CN112331837A - Organic-inorganic composite electrode material and preparation method and application thereof - Google Patents

Organic-inorganic composite electrode material and preparation method and application thereof Download PDF

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CN112331837A
CN112331837A CN202011330745.6A CN202011330745A CN112331837A CN 112331837 A CN112331837 A CN 112331837A CN 202011330745 A CN202011330745 A CN 202011330745A CN 112331837 A CN112331837 A CN 112331837A
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electrode material
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inorganic
electrode
battery
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索鎏敏
毛明磊
王舒
李泓
陈立泉
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Institute of Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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Abstract

The invention relates to an organic-inorganic composite electrode material and a preparation method and application thereof, wherein the organic-inorganic composite electrode material is formed by compounding an organic electrode material and an inorganic electrode material; the organic electrode material is an organic substance having a redox active group, and comprises: one or more of carbonyl compounds, nitrile compounds, organic free radical compounds, imino compounds, azo compounds and organic sulfides; the inorganic electrode material includes: one or more of transition metal oxide, transition metal sulfide, and transition metal selenide; the specific capacity of the inorganic electrode material is more than 100mAh/g, and the forbidden band width is zero; in the organic-inorganic composite electrode material, the inorganic electrode material is used as an active substance to store embedded ions and is used as an organic electrode material to transfer electrons, so that the proportion of the active material in the electrode is increased, the overall porosity and liquid absorption of the electrode are reduced, and the capacity and energy density of the electrode are increased.

Description

Organic-inorganic composite electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of materials, in particular to an organic-inorganic composite electrode material and a preparation method and application thereof.
Background
In the existing mature secondary battery technology, the anode material is generally transition metal oxide. However, with the large-scale application of secondary batteries, the resource and price problems of noble metals (particularly, cobalt and nickel) become more and more significant.
Therefore, the focus in the industry is turning to organic electrode materials with the advantages of sufficient resources, environmental friendliness, strong chemical designability, capability of matching with various metal ions and the like. However, most organic electrode materials are semiconductors or even insulators, and the electronic conductivity is low, so that the exertion of the theoretical specific capacity is limited.
Therefore, in order to exert more capacity of the organic electrode material during the use process, those skilled in the art adopt a mode of adding a large amount of conductive carbon (20-60% by mass) into the electrode to transport electrons to the organic electrode material.
However, since these conductive carbons cannot store ions, not only the mass ratio of active materials in the electrode is decreased, but also the porosity and liquid absorption amount of the electrode are increased, and the energy density of the electrode is greatly impaired.
Disclosure of Invention
The embodiment of the invention provides an organic-inorganic composite electrode material and a preparation method and application thereof. The inorganic active material with a certain mass fraction is adopted to replace the non-activated carbon in the organic electrode. The electrode can contribute a certain capacity and ensure a complete conductive network in the electrode.
In a first aspect, embodiments of the present invention provide an organic-inorganic composite electrode material, where the organic-inorganic composite electrode material is formed by compositing an organic electrode material and an inorganic electrode material;
the organic electrode material is an organic substance having a redox active group, and comprises: one or more of carbonyl compounds, nitrile compounds, organic free radical compounds, imino compounds, azo compounds and organic sulfides;
the inorganic electrode material includes: one or more of transition metal oxide, transition metal sulfide, and transition metal selenide; the specific capacity of the inorganic electrode material is more than 100mAh/g, and the forbidden band width is zero; in the organic-inorganic composite electrode material, the inorganic electrode material is used as an active substance to store embedded ions and is used for transferring electrons for the organic electrode material, so that the proportion of the active material in the electrode is increased, the overall porosity and liquid absorption of the electrode are reduced, and the capacity and energy density of the electrode are increased.
Preferably, the inorganic electrode material specifically includes: mo6S8,TiS2,TiSe2,NbS2,NbSe2,NbSe3One or more of (a).
