CN114573484A - Organic electrode material, intermediate thereof, positive plate and battery - Google Patents
Organic electrode material, intermediate thereof, positive plate and battery Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
- C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C311/08—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
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- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
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- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
- C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
- C07C2603/50—Pyrenes; Hydrogenated pyrenes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides an organic electrode material, an intermediate thereof, a positive plate and a battery, wherein the intermediate has a structure shown in a formula (I):
wherein ring A is aryl or heteroaryl, R1Unsubstituted or substitutedAlkyl groups of (a); r2Is halogen or hydroxy; m is an integer of 0 to 3; n is an integer of 1 to 20. The organic electrode material with the structure of the formula (II) is formed by adopting the intermediate with the structure of the formula (I) and alkali metal, has obviously improved discharge capacity, and obviously improves the cycle performance.
Description
Technical Field
The invention relates to the field of batteries, in particular to an organic electrode material, an intermediate thereof, a positive plate and a battery.
Background
Compared with the traditional secondary batteries such as lead storage batteries, nickel-metal hydride batteries and the like, the lithium batteries and sodium batteries have the advantages of high energy density, wide voltage window, long service life and the like, and particularly, the lithium batteries are widely applied to the fields of high-value consumer electronics and power batteries. It can be seen from the '2021 report on the development of the Chinese automobile industry', the sales volume of electric automobiles exceeds 100 million, the matched power lithium battery reaches the level of hundreds of GWh, and the lack of lithium resources and sodium resources is a significant influence factor influencing the productivity. However, the current electrode materials are still limited to inorganic electrode materials, such as nickel-cobalt-manganese ternary materials, lithium iron phosphate, lithium cobaltate, and the like. The limited natural reserves of these inorganic materials, high production costs, severe environmental pollution and personal problems limit their rapid capacity expansion.
Compared with the conventional inorganic electrode materials, the organic electrode has the advantages that the raw materials (C, H, O, S and the like) are from mature industrial systems, the cost is low, the variety is large, the stability is good, and the like, and the organic electrode becomes one of the new research and development directions in the field of battery materials.
The current common organic electrode materials mainly comprise the following materials: firstly, conducting organic polymer anode material; secondly, organic sulfide anode material; and thirdly, an oxygen-containing conjugated organic matter anode material. The single-state conductive organic polymer material has many defects, a large amount of electrolyte is needed in the reaction process, the conductivity is generally poor, and a large amount of conductive agent needs to be doped, so that the capacity is low. The organic sulfide anode material introduces S-S bonds into an organic molecular structure, and can obviously improve the electrochemical activity of the electrode. But the organic sulfide has the characteristics of easy dissolution, poor conductivity and undesirable performance at room temperature. Oxygen-containing conjugated organic matters are widely concerned by people because of the advantages of high energy density, fast reaction kinetics and the like. Carbonyl compounds represented by anthraquinone and conjugated acid anhydride have become a new research hotspot. However, these organic electrode materials have poor cycling performance and are far from commercial applications.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect of poor cycle performance of the organic electrode material in the prior art, so as to provide the organic electrode material and the intermediate thereof, the positive plate and the battery.
The invention provides an intermediate of an organic electrode material, which has a structure shown in a formula (I):
wherein ring A is aryl or heteroaryl, R1Hydrogen, or unsubstituted or substituted alkyl; r2Is halogen or hydroxy; m is an integer of 0 to 3; n is an integer of 1 to 20.
Further, the intermediate satisfies at least one of the following (1) to (5):
(1) the ring A is C6-C30 aryl or C5-C25 heteroaryl, preferably benzene ring, biphenyl ring, anthracene ring, phenanthrene ring, furan, pyrrole, indole, pyridine or pyrene ring;
(2)R1is hydrogen, C1-C6 alkyl, preferably methyl, ethyl or n-propyl;
(3) n is an integer of 1 to 8, preferably an integer of 1 to 4;
(4) the R is2Is chlorine, hydroxyl or bromine.
Further, the ring A is a pyrene ring, R1Is methyl, n is 4 and m is 0.
Further, the intermediate is selected from the following structures:
The invention also provides a preparation method of the intermediate of any one of the organic electrode materials, which comprises the following steps of
With Cl-SO3R1Reacting to obtain an intermediate shown as a formula (I), andmiddle ring A, R1、R2M and n are as defined in any one of the present inventions.
