the weight of the optional processing solvent.
The method further comprises applying the compound to a substrate. The substrate can be any substrate, such as a Teflon sheet or glass, and can also be the anode or the cathode of a battery cell. The application of the compound to the substrate can be done by means known in the art, for example, without being limited thereto, casting, pressing, which can be hot pressing or cold pressing, and application without applying any pressure, such as by means of a spatula. Advantageously, upon applying the compound to the substrate, a film of compound is obtained.
When the compound comprises a processing solvent, the method further comprises removal of thereof, thereby obtaining a substantially processing solvent-free compound.
The method further comprises exposing the (substantially processing solvent-free) compound to one or more of UV radiation, IR radiation or a temperature up to 100° C. Upon exposure to one or more of UV radiation, IR radiation or a temperature up to 100° C., a thiol-ene reaction of the (substantially processing solvent-free) compound, in particular of the thiol-ene reaction agent and the third polymaleimide repeat units, is initiated, thereby obtaining the polymer electrolyte with a thio-ether linkage, i.e. a sulphur-carbon covalent bond.
Advantageously, the thiol-ene reaction allows cross-linking of the compound, in particular of the third polymaleimide repeat units, thereby obtaining the polymer electrolyte with a thio-ether linkage. In particular, a film or sheet of polymer electrolyte is obtained on the substrate.
Advantages of the methods of the invention include the possibility to reduce or eliminate the use of a processing solvent, which renders the methods more environmentally friendly.
Advantages of the presence of the second polymaleimide repeat units and the optional plasticizing agent in the polymer electrolyte of the present disclosure include a high ionic conductivity and a high stability over time. Advantages of the presence of the first polymaleimide repeat units in the polymer electrolyte of the present disclosure include a high thermal, structural and mechanical stability over time. Advantages of the polymer electrolyte of the present disclosure in general is the capability to resist high voltages, allowing the use in combination with active materials operating at high voltages.
Advantages of the battery cells of the invention, i.e. battery cells comprising the polymer electrolyte of the invention, include a high ionic conductivity, and an excellent resistance against repeated charging/discharging, thereby having an excellent lifetime.
Aspects of the invention will now be described in more detail with reference to the appended drawings, wherein same reference numerals illustrate same features and wherein:
The polymer electrolyte comprises or substantially consists of a first polymaleimide polymer, a second polymaleimide polymer, and optionally a plasticizing agent. The first polymaleimide polymer advantageously comprises or substantially consists of first polymaleimide repeat units. The second polymaleimide polymer advantageously comprises or substantially consists of second polymaleimide repeat units.
The first polymaleimide repeat units are according to R3(Q)μ.
μ, individually, is at least 2, preferably between 2 and 4.
Q, individually, is according to formula (I):
Advantageously, R2, individually, is C1-C16 alkyl, preferably C1-C10 alkyl, more preferably C1-C8 alkyl, most preferably C1-C6 alkyl, such as methyl, ethyl, propyl and butyl. R2 can be linear or branched.
Alternatively or additionally, yet advantageously, R2, individually, is C2-C16 alkenyl, comprising one or more C═C bonds, preferably C2-C10 alkenyl, more preferably C2-C8 alkenyl, most preferably C2-C6 alkenyl. R2 can be linear or branched.
Alternatively or additionally, yet advantageously, R2, individually, is C2-C16 alkynyl, comprising one or more C≡C bonds, preferably C2-C10 alkynyl, more preferably C2-C8 alkynyl, most preferably C2-C6 alkynyl. R2 can be linear or branched.
Alternatively or additionally, yet advantageously, R2, individually, is aryl, such as benzyl or phenyl.
Advantageously, R4 is H, C1-C16 alkyl, C2-C16 alkenyl or C2-C16 alkynyl, preferably H, C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl, most preferably H, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl. The alkyl, alkenyl and alkynyl can each be linear or branched.
A preferred example of the Q is
wherein R4 is H.
Advantageously, Q is covalently bound to R3 via the sulphur atom of Q.
Advantageously, R3, individually, is a polyether. With “individually” is meant that the first polymaleimide repeat units can be different from one another, by comprising, for example, a different R3. Advantageously, R3 is a polyether according to , wherein ω is between 0 and 6, preferably between 0 and 4, more preferably between 1 and 4,
is between 1 and 4, preferably between 1 and 3, such as 2, and α is between 1 and 10, preferably between 1 and 5, more preferably between 2 and 4.
