Polymers containing ferrocenyl groups, process for their preparation and use thereof

Abstract

The present application provides a polymer having a structure shown in Formula 1, a composite material comprising the polymer and a conductive carbon, wherein R is a C6-C 60 arylene group or a C3-C 60 heteroarylene group, and n is a polymerization degree, and 5≤n≤10 5 , preferably 10≤n≤1000. The present application also provides a preparation method of the polymer and the composite material, and their use in lithium ion batteries, particularly as electrode materials such as positive electrode materials. The polymer has a physically and chemically stable structure, has abundant electrochemically active functional groups and a stable polymer backbone, and thus the lithium ion battery prepared thereby has a higher mass specific capacity and an ultra-long cycle life, and also has a higher output voltage and energy density.

Description

Technical Field

[0001] The present invention generally relates to the field of lithium-ion batteries. In particular, the present invention relates to a polymer containing ferrocene groups and a method for preparing the same, as well as the use of the polymer in lithium-ion batteries, especially as a cathode material. Background Art

[0002] With the development of society and the advancement of human civilization, people's demand for energy is growing, which has promoted the development of clean energy and the advancement of energy storage technology. Lithium-ion batteries are rechargeable secondary batteries that have received extensive attention and research. Due to their advantages such as high operating voltage, high energy density, and zero memory effect, lithium-ion batteries are used in various fields, such as electric vehicles, the Internet of Things, and portable electronic devices such as mobile phones and laptops.

[0003] However, traditional lithium-ion battery cathode materials include some inorganic metal compound materials, such as LiCoO2, LiMn2O4 and ternary materials, and anode materials include graphite and Li4Ti5O 12 These representative electrode materials usually contain metal elements such as Co, Mn and Ni, so they have a large atomic mass and a low mass-specific capacity, which limits the further improvement of the energy density of lithium-ion batteries. In addition, these heavy metal elements are relatively scarce, expensive, and have high preparation costs. They also have certain environmental pollution and toxicity, which are not conducive to meeting the growing energy demand and sustainable development needs.

[0004] Therefore, in order to overcome these problems, new materials, especially positive electrode materials for lithium-ion batteries, have been sought and developed, hoping that such materials can simultaneously achieve higher mass specific capacity and longer cycle life. Summary of the Invention

[0005] Therefore, in the first aspect, the present application first provides a polymer having a structure shown in Formula 1:

[0006]

[0007] Where n is the degree of polymerization. Generally, 5≤n≤10 5 , preferably 10≤n≤1000.

[0008] In some embodiments, R can be C6-C 60 Arylene group or C3-C 60 Heteroarylene group, wherein the C6-C 60 Arylene group and the C3-C 60The heteroarylene group can be unsubstituted or substituted by one or more substituents selected from the group consisting of oxo, halogen, hydroxyl, cyano, nitro, C1-C 10 alkyl, C2-C 10 alkenyl or C1-C 10 alkoxy.

[0009] In a preferred embodiment, R can be phenylene, naphthylene, anthracylene, phenanthrylene, benzophenylene, heterophenylene, heteronaphthylene, heteroanthracylene, heterophenanthrylene, heterobenzophenylene, which can be unsubstituted or substituted by one or more substituents selected from the group consisting of oxo, halogen, hydroxyl, cyano, nitro, C1-C 10 alkyl, C2-C 10 alkenyl or C1-C 10 alkoxy, more particularly unsubstituted or substituted by one or more oxo groups.

[0010] In a more preferred embodiment, R can be phenylene, pyridylene, pyrazylene, pyrimidylene, pyridazylene, quinolyiene, naphthoquinolyiene, anthraquinolyiene or phenanthraquinolyiene. In a particular case, R can be selected from the group consisting of:

[0011]

[0012] wherein … indicates the position of attachment to the adjacent atom. It is understood that the position of attachment to the adjacent atom can also be at other feasible positions.

[0013] In other words, Formula 1 can be selected from any one of Formula 1-1 to Formula 1-8:

[0014]

[0015]

[0016]

[0017] In another aspect, the present application also provides a composite material comprising the above-mentioned polymer and conductive carbon. Preferably, the conductive carbon can be selected from carbon nanotube, graphene oxide, mesocarbon microbead or any combination thereof. Generally, the conductive carbon can account for 10 mass% to 90 mass%, preferably 20 mass% to 40 mass% of the composite material.

[0018] In yet another aspect, the present application also provides a method for preparing the above-mentioned polymer and the above-mentioned composite material.

[0019] The method for producing the polymer comprises subjecting 1,1'-ferrocenedicarboxaldehyde and a diamine R(NH2)2 to a polycondensation reaction in a molar ratio of (0.8-1.2): 1, preferably about 1:1, whereby the polymer is obtained, wherein R is as defined above.

[0020] The method for producing the composite material comprises mixing 1,1'-ferrocenedicarboxaldehyde, a diamine R(NH2)2 and an electrically conductive carbon, and then subjecting 1,1'-ferrocenedicarboxaldehyde and the diamine R(NH2)2 to a polycondensation reaction while being in situ complexed with the electrically conductive carbon, whereby the composite material is obtained, wherein R is as defined above. In this method, the molar ratio of 1,1'-ferrocenedicarboxaldehyde and the diamine R(NH2)2 can be (0.8-1.2): 1, preferably about 1:1. The electrically conductive carbon can account for 10 mass% to 90 mass%, preferably 20 mass% to 40 mass%, of the composite material.

[0021] It is understood that the raw materials such as 1,1'-ferrocenedicarboxaldehyde, a diamine R(NH2)2 and an electrically conductive carbon in the above-mentioned methods can be provided in their suitable forms (such as salt forms).

[0022] In still another aspect, the present application also provides the use of the aforementioned polymer or composite material in an (active) electrode material, including an (active) positive electrode material, and the use of the polymer or composite material in a lithium ion battery. In a lithium ion battery, the polymer or composite material can serve as an active positive electrode material.

[0023] Correspondingly, the present application in another aspect provides an electrode material (such as a positive electrode material) or a lithium ion battery comprising the aforementioned polymer or composite material. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 A schematic diagram of the structure of the polymer according to the present application.

[0025] Figure 2 A Fourier transform infrared spectrogram of the organometallic polymer 1 obtained in Example 1.

[0026] Figure 3 A thermogravimetric analysis spectrogram of the organometallic polymer 2 obtained in Example 2.

[0027] Figure 4 A Fourier transform infrared spectrogram of the organometallic polymer 2 obtained in Example 2.

[0028] Figure 5 A Fourier transform infrared spectrogram of the composite material comprising the organometallic polymer 3 obtained in Example 3.

[0029] Figure 6Fourier transform infrared spectrogram of the organometallic polymer 4 obtained in Example 4.

[0030] Figure 7 Fourier transform infrared spectrogram of the organometallic polymer 5 obtained in Example 5.

[0031] Figure 8 Fourier transform infrared spectrogram of the organometallic polymer 9 obtained in Example 9.