Preferably, in the organic-inorganic composite electrode material, the mass ratio of the organic electrode material to the inorganic electrode material is 1: 5-8.5: 1.
in a second aspect, embodiments of the present invention provide a method for preparing an organic-inorganic composite electrode material according to the first aspect, the method comprising:
according to the mass ratio of 1: 5-8.5: 1, weighing an organic electrode material and an inorganic electrode material, placing the organic electrode material and the inorganic electrode material in a ball milling tank, and carrying out sealed ball milling for 0.1-72 hours to obtain an organic-inorganic composite electrode material; alternatively, the first and second electrodes may be,
according to the mass ratio of 1: 5-8.5: 1, weighing an organic electrode material and an inorganic electrode material according to a certain proportion, adding a certain amount of solvent, stirring for 1-48 hours in an inert gas atmosphere, and volatilizing the solvent to obtain an organic-inorganic composite electrode material;
wherein the organic electrode material is an organic substance having a redox active group, and comprises: one or more of carbonyl compounds, nitrile compounds, organic free radical compounds, imino compounds, azo compounds and organic sulfides;
the inorganic electrode material includes: one or more of transition metal oxide, transition metal sulfide, and transition metal selenide; the specific capacity of the inorganic electrode material is more than 100mAh/g, and the forbidden band width is zero; in the organic-inorganic composite electrode material, the inorganic electrode material is used as an active substance to store embedded ions and is used for transferring electrons for the organic electrode material, so that the proportion of the active material in the electrode is increased, the overall porosity and liquid absorption of the electrode are reduced, and the capacity and energy density of the electrode are increased.
Preferably, the inorganic electrode material specifically includes: mo6S8,TiS2,TiSe2,NbS2,NbSe2,NbSe3One or more of (a).
In a third aspect, embodiments of the present invention provide a battery electrode comprising an organic-inorganic composite electrode material as described in the first aspect above.
Preferably, the content of the organic electrode material in the organic-inorganic composite electrode material in the battery electrode is 10-85 wt%, and the content of the inorganic electrode material in the battery electrode is 10-50 wt%.
Preferably, the battery electrode further comprises: the conductive additive accounts for 1-30% of the mass ratio of the battery electrode, and the binder accounts for 1-10% of the mass ratio of the battery electrode;
the conductive additive specifically includes: one or more of Ketjen black, acetylene black, graphene, carbon nanotubes and Super-P carbon black;
the adhesive comprises: one or more of Polytetrafluoroethylene (PTFE), hydroxymethyl cellulose (CMC), sodium alginate, polyvinylidene fluoride (PVDF), polyacrylic acid (PAA) and Styrene Butadiene Rubber (SBR).
In a fourth aspect, embodiments of the present invention provide a secondary battery including the battery electrode of the third aspect described above.
Preferably, the battery electrode is used as a positive electrode in the secondary battery;
the secondary battery includes: any one of a lithium ion battery, a lithium metal battery, a sodium ion battery, a sodium metal battery, a magnesium ion battery, a magnesium metal battery, a potassium ion battery, a potassium metal battery, an aluminum ion battery, an aluminum metal battery, a zinc ion battery, a zinc metal battery, a calcium ion battery, and a calcium metal battery.
