Battery comprising a polymeric organic electrode material decomposable into monomers by chemical and / or enzymatic reactions, production process, use, and method for recycling the battery

Abstract

Batteries are described which comprise, as redox-active electrode material, specific organic compounds that are recyclable by depolymerization. The present invention further relates to the use of these specific recyclable compounds as electrode material in batteries and to a process for producing batteries starting from corresponding recycled compounds.

Description

[0001] BATTERY COMPREHENSIVE OF A POLYMER ORGANIC ELECTRODE MATERIAL DETOXIFIABLE TO MONOMERS BY CHEMICAL AND / OR ENZYMATIC REACTIONS, METHOD FOR MANUFACTURING, USE AND METHOD FOR RECYCLING THE BATTERY

[0002] Description

[0003] The present invention relates to batteries comprising specific compounds recyclable by depolymerization as redox-active electrode material. A further subject of the present invention is the use of these specific recyclable compounds as electrode material in batteries, as well as a method for producing ion batteries, such as lithium-ion batteries, sodium-ion batteries, and potassium-ion batteries, starting from corresponding recycled compounds.

[0004] Energy storage systems are of great interest due to the increasing demand for better storage options for renewable energies such as water, wind, or solar power. When high energy density is required, lithium-ion batteries (LIBs) are particularly widespread today.

[0005] Lithium-ion batteries also include rechargeable batteries, which are widely used in many electronic devices, including energy storage systems, mobile phones, laptops, cameras, and electric cars. The advantages of lithium-ion batteries lie in their high energy density and their ability to maintain a constant voltage over extended periods. Due to the greater availability of sodium (Na) compared to lithium, sodium-ion batteries are also increasingly coming into focus.

[0006] In their simplest form, batteries consist of an anode and a cathode, separated by a separator, and an electrolyte that enables the transport of ions between the anode and cathode. In conventional lithium-ion batteries, the anode is usually made of Li-ion intercalated graphite, while the cathode can contain various materials such as lithium iron phosphate, lithium cobalt oxide, or lithium nickel manganese cobalt oxide. During charging, lithium ions migrate from the cathode to the anode, converting electrical energy into chemical energy. During discharging, the lithium ions migrate back from the anode to the cathode, converting the chemical energy back into electrical energy, which can then be used to power external electronic devices.

[0007] Lithium-ion batteries offer several key advantages compared to other battery types. These include, as previously mentioned, a high energy density, meaning they can store a lot of energy per unit of weight. They also have a low self-discharge rate compared to other rechargeable batteries, meaning the stored energy is retained for a longer period when not in use.

[0008] Although lithium-ion batteries offer many advantages, they also have some disadvantages. Due to the costly raw materials, they are more expensive to manufacture than other battery types such as nickel-cadmium or nickel-metal hydride batteries. Additionally, it must be considered that the necessary raw materials, such as nickel, manganese, cobalt, and lithium, are often mined under questionable conditions with regard to environmental protection, working conditions, and the health impact on the population. Their extraction sometimes causes significant environmental damage, and the poor working conditions and health problems to which people are exposed during mining and in the surrounding areas represent a major unresolved issue.

[0009] Against this background, energy storage devices with organic electrode materials are seen as an interesting option when it comes to reducing the extraction of the environmentally critical and, in the case of mining, harmful inorganic materials cobalt, manganese and nickel.

[0010] In "organic" batteries, organic materials are used as the active material in the anode or cathode, as the electrolyte, or for all three. Compared to conventional inorganic batteries, which use inorganic cathode materials such as lithium cobalt oxide, lithium iron phosphate, or lithium nickel manganese cobalt oxide, batteries with organic cathode materials offer some potential advantages, but also present challenges.

[0011] Many organic cathode materials exhibit high cycle stability and thus great durability. Furthermore, their plasticity makes them highly compatible with flexible substrates, opening up new design possibilities for certain applications, such as wearable or flexible electronics, which is advantageous.

[0012] Organic compounds used as active materials in the anode or cathode can be carbon-based molecules, such as organic polymers, or small organic molecules capable of being redox-active themselves while simultaneously storing and releasing ions. Organic redox-active materials could potentially lead to more cost-effective and environmentally friendly batteries, as they consist predominantly of the ubiquitously available elements carbon, hydrogen, oxygen, and nitrogen (with small amounts of sulfur and halogens also possible) and can therefore, in principle, be synthesized from renewable resources.

[0013] Recycling electrode materials is another important aspect of sustainability in battery technology. In Europe, only about half of all batteries are recycled after their typical lifespan. The raw materials from the other half are lost and pose an environmental problem when disposed of or stored in landfills, as the toxic metals cobalt and nickel can leach into the environment.

[0014] Even though the recycling of inorganic electrode materials is not yet widespread, the recovery of raw materials from old conventional batteries and from production rejects during manufacturing is now an established technique.

[0015] The conventional recycling method for lithium-ion batteries, for example, usually involves a combination of pyrometallurgy and hydrometallurgy. During pyrometallurgy, the organic compounds in the lithium-ion batteries are burned, and the metals are melted down to form an alloy. A disadvantage of pyrometallurgy is the high energy input required.

[0016] In the subsequent hydrometallurgy process, iron, copper, cobalt, and nickel are extracted. Manganese, lithium, and aluminum are difficult to recover using this method. Hydrometallurgy is less energy-intensive and more cost-effective, but it produces large quantities of contaminated water, for example, due to electrolyte residues. Further extraction of the metals is achieved through processing using selective precipitation, ion exchange, and, if necessary, newer membrane processes.

[0017] In addition to the aforementioned conventional recycling methods, a more modern alternative is biohydrometallurgy, in which metal ions are leached out using microorganisms and their metabolic products through so-called biological leaching. However, this method has the disadvantage of being very time-consuming due to the difficult cultivation of the bacteria.

[0018] Regarding organic electrode materials, it should be noted that the raw materials used are predominantly based on the readily available elements H, C, N, and O, rather than on the expensively mined (heavy) metals required for the production of conventional inorganic lithium-ion batteries. Therefore, when organic batteries are discussed, sustainability and "green" energy are often cited as advantages. However, initial studies have shown that the production of organic cathode materials has a 10-100 times worse environmental footprint (averaged across all midpoint categories) than the production of an inorganic cathode material.

[0019] The reasons for the poorer environmental footprint compared to inorganic materials lie not only in their lower specific capacity but also in the large number of consecutive synthesis steps required to synthesize suitable redox-active systems from primary chemicals. These synthesis steps sometimes involve the use of solvents or reactants, which negatively impact the overall environmental footprint. Furthermore, the necessary heating in some reaction steps and the energy required for this are considerable. In addition, solvent-intensive purification steps must be carried out between the synthesis steps.One way to reduce the environmental and economic costs of producing organic electrode materials and thus make them competitive (both economically and ecologically) is to recycle these materials so they can be reused. Ideally, the organic electrode materials should be broken down into their original molecules during the recycling process so that new electrode materials can be produced from them.

[0020] If soluble materials could be used as redox materials in electrodes, recycling would be simple. However, materials that are soluble in the electrolyte in both charged and uncharged states are poorly suited as electrode materials. They dissolve in the electrolyte during use, and the energy storage device thus gradually loses capacity.

[0021] For the lifespan of an energy storage device, it is therefore crucial that the electrode material does not dissolve in the electrolyte, whether charged or uncharged. Polymers with many redox units are ideal for this purpose. Due to polymerization and / or cross-linking, they are insoluble in the electrolyte, but the redox properties of the individual units can be utilized.

[0022] However, polymers are difficult to recycle. To recover the individual redox units, the polymerization process must be reversed, which is not always possible.

[0023] US 2024 / 0010624 A describes a tricyclic compound with a redox potential of 0.2 V to 2.0 V that can be used as an electrode material in lithium batteries. It further describes that the tricyclic compound can be polymerized via a linker, such as an alkyl spacer. The resulting polymer cannot be depolymerized; therefore, recycling the electrode material by depolymerization, for example, via chemical and / or enzymatic reactions, is not possible.

[0024] US 2022 / 006089 A describes an electrode material that includes, among other things, an organic redox polymer. An example of the redox polymer is MPT (N-methylphenothiazine), which does not contain a linker that can be depolymerized.

[0025] Therefore, this publication does not teach how the organic electrode material can be recycled.

[0026] US 11,739,173 B describes an electrode material based on 9,10-phenanthrenquinone, which is linked to form a polymer by a linker that does not participate in the redox reaction. The linker is di- or trivalent and its structure is based on a phenyl ring. The resulting polymer comprises an alternating structure between the redox-active unit and the linker. This publication provides no indication that the resulting electrode material can be recycled by depolymerization after use.

