CN114573484B - 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
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- 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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- 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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- 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
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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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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- 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, R 1 Unsubstituted or substituted alkyl; r is R 2 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) formed by the intermediate with the structure of the formula (I) and alkali metal has obviously improved discharge capacity and 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-hydrogen batteries and the like, the lithium battery and the sodium battery have the advantages of high energy density, wide voltage window, long service life and the like, and particularly, the lithium battery is widely applied to the fields of high-value consumer electronics and power batteries. As can be seen from the 'China automobile industry development annual report 2021', the sales of electric automobiles exceeds 100 ten thousand, the matched power lithium battery reaches the level of hundred GWh, and the deficiency of lithium resources and sodium resources is a significant influencing factor for 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 natural reserves of the inorganic materials are limited, the production cost is high, the environmental pollution and the personnel right problem are serious, and the rapid capacity expansion of the inorganic materials is limited.
Compared with the conventional inorganic electrode materials, the raw materials (C, H, O, S and the like) of the organic electrode are derived from a mature industrial system, have lower cost, various types, better stability and the like, and become one of new research and development directions in the field of battery materials.
The organic electrode materials commonly used at present mainly comprise the following materials: 1. a conductive organic polymer positive electrode material; 2. an organic sulfide positive electrode material; 3. an oxygen-containing conjugated organic positive electrode material. The single-state conductive organic polymer material has a plurality of defects, a large amount of electrolyte is needed in the reaction process, the conductivity is generally poor, and a large amount of conductive agent is needed to be doped, so that the capacity is low. The organic sulfide positive electrode material introduces S-S bond into organic molecular structure, and can obviously improve electrochemical activity of the electrode. However, organic sulfides generally have the characteristic of being easily dissolved, have poor conductivity, and have unsatisfactory performance at room temperature. Oxygen-containing conjugated organics are receiving attention because of the advantages of high energy density, fast reaction kinetics, etc. Carbonyl compounds represented by anthraquinones and conjugated anhydrides have become a new research focus. However, these organic electronic materials have poor cycle performance and are far from commercial applications.
Disclosure of Invention
Therefore, the invention aims to overcome the defect of poor cycle performance of organic electrode materials in the prior art, thereby providing an organic electrode material, an intermediate thereof, a positive plate and a 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, R 1 Hydrogen, or unsubstituted or substituted alkyl; r is R 2 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, terphenyl ring, anthracene ring, phenanthrene ring, furan, pyrrole, indole, pyridine or pyrene ring;
(2)R 1 is hydrogen, C1-C6 alkyl, preferably methyl, ethyl or n-propylA base;
(3) n is an integer from 1 to 8, preferably an integer from 1 to 4;
(4) The R is 2 Is chlorine, hydroxyl or bromine.
Further, the ring A is a pyrene ring, R 1 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 the organic electrode material, which is prepared by the following steps
With Cl-SO 3 R 1 Reaction to give an intermediate of formula (I) wherein ring A, R 1 、R 2 M and n are as defined in any one of the present inventions.
Further, the reaction temperature is 20 to 60 ℃, preferably 40 to 60 ℃.
The reaction time is at least 10 hours, for example, may be 18 to 25 hours.
Wherein, the liquid crystal display device comprises a liquid crystal display device,
with Cl-SO 3 R 1 The volume ratio of (3) is 0.7-0.9:1.
will be
Dissolving in conventional alkaline organic solvent (such as pyridine), adding Cl-SO 3 R 1 And (3) 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 steps of taking an intermediate shown in the formula (I) and reacting with alkali metal salt, and preferably, the preparation method also satisfies at least one of the following 1) -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 intermediate is reacted with alkali metal salt, and then glacial acetic acid and lead tetraacetate are added into the reaction liquid to react.
Specifically, the intermediate shown in the formula (I) is dissolved in an alkaline organic solvent (such as dimethylformamide), and alkali metal salt is added for reaction, so that the compound is obtained.
The reaction time is at least 5 hours, for example, may be from 10 to 25 hours.
The invention also includes purification of the target product by conventional methods, such as filtration, collection of solids, washing and drying.
The drying temperature is 180-220 ℃ and the drying time is 1-2 hours.