The organic-inorganic composite electrode material is based on a composite strategy of an organic electrode material and an inorganic electrode material, and an inorganic active substance with specific capacity of more than 100mAh/g and zero forbidden bandwidth is used for replacing an inactive carbon additive adopted in the prior art, so that the proportion of the inactive substance in the electrode is reduced, the porosity and the liquid absorption of the electrode are reduced, and the integral energy density of the electrode is improved. In the electrode using the material, the inorganic electrode material in the material and conductive carbon as a conductive additive together form a three-dimensional electron transport network. The organic-inorganic composite electrode material and the composite method strategy are suitable for various organic electrode materials and inorganic electrode materials, can be applied to various metal ion secondary batteries, and have high energy density and stable cycle performance.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
Fig. 1 is a schematic structural view of a secondary battery including an organic-inorganic composite electrode material according to an embodiment of the present invention;
FIG. 2 shows perylene tetracarboxylic dianhydride (PTCDA) and Mo provided in example 1 of the present invention6S8Constant current charge and discharge curve of the composite electrode in the lithium ion battery;
FIG. 3 shows PTCDA and Mo provided in example 1 of the present invention6S8A cycle performance diagram of the composite electrode in a lithium ion battery;
FIG. 4 is PTCDA and TiS provided in example 2 of the present invention2Constant current charge and discharge curve of the composite electrode in the lithium ion battery;
FIG. 5 is PTCDA and TiS provided in example 2 of the present invention2A cycle performance diagram of the composite electrode in a lithium ion battery;
FIG. 6 is PTCDA and TiS provided in example 3 of the present invention2Constant current charge and discharge curve of the composite electrode in the sodium ion battery;
FIG. 7 is PTCDA and TiS provided in example 3 of the present invention2A cycle performance diagram of the composite electrode in a sodium ion battery;
FIG. 8 shows the polymerization of Hexaazanaphthalene (HATN) and Mo provided in example 4 of the present invention6S8Constant current charge and discharge curve of the composite electrode in the lithium ion battery;
FIG. 9 shows HATN and Mo provided in example 4 of the present invention6S8A cycle performance diagram of the composite electrode in a lithium ion battery;
fig. 10 is a constant current charge and discharge curve of PTCDA and conductive carbon composite electrode provided in comparative example 1 of the present invention in a lithium ion battery.
Detailed Description
The invention is further illustrated by the following figures and specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as in any way limiting the present invention, i.e., as in no way limiting its scope.
The invention provides an organic-inorganic composite electrode material, which is formed by compounding an organic electrode material and an inorganic electrode material; the mass ratio of the organic electrode material to the inorganic electrode material is 1: 5-8.5: 1.
wherein, the organic electrode material is an organic matter with redox active groups, and comprises: one or more of carbonyl compounds, nitrile compounds, organic free radical compounds, imino compounds, azo compounds and organic sulfides;
the inorganic electrode material includes: one or more of transition metal oxide, transition metal sulfide, and transition metal selenide; wherein the specific capacity of the inorganic electrode material is more than 100mAh/g, and the forbidden band width is zero;
preferably, the inorganic electrode material is selected from: mo6S8,TiS2,TiSe2,NbS2,NbSe2,NbSe3One or more of (a).
In the organic-inorganic composite electrode material, the inorganic electrode material is used as an active substance to store embedded ions and also used as an organic electrode material to transfer electrons, so that the proportion of the active material in the electrode is increased, the overall porosity and liquid absorption of the electrode are reduced, and the capacity and energy density of the electrode are increased.
The main preparation method of the organic-inorganic composite electrode material provided above can include the following two methods:
the first method comprises the following steps of: 5-8.5: 1 weighing organic electrode materials and inorganic electrode materials, placing the organic electrode materials and the inorganic electrode materials in a ball milling tank, and carrying out sealed ball milling for 0.1-72 hours to obtain the organic-inorganic composite electrode material.
And the second, the mass ratio of 1: 5-8.5: 1, weighing the organic electrode material and the inorganic electrode material according to the proportion, adding a certain amount of solvent, stirring for 1-48 hours in an inert gas atmosphere, and volatilizing the solvent to obtain the organic-inorganic composite electrode material. Wherein, the solvent volatilization can be natural volatilization or can be kept for 1 to 48 hours at the temperature of between 20 and 80 ℃ so as to volatilize the solvent.
In the above two methods, the organic electrode material is the above organic material having a redox active group, and includes: one or more of carbonyl compounds, nitrile compounds, organic free radical compounds, imino compounds, azo compounds and organic sulfides;
the inorganic electrode material is also the above, and includes: one or more of transition metal oxide, transition metal sulfide, and transition metal selenide; the specific capacity of the inorganic electrode material is more than 100mAh/g, and the forbidden band width is zero. Preferably Mo6S8,TiS2,TiSe2,NbS2,NbSe2,NbSe3One or more of (a).