[0032] Figure 9 Charge-discharge cycle test graph of the lithium ion battery 1 assembled in Example 11 in the charge-discharge voltage window 1.2-4.0 V (vs Li / Li + ) at a charge-discharge current density of 2000 mA / g.

[0033] Figure 10 Charge-discharge cycle test graph of the lithium ion battery 2 assembled in Example 12 in the charge-discharge voltage window 1.2-4.0 V (vs Li / Li + ) at a charge-discharge current density of 2000 mA / g.

[0034] Figure 11 Charge-discharge cycle test graph of the lithium ion battery 3 assembled in Example 13 in the charge-discharge voltage window 1.5-4.0 V (vs Li / Li + ) at a charge-discharge current density of 50 mA / g. DETAILED DESCRIPTION

[0035] Although the present application contains many details, these should not be construed as limiting the application or any scope of protection sought. Some of the features described in separate embodiments of the present application can also be implemented in combination in a single embodiment. Conversely, multiple features described in a single embodiment can also be implemented separately or in any suitable subcombination in multiple embodiments. Furthermore, although these features can be described above as acting in certain combinations and even initially so claimed, one or more features from a claimed combination can in some cases be excluded from the combination in some instances, and the claimed combinations can refer to a subcombination or variation of a subcombination.

[0036] Unless otherwise indicated, the meaning of terms used in this text are the same as those commonly understood by a person skilled in the art, for example, terms relating to reaction raw materials and reaction products, experimental operation steps, process technical parameters, use of instrument equipment and tools, and various numerical units.

[0037] In the present text, the term "about" (e.g., in parameters of component amounts and reaction conditions) is to be interpreted in the manner that a person of ordinary skill in the art would understand. Generally, the term "about" can be understood to mean any number falling within a range of plus or minus 5% of a given value, e.g., about X can mean any number in a range of 95% X to 105% X.

[0038] It is also to be understood that the specific numerical values given in the present text (e.g., in various component ratios, reaction temperatures, and durations of reaction) are to be interpreted as being only approximations of certain ranges of end points and can be combined with each other to provide other ranges. For example, when a reaction is disclosed as being carried out for 24 hours or 72 hours, it is also disclosed that the reaction can be carried out for 24-72 hours. Furthermore, the specific numerical values given in the present text are to be understood as being modified in all instances by the term "about." Thus, unless otherwise specified, the numerical values given in the present application are approximations that can vary from the stated values. For example, a duration of 24 hours can be understood to mean a duration of about 24 hours, and a duration of 24-72 hours can be understood to mean a duration of about 24 hours to about 72 hours or about 24 to 72 hours.

[0039] In the present text, "room temperature" generally refers to a temperature of about 25 °C.

[0040] As used herein, the term "C6-C 60 aryl group" refers to a monovalent radical having a carbocyclic aromatic system containing 6 to 60 carbon atoms. As used herein, the term "C6-C 60 arylene group" refers to a divalent radical having a carbocyclic aromatic system containing 6 to 60 carbon atoms. C6-C 60 Examples of aryl groups can include phenyl groups, heptalenyl groups, naphthyl groups, azulenyl groups, indacenyl groups, acenaphthyl groups, phenalenyl groups, phenanthryl groups, anthryl groups, fluoranthenyl groups, triphenylenyl groups, pyrenyl groups, perylenyl groups, pentaphenyl groups, heptalenyl groups, tetracenyl groups, chrysenyl groups, hexacenyl groups, pentacenyl groups, rubicenyl groups, coronenyl groups, ovalenyl groups, and the like. It is to be understood that the term "C6-C 60 aryl group" as used herein can include C6-C 40 aryl groups, C6-C 30 aryl groups, C6-C 20 aryl groups, C6-C 14 aryl groups, and the like. As used herein, the term "C6-C 60 arylene group" as used herein can include C6-C 40 arylene groups, C6-C 30 arylene groups, C6-C20 C6-C12arylene group, etc. 14 C6-C12arylene group, etc.

[0041] As used herein, the term "C3-C 60 C6-C12arylene group, etc. 60 C6-C12arylene group, etc. 60 Examples of the heteroaryl group can include a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolyl group, a benzoquinolyl group, an isoquinolyl group, a benzoisoquinolyl group, a quinoxalyl group, a benzoquinoxalyl group, a quinazolyl group, a benzoquinazolyl group, a cinnolinyl group, a phenanthrolinyl group, a phthalazinyl group, and a naphthyridinyl group. It can be appreciated that the term "C3-C 60 C6-C12arylene group, etc. 40 C6-C12arylene group, etc. 30 C6-C12arylene group, etc. 20 C6-C12arylene group, etc. 14 C6-C12arylene group, etc. 10 C6-C12arylene group, etc. 60 C6-C12arylene group, etc. 40 C6-C12arylene group, etc. 30 C6-C12arylene group, etc. 20 C6-C12arylene group, etc. 14 C6-C12arylene group, etc. 10 C6-C12arylene group, etc.

[0042] As used herein, "oxo" is a =0 group.

[0043] As used herein, "halogen" includes fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), etc.

[0044] As used herein, "hydroxy" refers to a -OH group.

[0045] As used herein, "cyano" refers to a -CN group.

[0046] As used herein, "nitro" refers to a -NO2 group.

[0047] As used herein, "C1-C 10The “alkyl group” may be a linear or branched aliphatic hydrocarbon monovalent group having one to ten carbon atoms, and examples thereof may include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, and a tert-decyl group. The term “C1-C1” as used herein 10 The "alkylene group" may be a C1-C 10 A divalent group of the same structure as an alkyl group.

[0048] The “C2-C 10 "Alkenyl" can be a C2-C 10 The alkyl group is a monovalent hydrocarbon group having at least one carbon-carbon double bond in the middle or at the terminal, and examples thereof may include a vinyl group, a propenyl group, and a butenyl group. As used herein, “C2-C 10 The "alkenylene group" may be a 10 Alkenyl groups are divalent groups of the same structure.

[0049] The “C1-C 10 "Alkoxy" can be -O(A 101 )(where A 101 Can be C1-C 10 An alkyl group) is a monovalent group, and examples thereof may include a methoxy group, an ethoxy group, and an isopropoxy group.

[0050] As used herein, the term "heteroatom" refers to any atom other than a carbon atom. Examples of heteroatoms are O, S, N, P, Si, B, Ge, Se, or a combination of one or more thereof. In particular, in the present application, heteroatoms are preferably N, P, and / or O, in particular N and O.

[0051] In this application, ferrocene is an aromatic organic transition metal compound having the following structure:

[0052]

[0053] The reactive monomer 1,1'-ferrocene dicarboxaldehyde used in this application has the following structure:

[0054]

[0055] It is understood that the oxidation state of Fe in the ferrocenyl group is +2. Thus, in the representation of the ferrocenyl group, the core Fe is sometimes denoted as Fe 2+ Herein, it means the oxidation valence state.

