CN111224115B - Zinc-based battery negative electrode and preparation and application thereof - Google Patents
Zinc-based battery negative electrode and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a zinc-based battery negative electrode and preparation and application thereof, wherein one or more than two target materials of metal, metal alloy and metal oxide are deposited on an electrode substrate by a magnetron sputtering method to obtain the zinc-based flow battery negative electrode; by controlling the preparation conditions and the material composition of the electrode, the material has the advantages of obvious crystallization control function, excellent electronic conductivity, stable structure and high specific surface area. It can be applied to aqueous and organic zinc-based batteries.
Description
Technical Field
The invention relates to the technical field of zinc-based batteries, in particular to a zinc-based battery negative electrode.
Background
With the continuous increase of the demand of people on renewable energy sources, a series of complex problems exist in the production and utilization of the renewable energy sources, and the arrangement of a large-scale energy storage system is considered to be a feasible solution, so that the market prospect of the energy storage power station is wide at present. However, many lithium batteries used for power storage have some potential safety hazards, such as possible explosion, and the safety problem of large-scale energy storage systems needs to be solved.
The zinc metal has the characteristics of relatively negative electrode potential, two-electron transfer reaction, high solubility, rapid kinetics, good cyclicity, rich reserves and relatively low price, so that the zinc-based battery has the advantages of normal-temperature and normal-pressure operation, no harmful substance emission, relatively high safety, high energy conversion efficiency and low cost, becomes an ideal choice for large-scale energy storage, is widely concerned, and has wide application prospects. At present, metallic zinc is applied to many energy storage systems, such as Zn-ion, Zn-Ce, Zn-Cl2、Zn-I2、Zn-Br2、Zn-V、Zn-Fe、Zn-Ni、Zn-O2An isoelectric cell system, which reacts as follows:
however, the rapid development of zinc-based battery metallic zinc negative electrodes is limited, and the large-scale commercialization of the zinc-based battery is faced with great challenges. The metal zinc is subjected to dissolution/deposition reaction at the negative electrode, so that the metal zinc is subjected to severe shape change in the circulation process, and the structure of the battery is damaged; the zinc is electrochemically crystallized on the negative current collector rapidly, so that the metal zinc is distributed on the current collector unevenly, zinc dendrites grow rapidly, and a diaphragm is punctured to cause the battery to lose efficacy; repeated cycling to form a loose structure and fall off during cycling results in a reduction in coulombic efficiency and cycle life. Therefore, the regulation and control of the electrochemical crystallization behavior of the zinc metal to enable the zinc metal to be deposited uniformly, compactly and smoothly is significant and extremely challenging.
Disclosure of Invention
The invention aims to prepare a high-performance zinc electrode, which has a remarkable crystallization control function, excellent electronic conductivity, a stable structure and a high specific surface area by controlling preparation conditions and the material composition of the electrode. It can be applied to aqueous and organic zinc-based batteries.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a high-performance zinc electrode is prepared from one or more of metal, metal alloy and metal oxide through magnetically controlled sputtering to deposit them on substrate in a certain atmosphere to a thickness of 10 nm-5 microns. The method can effectively prevent the shape of the zinc electrode from seriously changing, inhibit the growth of dendritic crystals and ensure that the metal zinc is deposited more compactly and uniformly. The electrode is simple in preparation process, environment-friendly in process, controllable in appearance and composition, easy to realize batch production and wide in application range. The assembled battery has good coulombic efficiency and cycle life.
The metal is one or more than two of magnesium, aluminum, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, tin, lead, bismuth and silver.
The metal alloy is two or more than three of magnesium, aluminum, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, tin, lead, bismuth and silver.
The specific atmosphere is one or two of argon, nitrogen, oxygen and hydrogen.
The electrode substrate comprises a copper foil, an aluminum foil, a nickel foil, a titanium foil, an iron foil, a zinc foil, a silver foil, a gold-silver alloy foil, a foam copper, a foam nickel, a foam titanium, a porous gold foil, a carbon paper, a carbon cloth, a carbon fiber, a carbon felt, a graphite electrode and a glassy carbon electrode.