The organic-inorganic electrode material composite strategy provided by the invention provides a feasible scheme for the practical application of the organic active material.
The organic-inorganic electrode material provided by the invention can be used as an electrode material and applied to battery electrodes. The content of the organic electrode material in the organic-inorganic composite electrode material in the battery electrode is 10 wt% -85 wt%, and the content of the inorganic electrode material in the battery electrode is 10 wt% -50 wt%.
The battery electrode includes, in addition to the organic-inorganic composite electrode material: the conductive additive accounts for 1-30% of the mass ratio of the battery electrode, and the binder accounts for 1-10% of the mass ratio of the battery electrode; wherein the conductive additive specifically comprises: one or more of Ketjen black, acetylene black, graphene, carbon nanotubes and Super-P carbon black; the binder specifically includes: one or more of Polytetrafluoroethylene (PTFE), hydroxymethyl cellulose (CMC), sodium alginate, polyvinylidene fluoride (PVDF), polyacrylic acid (PAA) and Styrene Butadiene Rubber (SBR).
Fig. 1 is a schematic structural view of a secondary battery containing an organic-inorganic composite electrode material according to an embodiment of the present invention, in which the above battery electrode is used as a positive electrode, and a secondary battery is constructed together with a negative electrode and an electrolyte.
The secondary battery to which the battery electrode of the present invention is applied may specifically include: any one of a lithium ion battery, a lithium metal battery, a sodium ion battery, a sodium metal battery, a magnesium ion battery, a magnesium metal battery, a potassium ion battery, a potassium metal battery, an aluminum ion battery, an aluminum metal battery, a zinc ion battery, a zinc metal battery, a calcium ion battery, and a calcium metal battery.
In order to better understand the technical scheme provided by the present invention, the following description will respectively illustrate the specific processes for preparing the composite electrode by applying the method provided by the above embodiments of the present invention, and the method and battery characteristics for applying the same to the secondary battery.
Example 1
This example provides an organic PTCDA and inorganic Mo6S8The composite anode and the electrochemical performance test of the composite anode in the lithium ion battery.
(1)Mo6S8The synthesis of (2): mixing the components in a molar ratio of 2: 1: 1 MoS2Ball milling copper powder and molybdenum powder for 2 hours at 300rpm under argon; adding a small amount of iodine simple substance, pressing into blocks by using a die, sealing in a stainless steel container, then placing in a tube furnace, heating to 800 ℃ at a heating rate of 2 ℃/min under the argon atmosphere, and preserving heat for 24 hours to obtain an intermediate product Cu2Mo6S8(ii) a Then putting the mixture into 6M hydrochloric acid, and introducing oxygen to wash the mixture for 12 hours; finally, centrifugally washing the obtained product by using a large amount of deionized water, and drying the obtained product in vacuum at 60 ℃ to obtain a product Mo6S8。
(2) PTCDA and Mo6S8Compounding: the organic electrode material PTCDA and the inorganic electrode material Mo6S8According to the mass ratio of 2: 1, adding the mixture into a ball milling tank, sealing the ball milling tank in a glove box filled with argon, and carrying out ball milling for 12 hours to obtain the uniformly mixed organic-inorganic composite electrode material.
(3) According to the mass ratio of 90: 5: 5, weighing the organic-inorganic composite electrode material, Keqin black and vinylidene fluoride, uniformly grinding, adding a proper amount of solvent N-methyl pyrrolidone (NMP), and stirring to obtain uniform slurry. And (3) uniformly coating the slurry on a current collector aluminum foil, and drying to obtain the positive pole piece.
(4) And assembling a positive plate, a lithium metal negative electrode and 3mol/L LiTFSI/ethylene glycol dimethyl ether (DME) electrolyte into a button cell in a glove box filled with argon. And the battery is subjected to constant-current charge and discharge tests, and the voltage range is 1.5-3V vs. Li/Li+The current density was 100 mA/g.