[0056] To solve the problems mentioned in the beginning of this document in lithium ion batteries, in particular organic lithium ion batteries, the present application provides in particular a polymer having the structure shown in Formula 1 :

[0057]

[0058] wherein,

[0059] n is the degree of polymerization.

[0060] In this document, the degree of polymerization n is not particularly limited. However, depending on the specific reactants and their amounts, the reaction conditions, etc., it is generally true that 5 < n < 10 5 , preferably 10 < n < 1000. In Formula 1, Fe 2+ 2+ means the oxidation valence state of Fe. As can be seen from the structural formula, the polymer having the structure shown in Formula 1 is a polymer based on a ferrocenyl group, which is sometimes also referred to herein as “organic metal polymer” or “(organic metal) polymer according to the present application”. Furthermore, the inventors found that the (organic metal) polymer having the structure shown in Formula 1 can form a certain arrangement in space in addition to the extension of the repeat unit shown to both ends (determining the degree of polymerization n) of the polymer molecule chain.

[0061] In Formula 1, R can be a divalent group having aromaticity. For example, R can be a C6-C 60 arylene group or a C3-C 60 heteroarylene group, wherein the C6-C 60 arylene group and the C3-C 60 heteroarylene group can be unsubstituted or substituted by one or more substituents selected from the group consisting of oxo, halogen, hydroxy, cyano, nitro, C1-C 10 alkyl, C2-C 10 alkenyl or C1-C 10 alkoxy. In preferred embodiments, R can be an unsubstituted C6-C 60 arylene group and an unsubstituted C3-C 60 heteroarylene group. In preferred embodiments, R can be a C6-C 60 arylene group substituted by one or more (e.g. 1, 2, 3 or 4) oxo groups and a C3-C 60 heteroarylene group substituted by one or more (e.g. 1, 2, 3 or 4) oxo groups.

[0062] In preferred embodiments, R can be phenylene, naphthylene, anthrylene, phenanthrylene, benzophenanthrylene, heterophenylene, heteronaphthylene, heteroanthrylene, heterophenanthrylene, heterobenzophenanthrylene, wherein the aforementioned groups can be unsubstituted or substituted by one or more substituents selected from the group consisting of oxo, halogen, hydroxyl, cyano, nitro, C1-C6alkyl, C2-C6alkenyl or C1-C6alkoxy. In further preferred embodiments, R can be unsubstituted phenylene, naphthylene, anthrylene, phenanthrylene, benzophenanthrylene, heterophenylene, heteronaphthylene, heteroanthrylene, heterophenanthrylene or heterobenzophenanthrylene. In further preferred embodiments, R can be phenylene, naphthylene, anthrylene, phenanthrylene, benzophenanthrylene, heterophenylene, heteronaphthylene, heteroanthrylene, heterophenanthrylene or heterobenzophenanthrylene substituted by one or more (e.g. 1, 2, 3 or 4) oxo groups. 10 C1-C6alkyl, C2-C6alkenyl or C1-C6alkoxy. In further preferred embodiments, R can be unsubstituted phenylene, naphthylene, anthrylene, phenanthrylene, benzophenanthrylene, heterophenylene, heteronaphthylene, heteroanthrylene, heterophenanthrylene or heterobenzophenanthrylene. In further preferred embodiments, R can be phenylene, naphthylene, anthrylene, phenanthrylene, benzophenanthrylene, heterophenylene, heteronaphthylene, heteroanthrylene, heterophenanthrylene or heterobenzophenanthrylene substituted by one or more (e.g. 1, 2, 3 or 4) oxo groups. 10 C1-C6alkyl, C2-C6alkenyl or C1-C6alkoxy. In further preferred embodiments, R can be unsubstituted phenylene, naphthylene, anthrylene, phenanthrylene, benzophenanthrylene, heterophenylene, heteronaphthylene, heteroanthrylene, heterophenanthrylene or heterobenzophenanthrylene. In further preferred embodiments, R can be phenylene, naphthylene, anthrylene, phenanthrylene, benzophenanthrylene, heterophenylene, heteronaphthylene, heteroanthrylene, heterophenanthrylene or heterobenzophenanthrylene substituted by one or more (e.g. 1, 2, 3 or 4) oxo groups. 10 C1-C6alkyl, C2-C6alkenyl or C1-C6alkoxy. In further preferred embodiments, R can be unsubstituted phenylene, naphthylene, anthrylene, phenanthrylene, benzophenanthrylene, heterophenylene, heteronaphthylene, heteroanthrylene, heterophenanthrylene or heterobenzophenanthrylene. In further preferred embodiments, R can be phenylene, naphthylene, anthrylene, phenanthrylene, benzophenanthrylene, heterophenylene, heteronaphthylene, heteroanthrylene, heterophenanthrylene or heterobenzophenanthrylene substituted by one or more (e.g. 1, 2, 3 or 4) oxo groups.

[0063] In more preferred embodiments, R can be selected from phenylene, pyridylene, pyrazylene, pyrimidylene, pyridazylene, quinolylyene, naphthoquinolylyene, anthraquinolylyene or phenanthraquinolylylene. In more specific embodiments, R can be selected from:

[0064]

[0065] wherein... indicates the position of attachment to the adjacent atom. It is to be understood that the... in the above groups is only given schematically for possible positions of substitution. For each specific group, the possible positions of substitution are not limited to the positions shown, i.e. the position of attachment to the adjacent atom can also be at other possible positions.

[0066] In more preferred embodiments, Formula 1 can be selected from any one of Formula 1-1 to Formula 1-8:

[0067]

[0068]

[0069]

[0070] The present application also provides a method for preparing a polymer having Formula 1. The polymer having Formula 1 according to the present application can be obtained by a polycondensation reaction of 1,1’-diferrocenedicarboxaldehyde and a diamine R(NH2)2. In particular, it is preferred herein to use a diamine R(NH2)2having aromaticity, in particular wherein R is as defined above.

[0071] It is understood that the reactants, 1,1'-ferrocenedicarboxaldehyde and diamine R(NH2)2, can be provided in any suitable form thereof, such as a salt (e.g., hydrochloride salt), as long as the reactants involved in the reaction can provide 1,1'-ferrocenedicarboxaldehyde and diamine R(NH2)2in the reaction environment.

[0072] It is understood by those skilled in the art that the end groups of the polymer can vary somewhat depending on the reaction conditions, etc., but the polymer thus obtained still retains the structure shown in Formula 1 for its main chain (backbone), and thus still falls within the scope of the polymer claimed in the present application.

[0073] In a specific embodiment, the molar ratio of 1,1'-ferrocenedicarboxaldehyde to diamine R(NH2)2in the polycondensation reaction can be about (0.8-1.2): 1. Preferably, the molar ratio of 1,1'-ferrocenedicarboxaldehyde to diamine R(NH2)2may be about 1:1.