The high performance zinc electrode is used in a zinc-based battery.
The zinc-based battery comprises a water system and/or organic system zinc ion battery, a zinc-cerium battery, a zinc-chlorine battery, a zinc-iodine battery, a zinc-bromine battery, a zinc-vanadium battery, a zinc-iron battery, a zinc-nickel battery and a zinc-air battery.
The electrode with the zinc electrochemical crystallization regulation function is prepared by the following steps:
(1) cleaning an electrode substrate to be plated with ethanol, acetone and water respectively, and then drying the electrode substrate in a vacuum oven at the temperature of 30-100 ℃ for 2-12 hours;
(2) placing the electrode substrate prepared in the step (1) on a sample table of a magnetron sputtering device which is pre-equipped with a specific target material, and pumping a main sputtering cavity to 1 x 10 by utilizing a mechanical pump and a molecular pump-4～5×10-2Pa. Closing the sample baffle, controlling the flow of the sputtering gas to be 5-150 sccm and the power to be 5-30W/cm2Keeping the pressure of air at 0.1-15 Pa, pre-sputtering for 2-30 minutes, opening a sample baffle plate after glow and power indication are relatively stable, starting sputtering to an electrode substrate, and controlling the power at 10-100W/cm2The flow rate of the sputtering gas is controlled to be 20 to 150sccm, and the pressure gas is maintained to be 0.1 to 15 Pa. And after the sputtering is finished, taking out the sample for use.
The zinc-based battery includes an aqueous and/or organic zinc ion battery, a zinc-cerium battery, a zinc-chlorine battery, a zinc-iodine battery, a zinc-bromine battery, a zinc-vanadium battery, a zinc-iron battery, a zinc-nickel battery, or a zinc-air battery.
The zinc-based battery negative electrode is an electrode with a zinc electrochemical crystallization regulation function, and can effectively prevent the shape of the zinc electrode from being seriously changed, inhibit the growth of dendritic crystals and ensure that metal zinc is more compactly and uniformly deposited.
The invention has the following beneficial results:
1. the high-performance zinc electrode prepared by the invention has compact sedimentary deposit and adjustable thickness, and is easy to realize mass production.
2. The electrode with the zinc electrochemical crystallization control function is prepared by the magnetron sputtering method, a physical vapor deposition technology is used, toxic and harmful chemical solvents are not used, and the production method is environment-friendly.
3. The high-performance zinc electrode prepared by the method has clean surface and no impurity interference.
4. The invention can realize the effective control of zinc deposition of the zinc-based battery, so that the zinc-based battery can be uniformly and compactly deposited, and the shape of the zinc electrode can be prevented from being seriously changed.
Drawings
Scanning electron micrographs of the high performance zinc electrode prepared in fig. 1 (fig. 1a and b) and a commercial carbon felt without any treatment (fig. 1c and d).
Scanning electron micrographs of the zinc deposition topography of the high performance zinc electrode prepared in fig. 2 (fig. 2a and b) and the commercial carbon felt without any treatment (fig. 2c and d).
Figure 3 compares the charge and discharge curves of the prepared high performance zinc electrode with a commercial carbon felt negative electrode without any treatment in a zinc-zinc flow battery.
Figure 4 compares the coulombic efficiency of the prepared high performance zinc electrode to a commercial carbon felt negative electrode without any treatment in a zinc-zinc flow battery.
Figure 5 compares the charge and discharge curves of the prepared high performance zinc electrode with a commercial carbon felt negative electrode without any treatment in a zinc-iron flow battery.