FIG. 2 shows PTCDA and Mo provided in example 1 of the present invention6S8Constant current charge and discharge curve of the composite electrode; as can be seen from FIG. 2, PTCDA and Mo6S8The composite electrode can obtain a specific capacity of 110mAh/g (based on the mass of the whole electrode, including PTCDA, Mo6S8Carbon, binder). In the examples of the present invention, all specific capacities were calculated based on the mass of the entire electrode, unless otherwise specified. FIG. 3 shows PTCDA and Mo provided in example 1 of the present invention6S8Cycle performance of the composite electrode, as can be seen in FIG. 3PTCDA and Mo6S8The composite electrode can obtain stable cycle performance. After 200 cycles, the capacity can still be maintained at 94.4% and the average coulombic efficiency approaches 99.7%.
Example 2
This example provides an organic PTCDA and an inorganic TiS2The composite anode and the electrochemical performance test of the composite anode in the lithium ion battery.
(1) PTCDA and TiS2Compounding: the organic electrode material PTCDA and the inorganic electrode material TiS are mixed2According to the mass ratio of 2: 1, adding the mixture into a mortar, and manually grinding the mixture for 72 hours in a glove box filled with argon to obtain the uniformly mixed organic-inorganic composite electrode material.
(2) According to the mass ratio of 90: 2: 8, weighing the organic-inorganic composite electrode material, Keqin black and vinylidene fluoride, uniformly grinding, adding a proper amount of solvent NMP, and stirring to obtain uniform slurry. And (3) uniformly coating the slurry on a current collector aluminum foil, and drying to obtain the positive pole piece.
(3) In a glove box filled with argon, a positive plate, a lithium metal negative electrode and 3mol/L LiTFSI/DME electrolyte are assembled into a button cell. And the battery is subjected to constant-current charge and discharge tests, and the voltage range is 1.5-3V vs. Li/Li+The current density was 100 mA/g.
FIG. 4 is PTCDA and TiS provided in example 2 of the present invention2Constant current charge and discharge curves of the composite electrode, as can be seen from FIG. 4, PTCDA and TiS2The specific capacity of the composite electrode can reach 135 mAh/g. FIG. 5 is PTCDA and TiS provided in example 2 of the present invention2Cycle performance of the composite electrode, PTCDA and TiS, as can be seen in FIG. 52The composite electrode can obtain stable cycle performance. After 200 cycles, the capacity can still be maintained at 92.6% and the average coulombic efficiency approaches 99.8%.
Example 3
This example provides an organic PTCDA and an inorganic TiS2The composite positive electrode and the electrochemical performance test of the composite positive electrode in the sodium ion battery.
(1) PTCDA and TiS2Compounding: organic electrode materialPTCDA material and TiS inorganic electrode material2According to the mass ratio of 3: 2, adding the mixture into a ball milling tank, and carrying out sealed ball milling for 1 hour in a glove box filled with argon to obtain the uniformly mixed organic-inorganic composite electrode material.
(2) According to the mass ratio of 95: 2: 3, weighing the organic-inorganic composite electrode material, Keqin black and vinylidene fluoride, uniformly grinding, adding a proper amount of solvent NMP, and stirring to obtain uniform slurry. And (3) uniformly coating the slurry on a current collector aluminum foil, and drying to obtain the positive pole piece.
(3) In a glove box filled with argon, a positive plate, a sodium metal negative electrode and 1mol/L NaTFSI/DME electrolyte are assembled into a button cell. And performing constant current charge and discharge test on the battery, wherein the voltage range is 1-3V vs+The current density was 100 mA/g.
FIG. 6 is PTCDA and TiS provided in example 3 of the present invention2Constant current charge and discharge curves of the composite electrode in sodium batteries, as can be seen from fig. 6, PTCDA and TiS2The specific capacity of the composite electrode can be 130 mAh/g. FIG. 7 is PTCDA and TiS provided in example 3 of the present invention2A cycle performance profile of the composite electrode in a sodium battery; as can be seen from FIG. 7, PTCDA and TiS2The composite electrode can obtain stable cycle performance. After 100 cycles, the capacity can still be maintained at 118.5mA h/g, and the average coulombic efficiency approaches 99.5%.