[0074] In a specific embodiment, the polycondensation reaction can be carried out in a solvent. Preferably, the solvent can be selected from the group consisting of 1,2-dichlorobenzene, n-butanol, 1,3,5-trimethylbenzene, 1,4-dioxane, tetrahydrofuran, toluene, water, ethanol, N,N-dimethylformamide, N,N-dimethylacetamide, and any combination thereof.

[0075] In a preferred embodiment, the polycondensation reaction can be carried out in an acid-containing solvent. Preferably, the solvent can be a solvent as described above, and the acid can be selected from the group consisting of acetic acid, sulfuric acid, phosphoric acid, and any combination thereof.

[0076] In a specific embodiment, the polycondensation reaction can be carried out under anaerobic conditions.

[0077] In a specific embodiment, the polycondensation reaction can be carried out under heating conditions. For example, the polycondensation reaction can be carried out at a temperature of about 80-150°C, preferably about 100-130°C, most preferably about 120°C. Under heating conditions, the polycondensation reaction can be carried out for about 24-72 hours.

[0078] In a specific embodiment, the preparation method according to the present application optionally includes the steps of cooling, washing, suction filtration, and / or drying after the completion of the polycondensation reaction.

[0079] The polymer obtained from the polycondensation reaction as described above has the structure of Formula 1 according to the present application. The method according to the present application is not only simple, but also low in energy consumption and environmentally friendly.

[0080] The polymer obtained from the polycondensation reaction as described above was characterized. In particular, it was found that the polymer according to the present application has a peak at 1575±10 cm -1having a characteristic peak at 1650 cm"1(corresponding to C=N bond). It can be understood that the presence of this infrared peak is sufficient to indicate that the polycondensation reaction has been successful and a polymer according to the present application has been obtained.

[0081] In addition, in the thermogravimetric analysis profile, the polymer according to the present application can maintain 98% or more of the mass at 300±5°C in a nitrogen atmosphere.

[0082] The present application also provides a composite material comprising or consisting of the (organometallic) polymer according to the present application and conductive carbon. In the composite material, the mass ratio of the polymer according to the present application to the conductive carbon can be 9:1-1:9, preferably about 8:2-6:4. That is, the conductive carbon can account for 10 mass% to 90 mass%, preferably 20 mass% to 40 mass% of the composite material. It can be understood that in the case where the composite material comprises the (organometallic) polymer according to the present application and the conductive carbon, the composite material can comprise other inorganic or organic materials that can be used in lithium batteries (such as cathode materials), in particular conductive materials.

[0083] Accordingly, the present application provides a method for preparing such a composite material. The composite material according to the present application can be obtained by adding conductive carbon to 1,1'-ferrocenedicarboxaldehyde, diamine R(NH2)2, and then performing a polycondensation reaction. That is, in the presence of the conductive carbon, the polycondensation reaction and in-situ compounding occur simultaneously, and finally a composite material comprising a polymer having the structure of Formula 1 and conductive carbon is obtained. It can be understood that in the composite material, the polymer and the conductive carbon are in a uniformly distributed state.

[0084] In this context, the conductive carbon used is not particularly limited. Preferably, the conductive carbon is selected from carbon nanotubes, graphene oxide, mesocarbon microbeads, and any combination thereof.

[0085] The method for preparing a composite material according to the present application comprises (i) mixing 1,1'-ferrocenedicarboxaldehyde, diamine R(NH2)2, and conductive carbon, and (ii) then simultaneously performing a polycondensation reaction of 1,1'-ferrocenedicarboxaldehyde and diamine R(NH2)2 with in-situ compounding with the conductive carbon, thereby obtaining the composite material. As described in the aforementioned polycondensation reaction, the molar ratio of 1,1'-ferrocenedicarboxaldehyde and diamine R(NH2)2 can be about (0.8-1.2):1; preferably, the molar ratio of 1,1'-ferrocenedicarboxaldehyde and diamine R(NH2)2 can be about 1:1. In a preferred embodiment, the conductive carbon can account for 10 mass% to 90 mass%, in particular 20 mass% to 40 mass% of the composite material.

[0086] In a particularly specific embodiment, the (organometallic) polymer according to the present application or the composite material according to the present application is prepared as follows: two reaction monomers (i.e. 1,1'-ferrocenedicarboxaldehyde and (aromatic) diamine) are separately added into a Schlenk tube, a solvent, an acid and optionally a conductive carbon are added at room temperature, after ultrasonic mixing and dispersion, a cycle of freeze-pumping and thawing is performed, then the tube is sealed under vacuum, the reaction system is kept at a constant temperature under heating for a period of time, after the reaction is completed, the reaction system is allowed to cool to room temperature, after repeated washing and suction filtration, the product organometallic polymer or the composite material comprising the organometallic polymer and the conductive carbon is obtained by vacuum heating and drying.

[0087] The inventors have found that the organometallic polymers according to the present application have excellent properties, in particular suitable for use in lithium ion batteries, for example as (active) electrode materials, in particular (active) cathode materials.

[0088] Accordingly, the present application also provides (active) electrode materials, for example (active) cathode materials, comprising a polymer having the structure shown in Formula 1 according to the present application or a composite material according to the present application.

[0089] Accordingly, the present application also provides lithium ion batteries comprising a polymer having the structure shown in Formula 1 according to the present application or a composite material according to the present application. In the lithium ion battery, the polymer can be used as an (active) electrode material, for example as an (active) cathode material.

[0090] The lithium ion battery prepared using the organometallic polymer according to the present application has a relatively high mass specific capacity and output voltage, a relatively high energy density and cycle stability.

[0091] Accordingly, the present application also provides the use of the (organometallic) polymer according to the present application or the composite material according to the present application in a lithium ion battery, in particular as an active electrode material, for example as an (active) cathode material.

[0092] As an example, the lithium ion battery can be prepared by conventional techniques known in the art.

[0093] In some embodiments, the preparation of the lithium ion battery can be as follows: the organometallic polymer according to the present application or the composite material according to the present application, a conductive additive and a binder PVDF are ground uniformly in a solvent N-methylpyrrolidone to form a slurry, the slurry is coated on the surface of a corresponding carbon-coated aluminum foil current collector, and a positive electrode film is prepared by vacuum heating and drying, the positive electrode film is cut to form a corresponding positive electrode sheet; the positive electrode sheet and a reference electrode sheet lithium foil are separated by a separator, an appropriate amount of electrolyte is added, and a coin-type lithium ion battery is assembled.

[0094] In a preferred experimental protocol, the conductive additive can be Super P, conductive carbon black, Ketjen black, or carbon nanotube, or a combination thereof. The mass ratio of the organic metal polymer active material, the conductive additive, and the binder according to the present application is (30-80):(60-10):10.