Figure 6 coulombic efficiency versus energy efficiency of the prepared high performance zinc electrode versus a commercial carbon felt negative electrode without any treatment in a zinc-iron flow battery.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Comparative example
An alkaline zinc-zinc flow battery was assembled using a commercial carbon felt as a negative electrode without any treatment, and a positive electrode portion thereof was composed of a zinc plate and a carbon felt. The polyether sulfone porous membrane is used as a diaphragm, the graphite plate is used as a current collecting plate, and the effective area of the electrode is aboutIs 36cm2The current density is 80mA/cm2The concentration of zincate radicals in the electrolyte is 0.4mol L-1The NaOH concentration is 2.2mol L-1. The 100-time circulation coulombic efficiency before the commercial carbon felt negative electrode without any treatment is used for assembling the zinc-zinc symmetrical flow battery is lower than 60 percent.
An alkaline zinc-iron flow battery was assembled using a commercial carbon felt without any treatment as the negative electrode, the positive electrode portion of which was composed of the carbon felt. The polyether sulfone porous membrane is used as a diaphragm, the graphite plate is used as a current collecting plate, and the effective area of the electrode is about 36cm2The current density is 80mA/cm2The concentration of zincate radicals in the negative electrolyte is 0.4mol L-1The NaOH concentration is 2.2mol L-1(ii) a The concentration of sodium ferrocyanide in the electrolyte of the positive electrode is 0.8mol L-1KOH concentration of 2.5mol L-1. A commercial untreated carbon felt negative electrode is used for assembling a zinc-iron flow battery, and the zinc-iron flow battery is continuously charged and discharged for 30 cycles, wherein the coulombic efficiency is 85.74%, and the energy efficiency is 64.31%.
Example 1
The preparation method comprises the following steps:
(1) cleaning a commercial carbon felt as a negative electrode substrate with ethanol, acetone and water in sequence, and drying the cleaned carbon felt in a vacuum oven at 80 ℃ for 4 hours;
(2) placing the electrode substrate prepared in the step (1) on a sample table of a magnetron sputtering device which is provided with a target material in advance, and pumping a main sputtering cavity to 1 x 10 by utilizing a mechanical pump and a molecular pump-3Pa; closing a sample baffle, wherein the sputtering gas is argon, the flow is controlled to be 50sccm, and the power is 10W/cm2Keeping the pressure of air at 1Pa, pre-sputtering for 10 minutes, opening a sample baffle plate after glow and power supply indication are relatively stable, starting sputtering to the electrode substrate, and controlling the power at 20W/cm2The sputtering gas is argon, the flow is controlled to be 50sccm, and the compressed gas is maintained at 1 Pa; and after the sputtering is finished, taking out the sample for use. The sputtering thickness is 1 μm.
And (3) assembling the alkaline zinc-zinc flow battery by using the carbon felt after magnetron sputtering tinning as a negative electrode, wherein the positive electrode part of the alkaline zinc-zinc flow battery consists of a zinc plate and the carbon felt. The polyether sulfone porous membrane is used as a diaphragm, and the graphite plate is used as a current collecting plateThe effective area of the electrode is about 36cm2The current density is 80mA/cm2The concentration of zincate radicals in the electrolyte is 0.4mol L-1The NaOH concentration is 2.2mol L-1. The 100-time circulation coulombic efficiency of the zinc-zinc symmetrical flow battery assembled by the magnetron sputtering tinned carbon felt negative electrode is higher than 70%.
And (3) assembling the alkaline zinc-iron flow battery by using the carbon felt after magnetron sputtering tinning as a negative electrode, wherein the positive electrode part of the alkaline zinc-iron flow battery is formed by the carbon felt. The polyether sulfone porous membrane is used as a diaphragm, the graphite plate is used as a current collecting plate, and the effective area of the electrode is about 36cm2The current density is 80mA/cm2The concentration of zincate radicals in the negative electrolyte is 0.4mol L-1The NaOH concentration is 2.2mol L-1(ii) a The concentration of sodium ferrocyanide in the electrolyte of the positive electrode is 0.8mol L-1KOH concentration of 2.5mol L-1. The zinc-iron flow battery is assembled by the magnetron sputtering tinned carbon felt negative electrode for 30 continuous charging and discharging cycles, the coulombic efficiency is 98.01 percent, and the energy efficiency is 79.99 percent.
