CN106848242B - Application of high-capacity organic lithium storage material - Google Patents
Application of high-capacity organic lithium storage material Download PDFInfo
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- CN106848242B CN106848242B CN201710106184.3A CN201710106184A CN106848242B CN 106848242 B CN106848242 B CN 106848242B CN 201710106184 A CN201710106184 A CN 201710106184A CN 106848242 B CN106848242 B CN 106848242B
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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
- H01M4/364—Composites as mixtures
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a high-capacity organic lithium storage material, which is a mixture of one or more of organic acid with a butenedioic acid conjugated bond structure and salts thereof, wherein the mixture of one or more of the organic acid with the butenedioic acid conjugated bond structure and the salts thereof is selected, so that lithium can be stored by utilizing the transformation of conjugated double bonds in molecular space, and lithium ions can be stored on a carboxyl group and can be reversibly formed into L i through the chemical bond change of the carboxyl site2O is stored in the electrode micropores; the material has a plurality of active lithium storage sites, and one molecule with a butenedioic acid structure can store 8-12 lithium ions.
Description
Technical Field
The invention belongs to the field of electrode materials of batteries or super capacitors, relates to a lithium storage material, and particularly relates to an organic lithium storage material with high capacity, high power and long service life and application thereof.
Background
With the development of power automobiles and large-scale energy storage technologies, batteries and capacitors with high capacity, high power and long service life have become the most promising chemical energy storage power sources. The active material is the key and core of chemical energy storage devices such as lithium ion batteries, sodium ion batteries, super capacitors and the like. Traditional inorganic lithium storage materials are numerous and widely applied, however, the inorganic lithium storage materials are limited by factors such as stoichiometric ratio and the like, and the lithium storage capacity is limited; moreover, the inorganic lithium storage material has high brittleness, the obvious volume effect in the process of lithium ion intercalation and deintercalation can cause the change of the structure and the surface of the material, and the silicon negative electrode and the metal oxide negative electrode material are particularly obvious, which greatly restrict the further development and the large-scale application of the inorganic lithium storage material. In contrast, organic materials have good elasticity and flexibility, have a small volume effect in the lithium storage process, and have the characteristics of greenness and reproducibility, and are an important development direction for developing next-generation batteries and capacitors with high specific energy and long service life.
Organic lithium storage materials and chemical power sources based on the materials have the characteristics of environmental friendliness, reproducibility, good processability, low price and the like, and have attracted more and more attention in recent years. However, up to now, most organic lithium storage materials show properties of low lithium storage capacity, poor high-rate charge and discharge performance and short cycle life, for example, pyrene-4, 5, 9, 10 tetraketone has a specific capacity of only 275mAh/g, and the capacity is reduced to 120mAh/g after 20 cycles; the naphthoquinone has a specific capacity of 190mAh/g, and the capacity retention rate after 100 cycles is less than 40%; anthraquinone has specific capacity of 250mAh/g, and the capacity is reduced to 30mAh/g after 100 cycles; the 2-vinyl-4, 8-dihydrobenzo- [1,2-b:4, 5-b' ] -dithiophene-4, 8-dione organic material has a specific capacity of 225mAh/g, and the capacity is reduced to 50mAh/g after 25 cycles. In order to solve the problem, the molecular weight of the material is increased by means of molecular polymerization, grafting and the like so as to reduce the solubility of the material in the organic solvent, however, the polymerization of small organic molecules leads to reduction and even disappearance of active sites, and the molecular weight of the material is greatly increased, thereby further reducing the specific capacity of the material. Moreover, the organic lithium storage material has poor conductivity and poor high-rate charge and discharge performance, and the charge and discharge rates of many experimental researches are only limited to 0.1-1C, which is far from the requirements of industrial application. Therefore, the low lithium storage capacity, the poor rate capability and the poor cycle performance are the key and bottleneck for restricting the further development and the scale application of the organic lithium storage material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an organic lithium storage material with high capacity, high power and long service life.
In order to achieve the purpose, the invention adopts the technical scheme that: a high-capacity organic lithium-storing material is a mixture of one or more of organic acids with a butenedioic acid conjugated bond structure and salts thereof.
Preferably, the organic acid includes maleic acid and fumaric acid, and the organic acid salt includes lithium maleate, sodium maleate, iron maleate, cobalt maleate, aluminum maleate, nickel maleate, copper maleate, calcium maleate, lithium fumarate, sodium fumarate, iron fumarate, cobalt fumarate, aluminum fumarate, nickel fumarate, copper fumarate, and calcium fumarate. More preferably an organic complex salt such as cobalt maleate, nickel fumarate, aluminum fumarate or the like which forms little solubility in organic carbonate solvents after complexing with cations.
It is still another object of the present invention to provide a use of the above high capacity organic lithium storage material as an active material for an electrode.
Optimally, the preparation of the electrode comprises the following steps:
(a) mixing the high-capacity organic lithium storage material with a binder and a conductive agent in a dispersing agent to prepare electrode slurry; the mass ratio of the high-capacity organic lithium storage material to the binder to the conductive agent is 4-6: 3-5: 1;
(b) and coating the electrode slurry on a current collector, drying, pressing, cutting and further drying.