For example, R3 is —(CH2)2(O(CH2)2)α—, (i.e. ω is 2, is 2), such as —(CH2)2(O(CH2)2)2— (i.e. α is 2) or —(CH2)2(O(CH2)2)3— (i.e. a is 3).
Alternatively or additionally, yet advantageously, R3, individually, is according to C(H)h(CxH2x+1)i((CH2)ψ)j(CH2OC(O)(CH2)σ)k. Advantageously, x is between 1 and 6, preferably between 1 and 4, more preferably 1 or 2. Advantageously, ψ is between 1 and 10, preferably between 1 and 8, more preferably between 1 and 6, such as between 1 and 4. Advantageously, σ is between 1 and 20, preferably between 1 and 10, such as between 1 and 6, more preferably between 1 and 4. Further, i is between 0 and 2, and j and k, individually, are between 0 and 4. Further, h is 4-i-j-k. The sum of h and i is between 0 and 2.
For example, R3 is —(CH2)β, wherein β is between 1 and 20 (i.e. h is 2, i is 0, j is 2, k is 0, and β equals 2*ψ+1).
For example, R3 is C(C2H5)(CH2OC(O)(CH2)σ)3— (i.e. h is 0, i is 1, j is 0, k is 3 and x is 2).
For example, R3 is C(CH2OC(O)(CH2)σ)4— (i.e. h is 0, i is 0, j is 0, k is 4 and x is 2).
The second polymaleimide units are according to formula (II)
Advantageously, R1 is H, C1-C16 alkyl, C2-C16 alkenyl or C2-C16 alkynyl, preferably H, C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl, more preferably H, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl. The alkyl, alkenyl and alkynyl can each be linear or branched.
Advantageously, X is H, F, C1-C16 alkyl, C1-C16 fluoroalkyl, preferably H, F, C1-C6 alkyl or C1-C6 fluoroalkyl, more preferably H, F, CH3 or CF3. The alkyl and fluoroalkyl can be linear or branched.
Advantageously, M+ is independently an alkali metal ion. Advantageously, the alkali metal is lithium, sodium or potassium. In other words, the alkali metal ion advantageously is a lithium ion (Li+), a sodium ion (Na+), or a potassium ion (K+).
Advantageously, m is between 1 and 5.
A preferred example of the second polymaleimide repeat unit is a repeat unit according to formula IV:
A non-limiting example of the first polymaleimide polymer is given by formula V:
Yet another non-limiting example of the polymer electrolyte is given by formula VI:
Yet another non-limiting example of the polymer electrolyte is given by formula VII:
The polymer electrolyte can further comprise a polymaleimide copolymer comprising or substantially consisting of first and second polymaleimide repeat units covalently bonded to one another, preferably by a carbon-carbon bond.
Advantageously, the polymer electrolyte is thermally stable up to at least 75° C., preferably up to at least 100° C., or up to temperatures up to at least 125° C.
Advantageously, the polymer electrolyte has an ionic conductivity at 70° C. of at least 0.25 mS/cm, preferably at least 0.3 mS/cm, more preferably at least 0.4 mS/cm.
Advantageously, the polymer electrolyte has an oxidation stability at 70° C. of at least 3 V, preferably at least 4 V.
Advantageously, the polymer electrolytes of the present invention are self-standing. The terms “self-standing” and “self-supporting” are used interchangeably to indicate a film, substrate, product or article that has sufficient mechanical strength to be manipulated, such as being cut, shaped or handled, without the need for a carrier or a support onto which the film is placed to avoid damage thereto.
The polymer electrolyte of the present disclosure is advantageously manufactured (i.e. produced or prepared) by methods of the present disclosure.
In a first step, a compound is prepared. The compound comprises a third polymaleimide polymer comprising third polymaleimide repeat units, a second polymaleimide polymer comprising second polymaleimide repeat units, a thiol-ene reaction agent and a free radical initiator.
Optionally, the compound further comprises a plasticizing agent. Optionally, the compound further comprises a processing solvent.
The third polymaleimide repeat unit has a pendant vinyl group and is according to Formula III:
Advantageously, the number of third polymaleimide repeat units, n, comprised in the third polymaleimide polymer is between 10 and 10000, preferably between 100 and 7500, more preferably between 500 and 4000.
Advantageously, the average number molecular weight of the third polymaleimide polymer is between 1 kDa and 1500 kDa, preferably between 15 kDa and 1000 kDa, more preferably between 75 kDa and 800 kDa.