Further, the reaction temperature is 20-60 ℃, preferably 40-60 ℃.
The reaction time is at least 10h, for example 18-25 h.
Wherein the content of the first and second substances,
with Cl-SO3R1In a volume ratio of 0.7-0.9: 1.
will be provided with
Dissolving in conventional alkaline organic solvent (such as pyridine), and adding Cl-SO3R1And (4) reacting.
The invention also provides an organic electrode material, which has a structure shown in a formula (II):
Preferably, the organic electrode material has a structure as shown below:
The invention also provides a preparation method of the organic electrode material, which comprises the following steps of reacting the intermediate shown in the formula (I) with alkali metal salt, and preferably at least one of the following steps 1) to 2):
1) the alkali metal salt is lithium salt or sodium salt; preferably, the alkali metal salt is selected from lithium hydride, methyllithium, lithium carbonate, lithium acetate, sodium methoxide or sodium hydride;
2) the reaction of the intermediate with alkali metal salt includes the step of adding glacial acetic acid and lead tetraacetate into the reaction liquid for reaction.
Specifically, the intermediate shown in the formula (I) is dissolved in an alkaline organic solvent (such as dimethylformamide) and added with alkali metal salt for reaction, so as to obtain the intermediate.
The reaction time is at least 5h, for example from 10 to 25 h.
The invention also includes the purification of the desired product by conventional methods, such as filtration, collection of the solid, washing and drying.
The drying temperature is 180 ℃ and 220 ℃, and the drying time is 1-2 hours.
The mass ratio of the intermediate to the alkali metal salt is 500: 10-500.
The invention also provides a positive plate, which comprises a current collector and a positive material attached to the surface of the current collector, wherein the positive material comprises the organic electrode material or the organic positive material prepared by the preparation method, and preferably, the organic positive material accounts for 40-95% of the total mass of the positive material.
The invention also provides a battery comprising the positive plate.
The technical scheme of the invention has the following advantages:
1. the invention provides an intermediate of an organic electrode material and the organic electrode material, which adopts the intermediate of the structure of formula (I) and an alkali metal to form the organic electrode material of the structure of formula (II), and the organic electrode material has n-NHSO2R1The structure of the aryl or heteroaryl substituted by the group, and the combination of the amino and the alkali metal ions ensure that the organic electrode material has obviously improved discharge capacity and obviously improved cycle performance.
2. According to the preparation method of the organic electrode material intermediate, the reaction temperature is controlled to be 20-60 ℃, particularly the reaction is carried out at the temperature of 25-30 ℃, the intermediate can be obtained by using a simple sulfonation reaction, and the preparation method is suitable for large-scale production.
3. Compared with other lithium salts or sodium salts, the preparation method of the organic electrode material provided by the invention adopts lithium hydride or sodium hydride, the yield can reach more than 80%, and no harsh synthesis conditions are required.
4. The organic electrode material provided by the invention can be a lithium-containing organic anode material or a sodium-containing organic anode material, both of which have high capacity, can be compatible with the existing lithium ion battery and sodium ion battery industrial systems, and the material is insensitive to moisture and oxygen, so that the production cost is greatly reduced, especially the cost of a battery cell of the lithium ion battery is lower than 0.2 yuan/Wh, and the commercial application can be realized in a short time. In addition, the electrode has high cycle stability (lithium-containing organic anode material is more than 1000 circles @ 80%, and sodium-containing organic anode material is more than 800 circles @ 80%) and a higher voltage interval (3-3.5V), and has potential in the low-speed power battery market.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a structural view of an organic electrode material in example 1 of the present invention;
FIG. 2 is a diagram showing a mechanism of lithium intercalation and deintercalation of an organic electrode material during cyclic charge and discharge in example 1 of the present invention;
FIG. 3 is a structural diagram of an intermediate in example 7 of the present invention;
FIG. 4 is a structural view of an organic electrode material in example 7 of the present invention;
FIG. 5 is a structural diagram of an intermediate in example 8 of the present invention;
FIG. 6 is a structural view of an organic electrode material in example 8 of the present invention;
FIG. 7 is a structural diagram of an intermediate in example 10 of the present invention;
FIG. 8 is a structural view of an organic electrode material in example 10 of the present invention;
FIG. 9 is a structural diagram of pyrene-4, 5,9, 10-tetraamine.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not indicate specific experimental procedures or conditions, and can be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Pyrene-4, 5,9, 10-tetramine (4,5,9,10-pyrenetetramine, CAS: 765301-94-8) having a structure formula shown in FIG. 9.
