CN111244561A - Preparation method of high-energy-density and high-voltage graphite-zinc-based ion battery based on aqueous electrolyte - Google Patents

Preparation method of high-energy-density and high-voltage graphite-zinc-based ion battery based on aqueous electrolyte Download PDF

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CN111244561A
CN111244561A CN202010154573.5A CN202010154573A CN111244561A CN 111244561 A CN111244561 A CN 111244561A CN 202010154573 A CN202010154573 A CN 202010154573A CN 111244561 A CN111244561 A CN 111244561A
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zinc
graphite
electrolyte
ion battery
battery
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CN111244561B (en
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师唯
刘洪文
杨皓
程鹏
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Nankai 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The preparation method of the high-energy density and high-voltage graphite-zinc-based ion battery based on the water system electrolyte comprises the following steps: (1) Soluble bromine salt is dissolved in saturated zinc chloride solution to obtain high-concentration (30 mol/L) electrolyte. (2) And coating the graphite positive electrode material by using a wet film-making method to obtain the positive electrode piece. (3) And assembling the electrolyte, the positive pole piece and the negative metal zinc foil into the simple soft package battery. The invention designs novel high-concentration zinc chloride + bromine salt aqueous electrolyte as a core, and reversible intercalation reaction can be carried out in a graphite electrode based on the electrolyte, and the average potential is 1.71V (for Zn/Zn) 2+ ) In the case of (1), 257mAh g was obtained ‑1 High capacity of (2). The graphite-zinc-based dual-ion battery with the limit voltage of more than 2V is assembled, and the energy density of the battery can reach 440Wh kg ‑1 . The halogen anion intercalation mechanism combines the high energy density of the conversion reaction, and greatlyThe energy density of the aqueous zinc-based battery is improved.

Description

Preparation method of high-energy-density and high-voltage graphite-zinc-based ion battery based on aqueous electrolyte
Technical Field
The invention belongs to the technical field of secondary ion battery preparation, and particularly relates to preparation of a water system electrolyte graphite-zinc base ion battery capable of realizing high voltage and high energy density.
Background
Since the invention of zinc-manganese batteries in the 60's of the 19 th century, zinc batteries have been widely used in the field of primary batteries. In the 60's of the 20 th century, secondary alkaline zinc manganese batteries were widely developed, but their cycle life was short due to irreversible byproducts generated during discharge. The development of electric vehicles and smart grids, and the increasing popularity of intermittent energy sources such as solar energy, wind energy and tides, has made it urgent to develop new large-scale energy storage systems. Secondary batteries are one of the important large-scale energy storage systems. An ideal secondary battery for large-scale energy storage is required to have not only excellent electrochemical performance, but also rich raw material reserves, low price, economic and social benefit indexes such as environmental protection and high safety. Recently, rechargeable zinc-based ion batteries based on aqueous electrolytes have drawn attention due to advantages such as abundant and inexpensive raw material resources and safety of aqueous electrolytes. However, there is a significant gap in energy density between aqueous zinc-based ion cells and organic electrolyte system cells, and the narrow electrochemical stability window, mainly due to aqueous electrolytes, limits the choice of electrode materials, resulting in low cell voltages.
The existing water-based electrolyte commonly used by the water-based zinc-based ion battery can cause electrochemical side reaction and uncontrollable solid-liquid interface reaction due to the existence of a large amount of water with high reaction activity; an ideal aqueous zinc-based ion battery electrolyte should also have a wide and stable voltage window to match the zinc foil negative electrode with a positive electrode material with high theoretical capacity. The problems can be comprehensively solved by reducing the content of active water through the high-concentration electrolyte provided by the invention, and the electrolyte has an important promoting effect on the development of the water-based zinc-based ion battery.
