CN111934029A - High-rate and low-self-discharge zinc-organic battery and application thereof - Google Patents

High-rate and low-self-discharge zinc-organic battery and application thereof Download PDF

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CN111934029A
CN111934029A CN202010619628.5A CN202010619628A CN111934029A CN 111934029 A CN111934029 A CN 111934029A CN 202010619628 A CN202010619628 A CN 202010619628A CN 111934029 A CN111934029 A CN 111934029A
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卢锡洪
张昊喆
房远斌
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Sun Yat Sen University
National Sun Yat Sen University
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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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
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Abstract

The invention discloses a high-rate and low-self-discharge zinc-organic battery and application thereof. The zinc-organic battery Zn// r-PTCDA anode material is an r-PTCDA material, the cathode material is zinc, the electrolyte is an inorganic zinc ion aqueous solution, has a high specific capacity of 126.4mA h/g, has a capacity retention rate of 62.6% under the condition that the current density is increased by 160 times and reaches 32A/g, has excellent rate performance, can maintain 70% of capacity after being cycled for 1000 times, has good cycle stability, basically has no capacity loss after the battery is stood for 24 hours, has a capacity retention rate of more than 99.9%, has low self-discharge of the battery, has high rate and long service life, can be repeatedly charged and discharged, has low self-discharge, and has a great application prospect in the aspect of energy storage.

Description

High-rate and low-self-discharge zinc-organic battery and application thereof
Technical Field
The invention relates to the technical field of electrochemical energy storage batteries, in particular to a high-rate and low-self-discharge zinc-organic battery and application thereof.
Background
With the rapid growth of the world population and the continuous development of the human society, various demands for energy are increasing. With the exhaustion of fossil energy and the increasing environmental pollution, a lot of green and environmental-friendly renewable energy sources and clean energy sources, such as wind energy, solar energy, tidal energy, geothermal energy and the like, have been developed in recent years. However, since renewable energy sources all have the disadvantages of intermittency and geographical dispersion, and cannot provide large-scale, continuous and stable electric energy, there is a need to develop a safe and reliable novel electric energy storage device to realize the storage and transportation of energy. The novel energy storage device has the advantages of large specific capacity, good cycle stability and high power density and energy density, can improve the utilization rate and the application range of renewable energy sources, meet the requirements of daily life, and can promote the development of high and new technologies.
The zinc-organic battery is a novel energy storage device with low cost, high efficiency and practicability, and has the advantages of low cost, good cycling stability and the like. The zinc-ion-containing electrolyte adopts metal zinc as a negative electrode, an organic compound as a positive electrode and an aqueous solution containing zinc ions as an electrolyte, and is safe, non-toxic and environment-friendly. The zinc electrode is different from the very active lithium and sodium metal electrodes, and is stable in air and water, so that the zinc electrode is very suitable for being used as a water system energy storage device. Compared with the traditional transition metal compound, the organic compound anode has much lower cost and recovery difficulty, and has capacity and cycling stability even superior to those of a metal-based anode, thereby having great development prospect. The development of zinc-organic batteries is still in the beginning at present, and many aspects are not mature, such as the rate capability of the zinc-organic batteries at high current density is not good enough and the zinc-organic batteries can not store enough electric energy under the condition of rapid discharge due to the sharply increased ion/electron diffusion resistance under the condition of high loading. Meanwhile, the self-discharge of the zinc-organic battery formed by the organic materials is serious due to the mechanism that the cations are absorbed and desorbed on the surface in the charge and discharge processes of a plurality of organic materials. Therefore, it remains a challenge to develop a zinc-organic battery with high rate performance and low self-discharge through structural optimization.
CN107069089A discloses an electrolyte and a lithium ion battery, wherein the electrolyte comprises lithium salt, an additive, an organic solvent and metal salt, and the metal salt is at least one of sodium salt, potassium salt, calcium salt, copper salt, zinc salt and nickel salt. The method mainly comprises the steps of adding metal salt into the electrolyte, improving the conductivity of the electrolyte, reducing the internal resistance of the battery and improving the rate capability of the battery. The radius of sodium ions in sodium salt, potassium ions in potassium salt, calcium ions in calcium salt, copper ions in copper salt, zinc ions in zinc salt or nickel ions in nickel salt is larger than that of lithium ions in lithium salt, so that the aperture of the SEI film is properly increased, the generated SEI film is beneficial to the inlet and outlet of lithium ions, the internal resistance of the battery is reduced, and the rate capability and the cycle performance of the battery are improved. However, the rate capability and the self-discharge capability of the zinc-organic battery under high current density are not improved, the rate capability improvement effect is limited, and the problem of improving the rate capability and the self-discharge capability of the existing zinc-organic battery cannot be solved.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and the defects of the rate capability and the self-discharge capability of the existing zinc-organic battery and providing a zinc-organic battery with high rate and low self-discharge.
