CN112968146A - Preparation method of titanium nitride coating of negative electrode of long-cycle secondary zinc battery - Google Patents

Preparation method of titanium nitride coating of negative electrode of long-cycle secondary zinc battery Download PDF

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CN112968146A
CN112968146A CN202110136980.8A CN202110136980A CN112968146A CN 112968146 A CN112968146 A CN 112968146A CN 202110136980 A CN202110136980 A CN 202110136980A CN 112968146 A CN112968146 A CN 112968146A
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zinc
titanium nitride
nitride coating
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王周成
郑加贤
梁汉锋
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Xiamen University
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Abstract

A preparation method of a titanium nitride coating of a cathode of a long-cycle secondary zinc battery relates to a secondary zinc battery. The method comprises the following steps: polishing a zinc electrode substrate, sequentially ultrasonically cleaning the substrate by using acetone, ethanol and deionized water, and then drying the substrate in a vacuum oven; then placing the mixture in a cavity of magnetron sputtering equipment and bombarding and cleaning the mixture by using an ion source; heating the chamber and the sample stage, and using the machineThe mechanical pump and the molecular pump vacuumize the chamber; introducing Ar gas, pre-sputtering a titanium metal target on the substrate, and introducing N2Sputtering a titanium metal target material, and depositing a titanium nitride coating on the zinc electrode substrate to obtain the long-circulation secondary zinc battery cathode titanium nitride coating. The titanium nitride coating is used for zinc cathode protection, and the preparation of the zinc cathode with long service life and corrosion resistance is realized. The titanium nitride coating with smaller lattice mismatch degree with zinc metal can guide zinc ions to uniformly nucleate and grow on the surface of the negative electrode in an epitaxial electrodeposition mode, and effectively inhibits dendritic crystal generation and corrosion. The prepared secondary zinc battery has high cycle stability and safety.

Description

Preparation method of titanium nitride coating of negative electrode of long-cycle secondary zinc battery
Technical Field
The invention relates to a secondary zinc battery, belongs to the field of novel chemical power sources, and particularly relates to a preparation method of a long-cycle secondary zinc battery cathode titanium nitride coating.
Background
Energy storage carriers for zinc ion batteries such as zinc-manganese batteries, nickel-zinc batteries, and silver-zinc batteries play an important role in human daily life in the past decades. However, zinc metal cannot be applied to the secondary battery market on a large scale because it is liable to cause dendrite short-circuiting and the like upon cyclic charge and discharge under alkaline or acidic electrolyte conditions. Today the secondary battery market is mainly occupied by lithium ion batteries, lead acid batteries and fuel cells. However, lithium ion batteries have the disadvantages of flammability, explosiveness, high cost and the like, lead-acid batteries have great pollution to the environment, and fuel cell technologies are not yet mature and have complex working conditions. Therefore, development of a secondary battery having environmental protection and excellent performance is urgently required.
Zinc is used as a nontoxic, harmless, safe and cheap metal to return to the field of vision of people. In recent years, a large number of scientists have conducted intensive research on a series of problems such as dendrite and corrosion of the negative electrode in the zinc battery. Strategies have been proposed to direct zinc ion deposition behavior to suppress dendrites and corrosion by means of protective coatings, modified separators, electrolyte additives, and the like. Among these, functional protective coatings are certainly the better choice. Not only can avoid using expensive and combustible organic electrolyte, but also can avoid using the problems of easy breakage and the like of the modified diaphragm. More importantly, the zinc ion deposition can be effectively guided by adjusting the microstructure and the crystal lattice orientation of the protective coating. Lynden a. Archer et al achieve directing zinc to be regularly electrodeposited epitaxially on graphene coatings by preparing graphene coatings with small lattice mismatching values with zinc metal (lattice mismatching <25% is considered a prerequisite for directing zinc to achieve epitaxial electrodeposition) (Zheng Jingxu, lynden a. Archer, et al, science,366 (2019) 6465). Although the method fundamentally inhibits the growth of zinc dendrites, the method is not suitable for the preparation of large-capacity zinc ion batteries because the zinc is directly contacted with the electrolyte and is easy to corrode and passivate. In addition to this, there is currently no other way of achieving both the guiding of the zinc epitaxial electrodeposition and the simultaneous protection of the zinc from the electrolyte. The protective coating prepared up to now still has the problems of poor binding force with an electrode, irregular zinc ion deposition, easy deformation of the coating and the like, and seriously hinders the large-scale application of the secondary zinc ion battery.
Aiming at the problems, the development of a protective coating which has strong binding force, is stable and reliable and can guide the regular deposition of zinc ions on the surface of an electrode is very important for prolonging the service life of the secondary zinc battery. The preparation of nitride films by magnetron sputtering has the advantages of controllable structure, uniform film layer composition, stable quality and the like, and is used for preparing a large amount of nitride films. The invention proves that if the titanium nitride coating has smaller lattice mismatch degree with zinc metal, the problems of dendritic crystal generation, corrosion and the like can be effectively inhibited, and the cycle life of the zinc cathode is greatly prolonged. Therefore, the titanium nitride coating which is prepared by magnetron sputtering and has smaller lattice mismatch with zinc metal is used for zinc electrode protection, and the method has important significance for prolonging the cycle life of a zinc cathode and promoting the large-scale application of a secondary zinc ion battery.
Disclosure of Invention
The invention aims to provide a preparation method of a long-cycle secondary zinc battery cathode titanium nitride coating, which is used for guiding zinc to carry out epitaxial electrodeposition on the surface of the zinc so that the zinc has long cycle life and corrosion resistance.
The invention comprises the following steps:
1) Polishing a zinc electrode substrate, sequentially ultrasonically cleaning the zinc electrode substrate by using acetone, ethanol and deionized water, and then drying the zinc electrode substrate in a vacuum oven;
2) Placing the zinc electrode substrate obtained in the step 1) in a cavity of a magnetron sputtering device, and bombarding and cleaning the zinc electrode substrate by using an ion source to obtain a pretreated zinc electrode substrate;
3) Heating the chamber and the sample stage, and vacuumizing the chamber by using a mechanical pump and a molecular pump; introducing Ar gas, pre-sputtering a titanium metal target on a zinc electrode substrate, and introducing N 2 And sputtering a titanium metal target to obtain the titanium nitride coating of the cathode of the long-cycle secondary zinc battery.
In the step 1), the zinc electrode substrate comprises at least one of zinc foil, foamed zinc, metal zinc sheet, porous zinc and zinc alloy electrode with any thickness and any area specification; the grinding can be performed by 400-7000-mesh sand paper; the drying temperature can be 20-80 ℃, and the drying time can be 0.5-5 h.
In the step 2), the bombardment cleaning by the ion source can adopt a Hall ion source to clean the substrate for 1-10 min, and the environmental pressure is 1.5 multiplied by 10 -2 Pa, ar flow rate of 15sccm, substrate bias voltage of-125V, cathode current of 32A, cathode voltage of 30V, anode current of 4.5A, and anode voltage of 60V.