Example 4
This example provides an organic polymeric Hexaazanaphthalene (HATN) and inorganic Mo6S8The composite anode and the electrochemical performance test of the composite anode in the lithium ion battery.
(1) Synthesis of HATN: in a flask in an ice-water bath under a nitrogen atmosphere, a solution of a mixture of 2: 3 and 3,3' -diaminobenzidine, and then slowly adding deoxygenated N-methylpyrrolidone (NMP) and sulfuric acid; the flask was slowly warmed to room temperature over 3 hours; subsequently transferred to an oil bath maintained at 60 ℃ for 12 hours; after cooling to room temperature, a large amount of water is added for centrifugal washing, and the HATN is obtained after vacuum drying.
(2) HATN and Mo6S8Compounding: organic electrode materialMaterial HATN, inorganic electrode material Mo6S8According to the mass ratio of 2: 1, adding the mixture into a ball milling tank, sealing the ball milling tank in a glove box filled with argon, and carrying out ball milling for 24 hours to obtain the organic and inorganic composite electrode material which is uniformly mixed.
(3) According to the mass ratio of 85: 5: 10, weighing the composite electrode material, carbon black and polytetrafluoroethylene, grinding uniformly, adding a proper amount of solvent, and stirring to obtain uniform slurry. And (3) uniformly coating the slurry on a current collector, and drying to obtain the positive pole piece.
(4) In a glove box filled with argon, a positive plate, a lithium metal negative electrode, and 1mol/L LiPF6The/ethylene carbonate-dimethyl carbonate (EC-DMC) electrolyte is assembled into a button cell. And the battery is subjected to constant-current charge and discharge tests, and the voltage range is 1.5-3.5V vs. Li/Li+The current density was 100 mA/g.
FIG. 8 shows HATN and Mo provided in example 4 of the present invention6S8Constant current charge and discharge curve of the composite electrode in the lithium ion battery; as can be seen from FIG. 9, HATN and Mo6S8The specific capacity of the composite electrode can reach 122 mAh/g. FIG. 9 shows HATN and Mo provided in example 4 of the present invention6S8A cycle performance diagram of the composite electrode in a lithium ion battery; as can be seen from FIG. 9, HATN and Mo6S8The composite electrode can obtain stable cycle performance. After 100 cycles, the capacity can still be maintained at 110mAh/g, and the average coulombic efficiency approaches 99.9%.
Example 5
This example provides an organic 2,3,5, 6-tetranaphtylimidazolium p-benzoquinone (2,3,5, 6-tetranaphtalimido-p-benzoquinone, TPBQ) and an inorganic TiSe2The composite positive electrode of (1), and electrochemical performance test of the composite positive electrode in a magnesium battery.
(1) TPBQ and TiSe2Compounding: according to the mass ratio of 5: 1 weighing organic electrode material TPBQ and inorganic electrode material TiSe2Adding a certain amount of solvent NMP, stirring for 24 hours in an inert gas atmosphere, and volatilizing the solvent to obtain the uniformly mixed composite organic and inorganic electrode material.
(2) According to the mass ratio of 90: 2: and 8, weighing the composite electrode material, the carbon nano tube and the CMC, uniformly grinding, adding a proper amount of solvent, and stirring to obtain uniform slurry. And (3) uniformly coating the slurry on a current collector, and drying to obtain the positive pole piece.
(3) In a glove box filled with argon, a positive plate, a magnesium metal negative electrode, and 0.4mol/L phenylmagnesium chloride (PhMgCl) -MgCl 2/Tetrahydrofuran (THF) electrolyte were assembled into a battery. And the battery is subjected to constant-current charge and discharge tests, and the voltage range is 0.5-2.5V vs. Mg/Mg2+The current density was 20 mA/g.
Example 6
This example provides an organic TPBQ and inorganic Mo6S8The composite positive electrode of (1), and electrochemical performance test of the composite positive electrode in an aluminum battery.