Example 2
The preparation method comprises the following steps:
(1) cleaning a commercial carbon felt as a negative electrode substrate with ethanol, acetone and water in sequence, and drying the cleaned carbon felt in a vacuum oven at 80 ℃ for 4 hours;
(2) placing the electrode substrate prepared in the step (1) on a sample table of a magnetron sputtering device which is provided with a target material in advance, and pumping a main sputtering cavity to 1 x 10 by utilizing a mechanical pump and a molecular pump-3Pa; closing a sample baffle, wherein the sputtering gas is argon, the flow is controlled to be 50sccm, and the power is 10W/cm2Keeping the pressure of air at 1Pa, pre-sputtering for 10 minutes, opening a sample baffle plate after glow and power supply indication are relatively stable, starting sputtering to the electrode substrate, and controlling the power at 20W/cm2The sputtering gas is argon, the flow is controlled to be 50sccm, and the compressed gas is maintained at 1 Pa; and after the sputtering is finished, taking out the sample for use. The sputtering thickness was 5 nm.
And (3) assembling the alkaline zinc-zinc flow battery by using the carbon felt after magnetron sputtering tinning as a negative electrode, wherein the positive electrode part of the alkaline zinc-zinc flow battery consists of a zinc plate and the carbon felt. The polyether sulfone porous membrane is used as a diaphragm, the graphite plate is used as a current collecting plate,the effective electrode area is about 36cm2The current density is 80mA/cm2The concentration of zincate radicals in the electrolyte is 0.4mol L-1The NaOH concentration is 2.2mol L-1. The 100-time circulation coulombic efficiency of the zinc-zinc symmetrical flow battery assembled by the magnetron sputtering tinned carbon felt negative electrode is higher than 70%.
And (3) assembling the alkaline zinc-iron flow battery by using the carbon felt after magnetron sputtering tinning as a negative electrode, wherein the positive electrode part of the alkaline zinc-iron flow battery is formed by the carbon felt. The polyether sulfone porous membrane is used as a diaphragm, the graphite plate is used as a current collecting plate, and the effective area of the electrode is about 36cm2The current density is 80mA/cm2The concentration of zincate radicals in the negative electrolyte is 0.4mol L-1The NaOH concentration is 2.2mol L-1(ii) a The concentration of sodium ferrocyanide in the electrolyte of the positive electrode is 0.8mol L-1KOH concentration of 2.5mol L-1. The zinc-iron flow battery is assembled by the magnetron sputtering tin-plated carbon felt negative electrode for 30 continuous charging and discharging cycles, the coulombic efficiency is 88.67%, and the energy efficiency is 68.31%.
Example 3
The preparation method comprises the following steps:
(1) cleaning an electrode substrate to be plated with ethanol, acetone and water sequentially and respectively, and drying the electrode substrate in a vacuum oven at 80 ℃ for 4 hours;
(2) placing the electrode substrate prepared in the step (1) on a sample table of a magnetron sputtering device which is provided with a target material in advance, and pumping a main sputtering cavity to 1 x 10 by utilizing a mechanical pump and a molecular pump-3Pa; closing a sample baffle, wherein the sputtering gas is argon, the flow is controlled to be 50sccm, and the power is 10W/cm2Keeping the pressure of air at 1Pa, pre-sputtering for 10 minutes, opening a sample baffle plate after glow and power supply indication are relatively stable, starting sputtering to the electrode substrate, and controlling the power at 20W/cm2The sputtering gas is oxygen, the flow is controlled at 50sccm, and the compressed gas is maintained at 1 Pa; and after the sputtering is finished, taking out the sample for use. The sputtering thickness was-1 μm.