In the step 3), the heating temperature can be 100-200 ℃; the vacuum pumping of the cavity can be carried out to less than or equal to 1.0 multiplied by 10 -2 Pa; the specific conditions for introducing Ar gas and pre-sputtering the titanium metal target material can be as follows: setting the flow rate of Ar at 30-45 sccm, adjusting the deposition pressure in the chamber to 1.0-1.3 Pa, adjusting the power of the titanium target to 150-250W, and pre-sputtering for 2-15 min; the introduction of N 2 The specific conditions for sputtering the titanium metal target material may be: introduction of N 2 Control of different N 2 The flow rate partial pressure ratio is 2-60%, and the total flow rate of the gas is 50-80 sccm; adjusting the power of the titanium target material to 200-300W, keeping the sputtering pressure at 0.5-4.5 Pa, and keeping the sputtering time at 5-150 min; the titanium nitride coating may be deposited to a thickness of 100 to 4000nm, preferably 100 to 2000nm.
The titanium nitride coating for the long-life corrosion-resistant zinc electrode is deposited on the electrode substrate in a specific atmosphere by a magnetron sputtering method, and the zinc electrode plated with the titanium nitride coating can effectively guide zinc ions in electrolyte to carry out epitaxial electrodeposition on the surface of the electrode due to smaller lattice mismatch with zinc metal, promote uniform nucleation and growth of zinc and effectively inhibit generation of dendritic crystals. Meanwhile, the titanium nitride coating with good chemical stability can prevent zinc metal covered by the coating from being further corroded by electrolyte. Thus achieving long cycle life and corrosion resistance of the zinc cathode.
Compared with the prior art, the invention has the following outstanding advantages:
the titanium nitride coating is used for zinc cathode protection, and the preparation of the corrosion-resistant zinc cathode with long service life is realized. The titanium nitride coating with smaller lattice mismatch degree with zinc metal can guide zinc ions to uniformly nucleate and grow on the surface of the negative electrode in an epitaxial electrodeposition mode, and effectively inhibits dendritic crystal generation and corrosion. Sputtering under 0.5-4.5 Pa and N 2 The zinc cathode protected by the titanium nitride coating prepared has high cycling stability under the conditions that the flow partial pressure percentage is 2-60%, the sputtering power and the sputtering time are respectively 200-300W and 5-150 min. In a symmetrical cell, the test current density was 0.5mA cm -2 The zinc electrode achieves stable cycling for greater than 3000 hours and cycling capability greater than 400 times in a zinc-manganese dioxide cell.
Drawings
FIG. 1 is a blank zinc foil XRD spectrum.
Figure 2 is an XRD spectrum of the titanium nitride coating.
Fig. 3 is an SEM topography of the comparative and example zinc foils before and after 10h cycling in a symmetric cell.
FIG. 4 shows comparative and example zinc foils as Zn-MnO 2 Cycle number-discharge specific capacity diagram of zinc-manganese cell at cell cathode.
FIG. 5 shows comparative and example zinc foils as Zn-MnO 2 Discharge specific capacity map of zinc-manganese cell at 50 cycles of cell cathode.
FIG. 6 shows the zinc foils of comparative example and example as positive and negative electrodes of a symmetrical cell at 0.5mA cm -2 Statistical plot of cycle duration at current density.
Detailed Description
The following examples are provided to further illustrate the present invention in conjunction with the accompanying drawings. It should be noted that the present embodiment is only for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and that the skilled person in the art may make some insubstantial modifications and adaptations in accordance with the present invention.
Comparative example 1
1. Blank zinc cathode preparation
The thickness of the mixture is 0.1mm, and the area is 1.32cm 2 The zinc foil is polished by 400-mesh sand paper, then is ultrasonically cleaned by acetone, ethanol and deionized water in sequence, and is dried in a vacuum oven at 30 ℃ for 1 hour.
2. Preparation of manganese dioxide electrode
1.4g of manganese dioxide powder, 0.4g of acetylene black and 0.2g of polyvinylidene fluoride (PVDF) powder were mixed uniformly, 2mL of N-methylpyrrolidone (NMP) solution was added, and the active material was dispersed by magnetic stirring for 12 hours.
1. Characterization of the Zinc foil phase Structure by XRD
FIG. 1 is an XRD spectrum of a blank zinc foil demonstrating the preferential orientation of the zinc foil to the (101) crystal plane (Zn: PDF # 65-5973).
2. Adopting SEM to observe blank zinc foil structure
Fig. 3 (a) is an SEM surface topography before and after the blank zinc foil is used in a symmetrical battery for charging and discharging. The surface of the zinc foil before reaction is relatively flat and smooth, and obvious corrosion pits or other impurities do not appear. The blank zinc foil is assembled into a symmetrical battery at 0.5mA cm -2 After 23h of cycling at the current density of (c), it can be seen from fig. 3 (b) that a large amount of by-products and protruding plate-like dendrites are formed.
3、Zn-MnO 2 Battery performance testing
And assembling the blank zinc foil as a negative electrode and the manganese dioxide electrode as a positive electrode to form a button battery of CR-2032 type for testing the cycle performance of the zinc-manganese battery. In the CR-2032 cell, GF/D, manufactured by Whatman corporation, was used as positive and negative separators. The electrolyte contains 2mol/L ZnSO 4 And 0.1mol/L MnSO 4 Solution 100. Mu.L. Setting the test parameters to constant currentAnd charging and constant-current discharging, wherein the upper limit charging voltage is 1800mV, and the lower limit discharging voltage is 900mV. Fig. 4 is a graph of cycle number and corresponding discharge specific capacity of a blank zinc foil-based zinc-manganese battery with a negative electrode, and it can be seen from the graph that the capacity of the zinc-manganese battery rapidly decays within 200 cycles when the blank zinc foil is used as the negative electrode. FIG. 5 is a corresponding charge-discharge curve diagram, in which the specific discharge capacity of the battery after 50 charging and discharging cycles is about 53mAh g when the blank zinc foil is used as the negative electrode -1 。
4. Zn-Zn symmetrical battery performance test
And assembling the blank zinc foil into a CR-2032 type symmetrical battery to perform a cycle stability test. In the CR-2032 cell, GF/D, manufactured by Whatman, was used as a separator for the cathode and anode. The electrolyte used is 2mol/L ZnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 0.5mA cm -2 . Fig. 6 demonstrates the effective cycle time of the blank zinc foil at the current densities described above, which is about 23 hours, and it can be seen that the blank protected by the titanium nitride coating failed in a shorter period of time.
Example 1
1. Pretreatment of substrate
(1) The thickness of the mixture is 0.1mm, and the area is 1.32cm 2 The zinc foil is polished by 400-mesh sand paper, then is ultrasonically cleaned by acetone, ethanol and deionized water in sequence, and is dried in a vacuum oven at 30 ℃ for 1 hour.
(2) And (2) placing the electrode substrate prepared in the step (1) in a cavity of a magnetron sputtering device, and performing bombardment cleaning treatment by using an ion source. Cleaning the substrate with Hall ion source for 2min at an environmental pressure of 1.5 × 10 -2 Pa, argon flow of 15sccm, substrate bias of-125V, cathode current of 32A, cathode voltage of 30V, anode current of 4.5A, and anode voltage of 60V.