Example 1
The embodiment provides a preparation method of an organic electrode material and a battery comprising the same, comprising the following steps,
preparing an intermediate: dissolving 0.8L of pyrene-4, 5,9, 10-tetramine in pyridine (10L), slowly adding methylsulfonyl chloride (1L) into the solution, slowly heating the solution system to 25 ℃, stirring for 3h, and refluxing for 20 h. Then, the reflux is cooled to 0 ℃, and then filtered to obtain pyrene-4, 5,9, 10-tetrasulfonic acid powder. Finally, the powder was washed with 2 mol/l aqueous hydrochloric acid and pure water, and dried at 60 ℃ for 12 hours to obtain 1.29kg of an intermediate.
Preparation of organic electrode material: 500 g of the intermediate is weighed and dispersed in 2L of dimethylformamide, 30 g of lithium hydride is added, and stirring is carried out for 10 hours at normal temperature in an argon protective atmosphere. The precipitate was collected by filtration, washed with ether, and then baked in an oven at 200 ℃ for 2 hours to obtain 475g of an organic electrode material (structural formula shown in FIG. 1).
Preparing an electric core: mixing the organic electrode material with conductive agent carbon black (SP) and binder polyvinylidene fluoride (PVDF) according to the mass percentage of 60%, 35% and 5%,adding solvent N-methyl-2-pyrrolidone (NMP) to obtain slurry (solid content is 72%), selecting aluminum foil with thickness of 12 μm as current collector, and making into powder with single-side surface density of 15mg/cm2After the surface density coating, rolling and drying, obtaining a positive pole piece; the cathode is a conventional graphite cathode G49, the electrolyte takes tetraethylene glycol dimethyl ether as a solvent and contains 1.15mol/L LiFSI (lithium bis (fluorosulfonyl) imide). The diaphragm is a PE diaphragm. The rated capacity of the small soft package battery is 2 Ah.
Example 2
This example provides a method for preparing an organic electrode material and a battery comprising the same, which is substantially the same as example 1 except that 100 g of methyllithium is used instead of 30 g of lithium hydride in the step of preparing the organic electrode material, to finally obtain 440g of the organic electrode material.
Example 3
This example provides a method for preparing an organic electrode material and a battery comprising the same, substantially the same as in example 1, except that the reaction temperature is 60 ℃ in the intermediate preparation step, and 1.24kg of an intermediate is finally obtained.
Example 4
This example provides a method for preparing an organic electrode material and a battery including the same, which is substantially the same as example 1 except that the organic electrode material is mixed with 80%, 18%, and 2% by mass of conductive agent carbon black (SP) and binder polyvinylidene fluoride (PVDF) in the step of preparing a cell.
Example 5
The embodiment provides an organic electrode material and a preparation method of a battery comprising the same, which are basically the same as the embodiment 1, and only differ in that in the preparation step of a battery core, an electrolyte contains 1.15mol/L LiFSI by taking 1, 3-dioxolane and ethylene glycol dimethyl ether with a volume ratio of 1:9 as solvents.
Example 6
The embodiment provides a preparation method of an organic electrode material and a battery comprising the same, and the preparation method comprises the following steps:
preparing an intermediate: phenylenediamine (1kg, 0.83L) was dissolved in pyridine (10L) and then methanesulfonyl chloride (1L) was slowly added to the above solution. After the addition, the solution system was slowly warmed up to 25 ℃, stirred for 3h, and refluxed for 20 h. Then, the reflux liquid was cooled to 0 ℃ and filtered to obtain a powder. Finally, the powder was washed with 2 mol/l hydrochloric acid and pure water, respectively, and dried at 60 ℃ for 12 hours to obtain 1.56kg of an intermediate.
Preparation of organic electrode material: 500 g of the intermediate is weighed and dispersed in 2L of dimethylformamide, 30 g of lithium hydride is added, and stirring is carried out for 10 hours at normal temperature in an argon protective atmosphere. And filtering to obtain precipitate, washing with diethyl ether, and then baking in an oven at 200 ℃ for 2 hours to obtain 485g of organic electrode material.
Preparing an electric core: cells were prepared as in example 1.
Example 7
The embodiment provides a preparation method of an organic electrode material and a battery comprising the same, and the preparation method comprises the following steps:
preparing an intermediate: prepared as the intermediate of example 6.