And (3) assembling the alkaline zinc-zinc flow battery by using the carbon felt after magnetron sputtering tinning as a negative electrode, wherein the positive electrode part of the alkaline zinc-zinc flow battery consists of a zinc plate and the carbon felt. The polyether sulfone porous membrane is used as a diaphragm, the graphite plate is used as a current collecting plate, and the effective area of the electrodeAbout 36cm2The current density is 80mA/cm2The concentration of zincate radicals in the electrolyte is 0.4mol L-1The NaOH concentration is 2.2mol L-1. The 100-time circulation coulombic efficiency of the zinc-zinc symmetrical flow battery assembled by the magnetron sputtering tinned carbon felt negative electrode is higher than 70%.
And (3) assembling the alkaline zinc-iron flow battery by using the carbon felt after magnetron sputtering tinning as a negative electrode, wherein the positive electrode part of the alkaline zinc-iron flow battery is formed by the carbon felt. The polyether sulfone porous membrane is used as a diaphragm, the graphite plate is used as a current collecting plate, and the effective area of the electrode is about 36cm2The current density is 80mA/cm2The concentration of zincate radicals in the negative electrolyte is 0.4mol L-1The NaOH concentration is 2.2mol L-1(ii) a The concentration of sodium ferrocyanide in the electrolyte of the positive electrode is 0.8mol L-1KOH concentration of 2.5mol L-1. The zinc-iron flow battery is assembled by magnetron sputtering tin-plated carbon felt negative electrodes for 30 continuous charging and discharging cycles, the coulombic efficiency is 92.61%, and the energy efficiency is 71.63%.
As can be seen from fig. 1, tin nanoparticles are uniformly loaded on the carbon felt fibers, and the original structure of the carbon fibers is not damaged.
The carbon felt fiber after tinning in fig. 2 can enable the deposition of zinc to be more compact and smoother, and zinc grows along the carbon felt fiber, so that the binding force between zinc particles and an electrode is increased, and the zinc particles can be effectively prevented from being separated from the electrode to form dead zinc, so that the coulomb efficiency is reduced.
Fig. 3 shows that the overpotential of charging of the carbon felt electrode after tin plating is significantly lower than that of the carbon felt without any treatment, that is, the carbon felt after tin plating has the effect of reducing the overpotential of zinc deposition.
The coulombic efficiency during cycling of the tin-plated carbon felt negative electrode of fig. 4 is significantly higher than that of the carbon felt negative electrode without any treatment. Further, the tin-plated carbon felt cathode can effectively improve the electrochemical performance of the zinc cathode by controlling the compact and uniform deposition of zinc.
The tin-plated carbon felt cathode in fig. 5 has significantly better cycling stability in a zinc-iron flow battery system than the carbon felt without any treatment and has significant advantages in charging overpotential.
FIG. 6 shows that coulomb efficiency and energy efficiency of the carbon felt cathode after tin plating are remarkably improved. The improvement of the performance of the zinc-based battery by the tin-plated carbon felt is verified in a zinc-iron flow battery system.
Claims (8)
1. A zinc-based battery negative electrode, characterized by: depositing one or more than two target materials of metal, metal alloy and metal oxide on an electrode substrate by a magnetron sputtering method to obtain a zinc-based flow battery cathode;
the metal is one or more than two of magnesium, aluminum, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, tin, lead, bismuth and silver;
the metal alloy is two or more than three of magnesium, aluminum, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, tin, lead, bismuth and silver;
the preparation method comprises the following steps:
(1) cleaning an electrode substrate to be plated with ethanol, acetone and water sequentially and respectively, and then drying the electrode substrate in a vacuum oven at the temperature of 30-100 ℃ for 2-12 hours;
(2) placing the electrode substrate prepared in the step (1) on a sample table of a magnetron sputtering device which is provided with a target material in advance, and pumping a main sputtering cavity to 1 x 10 by utilizing a mechanical pump and a molecular pump-4~5×10-2Pa; closing the sample baffle, controlling the flow of the sputtering gas to be 5-150 sccm and the power to be 5-30W/cm2Keeping the pressure of air at 0.1-15 Pa, pre-sputtering for 2-30 minutes, opening a sample baffle plate after glow and power indication are stable, starting sputtering to an electrode substrate, and controlling the power at 10-100W/cm2Controlling the flow rate of the sputtering gas to be 20-150 sccm and maintaining the pressure of the compressed gas to be 0.1-15 Pa; and after the sputtering is finished, taking out the sample for use.
