CA3054448C - Block copolymer electrolyte for lithium batteries - Google Patents
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- CA3054448C CA3054448C CA3054448A CA3054448A CA3054448C CA 3054448 C CA3054448 C CA 3054448C CA 3054448 A CA3054448 A CA 3054448A CA 3054448 A CA3054448 A CA 3054448A CA 3054448 C CA3054448 C CA 3054448C
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L101/00—Compositions of unspecified macromolecular compounds
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- 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
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- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- 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
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
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- 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
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Abstract
A solid polymer electrolyte for a battery is disclosed. The solid polymer electrolyte includes solid polymer electrolyte including a diblock copolymer AB or a triblock copolymer of the BAB type, in which block A is an unsubstituted polyethylene oxide chain having a number- average molecular weight less than 80,000 g/mol; block B is an anionic polymer prepared from one or more monomers selected from vinyl monomers and derivatives thereof to which is grafted an anion of lithium salt, and a second monomer having cross-linking functions.
Description
BLOCK COPOLYMER ELECTROLYTE FOR LITHIUM BATTERIES
FIELD OF THE INVENTION
[0001] The present invention relates to a solid polymer electrolyte for lithium batteries and more specifically to a crosslinked block copolymer electrolyte which has increased mechanical resistance and improved ionic conductivity.
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
[0001] The present invention relates to a solid polymer electrolyte for lithium batteries and more specifically to a crosslinked block copolymer electrolyte which has increased mechanical resistance and improved ionic conductivity.
BACKGROUND OF THE INVENTION
[0002] A
lithium battery using a lithium metal as a negative electrode has excellent energy density. However, with repeated cycles, such a battery can be subject to dendrites' growths on the surface of the lithium metal electrode when recharging the battery as the lithium ions are unevenly re-plated on the surface of the lithium metal electrode. To minimize the effect of the morphological evolution of the surface of the lithium metal anode including dendrites growth, a lithium metal battery typically uses a pressure system and a solid polymer electrolyte adapted to resist the pressure applied thereto as described in US
Pat. No. 6,007,935. Over numerous cycles, the dendrites on the surface of the lithium metal anode may still grow to penetrate the solid polymer electrolyte even though the electrolyte is solid and eventually cause 'soft' short circuits between the negative electrode and the positive electrode, resulting in decreasing or poor performance of the battery.
Therefore, the growth of dendrites may still deteriorate the cycling characteristics of the battery and constitutes a major limitation with respect to the optimization of the performances of lithium batteries having a metallic lithium anode.
lithium battery using a lithium metal as a negative electrode has excellent energy density. However, with repeated cycles, such a battery can be subject to dendrites' growths on the surface of the lithium metal electrode when recharging the battery as the lithium ions are unevenly re-plated on the surface of the lithium metal electrode. To minimize the effect of the morphological evolution of the surface of the lithium metal anode including dendrites growth, a lithium metal battery typically uses a pressure system and a solid polymer electrolyte adapted to resist the pressure applied thereto as described in US
Pat. No. 6,007,935. Over numerous cycles, the dendrites on the surface of the lithium metal anode may still grow to penetrate the solid polymer electrolyte even though the electrolyte is solid and eventually cause 'soft' short circuits between the negative electrode and the positive electrode, resulting in decreasing or poor performance of the battery.
Therefore, the growth of dendrites may still deteriorate the cycling characteristics of the battery and constitutes a major limitation with respect to the optimization of the performances of lithium batteries having a metallic lithium anode.
[0003] Various types of polymers have been proposed for solid electrolyte adapted for use with lithium metal electrodes. In particular, the use of polymers consisting of units of ethylene oxide (EO) has been widely known since the end of the 1970s, but it has been found that they do not have sufficient conductivity at room temperature. For example, poly(ethylene oxide) (PEO) of high molecular weight doped with lithium salt has very good mechanical properties at room temperature but is a semicrystalline polymer. The crystalline structure restricts the mobility of the chains and reduces the ionic conductivity of the polymer. Above the inciting point of PEO
(Tm 60-65 C), ionic conductivity increases considerably, but at these temperatures PEO
becomes a viscous liquid and loses its dimensional stability.
Date Recue/Date Received 2023-07-12
(Tm 60-65 C), ionic conductivity increases considerably, but at these temperatures PEO
becomes a viscous liquid and loses its dimensional stability.
Date Recue/Date Received 2023-07-12
[0004]
Research and development of polymer solid electrolytes have been continuously carried out to reinforce the mechanical properties of PEO by adding hard colloidal particles, by increasing the number-average molecular weight of the PEO or by crosslinking, but have generally caused a decrease in ionic conductivity.
Efforts have been made to improve the ionic conductivity of PEO by adding plasticizers but those have led to deterioration of the mechanical properties.
Research and development of polymer solid electrolytes have been continuously carried out to reinforce the mechanical properties of PEO by adding hard colloidal particles, by increasing the number-average molecular weight of the PEO or by crosslinking, but have generally caused a decrease in ionic conductivity.
Efforts have been made to improve the ionic conductivity of PEO by adding plasticizers but those have led to deterioration of the mechanical properties.
[0005] More recently, PEO matrix were developed by copolymerization of PEO
macromers to produce sequence of block copolymers based on PEO in order to increase the ionic conductivity of the solid polymer electrolyte while maintaining sufficient mechanical properties. Lately, solid polymer electrolytes including a block copolymer with micro-phase separation comprising an ionic conducting block and a second block not miscible with the ionic conducting block in which an anion is immobilized have been proposed with the aim of eliminating or reducing the use an additional lithium salt while maintaining sufficient ionic conductivity.
macromers to produce sequence of block copolymers based on PEO in order to increase the ionic conductivity of the solid polymer electrolyte while maintaining sufficient mechanical properties. Lately, solid polymer electrolytes including a block copolymer with micro-phase separation comprising an ionic conducting block and a second block not miscible with the ionic conducting block in which an anion is immobilized have been proposed with the aim of eliminating or reducing the use an additional lithium salt while maintaining sufficient ionic conductivity.
[0006] For example, US Pat No. 9,431,677 describes a solid polymer electrolyte consisting of a diblock copolymer of the BA type or a triblock copolymer of the BAB
type, in which block A is an unsubstituted polyoxyethylene chain having a number-average molecular weight less than or equal to 100 kDa; block B is an anionic polymer prepared from one or more monomers selected from the vinyl monomers and derivatives thereof, wherein the monomers are substituted with anion of (trifluoromethylsulfonypimide (TES1). The proposed solid polymer electrolyte displays good ionic conductivity but the mechanical properties at temperature above ambient are insufficient to resist the mechanical pressures in the electrochemical cell during operation.
type, in which block A is an unsubstituted polyoxyethylene chain having a number-average molecular weight less than or equal to 100 kDa; block B is an anionic polymer prepared from one or more monomers selected from the vinyl monomers and derivatives thereof, wherein the monomers are substituted with anion of (trifluoromethylsulfonypimide (TES1). The proposed solid polymer electrolyte displays good ionic conductivity but the mechanical properties at temperature above ambient are insufficient to resist the mechanical pressures in the electrochemical cell during operation.
[0007] Thus, there is a need for a solid polymer electrolyte including block copolymers which has increased mechanical resistance and improved ionic conductivity which is adapted to reduce or inhibit the effect of the growth of dendrites on the surface of the metallic lithium anode.