The invention aims to provide an application of a high-rate and low-self-discharge zinc-organic battery in the field of electrochemical energy storage.
The above purpose of the invention is realized by the following technical scheme:
a high-rate and low-self-discharge zinc-organic battery is characterized in that a positive electrode material of the zinc-organic battery is an r-PTCDA material, a negative electrode material of the zinc-organic battery is zinc, and an electrolyte is an inorganic zinc ion aqueous solution.
Wherein the r-PTCDA material is an r-PTCDA organic molecular crystal prepared by a sublimation-desublimation recrystallization method of a 3,4,9, 10-perylenetetracarboxylic dianhydride organic molecular crystal (PTCDA).
The zinc cathode material can be a nano material or commercial zinc materials such as commercial zinc sheets, zinc foils and zinc wires, wherein the nano zinc material is prepared by a constant current electrodeposition method, and the method specifically comprises the following steps:
50-150 g/L NaSO4、5～50g/L H3BO3、50～150g/L ZnSO4Or 50 to 150g/L ZnCl2The mixed aqueous solution is used as electrolyte, a graphite rod is used as an auxiliary electrode, a calomel electrode is used as a reference electrode, carbon paper is used as a working electrode, and the constant current density is-1-100 mA cm at room temperature-2And performing electrodeposition for 1-180 min.
The preferable preparation method of the Zn nano material is as follows:
125g/L NaSO4、20g/L H3BO3、125g/L ZnSO4·7H2The mixed water solution of O is used as electrolyte, a graphite rod is used as an auxiliary electrode, a calomel electrode is used as a reference electrode, and carbon paper is used as a working electrode. Constant current density of-30-70 mA cm at room temperature-2And carrying out electrodeposition for 1-60 min.
Preferably, the zinc-organic battery positive electrode is manufactured by an electrode film forming technology, and the specific operations are as follows: uniformly mixing r-PTCDA material with acetylene black and PVDF to obtain mixed powder slurry, coating a film on a substrate by taking NMP as a dispersing agent, drying for 5-48 hours under a vacuum heating condition to prepare the coating,
wherein the content of acetylene black in every 100mg of mixed powder slurry is 5-15 mg, the content of PVDF is 5-15 mg, 0.1-1 mL of NMP is dripped into every 100mg of mixed powder, and every 1cm of NMP2The substrate is coated with 0.1-15 mg of the mixed powder.
Preferably, the content of the acetylene black and the content of the PVDF in each 100mg of the mixed powder slurry are 5-15 mg respectively.
Preferably, the vacuum drying temperature for preparing the positive electrode of the zinc-organic battery by the electrode film forming technology is 60-80 ℃, the vacuum degree is 100-5000Pa, and the drying is carried out for 24 hours.
Preferably, the particle size of the r-PTCDA material is 0.002-50 μm.
Preferably, the r-PTCDA material is obtained by heating 3,4,9, 10-perylenetetracarboxylic dianhydride organic molecular crystals in an inert gas atmosphere, cooling, desublimation and recrystallization,
wherein the heating temperature is 400-600 ℃, the heat preservation time is 0.1-5 hours, the cooling temperature is 0-300 ℃, and the heat preservation time is 0.1-5 hours.
In the desublimation recrystallization process of the invention, the inert gas atmosphere is at low pressure N2Ar, He and the like under an inert gas atmosphere at a pressure of 1 to 30 kPa.
Preferably, the heating temperature is 400-500 ℃, and the heat preservation time is 0.1-2 hours.
Preferably, the cooling temperature is 100-200 ℃, and the heat preservation time is 0.1-2 hours.
Further preferably, in the desublimation recrystallization process, the heating temperature is 500 ℃, the heat preservation time is 1 hour, the cooling is to naturally cool from 500 ℃ to 100 ℃, and the heat preservation time is 1 hour.
Preferably, the molar concentration of the electrolyte is 0.5-3 mol/L, and the pH value is 1-5.5.
