CN110408043B - Tin-based coordination polymer lithium ion battery cathode material and preparation method thereof - Google Patents
Tin-based coordination polymer lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- CN110408043B CN110408043B CN201910571262.6A CN201910571262A CN110408043B CN 110408043 B CN110408043 B CN 110408043B CN 201910571262 A CN201910571262 A CN 201910571262A CN 110408043 B CN110408043 B CN 110408043B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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
- H01M4/36—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
- H01M4/602—Polymers
- H01M4/604—Polymers containing aliphatic main chain polymers
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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 the field of lithium ion battery preparation, and particularly discloses a tin-based coordination polymer lithium ion battery cathode material and a preparation method thereof, wherein the tin-based coordination polymer lithium ion battery cathode material comprises the following raw material components: a tin source, an activator, an organic ligand, and a liquid solvent. The method utilizes the alkaline activating reagent to generate the salt solution in situ from the organic ligand, can use water as a solvent in the reaction, can improve the yield of the coordination polymer, and is environment-friendly and efficient. The tin-based coordination polymer prepared by the method can be used as a negative electrode material of a lithium secondary battery, and has good cycling stability.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a tin-based coordination polymer lithium ion battery cathode material and a preparation method thereof.
Background
Due to the unique structure of the coordination polymer, the organic ligand separates metal ions and provides a larger space for the metal ions, so that the mutual contact or agglomeration of the metals can be avoided, and the advantage has important significance for the lithium ion battery cathode material with volume effect. However, the preparation of the prior coordination polymer has two problems, namely, the adoption of an organic solvent is not beneficial to the environment; secondly, the yield is lower. Therefore, it is very important to develop an environment-friendly and economical preparation method of coordination polymer.
Carbonaceous materials, such as hard carbon, graphite, and the like, are common negative electrode materials for lithium ion batteries, but the theoretical specific capacity is low, so researchers have moved their attention to novel non-carbon negative electrode materials with high specific capacity, and tin-based negative electrode materials are expected to become the next generation negative electrode materials for lithium ion batteries due to their abundant resources, environmental friendliness, and high theoretical specific capacity. However, the volume expansion problem of the tin-based negative electrode material in the charging and discharging process causes the continuous attenuation of the battery capacity, thereby hindering the practical application of the tin-based negative electrode material in the lithium ion battery.
Disclosure of Invention
Aiming at the technical problems, the invention provides a tin-based coordination polymer lithium ion battery cathode material and a preparation method thereof.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme. The invention provides a tin-based coordination polymer lithium ion battery cathode material which comprises the following raw material components: an organic ligand, an activator, a tin source, and a liquid solvent capable of dissolving the above raw materials.
Preferably, the organic ligand is an aliphatic small molecule containing more than two carboxyl groups.
Preferably, the aliphatic small molecule can be oxalic acid HOOC-COOH and succinic acid
Maleic acid
Fumaric acid
Tartaric acid
Or citric acid
And the like.
Preferably, the activator may be any one of lithium hydroxide, sodium hydroxide, or potassium hydroxide.
Preferably, the tin source is tin tetrachloride pentahydrate.
Preferably, the liquid solvent is deionized water.
The invention also provides a preparation method of the cathode material of the tin-based coordination polymer lithium ion battery, which comprises the following steps:
s1, weighing an activating agent, and dissolving the activating agent in a liquid solvent to form a first solution;
s2, weighing organic ligand, dissolving in a liquid solvent, mixing with the first solution, and stirring uniformly at constant temperature to form a second solution;
s3, weighing a tin source, dissolving the tin source in a liquid solvent to form a third solution, adding the third solution into the second solution, and enabling the mixed solution to become turbid; and transferring the mixed solution into a hydrothermal reaction kettle, heating at constant temperature for a certain time, naturally cooling, centrifuging, and drying to obtain the cathode material.
Preferably, the heating temperature of the constant temperature heating is 110 ℃, the reaction can be normally carried out at the temperature, and the safety problem caused by overhigh air pressure in the reaction kettle is avoided.
Preferably, the heating time of the constant temperature heating is 24 hours, which can allow the reaction to be completely performed.
The invention utilizes lithium hydroxide to lithiate organic ligand, improves the reaction activity, enables the organic ligand to fully react with metal tin ions, and then performs pressurized reaction in a reaction kettle to obtain the cathode material of the tin-based coordination polymer lithium ion battery.
The tin-based coordination polymer lithium ion battery cathode material prepared by the invention is mixed with a conductive agent and a bonding agent according to a proportion, added with a proper amount of solvent, uniformly stirred and coated on a copper foil to be used as an electrode of a battery.
Compared with the prior art, the invention has the following advantages and beneficial technical effects: the activating agent used in the invention can make the organic ligand which is insoluble in water dissolve in water in the form of carboxylate, therefore, the solvent adopted in the preparation process only needs deionized water, is environment-friendly and is easy to obtain; the activator used in the invention can effectively improve the reaction activity of the organic ligand, thereby greatly improving the yield of the tin-based coordination polymer.
Drawings
FIG. 1 is an X-ray diffraction diagram of a cathode material of a tin-based coordination polymer lithium ion battery prepared in example 2 of the present invention.