[0027] US 11,881,580 B describes polymeric electrode materials that can comprise a variety of different redox-active units. Furthermore, a variety of linkers are described in the document. However, the document does not provide any specific information on polymeric electrode materials that can be recycled by depolymerization after use.

[0028] The state of the art discussed above does not, in its entirety, provide a battery that, after completing a full life cycle with respect to the organic electrode material used, is subsequently subjected to extraction, depolymerization, separation, purification, and repolymerization for use in a new battery. Task

[0029] The objective of the present invention is therefore to provide organic polymeric and / or cross-linked electrode materials that can be reused by recycling after their use as electrode materials. This reuse improves the environmental footprint of these materials, which must be produced and purified via several synthesis steps, making them competitive or, depending on the category, superior to previously established (often inorganic / heavy metal-containing) electrode materials.

[0030] The battery according to the invention should simultaneously have a satisfactory capacity and discharge voltage and be able to undergo a large number of charging and discharging cycles.

[0031] Solution to the task

[0032] These tasks are solved by a battery comprising a polymeric organic electrode material which can be broken down into monomers by chemical and / or enzymatic reactions.

[0033] According to the invention, it has been found that it is possible to efficiently provide high-performance batteries comprising a polymeric and / or cross-linked electrode material which can be depolymerized and thus recycled by certain processes.

[0034] This allows for the provision of a battery that is both powerful and meets the aforementioned economic and environmental requirements.

[0035] The batteries according to the invention can, in principle, be any ionic batteries in which an organic electrode material is used that is recyclable. Examples of suitable batteries are lithium-ion batteries, sodium-ion batteries, potassium-ion batteries, magnesium-ion batteries, aluminum-ion batteries, zinc-ion batteries, and calcium-ion batteries, whereby, within the scope of the present invention, lithium-ion batteries and sodium-ion batteries, in particular lithium-ion batteries, are preferred.

[0036] The electrode material used in these batteries according to the invention is typically composed of organic redox-active units. This means that the structures can be reversibly oxidized and reduced, i.e., they can donate or accept electrons. The redox potential should be greater than 0.5 volts relative to a conventional battery anode, preferably greater than 2 volts, and even better, greater than 3 volts. Within the scope of the present invention, the electrode material composed of the redox-active units must be designed to be depolymerizable, so that the electrode material can be broken down into monomeric structures that constitute the electrode material.Within the scope of the present invention, the term redox-active units is therefore understood to mean organic structures of a polymeric compound which have the ability to donate and accept electrons in electrochemical reactions, i.e., to undergo redox reactions (oxidation and reduction).

[0037] For this purpose according to the invention, redox-active units linked via linkers (= linker molecules) are suitable, for example, wherein the covalent bonds between the redox-active units and the linkers can be cleaved by depolymerization reactions and the corresponding monomers (linker; redox-active unit) can be recovered. Furthermore, organic polymeric compounds consisting of redox-active units that do not require linkers are also suitable as electrode materials according to the invention, but whose covalent bonds between the redox-active units can likewise be cleaved by depolymerization reactions.

[0038] If, within the scope of the present invention, polymeric organic electrode materials in which redox-active units are linked via linkers are used, the linkers themselves can be either redox-inactive or redox-active. If the linker is redox-active, it can also be considered a redox-active unit. Thus, the resulting battery capacity can be increased compared to structures with redox-inactive linkers. Redox-active linkers are either the structurally identical counterpart to the redox-active unit used, required for polymerization, or a different redox-active unit capable of undergoing the desired polymerization.

[0039] Within the scope of the present invention, it is provided that the polymeric organic electrode material is depolymerizable. A polymeric organic electrode material that is depolymerizable within the scope of the present invention is understood to be an organic material that can be converted into its monomers by chemical and / or enzymatic degradation.

[0040] The following describes an organic polymeric electrode material that is produced using linkers.

[0041] In the case that an organic polymeric electrode material is used within the scope of the present invention, which is produced using linkers, the linker can connect at least two organic redox-active units.

[0042] In a further embodiment of the present invention, an organic polymeric electrode material is used which is produced using linkers, wherein the linker connects at least three organic redox-active units.

[0043] In a further embodiment of the present invention, an organic polymeric electrode material is used, which is produced using linkers, wherein the linker connects at least four organic redox-active units. In a further embodiment of the present invention, an organic polymeric electrode material is used, which is produced using linkers, wherein the linkers themselves are polymeric systems, e.g., L38 and L39, which are equipped with reactive groups and can connect at least two and at most 14,000 redox-active units.

[0044] If only a chain-like polymer is formed, it can remain soluble in the electrolyte solvent up to a relatively high number of monomer units (in charged or uncharged states). As soon as the polymer chains are crosslinked at a few points by at least a trivalent linker, they become insoluble in the electrolyte solution even at a significantly lower molecular weight. A higher degree of crosslinking results in a denser polymer network. The denser the network, the less able counterions, which are needed for charge balance in the electrode, can penetrate and egress. In a dense network, large counterions penetrate less readily than small counterions. Therefore, it is important to achieve a degree of crosslinking that is just high enough to make the electrode insoluble in the electrolyte solvent, while simultaneously creating a polymer network that is as flexible and open-pored as possible.The more flexible and less dense the polymer network, the better counterions can penetrate the electrode, and the more completely and quickly it can be charged and discharged. Furthermore, due to its flexibility, a loose network is more likely to expand and contract (breathe) during charging and discharging—that is, during the entry and exit of counterions—without sustaining mechanical damage.

[0045] As already explained, it is possible that the linker itself is redox-active or redox-inactive.

[0046] By using linkers that are redox-active, the capacity of the resulting battery according to the invention can be increased.

[0047] To ensure the requirement of depolymerizability of the organic electrode material according to the invention, the organic electrode material is preferably built up from the organic redox-active unit(s) and the linker(s) by a step growth reaction.

[0048] These step-growth reactions can, for example, be a polycondensation or a polyaddition reaction of the organic redox-active unit and the linker.

[0049] Within the scope of the present invention, electrode materials comprising monomers (redox-active unit and structurally identical or different linkers L') that react with one another to form polyesters, polyamides, polyimides, or polyazomethines are particularly advantageous. Other suitable polymer structures include polyurethanes, polyethers, and polyureas. The redox-active unit, entering the polymerization as a monomer, should have at least two functional groups A2 or A / B. A and B are -COOH and / or -OH for polyesters, -COOH and / or -NH2 for polyamides, -C(O)-OC(O)- and / or -NH2 for polyimides, -CHO and / or -NH2 for polyazomethines, -N=C=O and / or -OH for polyurethanes, -epoxy or -oxetane and / or -OH for polyethers, and -N=C=O and / or -NH2 for polyureas.The linker also has at least two functional groups B2 or B / A, which are the corresponding complementary groups necessary for polymerization.

[0050] In a first embodiment, it is preferred if the polymeric organic electrode material, comprising the redox-active unit and the linker L', comprises a general structure of the repeating unit selected from the group consisting of where

[0051] L' represents a linker that connects two redox-active units via a functional group (rFG), where rFG stands for -COO- for polyesters, -C(O)-NH- for polyamides, - (C(O))2-N- for polyimide, -C=N- for polyazomethines, -O-CO-NH- for polyurethanes, -O- for polyethers and -NH-CO-NH- for polyureas.

[0052] Ri for hydrogen, linear or branched Ci-Ce-alkyl; -O-(CH2)n-CH3 (with n being an integer < 6); -O-((CH2)2O)n -CH3 (where n is an integer < 6), -OMe, -F, -CI, -Br or -I, and

[0053] R2 stands for linear or branched Ci-Ce-acyl,

[0054] A and B represent the functional groups remaining as end groups (i.e., -COOH and / or -OH for polyesters, -COOH and / or -NH2 for polyamides, -C(O)-OC(O)- and / or -NH2 for polyimides, -CHO and / or -NH2 for polyazomethines, -N=C=O and / or -OH for polyurethanes, -epoxy or -oxetanes and / or -OH for polyethers, -N=C=O and / or -NH2 for polyureas).

[0055] The corresponding repeating units of the electrode materials are represented in the general formulas (1a), (1b), (Ic), (Ila), (Hb), (lie), (III), (IVa), and (IVb). The electrode materials may contain further structural units. In the general structures of the aforementioned repeating unit, several Ri residues of the same or different chemical structures may be present on an aromatic ring.

[0056] In one embodiment of the present invention, the repeating unit of the electrode materials is characterized in particular by the general formulas (1a), (1b), (1c), (Ha), (Hb), (He), (III), (IVa) and (IVb).