Further, the binder is a mixture consisting of one or more of polyvinylidene fluoride, sodium carboxymethylcellulose, sodium polyacrylate and sodium alginate; the conductive agent is a mixture consisting of one or more of acetylene black, conductive carbon black, graphene and carbon nano tubes; the dispersant is N-methyl pyrrolidone, N-dimethyl formamide or water.
Further, in the step (b), the pressure of the pressing is 1-3 MPa/cm2。
Further, in the step (b), the drying temperature is 100-170 ℃.
Optimally, the electrode can be used for electrochemical devices such as lithium ion batteries, sodium ion batteries or super capacitors.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the high-capacity organic lithium storage material of the invention adopts butenedioic acidOne or more of organic acid with a yoke bond structure and salt thereof, so that the lithium storage can be carried out by utilizing the change of conjugated double bonds in molecular space, and lithium ions can be stored on a carboxyl group and can be reversibly formed into L i by the chemical bond change of the carboxyl site2O is stored in the electrode micropores; the material has a plurality of active lithium storage sites, and one molecule with a butenedioic acid structure can store 8-12 lithium ions. Tests show that the reversible lithium storage capacity of the material is up to more than 1500mAh/g, which is improved by 4-5 times compared with the level of the existing material which is less than 300mAh/g, and the obvious technical breakthrough in the technical field is realized. The organic acid and the metal salt thereof have low solubility in the carbonate solvent, and particularly the organic composite salt formed by the composite of divalent cations hardly dissolves in the organic carbonate solvent; more importantly, the organic lithium storage material has good elasticity and toughness, and almost no obvious volume effect exists in the process of lithium ion intercalation and deintercalation, so that the material has excellent electrochemical cycling stability, and no obvious capacity attenuation exists after 500 cycles; after the electrode composition is optimized, the reversible capacity of the material under the condition of 100 ℃ still exceeds 570mAh/g, the traditional limitation of 0.1-1C multiplying power is broken through, and the material is an organic lithium storage material with high power property. The organic lithium storage material has the characteristics of reproducibility, abundant sources and low price, has important significance for reducing the cost and the manufacturing cost of a chemical power supply in the future, and is an important choice for developing the chemical power supply with high specific energy, high power, long service life and low manufacturing cost in the future.
Drawings
FIG. 1 is an SEM photograph of the maleic acid electrode sheet in example 1;
FIG. 2 is the first three charge-discharge curves of the maleic acid electrode in example 1;
FIG. 3 is a graph showing the rate charge and discharge properties of the maleic acid electrode in Experimental example 1.
FIG. 4 shows the long-term cycle performance of the maleic acid electrode in Experimental example 1.
FIG. 5 shows the variation of L i1S intensity of XPS chart of the maleic acid electrode in Experimental example 1 under different charging and discharging states.
Detailed Description
The high-capacity organic lithium storage material is a mixture consisting of one or more of organic acids with a butenedioic acid conjugated bond structure and salts thereof, wherein the organic acids comprise maleic acid and fumaric acid, and the organic acid salts comprise lithium maleate, sodium maleate, iron maleate, cobalt maleate, aluminum maleate, nickel maleate, copper maleate, calcium maleate, lithium fumarate, sodium fumarate, iron fumarate, cobalt fumarate, aluminum fumarate, nickel fumarate, copper fumarate and calcium fumarate2O is stored in the electrode micropores; the material has a plurality of active lithium storage sites, and one molecule with a butenedioic acid structure can store 8-12 lithium ions. Tests show that the reversible lithium storage capacity of the material is up to more than 1500mAh/g, which is improved by 4-5 times compared with the level of the existing material which is less than 300mAh/g, and the obvious technical breakthrough in the technical field is realized. Such organic acids and metal salts thereof have low solubility in carbonate solvents, and particularly form organic complex salts (such as cobalt maleate, nickel fumarate, aluminum fumarate, and the like) which are hardly dissolved in organic carbonate solvents after being complexed with cations; more importantly, the organic lithium storage material has good elasticity and toughness, and almost no obvious volume effect exists in the process of lithium ion intercalation and deintercalation, so that the material has excellent electrochemical cycling stability, and no obvious capacity attenuation exists after 500 cycles; after the electrode composition is optimized, the reversible capacity of the material under the condition of 100 ℃ still exceeds 570mAh/g, the traditional limitation of 0.1-1C multiplying power is broken through, and the material is an organic lithium storage material with high power property. The organic lithium storage material has the characteristics of reproducibility, abundant sources and low price, has important significance for reducing the cost and the manufacturing cost of a chemical power supply in the future, and is an important choice for developing the chemical power supply with high specific energy, high power, long service life and low manufacturing cost in the future.