Fig. 2 is a scanning electron microscope image of the cathode material of the tin-based coordination polymer lithium ion battery prepared in example 2 of the present invention.
Fig. 3 is a cyclic voltammetry curve of the cathode material of the tin-based coordination polymer lithium ion battery prepared in example 2 of the present invention.
FIG. 4 is a graph of cycle performance of the cathode material of the tin-based coordination polymer lithium ion battery prepared in example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to these examples.
Example 1:
(1) dissolving 10mmol of succinic acid and 20mmol of lithium hydroxide in 10mL of deionized water and 20mL of deionized water respectively, and mixing the two solutions to obtain a colorless transparent solution;
(2) dissolving 10mmol of tin tetrachloride pentahydrate in 10mL of deionized water to obtain a tin tetrachloride solution, then completely dripping the tin tetrachloride solution into the colorless transparent solution, and enabling the mixed solution to become turbid;
(3) and transferring the mixed turbid solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, reacting for 24 hours at 110 ℃, naturally cooling to room temperature, centrifuging, washing with deionized water and absolute ethyl alcohol for several times respectively, and drying in vacuum for 24 hours at 100 ℃ to obtain the cathode material.
Example 2:
(1) respectively dissolving 10mmol of citric acid monohydrate and 30mmol of lithium hydroxide in 10mL of deionized water and 30mL of deionized water, and then mixing the citric acid monohydrate and the lithium hydroxide to obtain a colorless transparent solution;
(2) dissolving 10mmol of tin tetrachloride pentahydrate in 10mL of deionized water to obtain a tin tetrachloride solution, then completely dripping the tin tetrachloride solution into the colorless transparent solution, and enabling the mixed solution to become turbid;
(3) and transferring the mixed turbid solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, reacting for 24 hours at 110 ℃, naturally cooling to room temperature, centrifuging, washing with deionized water and absolute ethyl alcohol for several times respectively, and drying in vacuum for 24 hours at 100 ℃ to obtain the cathode material.
FIG. 1 is an X-ray diffraction pattern of a tin-based coordination polymer lithium ion battery negative electrode material prepared in example 2, and comparative analysis shows that the diffraction peak of the tin-based coordination polymer lithium ion battery negative electrode material coincides with the (110), (101), (211) and (112) crystal planes of tin dioxide with a space group of P42/mnm, indicating that the negative electrode material has a crystal structure similar to that of tin dioxide.
FIG. 2 is a scanning electron micrograph of the cathode material of the lithium ion battery of the tin-based coordination polymer prepared in example 2, and it can be seen from FIG. 2 that the bulk tin-based coordination polymer is uniformly stacked and has a size range of 4 to 10 μm.
FIG. 3 shows that the negative electrode material of the tin-based coordination polymer lithium ion battery prepared in example 2 has a value of 0.1mV s-1The electrochemical behavior of the cell is based on the redox of metallic tin as can be seen from the curves in fig. 3.
FIG. 4 shows that the cathode material of the Sn-based coordination polymer lithium ion battery prepared in example 2 is at 100mA g-1The current density of the battery pack is shown in fig. 4, although the capacity of the battery is reduced in the first 30 cycles, the capacity of the battery is not obviously changed after 30 cycles, and the capacity is still as high as 637.5mAh g after 200 cycles-1Correspondingly, the coulombic efficiency of the cell was greater than 99% after 30 cycles.
Example 3:
(1) dissolving 10mmol of fumaric acid and 20mmol of lithium hydroxide in 10mL of deionized water and 20mL of deionized water respectively, and mixing the two solutions to obtain a colorless transparent solution;
(2) dissolving 10mmol of tin tetrachloride pentahydrate in 10mL of deionized water to obtain a tin tetrachloride solution, then completely dripping the tin tetrachloride solution into the colorless transparent solution, and enabling the mixed solution to become turbid;
(3) and transferring the mixed turbid solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, reacting for 24 hours at 110 ℃, naturally cooling to room temperature, centrifuging, washing with deionized water and absolute ethyl alcohol for several times respectively, and drying in vacuum for 24 hours at 100 ℃ to obtain the cathode material.
The tin-based coordination polymer lithium ion battery negative electrode materials prepared in the examples 1 and 3 have the performance equivalent to that of the negative electrode active material prepared in the example 2, and also show high specific capacity, high charge and discharge efficiency and good cycling stability.
The above description is only a preferred embodiment of the present invention, and does not limit the present invention, and all the simple modifications, changes and emulations made to the above embodiment in view of the technical content of the present invention belong to the protection scope of the technical solution of the present invention.
Claims (1)
1. A preparation method of a tin-based coordination polymer lithium ion battery cathode material is characterized by comprising the following steps:
s1, weighing an activating agent, and dissolving the activating agent in deionized water to form a first solution; the activating agent is lithium hydroxide;
s2, weighing organic ligand, dissolving in deionized water, mixing with the first solution, and stirring uniformly at constant temperature to form a second solution; the organic ligand is any one of oxalic acid, succinic acid, maleic acid, fumaric acid, tartaric acid or citric acid;
s3, weighing stannic chloride pentahydrate, dissolving in deionized water to form a third solution, adding the third solution into the second solution, heating at 110 ℃ for 24 hours, naturally cooling, centrifuging, and drying to obtain the cathode material.
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