The second polymaleimide repeat unit is according to Formula II. Advantageously, the number of second polymaleimide repeat units, p, comprised in the second polymaleimide polymer is between 10 and 10000, preferably between 100 and 7500, more preferably between 500 and 4000.
Advantageously, the average number molecular weight of the second polymaleimide polymer is between 3 kDa and 2000 kDa, preferably between 100 kDa and 1750 kDa, more preferably between 250 kDa and 1500 kDa.
A first example of the third polymaleimide polymer is given by formula VIII:
A second example of the third polymaleimide polymer is given by formula IX:
An example of the second polymaleimide polymer is given by formula XIV:
The thiol-ene reaction agent comprises thiol groups. The number of thiol groups, q, is at least two, such as two, three, four or more. Advantageously, the thiol-ene reaction agent is according to R3(SH)μ, wherein R3 and μ are as hereinabove described.
Non-limiting examples of the thiol-ene reaction agent include, without being limited thereto, compounds according to Formulas X (q=2), XI (q=2), XII (q=3) and XIII (q=4):
A preferred example of a free radical initiator is 2-Hydroxy-2-methylpropiophenone.
The inventors have found that the presence of a processing solvent in the compound is optional. Advantages of the processing solvent being optional is a reduced cost of the compound and the polymer electrolyte, a less complex process of producing the polymer electrolyte (i.e. less processing steps), no need for further (processing) solvent recuperation and recycling, and a reduced environmental impact.
However, depending on the exact composition of the compound, a processing solvent can be added to optimize its properties in view of conversion into a polymer electrolyte. Whether a processing solvent is added to the compound, depends thus on the type and amount of third and second polymaleimide repeat units, the thiol-ene reaction agent, the free radical initiator and the optional plasticizing agent.
When the compound comprises a processing solvent, the latter advantageously comprises or substantially consists of acetone, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, or a combination of two or more thereof.
When the compound comprises a plasticizing agent (i.e. a plasticizer), the plasticizing agent is advantageously selected from the group consisting of linear carbonates, cyclic carbonates, ethers, and nitriles. Particularly preferred examples of the plasticizing agent are propylene carbonate and ethylene carbonate. The compound can comprise two or more plasticizing agents, which are individually selected from the group consisting of linear carbonates, cyclic carbonates, ethers, and nitriles.
Optionally, the compound further comprises a crosslinking agent. Non-limited examples of crosslinking agents include polyethylene glycol diacrylate (PEGDA), trimethylolpropane triacrylate (TMPTA), pentaerythritol tetraacrylate (PETA), butyl acrylate (BA).
Optionally, the compound further comprises a metal salt. Advantageously, when the compound comprises a metal salt, the metal advantageously is lithium, sodium, magnesium or aluminium.
Advantageously, the compound comprises between 0% and 10% by weight of the metal salt, such as between 0.1% and 7.5% by weight, preferably between 0.2% and 5% by weight, more preferably between 0.5% and 5% by weight, based on the total weight of the compound minus the weight of the optional processing solvent.
Advantageously, the compound is applied to a substrate, thereby obtaining a film of the compound. Advantageously, the film has a thickness between 10 μm and 1000 μm, preferably between 20 μm and 750 μm, more preferably between 25 μm and 500 μm, such as between 50 μm and 250 μm. It is to be understood that the thickness can be varied based on the targeted or required thickness of the polymer electrolyte. Advantageously, the targeted or required thickness is determined based on the required total cell resistance and the required mechanical properties, such as mechanical strength and flexibility.
Advantageously, when the compound comprises a processing solvent, the processing solvent is removed after applying the compound to a substrate and prior to exposing the (substantially processing solvent-free) compound to one or more of UV radiation, IR radiation or a temperature up to 100° C.
Advantageously, the processing solvent is removed by heating the substrate comprising the compound to a temperature between 20° C. and 100° C., preferably between 20° C. and 50° C.
Advantageously, when the compound comprises a plasticizing agent, the substrate is heated to a temperature below the maximum continuous service temperature of the plasticizing agent, as defined by the Underwriter Laboratory (UL 746B) Relative Thermal Index (RTI), preferably to a temperature between 20° C. and Tv−10° C., wherein Tv is the maximum continuous service temperature of the plasticizing agent as defined by the Underwriter Laboratory (UL 746B) Relative Thermal Index (RTI). By doing so, evaporation and/or removal of the plasticizing agent will be avoided.
Alternatively or additionally, and advantageously, the processing solvent is removed by exposing the substrate comprising the compound to an atmosphere at a pressure below atmospheric pressure.