[0057] In a second embodiment, it is preferred if the polymeric organic electrode material, comprising the redox-active unit and the linker L', comprises a general structure of the repeating unit selected from the group consisting of

[0058] where

[0059] L' represents a linker that connects two redox-active units via a functional group (rFG), where rFG stands for -COO- for polyesters, -CONH- for polyamides, - (C(O))2-N- for polyimides, -C=N- for polyazomethines, -O-CO-NH- for polyurethanes, -O- for polyethers, and -NH-CO-NH- for polyureas.

[0060] Ri for hydrogen, linear or branched Ci-Ce-alkyl; -O-(CH2)n-CH3; -O-((CH2)2O) n - CH3 (where n is an integer < 6), -OMe, -F, -CI, -Br or -I, R2 stands for linear or branched Ci-Ce-acyl,

[0061] A or B represents the functional groups remaining as end groups (i.e., -COOH and / or -OH for polyesters, -COOH and / or -NH2 for polyamides, -C(O)-OC(O)- and / or -NH2 for polyimides, -CHO and / or -NH2 for polyazomethines or -N=C=O and / or -OH for polyurethanes, -epoxy or -oxetanes and / or -OH for polyethers, -N=C=O and / or -NH2 for polyureas), wherein the electrode material additionally comprises at least 1% of three-dimensional cross-links and wherein the three-dimensional cross-links are formed by the additional use of at least triple-functionalized linkers.

[0062] The number of three-dimensional cross-links in the electrode material of the second embodiment is preferably at least 2%, more preferably at least 3%, more preferably at least 4%, more preferably at least 5%, more preferably at least 6%, more preferably at least 7%, more preferably at least 8%, more preferably at least 9%, more preferably at least 10%, more preferably at least 11%, more preferably at least 12%, more preferably at least 13%, more preferably at least 14%, more preferably at least 15%, more preferably at least 16%, more preferably at least 17%, more preferably at least 18%, more preferably at least 19%, more preferably at least 20%, more preferably at least 25%, more preferably at least 30%, more preferably at least 35%, more preferably at least 40%, more preferably at least 45%, more preferably at least 50%, more preferably at least 55%.further preferably at least 60%, further preferably at least 65%, further preferably at least 70%, further preferably at least 75%, further preferably at least 80%, further preferably at least 85%, further preferably at least 90%, further preferably at least 95%, further preferably at most 100%. The number of three-dimensional crosslinks in the electrode material of the second embodiment of the present invention is understood to be the ratio of crosslinks via linkers that are covalently bonded to the redox-active units at at least three functional groups to linkers that are covalently bonded to the redox-active units at two functional groups.

[0063] For this purpose, the linker that creates the branch point comprises at least three functional groups suitable for polymerization.

[0064] There are basically two ways to construct the organic electrode material from a redox-active unit and a linker.

[0065] Either a polymeric system in the form of an A2B2 system or an AB system of the polymeric organic electrode material is provided. Corresponding polymerizations are shown in Figure 1 of the present application. Figure 1 schematically shows the polymerization of A2 and B2 monomers (top) and of A2B2 monomer (bottom) to form a polymer. If at least a trifunctional linker is used, a cross-linked polymer is formed instead of a linear polymer. As shown in Figure 1, in the case of the A2B2 polymerization, a monomer with two identical chemically reactive functional groups (A2) is required. The redox unit used is represented as a filled circle and possesses the desired properties for charge transport and storage. The reactive groups A are represented as unfilled circles, and the reactive groups B as unfilled semicircles.The line between the redox unit and the functional group symbolized a covalent chemical compound.

[0066] Examples of A2 monomers are those based on the redox unit triphenylamine (TPA, 1a, Ic). Other examples are redox units based on N-phenylcarbazole (PhCbz, Ib), triphenylamine dimer (TPD, Ia, lie), N-phenylcarbazole dimer (PhCbzD, Hb), phenothiazines (PT, III), or anthraquinone (AQ, IV). The B2 monomer can, as shown in Figure 1, function solely as a chemical compound, or it can also possess a redox unit between its functional groups.

[0067] The functional units A and B react to form a chemical bond. Therefore, in addition to the A2 monomer, the equally bifunctional complementary chemical B2 counterpart (linker) is required for the formation of a polymer through polymerization.

[0068] In the other case, a monomer (AB) can be synthesized which possesses two different functional groups, namely an A group and a B group. This can react with a monomer of the same structure. Here, too, the functional groups A and B form a chemical bond with each other. In these last two cases, a linear polymer is formed without the addition of a linker. However, the use of at least a bifunctional linker is not precluded; this linker must then also possess the functional groups A and B.

[0069] If, on the other hand, a cross-linked polymer is desired within the scope of the present invention, at least a trifunctional molecule is added as a linker, which is covered in the second embodiment described above according to the invention.

[0070] The redox-active linkers used in this way within the scope of the present invention according to the first and second embodiments for the formation of the polymeric organic electrode material can, for example, be selected from the group consisting of

[0071] HOJ OH

[0072] ' 'n (L1)

[0073] HOOCv COOH

[0074] ' ' n (L2) where the linkers L1 to L6 can have a carbon chain with 1 to 10 carbon atoms between the functional end groups, or the carbon chain can be replaced by -((CH2)2O)n with a number n equal to 1 to 10, ,) and x, y, z and w each represent 1 to 7000 repeating units, and the polymeric linkers L38 and L39 are present as alternating, block co- or statistical polymers.

[0075] The polymeric organic electrode material according to the invention, as defined by formulas (1a), (1b), (1lie), (1a), (Hb), (1le), (III), (IVa) and (IVb), preferably comprises reacted functional groups in the polymer structure corresponding to the following structural units: rFG = -COO- for polyesters, -CONH- for polyamides, -(C(O))2-N- for polyimide, -C=N- for polyazomethines or -O-CO-NH- for polyurethanes, -O- for polyethers, -NH-CO-NH- for polyureas rFG= -O-

[0076] -O(O)C- or -C(O)O-

[0077] -(C(O))2-N-

[0078] -C=N- or -N=C-

[0079] -C(O)NH- or -NHC(O) -

[0080] -O-CO-NH- or -NH-CO-O-

[0081] -NH-CO-NH- wherein the linkers L' may have two functional groups or more than two functional groups and are derived from the aforementioned linkers L1 to L42, and

[0082] A and B stand for the functional groups remaining as end groups (i.e., -COOH and / or -OH for polyesters, -COOH and / or -NH2 for polyamides, -C(O)-OC(O)- and / or -NH2 for polyimides, -CHO and / or -NH2 for polyazomethines, -N=C=O and / or -OH for polyurethanes, -epoxy or -oxetanes and / or -OH for polyethers, -N=C=O and / or -NH2 for polyureas).

[0083] Preferred embodiments of the polymeric organic electrode material are described below.

[0084] In a first embodiment, the polymeric organic electrode material comprises the general structure (1a) on where rFG and L' have the following meaning: rFG = -O-

[0085] -O(O)C- or -0(0)0-

[0086] -(C(0))2-N-

[0087] -C=N- or -N=C-

[0088] -C(O)NH- or -NHC(O)-

[0089] -O-CO-NH- or -NH-CO-O-

[0090] -NH-CO-NH- wherein the linkers L' may have two functional groups or more than two functional groups and are derived from the aforementioned linkers L1 to L42, and

[0091] Ri stands for hydrogen, linear or branched Ci-Ce-alkyl; -O-(CH2)ni-CH3 with n = 1 to 6, -F, -CI, -Br or -I, and

[0092] A and B stand for the functional groups remaining as end groups (i.e., -COOH and / or -OH for polyesters, -COOH and / or -NH2 for polyamides, -C(O)-OC(O)- and / or -NH2 for polyimides, -CHO and / or -NH2 for polyazomethines, -N=C=O and / or -OH for polyurethanes, -epoxy or -oxetanes and / or -OH for polyethers, -N=C=O and / or -NH2 for polyureas).

[0093] Specific examples of monomeric redox units that can be used to prepare organic compounds of the general formula (1a) are the following compounds:

[0094] (4) (5) (6)

[0095]

[0096] Specific examples of redox-active polymers corresponding to the compounds of the general formula (1a) are the following compounds: where n and m, each independently of each other, represent an integer number from 3 to 100 and * represents a branch point.