The mass ratio of the intermediate to the alkali metal salt was 500:10-500.
The invention also provides a positive plate, which comprises 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 or the organic positive electrode material prepared by the preparation method, and the proportion of the organic positive electrode material to the total mass of the positive electrode material is preferably 40-95%.
The invention also provides a battery, which comprises 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 an organic electrode material, which adopt an organic electrode material with a structure of a formula (II) formed by an intermediate with a structure of a formula (I) and alkali metal, wherein the organic electrode material is provided with n-number of quilt-NHSO (non-volatile organic Compounds) 2 R 1 The structure of aryl or heteroaryl substituted by the group, and the combination of the amino and alkali metal ions ensures that the organic electrode material has obviously improved discharge capacity and cycle performance.
2. According to the preparation method of the organic electrode material intermediate, the intermediate can be obtained by using a simple sulfonation reaction by controlling the reaction temperature to be 20-60 ℃, especially at the temperature of 25-30 ℃, 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 harsh synthesis conditions are not 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, has high capacity, can be compatible with the existing lithium ion battery and sodium ion battery industrial systems, is insensitive to moisture and oxygen, greatly reduces the production cost, particularly has the cell cost of the lithium ion battery lower than 0.2 yuan/Wh, and can realize commercial application in a short period of time. In addition, the electrode has high cycle stability (lithium-containing organic positive electrode material >1000 circles @80%, sodium-containing organic positive electrode material >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 that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a structural view of an organic electronic material in embodiment 1 of the present invention;
FIG. 2 is a diagram showing the mechanism of lithium intercalation and deintercalation of the organic electrode material in the cyclic charge and discharge process in example 1 of the present invention;
FIG. 3 is a block diagram of an intermediate in example 7 of the present invention;
FIG. 4 is a structural view of an organic electronic material in embodiment 7 of the present invention;
FIG. 5 is a block diagram of an intermediate in example 8 of the present invention;
FIG. 6 is a structural view of an organic electronic material in embodiment 8 of the present invention;
FIG. 7 is a block diagram of an intermediate in embodiment 10 of the present invention;
FIG. 8 is a structural view of an organic electronic material in embodiment 10 of the present invention;
FIG. 9 is a block diagram of pyrene-4, 5,9, 10-tetramine.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Pyrene-4, 5,9, 10-tetramine (CAS: 765301-94-8), the structural formula of which is shown in figure 9.
Example 1
The embodiment provides an organic electrode material and a preparation method of a battery containing the same, comprising the following steps,
intermediate preparation: 0.8L of pyrene-4, 5,9, 10-tetramine is dissolved in pyridine (10L), methylsulfonyl chloride (1L) is slowly added into the solution, the temperature of the solution system is slowly increased to 25 ℃, stirring is carried out for 3h, and reflux is carried out for 20h. Then, the reflux liquid was cooled to 0℃and 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, respectively, and dried at 60℃for 12 hours to give 1.29kg of intermediate.
Preparation of organic electrode materials: 500 g of the intermediate was weighed and dispersed in 2L of dimethylformamide, and then 30 g of lithium hydride was added thereto, followed by stirring at room temperature under an argon atmosphere for 10 hours. The precipitate was filtered, washed with diethyl ether, and then baked in an oven at 200 degrees celsius for 2 hours to give 475g of organic electronic material (structural formula see fig. 1).
And (3) preparation of an electric core: mixing the organic electrode material with carbon black (SP) serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder according to the mass percentage of 60%, 35% and 5%, adding the mixture into N-methyl-2-pyrrolidone (NMP) serving as a solvent to prepare slurry (the solid content is 72%), and selecting an aluminum foil with the thickness of 12 microns as a current collector according to the single-sided surface density of 15mg/cm 2 After the surface density coating, rolling and drying, obtaining a positive pole piece; the cathode is a conventional graphite cathode G49, and the electrolyte takes tetraethyleneglycol 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 pouch cell was 2Ah.
Example 2
The present example provides an organic electrode material and a method for preparing a battery including the same, which are basically the same as example 1, except that 100 g of methyllithium was used instead of 30 g of lithium hydride in the step of preparing an organic electrode material, and 440g of organic electrode material was finally obtained.