2. Titanium nitride coating preparation
Heating the chamber and the sample stage to 200 deg.C, and vacuumizing the chamber to less than or equal to 1.0 × 10 with a mechanical pump and a molecular pump - 2 Pa; introducing Ar gas, setting the flow rate to be 45sccm, and adjusting the deposition pressure in the chamber to 1.0Pa; adjusting the power of the titanium target material to 250W, and carrying out pre-sputtering for 10min; introducing N after the pre-sputtering is finished 2 Control N 2 The partial pressure percentage is 60 percent, and the total gas flow is 60sccm; the power of the titanium target is adjusted to 300W, and the sputtering pressure is maintained at 0.5Pa. The sputtering time was 150min. The thickness of the resulting coating was approximately 2140nm.
3. Preparation of manganese dioxide electrode
Manganese dioxide powder 1.4g, acetylene black 0.4g and polyvinylidene fluoride (PVDF) powder 0.2g were mixed uniformly, and 2mL of N-methylpyrrolidone (NMP) solution was added and magnetic stirring was carried out for 12 hours to disperse the active substance.
4. Characterization of titanium nitride coating phase Structure by XRD
The corresponding titanium nitride peak can not be observed because the zinc base peak is too strong. Thus, titanium nitride films were deposited on silicon substrates using conditions consistent with step 2. FIG. 2 is an XRD spectrum of a titanium nitride film, which shows that the titanium nitride coating has a sodium chloride crystal form and preferentially grows along a (111) crystal plane.
5. Observing zinc foil structure by SEM
And (c) in the figure, 3, is an SEM surface topography of the zinc foil prepared in the step 2 before being used for charging and discharging in a symmetrical battery, and the surface of the zinc foil is relatively flat and is uniformly covered by titanium nitride particles. Fig. 3 (d) shows that zinc grows predominantly vertically on top of the titanium nitride coating. The main reason is that the lattice mismatch of zinc is close to that of titanium nitride coatings.
The lattice mismatch degree calculation formula of the zinc and titanium nitride coating is as follows:
Figure BDA0002927082940000051
a:The lattice parameter of Zn,b:The lattice parameter of TiN film。
the calculated lattice mismatch between the zinc and titanium nitride coatings is shown in table 1.
TABLE 1
Figure BDA0002927082940000052
Although the mismatch between the (200) and (111) planes and the zinc (101) plane is within 25%, the mismatch between the titanium (200) and zinc (101) planes is significantly lower (1.4%) than the mismatch between the titanium (111) and zinc (101) planes (17.2%).
6.Zn-MnO 2 Battery performance testing
And (3) assembling the zinc foil prepared in the step (2) as a negative electrode and a manganese dioxide electrode as a positive electrode into a CR-2032 type zinc-manganese button battery for cycle performance test. In the CR-2032 cell, GF/D, manufactured by Whatman corporation, was used as positive and negative separators. The electrolyte used is 2mol/L ZnSO 4 And 0.1mol/L MnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, the upper limit charging voltage is 1800mV, and the lower limit discharging voltage is 900mV. Fig. 4 is a graph of the cycle number and the corresponding discharge specific capacity of the zinc-manganese battery using the zinc foil prepared in step 2 as the negative electrode, and the zinc-manganese battery can be cycled for 400 times. FIG. 5 is a corresponding charge-discharge curve chart, wherein the specific discharge capacity of the battery after 50 charging and discharging circles is about 140mAhg when the zinc foil prepared in step 2 is used as the negative electrode -1 。
Performance test of Zn-Zn symmetrical battery
And (3) assembling the zinc foil prepared in the step (2) into a CR-2032 type symmetrical battery to perform a cycle stability test. In the CR-2032 cell, GF/D, manufactured by Whatman, was used as separators for the positive and negative electrodes. The electrolyte used is 2mol/L ZnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 0.5mA cm -2 . Fig. 6 demonstrates that the effective cycle time of the zinc foil prepared in step 2 under the current density is over 200h, and the titanium nitride coating can obviously improve the cycle performance of the zinc cathode.
Example 2
1. Pretreatment of substrate
(1) The thickness of the mixture is 0.1mm, and the area is 1.32cm 2 The zinc foil is polished by 400-mesh sand paper, then is ultrasonically cleaned by acetone, ethanol and deionized water in sequence, and is dried in a vacuum oven at 30 ℃ for 1 hour.
(2) And (3) placing the electrode substrate prepared in the step (1) in a cavity of a magnetron sputtering device for ion source bombardment cleaning treatment. Cleaning the substrate for 2min by adopting Hall ion source and environment pressureIs 1.5X 10 -2 Pa, ar flow rate of 15sccm, substrate bias voltage of-125V, cathode current of 32A, cathode voltage of 30V, anode current of 4.5A, and anode voltage of 60V.
2. Titanium nitride coating preparation
Heating the chamber and the sample stage to 200 deg.C, and vacuumizing the chamber to less than or equal to 1.0 × 10 with a mechanical pump and a molecular pump - 2 Pa; introducing Ar gas, setting the flow rate to be 45sccm, and adjusting the deposition pressure in the chamber to 1.0Pa; adjusting the power of the titanium target material to 250W, and carrying out pre-sputtering for 10min; introducing N after the pre-sputtering is finished 2 Control N 2 The partial pressure percentage is 15 percent, and the total gas flow is 60sccm; adjusting the power of the titanium target to 250W, and maintaining the sputtering pressure at 2.0Pa; the sputtering time was 60min. The thickness of the resulting coating was approximately 1020nm.
3. Preparation of manganese dioxide electrode
The same as in example 1.
4. Characterization of the phase Structure of titanium nitride coatings by XRD
FIG. 2 is an XRD spectrum of a titanium nitride film showing that the titanium nitride coating prepared under this condition shows two crystal planes of (200) and (111).
5. Observing zinc foil structure by SEM
And (e) in fig. 3, the SEM surface topography of the zinc foil prepared in step 2 is shown before charging and discharging in a symmetrical battery, and the zinc foil surface is relatively flat and uniformly covered with titanium nitride particles. Fig. 3 (f) shows that zinc is deposited predominantly epitaxially on top of the titanium nitride coating, embodied as growth parallel to the electrode plane. The main reason is that the lattice mismatch of zinc is close to that of titanium nitride coating, and the calculation formula of the lattice mismatch is shown in table 1.