[0097] In a second embodiment, the polymeric organic electrode material comprises the general structure (Ib) where rFG and L' have the following meaning: rFG = -O-

[0098] -O(O)C- or -0(0)0-

[0099] -(C(0))2-N-

[0100] -C=N- or -N=C-

[0101] -C(O)NH- or -NHC(O) -

[0102] -O-CO-NH- or -NH-CO-O-

[0103] -NH-CO-NH- wherein the linkers L' may have two functional groups or more than two functional groups and are derived from the aforementioned linkers L1 to L42, and

[0104] Ri stands for hydrogen, linear or branched Ci-Ce-alkyl; -O-(CH2)ni-CH3 with n = 1 to 6, - F, -CI, -Br or -I, and A or B stands for the functional groups remaining as end groups (i.e., - COOH and / or -OH for polyesters, -COOH and / or -NH2 for polyamides, -C(O)-OC(O)- and / or -NH2 for polyimides, -CHO and / or -NH2 for polyazomethines or -N=C=O and / or -OH for polyurethanes, -epoxy or -oxetanes and / or -OH for polyethers, - N=C=O and / or -NH2 for polyureas).

[0105] Specific examples of monomeric redox units that can be used to prepare organic compounds of the general formula (Ib) are the following compounds:

[0106]

[0107] In a third embodiment, the polymeric organic electrode material has the general structure (I ala) where rFG and L' have the following meaning: rFG = -O-

[0108] -O(O)C- or -0(0)0-

[0109] -(C(0))2-N-

[0110] -C=N- or -N=C-

[0111] -C(O)NH- or -NHC(O)-

[0112] -O-CO-NH- or -NH-CO-O-

[0113] -NH-CO-NH- wherein the linkers L' may have two functional groups or more than two functional groups and are derived from the aforementioned linkers L1 to L42, and

[0114] Ri stands for hydrogen, linear or branched Ci-Ce-alkyl; -O-(CH2)ni-CH3 with n = 1 to 6, -F, -CI, -Br or -I, and

[0115] A and B stand for the functional groups remaining as end groups (i.e., -COOH and / or -OH for polyesters, -COOH and / or -NH2 for polyamides, -C(O)-OC(O)- and / or -NH2 for polyimides, -CHO and / or -NH2 for polyazomethines, -N=C=O and / or -OH for polyurethanes, -epoxy or -oxetanes and / or -OH for polyethers, -N=C=O and / or -NH2 for polyureas).

[0116] Specific examples of monomeric redox units that can be used to prepare organic compounds of the general formula (Ha) are the following compounds:

[0117] In a fourth embodiment, the polymeric organic electrode material has the general structure (II b) where rFG and L' have the following meaning: rFG = -O-

[0118] -O(O)C- or -0(0)0-

[0119] -(C(0))2-N-

[0120] -C=N- or -N=C-

[0121] -C(O)NH- or -NHC(O)-

[0122] -O-CO-NH- or -NH-CO-O-

[0123] -NH-CO-NH- wherein the linkers L' may have two functional groups or more than two functional groups and are derived from the aforementioned linkers L1 to L42, and

[0124] Ri stands for hydrogen, linear or branched Ci-Ce-alkyl; -O-(CH2)ni-CH3 with n = 1 to 6, - F, -CI, -Br or -I, and A or B stands for the functional groups remaining as end groups (i.e., - COOH and / or -OH for polyesters, -COOH and / or -NH2 for polyamides, -C(O)-OC(O)- and / or -NH2 for polyimides, -CHO and / or -NH2 for polyazomethines or -N=C=O and / or -OH for polyurethanes, -epoxy or -oxetanes and / or -OH for polyethers, - N=C=O and / or -NH2 for polyureas).

[0125] Specific examples of monomeric redox units that can be used to prepare organic compounds of the general formula (Hb) are the following compounds:

[0126]

[0127] In a fifth embodiment, the polymeric organic electrode material has the general structure (III).

[0128] (mi where rFG and L' have the following meaning: rFG= -O-

[0129] -O(O)C- or -0(0)0-

[0130] -(C(0))2-N-

[0131] -C=N- or -N=C- -C(O)NH- or -NHC(O)-

[0132] -O-CO-NH- or -NH-CO-O-

[0133] -NH-CO-NH- wherein the linkers L' may have two functional groups or more than two functional groups and are derived from the linkers L1 to L42 mentioned above,

[0134] Ri stands for hydrogen, linear or branched Ci-Ce-alkyl; -O-(CH2)ni-CH3 with n = 1 to 6, -F, -CI, -Br or -I, and

[0135] R2 stands for linear or branched Ci-alkyl to Ce-alkyl, and

[0136] A and B stand for the functional groups remaining as end groups (i.e., -COOH and / or -OH for polyesters, -COOH and / or -NH2 for polyamides, -C(O)-OC(O)- and / or -NH2 for polyimides, -CHO and / or -NH2 for polyazomethines, -N=C=O and / or -OH for polyurethanes, -epoxy or -oxetanes and / or -OH for polyethers, -N=C=O and / or -NH2 for polyureas).

[0137] Specific examples of monomeric redox units that can be used to prepare organic compounds of general formula (III) are the following compounds:

[0138] In a sixth embodiment, the polymeric organic electrode material has the general structure (IVa) or (IVb). where rFG and L' have the following meaning: rFG = -O-

[0139] -O(O)C- or -0(0)0-

[0140] -(C(0))2-N-

[0141] -C=N- or -N=C-

[0142] -C(O)NH- or -NHC(O)-

[0143] -O-CO-NH- or -NH-CO-O-

[0144] -NH-CO-NH- wherein the linkers L' may have two functional groups or more than two functional groups and are derived from the linkers L1 to L42 mentioned above,

[0145] Ri stands for hydrogen, linear or branched Ci-Ce-alkyl; -O-(CH2)ni-CH3 with n = 1 to 6, -F, -CI, -Br or -I, and

[0146] A and B represent the functional groups remaining as end groups (i.e., -COOH and / or -OH for polyesters, -COOH and / or -NH2 for polyamides, -C(O)-OC(O)- and / or -NH2 for polyimides, -CHO and / or -NH2 for polyazomethines, -N=C=O and / or -OH for polyurethanes, -epoxy or -oxetanes and / or -OH for polyethers, -N=C=O and / or -NH2 for polyureas). Specific examples of monomeric redox units that can be used to prepare organic compounds of general formula (IV) are the following compounds:

[0147]

[0148] In a seventh embodiment, the polymeric organic electrode material comprises the general structure (Ic) on where rFG and L' have the following meaning: rFG = -O-

[0149] -O(O)C- or -0(0)0-

[0150] -(C(0))2-N-

[0151] -C=N- or -N=C- -C(O)NH- or -NHC(O)-

[0152] -O-CO-NH- or -NH-CO-O-

[0153] -NH-CO-NH- wherein the linkers L' may have two functional groups or more than two functional groups and are derived from the aforementioned linkers L1 to L42, and

[0154] Ri for hydrogen, linear or branched Ci-Ce-alkyl; -O-(CH2)ni-CH3 with n = 1 to 6, -

[0155] F, -CI, -Br or -I stands for, and A or B stands for the functional groups remaining as end groups (i.e., -COOH and / or -OH for polyesters, -COOH and / or -NH2 for polyamides, -C(O)-OC(O)- and / or -NH2 for polyimides, -CHO and / or -NH2 for polyazomethines or -N=C=O and / or -OH for polyurethanes, -epoxy or -oxetanes and / or -OH for polyethers, -N=C=O and / or -NH2 for polyureas).

[0156] Specific examples of monomeric redox units that can be used to prepare organic compounds of the general formula (Ic) are the following compounds: In an eighth embodiment, the polymeric organic electrode material comprises the general structure (I Ic) on where rFG and L' have the following meaning: rFG = -O-

[0157] -O(O)C- or -0(0)0-

[0158] -(C(0))2-N-

[0159] -C=N- or -N=C-

[0160] -C(O)NH- or -NHC(O)-

[0161] -O-CO-NH- or -NH-CO-O-

[0162] -NH-CO-NH- wherein the linkers L' may have two functional groups or more than two functional groups and are derived from the aforementioned linkers L1 to L42, and

[0163] Ri stands for hydrogen, linear or branched Ci-Ce-alkyl; -O-(CH2)ni-CH3 with n = 1 to 6, -F, -CI, -Br or -I, and

[0164] A and B stand for the functional groups remaining as end groups (i.e., -COOH and / or -OH for polyesters, -COOH and / or -NH2 for polyamides, -C(O)-OC(O)- and / or -NH2 for polyimides, -CHO and / or -NH2 for polyazomethines, -N=C=O and / or -OH for polyurethanes, -epoxy or -oxetanes and / or -OH for polyethers, -N=C=O and / or -NH2 for polyureas).