[0095] In a preferred embodiment, the electrolyte used is a solution of different lithium salts dissolved in different organic solvents, and the concentration of the electrolyte salt can be 0.5-4.0 mol / L, and a more preferred concentration is about 1.0 mol / L. Preferably, the lithium salt can be selected from one of lithium perchlorate (LiClO4), lithium difluoro(oxalato)borate (LiDFOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), or lithium hexafluorophosphate (LiPF6), or a mixture of several thereof in any ratio. Preferably, the organic solvent used can be one of 1,3-dioxolane (DOL), ethylene glycol dimethyl ether (DME), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), or ethyl methyl carbonate (EMC), or a mixed solvent of several thereof in any ratio.

[0096] The inventors have found that the organic metal polymer according to the present application has a stable polymer skeleton, i.e. the structure as shown in Formula 1. Without intending to be bound by theory, the inventors believe that it can be due to the fact that the organic metal polymer contains a large number of redox-active Fe 2+ and unsaturated double bonds, while containing a small number of non-oxidation-reaction-active functional groups, and thus is suitable for use in metal (lithium) ion batteries, and in particular is suitable for use in lithium ion battery active positive electrode materials. The lithium ion battery thus prepared has a higher mass specific capacity and better cycle stability.

[0097] The inventors have also found that it can be due to the fact that the organic metal polymer skeleton contains a large number of electron-withdrawing groups containing oxygen and nitrogen heteroatoms, while also containing Fe 2+ with a high redox potential, which increases the redox potential of the active positive electrode material containing the organic metal polymer, which is beneficial to increasing the working potential and energy density of the lithium ion battery.

[0098] Regarding the composite material containing the organic metal polymer and conductive carbon, the inventors have found that, on the one hand, the polymer is dispersed on the surface of the conductive carbon with a large surface area, so that the active positive electrode material containing the organic metal polymer has a high electronic conductivity and ion diffusion coefficient, which is beneficial to improving the active site utilization rate and rate performance of the lithium ion battery electrode material. On the other hand, the conductive carbon network skeleton is also beneficial to the transmission of electrons, and can further improve the structural stability of the material, thereby enhancing the rate performance and cycle stability of the lithium ion battery.

[0099] The polymer according to the present application not only has simple synthesis method, low preparation cost, environmentally friendly raw materials and sustainability, but also has good electrochemical performance, including high mass specific capacity, high output voltage, high cycle stability and excellent rate performance.

[0100] Examples

[0101] The following examples are for illustrative purposes only and are not intended to limit the scope of the present application.

[0102] Material Sources

[0103] 1,1'-Biferrocenedicarboxaldehyde

[0104] Purchased from Bide Pharmaceutical Technology Co., Ltd., purity ≥ 98%.

[0105] 1,4-Phenylenediamine

[0106] Purchased from Shanghai Aladdin Bio-Chem Technology Co., Ltd., purity ≥ 99%.

[0107] Pyrazine-2,5-diamine

[0108] Purchased from Bide Pharmaceutical Technology Co., Ltd., purity ≥ 98%.

[0109] 2,6-Diaminopyrazine hydrochloride

[0110] Purchased from Bide Pharmaceutical Technology Co., Ltd., purity ≥ 99%.

[0111] 2,5-Diamino-2,5-cyclohexadiene-1,4-dione

[0112] Purchased from Zancheng (Tianjin) Technology Co., Ltd., purity ≥ 99%.

[0113] 1,4-Diaminoanthraquinone

[0114] Purchased from Shanghai Macklin Biochemical Technology Co., Ltd., purity ≥ 98%.

[0115] 1,5-Diaminoanthraquinone

[0116] Purchased from Shanghai Macklin Biochemical Technology Co., Ltd., purity ≥ 95%.

[0117] 2,6-Diaminoanthraquinone

[0118] Purchased from Shanghai Macklin Biochemical Technology Co., Ltd., purity ≥ 98%.

[0119] Diaminoanthraquinone

[0120] Purchased from Jilin Zhongke Research Technology Co., Ltd., purity ≥ 98%.

[0121] Example 1: Synthesis of organometallic polymer 1

[0122] Into a 5 mL Schlenk tube, 24.2 mg (0.1 mmol) of 1,1’-ferrocene dimethanol and 10.8 mg (0.1 mmol) of 1,4-p-phenylenediamine were added, 2 mL of 1,3,5-trimethylbenzene and 1,4-dioxane (1:1) mixed solvent was added, a few drops of 6M acetic acid aqueous solution was added, the monomers and solvents were dispersed uniformly by ultrasonic, after three cycles of liquid nitrogen freezing-pumping-thawing, the tube was sealed, the system was heated to 120°C and reacted for 48 hours, after the reaction was completed, the reaction system was cooled to room temperature, the product was taken out by opening the Schlenk tube, washed and filtered with methanol, N,N-dimethylformamide, tetrahydrofuran respectively, the solid was dried at 120°C for 12 hours under vacuum, and a purified brown-black solid powder product, organometallic polymer 1, having a structure shown in formula 1-1, was obtained, wherein the polymerization degree was about 112.

[0123] Example 2: Synthesis of organometallic polymer 2

[0124] Into a 5 mL Schlenk tube, 24.2 mg (0.1 mmol) of 1,1’-ferrocene dimethanol and 10.8 mg (0.1 mmol) of 1,4-p-phenylenediamine were added, 2 mL of 1,2-dichlorobenzene and n-butanol (1:1) mixed solvent was added, a few drops of 6M acetic acid aqueous solution was added, the monomers and solvents were dispersed uniformly by ultrasonic, after three cycles of liquid nitrogen freezing-pumping-thawing, the tube was sealed, the system was heated to 120°C and reacted for 60 hours, after the reaction was completed, the reaction system was cooled to room temperature, the product was taken out by opening the Schlenk tube, washed and filtered with ethanol, N,N-dimethylformamide, tetrahydrofuran respectively, the solid was dried at 120°C for 12 hours under vacuum, and a purified brown-black solid powder product, organometallic polymer 2, having a structure shown in formula 1-1, was obtained, wherein the polymerization degree was about 208.

[0125] Example 3: Synthesis of composite material of organometallic polymer 3

[0126] Example 1: Synthesis of organometallic polymer 1

[0127] Example 4: Synthesis of organometallic polymer 4

[0128] Example 4: Synthesis of organometallic polymer 4

[0129] Example 5: Synthesis of organometallic polymer 5

[0130] Into a 5 mL Schlenk tube, 24.2 mg (0.1 mmol) of 1,1’-ferrocenedicarboxaldehyde and 14.7 mg (0.1 mmol) of 2,6-diaminopyrazine hydrochloride were added, 2 mL of 1,2-dichlorobenzene and n-butanol (1.5:1) mixed solvent were added, a few drops of 6M aqueous acetic acid were added, the monomer and solvent were dispersed uniformly by ultrasonic, after three cycles of liquid nitrogen freezing-pumping-thawing, the tube was sealed, the system was heated to 100°C and reacted for 70 hours, after the reaction was completed, the reaction system was cooled to room temperature, the product was taken out by opening the Schlenk tube, and washing and filtration operations were carried out using ethanol, N,N-dimethylformamide, tetrahydrofuran respectively, and the solid was dried at 100°C under vacuum for 18 hours, to obtain the purified brown-black solid powder product, i.e. organometallic polymer 5, having the structure shown in formula 1-3, and the polymerization degree n was about 82.