STATEMENT OF THE INVENTION
STATEMENT OF THE INVENTION
[0008] One aspect of the present invention is to provide a solid polymer electrolyte for a battery, the solid polymer electrolyte including a diblock of the AB
type or a triblock copolymer of the BAB type, in which block A is an unsubstituted polyethylene oxide chain having a number-average molecular weight less than 80,000 g/mol; block B
is an anionic polymer prepared from one or more monomers selected from vinyl monomers and derivatives thereof to which is grafted an anion of lithium salt, and from one or more monomers which are cross-linkable polyfunctional monomers. The cross-linkable polyfunctional monomers having chemical functions RI and/or R2 that did not participate in the initial polymerization reaction that can be post-reacted for cross-linking. The grafted anions of lithium salt improving the electrochemical performance by increasing the Li ions transport number while the cross-linking functions of the second monomer improving the mechanical strength of the solid polymer electrolyte.
type or a triblock copolymer of the BAB type, in which block A is an unsubstituted polyethylene oxide chain having a number-average molecular weight less than 80,000 g/mol; block B
is an anionic polymer prepared from one or more monomers selected from vinyl monomers and derivatives thereof to which is grafted an anion of lithium salt, and from one or more monomers which are cross-linkable polyfunctional monomers. The cross-linkable polyfunctional monomers having chemical functions RI and/or R2 that did not participate in the initial polymerization reaction that can be post-reacted for cross-linking. The grafted anions of lithium salt improving the electrochemical performance by increasing the Li ions transport number while the cross-linking functions of the second monomer improving the mechanical strength of the solid polymer electrolyte.
[0009] The cross-linkable polyfunctional monomer includes reactive groups for the initial polymerisation reaction, the reactive groups selected from the group consisting of a vinyl phenyl substituted in ortho, meta or para position, an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide and a vinyl.
100101 The pendant chemical functions RI and/or R2 are localized at the end of the B
block of the copolymer chain or statistically or block or alternate or gradient distributed in the B block of the copolymer chain, in order to ensure a more efficient and easier multi-dimensional cross-linking and enabling to produce stronger and thinner electrolyte films, for example by thermal means or by ultra violet or electronic radiation.
Another aspect of the present invention is to provide a solid polymer electrolyte for a battery, the solid polymer electrolyte including a diblock of the CD type or a triblock copolymer of the DCD type in which block C is an unsubstituted polyethylene oxide chain having a number-average molecular weight less than 80,000 g/mol; block D is an anionic polymer prepared from one or more monomers selected from vinyl monomers and derivatives thereof to which is grafted an anion of lithium salt, the copolymer chains mixed with a cross-linkable polymer having low molecular weight (<20,000 g/mol) of at least one monomer selected from vinyl phenyl substituted in meta, ortho or para, acrylates and methacrylates, acrylamide, methacrylamide allyl, vinyl and compounds having at least one reactive double bond, the cross-linkable polymer being cross-linked to form a cross-linked copolymer network. The cross-linkable polymer having low molecular weight (<20,000 g/mol) is preferably a polyoxyethylene glycol diacrylate or dimethacrylate..
Another aspect of the invention is to provide a battery having a plurality of electrochemical cells, each electrochemical cell including a metallic lithium anode, a cathode, and a solid polymer electrolyte including a diblock of the BA type or a triblock copolymer of the BAB type, in which block A is an unsubstituted polyethylene oxide chain having a number-average molecular weight less than 80,000 g/mol; block B
is an anionic polymer prepared from one or more monomers selected from vinyl monomers and derivatives thereof to which is grafted an anion of lithium salt, and from one or more monomers which are a cross-linkable polyfunctional monomers. The cross-linkable polyfunctional monomer having a chemical function that did not participate in the initial polymerization reaction that can be post-reacted for cross-linking. The grafted anions improving the electrochemical performance by increasing the Li ions transport number while the cross-linking functions of the second monomer improving the mechanical strength of the solid polymer electrolyte to resist growth of dendrites on the surface of the metallic lithium anode.
Another aspect of the invention is to provide a battery having a plurality of electrochemical cells, each electrochemical cell including a metallic lithium anode, a cathode, and a solid polymer electrolyte including a diblock of the CD type or a triblock copolymer of the DCD type in which block C is an unsubstituted polyethylene oxide chain having a number-average molecular weight less than 80.000 g/mol; block D is an anionic polymer prepared from one or more monomers selected from vinyl monomers and derivatives thereof to which is grafted an anion of lithium salt, the copolymer chains mixed with a cross-linkable polymer having low molecular weight (<20,000 g/mol) of at least one monomer selected from vinyl phenyl substituted in meta, ortho or para, acrylates and methacrylates, acrylamide, methacrylamide ally!, vinyl and compounds having at least one reactive double bond, the cross-linkable polymer being cross-linked to form a cross-linked copolymer network improving the mechanical strength of the solid polymer electrolyte to resist growth of dendrites on the surface of the metallic lithium anode.
[0014]
Embodiments of the present invention each have at least one of the above-mentioned objects and/or aspects, but do not necessarily have all of them. It should be understood that some aspects of the present invention that have resulted from attempting to attain the above-mentioned objects may not satisfy these objects and/or may satisfy other objects not specifically recited herein.
[0015]
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] For a better understanding of the present invention as well as other aspects and further features thereof, reference is made to the following description which is to be used in conjunction with the accompanying drawings, where:
[0017] FIG. 1 is a schematic representation of a plurality of electrochemical cells forming a lithium metal polymer battery;
[0018] Fig. 2 is schematic representation of a triblock copolymer of the BAB
type included in the solid polymer electrolyte in accordance with the invention;
[0019] Fig. 3 is schematic representation of four specific synthesis routes for cross-linking PEO copolymer chains.
[0020] Fig. 4 is schematic representation of a triblock copolymer of the type P(STFSILi)-b-PEO-b-P(STFSILi) included in a solid polymer electrolyte in accordance with a second embodiment of the invention;
[0021] Fig. 5 is schematic representation of a bilayer solid polymer electrolyte in accordance with one embodiment of the invention; and [0022] Fig. 6 is schematic representation of a trilayer solid polymer electrolyte in accordance with one embodiment of the invention.
DESCRIPTION OF PREFERRED EMBODIMENT(S) [0023] Figure 1 illustrates schematically a lithium metal polymer battery 10 having a plurality of electrochemical cells 12 each including an anode or negative electrode 14 made of a sheet of metallic lithium, a solid electrolyte 16 and a cathode or positive electrode film 18 layered onto a current collector 20. The solid electrolyte 16 typically includes a lithium salt to provide ionic conduction between the anode 14 and the cathode 18. The sheet of lithium metal typically has a thickness ranging from 20 microns to 100 Date Recue/Date Received 2023-07-12 microns; the solid electrolyte 16 has a thickness ranging from 5 microns to 50 microns, and the positive electrode film 18 typically has a thickness ranging from 20 microns to 100 microns.
[0024] The lithium salt may be selected from LiCF3S03, Li B(C204)2, LiN(CF3S02)2, LiN(FS02)2, LiC(CF3S02)3, LiC(CH3)(CF3S02)2, LiCH(CF3S02)2, LiCH2(CF3S02), LiC2F5S03, LiN(C2F5S02)2, LiN(CF3S02), LiB(CF3S02)2, 1-iPF65 LiSbF6, LiC104, LiSCN, LiAsF6, and LiBF4.
[0025] The internal operating temperature of the battery 10 in the electrochemical cells 12 is typically between 40 C and 100 C. Lithium polymer batteries preferably include an internal heating system to bring the electrochemical cells 12 to their optimal operating temperature. The battery 10 may be used indoors or outdoors in a wide temperature range (between -40 C to +70 C).
[0026] The solid polymer electrolyte 16 according to the invention is composed of a diblock copolymer BA or a triblock copolymer of the BAB type as illustrated in Figure 2. Block A is an unsubstituted polyethylene oxide chain having a number-average molecular weight preferably less than 80,000 g/mol; block B is an anionic polymer prepared from one or more monomers selected from vinyl monomers and derivatives thereof to which is grafted an anion of lithium salt (LiTFS1 or others), and a cross-linkable polyfunctional monomer having a function R that did not participate in the initial polymerization reaction that can be post-reacted for cross-linking. The triblock copolymer illustrated is of the type P(STFSILi-co-S(R))-17-PEO-17-P(STFSILi-co-S(R)) in which the reactive cross-linking functions are R.