[0165] Specific examples of monomeric redox units that can be used to prepare organic compounds of the general formula (llc) are the following compounds:

[0166] (442) (443)

[0167] The linkers L used in the present invention, which are used to produce the above-described polymeric organic electrode materials according to formulas (1a), (1b), (1c), (1a), (Hb), (1le), (III), (IVa) and (IVb), have at least 2, preferably at least 3, more preferably at least 4, functional groups suitable for polymerization, which crosslink the structures of the redox-active units to form the polymers of the general formulas (I) to (IV).

[0168] The following describes an organic polymeric electrode material that is produced without a linker. Polymeric organic electrode materials according to the invention can also be formed from the aforementioned redox-active units without a linker, wherein redox-active units of the general formula (2-lc) to (2-IVc) are polymerized together, the redox-active units (2-lc) to (2-IVc) being either identical or different.

[0169] In a preferred embodiment, the redox-active units (2-1a) to (2-IVb) each have the same functional groups for polymerization.

[0170] A and B represent functional groups that can react with each other via polymerization to form rFGs, with the functional groups in each row resulting in the corresponding rFGs. Suitable examples of functional groups A and B are as follows:

[0171] Specific examples of organic compounds of the general formula (2-1a) to (A-4) (2-IVb) are the following compounds which are polymerized via the functional groups to form the polymeric organic electrode material:

[0172] Within the scope of the present invention, it is advantageous that the battery, in addition to the polymeric organic electrode material, also comprises a conductivity enhancer such as battery carbon, in particular carbon black, as an electrode material.

[0173] Other examples of conductivity-enhancing materials include carbon fibers, conductive carbon blacks (such as SuperP, SuperS, 350G), graphite particles, natural graphite, synthetic graphite, graphene, graphene oxide, expanded graphene, acetylene black and Ketjen black (e.g., CarbonECP, CarbonECP600JD), carbon nanotubes, and electrically conductive polymers, such as a polyphenylene derivative. The conductive material is not limited to those mentioned. Any material suitable as a conductive material according to the state of the art can be used, such as polypyrrole, polyphenylenevinylene, polyaniline, polythiophene, poly-3-hexylthiophene, and polyfluorene.

[0174] The batteries according to the invention can be obtained by the method described below, which is also the subject of the present invention.

[0175] The process according to the invention is characterized by the following process steps: a. Providing a depolymerizable electrode material as described above; b. Dissolving / dispersing the electrode material in a solvent (or grinding it in a solvent; or mixing it in a solvent); c. Mixing the dissolved / dispersed electrode material with the conductivity enhancer described above (e.g., battery carbon, in particular carbon black); d. Homogenizing the resulting mixture of the electrode material and the conductivity enhancer; e. Forming an electrode from the resulting mixture of the electrode material and the conductivity enhancer.

[0176] Within the framework of this process according to the invention, it has proven particularly advantageous if the weight ratio between the depolymerizable electrode material and the conductivity enhancer is 25:75 to 75:25, more preferably 35:65 to 65:35, and even more preferably 45:55 to 55:45. According to the invention, it has been found that batteries with the aforementioned weight ratio exhibit the best efficiencies. If the content of conductive material is too low, the cathode lacks conductivity; if the content is too high, the cathode becomes crumbly and difficult to process, and the capacity of the resulting battery is lower.

[0177] Figure 2 shows the specific capacity for different levels of conductivity enhancer (here Carbon Black) and thus the superiority of the batteries with the above-mentioned weight ratio.

[0178] In the process described above, in process step e. the formation of the electrode is carried out by applying the resulting mixture of the depolymerizable electrode material and the conductivity enhancer to an aluminum foil and drying the resulting mixture.

[0179] In this process step e. the electrode material can either be sprayed, printed or squeegeed on, with squeegee application generally yielding better polymeric organic electrode materials.

[0180] The subsequent drying of the obtained electrode is usually carried out at a temperature of 40 to 150 °C, more preferably 50 to 130 °C, and even more preferably 60 to 120 °C.

[0181] A further object of the present invention is the use of a previously described depolymerizable electrode material for the manufacture of batteries.

[0182] Furthermore, the present invention relates to a method for recycling a previously described polymeric organic electrode material, characterized by the following process steps: f. Separating the cathode, consisting of the polymeric organic electrode material, conductivity enhancer, and aluminum foil, from the other components of the battery; g. Depolymerizing the polymeric organic electrode material resulting from process step f.; h. Separating and purifying the depolymerized products / monomers resulting from process step g.; i. Converting the monomers resulting from process step h. to a new polymeric electrode material and reusing it according to process steps a. to e.

[0183] The process step g. of depolymerization is carried out according to usual methods known to those skilled in the art, depending on the selected polymeric organic electrode material.

[0184] The electrode material described above according to the invention can be used not only in batteries but also in the hole layer of OLED structures. Generally, an OLED consists of one or more organic layers embedded between two electrodes. The generated light is emitted through one of these electrodes. Indium tin oxide (ITO) is typically used as the transparent anode because it has a suitable work function and is transparent in the visible part of the spectrum. Metals with low work functions, such as barium or calcium, are used as cathode materials. Optimizing OLEDs typically involves improving the operating voltage, efficiency, and lifetime. Operating voltage and efficiency are significantly influenced by the charge carrier injection barriers (electrons and holes). Therefore, to optimize these parameters, it is necessary to improve charge carrier injection.

[0185] The electrode materials described above are suitable for improved hole injection. Furthermore, these electrode materials are suitable for removing the layers above the described materials from the substrate when recycling the OLED materials, as the described material can be dissolved as described. IMPLEMENTATION EXAMPLES

[0186] The present invention is explained in more detail with reference to the following exemplary embodiments. These exemplary embodiments do not limit the scope of protection of the present invention.

[0187] Under argon as a protective gas, 85 mg (0.0093 mmol, 0.5% mol) of tris(dibenzylidene acetone)dipalladium(O) and 54 mg (0.18 mmol, 1.0% mol) of tri-tert-butylphosphonium tetrafluoroborate were dissolved in 10 mL of toluene and stirred for 15 min at room temperature. Subsequently, 1000 mg (4.65 mmol, 2.5 eq) of methyl 4-bromobenzoate, 229 mg (1.86 mmol, 1.0 eq) of p-anisidine, and 536 mg (5.58 mmol, 3.0 eq) of sodium tert-butoxide in 10 mL of toluene were added in a single portion to the catalyst-ligand mixture. The reaction mixture was stirred for 17 hours at 50 °C. After the mixture cooled to room temperature, it was filtered over SiO₂ and rinsed with ethyl acetate. The solvent was removed under reduced pressure, and the residue was further purified by column chromatography over SiO₂ eluted with cHex / EtOAc 200:3. Product 3 was obtained as a yellow oil in a quantity of 433 mg (1.24 mmol, 66%). The purity of the product was verified by 2D NMR analysis and GC / MS.

[0188] 1 H-NMR: (300 MHz, CDCh) ö [ppm] = 7.91 (dt, J= 2.26, 9.06 Hz, 4H); 7.05-7.12 (m, 6H), 6.92 (dt, J = 2.77, 10.1 Hz, 2H); 3.90 (s, 6H); 3.85 (s, 3H). 13 C NMR (75 MHz, acetone-d6, 25 °C): Δp [ppm] = 166.63, 157.92, 151.21, 138.60, 131.46, 128.88, 123.65, 121.60, 115.05, 55.69, 52.07. LIFDI-MS m / z = 391.1417 (100%), 376.1195 (6%), 299.1525 (5%), 243.0906 (6%), which corresponds to the simulated pattern of [C23H2iNOs] + corresponds.

[0189] Production of TPA(OMe)(COOH)2(4)

[0190] Under ambient conditions, 1.08 g (2.76 mmol, 1.0 eq.) of TPA(OMe)(COOMe)₂ was dissolved in 11 mL of EtOH. Subsequently, 441 mg (11.04 mmol, 4.0 equivalents) of sodium hydroxide in 11 mL of H₂O was added, and the reaction mixture was stirred for 17 h. After completion of hydrolysis, the mixture was acidified with 8% HCl until a white solid precipitated and a pH of 3 was reached. The precipitate was filtered and washed with water. Purification was then carried out over RP silicon dioxide (POLYGOPREP 60-30C18) by elution with ethyl acetate. The desired product 4 was obtained as a pale yellow solid in a yield of 917 mg (2.52 mmol, 91%). The purity of the product was verified by 2D-NMR analysis and GC / MS.

[0191] 1 H-NMR: (300 MHz, acetone-d6) ö [ppm] = 7.95(dt, J = 2.19, 9.21 Hz, 4H); 7.10-7.19 (m, 6H); 7.01-7.05 (m, 2H); 3.85 (s, 3H). 13C NMR (75 MHz, acetone-d6, 25 °C): Δp [ppm] = 166.30, 158.02, 151.10, 138.75, 130.90, 128.78, 124.09, 121.39, 115.39, 115.31, 54.75. LIFDI-MS m / z = 363.11 (100%), 348.09 (16%), which corresponds to the simulated pattern of [C2I HI7NO5] + ' corresponds.