Disclosure of Invention
The invention aims to solve the problems of low energy density caused by low working voltage and narrow voltage window of zinc-based ions in the existing water system, and provides a method for realizing high powerA preparation method of a graphite-zinc-based ion battery with a water system electrolyte and high energy density. The high-concentration electrolyte is designed, the working voltage and the energy density of the water-based zinc-based ion battery are obviously improved, and a good prospect is provided for large-scale application of the water-based zinc-based ion battery. By the design of the electrolyte, the average working voltage of the water-based graphite zinc-based ion battery reaches 1.71V, the water-based graphite zinc-based ion battery respectively has two flat platforms at 1.80V and 1.65V, and 440Wh kg is obtained -1 High energy density and 257mAh g -1 High specific capacity of (2).
The technical scheme of the invention is as follows:
a preparation method of a high-energy density and high-voltage graphite-zinc-based ion battery based on an aqueous electrolyte comprises the following steps:
(1) Dissolving 0.001-1 equivalent of soluble bromine salt (such as potassium bromide) in saturated zinc chloride solution to obtain high-concentration electrolyte;
(2) Coating the artificial graphite positive electrode material by a wet film-making method, and performing vacuum drying at 60-100 ℃ for 6-12 hours to obtain the positive electrode piece.
(3) And (3) assembling the electrolyte obtained in the step (1), the positive pole piece obtained in the step (2) and the negative metal zinc foil into the simple soft package battery. The zinc ion battery provided by the invention comprises a positive electrode, a negative electrode, a diaphragm and high-concentration electrolyte.
The battery test voltage is 1.0V-2.0V, the working voltage window of the electrolyte is 0.01V-2.1V, the working mode is constant current charging and discharging, and the current is set to be 0.01-100Ag -1 The results shown in FIG. 8 were obtained after 100 weeks of charge and discharge.
The invention has the advantages and beneficial effects that:
the performance is as follows: the voltage window of the cheap combined electrolyte in the method is as high as 2.1V, which is much higher than the decomposition voltage of water by 1.23V. By the design of high-concentration electrolyte, the average working voltage of the water system graphite-zinc-based ion battery reaches 1.71V, the water system graphite-zinc-based ion battery respectively has two flat platforms at 1.80V and 1.65V, the two flat platforms are higher than that of a zinc-based ion battery based on common electrolyte, and 440Wh kg is obtained -1 Ultra high energy density of257mAh g -1 The ultra-high specific capacity of (2).
Cost: the electrolyte and the electrode material do not contain any transition metals other than the main salt zinc chloride. The used anode material has high element abundance and low price. The battery electrolyte and the material have extremely simple design, do not contain any extremely toxic components (especially fluorine-free and fluorinated components), are green batteries, are expected to be applied to energy storage equipment with low cost, high safety and high environmental protection, and are very important for large-scale energy collection/storage requirements. The battery can be directly assembled in the air, and is convenient and fast. The results presented provide new insights into alternative energy storage technologies. .
Drawings
FIG. 1 is an X-ray powder diffraction pattern of artificial graphite in an example of the present invention;
FIG. 2 is a field emission scanning electron microscope photograph of an artificial graphite in an embodiment of the present invention;
FIG. 3 is a graph showing a particle size distribution of artificial graphite in an example of the present invention;
FIG. 4 is a 77K nitrogen isothermal adsorption and desorption data graph of artificial graphite in the example of the invention;
FIG. 5 is a graph of the rate performance of an aqueous electrolyte graphite-zinc based ion battery at different voltage windows in an embodiment of the invention;
FIG. 6 is a graph of discharge curves of an aqueous electrolyte graphite-zinc based ion battery at different voltage windows in accordance with an embodiment of the present invention;
FIG. 7 is a cyclic voltammogram of an aqueous electrolyte graphite-zinc based ion battery in an example of the invention;
FIG. 8 is a graph of the cycling performance of an aqueous electrolyte graphite-zinc based ion battery in an example of the invention;
FIG. 9 is a graph showing the charge and discharge curves of an aqueous electrolyte graphite-zinc-based ion battery according to an embodiment of the present invention;
FIG. 10 is a graph of the rate capability of different potassium bromide concentrations for an aqueous electrolyte graphite-zinc based ion battery in an embodiment of the invention;
FIG. 11 is a multiplying power performance diagram of the aqueous electrolyte graphite-zinc-based ion battery added with the conductive additive in the embodiment of the invention;
fig. 12 is a graph of the cycle performance of the gel-state electrolyte of the aqueous electrolyte graphite-zinc-based ion battery in an example of the invention.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and examples, but the scope of the invention is not limited to the following specific examples.