[0027] The triblock or the diblock copolymers according to the invention can be prepared by any method of controlled radical polymerization (ATRP ("Atom Transfer Radical Polymerization-), RAFT (-Reversible Addition Fragmentation Chain Transfer"), NMP ("Nitroxide-Mediated Radical Polymerization")) and ionic polymerizations like anionic or cationic, either directly with a vinyl monomer bearing a salt of hydrogen or lithium or potassium or sodium group or indirectly with a functionalization of the polymer by grafting the KTFSI group. This polymerization or functionalization is then followed or not (in case of lithium) by a step of ionic exchange to replace the K+, El+ or Na + cation by a Li' cation. The final cross-linking reaction creates a cross-linking network between the various polymer chains thereby substantially increasing the mechanical strength of the solid polymer electrolyte 16 [0028] The relative proportions of the polymers of block A and B in the mixture may be adjusted so as to give the desired properties of mechanical hardness and adhesion of the films of electrolyte 16, to be able to use the most adequate process of coating, and depending on the molecular weight of the component of block B. Thus, a larger proportion of the compound of block B will lead to a film of higher mechanical hardness but less adhesive to the electrodes, and provide less viscous mixtures, which are easier to coat by gravure, reverse roll, extrusion or hot melt processes. On the other hand, a larger proportion of the polymer of block A will produce a film having a better adhesion to the electrodes which can be obtained by extrusion or hot melt processes. In a preferred embodiment, the proportions of the polymers of block A relative to block B is between 40% and 80%.
[0029] In order to prepare cross-linked triblock or diblock copolymer based on PEO as illustrated in Fig.2, several synthesis pathways are possible. There are four specific paths for cross-linking PEO copolymer chains between them as shown in Fig. 3.
In order to simplify, only the triblock copolymer are illustrated. Fig. 3 schematically represents PEO copolymer chains all carrying cross-linkable polyfunctional monomer having pendant chemical functions represented as cross-linking functions RI and/or R2, and grafted anionic groups of lithium salt (TFSI- Li or others) wherein the grafted anionic groups of lithium salt is omitted for simplification of illustration.
100301 The first path (1) involves two identical copolymer chains each having pendant chemical functions RI and R2. These functions RI and R2 are randomly distributed along the copolymer chains and cannot react with themselves but function RI
can react with function R2. In this way, the copolymer chains react with each other to form a cross-linked copolymer network.
[0031] The second path (2) involves two different copolymer chains, one carrying pendant chemical function RI only and the other carrying pendant chemical function R2 only. These two functions RI and R2 react with each other to form a cross-linked copolymer network.
[0032] The third path (3) is fundamentally different from the paths (1) and (2). The third path (3) involves two identical copolymer chains each carrying pendant chemical function RI only that cannot react with itself. In order for the cross-linking reaction to take place, a small molecule carrying at least two chemical functions R2 that can react with chemical function RI is added. When the identical copolymer chains are brought into contact with this small molecule carrying at least two chemical functions R2, a cross-linked copolymer network is obtained.
[0033] The fourth and last path (4) is the simplest. The identical copolymer chains each carry the same pendant chemical function RI that can react with itself.
When the identical copolymer chains are brought into contact, the pendant chemical functions RI of each chain react with each other thereby forming a cross-linked copolymer network.
100341 With regards to the first synthesis path (1), there is an example in which many copolymers carrying a function RI of the type azide and a function R2 of the type propargyl protected by a silane or not.
l's13 ['unction RI
function It2 SiMe, [0035] The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an ally!, an acrylamide, a methacrylamide or a vinyl. The two types of functions RI and R2 can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
[0036] With regards to the second synthesis path (2), there are multiple examples.
The first example is as follows: The first copolymer comprises a function R1 of the type alcohol or its salts. The second copolymer comprises a function R2 which may be a carboxylic acid or its salts, a isocyanate, or isothiocyanate, or oxirane, or sulfonic acid or its salts, or phosphonic acid or its salts, or carbonate or the halide (X :
Cl, 1 or Br).
4111 = 1401 0 0 { HO 0 NCO NCS functions R2 function RI HO
Oil IS I 01 0. 0,.., functions R2 X; Br, CI or I
100371 The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The two types of functions RI and R2 can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
[0038] Another example of the second synthesis path (2) can be: The first copolymer comprises a function RI of the type of an azide and a second copolymer includes a function R2 of the type of a propargyl protected by a silane or not.
N3 function RI
I limoion R2 Strit 100391 The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The two types of functions RI and R2 can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
third example of the second synthesis path (2) may be that the first copolymer comprises a group RI of the type an oxirane and a second copolymer comprises a group R2 of sulfonic acid or its salts or a phosphonic acid or its salts.
p03H2 so3H function R2 function RI
100411 The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The two types of functions RI and R2 can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
[0042]
Another example of the second synthesis path (2) may be: A first copolymer comprising a function RI of an amine primary or secondary (R:
hydrogen atom, alkyl or aryl) and a second copolymer comprising a function R2 which may be an oxirane, a carboxylic acid or its salts, an aldehyde, a ketone, a sulfonic acid or its salts, a phosphonic acid or its salts, a cyclic carbonate, an isocyanate, an isothiocyanate, or an halide (X: Cl. I or Br) so3H functions R2 NH function RI HO 0 0 R 0 ii 401 IS le 1401 401 NCS
X
X; Br, CI or I functions R2 [0043] The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The two types of groups RI and R2 can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
100441 With regards to the third synthesis path (3), there are also multiple examples. The first example brings together two copolymers comprising functions RI of the type alcohol or its salts. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a rnethacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be a carboxylic acid or its salts, an isocyanate, a thioisocyanate, an oxirane, an ester, a sulfonic acid or its salts, a phosphonic acid or its salts, a cyclic carbonate, an acid halide (X : Cl, I or Br) or an halide (X :
Cl, I or Br). The functions R2 may be linked together with R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
HOy0 R
NCS
functions R2 = function RI HOO
NCO NCS
HO ___________________________________________ 0 oofunctions R2 <0=\17,f X functions R2 X
so3H po3H2 RI
functions R2 X: CI, Br or I
100451 The second example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type primary or secondary amine (R:
hydrogen atom, alkyl chain, benzene rings). The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an ally!, an acrylarnide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be a carboxylic acid or its salts, an isocyanate, a thioisocyanate, an oxirane, an ester, a sulfonic acid or its salts, a phosphonic acid or its salts, a cyclic carbonate, an acid halide (X: Cl, I or Br), an aldehyde or a ketone. The functions R2 may be linked together with a R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
HOO \d/0 funclions R2 11:0 ROO SI O3H
SO,H functions 82 HN function R, A 80 tiR 0 functions 82 .õõõx X 0 y-0 R03112 Lss.x RO
functions 82 X. CI, Br or I
[0046] The third example of the third synthesis path (3) brings together two copolymers comprising functions R I of the type carboxylic acid or its salts.
The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be an alcohol or its salts, a primary amine or a secondary amine. The functions R2 may be linked together with a R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
functions R2 N HN
functions R2 HO 0 function RI
100471 The fourth example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type sulfonic acid or its salts. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be an alcohol or its salts, a primary amine, a secondary amine or an oxirane.
The functions R2 may be linked together with a R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
v0 functions R2 OH
A functions R2 0¨=S=0 function RI
o' __________________________________________________ OH
Another example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type halide. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be an alcohol or its salts, or a primary amine. The functions R2 may be linked together with a R
group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
OH NH2 functions R2 ii OH NH2 I functions R2 X: CI, I or Br function RI
X
[0049]
Another example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type oxirane. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be a phosphonic acid or its salts, a sulfonic acid or its salts, an alcohol or its salts, a primary amine or a secondary amine. The functions R2 may be linked together with a R
group that may a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, arnide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
runctit, ' P03H2 SO3H OH NH2 HN us R2 NH2 HNR functions function RI
[0050]
Another example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type cyclic carbonate. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be an alcohol or its salts, a primary amine or a secondary amine. The functions R2 may be linked together with a R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amities, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
NI-I2 HN/ 01-1functions R2 R R
/ functions R2 _______________ 0 function R 1 [0051]
Another example of the third synthesis path (3) brings together two copolymers comprising functions R I of the type isocyanate. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate. an allyl, an acrylannide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be an alcohol or its salts, a primary amine or a secondary amine. The functions R2 may be linked together with a R group that may a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
NH2 HN....,,R functions R2 OH
R
IOH I
R
I I
R
I
NH2 HN,,,,R 1 functions R2 NCO /function RI
[0052]
Another example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type isothiocyanate. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be an alcohol or its salts, a primary amine or a secondary amine. The functions R2 may be linked together with a R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
----..,,_ , functions R2 R
IOH I
R
I RI
NH2 HNI....