Advantageously, when a pressure below atmospheric pressure is applied, the pressure is 975 mbar or less, preferably 950 mbar or less, more preferably 930 mbar or less, for example 900 mbar or less, 750 mbar or less, or 500 mbar or less.
It will be understood that the optimal temperature and/or pressure for evaporating the processing solvent depend(s) on the composition of the compound. In particular, when the compound comprises a plasticizing agent, the optimal conditions for evaporating the processing solvent depend on the plasticizing agent that is used, wherein the conditions are advantageously chosen to avoid evaporation or degradation of the plasticizing agent.
Preferably, the processing solvent is acetone. Acetone is particularly preferred because of its relatively low boiling point (i.e. 56° C. at atmospheric pressure) and its relatively high vapour pressure (i.e. 230 mm Hg at 25° C.). Its boiling point and vapour pressure allow removal thereof by heating to moderate temperatures, e.g. about 40° C. to 65° C. at atmospheric pressure, preferably 50° C. to 60° C. at atmospheric pressure, and/or at a pressure slightly below atmospheric pressure, e.g. about 950 mbar.
Advantageously, exposure of the (substantially processing solvent-free) compound to one or more of UV radiation, IR radiation or a temperature up to 100° C. initiates a thiol-ene reaction of the thiol-ene reaction agent and the third polymaleimide repeat units, thereby obtaining a first polymaleimide polymer comprising or substantially consisting of first polymaleimide repeat units according to formula I.
In other words, upon exposure to one or more of UV radiation, IR radiation or a temperature up to 100° C., the (substantially processing solvent-free) compound is converted in a polymer electrolyte, in particular the polymer electrolyte of the present disclosure, comprising a first and a second polymaleimide polymer as described hereinabove, i.e. a first polymaleimide polymer comprising the first polymaleimide repeat units of formula I and a second polymaleimide polymer comprising the second polymaleimide repeat units of formula II.
Nine compounds comprising the same components, but in different amounts, were prepared. Table 1 shows the % by weight of each component for all nine compounds. For all compounds,
was 1, wherein n is the number of third polymaleimide repeating units, q the number of thiol groups, and a the number of thiol-ene reaction agent molecules.
The compounds comprised a third polymaleimide polymer comprising the third polymaleimide repeat units according to formula III, wherein R2 was CH2 and R4 was H. The third polymaleimide polymer (“3rd” in Table 1) had an average number molecular weight between 100 kDa and 650 kDa.
The compounds comprised a second polymaleimide polymer (“2nd” in Table 1) comprising the second polymaleimide repeat units according to Formula II, wherein R1 was H, m was 2, M+ was Li+, X was CF3, and the average number molecular weight was between 250 kDa and 1500 kDa.
The thiol-ene reaction agent (“2SH” in Table 1) comprised 2 thiol groups and was according to Formula X, wherein α was 2 and the molecular weight is 182 Da.
The plasticizing agent (“PC” in Table 1) was propylene carbonate having a molecular weight of 102 Da, and the free radical initiator (“Ini” in Table 1) was 2-Hydroxy-2-methylpropiophenone having a molecular weight of 164 Da.
Acetone as processing solvent was added to the nine compounds of Table 1 in an amount so that the compounds comprised 86% by weight of acetone, based on the total weight of the compound including the weight of the acetone. The acetone-comprising compounds were then applied to a Teflon substrate by casting, more particularly solvent casting.
The acetone was removed by placing the Teflon substrates comprising the compounds in an argon box, thereby supplying a flow of argon at room temperature and at atmospheric pressure for 24 h to the substrates.
Next, the substantially solvent-free compounds were exposed to UV radiation, which incited a thiol-ene reaction, thereby leading to polymer electrolyte films having a thickness of 150-200 μm. The films were self-standing. In other words, they have sufficient mechanical strength to be manipulated without the further need of the Teflon substrate as supporting material (see
Four reference polymer electrolytes were prepared as well.
The first reference electrolyte was prepared from a compound comprising the second polymaleimide polymer and the plasticizing agent of the 9 inventive compounds, as well as polyethylene glycol diacrylate (PEGDA, number average molecular weight 700 g/mol) as crosslinking agent, and a polyvinylidenedifluoride-hexafluoropropylene copolymer (PVdF-HFP) as mechanical support. The reference compound was then polymerized by means of radical polymerization. The resulting polymer electrolyte comprised 7.3% by weight of the second polymaleimide polymer, 5% by weight of the PVdF-HFP copolymer, 17.6% by weight of PEGDA, and 70.1% by weight of plasticizing agent, based on the total weight of the electrolyte.