6.Zn-MnO 2 Battery performance testing
And (3) assembling the zinc foil prepared in the step (2) as a negative electrode and the manganese dioxide electrode as a positive electrode to form a CR-2032 type zinc-manganese button battery for cycle performance test. In the CR-2032 cell, GF/D manufactured by Whatman was used as positive and negative electrode separators. The electrolyte is 2mol/L ZnSO 4 And 0.1mol/L MnSO 4 Solution 100. Mu.L. The test parameters were set to constant current charging and constant current discharging,the upper limit charging voltage is 1800mV, and the lower limit discharging voltage is 900mV. Fig. 4 is a graph of the cycle number and the corresponding discharge specific capacity of the zinc-manganese battery using the zinc foil prepared in step 2 as the negative electrode, and the corresponding zinc-manganese battery can stably cycle for 400 times. FIG. 5 is a corresponding charge-discharge curve chart, wherein the discharge capacity of the battery after 50 charging and discharging circles is about 190mAhg when the zinc foil prepared in step 2 is used as the negative electrode -1 。
Test of Zn-Zn symmetric Battery Performance
And (3) assembling the zinc foil prepared in the step (2) into a CR-2032 type symmetrical battery to perform a cycle stability test. In the CR-2032 cell, GF/D, manufactured by Whatman, was used as a separator for the cathode and anode. The electrolyte used is 2mol/L ZnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 0.5mA cm -2 . Fig. 6 demonstrates that the effective cycle time of the zinc foil produced in step 2 at the current density described above exceeds 1450h.
Example 3
1. Pretreatment of substrate
(1) The thickness of the film is 0.1mm, and the area is 1.32cm 2 The zinc foil is polished by 400-mesh sand paper, then is ultrasonically cleaned by acetone, ethanol and deionized water in sequence, and is dried in a vacuum oven at 30 ℃ for 1 hour.
(2) And (3) placing the electrode substrate prepared in the step (1) in a cavity of a magnetron sputtering device for ion source bombardment cleaning treatment. Cleaning the substrate with Hall ion source for 2min at an environmental pressure of 1.5 × 10 -2 Pa, ar flow of 15sccm, matrix bias voltage of-125V, cathode current of 32A, cathode voltage of 30V, anode current of 4.5A, and anode voltage of 60V.
2. Titanium nitride coating preparation
Placing the electrode substrate prepared in the pretreatment step into a cavity of a magnetron sputtering device, heating the cavity and a sample stage to 200 ℃, and vacuumizing the cavity to be less than or equal to 1.0 multiplied by 10 by using a mechanical pump and a molecular pump -2 Pa; introducing Ar gas, setting the flow rate to be 45sccm, and adjusting the deposition pressure in the chamber to 1.0Pa; adjusting the power of the titanium target material to 250W, and carrying out pre-sputtering for 10min; introducing N after the pre-sputtering is finished 2 Control N 2 Partial pressure percentage of 10%, total flow of gasIn an amount of 60sccm; adjusting the power of the titanium target material to 200W, starting sputtering, and maintaining the sputtering pressure at 3.0Pa; the sputtering time was 30min. The thickness of the resulting coating was about 620nm.
3. Preparation of manganese dioxide electrode
The same as in example 1.
4. Characterization of the Zinc foil phase Structure by XRD
As shown in the XRD pattern of the titanium nitride film of fig. 2, the prepared titanium nitride coating was predominantly in the (200) lattice orientation.
5. Observing zinc foil structure by SEM
And (g) in fig. 3, the SEM surface topography of the zinc foil prepared in step 2 is shown before charging and discharging in a symmetrical battery, and the zinc foil surface is relatively flat and uniformly covered with titanium nitride particles. Fig. 3 (h) is an SEM topography of the electrode after cyclic charge and discharge compared to the blank zinc foil reacted under the same conditions in comparative example 1. The nitrogen flow partial pressure was 10% and the sputtering pressure was 3.0 Pa. The zinc is uniformly epitaxially deposited on the surface of the titanium nitride film, and no obvious dendritic crystal appears.
6.Zn-MnO 2 Battery performance testing
And (3) assembling the zinc foil prepared in the step (2) as a negative electrode and a manganese dioxide electrode as a positive electrode into a CR-2032 type zinc-manganese button battery for cycle performance test. In the CR-2032 cell, GF/D, manufactured by Whatman corporation, was used as positive and negative separators. The electrolyte used is 2mol/L ZnSO 4 And 0.1mol/L MnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, the upper limit charging voltage is 1800mV, and the lower limit discharging voltage is 900mV. Fig. 4 is a graph of the cycle number and the corresponding discharge specific capacity of the zinc-manganese battery using the zinc foil prepared in step 2 as the negative electrode, and the corresponding zinc-manganese battery can stably cycle for 400 times. FIG. 5 is a corresponding charge-discharge curve chart, wherein the discharge capacity of the battery after 50 charging and discharging circles is about 130mAh g when the zinc foil prepared in step 2 is used as the negative electrode -1 。
Performance test of Zn-Zn symmetrical battery
And (3) assembling the zinc foil prepared in the step (2) into a CR-2032 type symmetrical battery to perform a cycle stability test. In the CR-2032 cell, the product was made by Whatman corporationGF/D as the cathode/anode separator. The electrolyte used is 2mol/L ZnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 0.5mA cm -2 . Fig. 6 demonstrates that the effective cycle time of the zinc foil produced in step 2 at the current density described above is over 3000h.
Example 4
1. Pretreatment of substrate
(1) The thickness of the mixture is 0.1mm, and the area is 1.32cm 2 The zinc foil is polished by 400-mesh sand paper, then is ultrasonically cleaned by acetone, ethanol and deionized water in sequence, and is dried in a vacuum oven at 30 ℃ for 1 hour.
(2) And (3) placing the electrode substrate prepared in the step (1) in a cavity of a magnetron sputtering device for ion source bombardment cleaning treatment. Cleaning the substrate with Hall ion source for 2min at an environmental pressure of 1.5 × 10 -2 Pa, ar flow rate of 15sccm, substrate bias voltage of-125V, cathode current of 32A, cathode voltage of 30V, anode current of 4.5A, and anode voltage of 60V.
2. Titanium nitride coating preparation
Placing the electrode substrate prepared in the pretreatment step into a cavity of a magnetron sputtering device, heating the cavity and a sample stage to 200 ℃, and vacuumizing the cavity to be less than or equal to 1.0 multiplied by 10 by using a mechanical pump and a molecular pump -2 Pa; introducing Ar gas, setting the flow rate to be 45sccm, and adjusting the deposition pressure in the chamber to 1.0Pa; adjusting the power of the titanium target material to 250W, and carrying out pre-sputtering for 10min; introducing N after the pre-sputtering is finished 2 Control N 2 The partial pressure percentage is 2 percent, and the total gas flow is 60sccm; adjusting the power of the titanium target material to 200W, starting sputtering, and maintaining the sputtering pressure at 4.5Pa; the sputtering time was 30min. The thickness of the resulting coating was about 510nm.
3. Preparation of manganese dioxide electrode
The same as in example 1.
4. Characterization of the Zinc foil phase Structure by XRD
As shown in the XRD pattern of the titanium nitride film of fig. 2, the titanium nitride coating was prepared with a predominantly (200) lattice orientation.
5. Observing zinc foil structure by SEM
And (i) in fig. 3, the surface appearance image of the SEM of the zinc foil prepared in step 2 is shown before charging and discharging in a symmetrical battery, and the surface of the zinc foil is relatively flat and uniformly covered with titanium nitride particles. Fig. 3 (j) is an SEM topography of the electrode after cyclic charge and discharge compared to the blank zinc foil reacted under equivalent conditions in comparative example 1. The nitrogen flow partial pressure is 2%, and the sputtering pressure is 4.5 Pa. The zinc is uniformly deposited in an epitaxial mode on the surface of the titanium nitride film, and no obvious dendritic crystal appears.