R functions R2 NCS function RI
[0053]
Another example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type aldehyde or ketone. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be a primary amine. The functions R2 may be linked together with a R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
NH, function R2 I -R
NH2 function R2 0 / function RI
[0054]
Another example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type alcohol. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be a trichlorosilane, a carboxylic acid or its salts, an acid halide (X: Cl, I or Br) or an halide (X: Cl, I or Br). The functions R2 may be linked together with a R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
x x I X HO.,..,..0 CI ,,..,...0 X
functions R2 '=-.. Si./
I
lel RI
I R RR
O 0..õ,%"\.. CI {-,,õ 1 functions R2 r' I H
function RI
X X
OH X
X
X: CI. Br, I : CI, Br, I
[0055] Another example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type azide. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be a propargyl. The functions R2 may be linked together with a R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane.
silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
--..,..
11 1 function R2 1 function RI 1 I 1 function R2 1005611 A final example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type propargyl protected by a silane or not.
The reactive group may be a vinyl phenyl substituted in ortho or meta or para position.
The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be an azide. The functions R2 may be linked together with a R
group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
N3 function R2 N3 function R2 I function RI
StlsAe3 }
100571 With regards to the fourth and last path (4), which brings into play identical copolymer chains each carry the same pendant chemical function RI that can react with itself. The first example brings together two copolymers comprising functions RI of the type thyntine. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
function RI
[0058] The second example of the fourth path (4) brings together two copolymers comprising functions RI of the type cinnamate. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, si lanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
function RI
[0059] The third example of the fourth path (4) brings together two copolymers comprising functions R of the type coumarine. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an ally!, an acrylamide, a methacrylamide or a vinyl. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
function RI
100601 The fourth example of the fourth path (4) brings together two copolymers comprising functions RI of the type phenyl 4-(3'-buten-1 '-oxy)-2,3,5,6-tetrafluoro. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
!Unction RI
[0061] As shown in Figure 2, the grafted anion of lithium salt is in the non-conductive portion of the triblock copolymer and as such, all grafted anions of lithium salt may not all be available during battery operation. In order to increase the accessibility of these grafted anions of lithium salt, the triblock copolymer may be mixed with a cross-linkable polyoxyethylene glycol diacrylate or dimethacrylate of low molecular weight (<20,000 g/mol) such as PEG200 commercially available from Sigma-Aldrich for example.
The PEG200 which is ion ically conductive is mixed with the triblock copolymer and cross-linked in the final formation of the solid polymer electrolyte 16 and provides access to the grafted anions of lithium salt such that these grafted anions become part of the ionic path for Li ions migrating through the solid polymer electrolyte 16.
[0062] In a specific embodiment as illustrated in Figure 4 , a triblock copolymer of the type P(STFSILi)-b-PEO-b-P(STFSILi) which does not have a remaining cross-linkable function may also be used when mixed with a cross-linkable polyoxyethylene glycol diacrylate or dimethacrylate of low molecular weight (<20,000 g/mol) such as commercially available from Sigma-Aldrich for example. The cross-linkable PEG200 when cross-linked provides added mechanical strength to the solid polymer electrolyte 16. As previously described, the PECI200 is ionically conductive and when mixed with the triblock copolymer and cross-linked in the final formation of the solid polymer electrolyte 16, provides better access to the grafted anions of lithium salt such that these grafted anions are more easily accessible and become part of the ionic path for Li ions migrating through the solid polymer electrolyte 16.
[0063] Other cross-linkable monomer, homopolymer or copolymer having low molecular weight (<20,000 g/mol) can also be used which include a functional group enabling cross-linking issued from a polymer of at least one monomer selected from vinyl phenyl substituted in meta, ortho or para, acrylates and methacrylates, acrylamide, methacrylamide allyl, vinyl or compounds having at least one reactive double bond.
[0064] It goes without saying that, whatever the mixture or proportion selected; a lithium salt should be added in the final mixture in order to provide adequate ionic conductivity to the fmal solid polymer electrolyte 16. The lithium salts previously described which provide added ionic conductivity to the solid polymer electrolyte 16 are respectively LiCF3S03, LiB(C204)2, LiN(CF3S02)2, LiN
(FS02)2, LiC(CF3S02)3, LiC(CH3)(CF3S02)2, LiCH(CF3S02)2, LiCH2(CF3S02), LiC2F5S03, LiN(C2F5S02)2, LiN(CF3S02), LiB(CF3S02)2, LiPF6, LiSbF6, LiSCN, LiAsF6, LiBF4, and LiCI04.
[0065] Tests performed show that the use of a including a triblock copolymer in accordance with the invention included in a solid polymer electrolyte in a lithium metal battery leads to an energy storage device having excellent mechanical resistance at temperature above ambient temperature and excellent ionic conductivity. The solid polymer electrolyte according to the present invention also has good mechanical strength and durability, and high thermal stability thereby limiting the development of concentration gradients in the electrolyte during discharge (or during charging). The use of this solid polymer electrolyte in a lithium metal battery makes it possible to limit dendritic growth of the lithium enabling quick and safe recharging. The solid polymer electrolyte according to the present invention substantially reduces the formation of heterogeneous electrodeposits of lithium (including dendrites) during recharging.
[0066] The solid polymer electrolyte 16 is stronger than prior art solid polymer electrolytes and may therefore be made thinner than prior art polymer electrolytes.
As outlined above the solid polymer electrolyte 16 may be as thin as 5 microns. A
thinner electrolyte in a battery results in a lighter battery and therefore a battery having a higher energy density. The increased strength of the solid polymer electrolyte 16 renders it more stable in manufacturing processes. The solid polymer electrolyte 16 is more tear resistant and may be less likely to wrinkle in the production process.
Date Recue/Date Received 2023-07-12 [0067] As illustrated in Figure 5, in one specific embodiment, the solid polymer electrolyte 25 consists of a bilayer assembly comprising a base layer 26 of between 5 and 50 microns consisting of a standard homopolymer or copolymer of polyethylene oxide as described in US Pat No. 6,855,788 or a blend of homopolymer or copolymer as described in EP2235784, and a thin surface layer 27 of less than 20 microns consisting of one of the triblock copolymer of the BAB type described above. The thin surface layer 27 being pressed against the lithium metal anode to provide a barrier against dendrites' growth. In another embodiment as illustrated in Figure 6, the solid polymer electrolyte 30 consists of a trilayer assembly comprising a base layer 26 of between 5 and 50 microns consisting of a standard homopolymer or copolymer of polyethylene oxide as described in US Pat No.
6,855,788 or a blend of homopolymer or copolymer as described in EP2235784, a thin layer 27 of less than 20 microns consisting of one of the triblock copolymer of the BAB type described above and a thin surface layer 31 consisting of a standard homopolymer or copolymer of polyethylene oxide described above acting as an adhesion promoter on the lithium metal anode.
Date Recue/Date Received 2023-07-12
100101 The pendant chemical functions RI and/or R2 are localized at the end of the B
block of the copolymer chain or statistically or block or alternate or gradient distributed in the B block of the copolymer chain, in order to ensure a more efficient and easier multi-dimensional cross-linking and enabling to produce stronger and thinner electrolyte films, for example by thermal means or by ultra violet or electronic radiation.
Another aspect of the present invention is to provide a solid polymer electrolyte for a battery, the solid polymer electrolyte including a diblock of the CD type or a triblock copolymer of the DCD type in which block C is an unsubstituted polyethylene oxide chain having a number-average molecular weight less than 80,000 g/mol; block D is an anionic polymer prepared from one or more monomers selected from vinyl monomers and derivatives thereof to which is grafted an anion of lithium salt, the copolymer chains mixed with a cross-linkable polymer having low molecular weight (<20,000 g/mol) of at least one monomer selected from vinyl phenyl substituted in meta, ortho or para, acrylates and methacrylates, acrylamide, methacrylamide allyl, vinyl and compounds having at least one reactive double bond, the cross-linkable polymer being cross-linked to form a cross-linked copolymer network. The cross-linkable polymer having low molecular weight (<20,000 g/mol) is preferably a polyoxyethylene glycol diacrylate or dimethacrylate..