The core of the invention is novel water system ZnCl 2 + KBr electrolyte, on the basis of which reversible intercalation reactions can be carried out in graphite electrodes, at an average potential of 1.71V (for Zn/Zn) 2+ ) In the case of (1), 257mAh g was obtained -1 High specific capacity of (2). The energy density of the graphite-zinc-based ion battery with the limit voltage of more than 2.0V can reach 440Wh kg -1 . The halogen anion intercalation mechanism combines the conversion reaction, and greatly improves the energy density of the water system zinc-based ion battery.
Example 1:
a preparation method of a high-energy-density and high-voltage graphite-zinc-based ion battery based on an aqueous electrolyte comprises the following steps:
(1) Synthesis of aqueous electrolyte:
the preparation concentration is 5.89mol kg -1 (30 mol/L) Zinc chloride and 0.38mol kg -1 (0.4 mol/L) of an aqueous solution of potassium bromide, the molar ratio of zinc chloride to potassium bromide in the aqueous solution being 750:1, as an electrolyte.
(2) 900mg of artificial graphite positive electrode material, 3.33g of 3% sodium carboxymethylcellulose aqueous solution was sufficiently stirred, and then coated by a wet film-forming method, and vacuum-dried at 80 ℃ for 10 hours to obtain a positive electrode sheet. The physical characterization of the used graphite cathode material is shown in figure 1, and the powder X-ray result shows the phase purity of the graphite; FIG. 2 is a field emission scanning electron microscope image showing the morphology of graphite as micron-sized particles; FIG. 3 shows the particle size distribution of graphite in the range of about 8 microns; FIG. 4 is a graph of adsorption and desorption of graphite under 77K nitrogen, which is a characteristic curve without micropores. These results are consistent with the intrinsic characteristics of graphite.
(3) And (3) assembling the electrolyte obtained in the step (1), the positive electrode sheet obtained in the step (2) and the negative electrode metal zinc foil into a simple soft package battery. FIG. 5 is a graph of the rate performance of the aqueous electrolyte graphite-zinc-based ion battery in different voltage windows in this experiment; the results show that the optimum voltage window is 1.0-2.0V. FIG. 6 is a graph of the discharge of the cell in this experiment over different voltage windows; the result shows that the optimal voltage window is 1.0-2.0V and has two stable discharge platforms. FIG. 7 is a cyclic voltammogram of the cell in this experiment; the result shows that the optimal voltage window is 1.0-2.0V and has two pairs of reversible redox peaks. FIG. 8 is a graph of the cycling performance of the cells in this experiment; the capacity of 83mAh/g can still be achieved after 100 cycles under the current density of 0.25A/g. FIG. 9 is a graph showing the charge and discharge curves of the battery in this experiment; the charge and discharge still have two stable discharge platforms under the current density of 0.25A/g, and the performance is excellent.
Example 2:
a preparation method of a high-energy density and high-voltage graphite-zinc-based ion battery based on an aqueous electrolyte comprises the following steps:
(1) Synthesis of electrolyte:
dissolving zinc chloride (81.78g, 0.6 mol) and potassium bromide (0.47g, 0.004mol) in water (20 mL) to obtain an electrolyte containing potassium bromide (0.2 mol/L) and zinc chloride (30 mol/L);
dissolving zinc chloride (81.78g, 0.6 mol) and potassium bromide (0.95g, 0.008mol) in water (20 mL) to obtain an electrolyte containing potassium bromide (0.4 mol/L) and zinc chloride (30 mol/L);
dissolving zinc chloride (81.78g, 0.6 mol) and potassium bromide (1.90g, 0.016 mol) in water (20 mL) to obtain an electrolyte containing potassium bromide (0.8 mol/L) and zinc chloride (30 mol/L);
zinc chloride (81.78g, 0.6 mol) and potassium bromide (3.57g, 0.03mol) were dissolved in water (20 mL) to give an electrolyte containing potassium bromide (1.5 mol/L) and zinc chloride (30 mol/L).