Preferably, the electrolyte is zinc chloride or zinc sulfate or zinc trifluoromethanesulfonate.
According to the technical scheme, the PTCDA crystal form is adjusted by a sublimation-desublimation recrystallization method, the zinc ion embedding and releasing kinetics of the material are optimized, and the rate performance of the material is improved and the self-discharge is reduced; the capacity and the cycle performance of the battery are improved by adjusting the type and the pH value of the electrolyte; the conductive performance and the cycle performance of the electrode are improved by adjusting the proportion of r-PTCDA positive electrode mixed powder, the drop number of NMP and the loading amount of a substrate.
The application of the high-rate and low-self-discharge zinc-organic battery in the electrochemical energy storage field is also within the protection scope of the invention.
The zinc-organic battery Zn// r-PTCDA can be packaged into a No. 5 battery, a button battery, a soft package battery and the like for use.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a zinc-organic battery which adjusts the crystal form of PTCDA through a sublimation-desublimation recrystallization method, optimizes the dynamics of embedding and removing zinc ions from the material, and realizes the improvement of the rate capability and the reduction of self-discharge of the material; the capacity and the cycle performance of the battery are improved by adjusting the type and the pH value of the electrolyte; the conductive performance and the cycle performance of the electrode are improved by adjusting the proportion of r-PTCDA positive electrode mixed powder, the drop number of NMP and the loading amount of a substrate.
The zinc-organic battery Zn// r-PTCDA has high specific capacity of 126.4mA h/g, capacity retention rate of 62.6% under the condition that the current density is increased by 160 times and reaches 32A/g, excellent rate capability, capacity of 70% after 1000 times of circulation, good circulation stability, basically no capacity loss after the battery is stood for 24 hours, capacity retention rate of 99.9%, low self-discharge of the battery, high rate, long service life, repeated charge and discharge, low self-discharge and great application prospect in the aspect of energy storage.
Drawings
FIG. 1: (a) the picture of the commercially available PTCDA powder, and (b) the picture of the r-PTCDA powder in example 1.
FIG. 2: comparative X-ray diffraction patterns of r-PTCDA powder in example 1 and a commercially available PTCDA powder.
FIG. 3: the charge and discharge curves of the Zn// r-PTCDA cell in example 1.
FIG. 4: cycle life testing of Zn// r-PTCDA cells in example 1.
FIG. 5: discharge curves after the Zn// r-PTCDA cell in example 1 was left to stand for 24 hours.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
A high-multiplying-power low-self-discharge zinc-organic battery Zn// r-PTCDA is characterized in that the positive electrode material of the zinc-organic battery is r-PTCDA material, the negative electrode material is zinc, and the electrolyte is inorganic zinc ion aqueous solution.
The preparation of the r-PTCDA positive electrode is realized by an electrode film forming technology, and the r-PTCDA powder is prepared by a sublimation-desublimation recrystallization method.
The preparation steps are as follows:
(a) starting from a commercially available PTCDA powder, the N at 20kPa was determined2Heating to 500 deg.C under atmosphere, maintaining the temperature for 1 hr, and separating N2Cooling to 100 deg.C, maintaining for 1 hr, and collecting desublimated powder as r-PTCDA powder;
(b) uniformly grinding 90mgr-PTCDA powder, 5mg acetylene black powder and 5mg PVDF powder, dripping 1mL of NMP, and uniformly stirring to be pasty;
(c) and (c) uniformly coating the pasty mixture in the step (b) on carbon paper (5cm multiplied by 10cm), drying for 24 hours in an environment with the vacuum degree of 200Pa and the temperature of 70 ℃, and naturally cooling to obtain the r-PTCDA cathode.
The electrolyte of the Zn// r-PTCDA battery is 2M ZnCl2The pH was 3.0.
Characterization and performance testing:
as shown in FIG. 1, r-PTCDA (b) obtained by sublimation-desublimation recrystallization was brown powder, which was darker in color than the commercially available PTCDA powder (a).
The obtained r-PTCDA powder was subjected to X-ray diffraction test, and its comparative image with PTCDA powder is shown in FIG. 2, and it can be seen that the crystal structure of the r-PTCDA powder was transformed to a certain extent, and the (102) plane (i.e., stacking layer) pitch thereof was determined by
Figure BDA0002564736470000053
Is reduced to
Figure BDA0002564736470000052
Illustrating the enhanced pi-pi stacking in r-PTCDA. And assembling the zinc sheets and commercial zinc sheets into a button cell.