[0192] General procedure of polymer synthesis using the synthesis of TPA-PE1 as an example

[0193] Under an argon atmosphere, 146 mg (3.44 mmol, 2.5 eq.) of lithium chloride and 924 mg (3.44 mmol, 2.5 eq.) of diphenylphosphorylate (DCPC) were dissolved in 3 mL of pyridine and stirred for 15 min at room temperature. In a separate inert flask, 278 mg (1.37 mmol, 1.0 eq.) of 4,4-oxydiphenol 5 and 500 mg (1.37 mmol, 1.0 eq.) of TPA(OMe)(COOH)24 were dissolved in 2 mL of pyridine and heated to 120 °C. After stirring the monomer mixture at 120 °C for 5 min, the coupling reagent mixture was added. The polymerization reaction was stirred at 120 °C for 17 h. The still-hot reaction solution was added dropwise to a vigorously stirring cold MeOH / FW (1:2) mixture. The precipitated polymer was filtered off and washed with 100 mL each of hot H₂O and MeOH. The polymer was then purified by Soxhlet extraction (methanol / acetone / chloroform), followed by vacuum drying for 24 hours.The desired polymer PE1 was dried under vacuum for 24 hours and obtained with a yield of 98%. The theoretical specific capacity of the resulting compound is 51 mAh / g.

[0194] The polymerization reaction described above is known from the literature and is carried out based on the disclosure in Liou et al., Eur. Polym. J., 2008, 44, 8, 2608-2618.

[0195] To manufacture the electrodes, the crude polymer obtained in this way is dissolved in chloroform and mixed with 50 wt% carbon black, where the 50 wt% refers to the mass of carbon black in the cathode (i.e., 50 mg of polymer are mixed with 50 mg of carbon black; the amount of solvent is irrelevant since it is subsequently removed). After homogenization for 30 min, the resulting slurry is sprayed onto an aluminum foil and dried for 2 h at 60 °C. Alternatively, the slurry is spread onto an aluminum foil 15 µm thick and then dried.

[0196] A button cell with a lithium metal anode is manufactured from the produced cathode. The electrolyte used is 1M LiPFe in a 1:1:1 mixture of ethylene carbonate, diethyl carbonate, and dimethyl carbonate.

[0197] Figures 3 to 7 show the characteristics of the resulting Li-ion battery with the polymer cathode according to the invention.

[0198] Figure 3 shows dQ / dV plotted against voltage, revealing that with increasing current, the charging voltage rises and the discharging voltage falls, which can be logically explained by the internal resistance. The battery voltage is 3.9 V, which is comparable to that of inorganic batteries and higher than that of many common organic cathode materials. The voltage of comparable TPA derivatives is 3.5 V. The voltage of these polyester derivatives increases due to the -I effect (electron withdrawal) of the introduced ester group. An overview of common redox units in organic batteries and their redox potentials can be found, for example, in the review by Birgit Esser, Journal of Power Sources 482 (2021) 228814.

[0199] Figure 4 shows galvanostatic measurements at different current intensities, with the voltage plotted against the specific discharge capacity. A specific capacity of 38 mAh / g is achieved.

[0200] Figure 5 shows the difference between the charging and discharging voltages. The linear relationship can be seen as a measure of the kinetic impedance of the charging and discharging process.

[0201] Figure 6 shows the specific capacity of the charge and discharge cycle at different C-rates. The C-rate, with the unit 1 / h, indicates how quickly a battery completes a charge and discharge cycle, or how many charge and discharge cycles a battery can undergo in one hour. At a C-rate of 10, a battery can be charged or discharged 10 times within one hour, meaning a charging process takes e minutes. The higher the C-rate, the faster and more efficiently the battery can be charged and discharged. The fast-charging capability of battery materials is a very important criterion. 10C is already considered fast for commercial inorganic batteries.

[0202] It can be seen that the battery reaches a specific capacity of 35 mAh / g within 6 minutes. Therefore, the lithium-ion battery according to the invention is suitable for rapid charging and discharging.

[0203] Figure 7 shows a high cycle stability of the polymeric electrode material.

[0204] During charging and discharging, corresponding counterions migrate into and out of the electrode. This causes the electrode to swell due to the increase in mass and then shrink again. This volume change, known as "breathing," can be considerable depending on the electrode type and is a known problem with conventional inorganic electrode materials. This results in significant mechanical stress on the electrode and, consequently, on the entire energy storage device. Possible consequences include cracking, chipping, loss of contact with the collector, etc., which, over numerous charging and discharging cycles, lead to a decrease in the energy storage device's capacity or even its complete failure.

[0205] This effect is reduced by the polymeric structure of the electrode material according to the invention, which remains sufficiently flexible to accommodate small volume changes. This manifests itself – as with other polymeric organic cathode materials (P. Acker, L. Rzesny, CFN Marchiori, CM Araujo, B. Esser, Adv. Funct. Mater. 2019, 29, 1906436, https: / / doi.org / 10.1002 / adfm.201906436) – in high cycle stability.

[0206] S. Muench et al. describe in “Polymer-based Organic Batteries” (Chem. Rev., 2016, Vol. 116, pp. 9438–9484) that intrinsic conductivity in redox polymers, particularly through conjugation between the redox units such as phenyl-phenyl linkages, leads to a variable cell voltage during charging and discharging. This limits the applications of such polymers.

[0207] In contrast, our approach involves creating a non-conjugated polymer in which the individual redox units are not conjugated and therefore not electronically coupled. In such a polymer, the redox potential of each unit is only minimally affected, if at all, by the charge state of neighboring redox units. Thus, the individual redox units remain independent of each other during charging and discharging, and the cell voltage remains largely constant at the redox potential of each individual redox unit.

[0208] Example of depolymerization

[0209] The recycling process of 29 batteries, each cycled 1000 times, was carried out according to the procedure described below, as shown in Figure 8. The batteries were cut open under a protective gas atmosphere, the lithium metal anode was removed, and the remaining battery components, including the separator, spacer, spring, positive and negative casings, and the aluminum foil cathode, were extracted in chloroform. After filtration to remove the battery casing and carbon black, the chloroform solution was washed several times with water to remove the electrolyte salt. The chloroform was removed, and the remaining polymer was absorbed in THF.

[0210] Following the reaction scheme shown above, an aqueous solution of sodium hydroxide (10%) was added, and the reaction mixture was refluxed for 24 hours. The resulting monomer mixture was acidified with 8% hydrochloric acid until a pH of 3 was reached, leading to the precipitation of the TPA monomer, which was filtered and washed with water. The filtered TPA monomer was dissolved in acetone and filtered through a reversed-phase chromatography column. The TPA monomer 4 was recovered in a yield of 90%. The remaining aqueous solution contains the dialcohol linker 4,4-oxyphenol 5, which was extracted from EtOAc and washed several times with water. The dialcohol was recycled in a quantity of 90%.

[0211] Both components can be used again to manufacture a lithium-ion battery according to the invention.

[0212] Example 2

[0213] Analogous to the synthesis procedure of embodiment 1, the following polymer was produced.

[0214] Corresponding results with this polymeric electrode material as cathode material in a battery are shown in Figures 8 to 11.

[0215] Further polymers were produced and investigated analogously to the synthesis procedure of embodiment 1:

[0216] Examples 3-6 TPA polyester

[0217] Examples of implementation 7-10 TPA polyamides

[0218] The synthesis was carried out according to the literature procedure by G.-S. Liou, N.-K. Huang and Y.-L. Yang, Polymer 2006 Vol. 47 Issue 20 Pages 7013-7020.

[0219] Example 11 MPT polyester

[0220] The following polymer was produced based on the synthesis procedure of embodiment 1. Here, as in embodiment 1 (TPA-PE1), a measurement was also carried out over 1000 cycles. A relative capacity of 72.5% was achieved after 1000 cycles, as shown in Figure 27.

[0221] Example of implementation 12 AQ-Polyester

[0222] The following polymer was produced based on the synthesis procedure of embodiment 1.

[0223]

[0224] The results for the electrode materials of embodiment 3 are summarized in the following table:

[0225] The term "irreversible" in this context means that this material is not suitable as a cathode material. The term "one cycle" in this context means that the battery is charged, or rather, the first cycle performed is the discharge. A capacity of 87.2 mAh / g was achieved. Further charge and discharge cycles are no longer possible, which is due to the degradation of the cathode material.