(2) 900mg of artificial graphite positive electrode material, 3.33g of a 3% sodium carboxymethylcellulose aqueous solution, was sufficiently stirred and then coated by a wet film-forming method, and was vacuum-dried at 100 ℃ for 6 hours to obtain a positive electrode sheet. The material characterization of the graphite cathode material is shown in figure 1, and the powder X-ray result shows the phase purity of graphite; FIG. 2 is a field emission scanning electron microscope image showing the morphology of graphite as micron-sized particles; FIG. 3 shows the particle size distribution of graphite in the range of about 8 microns; the adsorption and desorption curves of the graphite in the 77K nitrogen condition of the graphite in the figure 4 obtain the curve characteristics without holes, and the results all accord with the intrinsic characteristics of the graphite.
(3) And (3) assembling the electrolyte obtained in the step (1), the positive electrode sheet obtained in the step (2) and the negative electrode metal zinc foil into a simple soft package battery. Fig. 10 is a graph of rate performance of an aqueous zinc-ion battery at different concentrations of potassium bromide in accordance with an embodiment of the present invention; the test voltage of the battery is 1.0V-2.0V, the working mode is constant current charging and discharging, and the result shows that the optimal performance is obtained when the concentration of the potassium bromide is 0.4M.
Example 3:
a preparation method of a high-energy-density and high-voltage graphite-zinc-based ion battery based on an aqueous electrolyte comprises the following steps:
(1) Synthesizing an electrolyte:
zinc chloride (81.78g, 0.6 mol) and potassium bromide (0.95g, 0.008mol) were dissolved in water (20 mL) to obtain an electrolyte containing potassium bromide (0.4 mol/L) and zinc chloride (30 mol/L).
(2) 850mg of artificial graphite positive electrode material, 50mg of super P conductive agent and 3.33g of 3% sodium carboxymethylcellulose aqueous solution were sufficiently stirred, and then film-coated by a wet film-forming method, and vacuum-dried at 60 ℃ for 12 hours to obtain a positive electrode sheet. The physical characterization of the used graphite cathode material is shown in figure 1, and the powder X-ray result shows the high purity of the graphite; FIG. 2 is a field emission scanning electron microscope image showing the morphology of graphite as micron-sized particles; FIG. 3 shows the particle size distribution of graphite in the range of about 8 microns; the adsorption and desorption curves of the graphite in the 77K nitrogen condition of the graphite in the figure 4 obtain the curve characteristics without holes, and the results all accord with the intrinsic characteristics of the graphite.
(3) And (3) assembling the electrolyte obtained in the step (1), the positive electrode sheet obtained in the step (2) and the negative electrode metal zinc foil into a simple soft package battery. Fig. 11 is a rate performance diagram of the aqueous zinc ion battery added with the conductive additive in the embodiment of the invention, the test voltage of the battery is 1.0V-2.0V, and the working mode is constant-current charge and discharge, and the result shows that the discharge capacity is reduced when the conductive additive is added.
Example 4:
a preparation method of a high-energy density and high-voltage graphite-zinc-based ion battery based on a water system electrolyte comprises the following steps:
dissolving zinc chloride (81.78g, 0.6 mol) and potassium bromide (0.95g, 0.008mol) in water (20 mL) to obtain a solution containing potassium bromide (0.4 mol/L) and zinc chloride (30 mol/L); adding 10wt% of xanthan gum, heating at 80 ℃ for 2 hours, and naturally cooling to room temperature to obtain the gel electrolyte.