Another aspect of the invention is to provide a battery having a plurality of electrochemical cells, each electrochemical cell including a metallic lithium anode, a cathode, and a solid polymer electrolyte including a diblock of the BA type or a triblock copolymer of the BAB type, in which block A is an unsubstituted polyethylene oxide chain having a number-average molecular weight less than 80,000 g/mol; block B
is an anionic polymer prepared from one or more monomers selected from vinyl monomers and derivatives thereof to which is grafted an anion of lithium salt, and from one or more monomers which are a cross-linkable polyfunctional monomers. The cross-linkable polyfunctional monomer having a chemical function that did not participate in the initial polymerization reaction that can be post-reacted for cross-linking. The grafted anions improving the electrochemical performance by increasing the Li ions transport number while the cross-linking functions of the second monomer improving the mechanical strength of the solid polymer electrolyte to resist growth of dendrites on the surface of the metallic lithium anode.
Another aspect of the invention is to provide a battery having a plurality of electrochemical cells, each electrochemical cell including a metallic lithium anode, a cathode, and a solid polymer electrolyte including a diblock of the CD type or a triblock copolymer of the DCD type in which block C is an unsubstituted polyethylene oxide chain having a number-average molecular weight less than 80.000 g/mol; block D is an anionic polymer prepared from one or more monomers selected from vinyl monomers and derivatives thereof to which is grafted an anion of lithium salt, the copolymer chains mixed with a cross-linkable polymer having low molecular weight (<20,000 g/mol) of at least one monomer selected from vinyl phenyl substituted in meta, ortho or para, acrylates and methacrylates, acrylamide, methacrylamide ally!, vinyl and compounds having at least one reactive double bond, the cross-linkable polymer being cross-linked to form a cross-linked copolymer network improving the mechanical strength of the solid polymer electrolyte to resist growth of dendrites on the surface of the metallic lithium anode.
[0014]
Embodiments of the present invention each have at least one of the above-mentioned objects and/or aspects, but do not necessarily have all of them. It should be understood that some aspects of the present invention that have resulted from attempting to attain the above-mentioned objects may not satisfy these objects and/or may satisfy other objects not specifically recited herein.
[0015]
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] For a better understanding of the present invention as well as other aspects and further features thereof, reference is made to the following description which is to be used in conjunction with the accompanying drawings, where:
[0017] FIG. 1 is a schematic representation of a plurality of electrochemical cells forming a lithium metal polymer battery;
[0018] Fig. 2 is schematic representation of a triblock copolymer of the BAB
type included in the solid polymer electrolyte in accordance with the invention;
[0019] Fig. 3 is schematic representation of four specific synthesis routes for cross-linking PEO copolymer chains.
[0020] Fig. 4 is schematic representation of a triblock copolymer of the type P(STFSILi)-b-PEO-b-P(STFSILi) included in a solid polymer electrolyte in accordance with a second embodiment of the invention;
[0021] Fig. 5 is schematic representation of a bilayer solid polymer electrolyte in accordance with one embodiment of the invention; and [0022] Fig. 6 is schematic representation of a trilayer solid polymer electrolyte in accordance with one embodiment of the invention.
DESCRIPTION OF PREFERRED EMBODIMENT(S) [0023] Figure 1 illustrates schematically a lithium metal polymer battery 10 having a plurality of electrochemical cells 12 each including an anode or negative electrode 14 made of a sheet of metallic lithium, a solid electrolyte 16 and a cathode or positive electrode film 18 layered onto a current collector 20. The solid electrolyte 16 typically includes a lithium salt to provide ionic conduction between the anode 14 and the cathode 18. The sheet of lithium metal typically has a thickness ranging from 20 microns to 100 Date Recue/Date Received 2023-07-12 microns; the solid electrolyte 16 has a thickness ranging from 5 microns to 50 microns, and the positive electrode film 18 typically has a thickness ranging from 20 microns to 100 microns.
[0024] The lithium salt may be selected from LiCF3S03, Li B(C204)2, LiN(CF3S02)2, LiN(FS02)2, LiC(CF3S02)3, LiC(CH3)(CF3S02)2, LiCH(CF3S02)2, LiCH2(CF3S02), LiC2F5S03, LiN(C2F5S02)2, LiN(CF3S02), LiB(CF3S02)2, 1-iPF65 LiSbF6, LiC104, LiSCN, LiAsF6, and LiBF4.
[0025] The internal operating temperature of the battery 10 in the electrochemical cells 12 is typically between 40 C and 100 C. Lithium polymer batteries preferably include an internal heating system to bring the electrochemical cells 12 to their optimal operating temperature. The battery 10 may be used indoors or outdoors in a wide temperature range (between -40 C to +70 C).
[0026] The solid polymer electrolyte 16 according to the invention is composed of a diblock copolymer BA or a triblock copolymer of the BAB type as illustrated in Figure 2. Block A is an unsubstituted polyethylene oxide chain having a number-average molecular weight preferably less than 80,000 g/mol; block B is an anionic polymer prepared from one or more monomers selected from vinyl monomers and derivatives thereof to which is grafted an anion of lithium salt (LiTFS1 or others), and a cross-linkable polyfunctional monomer having a function R that did not participate in the initial polymerization reaction that can be post-reacted for cross-linking. The triblock copolymer illustrated is of the type P(STFSILi-co-S(R))-17-PEO-17-P(STFSILi-co-S(R)) in which the reactive cross-linking functions are R.
[0027] The triblock or the diblock copolymers according to the invention can be prepared by any method of controlled radical polymerization (ATRP ("Atom Transfer Radical Polymerization-), RAFT (-Reversible Addition Fragmentation Chain Transfer"), NMP ("Nitroxide-Mediated Radical Polymerization")) and ionic polymerizations like anionic or cationic, either directly with a vinyl monomer bearing a salt of hydrogen or lithium or potassium or sodium group or indirectly with a functionalization of the polymer by grafting the KTFSI group. This polymerization or functionalization is then followed or not (in case of lithium) by a step of ionic exchange to replace the K+, El+ or Na + cation by a Li' cation. The final cross-linking reaction creates a cross-linking network between the various polymer chains thereby substantially increasing the mechanical strength of the solid polymer electrolyte 16 [0028] The relative proportions of the polymers of block A and B in the mixture may be adjusted so as to give the desired properties of mechanical hardness and adhesion of the films of electrolyte 16, to be able to use the most adequate process of coating, and depending on the molecular weight of the component of block B. Thus, a larger proportion of the compound of block B will lead to a film of higher mechanical hardness but less adhesive to the electrodes, and provide less viscous mixtures, which are easier to coat by gravure, reverse roll, extrusion or hot melt processes. On the other hand, a larger proportion of the polymer of block A will produce a film having a better adhesion to the electrodes which can be obtained by extrusion or hot melt processes. In a preferred embodiment, the proportions of the polymers of block A relative to block B is between 40% and 80%.
[0029] In order to prepare cross-linked triblock or diblock copolymer based on PEO as illustrated in Fig.2, several synthesis pathways are possible. There are four specific paths for cross-linking PEO copolymer chains between them as shown in Fig. 3.
In order to simplify, only the triblock copolymer are illustrated. Fig. 3 schematically represents PEO copolymer chains all carrying cross-linkable polyfunctional monomer having pendant chemical functions represented as cross-linking functions RI and/or R2, and grafted anionic groups of lithium salt (TFSI- Li or others) wherein the grafted anionic groups of lithium salt is omitted for simplification of illustration.
100301 The first path (1) involves two identical copolymer chains each having pendant chemical functions RI and R2. These functions RI and R2 are randomly distributed along the copolymer chains and cannot react with themselves but function RI
can react with function R2. In this way, the copolymer chains react with each other to form a cross-linked copolymer network.