[0131] Example 6: Synthesis of organometallic polymer 6

[0132] Into a 5 mL Schlenk tube, 24.2 mg (0.1 mmol) of 1,1’-ferrocenedicarboxaldehyde and 14.7 mg (0.1 mmol) of 2,6-diaminopyrazine hydrochloride were added, 2 mL of 1,2-dichlorobenzene and n-butanol (1:2) mixed solvent were added, a few drops of 6M aqueous acetic acid were added, the mixture was dispersed uniformly by ultrasonic, after three cycles of liquid nitrogen freezing-pumping-thawing, the tube was sealed, the system was heated to 80°C and reacted for 72 hours, after the reaction was completed, the reaction system was cooled to room temperature, the product was taken out by opening the Schlenk tube, and washing and filtration operations were carried out using methanol, N,N-dimethylformamide, acetone respectively, and the solid was dried at 80°C under vacuum for 24 hours, to obtain the purified black-brown solid powder product, i.e. organometallic polymer 6, having the structure shown in formula 1-4, and the polymerization degree n was about 65.

[0133] Example 7: Synthesis of organometallic polymer 7

[0134] Into a 5 mL Schlenk tube, 24.2 mg (0.1 mmol) of 1,1’-ferrocenedicarboxaldehyde and 23.8 mg (0.1 mmol) of 2,6-diaminoanthraquinone were added, 2 mL of 1,2-dichlorobenzene and 1,3,5-trimethylbenzene (3:1) mixed solvent was added, a few drops of 6M acetic acid aqueous solution was added dropwise, the mixture was dispersed uniformly by ultrasonic, after three cycles of liquid nitrogen freezing-pumping-thawing, the tube was sealed, the system was heated to 140°C and reacted for 70 hours, after the reaction was completed, the reaction system was cooled to room temperature, the product was taken out by opening the Schlenk tube, washed and filtered with ethanol, N,N-dimethylformamide, acetone respectively, the solid was dried at 140°C for 15 hours in vacuum, and a purified black-brown solid powder product, i.e. organometallic polymer 7, having a structure shown in formula 1-5, was obtained, and the polymerization degree n was about 340.

[0135] Example 8: Synthesis of organometallic polymer 8

[0136] Into a 5 mL Schlenk tube, 24.2 mg (0.1 mmol) of 1,1’-ferrocenedicarboxaldehyde and 23.8 mg (0.1 mmol) of 1,5-diaminoanthraquinone were added, 2 mL of n-butanol solvent was added, a few drops of 6M acetic acid aqueous solution was added dropwise, the monomer and solvent were dispersed uniformly by ultrasonic, after three cycles of liquid nitrogen freezing-pumping-thawing, the tube was sealed, the system was heated to 80°C and reacted for 72 hours, after the reaction was completed, the reaction system was cooled to room temperature, the product was taken out by opening the Schlenk tube, washed and filtered with methanol, N,N-dimethylacetamide, tetrahydrofuran respectively, the solid was dried at 80°C for 24 hours in vacuum, and a purified black-brown solid powder product, i.e. organometallic polymer 8, having a structure shown in formula 1-6, was obtained, and the polymerization degree n was about 177.

[0137] Example 9: Synthesis of organometallic polymer 9

[0138] Into a 5 mL Schlenk tube, 24.2 mg (0.1 mmol) of 1,1’-ferrocenedicarboxaldehyde and 23.8 mg (0.1 mmol) of 1,4-diaminoanthraquinone were added, 2 mL of 1,2-dichlorobenzene and 1,4-dioxane (1:1) mixed solvent was added, a few drops of 6M acetic acid aqueous solution was added dropwise, the mixture was dispersed uniformly by ultrasonic, after three cycles of liquid nitrogen freezing-pumping-thawing, the tube was sealed, the system was heated to 120°C and reacted for 72 hours, after the reaction was completed, the reaction system was cooled to room temperature, the product was taken out by opening the Schlenk tube, washed and filtered with methanol, N,N-dimethylformamide, acetone respectively, the solid was dried at 120°C for 13 hours in vacuum, and a purified black-brown solid powder product, i.e. organometallic polymer 9, having a structure shown in formula 1-7, was obtained, and the polymerization degree n was about 183.

[0139] Example 10: Synthesis of organometallic polymer 10

[0140] Into a 5 mL Schlenk tube, 24.2 mg (0.1 mmol) of 1,1'-ferrocenedicarboxaldehyde and 23.8 mg (0.1 mmol) of diaminophenazine were added, 2 mL of 1,2-dichlorobenzene and 1,4-dioxane (2:1) mixed solvent was added, a few drops of 6M aqueous acetic acid was added, the mixture was dispersed uniformly by ultrasonic, after three cycles of liquid nitrogen freezing-pumping-thawing, the tube was sealed, the system was heated to 110°C and reacted for 72 hours, after the reaction was completed, the reaction system was cooled to room temperature, the product was taken out by opening the Schlenk tube, methanol, N,N-dimethylformamide, acetone were used for washing and filtration, the solid was dried at 110°C for 20 hours in vacuum, and a purified black-brown solid powder product, i.e. organometallic polymer 10, was obtained, which had a structure shown in formula 1-8 and a polymerization degree n of about 280.

[0141] Example 11: Structural characterization of organometallic polymers

[0142] The ten solid products in examples 1 to 10 were structurally characterized by infrared spectroscopy and thermogravimetric analysis technology. The results showed that the products of examples 1 to 10 were all target organometallic polymers. The infrared spectrum of the organometallic polymer 1 prepared in example 1 is shown in Figure 2 , and the infrared characteristic peak of C=N at 1575 cm -1 can be clearly seen. The thermogravimetric analysis spectrum of the organometallic polymer 2 is shown in Figure 3 , which can maintain more than 98% of the mass at 300°C. The infrared spectrum of the organometallic polymer 2 is shown in Figure 4 , and the infrared characteristic peak of C=N at 1573 cm -1 can be clearly seen. The infrared spectrum of the composite material containing the organometallic polymer 3 is shown in Figure 5 , and the infrared characteristic peak of C=N at 1580 cm -1 can be clearly seen. The infrared spectrum of the organometallic polymer 4 is shown in Figure 6 , and the infrared characteristic peak of C=N at 1577 cm -1 can be clearly seen. The infrared spectrum of the organometallic polymer 5 is shown in Figure 7 , and the infrared characteristic peak of C=N at 1576 cm -1 can be clearly seen. The infrared spectrum of the organometallic polymer 9 is shown in Figure 8 , and the infrared characteristic peak of C=N at 1577 cm -1 can be clearly seen.

[0143] Thus, in each of Examples 1-10, a polymer according to the present application or a composite material according to the present application was obtained.