6.Zn-MnO 2 Battery performance testing
And (3) assembling the zinc foil prepared in the step (2) as a negative electrode and a manganese dioxide electrode as a positive electrode into a CR-2032 type zinc-manganese button battery for cycle performance test. In the CR-2032 cell, GF/D, manufactured by Whatman corporation, was used as positive and negative separators. The electrolyte used is 2mol/L ZnSO 4 And 0.1mol/L MnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, the upper limit charging voltage is 1800mV, and the lower limit discharging voltage is 900mV. Fig. 4 is a graph of the cycle number and the corresponding discharge specific capacity of the zinc-manganese battery using the zinc foil prepared in step 2 as the negative electrode, and the corresponding zinc-manganese battery can stably cycle for 400 times. FIG. 5 is a corresponding charge-discharge curve chart, in which the discharge capacity of the battery after 50 charging and discharging circles is about 170mAh g when the zinc foil prepared in step 2 is used as the negative electrode -1 。
Test of Zn-Zn symmetric Battery Performance
And assembling the blank zinc foil into a CR-2032 type symmetrical battery to perform a cycle stability test. In the CR-2032 cell, GF/D, manufactured by Whatman, was used as a separator for the cathode and anode. The electrolyte used is 2mol/L ZnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 0.5mA cm -2 . Fig. 6 demonstrates that the effective cycle time of the zinc foil produced in step 2 at the current density described above is over 2490h.
Example 5
1. Pretreatment of substrate
(1) The thickness of the mixture is 0.1mm, and the area is 1.32cm 2 The zinc foil is polished by 2000-mesh sand paper, then is ultrasonically cleaned by acetone, ethanol and deionized water in sequence, and is dried in a vacuum oven at the temperature of 80 ℃ for 0.5h.
(2) And (3) placing the electrode substrate prepared in the step (1) in a cavity of a magnetron sputtering device for ion source bombardment cleaning treatment. The same as in example 1.
2. Titanium nitride coating preparation
Placing the electrode substrate prepared in the pretreatment step into a cavity of a magnetron sputtering device, heating the cavity and a sample stage to 200 ℃, and vacuumizing the cavity to be less than or equal to 1.0 multiplied by 10 by using a mechanical pump and a molecular pump -2 Pa; introducing Ar gas, setting the flow rate to be 45sccm, and adjusting the deposition pressure in the chamber to 1.0Pa; adjusting the power of the titanium target material to 250W, and carrying out pre-sputtering for 10min; introducing N after the pre-sputtering is finished 2 Control N 2 The partial pressure percentage is 15 percent, and the total gas flow is 60sccm; adjusting the power of the titanium target material to 200W, starting sputtering, and maintaining the sputtering pressure at 2.0Pa; the sputtering time was 5min. The thickness of the resulting coating was about 100nm.
3. Preparation of manganese dioxide electrode
The same as in example 1.
4. Characterization of the Zinc foil phase Structure by XRD
5. Observing zinc foil structure by SEM
6.Zn-MnO 2 Battery performance testing
And (3) assembling the zinc foil prepared in the step (2) as a negative electrode and a manganese dioxide electrode as a positive electrode into a CR-2032 type zinc-manganese button battery for cycle performance test. In the CR-2032 cell, GF/D, manufactured by Whatman corporation, was used as positive and negative separators. The electrolyte used is 2mol/L ZnSO 4 And 0.1mol/L MnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, the upper limit charging voltage is 1800mV, and the lower limit discharging voltage is 900mV.
Performance test of Zn-Zn symmetrical battery
And assembling the blank zinc foil into a CR-2032 type symmetrical battery to perform a cycle stability test. In the CR-2032 cell, GF/D manufactured by Whatman was used as a separator for a cathode and an anode. The electrolyte used is 2mol/L ZnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 0.5mA cm -2 。
Example 6
1. Pretreatment of substrate
(1) The thickness of the mixture is 0.1mm, and the area is 1.32cm 2 The zinc foil is polished by 7000-mesh sand paper, then is ultrasonically cleaned by acetone, ethanol and deionized water in sequence, and is dried in a vacuum oven at 20 ℃ for 5 hours.
(2) And (3) placing the electrode substrate prepared in the step (1) in a cavity of a magnetron sputtering device for ion source bombardment cleaning treatment. The same as in example 1.
2. Titanium nitride coating preparation
Placing the electrode substrate prepared in the pretreatment step into a cavity of a magnetron sputtering device, heating the cavity and a sample stage to 200 ℃, and vacuumizing the cavity to be less than or equal to 1.0 multiplied by 10 by using a mechanical pump and a molecular pump -2 Pa; introducing Ar gas, setting the flow rate to be 45sccm, and adjusting the deposition pressure in the chamber to 1.0Pa; adjusting the power of the titanium target material to 250W, and carrying out pre-sputtering for 10min; introducing N after the pre-sputtering is finished 2 Control N 2 The partial pressure percentage is 2 percent, and the total gas flow is 60sccm; adjusting the power of the titanium target material to 300W, starting sputtering, and maintaining the sputtering pressure at 4.5Pa; the sputtering time was 150min. The thickness of the resulting coating was approximately 4020nm.
3. Preparation of manganese dioxide electrode
The same as in example 1.
4. Characterization of the Zinc foil phase Structure by XRD
5. Observing zinc foil structure by SEM
6.Zn-MnO 2 Battery performance testing
And (3) assembling the zinc foil prepared in the step (2) as a negative electrode and a manganese dioxide electrode as a positive electrode into a CR-2032 type zinc-manganese button battery for cycle performance test. In the CR-2032 cell, GF/D, manufactured by Whatman corporation, was used as positive and negative separators. The electrolyte used is 2mol/L ZnSO 4 And 0.1mol/L MnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, the upper limit charging voltage is 1800mV, and the lower limit discharging voltage is 900mV.
Performance test of Zn-Zn symmetrical battery
Assembling blank zinc foil into CR-2032 type symmetrical electric deviceThe cell was tested for cycling stability. In the CR-2032 cell, GF/D manufactured by Whatman was used as a separator for a cathode and an anode. The electrolyte used is 2mol/L ZnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 0.5mA cm -2 。
Example 7
1. Pretreatment of substrate
(1) The thickness of the mixture is 0.2mm, and the area is 1.32cm 2 The zinc sheet is polished by 400-mesh sand paper, then is ultrasonically cleaned by acetone, ethanol and deionized water in sequence, and is dried in a vacuum oven at the temperature of 80 ℃ for 0.5h.
(2) And (3) placing the electrode substrate prepared in the step (1) in a cavity of a magnetron sputtering device for ion source bombardment cleaning treatment. The same as in example 1.