Preparation of organic electrode material: 500 g of the intermediate is weighed out and dispersed in 2L of dimethylformamide, 30 g of sodium hydride is added, and stirring is carried out for 10 hours in an argon protective atmosphere. And (3) taking the precipitate, washing the precipitate with diethyl ether, and then placing the precipitate in an oven to be baked for 2 hours at 200 ℃ to obtain 470g of the organic electrode material (structural formula shown in figure 4).
Preparing an electric core: mixing the organic electrode material with conductive agent carbon black (SP) and binder polyvinylidene fluoride (PVDF) according to the mass percent of 60%, 35% and 5%, adding the mixture into solvent N-methyl-2-pyrrolidone (NMP) to prepare slurry (the solid content is 72%), selecting aluminum foil with the thickness of 12 microns as a current collector, and selecting the aluminum foil according to the single-side surface density of 15mg/cm2After the surface density coating, rolling and drying, obtaining a positive pole piece; the cathode is a conventional graphite cathode G49, the electrolyte takes tetraethylene glycol dimethyl ether as a solvent and contains 1.15mol/L NaFP6(sodium hexafluorophosphate). The diaphragm is a PE diaphragm. The rated capacity of the small soft package battery is 2 Ah.
Example 8
The embodiment provides a preparation method of an organic electrode material and a battery comprising the same, comprising the following steps,
preparing an intermediate: phenylenediamine (1kg) was dissolved in methylene chloride (10L), and then the temperature of the mixed solution was controlled to about 0 ℃. Subsequently, methanesulfonyl chloride (1L) was slowly added to the above solution. After the addition, the solution system was slowly warmed up to 25 ℃, stirred for 3h, and refluxed for 20 h. Then, the reflux liquid was cooled to 0 ℃ and filtered to obtain a powder. Weighing 1kg of the powder, dispersing the powder into 25L of glacial acetic acid, adding 1.7kg of lead tetraacetate powder under stirring, reacting for 6h at room temperature, filtering to obtain powder, washing the powder with 2 mol of hydrochloric acid and pure water per liter respectively, and drying at 60 ℃ for 12 h to obtain 1.36kg of an intermediate (structural formula shown in figure 5).
Preparation of organic electrode material: 500 g of the intermediate is weighed out and dispersed in 2L of dimethylformamide, 30 g of sodium hydride is added, and stirring is carried out for 10 hours in an argon protective atmosphere. The precipitate was washed with diethyl ether and then baked in an oven at 200 ℃ for 2 hours to obtain 425g of an organic electrode material (structural formula shown in FIG. 6).
Preparing an electric core: cells were prepared as in example 7.
Example 9
This example provides a method for preparing an organic electrode material and a battery including the same, which is substantially the same as example 7 except that 100 g of sodium methoxide is used instead of 30 g of sodium hydride in the preparation step of the organic electrode material, to finally obtain 410g of the organic electrode material.
Example 10
This example provides a method for preparing an organic electrode material and a battery comprising the same, which is substantially the same as example 1 except that 30 g of sodium hydride is used instead of 30 g of lithium hydride in the step of preparing the organic electrode material, to finally obtain 405g of the organic electrode material.
Example 11
The difference from example 7 lies only in the preparation of the cell, and the following steps are adopted: preparing the positive pole piece by mixing the organic electrode material, the conductive agent (SP) and the binder (PVDF) according to the mass ratio of 80%, 15% and 5%Selecting an aluminum foil with the thickness of 12 microns as a current collector, and carrying out procedures such as homogenate coating, rolling, drying and the like to obtain a positive pole piece; according to the single-sided surface density of 15mg/cm2After the surface density coating, rolling and drying, obtaining a positive pole piece; the cathode is a conventional graphite cathode QCGX9 (produced by fir company), the electrolyte takes a tetraethylene glycol dimethyl ether solution as a solvent, and 1.15mol/L NaFP6(sodium hexafluorophosphate). The diaphragm is a PE diaphragm. The rated capacity of the small soft package battery is 2 Ah.