[0144] Example 12: Preparation of lithium ion battery 1 and test of positive electrode electrochemical performance

[0145] The organic metal polymer 2 was used as the active positive electrode material, Ketjen black was used as the conductive additive, and PVDF was used as the binder. The three were mixed and ground in N-methyl pyrrolidone solvent at a mass ratio of 6:3:1 to form a uniform slurry. The slurry was coated on the surface of a carbon-coated aluminum foil current collector. After vacuum drying at 120°C for 12 hours, a positive electrode film was obtained. The positive electrode film was cut to obtain a positive electrode sheet. The positive electrode sheet was used as the positive electrode, a metal lithium foil was used as the negative electrode, Celgard 2325 was used as the separator, and a solution of 1M LiPF6 in a mixed solvent of EC and DMC at a volume ratio of 1:1 was used as the electrolyte. A coin-type lithium ion battery 1 was assembled in an argon-filled glove box.

[0146] The positive electrode electrochemical performance of the lithium ion battery 1 was tested, and the test results are shown in Figure 9 The first cycle discharge specific capacity can reach 110mAh / g at a current density of 2000mA / g within the test voltage window range of 1.2-4.0V (vs Li / Li + ), and the average capacity retention rate per cycle can reach 99.999% in a 5000-cycle charge-discharge cycle test, showing good charge-discharge cycle stability.

[0147] Example 13: Preparation of lithium ion battery 2 and test of full cell electrochemical performance

[0148] The organic metal polymer composite material 3 was used as the active positive electrode material, Ketjen black was used as the conductive additive, and PVDF was used as the binder. The three were mixed and ground in N-methyl pyrrolidone solvent at a mass ratio of 6:3:1 to form a uniform slurry. The slurry was coated on the surface of a carbon-coated aluminum foil current collector. After vacuum drying at 120°C for 12 hours, a positive electrode film was obtained. The positive electrode film was cut to obtain a positive electrode sheet. The positive electrode sheet was used as the positive electrode, pre-lithiated graphite was used as the negative electrode, Celgard 2325 was used as the separator, and a solution of 1M LiPF6 in a mixed solvent of EC, DMC, and EMC at a volume ratio of 1:1:1 was used as the electrolyte. A coin-type lithium ion battery 2 was assembled in an argon-filled glove box.

[0149] The full cell electrochemical performance of the lithium ion battery 2 was tested, and the test results are shown in Figure 10As shown, in the test voltage window range 1.2-4.0V, at a current density of 2000mA / g, the first circle discharge specific capacity can reach 137mAh / g, and the average output voltage can reach 2.3V. In the 1000 circle charge-discharge cycle test, it shows good charge-discharge cycle stability.

[0150] Example 14: Preparation of lithium ion battery 3 and test of positive electrode electrochemical performance

[0151] The organic metal polymer 8 was used as the active positive electrode material, Ketjen black was used as the conductive additive, and PVDF was used as the binder. The three were mixed and ground in N-methyl pyrrolidone solvent at a mass ratio of 6:3:1 to form a uniform slurry. The slurry was coated on the surface of a carbon-coated aluminum foil current collector. After vacuum drying at 120°C for 12 hours, a positive electrode film was obtained. The positive electrode film was cut to obtain a positive electrode sheet. The positive electrode sheet was used as the positive electrode, a metal lithium foil was used as the negative electrode, Celgard 2325 was used as the separator, and a 1M LiPF6 solution in a mixed solvent of EC and DMC at a volume ratio of 1:1 was used as the electrolyte. A coin-type lithium ion battery 3 was assembled in an argon-filled glove box.

[0152] The positive electrode electrochemical performance of the lithium ion battery was tested, and the test results are shown in Figure 11 As shown, in the test voltage window range 1.5-4.0V(vs Li / Li + ), at a current density of 50mA / g, the first circle discharge specific capacity can reach 150mAh / g, and in the 200 circle charge-discharge cycle test, the capacity retention rate can reach 96.7%, showing high capacity and good charge-discharge cycle stability.

[0153] From Examples 12 to 14, it can be seen that in lithium ion batteries, using the polymer according to the present application or the composite material according to the present application to prepare the active positive electrode material, lithium ion batteries with excellent performance such as high capacity retention rate and good charge-discharge cycle stability can be obtained.

Claims

1. Use of a polymer having a structure represented by Formula 1 in an electrode material or a lithium ion battery, Formula 1 wherein, n is the degree of polymerization and 5 < n < 10 5 ; R is C6-C 60 Arylene group or C3-C 60 Heteroarylene group, wherein the C6-C 60 Arylene group and the C3-C 60 The heteroarylene group is unsubstituted or substituted with one or more substituents selected from the group consisting of oxo, halogen, hydroxy, cyano, nitro, C1-C 10 Alkyl, C2-C 10 Alkenyl or C1-C 10 Alkoxy.

2. Use according to claim 1, wherein, The electrode material comprises a cathode material.

3. Use according to claim 1, wherein, 10≤n≤1000。 4. The use according to claim 1, wherein, R is phenylene, naphthylene, anthrylene, phenanthrylene, benzophenanthrylene, heterophenylene, heteronaphthylene, heteroanthrylene, heterophenanthrylene, heterobenzophenanthrylene, the aforementioned radicals being unsubstituted or substituted by one or more substituents selected from the group consisting of oxo, halogen, hydroxyl, cyano, nitro, Ci-C 10 alkyl, C2-C 10 alkenyl or Ci-C 10 alkoxy.

5. The use according to claim 1, wherein, R is phenylene, naphthylene, anthrylene, phenanthrylene, benzophenylene, heterophenylene, heteronaphthylene, heteroanthrylene, heterophenanthrylene, heterobenzophenylene, each of which is unsubstituted or substituted with one or more oxo groups.

6. The use according to claim 1, wherein, R is phenylene, pyridylene, pyrazylene, pyrimidylene, pyridazylene, quinolylene, naphthoquinolyiene, anthraquinolyiene, or phenanthroquinolyiene.

7. The use according to claim 1, wherein, Formula 1 is selected from any one of Formulae 1-1 to 1-8: Formula 1-1 Formula 1-2 Formula 1-3 Formula 1-4 Formula 1-5 Formula 1-6 , and Formula 1-7 Formula 1-8.

8. The use according to any one of claims 1 to 7, wherein, A method of preparing a polymer having a structure represented by Formula 1 comprises: polymerization of 1,1 '-ferrocenedicarboxaldehyde and a diamine R(NH2)2 in a molar ratio of (0.8-1.2) : 1, wherein R is C6-C 60 C6-C 60 C3-C 60 C6-C 60 C3-C 10 C1-C 10 C2-C 10 C1-C 9. Use according to claim 8, wherein, polycondensing 1,1’-ferrocene dimethylaldehyde and a diamine R(NH2)2 in a molar ratio of 1 :

1.