2. Titanium nitride coating preparation
Placing the electrode substrate prepared in the pretreatment step into a cavity of a magnetron sputtering device, heating the cavity and a sample stage to 200 ℃, and vacuumizing the cavity to be less than or equal to 1.0 multiplied by 10 by using a mechanical pump and a molecular pump -2 Pa; introducing Ar gas, setting the flow rate to be 45sccm, and adjusting the deposition pressure in the chamber to 1.0Pa; adjusting the power of the titanium target material to 250W, and carrying out pre-sputtering for 10min; introducing N after the pre-sputtering is finished 2 Control N 2 The partial pressure percentage is 60 percent, and the total gas flow is 60sccm; adjusting the power of the titanium target material to 300W, starting sputtering, and maintaining the sputtering pressure at 0.5Pa; the sputtering time was 150min. The resulting coating had a thickness of about 2090nm.
3. Preparation of manganese dioxide electrode
The same as in example 1.
4. Characterization of the Zinc foil phase Structure by XRD
5. Observing zinc foil structure by SEM
6.Zn-MnO 2 Battery performance testing
And (3) assembling the zinc foil prepared in the step (2) as a negative electrode and a manganese dioxide electrode as a positive electrode into a CR-2032 type zinc-manganese button battery for cycle performance test. In the CR-2032 cell, GF/D, manufactured by Whatman corporation, was used as positive and negative separators. The electrolyte used is 2mol/L ZnSO 4 And 0.1mol/L MnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, the upper limit charging voltage is 1800mV, and the lower limit discharging voltage is 900mV.
Performance test of Zn-Zn symmetrical battery
And assembling the blank zinc foil into a CR-2032 type symmetrical battery to perform a cycle stability test. In the CR-2032 cell, GF/D, manufactured by Whatman, was used as a separator for the cathode and anode. The electrolyte used is 2mol/L ZnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 0.5mA cm -2 。
Example 8
1. Pretreatment of substrate
(1) The thickness of the film is 0.2mm, and the area is 1.32cm 2 After being polished by 2000-mesh abrasive paper, the zinc sheet is sequentially ultrasonically cleaned by acetone, ethanol and deionized water, and then is dried in a vacuum oven at 30 ℃ for 1 hour.
(2) And (3) placing the electrode substrate prepared in the step (1) in a cavity of a magnetron sputtering device for ion source bombardment cleaning treatment. The same as in example 1.
2. Titanium nitride coating preparation
Placing the electrode substrate prepared in the pretreatment step into a cavity of a magnetron sputtering device, heating the cavity and a sample stage to 200 ℃, and vacuumizing the cavity to be less than or equal to 1.0 multiplied by 10 by using a mechanical pump and a molecular pump -2 Pa; introducing Ar gas, setting the flow rate to be 45sccm, and adjusting the deposition pressure in the chamber to 1.0Pa; adjusting the power of the titanium target material to 250W, and carrying out pre-sputtering for 10min; introducing N after the pre-sputtering is finished 2 Control N 2 The partial pressure percentage is 15 percent, and the total gas flow is 60sccm; adjusting the power of the titanium target to 250W, starting sputtering, and maintaining the sputtering pressure at 2.0Pa; the sputtering time was 60min. The resulting coating had a thickness of about 990nm.
3. Preparation of manganese dioxide electrode
The same as in example 1.
4. Characterization of the Zinc foil phase Structure by XRD
5. Observing zinc foil structure by SEM
6.Zn-MnO 2 Battery performance testing
And (3) assembling the zinc foil prepared in the step (2) as a negative electrode and a manganese dioxide electrode as a positive electrode into a CR-2032 type zinc-manganese button battery for cycle performance test. In the CR-2032 cell, GF/D, manufactured by Whatman corporation, was used as positive and negative separators. The electrolyte used is 2mol/L ZnSO 4 And 0.1mol/L MnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, the upper limit charging voltage is 1800mV, and the lower limit discharging voltage is 900mV.
Performance test of Zn-Zn symmetrical battery
And assembling the blank zinc foil into a CR-2032 type symmetrical battery to perform a cycle stability test. In the CR-2032 cell, GF/D, manufactured by Whatman, was used as a separator for the cathode and anode. The electrolyte used is 2mol/L ZnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 0.5mA cm -2 。
Example 9
1. Pretreatment of substrate
(1) The thickness of the mixture is 0.2mm, and the area is 1.32cm 2 The zinc sheet is polished by 7000-mesh sand paper, then is ultrasonically cleaned by acetone, ethanol and deionized water in sequence, and is dried in a vacuum oven at 30 ℃ for 4.5 hours.
(2) And (3) placing the electrode substrate prepared in the step (1) in a cavity of a magnetron sputtering device for ion source bombardment cleaning treatment. The same as in example 1.
2. Titanium nitride coating preparation
Placing the electrode substrate prepared in the pretreatment step into a cavity of a magnetron sputtering device, heating the cavity and a sample stage to 200 ℃, and vacuumizing the cavity to be less than or equal to 1.0 multiplied by 10 by using a mechanical pump and a molecular pump -2 Pa; introducing Ar gas, setting the flow rate to be 45sccm, and adjusting the deposition pressure in the chamber to 1.0Pa; adjusting the power of the titanium target material to 250W, and carrying out pre-sputtering for 10min; introducing N after the pre-sputtering is finished 2 Control of N 2 The partial pressure percentage is 2 percent, and the total gas flow is 60sccm; adjusting the power of the titanium target material to 200W, starting sputtering, and maintaining the sputtering pressure at 4.5Pa; the sputtering time was 30min. The thickness of the resulting coating was about 530nm.
3. Preparation of manganese dioxide electrode
The same as in example 1.
4. Characterization of the Zinc foil phase Structure by XRD
5. Observing zinc foil structure by SEM
6.Zn-MnO 2 Battery performance testing
And (3) assembling the zinc foil prepared in the step (2) as a negative electrode and a manganese dioxide electrode as a positive electrode into a CR-2032 type zinc-manganese button battery for cycle performance test. In the CR-2032 cell, GF/D, manufactured by Whatman corporation, was used as positive and negative separators. The electrolyte used is 2mol/L ZnSO 4 And 0.1mol/L MnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, the upper limit charging voltage is 1800mV, and the lower limit discharging voltage is 900mV.
Performance test of Zn-Zn symmetrical battery
And assembling the blank zinc foil into a CR-2032 type symmetrical battery to perform a cycle stability test. In the CR-2032 cell, GF/D manufactured by Whatman was used as a separator for a cathode and an anode. The electrolyte used is 2mol/L ZnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 0.5mA cm -2 。
Example 10
1. Pretreatment of substrate
(1) The thickness of the mixture is 0.05mm, and the area is 1.32cm 2 The porous zinc electrode is polished by 400-mesh sand paper, then is ultrasonically cleaned by acetone, ethanol and deionized water in sequence, and is dried in a vacuum oven at the temperature of 20 ℃ for 5 hours.
(2) And (3) placing the electrode substrate prepared in the step (1) in a cavity of a magnetron sputtering device for ion source bombardment cleaning treatment. The same as in example 1.