Fig. 3 the rate performance of the cells was tested using different current densities. As can be seen from the figure, the resulting Zn// r-PTCDA cell had a high specific capacity of 126.4mA h/g. The zinc-organic battery prepared under the condition that the current density is increased by 160 times and reaches 32A/g also has 62.6 percent of capacity retention rate, which indicates that the material has excellent rate performance.
As can be seen from fig. 4, the battery also maintained 70% of the capacity after 1000 cycles, indicating that the material had good cycling stability. As can be seen from fig. 5, the battery had substantially no capacity loss (capacity retention rate > 99.9%) after 24 hours of standing, indicating that the self-discharge of the battery was low.
In conclusion, the zinc-organic battery has high multiplying power, long service life, low self-discharge and can be repeatedly charged and discharged, and has great application prospect in the aspect of energy storage.
Examples 2 to 17
Examples 2 to 17 were prepared in the same manner as in example 1, except that the temperature and the corresponding time period for sublimation-desublimation recrystallization, the ratio of acetylene black and PVDF in the mixed powder, and the composition of the electrolyte were used.
The specific temperatures and times, composition ratios, electrolyte compositions, and results of each example are shown in tables 1-4.
TABLE 1 sublimation-desublimation recrystallization Regulation
Figure BDA0002564736470000051
Figure BDA0002564736470000061
TABLE 2 Regulation of desublimation conditions by sublimation-desublimation recrystallization
Figure BDA0002564736470000062
TABLE 3 Mixed powder slurry ratio control
Figure BDA0002564736470000063
TABLE 4 Battery electrolyte composition control
Figure BDA0002564736470000064
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. 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. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. The high-rate and low-self-discharge zinc-organic battery is characterized in that a positive electrode material of the zinc-organic battery is an r-PTCDA material, a negative electrode material of the zinc-organic battery is zinc, and an electrolyte is an inorganic zinc ion aqueous solution.
2. The high-rate, low-self-discharge zinc-organic cell of claim 1, wherein said zinc-organic cell positive electrode is fabricated by an electrode film-forming technique, comprising the steps of: the preparation method comprises the steps of uniformly mixing an r-PTCDA material, acetylene black and PVDF to obtain mixed powder slurry, coating a film on a substrate by taking NMP as a dispersing agent, and drying for 5-48 hours under a vacuum heating condition.
Wherein the content of acetylene black in every 100mg of mixed powder slurry is 5-15 mg, the content of PVDF is 5-15 mg, 0.1-1 mL of NMP is dripped into every 100mg of mixed powder, and every 1cm of NMP2The substrate is coated with 0.1-15 mg of the mixed powder.
3. The high-rate, low-self-discharge zinc-organic battery according to claim 2, wherein the content of acetylene black is 5-15 mg and the content of PVDF is 5mg per 100mg of the mixed powder slurry.
4. The high-rate, low-self-discharge zinc-organic cell of claim 2, wherein said r-PTCDA material has a particle size of 0.002 to 50 μm.
5. The high-rate, low-self-discharge zinc-organic battery according to claim 4, wherein the r-PTCDA material is obtained by heating 3,4,9, 10-perylenetetracarboxylic dianhydride organic molecular crystals in an inert gas atmosphere, cooling, desublimation and recrystallization.
Wherein the heating temperature is 400-600 ℃, the heat preservation time is 0.1-5 hours, the cooling temperature is 0-300 ℃, and the heat preservation time is 0.1-5 hours.
6. The high-rate, low-self-discharge zinc-organic battery according to claim 5, wherein the heating temperature is 400 to 500 ℃ and the holding time is 0.1 to 2 hours.
7. The high-rate, low-self-discharge zinc-organic battery according to claim 5, wherein said cooling temperature is 100 to 200 ℃ and the holding time is 0.1 to 2 hours.
8. The high-rate, low-self-discharge zinc-organic battery according to claim 1, wherein the electrolyte has a molar concentration of 0.5 to 3mol/L and a pH of 5.5 to 1.
9. The high-rate, low self-discharge zinc-organic cell of claim 8, wherein said electrolyte is zinc chloride or zinc sulfate or zinc triflate.
10. Use of a high-rate, low-self-discharge zinc-organic cell according to any one of claims 1 to 9 in the field of electrochemical energy storage.
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