[0031] The second path (2) involves two different copolymer chains, one carrying pendant chemical function RI only and the other carrying pendant chemical function R2 only. These two functions RI and R2 react with each other to form a cross-linked copolymer network.
[0032] The third path (3) is fundamentally different from the paths (1) and (2). The third path (3) involves two identical copolymer chains each carrying pendant chemical function RI only that cannot react with itself. In order for the cross-linking reaction to take place, a small molecule carrying at least two chemical functions R2 that can react with chemical function RI is added. When the identical copolymer chains are brought into contact with this small molecule carrying at least two chemical functions R2, a cross-linked copolymer network is obtained.
[0033] The fourth and last path (4) is the simplest. The identical copolymer chains each carry the same pendant chemical function RI that can react with itself.
When the identical copolymer chains are brought into contact, the pendant chemical functions RI of each chain react with each other thereby forming a cross-linked copolymer network.
100341 With regards to the first synthesis path (1), there is an example in which many copolymers carrying a function RI of the type azide and a function R2 of the type propargyl protected by a silane or not.
l's13 ['unction RI
function It2 SiMe, [0035] The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an ally!, an acrylamide, a methacrylamide or a vinyl. The two types of functions RI and R2 can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
[0036] With regards to the second synthesis path (2), there are multiple examples.
The first example is as follows: The first copolymer comprises a function R1 of the type alcohol or its salts. The second copolymer comprises a function R2 which may be a carboxylic acid or its salts, a isocyanate, or isothiocyanate, or oxirane, or sulfonic acid or its salts, or phosphonic acid or its salts, or carbonate or the halide (X :
Cl, 1 or Br).
4111 = 1401 0 0 { HO 0 NCO NCS functions R2 function RI HO
Oil IS I 01 0. 0,.., functions R2 X; Br, CI or I
100371 The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The two types of functions RI and R2 can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
[0038] Another example of the second synthesis path (2) can be: The first copolymer comprises a function RI of the type of an azide and a second copolymer includes a function R2 of the type of a propargyl protected by a silane or not.
N3 function RI
I limoion R2 Strit 100391 The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The two types of functions RI and R2 can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
third example of the second synthesis path (2) may be that the first copolymer comprises a group RI of the type an oxirane and a second copolymer comprises a group R2 of sulfonic acid or its salts or a phosphonic acid or its salts.
p03H2 so3H function R2 function RI
100411 The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The two types of functions RI and R2 can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
[0042]
Another example of the second synthesis path (2) may be: A first copolymer comprising a function RI of an amine primary or secondary (R:
hydrogen atom, alkyl or aryl) and a second copolymer comprising a function R2 which may be an oxirane, a carboxylic acid or its salts, an aldehyde, a ketone, a sulfonic acid or its salts, a phosphonic acid or its salts, a cyclic carbonate, an isocyanate, an isothiocyanate, or an halide (X: Cl. I or Br) so3H functions R2 NH function RI HO 0 0 R 0 ii 401 IS le 1401 401 NCS
X
X; Br, CI or I functions R2 [0043] The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The two types of groups RI and R2 can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
100441 With regards to the third synthesis path (3), there are also multiple examples. The first example brings together two copolymers comprising functions RI of the type alcohol or its salts. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a rnethacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be a carboxylic acid or its salts, an isocyanate, a thioisocyanate, an oxirane, an ester, a sulfonic acid or its salts, a phosphonic acid or its salts, a cyclic carbonate, an acid halide (X : Cl, I or Br) or an halide (X :
Cl, I or Br). The functions R2 may be linked together with R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
HOy0 R
NCS
functions R2 = function RI HOO
NCO NCS
HO ___________________________________________ 0 oofunctions R2 <0=\17,f X functions R2 X
so3H po3H2 RI
functions R2 X: CI, Br or I
100451 The second example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type primary or secondary amine (R:
hydrogen atom, alkyl chain, benzene rings). The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an ally!, an acrylarnide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be a carboxylic acid or its salts, an isocyanate, a thioisocyanate, an oxirane, an ester, a sulfonic acid or its salts, a phosphonic acid or its salts, a cyclic carbonate, an acid halide (X: Cl, I or Br), an aldehyde or a ketone. The functions R2 may be linked together with a R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
HOO \d/0 funclions R2 11:0 ROO SI O3H
SO,H functions 82 HN function R, A 80 tiR 0 functions 82 .õõõx X 0 y-0 R03112 Lss.x RO
functions 82 X. CI, Br or I
[0046] The third example of the third synthesis path (3) brings together two copolymers comprising functions R I of the type carboxylic acid or its salts.
The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be an alcohol or its salts, a primary amine or a secondary amine. The functions R2 may be linked together with a R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
functions R2 N HN
functions R2 HO 0 function RI
100471 The fourth example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type sulfonic acid or its salts. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be an alcohol or its salts, a primary amine, a secondary amine or an oxirane.
The functions R2 may be linked together with a R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
v0 functions R2 OH
A functions R2 0¨=S=0 function RI
o' __________________________________________________ OH
Another example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type halide. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be an alcohol or its salts, or a primary amine. The functions R2 may be linked together with a R
group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
OH NH2 functions R2 ii OH NH2 I functions R2 X: CI, I or Br function RI
X
[0049]
Another example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type oxirane. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be a phosphonic acid or its salts, a sulfonic acid or its salts, an alcohol or its salts, a primary amine or a secondary amine. The functions R2 may be linked together with a R
group that may a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, arnide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
runctit, ' P03H2 SO3H OH NH2 HN us R2 NH2 HNR functions function RI
[0050]
Another example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type cyclic carbonate. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be an alcohol or its salts, a primary amine or a secondary amine. The functions R2 may be linked together with a R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amities, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
NI-I2 HN/ 01-1functions R2 R R
/ functions R2 _______________ 0 function R 1 [0051]
Another example of the third synthesis path (3) brings together two copolymers comprising functions R I of the type isocyanate. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate. an allyl, an acrylannide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be an alcohol or its salts, a primary amine or a secondary amine. The functions R2 may be linked together with a R group that may a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
NH2 HN....,,R functions R2 OH
R
IOH I
R
I I
R
I
NH2 HN,,,,R 1 functions R2 NCO /function RI
[0052]
Another example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type isothiocyanate. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be an alcohol or its salts, a primary amine or a secondary amine. The functions R2 may be linked together with a R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
----..,,_ , functions R2 R
IOH I
R
I RI
NH2 HNI....
R functions R2 NCS function RI
[0053]
Another example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type aldehyde or ketone. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be a primary amine. The functions R2 may be linked together with a R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
NH, function R2 I -R
NH2 function R2 0 / function RI
[0054]
Another example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type alcohol. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be a trichlorosilane, a carboxylic acid or its salts, an acid halide (X: Cl, I or Br) or an halide (X: Cl, I or Br). The functions R2 may be linked together with a R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
x x I X HO.,..,..0 CI ,,..,...0 X
functions R2 '=-.. Si./
I
lel RI
I R RR
O 0..õ,%"\.. CI {-,,õ 1 functions R2 r' I H
function RI
X X
OH X
X
X: CI. Br, I : CI, Br, I
[0055] Another example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type azide. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be a propargyl. The functions R2 may be linked together with a R group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane.
silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
--..,..
11 1 function R2 1 function RI 1 I 1 function R2 1005611 A final example of the third synthesis path (3) brings together two copolymers comprising functions RI of the type propargyl protected by a silane or not.
The reactive group may be a vinyl phenyl substituted in ortho or meta or para position.