2. Titanium nitride coating preparation
Placing the electrode substrate prepared in the pretreatment step into a cavity of a magnetron sputtering device, heating the cavity and a sample stage to 200 ℃, and vacuumizing the cavity to be less than or equal to 1.0 multiplied by 10 by using a mechanical pump and a molecular pump -2 Pa; introducing Ar gas, setting the flow rate to be 45sccm, and adjusting the deposition pressure in the chamber to 1.0Pa; adjusting the power of the titanium metal target to 250W for 10minPre-sputtering; introducing N after the pre-sputtering is finished 2 Control N 2 The partial pressure percentage is 60 percent, and the total gas flow is 60sccm; adjusting the power of the titanium target material to 200W, starting sputtering, and maintaining the sputtering pressure at 0.5Pa; the sputtering time was 5min. The thickness of the resulting coating was about 86nm.
3. Preparation of manganese dioxide electrode
The same as in example 1.
4. Characterization of the Zinc foil phase Structure by XRD
5. Observing zinc foil structure by SEM
6.Zn-MnO 2 Battery performance testing
And (3) assembling the zinc foil prepared in the step (2) as a negative electrode and a manganese dioxide electrode as a positive electrode into a CR-2032 type zinc-manganese button battery for cycle performance test. In the CR-2032 cell, GF/D, manufactured by Whatman corporation, was used as positive and negative separators. The electrolyte used is 2mol/L ZnSO 4 And 0.1mol/L MnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, the upper limit charging voltage is 1800mV, and the lower limit discharging voltage is 900mV.
Performance test of Zn-Zn symmetrical battery
And assembling the blank zinc foil into a CR-2032 type symmetrical battery to perform a cycle stability test. In the CR-2032 cell, GF/D, manufactured by Whatman, was used as a separator for the cathode and anode. The electrolyte used is 2mol/L ZnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 0.5mA cm -2 。
Example 11
1. Pretreatment of substrate
(1) The thickness of the film is 0.05mm, and the area is 1.32cm 2 After the porous zinc electrode is polished by 2000-mesh abrasive paper, the porous zinc electrode is sequentially ultrasonically cleaned by acetone, ethanol and deionized water, and then is dried in a vacuum oven at 30 ℃ for 1 hour.
(2) And (3) placing the electrode substrate prepared in the step (1) in a cavity of a magnetron sputtering device for ion source bombardment cleaning treatment. The same as in example 1.
2. Titanium nitride coating preparation
Will be pretreatedPlacing the electrode substrate prepared in the step into a cavity of a magnetron sputtering device, heating the cavity and a sample stage to 200 ℃, and vacuumizing the cavity to be less than or equal to 1.0 multiplied by 10 by using a mechanical pump and a molecular pump -2 Pa; introducing Ar gas, setting the flow rate to be 45sccm, and adjusting the deposition pressure in the chamber to 1.0Pa; adjusting the power of the titanium target material to 250W, and carrying out pre-sputtering for 10min; introducing N after the pre-sputtering is finished 2 Control N 2 The partial pressure percentage is 15 percent, and the total gas flow is 60sccm; adjusting the power of the titanium target material to 250W, starting sputtering, and maintaining the sputtering pressure at 2.0Pa; the sputtering time was 60min. The thickness of the resulting coating was about 1100nm.
3. Preparation of manganese dioxide electrode
The same as in example 1.
4. Characterization of the Zinc foil phase Structure by XRD
5. Observing zinc foil structure by SEM
6.Zn-MnO 2 Battery performance testing
And (3) assembling the zinc foil prepared in the step (2) as a negative electrode and a manganese dioxide electrode as a positive electrode into a CR-2032 type zinc-manganese button battery for cycle performance test. In the CR-2032 cell, GF/D, manufactured by Whatman corporation, was used as positive and negative separators. The electrolyte used is 2mol/L ZnSO 4 And 0.1mol/L MnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, the upper limit charging voltage is 1800mV, and the lower limit discharging voltage is 900mV.
Performance test of Zn-Zn symmetrical battery
And assembling the blank zinc foil into a CR-2032 type symmetrical battery to perform a cycle stability test. In the CR-2032 cell, GF/D, manufactured by Whatman, was used as a separator for the cathode and anode. The electrolyte used is 2mol/L ZnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 0.5mA cm -2 。
Example 12
1. Pretreatment of substrate
(1) The thickness of the mixture is 0.05mm, and the area is 1.32cm 2 The porous zinc electrode is polished by 7000-mesh abrasive paper, then is sequentially ultrasonically cleaned by acetone, ethanol and deionized water,and then the mixture is placed in a vacuum oven at 80 ℃ to be dried for 0.5h.
(2) And (3) placing the electrode substrate prepared in the step (1) in a cavity of a magnetron sputtering device for ion source bombardment cleaning treatment. The same as in example 1.
2. Titanium nitride coating preparation
Placing the electrode substrate prepared in the pretreatment step into a cavity of a magnetron sputtering device, heating the cavity and a sample stage to 200 ℃, and vacuumizing the cavity to be less than or equal to 1.0 multiplied by 10 by using a mechanical pump and a molecular pump -2 Pa; introducing Ar gas, setting the flow rate to be 45sccm, and adjusting the deposition pressure in the chamber to 1.0Pa; adjusting the power of the titanium target material to 250W, and carrying out pre-sputtering for 10min; introducing N after the pre-sputtering is finished 2 Control N 2 The partial pressure percentage is 2 percent, and the total gas flow is 60sccm; adjusting the power of the titanium target material to 300W, starting sputtering, and maintaining the sputtering pressure at 4.5Pa; the sputtering time was 150min. The thickness of the coating produced was about 3980nm.
3. Preparation of manganese dioxide electrode
The same as in example 1.
4. Characterization of the Zinc foil phase Structure by XRD
5. Observing zinc foil structure by SEM
6.Zn-MnO 2 Battery performance testing
And (3) assembling the zinc foil prepared in the step (2) as a negative electrode and a manganese dioxide electrode as a positive electrode into a CR-2032 type zinc-manganese button battery for cycle performance test. In the CR-2032 cell, GF/D, manufactured by Whatman corporation, was used as positive and negative separators. The electrolyte used is 2mol/L ZnSO 4 And 0.1mol/L MnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, the upper limit charging voltage is 1800mV, and the lower limit discharging voltage is 900mV.
Test of Zn-Zn symmetric Battery Performance
And assembling the blank zinc foil into a CR-2032 type symmetrical battery to perform a cycle stability test. In the CR-2032 cell, GF/D manufactured by Whatman was used as a separator for a cathode and an anode. The electrolyte used is 2mol/L ZnSO 4 Solution 100. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 0.5mA cm -2 。
Example 13
Similar to example 1, with the difference that in step 3), the temperature of the heating is 100 ℃; introducing Ar gas, setting the flow rate of the Ar gas to be 30sccm, adjusting the deposition pressure in the chamber to be 1.3Pa, adjusting the power of the titanium target to be 250W, and pre-sputtering for 10min; the introduction of N 2 Control of different N 2 The flow rate partial pressure ratio is 2% -60%, and the total flow rate of the gas is 50sccm; the power of the titanium target is adjusted to 300W, the sputtering pressure is maintained at 1Pa, and the sputtering time is 50min.