(1) TPBQ and Mo6S8Compounding: organic electrode material TPBQ and inorganic electrode material Mo6S8According to the mass ratio of 1: 2, adding the mixture into a ball milling tank, and carrying out ball milling for 24 hours in a glove box filled with argon to obtain the organic and inorganic composite electrode material which is uniformly mixed.
(2) According to the mass ratio of 80: 10: 10, weighing the composite electrode material, graphene and polytetrafluoroethylene, grinding uniformly, adding a proper amount of solvent, and stirring to obtain uniform slurry. And (3) uniformly coating the slurry on a current collector, and drying to obtain the positive pole piece.
(3) In a glove box filled with argon, a positive plate, an aluminum metal negative electrode and AlCl are put in3And 1-ethyl-3-methylimidazolium chloride (1-ethyl-3-methyl-imidazolium chloride, EMImCl) ionic liquid electrolyte to assemble the battery. And the battery is subjected to constant-current charge and discharge tests, and the voltage range is 0.2-1.2V vs3+The current density was 20 mA/g.
To better illustrate the effects of the examples of the present invention, comparative example 1 was compared with the above examples, especially example 2.
Comparative example 1
The present comparative example provides a composite positive electrode of organic PTCDA and conductive carbon, and its electrochemical performance testing in a lithium ion battery.
(1) Complexing PTCDA with carbon: mixing an organic electrode material PTCDA and acetylene black according to a mass ratio of 2: 1, adding the mixture into a mortar, and manually grinding the mixture for 2 hours in a glove box filled with argon to obtain the organic and carbon composite electrode material which is uniformly mixed.
(2) According to the mass ratio of 90: 2: and 8, weighing the composite electrode material, Keqin black and vinylidene fluoride, uniformly grinding, adding a proper amount of solvent NMP, and stirring to obtain uniform slurry. And (3) uniformly coating the slurry on a current collector aluminum foil, and drying to obtain the positive pole piece.
(3) In a glove box filled with argon, a positive plate, a lithium metal negative electrode and 3mol/L LiTFSI/DME electrolyte are assembled into a button cell. And the battery is subjected to constant-current charge and discharge tests, and the voltage range is 1.5-3V vs. Li/Li+The current density was 100 mA/g.
Fig. 10 is a constant current charge and discharge curve of PTCDA and conductive carbon composite electrode provided in comparative example 1 of the present invention in a lithium ion battery; as can be seen from fig. 10, the specific capacity of the PTCDA and conductive carbon composite electrode was 77mAh/g, which is much lower than the specific capacity of 135mAh/g of comparative example 2.
The organic-inorganic composite electrode material provided by the invention adopts a composite strategy of an organic electrode material and an inorganic electrode material, and the inorganic electrode material with higher electronic conductance is used for replacing part of conductive carbon, so that the proportion of an active material in the composite electrode is increased, and the specific capacity of the whole electrode is increased. Meanwhile, the porosity and the liquid absorption of the composite electrode are greatly reduced, and the energy density of the electrode is further improved.
The organic-inorganic composite electrode material and the composite strategy of the organic electrode material and the inorganic electrode material are not only suitable for various organic matters with redox active sites, but also suitable for various inorganic electrode materials, are widely suitable for various metal secondary batteries of lithium, sodium, potassium, magnesium, aluminum and the like, have strong universality, and can obtain high energy density and stable cycle performance.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. An organic-inorganic composite electrode material is characterized in that the organic-inorganic composite electrode material is formed by compounding an organic electrode material and an inorganic electrode material;
the organic electrode material is an organic substance having a redox active group, and comprises: one or more of carbonyl compounds, nitrile compounds, organic free radical compounds, imino compounds, azo compounds and organic sulfides;
the inorganic electrode material includes: one or more of transition metal oxide, transition metal sulfide, and transition metal selenide; the specific capacity of the inorganic electrode material is more than 100mAh/g, and the forbidden band width is zero; in the organic-inorganic composite electrode material, the inorganic electrode material is used as an active substance to store embedded ions and is used as an organic electrode material to transfer electrons, so that the proportion of the active material in the electrode is increased, the overall porosity and liquid absorption of the electrode are reduced, and the capacity and energy density of the electrode are increased.