The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The small molecule includes multiple functions R2 (at least two) that can be an azide. The functions R2 may be linked together with a R
group that may be a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
N3 function R2 N3 function R2 I function RI
StlsAe3 }
100571 With regards to the fourth and last path (4), which brings into play identical copolymer chains each carry the same pendant chemical function RI that can react with itself. The first example brings together two copolymers comprising functions RI of the type thyntine. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
function RI
[0058] The second example of the fourth path (4) brings together two copolymers comprising functions RI of the type cinnamate. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, si lanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
function RI
[0059] The third example of the fourth path (4) brings together two copolymers comprising functions R of the type coumarine. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an ally!, an acrylamide, a methacrylamide or a vinyl. The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
function RI
100601 The fourth example of the fourth path (4) brings together two copolymers comprising functions RI of the type phenyl 4-(3'-buten-1 '-oxy)-2,3,5,6-tetrafluoro. The reactive group may be a vinyl phenyl substituted in ortho or meta or para position. The vinyl phenyl may be replaced by an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide or a vinyl The function RI can be linked to the reactive function of the monomer by a linear or cyclic alkyl or aryl or alkyl fluoride, an ether, ester, amide, thioether, tertiary amines, quaternary ammoniums, urethanes, thiourethane, silanes, ethylene glycol, propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol) or a mixture of these groups.
!Unction RI
[0061] As shown in Figure 2, the grafted anion of lithium salt is in the non-conductive portion of the triblock copolymer and as such, all grafted anions of lithium salt may not all be available during battery operation. In order to increase the accessibility of these grafted anions of lithium salt, the triblock copolymer may be mixed with a cross-linkable polyoxyethylene glycol diacrylate or dimethacrylate of low molecular weight (<20,000 g/mol) such as PEG200 commercially available from Sigma-Aldrich for example.
The PEG200 which is ion ically conductive is mixed with the triblock copolymer and cross-linked in the final formation of the solid polymer electrolyte 16 and provides access to the grafted anions of lithium salt such that these grafted anions become part of the ionic path for Li ions migrating through the solid polymer electrolyte 16.
[0062] In a specific embodiment as illustrated in Figure 4 , a triblock copolymer of the type P(STFSILi)-b-PEO-b-P(STFSILi) which does not have a remaining cross-linkable function may also be used when mixed with a cross-linkable polyoxyethylene glycol diacrylate or dimethacrylate of low molecular weight (<20,000 g/mol) such as commercially available from Sigma-Aldrich for example. The cross-linkable PEG200 when cross-linked provides added mechanical strength to the solid polymer electrolyte 16. As previously described, the PECI200 is ionically conductive and when mixed with the triblock copolymer and cross-linked in the final formation of the solid polymer electrolyte 16, provides better access to the grafted anions of lithium salt such that these grafted anions are more easily accessible and become part of the ionic path for Li ions migrating through the solid polymer electrolyte 16.
[0063] Other cross-linkable monomer, homopolymer or copolymer having low molecular weight (<20,000 g/mol) can also be used which include a functional group enabling cross-linking issued from a polymer of at least one monomer selected from vinyl phenyl substituted in meta, ortho or para, acrylates and methacrylates, acrylamide, methacrylamide allyl, vinyl or compounds having at least one reactive double bond.
[0064] It goes without saying that, whatever the mixture or proportion selected; a lithium salt should be added in the final mixture in order to provide adequate ionic conductivity to the fmal solid polymer electrolyte 16. The lithium salts previously described which provide added ionic conductivity to the solid polymer electrolyte 16 are respectively LiCF3S03, LiB(C204)2, LiN(CF3S02)2, LiN
(FS02)2, LiC(CF3S02)3, LiC(CH3)(CF3S02)2, LiCH(CF3S02)2, LiCH2(CF3S02), LiC2F5S03, LiN(C2F5S02)2, LiN(CF3S02), LiB(CF3S02)2, LiPF6, LiSbF6, LiSCN, LiAsF6, LiBF4, and LiCI04.
[0065] Tests performed show that the use of a including a triblock copolymer in accordance with the invention included in a solid polymer electrolyte in a lithium metal battery leads to an energy storage device having excellent mechanical resistance at temperature above ambient temperature and excellent ionic conductivity. The solid polymer electrolyte according to the present invention also has good mechanical strength and durability, and high thermal stability thereby limiting the development of concentration gradients in the electrolyte during discharge (or during charging). The use of this solid polymer electrolyte in a lithium metal battery makes it possible to limit dendritic growth of the lithium enabling quick and safe recharging. The solid polymer electrolyte according to the present invention substantially reduces the formation of heterogeneous electrodeposits of lithium (including dendrites) during recharging.
[0066] The solid polymer electrolyte 16 is stronger than prior art solid polymer electrolytes and may therefore be made thinner than prior art polymer electrolytes.
As outlined above the solid polymer electrolyte 16 may be as thin as 5 microns. A
thinner electrolyte in a battery results in a lighter battery and therefore a battery having a higher energy density. The increased strength of the solid polymer electrolyte 16 renders it more stable in manufacturing processes. The solid polymer electrolyte 16 is more tear resistant and may be less likely to wrinkle in the production process.
Date Recue/Date Received 2023-07-12 [0067] As illustrated in Figure 5, in one specific embodiment, the solid polymer electrolyte 25 consists of a bilayer assembly comprising a base layer 26 of between 5 and 50 microns consisting of a standard homopolymer or copolymer of polyethylene oxide as described in US Pat No. 6,855,788 or a blend of homopolymer or copolymer as described in EP2235784, and a thin surface layer 27 of less than 20 microns consisting of one of the triblock copolymer of the BAB type described above. The thin surface layer 27 being pressed against the lithium metal anode to provide a barrier against dendrites' growth. In another embodiment as illustrated in Figure 6, the solid polymer electrolyte 30 consists of a trilayer assembly comprising a base layer 26 of between 5 and 50 microns consisting of a standard homopolymer or copolymer of polyethylene oxide as described in US Pat No.
6,855,788 or a blend of homopolymer or copolymer as described in EP2235784, a thin layer 27 of less than 20 microns consisting of one of the triblock copolymer of the BAB type described above and a thin surface layer 31 consisting of a standard homopolymer or copolymer of polyethylene oxide described above acting as an adhesion promoter on the lithium metal anode.
Date Recue/Date Received 2023-07-12
Claims (15)
1. A solid polymer electrolyte for a battery, the solid polymer electrolyte including a diblock of the AB type or a triblock copolymer of the BAB type, in which:
block A is an unsubstituted polyethylene oxide chain having a number-average molecular weight less than 80,000 g/mol;
block B is an anionic polymer prepared from:
(i) one or more monomers selected from vinyl monomers or derivatives thereof to which is grafted an anion of lithium salt, and (ii) one or more monomers which are cross-linkable polyfunctional monomers having pendant chemical functions R1 and/or R2 that did not participate in the initial polymerization reaction that is post-reacted for cross-linking to form a cross-linked copolymer network.
block A is an unsubstituted polyethylene oxide chain having a number-average molecular weight less than 80,000 g/mol;
block B is an anionic polymer prepared from:
(i) one or more monomers selected from vinyl monomers or derivatives thereof to which is grafted an anion of lithium salt, and (ii) one or more monomers which are cross-linkable polyfunctional monomers having pendant chemical functions R1 and/or R2 that did not participate in the initial polymerization reaction that is post-reacted for cross-linking to form a cross-linked copolymer network.
2. The solid polymer electrolyte as defined in claim 1, wherein the cross-linkable polyfunctional monomers include reactive groups for the initial polymerisation reaction, wherein the reactive group is a vinyl phenyl substituted in ortho, meta or para position, an acrylate, a methacrylate, an allyl, an acrylamide, a methacrylamide, or a vinyl.
3. The solid polymer electrolyte as defined in claim 1, wherein the pendant chemical functions R1 and/or R2 are localized at an end of the B block of the copolymer chain or statistically or block or alternate or gradient distributed in the B block of the copolymer chain.
4. The solid polymer electrolyte as defined in claim 2, wherein the pendant chemical functions R1 and/or R2 are linked to the reactive groups of the polyfunctional monomers by a linear or cyclic alkyl, an aryl, an alkyl fluoride, an ether, an ester, an amide, a thioether, a tertiary amine, a quaternary ammonium, a urethane, a thiourethane, a silane, an ethylene glycol, a propylene glycol, a low molecular weight poly(ethylene glycol), a low molecular weight poly(propylene glycol), or a mixture of these groups.