10. The use according to claim 9, wherein, The polycondensation reaction is performed in an acid-containing solvent, wherein the acid is selected from acetic acid, sulfuric acid, phosphoric acid, or a combination thereof; the solvent is selected from 1,2-dichlorobenzene, n-butanol, mesitylene, 1,4-dioxane, tetrahydrofuran, toluene, water, ethanol, N,N-dimethylformamide, N,N-dimethylacetamide, or any combination thereof; and / or The polycondensation reaction is reacted under heating for 24 to 72 hours under oxygen-free conditions.

11. Use according to claim 10, wherein, The temperature of the heating condition is 80 to 150 °C.

12. The use according to claim 10, wherein, The temperature of the heating condition is 100 to 130 °C.

13. The use according to claim 10, wherein, The temperature of the heating condition is 120 °C.

14. The use according to claim 10, wherein, A step of standing cooling, washing, suction filtration, and drying is performed after the polycondensation reaction is completed.

15. The use of claim 8, wherein, The polymer having a structure represented by Formula 1 has one or both of the following characteristics: (1) in the infrared spectrum, a characteristic peak at 1575 ± 10 cm -1 and (2) In a thermogravimetric analysis, the mass is maintained at 300 ± 5 °C under a nitrogen atmosphere by 98% or more.

16. Use of a composite material in an electrode material or a lithium ion battery, wherein, The composite material comprises a polymer having a structure represented by Formula 1, and a conductive carbon, Formula 1 wherein n is the degree of polymerization, and 5 < n < 10 5 ; R is a C6-C 60 arylene group or a C3-C 60 heteroarylene group, wherein the C6-C 60 arylene group and the C3-C 60 heteroarylene group are unsubstituted or substituted by one or more substituents selected from the group consisting of oxo, halogen, hydroxyl, cyano, nitro, C1-C 10 alkyl, C2-C 10 alkenyl or C1-C 10 alkoxy.

17. The use according to claim 16, wherein, The electrode material comprises a cathode material.

18. The use of claim 16, wherein, The conductive carbon is selected from carbon nanotubes, graphene oxide, mesocarbon microbeads, or any combination thereof.

19. The use of claim 16, wherein, The conductive carbon accounts for 10 mass% to 90 mass% of the composite material.

20. The use according to claim 19, wherein, The conductive carbon accounts for 20 mass% to 40 mass% of the composite material.

21. The use according to any one of claims 16-20, wherein, A method of preparing the composite material comprises: The composite material is obtained by mixing ferrocene dicarboxaldehyde, a diamine R(NH2)2 and conductive carbon and simultaneously performing a polycondensation reaction of ferrocene dicarboxaldehyde and diamine R(NH2)2 while in situ complexing with conductive carbon, whereby the molar ratio of ferrocene dicarboxaldehyde to diamine R(NH2)2 is (0.8-1.2) : 1, and whereby R in diamine R(NH2)2 is C6-C 60 an arylene group or a C3-C 60 heteroarylene group, whereby said C6-C 60 arylene group and said C3-C 60 heteroarylene group are unsubstituted or substituted by one or more substituents selected from the group consisting of oxo, halogen, hydroxyl, cyano, nitro, C1-C 10 alkyl, C2-C 10 alkenyl or C1-C 10 alkoxy.

22. The use of claim 21, wherein, The molar ratio of 1,1’-ferrocene dimethylaldehyde and the diamine R(NH2)2 is 1 :

1.

23. The use of claim 21, wherein, In the diamin R(NH2)2, R is phenylene, naphthylene, anthrylene, phenanthrylene, benzophenanthrylene, heterophenylene, heteronaphthylene, heteroanthrylene, heterophenanthrylene, heterobenzophenanthrylene, the aforementioned radicals being unsubstituted or substituted by one or more substituents selected from the group consisting of oxo, halogen, hydroxyl, cyano, nitro, Ci-C 10 alkyl, C2-C 10 alkenyl or Ci-C 10 alkoxy.

24. The use of claim 21, wherein, In the diamine R(NH2)2, R is phenylene, naphthylene, anthrylene, phenanthrylene, benzophenylene, heterophenylene, heteronaphthylene, heteroanthrylene, heterophenanthrylene, heterobenzophenylene, each of which is unsubstituted or substituted with one or more oxo groups.

25. The use of claim 21, wherein, In the diamine R(NH2)2, R is phenylene, pyridylene, pyrazylene, pyrimidylene, pyridazylene, quinolylene, naphthoquinolyiene, anthraquinolyiene, or phenanthroquinolyiene.

26. The use according to claim 21, wherein, the acid is selected from the group consisting of acetic acid, sulfuric acid, phosphoric acid, or a combination thereof; the solvent is selected from the group consisting of 1,2-dichlorobenzene, n-butanol, 1,3,5-trimethylbenzene, 1,4-dioxane, tetrahydrofuran, toluene, water, ethanol, N,N-dimethylformamide, N,N-dimethylacetamide, or any combination thereof; and / or the polycondensation reaction is reacted under heating conditions for 24 to 72 hours under oxygen-free conditions.

27. The use of claim 26, wherein, the temperature of the heating conditions is 80 to 150 °C.

28. The use of claim 26, wherein, the temperature of the heating conditions is 100 to 130 °C.

29. The use of claim 26, wherein, the temperature of the heating conditions is 120 °C.

30. The use of claim 26, wherein, the steps of standing cooling, washing, suction filtration, and drying are performed after the completion of the polycondensation reaction.

31. The use according to any one of claims 26-30, wherein, the polymer having the structure of Formula 1 has one or both of the following characteristics: (1) in the infrared spectrum, a characteristic peak at 1575 ± 10 cm -1 and (2) in thermal gravimetric analysis, the mass is maintained at 98% or more when heated to 300 ± 5 °C in a nitrogen atmosphere.

32. An electrode material, wherein, comprising the polymer having the structure of Formula 1 or a composite material comprising the polymer having the structure of Formula 1 and an electrically conductive carbon, Formula 1 wherein n is the degree of polymerization, and 5 < n < 10 5 ; R is C6-C 60 Arylene group or C3-C 60 Heteroarylene group, wherein the C6-C 60 Arylene group and the C3-C 60 The heteroarylene group is unsubstituted or substituted with one or more substituents selected from the group consisting of oxo, halogen, hydroxy, cyano, nitro, C1-C 10 Alkyl, C2-C 10 Alkenyl or C1-C 10 Alkoxy.

33. The electrode material of claim 32, wherein, the electrode material is a cathode material.

34. A lithium ion battery comprising the polymer having the structure of Formula 1 or a composite material comprising the polymer having the structure of Formula 1 and an electrically conductive carbon, Formula 1 wherein, n is the degree of polymerization and 5 < n < 10 5 ; R is a C6-C 60 arylene group or a C3-C 60 heteroarylene group, wherein the C6-C 60 arylene group and the C3-C 60 heteroarylene group are unsubstituted or substituted by one or more substituents selected from the group consisting of oxo, halogen, hydroxyl, cyano, nitro, C1-C 10 alkyl, C2-C 10 alkenyl or C1-C 10 alkoxy.

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