Comparative example 1
Purchase polyporus-4, 5,9, 10-tetraone (CAS: 14727-71-0, molecular formula C)16H6O4) The method comprises the following steps of carrying out pre-lithiation treatment by using lithium oxalate: 500 g of pyrene-4, 5,9, 10-tetraone was weighed and dispersed in 2L of dimethylformamide, and 30 g of lithium oxalate was added thereto, followed by stirring at normal temperature for 10 hours in an argon-protected atmosphere. And (3) taking the precipitate, washing the precipitate by using ether, and then baking the precipitate for 2 hours in an oven at the temperature of 200 ℃ to obtain a final target product. The subsequent cell preparation method was the same as in example 1.
Comparative example 2
The method comprises the following steps of carrying out sodium treatment on N, N' -bis (2-anthraquinone) ] -perylene-3, 4,9, 10-tetracarboxydiimide by using sodium hydride, wherein the specific steps are as follows: 500 g of N, N' -bis (2-anthraquinone) ] -perylene-3, 4,9, 10-tetracarboxydiimide was weighed and dispersed in 2L of dimethylformamide, and 30 g of sodium methoxide was added thereto, and stirred for 10 hours at normal temperature in an argon protective atmosphere. And (3) taking the precipitate, washing the precipitate by using ether, and then baking the precipitate for 2 hours in an oven at the temperature of 200 ℃ to obtain a final target product. The subsequent cell preparation was the same as in example 7.
N, N' -bis (2-anthraquinone) ] -perylene-3, 4,9, 10-tetracarboxydiimides were prepared according to the following literature. Y.Hu, Q.Yu, W.Tang, M.Cheng, X.Wang, S.Liu, J.Gao, M.Wang, M.Xiong, J.Hu, C.Liu, T.Zou, C.Fan, "Ultra-Stable, Ultra-Long-Life and Ultra-High-Rate Na-ion Batteries Using Small-molecular Organic catalysts", Energy Storage Material, 2021, DOI:10.1016/j.ensm.2021.07.008.
Experimental example 1
The lithium batteries prepared in each group of examples and comparative examples are taken, electrochemical performance is tested by a blue test system and a Princeton electrochemical workstation, the first discharge capacity and the charge capacity are tested under the conditions that the charge-discharge multiplying power is 0.2C and the charge-discharge voltage range is 1.0V-3.7V at 25 ℃, the first coulombic efficiency is calculated, the charge-discharge multiplying power is 1C/1C and the charge-discharge voltage range is 1.0V-3.7V at 25 ℃, and the capacity retention rate (%) of 100 cycles is calculated, and the result is shown in the following table.
Table 1 performance results for lithium batteries
The sodium batteries prepared in each group of examples and comparative examples are taken, electrochemical performance is tested by a blue test system and a Princeton electrochemical workstation, the first discharge capacity and the charge capacity are tested under the conditions that the charge-discharge multiplying power is 0.2C and the charge-discharge voltage range is 1.0V to 3.5V at 25 ℃, the first coulombic efficiency is calculated, and the capacity retention rate (%) of 100 cycles is calculated under the conditions that the charge-discharge multiplying power is 1C/1C and the charge-discharge voltage range is 1.0V to 3.5V at 25 ℃, and the results are shown in the following table.
Table 2 performance results for sodium cells
Compared with the comparative example 1, the organic materials prepared in the examples 1 to 6 of the invention have more stable structure after being lithiated, have low requirements on processing environment, and show longer cycling stability and higher capacity under the same assembly test condition.
Compared with the comparative example 2, the sodium batteries prepared in the examples 7 to 11 of the invention have more stable material structure after sodium modification, have low requirements on processing environment, and show longer cycle stability and higher capacity under the same assembly test condition.
Among them, as can be seen from comparison of tables 1 and 2, lithium batteries have higher capacity and battery cycle stability than sodium batteries, and examples 1 to 5 and 10 have higher capacity than batteries made of other organic electrolytic materials having benzene rings due to organic electrode materials having pyrene rings. Example 1 has higher capacity and cycle stability compared to example 2 with methyllithium due to the reaction with lithium hydride. Example 7 uses sodium hydride, which has higher capacity and cycle stability than example 8 using sodium methoxide.
Experimental example 2
The lithium batteries and sodium batteries prepared in each group of examples and comparative examples are taken, tested by using a battery intelligent thickness detector, charged to 100% SOC at a rate of 0.5C at 25 ℃, then discharged to 0% SOC at 1C, cycled for 500 weeks, the thickness change of the battery cell pole group under the full-electricity condition and the empty-electricity condition is measured, namely the full-electricity thickness and the empty-electricity thickness are cycled for 500 weeks, and the expansion rate is calculated.