5. The solid polymer electrolyte as defined in claim 1, wherein the anion of lithium salt is LiCF3S03, LiB(C204)2, LiN(CF3S02)2, LiN(FS02)2, LiC(CF3S02)3, LiC(CH3)(CF3S02)2, LiCH(CF3S02)2, LiCH2(CF3S02), LiC2F5S03, LiN(C2F5S02)2, LiN(CF3S02), LiB(CF3S02)2, LiPF6, LiSbF6, LiC104, LiSCN, LiAsF6, or LiBF4.
6. The solid polymer electrolyte as defined in claim 1, wherein the proportion of the polymers of block A relative to block B is between 40% and 80% weight.
7. The solid polymer electrolyte as defined in claim 1, comprising identical copolymer chains each having cross-linkable polyfunctional monomers having pendant chemical functions R1 and R2 randomly distributed along the B block of the copolymer chain, and wherein functions R1 and R2 react with each other to form the cross-linked copolymer network.
8. The solid polymer electrolyte as defined in claim 1, comprising two different copolymer chains having cross-linkable polyfunctional monomers, a first copolymer chain carrying pendant chemical function R1 only and a second copolymer chain carrying pendant chemical function R2 only, and wherein functions RI and R2 react with each other to form the cross-linked copolymer network.
9. The solid polymer electrolyte as defined in claim 1, comprising identical copolymer chains each having cross-linkable polyfunctional monomers having pendant chemical function RI only that cannot react with itself, and a molecule carrying at least two chemical functions R2 that can react with chemical function RI , wherein the pendant chemical function RI of the identical copolymer chains reacts with the at least two chemical functions R2 of the molecule carrying at least two chemical functions R2 to form the cross-linked copolymer network.
10. The solid polymer electrolyte as defined in claim 1, comprising identical copolymer chains each having cross-linkable polyfunctional monomers having pendant chemical function RI only that can react with itself, wherein the pendant chemical functions RI of each identical copolymer chains react with each other to form the cross-linked copolymer network.
11. The solid polymer electrolyte as defined in claim 7, wherein the copolymer chains each carry as a function RI , an azide and as a function R2, a propargyl protected by a silane or not.
12. The solid polymer electrolyte as defined in claim 8, wherein the first copolymer chain comprises a function RI of the type alcohol or its salts and the second copolymer chain comprises a function R2 being a carboxylic acid or its salts, a isocyanate, a isothiocyanate, an oxirane, a sulfonic acid or its salts, a phosphonic acid or its salts, a carbonate, or a halide.
13. The solid polymer electrolyte as defined in claim 8, wherein the first copolymer chain comprises a function RI of the type azide and the second copolymer chain comprises a function R2 of the type propargyl protected by a silane or not.
14. The solid polymer electrolyte as defined in claim 8, wherein the first copolymer chain comprises a function RI of the type oxirane and the second copolymer chain comprises a function R2 being sulfonic acid or its salts, or phosphonic acid or its salts.
15. A battery having a plurality of electrochemical cells, each electrochemical cell including a metallic lithium anode, a cathode, and a solid polymer electrolyte layer, the solid polymer electrolyte layer including the solid polymer electrolyte according to claim 1.
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| US201762469242P | 2017-03-09 | 2017-03-09 | |
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| US15/821,991 US10854919B2 (en) | 2017-03-09 | 2017-11-24 | Block copolymer electrolyte for lithium batteries |
| US15/821,991 | 2017-11-24 | ||
| PCT/CA2018/000050 WO2018161150A1 (en) | 2017-03-09 | 2018-03-09 | Block copolymer electrolyte for lithium batteries |
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| FR3083006A1 (en) * | 2018-06-22 | 2019-12-27 | Institut Polytechnique De Grenoble | SOLID POLYMER ELECTROLYTE, PREPARATION METHOD THEREOF, AND ELECTROCHEMICAL ACCUMULATOR / CELL COMPRISING SAME |
| EP3861580A4 (en) * | 2018-10-03 | 2022-08-03 | The Board of Trustees of the Leland Stanford Junior University | ION-CONDUCTING ORGANIC NETWORKS FOR BATTERY APPLICATIONS |
| FR3088932B1 (en) * | 2018-11-27 | 2020-11-20 | Blue Solutions | POLYMERIC ELECTROLYTE FOR LITHIUM METAL POLYMER BATTERY WITH IMPROVED PERFORMANCE |
| CN112635840B (en) * | 2020-12-21 | 2021-12-14 | 中南大学 | Preparation method of HNTs plasticized PAN/P (LLA-EG-MA) biogel polymer electrolyte and product thereof |
| CN112652813B (en) * | 2020-12-21 | 2022-04-08 | 中南大学 | A kind of biogel electrolyte composed of PAN and modified PLLA and preparation method thereof |
| US12407020B2 (en) * | 2021-03-25 | 2025-09-02 | Ut-Battelle, Llc | High ionic conductivity polymer electrolyte compositions for alkali and beyond alkali metal batteries |
| CN115528320B (en) * | 2021-06-24 | 2025-11-07 | 惠州比亚迪电池有限公司 | Metal lithium negative electrode, lithium secondary battery and vehicle |
| EP4303961A1 (en) * | 2022-07-04 | 2024-01-10 | The Swatch Group Research and Development Ltd | Polymerisable composition for solid polymer electrolyte |
| CN116315067A (en) * | 2023-03-02 | 2023-06-23 | 苏州清陶新能源科技有限公司 | A kind of polymer composite solid state electrolyte and its preparation method and lithium ion battery |
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| JP3396390B2 (en) * | 1997-03-04 | 2003-04-14 | 信越化学工業株式会社 | Block-graft copolymer, self-crosslinking polymer solid electrolyte produced using the same, and method for producing the same |
| WO2000005774A1 (en) | 1998-07-23 | 2000-02-03 | Massachusetts Institute Of Technology | Block copolymer electrolyte |
| US6956083B2 (en) | 2001-05-31 | 2005-10-18 | The Regents Of The University Of California | Single ion conductor cross-linked polymeric networks |
| WO2005117188A1 (en) | 2004-05-27 | 2005-12-08 | Dutch Polymer Institute | Polymer electrolyte; and an electrochemical device equipped with such a polymer electrolyte |
| FR2899235B1 (en) | 2006-03-31 | 2012-10-05 | Arkema | SOLID POLYMER ELECTROLYTES BASED ON TRIBLOC COPOLYMERS, IN PARTICULAR POLYSTYRENE-POLY (OXYETHYLENE) -POLYSTYRENE |
| WO2008149815A1 (en) | 2007-06-04 | 2008-12-11 | Kuraray Co., Ltd. | Polymer electrolyte, polymer electrolyte membrane, membrane-electrode assembly, and solid polymer fuel cell |
| WO2010027716A1 (en) * | 2008-08-25 | 2010-03-11 | Seeo, Inc | Polymer electrolyte materials based on block copolymers |
| KR101041722B1 (en) * | 2009-01-09 | 2011-06-14 | 주식회사 엘지화학 | Electrolyte including eutectic mixture and nitrile compound and electrochemical device having same |
| US9252456B2 (en) * | 2009-02-27 | 2016-02-02 | University Of Maryland, College Park | Polymer solid electrolyte for flexible batteries |
| FR2979630B1 (en) | 2011-09-05 | 2013-10-04 | Univ Provence Aix Marseille 1 | BLOCK COPOLYMERS HAVING A POLYANIONIC BASED ON ANION MONOMER TYPE TFSILI AS ELECTROLYTE BATTERY. |
| CN103509153B (en) | 2012-06-15 | 2016-05-25 | 华中科技大学 | A kind of polymer list ionic electrolytes and preparation method thereof |
| US10608280B2 (en) | 2015-03-09 | 2020-03-31 | California Institute Of Technology | Brush block copolymer electrolytes and electrocatalyst compositions |
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| CA3054448A1 (en) | 2018-09-13 |
| EP3593399B1 (en) | 2022-05-04 |
| KR20190125420A (en) | 2019-11-06 |
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