(2) 900mg of artificial graphite positive electrode material, 3.33g of a 3% sodium carboxymethylcellulose aqueous solution, was sufficiently stirred and then coated by a wet film-forming method, and was vacuum-dried at 80 ℃ for 10 hours to obtain a positive electrode sheet. The physical characterization of the used graphite cathode material is shown in figure 1, and the powder X-ray result shows the high purity of the graphite; FIG. 2 is a field emission scanning electron microscope image showing the morphology of graphite as micron-sized particles; FIG. 3 shows the particle size distribution of graphite in the range of about 8 microns; the adsorption and desorption curves of the graphite in the 77K nitrogen condition of the graphite in the figure 4 obtain the curve characteristics without holes, and the results all accord with the intrinsic characteristics of the graphite.
(3) And (3) assembling the electrolyte obtained in the step (1), the positive electrode sheet obtained in the step (2) and the negative electrode metal zinc foil into a simple soft package battery. Fig. 12 is a graph showing the cycle performance of the gel-state electrolyte of the aqueous zinc-ion battery in accordance with the example of the present invention. The test voltage of the battery is 1.0V-2.0V, the working mode is constant current charging and discharging, and the result shows that the gel electrolyte can inhibit the dissolution of halogen ions and stabilize the cycle performance.
The above description is intended to be illustrative of the preferred embodiments, and should not be taken as limiting the scope of the invention, which is intended to include all substantially equivalent alternatives, process optimizations, and modifications and combinations of conditions within the scope of the invention. A few terms are necessary in the description and illustration, nor are they intended to be limiting of the invention.

Claims (3)

1. A preparation method of a high-energy-density and high-voltage graphite-zinc-based ion battery based on a water system electrolyte is characterized by comprising the following steps:
(1) Dissolving 0.001-1 equivalent of soluble bromine salt in a saturated zinc chloride solution to obtain a high-concentration electrolyte;
(2) Coating the artificial graphite positive electrode material by a wet film making method, and drying in vacuum at 60-100 ℃ for 6-12 hours to obtain a positive electrode piece;
(3) And (3) assembling the electrolyte obtained in the step (1), the positive pole piece obtained in the step (2) and the negative metal zinc foil into a simple soft package battery.
2. The method for preparing an aqueous electrolyte based high energy density, high voltage graphite-zinc based ion battery of claim 1, wherein the battery has a voltage window of 0.01V to 2.1V, and is operated by constant current charging and discharging with a current setting of 0.01 to 100Ag -1 。
3. The method for preparing a high energy density, high voltage graphite-zinc based ion battery based on an aqueous electrolyte according to claim 1, characterized in that the high concentration zinc chloride and bromine salt are mixed in an aqueous solution.
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CN113471550A (en) * 2021-07-06 2021-10-01 浙江恒威电池股份有限公司 Double-active-ion-enhanced chargeable and dischargeable hybrid zinc ion battery energy storage device
WO2021217684A1 (en) * 2020-05-01 2021-11-04 浙江大学 High concentration solution, application thereof, and preparation method
CN113644326A (en) * 2021-10-18 2021-11-12 北京金羽新能科技有限公司 Water-based zinc ion battery and formation method
CN116135788A (en) * 2023-03-13 2023-05-19 浙江师范大学 Preparation method, product and application of halogen intercalation vanadium pentoxide nanoflower
CN118040094A (en) * 2024-02-04 2024-05-14 广东工业大学 High-energy-density water-based zinc-halogen battery without metal negative electrode and preparation method thereof

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CN113644326A (en) * 2021-10-18 2021-11-12 北京金羽新能科技有限公司 Water-based zinc ion battery and formation method
CN113644326B (en) * 2021-10-18 2022-01-04 北京金羽新能科技有限公司 Water-based zinc ion battery and formation method
CN116135788A (en) * 2023-03-13 2023-05-19 浙江师范大学 Preparation method, product and application of halogen intercalation vanadium pentoxide nanoflower
CN116135788B (en) * 2023-03-13 2023-11-14 浙江师范大学 Preparation method, product and application of halogen intercalation vanadium pentoxide nanoflower
CN118040094A (en) * 2024-02-04 2024-05-14 广东工业大学 High-energy-density water-based zinc-halogen battery without metal negative electrode and preparation method thereof

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