2. The organic-inorganic composite electrode material according to claim 1, wherein the inorganic electrode material specifically comprises: mo6S8,TiS2,TiSe2,NbS2,NbSe2,NbSe3One or more of (a).
3. The organic-inorganic composite electrode material according to claim 1, wherein the organic-inorganic composite electrode material has a mass ratio of the organic electrode material to the inorganic electrode material of 1: 5-8.5: 1.
4. a method for preparing the organic-inorganic composite electrode material according to claim 1, comprising:
according to the mass ratio of 1: 5-8.5: 1, weighing an organic electrode material and an inorganic electrode material, placing the organic electrode material and the inorganic electrode material in a ball milling tank, and carrying out sealed ball milling for 0.1-72 hours to obtain an organic-inorganic composite electrode material; alternatively, the first and second electrodes may be,
according to the mass ratio of 1: 5-8.5: 1, weighing an organic electrode material and an inorganic electrode material according to a certain proportion, adding a certain amount of solvent, stirring for 1-48 hours in an inert gas atmosphere, and volatilizing the solvent to obtain an organic-inorganic composite electrode material;
wherein the organic electrode material is an organic substance having a redox active group, and comprises: one or more of carbonyl compounds, nitrile compounds, organic free radical compounds, imino compounds, azo compounds and organic sulfides;
the inorganic electrode material includes: one or more of transition metal oxide, transition metal sulfide, and transition metal selenide; the specific capacity of the inorganic electrode material is more than 100mAh/g, and the forbidden band width is zero; in the organic-inorganic composite electrode material, the inorganic electrode material is used as an active substance to store embedded ions and is used for transferring electrons for the organic electrode material, so that the proportion of the active material in the electrode is increased, the overall porosity and liquid absorption of the electrode are reduced, and the capacity and energy density of the electrode are increased.
5. The organic-inorganic composite electrode material according to claim 4, wherein the inorganic electrode material specifically comprises: mo6S8,Ti S2,Ti Se2,NbS2,NbSe2,NbSe3One or more of (a).
6. A battery electrode comprising the organic-inorganic composite electrode material according to claim 1.
7. The battery electrode according to claim 6, wherein the organic electrode material of the organic-inorganic composite electrode material is contained in the battery electrode in an amount of 10 wt% to 85 wt%, and the inorganic electrode material is contained in the battery electrode in an amount of 10 wt% to 50 wt%.
8. The battery electrode of claim 6, further comprising: the conductive additive accounts for 1-30% of the mass ratio of the battery electrode, and the binder accounts for 1-10% of the mass ratio of the battery electrode;
the conductive additive specifically includes: one or more of Ketjen black, acetylene black, graphene, carbon nanotubes and Super-P carbon black;
the adhesive comprises: one or more of Polytetrafluoroethylene (PTFE), hydroxymethyl cellulose (CMC), sodium alginate, polyvinylidene fluoride (PVDF), polyacrylic acid (PAA) and Styrene Butadiene Rubber (SBR).
9. A secondary battery characterized in that it comprises the battery electrode according to any one of claims 6 to 8.
10. The secondary battery according to claim 9, wherein the battery electrode is used as a positive electrode in the secondary battery;
the secondary battery includes: any one of a lithium ion battery, a lithium metal battery, a sodium ion battery, a sodium metal battery, a magnesium ion battery, a magnesium metal battery, a potassium ion battery, a potassium metal battery, an aluminum ion battery, an aluminum metal battery, a zinc ion battery, a zinc metal battery, a calcium ion battery, and a calcium metal battery.
CN202011330745.6A 2020-11-24 2020-11-24 Organic-inorganic composite electrode material and preparation method and application thereof Pending CN112331837A (en)

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