[0226] Example 12: Carbazole

[0227] In a further embodiment, a dQ / dV vs. V curve of an N-phenylcarbazole (PhCbz, l1a) redox-active unit according to the invention was plotted as a redox-active cathode material in a lithium-ion battery. Figure 28 shows the redox potential of approximately 3.9 V and the reversibility of the redox material during the charge and discharge cycles.

[0228] Example 13: Sodium-ion battery

[0229] In another embodiment, a cyclic voltammogram of a polymeric redox-active material according to the invention, which was used as a cathode with a sodium ion anode, was recorded. The redox potential of approximately 4.0 V can be seen (see Figure 29).

[0230] The invention described herein has several advantages:

[0231] The invention described herein makes it possible to render an organic electrode material completely insoluble in the electrolyte or electrolyte solvent through polymerization and / or cross-linking. This is highly advantageous and of great importance for the durability and lifespan of a battery.

[0232] Additionally, after the battery's service life, it is possible to reverse the polymerization or cross-linking. The present invention makes it possible to reuse, i.e., recycle, the intact, recovered redox units after purification. The monomers recovered from the polymer can be directly transferred to the next application cycle after purification, i.e., used multiple times.

[0233] Compared to other organic electrode materials that cannot be recycled, this significantly improves the environmental footprint and also the economic efficiency, because far fewer raw materials and energy are consumed compared to a new synthesis, and less waste is also produced.

[0234] This chemical recycling process achieves an improved environmental footprint compared to a thermal recycling process, such as that used for inorganic lithium-ion batteries, because less energy is required for recycling and the use of organic redox materials avoids the extraction of environmentally critical raw materials.

[0235] Furthermore, the electrode materials according to the invention consist predominantly of the ubiquitously available elements C, H, O, N (and possibly very small amounts of S and / or halogen) and can prospectively be synthesized from renewable raw materials.

[0236] Example A:

[0237] Polymer production Application example A

[0238] The syntheses of the polymers of application examples A follow the procedure already described in the application text in embodiment 1. The redox-active unit and the linker have the general structure (1a). The linker and the redox-active unit are linked to the functional group (rFG) -COO- for polyester. L31 and / or L36 was selected as the linker unit of the organic electrode material according to the present application.

[0239] Figure 30 shows: a) general chemical structural formula of application example A, b) equivalents of linkers L31 and L36 used to fine-tune the corresponding degree of crosslinking, and c) glass transition temperature in °C of the polymers at different f values ​​and representation of the linear relationship by means of a linear fit.

[0240] In embodiment A, the polyester has the general molecular structure shown in Figure 1a. The degree of crosslinking could be adjusted by controlling the equivalents of di-functional linker (hydroquinone, L31, pink) and tri-functional linker (phloroglucinol, L36, blue) used. Using 1.0 eq. of TPA(OMe)(COOH)2 (4) and 1.0 eq. of L31 results in a linear polymer, already described as embodiment 2, subsequently designated as ≤ 2.0. Using 1.0 eq. of TPA(OMe)(COOH)2 (4) and 0.66 eq. of L36 results in a (most highly) crosslinked polymer, designated as ≤ 3.0 (embodiment 5).

[0241] Both linkers can be mixed in different equivalents during the synthesis, see Figure 30 b), where the degree of crosslinking / in this embodiment was set between 2.0 and 3.0 (in principle, higher degrees of crosslinking are also possible), described by formula 1 where rij is the amount of substance, fj is the number of polymerizable groups, and Q = — fi is a correction factor, where f« is the number of polymerizable functional groups of monomer 4 (= 2) and f is the number of polymerizable functional groups of (f L 3i=2 and f L 36 = 3) is. A summary of the synthesized polyesters can be found in Table 1. The degree of crosslinking could be determined by measuring the glass transition temperature T. g can be checked using DSC measurements, see Figure 1c.

[0242] The following table shows an overview of the polymers from the exemplary embodiment.

[0243] A, the amounts used in the synthesis, the yield, theoretical capacity and T g .

[0244] Ver- m4m L3i m L3 4 _ . x .. , urrr T Yield Mw(la) Cfheor. cap. Tg f -“to"™- I"«] I"«] ["«[h] [o / o] [0 / m O [mAh / g] [°C]

[0245] 2.0 300 17 437.45 61.3 142

[0246] 2.3 250 17 441.90 60.6 160

[0247] 2.5 250 17 444.95 60.2 209

[0248] 2.6 250 17 446.44 60.0 224

[0249] 2.7 250 17 447.94 59.8 235

[0250] 2.8 500 6 449.44 59.6 242

[0251] 2.9 250 17 450.94 59.4 267

[0252] 3.0 800 17 452.44 59.2 278

[0253] 3.0 250 17 452.44 59.2 280

[0254] Production of electrode material

[0255] The electrode material is produced as described in embodiment 1. However, homogenization of the slurry must be carried out using a high-performance mixer (ULTRATURRAX at 25,000 rpm for 10 min). The slurry was applied to carbon-coated aluminum foil using doctor blades.

[0256] The characteristics of the resulting Li-ion batteries with the polymer cathode according to the invention are described below (see Figure 31).

[0257] Figure 31 shows: a) dQ / dV plotted against voltage for all polymers falling under application example A, which differ in their degree of crosslinking f and were used as electrode material in a Li-ion battery. This plot shows the reversibility of the electrode material's oxidation. b) The specific capacitance is plotted over several cycles of galvanostatic measurements at different current intensities.

[0258] The button cell is manufactured as described in Example 1. Alternatively, LiTFSI and UCIO4 were also tested instead of LiPFe in the same solvent mixture and concentration, see Figure 32:

[0259] Figure 32 shows the ratio of the specific experimental and the theoretical capacity as utilization for batteries with the electrode material according to the invention f = 2.8 in galvanostatic measurements at different C rates. The batteries differ in the electrolyte salt used. The solvent remained constant with a volume ratio of DEC / DC / EC 1:1:1.

[0260] Example B:

[0261] Example of depolymerization and recycling of the cathode used from Example A

[0262] For cross-linked polymers (f < 2.3) and thus insoluble electrode materials, the depolymerization process must follow a slightly different procedure. After cutting open the batteries, the cathode is removed from the aluminum foil, and the other battery components are discarded. The electrode material is mechanically removed from the aluminum foil and then washed with water. After filtration, the filter cake, containing the polymer and battery carbon black, is treated with THF and 10% aqueous sodium hydroxide solution and refluxed for 24 hours.

[0263] This is followed by the processing, as described in embodiment 1 above.

[0264] An application example was carried out for the polymer f= 3.0. Since this is the most highly cross-linked polymer described in the embodiments, it can be assumed that the depolymerization is also applicable to the other polymers mentioned in embodiment A.

[0265] Figure 33 shows NMR spectra of pure TPA monomer 4 before polymerization (top), of recycled TPA monomer 4 processed as electrode material without having been previously used in the battery (middle), and of recycled electrode material used in a Li-ion battery after 5000 cycles (bottom). The characteristic peaks attributable to TPA monomer 4 are visible after the recycling process, demonstrating the depolymerizability of the polymer cathode according to the invention. After use in the battery, 77% of TPA monomer 4 could be recovered. Figure 33 shows 1¹H NMR spectra (recorded in acetone-dβ, with 0.03% TMS as reference) of the synthesized TPA-COOH2-OMe (4) (top); recycled TPA-COOH2-OMe (4) not previously used in a battery (middle); and TPA-COOH2-OMe (4) recycled after use in a battery for 5000 cycles (bottom). The outlines indicate impurities from the solvent ethyl acetate, water, and impurities commonly referred to as "grease," which denote long-chain linear aliphatic hydrocarbons.

[0266] Example C:

[0267] In embodiment C, the redox-active unit and the linker have the general structure (1a). The linker and the redox-active unit are linked to the functional group (rFG) -COO- for polyester. According to the invention, L1, with a carbon chain consisting of two carbon atoms, was selected as the linker unit of the organic electrode material, as shown in Figure 34.

[0268] Figure 34 shows the synthesis step for the production of the polymer for application example C.

[0269] The polymer synthesis process differs from the synthesis described in Exemplar 1 in that the polymerization is carried out catalytically instead of using coupling reagents. Antimony(III) oxide (Sb₂O₃), germanium(IV) oxide (GeÜ₂), Sn(acetylene), or Ti(OiPr)₄ was used as the catalyst. The catalyst was placed in a Schlenk tube with the TPA-COOH₂-OMe₄ monomer (1.0 eq.) and purged with argon. Then, 3.0 eq. of the linker L₁ (n=2) were added. The reaction was stirred at 135 °C for 6 h under argon flow, followed by 22 h under 5 mbar vacuum. The polymer can be used without purification.