The high-capacity organic lithium storage material is used as an active material of an electrode and can be used for electrochemical devices such as lithium ion batteries, sodium ion batteries or super capacitors. The specific preparation comprisesThe following steps: (a) mixing the high-capacity organic lithium storage material with a binder and a conductive agent in a dispersing agent to prepare electrode slurry; the mass ratio of the high-capacity organic lithium storage material to the binder to the conductive agent is 4-6: 3-5: 1; (b) and coating the electrode slurry on a current collector, drying, pressing, cutting and further drying. The thickness of the dried electrode was about 10 μm. The binder is a mixture consisting of one or more of polyvinylidene fluoride, sodium carboxymethylcellulose (CMC), sodium polyacrylate (PAANa) and sodium alginate; the conductive agent is a mixture consisting of one or more of acetylene black, conductive carbon black, graphene and carbon nano tubes; the dispersant is N-methyl pyrrolidone, N-dimethyl formamide or water. The pressing pressure is 1-3 MPa/cm2. The drying temperature is 100-170 ℃.
The invention will be further explained with reference to the embodiments of the drawings.
Example 1
(a) an electrode slurry was prepared by thoroughly and uniformly mixing 5g of maleic acid, 1g of PVDF (commercially available) and 4g of acetylene black (commercially available) in 20g N-methylpyrrolidone (NMP, commercially available);
(b) the electrode slurry was coated on a copper foil current collector (commercially available), dried and used at 2MPa/cm2Pressing under the pressure, cutting, and drying at 140 deg.C under vacuum for 10 hr;
the SEM image of the prepared maleic acid electrode sheet is shown in fig. 1, and it can be seen that the maleic acid pellets and the acetylene black conductive agent are uniformly dispersed, and the thickness of the electrode is about 10 μm.
The maleic acid electrode is prepared according to the existing battery manufacturing method, a battery assembled by using metal lithium as a counter electrode is subjected to a charge and discharge test, and the result is shown in fig. 2-4. as can be seen from fig. 2, the first reversible capacity of the electrode exceeds 1300mAh/g, and the reversible capacity of the electrode is stabilized above 1500mAh/g after 5 cycles, the rate charge and rate discharge properties of the electrode are shown in fig. 3. as can be seen, the material not only has very excellent high rate discharge properties, but also has a reversible capacity of 570mAh/g under the condition of 100C, and has particularly excellent high rate charge properties, can be charged under the condition of 100C (corresponding to 46.2A/g) of overlarge current, and cannot damage the electrode, the property is comparable to all inorganic lithium storage materials, and shows intentional power properties, after 500 cycles, the capacity of the electrode hardly has any attenuation (see fig. 4), which shows that the material has very excellent long-term cycle properties, fig. 5 shows that the maleic acid electrode has very excellent long-term cycle properties, under different states, the electrode shows that the strength of the electrode gradually increases along with the high lithium intercalation and the high lithium intercalation strength of an XPS 1, the material is gradually reduced by S, and the reversible intercalation of the high-insertion and the lithium insertion and the high-insertion and desorption of the lithium insertion of the material in the high-insertion and-insertion.
Examples 2 to 12
Examples 2 to 12 each provide the use of a high capacity organic lithium storage material, differing only in the kind and quality of the organic lithium storage material, binder, conductive agent and dispersant, see in particular table 1; the electrode made of insoluble ferric fumarate has slightly low first reversible capacity, and may be the reason for more active electrochemical properties.
TABLE 1 formulation proportion table for high capacity organic lithium storage material application in examples 2-12
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (4)
1. The application of a high-capacity organic lithium storage material is characterized in that the high-capacity organic lithium storage material is a mixture consisting of one or more organic acid salts with a butenedioic acid conjugated bond structure, and the organic acid salts are cobalt fumarate and nickel fumarate, and the application is characterized in that: it is used as an active material for an electrode for a lithium ion battery, a sodium ion battery or a supercapacitor;
the preparation of the electrode comprises the following steps:
(a) mixing the high-capacity organic lithium storage material with a binder and a conductive agent in a dispersing agent to prepare electrode slurry; the mass ratio of the high-capacity organic lithium storage material to the binder to the conductive agent is 4-6: 3-5: 1;
(b) and coating the electrode slurry on a current collector, drying, pressing, cutting and further drying.
2. The use of the high capacity organic lithium storage material of claim 1, wherein: the binder is a mixture consisting of one or more of polyvinylidene fluoride, sodium carboxymethylcellulose, sodium polyacrylate and sodium alginate; the conductive agent is a mixture consisting of one or more of acetylene black, conductive carbon black, graphene and carbon nano tubes; the dispersant is N-methyl pyrrolidone, N-dimethyl formamide or water.
3. The use of the high capacity organic lithium storage material of claim 1, wherein: in the step (b), the pressing pressure is 1-3 MPa/cm2。
4. The use of the high capacity organic lithium storage material of claim 1, wherein: in the step (b), the drying temperature is 100-170 ℃.
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Effective date of registration: 20211022 Address after: 215000 building 12 (F3), No. 2288, Yuexi Wuzhong Avenue, Wuzhong District, Suzhou City, Jiangsu Province Patentee after: Suzhou Huaying New Energy Materials Technology Co.,Ltd. Address before: 215123 No. 199 benevolence Road, Suzhou Industrial Park, Jiangsu, China Patentee before: SOOCHOW University |