2. A zinc-based battery negative electrode according to claim 1, wherein: the electrode substrate comprises one or more than two of copper foil, aluminum foil, nickel foil, titanium foil, iron foil, zinc foil, silver foil, gold-silver alloy foil, foamed copper, foamed nickel, foamed titanium, porous gold foil, carbon paper, carbon cloth, carbon fiber, carbon felt, graphite electrode and glassy carbon electrode.
3. A zinc-based battery negative electrode according to claim 1, wherein: the deposition atmosphere is one or more than two of argon, nitrogen, oxygen and hydrogen.
4. A method of making a negative electrode for a zinc-based battery according to any of claims 1 to 3, characterized in that: the preparation method comprises the following steps:
(1) cleaning an electrode substrate to be plated with ethanol, acetone and water sequentially and respectively, and then drying the electrode substrate in a vacuum oven at the temperature of 30-100 ℃ for 2-12 hours;
(2) placing the electrode substrate prepared in the step (1) on a sample table of a magnetron sputtering device which is provided with a target material in advance, and pumping a main sputtering cavity to 1 x 10 by utilizing a mechanical pump and a molecular pump-4~5×10-2Pa; closing the sample baffle, controlling the flow of the sputtering gas to be 5-150 sccm and the power to be 5-30W/cm2Keeping the pressure of air at 0.1-15 Pa, pre-sputtering for 2-30 minutes, opening a sample baffle plate after glow and power indication are stable, starting sputtering to an electrode substrate, and controlling the power at 10-100W/cm2Controlling the flow rate of the sputtering gas to be 20-150 sccm and maintaining the pressure of the compressed gas to be 0.1-15 Pa; and after the sputtering is finished, taking out the sample for use.
5. The method of claim 4, wherein: the thickness of the deposition layer is 10 nm-5 μm.
6. Use of a negative electrode of a zinc-based battery according to any of claims 1 to 5 in a zinc-based battery.
7. Use according to claim 6, characterized in that: the zinc-based battery includes an aqueous and/or organic zinc ion battery, a zinc-cerium battery, a zinc-chlorine battery, a zinc-iodine battery, a zinc-bromine battery, a zinc-vanadium battery, a zinc-iron battery, a zinc-nickel battery, or a zinc-air battery.
8. Use according to claim 6 or 7, characterized in that:
the zinc-based battery negative electrode is an electrode with a zinc electrochemical crystallization regulation function, and can effectively prevent the shape of the zinc electrode from being seriously changed, inhibit the growth of dendritic crystals and ensure that metal zinc is more compactly and uniformly deposited.
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| CN112290007B (en) * | 2020-10-27 | 2021-08-20 | 燕山大学 | Preparation method of zinc-copper alloy cathode with self-supporting structure |
| CN114551911B (en) * | 2020-11-25 | 2023-09-19 | 中国科学院大连化学物理研究所 | Preparation and application of negative electrode structure for zinc-based flow battery |
| CN112968146B (en) * | 2021-02-01 | 2022-06-03 | 厦门大学 | Preparation method of long-cycle secondary zinc battery cathode titanium nitride coating |
| CN113036152B (en) * | 2021-03-08 | 2022-08-23 | 山东大学 | High-energy-density and high-safety zinc metal battery without negative electrode and preparation method and application thereof |
| CN113972351A (en) * | 2021-10-22 | 2022-01-25 | 中南大学 | Zinc alloy cathode and preparation method and application thereof |
| CN114141545A (en) * | 2021-10-29 | 2022-03-04 | 海南大学 | Cathode-free zinc ion hybrid capacitor and preparation method thereof |
| CN114094035B (en) * | 2021-11-16 | 2023-08-22 | 厦门大学 | Preparation method of high-cycle stable secondary zinc battery negative electrode aluminum zinc alloy coating |
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