Three further reference electrolytes comprised the second polymaleimide polymer and polyethylene glycol dimethyl ether—MW 500 (PEGDME) as plasticizer in a 5M polyethylene oxide (PEO) powder in acetonitrile solution. All three had a ratio of ethylene oxide units to lithium ions of 20, and a weight ratio of PEO to PEGDME of 20/80, 30/70 and 40/60, respectively.
The ionic conductivity of the nine polymer electrolytes according to the present invention, as well as of the four reference polymer electrolytes (all as prepared in Example 1) and of 100% polyethylene oxide (PEO) as benchmark was measured by alternating current (AC) impedance spectroscopy using a BT lab potentiostat (Bio-Logic Science Instruments). The measurements were performed in the frequency range from 10 kHz to 0.1 Hz at a temperature varying between 25° C. and 70° C. The ionic conductivity is a measure for the suitability of the polymer electrolyte to be used in a battery cell.
From
All nine inventive electrolytes (
The lithium transference number and the lithium conductivity were measured for the polymer electrolytes obtained from compounds Nos. 2, 3 and 5 of Table 1 and Example 1, as well as for the four reference polymer electrolytes. The Li transference number was measured by a combined measurement of AC impedance and DC polarization method described in “Electrochemical measurement of transference numbers in polymer electrolytes”, Evans et al., Polymer Volume 28, Issue 13 (1987), 2324-2328. A lithium symmetric cell was used to this end, having as electrolyte the polymer electrolytes. The temperature of the cell was controlled by a temperature chamber at 70° C. The lithium transference number was calculated by the Equation 1
The Li conductivity was calculated by multiplying the total ionic conductivity of the electrolytes and the lithium transference number. The lithium transference number is defined as the ratio of the electric current derived from the lithium cation of the polymer electrolyte to the total electric current. A lithium transference number close to 1 implies that the ion conducting performance in the polymer electrolyte is mainly accomplished by the lithium cation. Table 2 gives the calculated lithium transference number for the three polymer electrolytes that were tested.
It follows from Table 2 that the three polymer electrolytes according to the invention and the reference electrolytes show a high lithium transference number, for values of at least 0.5 are considered high in the technical field.
The lithium conductivity is a measure for the conductivity realised by the lithium cation. In other words, a higher lithium transference number implies a smaller difference between the ionic conductivity (measured in Example 2) and the lithium conductivity.
The electrochemical anodic stability was tested by means of a linear sweep voltammetry in a VMP3 potentiostat at 70° C. A two-electrode set-up was used, using a lithium foil as reference electrode and counter electrode. To this end, CR2032 type coin cells were prepared, having a lithium foil as reference and counter electrode and stainless steel as working electrode. The polymer electrolytes used in the coin cells were the electrolytes obtained from compounds Nos. 3 and 5, as well as reference electrolyte 1 and reference electrolyte 4 (40/60) of Example 1. All other components of a CR2032 type coin cell were as typically used in the field. The coin cells were assembled in an argon glovebox.
The linear sweep voltammetry was carried out from the open circuit voltage (OCV) up to 6.0 V vs. Li+/Li at a scan rate of 1 mV/s.
The electrochemical cathodic stability of the polymer electrolytes obtained in example 1 was tested by means of cyclic voltammetry at 70° C. To this end, two CR2032 type coin cells were prepared, each having a lithium foil as reference and counter electrode and a copper foil as working electrode. As electrolyte, the polymer electrolyte obtained from compounds Nos. 3 and 5 was used (one electrolyte per coin cell). All other components of a CR2032 type coin cell were as typically used. The coin cells were assembled in an argon glovebox.
The cyclic voltammetry comprised six scans in the voltage range between 3.00 V and −0.05 V vs. Li+/Li at a scan rate of 1 mV/s.
A critical current density test was also performed, using a VMP3 potentiostat. To this end, two CR2032 type coin cells were prepared, each having a lithium foil as cathode and as anode (i.e. symmetrical coin cells). As electrolyte, the polymer electrolyte obtained from compounds Nos. 3 and 5 was used (one electrolyte per coin cell). All other components of a CR2032 type coin cell were as typically used. The coin cells were assembled in an argon glovebox.
The critical current density test was performed by galvanostatically cycling the coin cells with a variable current density from 0.1 mA/cm2 to 5 mA/cm2, while keeping the total capacity constant at 0.2 mAh/cm2.