Example 3
This example provides a method for preparing an organic electrode material and a battery comprising the same, which is basically the same as example 1, except that the reaction temperature in the preparation step of the intermediate is 60 ℃, and finally 1.24kg of intermediate is obtained.
Example 4
The present embodiment provides a method for preparing an organic electrode material and a battery including the same, which is substantially the same as embodiment 1, except that the organic electrode material is mixed with carbon black (SP) as a conductive agent and polyvinylidene fluoride (PVDF) as a binder in a mass percentage of 80%, 18% and 2% in the preparation step of the battery.
Example 5
The present embodiment provides an organic electrode material and a method for preparing a battery including the same, which are substantially the same as those of embodiment 1, except that in the step of preparing a battery cell, 1, 3-dioxolane and ethylene glycol dimethyl ether with a volume ratio of 1:9 are used as solvents in the electrolyte, and LiFSI is contained in an amount of 1.15 mol/L.
Example 6
The embodiment provides an organic electrode material and a preparation method of a battery comprising the same, and the preparation method comprises the following steps:
intermediate preparation: phenylenediamine (1 kg, 0.83L) was dissolved in pyridine (10L), and then methylsulfonyl chloride (1L) was slowly added to the above solution. After the addition, the solution system was slowly warmed to 25℃again, stirred for 3h and refluxed for 20h. Then, the reflux was cooled to 0 degrees celsius 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 give 1.56kg of intermediate.
Preparation of organic electrode materials: 500 g of the intermediate was weighed and dispersed in 2L of dimethylformamide, and then 30 g of lithium hydride was added thereto, followed by stirring at room temperature under an argon atmosphere for 10 hours. The precipitate was filtered, washed with diethyl ether, and then baked in an oven at 200 degrees celsius for 2 hours to yield 485g of organic electrode material.
And (3) preparation of an electric core: the same cell as in example 1 was prepared.
Example 7
The embodiment provides an organic electrode material and a preparation method of a battery comprising the same, and the preparation method comprises the following steps:
intermediate preparation: prepared as an intermediate in example 6.
Preparation of organic electrode materials: 500 g of the intermediate was weighed and dispersed in 2L of dimethylformamide, and then 30 g of sodium hydride was added thereto, followed by stirring under an argon atmosphere for 10 hours. The precipitate was taken, washed with diethyl ether, and then baked in an oven at 200℃for 2 hours to obtain 470g of organic electronic material (structural formula shown in FIG. 4).
And (3) preparation of an electric core: mixing the organic electrode material with carbon black (SP) serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder according to the mass percentage of 60%, 35% and 5%, adding the mixture into N-methyl-2-pyrrolidone (NMP) serving as a solvent to prepare slurry (the solid content is 72%), and selecting an aluminum foil with the thickness of 12 microns as a current collector according to the single-sided surface density of 15mg/cm 2 After the surface density coating, rolling and drying, obtaining a positive pole piece; the cathode is a conventional graphite cathode G49, and the electrolyte takes tetraethyleneglycol dimethyl ether as a solvent and contains NaFP of 1.15mol/L 6 (sodium hexafluorophosphate). The diaphragm is a PE diaphragm. The rated capacity of the small pouch cell was 2Ah.
Example 8
The embodiment provides an organic electrode material and a preparation method of a battery containing the same, comprising the following steps,
intermediate preparation: phenylenediamine (1 kg) 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 to 25℃again, stirred for 3h and refluxed for 20h. Then, the reflux was cooled to 0 degrees celsius and filtered to obtain a powder. 1kg of the above powder was weighed, dispersed into 25L of glacial acetic acid, 1.7kg of lead tetraacetate powder was added with stirring, reacted at room temperature for 6 hours, filtered to obtain a powder, and finally the powder was washed with 2 mol/liter of hydrochloric acid and pure water, respectively, and dried at 60℃for 12 hours to obtain 1.36kg of an intermediate (structural formula: see FIG. 5).
Preparation of organic electrode materials: 500 g of the intermediate was weighed and dispersed in 2L of dimethylformamide, and then 30 g of sodium hydride was added thereto, followed by stirring under an argon atmosphere for 10 hours. The precipitate was taken, 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).