[0270] In one polymerization reaction (designated PA18), toluene was added in the first esterification step (under argon) and subsequently removed during the reaction to form longer polymer chains under vacuum. In two reactions (designated PA19 and PA20), black carbon was added to the polymerization mixture to ensure good homogenization of the polymer and conductivity enhancer. An overview of the synthesized polymers is shown in the table below: f Ver r catalyst

[0271] 7 search

[0272] The table above shows an overview of the polymers from embodiment C, the catalysts used in the synthesis, the yield, theoretical capacity and Tg.

[0273] The formation of a polymer can be easily verified by thermogravimetric analysis (TGA), as shown in Figure 35. While the TPA monomer 4 initially undergoes simple decarboxylation at 140 °C, followed by complete decomposition at 306 °C, the polymer shows no decarboxylation and only decomposes at 325 °C. Therefore, it can be assumed that the carboxyl groups were successfully esterified.

[0274] Figure 35 shows the TGA measurement of TPA-COOH2-OMe 4 and, by way of example, TPA-PE with Linker L1 (n= 2).

[0275] Production of electrode material

[0276] The electrode material is produced as described in Example 1, except that THF or NMP is used for the slurry. The head cell production also proceeds as previously described. The reversible oxidation process of the electrode material can be observed in the galvanostatic measurement of a Li-ion battery (see Figure 36a). It is evident that the charging voltage increases with increasing current, and this process is reversible. The battery voltage is 3.85 V, which is comparable to that of the previously described application examples. The batteries can be used for several cycles with different current intensities, as shown in Figure 36b.

[0277] Figure 36 shows a) a representation of a dQ / dV curve of two Li-ion batteries with the electrode material according to the invention, and b) the specific capacity over several cycles at different current intensities (C-rates).

[0278] Example D:

[0279] The syntheses of the polymers in application examples D follow the procedure already described in the application text in embodiment 1. In embodiment D, the redox-active unit and the linker have the general structure (llc). The linker and the redox-active unit are linked to the functional group (rFG) -COO- for polyester. L11 was selected as the linker unit of the organic electrode material, see Figure 37. The yield was 63%.

[0280] Figure 37 shows the synthesis step for the production of the polymer for application example D.

[0281] Production of electrode material

[0282] The electrode material is manufactured as described in Example 1. The head cell manufacturing process is also carried out as previously described. The reversible oxidation process of the electrode material can be observed in the galvanostatic measurement of a Li-ion battery, see Figure 38a).

[0283] The plot of dQ / dV against voltage shows that the charging voltage increases with increasing current. This process occurs twice, which can be logically explained by the physical fact that there are two reducible nitrogen units per redox unit. The battery voltage is 3.8 V for the first oxidation and approximately 4.1 V for the second. The batteries can be used for several cycles with different currents, as shown in Figure 38 b).

[0284] Figure 38 shows: a) the representation of a dQ / dV curve of a Li-ion battery with the electrode material C according to the invention, measured at different current intensities (C rates) and b) the specific capacity, which is shown over several cycles at different current intensities (C rates).

[0285] Example E:

[0286] The syntheses of the polymers in application examples D follow the procedure already described in the application text in embodiment 1. In embodiment E, the redox-active unit and the linker have the general structure (Ic). The linker and the redox-active unit are linked to the functional group (rFG) -COO- for polyester. L11 was selected as the linker unit of the organic electrode material, see Figure 39. The yield was 63%.

[0287] Figure 39 shows the synthesis step for the production of the polymer for application example E.

[0288] Production of electrode material

[0289] The electrode material is manufactured as described in Example 1. The head cell manufacturing process is also as previously described. The reversible oxidation process of the electrode material can be observed in the galvanostatic measurement of a lithium-ion battery (see Figure 40a). The plot of dQ / dV against the voltage shows that the charging voltage increases with increasing current. This process is observed twice, which can be logically explained by the physical phenomenon of two reducible nitrogen units per redox unit. The battery voltage is 3.85 V. The batteries can be used for several cycles with different current intensities, as shown in Figure 39b).

[0290] Figure 40 shows: a) the representation of a dQ / dV curve of a Li-ion battery with the electrode material C according to the invention, measured at different current intensities (C rates) and b) the specific capacity, which is shown over several cycles at different current intensities (C rates).

Claims

1. Claims 1. Battery comprising a polymeric organic electrode material which is degradable into monomers by chemical and / or enzymatic reactions.

2. Battery according to claim 1, characterized in that the polymeric organic electrode material is composed of organic redox-active units and linkers which connect the organic redox-active units.

3. Battery according to claim 2, characterized in that the linkers in the polymeric organic electrode material are also redox-active.

4. Battery according to one of claims 2 or 3, characterized in that the linker connects at least two organic redox-active units.

5. Battery according to one of claims 2 to 4, characterized in that the organic electrode material is constructed by a polycondensation or a polyaddition reaction of the organic redox-active unit and the linker.

6. Battery according to one of claims 2 to 5, characterized in that the polymeric organic electrode material, comprising the redox-active unit and the linker, has a general structure selected from the group consisting of where L' represents a linker that connects two redox-active units via a functional group (rFG), where rFG stands for -COO- for polyesters, -C(O)-NH- for polyamides, -(C(O))2-N- for polyimides, -C=N- for polyazomethines, -O-CO-NH- for polyurethanes, -O- for polyethers and -NH-CO-NH- for polyureas. Ri for hydrogen, linear or branched Ci-Ce-alkyl; -O-(CH2)n-CH3 (with n being an integer < 6); -O-((CH2)2O) n -CH3 (where n is an integer < 6), -OMe, -F, -CI, -Br or -I, and R2 stands for linear or branched Ci-Ce-acyl, A and B represent the functional groups remaining as end groups, selected from the group consisting of -COOH and / or -OH for polyesters, -COOH and / or -NH2 for polyamides, -C(O)-OC(O)- and / or -NH2 for polyimides, -CHO and / or -NH2 for polyazomethines, -N=C=O and / or -OH for polyurethanes, -epoxy or -oxetanes and / or -OH for polyethers, -N=C=O and / or -NH2 for polyureas.

7. Battery according to claim 6, characterized in that the electrode material additionally comprises at least 1% of three-dimensional cross-links and wherein the three-dimensional cross-links are formed by the additional use of at least triple-functionalized linkers.

8. Battery according to one of claims 2 to 7, characterized in that the linker unit of the organic electrode material is selected from the group consisting of HOJ VOH ' 'n (L1) where the linkers L1 to L6 can have a carbon chain with 1 to 10 carbon atoms between the functional end groups or the carbon chain can be extended by -((CH2)2O) n can be replaced with a number n equal to 1 to 10, and x, y, z and w each represent 1 to 7000 repeat units, and the polymeric linkers L38 and L39 are present as alternating, block co- or statistical polymers.

9. Battery according to one of claims 1 to 8, characterized in that the battery comprises, in addition to the polymeric organic electrode material, a conductivity mediator selected from the group consisting of carbon black, carbon fibers, conductive carbon blacks, graphite particles, natural graphites, synthetic graphites, graphene, graphene oxides, expanded graphene, acetylene black, Ketjen black, carbon nanotubes and electrically conductive polymers.

10. Battery according to one of claims 1 to 9, characterized in that the battery comprises a current collector on which the electrode material, in particular the cathode material, is applied and which is an aluminum foil or carbon-coated aluminum foil.

11. A method for producing an electrode material for batteries according to any one of claims 1 to 10, characterized by the following process steps: a. Providing a depolymerizable electrode material according to any one of claims 1 to 9; b. Dissolving and / or dispersing the electrode material in a solvent; c. Mixing the dissolved and / or dispersed electrode material with carbon black; d. Homogenizing the resulting mixture of the electrode material and carbon black; e. Formation of an electrode from the obtained mixture of the electrode material and carbon black.

12. Method according to claim 11, characterized in that the weight ratio of electrode material and carbon black is 25 : 75 to 75 : 25, more preferably 35 : 65 to 65 : 35, and even more preferably 45 : 55 to 55 :

45.

13. Use of a depolymerizable electrode material according to any one of claims 1 to 8 for the manufacture of lithium-ion batteries.

14. A method for recycling a polymeric organic electrode material according to any one of claims 1 to 8, characterized by the following process steps: a. Separating the cathode, consisting of the polymeric organic electrode material according to any one of claims 1 to 8, conductivity enhancer, and current collector, from the other components of the battery; b. Depolymerizing the polymeric organic electrode material resulting from process step f.; c. Separating and purifying the depolymerized products / monomers resulting from process step g.; d. Converting the monomers resulting from process step c. to a new polymeric electrode material and reusing it according to process steps a. to e.

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