TABLE 3 Performance results for lithium and sodium batteries
The sodium and lithium batteries prepared in examples 1 to 11 according to the present invention had lower expansion rates and exhibited better cycle stability than those of comparative examples 1 and 2.
Experimental example 3 moisture sensitivity test
The organic electrode materials of example 1, example 7, comparative example 1 and comparative example 2 were stored in a constant temperature and humidity chamber at 25 ℃ and a dew point of-10 ℃ for 48 hours. The organic electrode materials before and after storage are respectively assembled into button type half cells (2032 type) by using the organic electrode materials as positive electrode materials according to the conventional technology and the same process, the first-effect and first-time discharge capacity of the cells are tested, the test temperature is 25 ℃, the charge-discharge multiplying power is 0.2C, wherein the charge-discharge voltage ranges of the embodiment 1 and the comparative example 1 are 1.0V-3.7V, and the charge-discharge voltage ranges of the embodiment 7 and the comparative example 2 are 1.0V-3.5V.
TABLE 4 moisture sensitivity test
The positive electrode materials of comparative examples 1 and 2 are deteriorated and discolored during storage, the battery is invalid, normal charge and discharge cannot be carried out, and the first discharge capacity is lower than 10 mAh/g. In examples 1 and 7 of the present invention, the sulfamic acid-substituted pyrene ring or benzene ring was used as the positive electrode material, and the first effect and the first discharge capacity did not change much before and after storage, especially in example 7.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications derived therefrom are intended to be within the scope of the invention.
Claims (10)
1. An intermediate for an organic electrode material, the intermediate having a structure represented by formula (I):
wherein Ring A is aryl or heteroaryl, R1Is hydrogen, or unsubstituted or substituted alkyl, R2Is halogen or hydroxy; m is an integer of 0 to 3; n is an integer of 1 to 20.
2. The intermediate for an organic electrode material according to claim 1, wherein the intermediate satisfies at least one of the following (1) to (4):
(1) the ring A is C6-C30 aryl or C5-C25 heteroaryl, preferably benzene ring, biphenyl ring, anthracene ring, phenanthrene ring, furan, pyrrole, indole, pyridine or pyrene ring;
(2)R1is hydrogen, C1-Alkyl of C6, preferably methyl, ethyl or n-propyl;
(3) n is an integer of 1 to 8, preferably 1 to 4;
(4) the R is2Is chlorine, hydroxyl or bromine.
3. The intermediate of the organic electrode material according to claim 1, characterized in that it has in particular the following structure:
4. a process for producing an intermediate of the organic electrode material as claimed in any one of claims 1 to 3, characterized in that the intermediate is obtained
With Cl-SO3R1Reaction to produce an intermediate of formula (I), wherein ring A, R1、R2M and n are as defined in any one of claims 1 to 3.
5. The production method according to claim 4, wherein the production method satisfies at least one of the following A to C:
A. the reaction temperature is 20-60 ℃, and preferably 25-30 ℃;
B、
with Cl-SO3R1In a volume ratio of 0.7-0.9: 1;
C. the reaction time is at least 10 hours, preferably 18-25 hours.
6. An organic electrode material, characterized in that the organic electrode material has a structure represented by formula (II);
7. The organic electrode material according to claim 6, wherein M is sodium or lithium; preferably, the organic electrode material has a structure as shown below:
8. A method for preparing an organic electrode material according to claim 6 or 7, comprising reacting an intermediate according to any one of claims 1 to 3 or an intermediate prepared by the preparation method according to claim 4 or 5 with an alkali metal salt, preferably wherein the preparation method further satisfies at least one of the following 1) to 2):
1) the alkali metal salt is lithium salt or sodium salt; preferably, the alkali metal salt is selected from lithium hydride, methyllithium, lithium carbonate, lithium acetate, sodium methoxide or sodium hydride;
2) the reaction of the intermediate with alkali metal salt includes the step of adding glacial acetic acid and lead tetraacetate into the reaction liquid for reaction.
9. A positive plate is characterized by comprising a current collector and a positive electrode material attached to the surface of the current collector, wherein the positive electrode material comprises the organic electrode material in claim 6 or 7 or the organic positive electrode material prepared by the preparation method in claim 8, and preferably, the organic positive electrode material accounts for 40-95% of the total mass of the positive electrode material.
10. A battery comprising the positive electrode sheet according to claim 9.
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