And (3) preparation of an electric core: the same cell was prepared as in example 7.
Example 9
The present example provides an organic electrode material and a method for preparing a battery including the same, which are basically the same as example 7, except that 100 g of sodium methoxide was used instead of 30 g of sodium hydride in the step of preparing an organic electrode material, and 410g of organic electrode material was finally obtained.
Example 10
This example provides an organic electrode material and a method for preparing a battery comprising the same, which are basically 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, and 405g of the organic electrode material is finally obtained.
Example 11
The only difference from example 7 is the preparation of the cells, using the following steps: manufacturing a positive electrode plate by using an organic electrode material, a conductive agent (SP) and a 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 performing processes such as homogenate coating, rolling, drying and the like to obtain the positive electrode plate; according to a single-sided area density of 15mg/cm 2 After the surface density coating, rolling and drying, obtaining a positive pole piece; the cathode is a conventional graphite cathode QCGX9 (manufactured by fir company), and the electrolyte takes tetraethyleneglycol dimethyl ether solution as a solvent, and NaFP of 1.15mol/L 6 (sodium hexafluorophosphate). The diaphragm is a PE diaphragm. The rated capacity of the small pouch cell was 2Ah.
Comparative example 1
Purchase of porous pyrene-4, 5,9, 10-tetraketone (CAS: 14727-71-0, molecular formula C) 16 H 6 O 4 ) The lithium oxalate is utilized for carrying out the pre-lithiation treatment, and the specific steps are as follows: 500 g of pyrene-4, 5,9, 10-tetraketone is weighed and dispersed into 2L of dimethylformamide, 30 g of lithium oxalate is added, and stirring is carried out for 10 hours at normal temperature in an argon protection atmosphere. Taking the precipitate, cleaning with diethyl ether, and then placing the precipitate in an oven for baking at 200 ℃ for 2 hours to obtain a final target product. The subsequent cell preparation was the same as in example 1.
Comparative example 2
N, N' -bis (2-anthraquinone) ] -perylene-3, 4,9, 10-tetracarboxylic diimine is subjected to sodium treatment by sodium hydride, and the specific steps are as follows: 500 g of N, N' -bis (2-anthraquinone) ] -perylene-3, 4,9, 10-tetracarboxylic acid diimine was weighed and dispersed into 2L of dimethylformamide, and then 30 g of sodium methoxide was added thereto, followed by stirring at room temperature under an argon atmosphere for 10 hours. Taking the precipitate, cleaning with diethyl ether, and then placing the precipitate in an oven for baking at 200 ℃ for 2 hours 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-tetracarboxylic diimide was 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-Lifespan and Ultra-High-Rate Na-ion Batteries Using Small-Molecule Organic Cathodes," 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 were tested for electrochemical performance using a blue electric test system and a Prlington electrochemical workstation, were tested for first discharge capacity and charge capacity at 25℃with a charge-discharge rate of 0.2C and a charge-discharge voltage ranging from 1.0V to 3.7V, and were calculated for first coulombic efficiency, and were cycled for 100 weeks at 25℃with a charge-discharge rate of 1C/1C with a charge-discharge voltage ranging from 1.0V to 3.7V with the results shown in the following table.
Table 1 performance results of lithium batteries
The electrochemical performance of the sodium batteries prepared in each group of examples and comparative examples was tested by using a blue electric test system and a Prlington electrochemical workstation, the first discharge capacity and the charge capacity were tested at 25℃with a charge-discharge rate of 0.2C and a charge-discharge voltage ranging from 1.0V to 3.5V, the first coulombic efficiency was calculated, and the capacity retention (%) was calculated at 25℃with a charge-discharge rate of 1C/1C and a charge-discharge voltage ranging from 1.0V to 3.5V for 100 weeks, the results are shown in the following table.
Table 2 performance results of sodium cells
Compared with comparative example 1, the organic materials prepared in examples 1-6 of the invention have more stable material structure after lithiation, have low requirements on processing environment, and show longer cycle stability and higher capacity under the same assembly test conditions.
Compared with comparative example 2, the sodium battery prepared in examples 7-11 of the invention has more stable material structure after sodium treatment, has low requirements on processing environment, and shows longer cycle stability and higher capacity under the same assembly test conditions.