Further CR2032 type symmetrical coin cells with the polymer electrolyte obtained from compounds Nos. 3 and 5 (one electrolyte per coin cell) were tested by repeated charging/discharging (cyclic testing) at a constant current density of 0.61 mA/cm2 at 70° C., while keeping the total capacity constant at 0.2 mAh/cm2. Two different types of lithium foils were used, referred to as A and B. Type A was a raw lithium metal foil of 500 μm thick. Type B was a 50 μm thick layer of lithium metal casted on top of a copper foil.
A first lithium metal battery cell was assembled using the polymer electrolyte obtained in Example 1 from compound No. 3. The cathode comprised 80% by weight of LiFePO4 (LFP), 10% of weight of the second polymaleimide polymer of Example 1, and 10% by weight of carbon black, based on the total weight of the cathode. The active material loading was so that the theoretical capacity of the battery cell was close to 1 mAh/cm2. It is known that the voltage window for LFP is between 2.7 V and 3.8 V. The anode was a copper foil coated with lithium metal having 0.3 wt. % aluminium doping.
The first lithium metal battery cell was tested by repeated charging/discharging cycles, at 70° C. for up to 100 cycles (
A second lithium metal battery cell was assembled using as electrolyte the polymer electrolyte obtained in Example 1 from compound No. 3. The cathode comprised 80% by weight of NMC 622 (nickel manganese cobalt), 10% of weight of the second polymaleimide polymer of Example 1, and 10% by weight of carbon black, based on the total weight of the cathode. The active material loading was so that the theoretical capacity of the battery cell was close to 1 mAh/cm2. It is known that the voltage window for NMC 622 is between 3.0 V and 4.25 V. The anode was a copper foil coated with lithium metal having 0.3 wt. % aluminium doping.
The second lithium metal battery cell was tested by repeated charging/discharging cycles, at 70° C. for up to 100 cycles (
A further compound according to the invention was prepared by adding 0.12 g of the third polymaleimide polymer of Example 1, 0.48 g of the second polymaleimide polymer of Example 2, 0.083 g of pentaerythritol tetrakis(2-mercaptoacetate) as the thiol-ene reaction agent (a thiol-ene reaction agent according to Formula V, wherein η, θ, λ, and ξ are all 0), 0.6953 g of propylene carbonate and 0.3275 g of ethylene carbonate as plasticizing agents, 2-Hydroxy-2-methylpropiophenone as free radical initiator to acetone as solvent.
0.0853 g lithium bis-fluorosulphonyl)imide was further added as lithium salt, which corresponded to 4.76% by weight based on the total weight of the compound excluding the weight of the acetone.
The amount of acetone was such that the compound comprised 86% by weight of acetone, based on the total weight of the compounds including the weight of the acetone.
The acetone-comprising compound was then applied to a Teflon substrate by casting, more particularly solvent casting.
The acetone was removed by placing the Teflon substrate comprising the compound in an argon box, thereby supplying a flow of argon at room temperature and at atmospheric pressure for 24 h to the substrate.
Next, the substantially solvent-free compound was exposed to UV radiation, which incited a thiol-ene reaction, thereby obtaining a polymer electrolyte film having a thickness of 150-200 μm.
A first lithium metal battery cell was assembled using the polymer electrolyte film as electrolyte. The cathode comprised 80% by weight of LiFePO4 (LFP), 10% of weight of the second polymaleimide polymer and 10% by weight of carbon black, based on the total weight of the cathode. The active material loading was so that the theoretical capacity of the battery cell was close to 1 mAh/cm2. It is known that the voltage window for LFP is between 2.7 V and 3.8 V. The anode was a copper foil coated with lithium metal having 0.3 wt. % aluminium doping.
A second lithium metal battery cell was assembled using the polymer electrolyte film as electrolyte. The cathode comprised 80% by weight of NMC 622 (nickel manganese cobalt), 10% of weight of the second polymaleimide polymer and 10% by weight of carbon black, based on the total weight of the cathode. The active material loading was so that the theoretical capacity of the battery cell was close to 1 mAh/cm2. It is known that the voltage window for NMC 622 is between 3.0 V and 4.25 V. The anode was a copper foil coated with lithium metal having 0.3 wt. % aluminium doping.
The lithium metal battery cells were tested by repeated charging/discharging cycles at 40° C. for up to 40 cycles (first battery cell,
| Number | Date | Country | Kind |
|---|---|---|---|
| 23219803.6 | Dec 2023 | EP | regional |