Among them, as can be seen from comparison of table 1 and table 2, the lithium battery has higher capacity and battery cycle stability than the sodium battery, and examples 1 to 5 and 10 have higher capacity than the battery made of other organic electrolytic materials having benzene rings due to the organic electrolytic material having pyrene rings. Example 1 has higher capacity and cycle stability than example 2 using methyllithium due to the reaction with lithium hydride. Example 7 uses sodium hydride with higher capacity and cycle stability than example 8 uses sodium methoxide.
Experimental example 2
The lithium battery and the sodium battery prepared by each group of examples and comparative examples are tested by using a battery intelligent thickness detector, charged to 100% SOC at a rate of 0.5C at 25 ℃, discharged to 0% SOC at 1C, circulated for 500 weeks, and the thickness change of the battery cell electrode group under the condition of full electricity and empty electricity, namely, the full electricity thickness and the empty electricity thickness at 500 weeks are measured, and the expansion rate is calculated.
Table 3 performance results for lithium and sodium batteries
The sodium and lithium batteries produced in examples 1 to 11 of the present invention have lower expansion rates and exhibit better cycle stability than comparative examples 1 and 2.
Experimental example 3 moisture sensitivity test
The organic electronic materials of example 1, example 7, comparative example 1 and comparative example 2 were placed in a constant temperature and humidity cabinet at 25 degrees celsius and dew point-10 degrees celsius and stored for 48 hours. Organic electrode materials before and after storage are respectively assembled into button half batteries (2032 type) by adopting the same process by taking the organic electrode materials as positive electrode materials according to the conventional technology, the initial effect and the initial discharge capacity of the test batteries are tested, the test temperature is 25 ℃, the charge-discharge multiplying power is 0.2C, wherein the charge-discharge voltage ranges of the example 1 and the comparative example 1 are 1.0V-3.7V, and the charge-discharge voltage ranges of the example 7 and the comparative example 2 are 1.0V-3.5V.
TABLE 4 moisture sensitivity test
The positive electrode materials of comparative example 1 and comparative example 2 were deteriorated and discolored during storage, the battery failed, and could not be charged and discharged normally, and the first discharge capacity was lower than 10mAh/g. In the present invention, in example 1 and example 7, 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 is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (12)
1. An intermediate of an organic electrode material, characterized in that the intermediate has the following structure:
2. a method for preparing an intermediate of an organic electrode material according to claim 1, wherein pyrene-4, 5,9, 10-tetramine and methylsulfonyl chloride are taken to react to prepare the intermediate.
3. The preparation method according to claim 2, wherein the preparation method satisfies at least one of the following a-C:
A. the reaction temperature is 20-60 ℃;
B. the volume ratio of pyrene-4, 5,9, 10-tetramine to methylsulfonyl chloride is 0.7-0.9:1, a step of;
C. the reaction time is at least 10h.
4. A method of preparation according to claim 3, wherein the reaction temperature is 25-30 ℃.
5. A process according to claim 3, wherein the reaction time is from 18 to 25 hours.
6. An organic electrode material, characterized in that the organic electrode material has a structure as shown below:
7. A method for preparing the organic electrode material according to claim 6, which comprises reacting the intermediate according to claim 1 with an alkali metal salt.
8. The method of preparation according to claim 7, wherein the method of preparation further satisfies at least one of the following 1) -2):
1) The alkali metal salt is lithium salt or sodium salt;
2) The intermediate is reacted with alkali metal salt, and then glacial acetic acid and lead tetraacetate are added into the reaction liquid to react.
9. The method according to claim 8, wherein the alkali metal salt is selected from lithium hydride, methyllithium, lithium carbonate, lithium acetate, sodium methoxide or sodium hydride.
10. A positive electrode sheet comprising a current collector and a positive electrode material attached to the surface of the current collector, the positive electrode material comprising the organic electrode material according to claim 6 or the organic positive electrode material produced by the production method according to any one of claims 7 to 9.
11. The positive electrode sheet according to claim 10, wherein the proportion of the organic positive electrode material to the total mass of the positive electrode material is 40% to 95%.
12. A battery comprising the positive electrode sheet according to claim 10.
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