Example 14
Similar to example 7, with the difference that in step 3), the temperature of the heating may be 200 ℃; the vacuum pumping of the cavity can be carried out to less than or equal to 1.0 multiplied by 10 -2 Pa; the specific conditions for introducing Ar gas and pre-sputtering the titanium metal target material can be as follows: setting the flow rate of Ar at 45sccm, adjusting the deposition pressure in the chamber to 1.0Pa, adjusting the power of the titanium target to 150W, and pre-sputtering for 2min; the introduction of N 2 Control of different N 2 The flow rate partial pressure ratio is 2-60%, and the total flow rate of the gas is 80sccm; the power of the titanium target is adjusted to 300W, the sputtering pressure is maintained at 0.5Pa, and the sputtering time is 150min.
Example 15
Similar to example 10, in step 3), the temperature of the heating may be 120 ℃; the vacuum pumping of the cavity can be carried out to be less than or equal to 1.0 multiplied by 10 -2 Pa; introducing Ar gas, setting the flow rate of the Ar gas to be 35sccm, adjusting the deposition pressure in the chamber to 1.2Pa, adjusting the power of the titanium metal target to 200W, and pre-sputtering for 5min; the introduction of N 2 Control of different N 2 The flow rate partial pressure ratio is 2% -60%, and the total flow rate of the gas is 60sccm; the power of the titanium target is adjusted to 250W, the sputtering pressure is maintained at 4.5Pa, and the sputtering time is 5min.
The invention deposits the titanium nitride coating on the zinc electrode substrate by a magnetron sputtering method to obtain the cathode of the secondary zinc battery. By controlling the preparation conditions, the lattice mismatch degree of the titanium nitride coating and the zinc metal is reduced, so that the zinc metal and the zinc-containing material are guided to uniformly nucleate and grow on the surface of the zinc metal in an epitaxial electrodeposition mode, and the generation of dendrites is inhibited. The titanium nitride coating may also serve to prevent corrosion of the zinc metal underlying the coating by direct contact with the electrolyte. The secondary zinc battery using the zinc electrode protected by the titanium nitride coating has excellent cycle stability and safety.

Claims (10)

1. A preparation method of a titanium nitride coating of a long-cycle secondary zinc battery cathode is characterized by comprising the following steps:
1) Polishing a zinc electrode substrate, ultrasonically cleaning, and then placing in a vacuum oven for drying;
2) Placing the electrode substrate obtained in the step 1) in a cavity of a magnetron sputtering device, and bombarding and cleaning the electrode substrate by using an ion source to obtain a pretreated zinc electrode substrate;
3) Heating the chamber and the sample stage, and vacuumizing the chamber by using a mechanical pump and a molecular pump; introducing Ar gas, pre-sputtering a titanium metal target on the pretreated zinc electrode substrate, and introducing N 2 And sputtering a titanium metal target to obtain the titanium nitride coating of the cathode of the long-cycle secondary zinc battery.
2. The method for preparing the titanium nitride coating on the cathode of the long-cycle secondary zinc battery as claimed in claim 1, wherein in the step 1), the zinc electrode substrate comprises at least one of zinc foil, zinc sheet and porous zinc electrode with any thickness and any area specification.
3. The method for preparing the titanium nitride coating of the cathode of the long-cycle secondary zinc battery as claimed in claim 1, wherein in the step 1), the ultrasonic cleaning is ultrasonic cleaning with acetone, ethanol and deionized water in sequence; the grinding is carried out by 400-7000 mesh sand paper.
4. The method for preparing the titanium nitride coating of the cathode of the long-cycle secondary zinc battery as claimed in claim 1, wherein in the step 1), the drying temperature is 20-80 ℃ and the drying time is 0.5-5 h.
5. The method for preparing the titanium nitride coating on the cathode of the long-cycle secondary zinc battery as claimed in claim 1, wherein in the step 2), the substrate is cleaned by using a Hall ion source for 1-10 min under the environmental pressure of 1.5 x 10 by bombarding and cleaning with an ion source -2 Pa, ar flow rate of 15sccm, substrate bias voltage of-125V, cathode current of 32A, cathode voltage of 30V, anode current of 4.5A, and anode voltage of 60V.
6. The method for preparing the titanium nitride coating of the negative electrode of the long-cycle secondary zinc battery as claimed in claim 1, wherein the heating temperature in the step 3) is 100-200 ℃.
7. The method for preparing the titanium nitride coating on the cathode of the long-cycle secondary zinc battery as claimed in claim 1, wherein in the step 3), the chamber is vacuumized to be less than or equal to 1.0 x 10 -2 Pa。
8. The method for preparing the titanium nitride coating of the cathode of the long-cycle secondary zinc battery as claimed in claim 1, wherein in the step 3), the specific conditions for introducing the Ar gas and pre-sputtering the titanium metal target material are as follows: setting the flow rate of Ar at 30-45 sccm, adjusting the deposition pressure in the chamber to 1.0-1.3 Pa, adjusting the power of the titanium target to 150-250W, and pre-sputtering for 2-15 min.
9. The method for preparing the titanium nitride coating of the cathode of the long-cycle secondary zinc battery as claimed in claim 1, wherein in the step 3), N is introduced 2 The specific conditions for sputtering the titanium metal target material can be as follows: introduction of N 2 Control of different N 2 The flow rate partial pressure ratio is 2-60%, and the total flow rate of the gas is 50-80 sccm; the power of the titanium target is adjusted to 200-300W, the sputtering pressure is maintained at 0.5-4.5 Pa, and the sputtering time is 5-150 min.
10. The method for preparing the titanium nitride coating of the cathode of the long-cycle secondary zinc battery as claimed in claim 1, wherein in the step 3), the titanium nitride coating is deposited to a thickness of 100 to 4000nm, preferably 100 to 2000nm.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114540752A (en) * 2022-03-02 2022-05-27 西安工业大学 Fuel cell metal polar plate with conductive corrosion-resistant coating and preparation method thereof
CN114566608A (en) * 2022-03-14 2022-05-31 郑州大学 Silver-zinc alloy coating with zinc sheet as substrate and preparation method thereof
CN114824229A (en) * 2022-05-23 2022-07-29 厦门大学 Preparation method of high-performance secondary zinc battery cathode silver-doped aluminum nitride coating

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103915604A (en) * 2012-12-28 2014-07-09 财团法人工业技术研究院 Protected active metal electrode, lithium metal electrode and element having such electrode
US20170324072A1 (en) * 2015-02-27 2017-11-09 Massachusetts Institute Of Technology Electrochemical Cell with Bipolar Faradaic Membrane
CN111224115A (en) * 2018-11-27 2020-06-02 中国科学院大连化学物理研究所 Zinc-based battery negative electrode and preparation and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103915604A (en) * 2012-12-28 2014-07-09 财团法人工业技术研究院 Protected active metal electrode, lithium metal electrode and element having such electrode
US20170324072A1 (en) * 2015-02-27 2017-11-09 Massachusetts Institute Of Technology Electrochemical Cell with Bipolar Faradaic Membrane
CN111224115A (en) * 2018-11-27 2020-06-02 中国科学院大连化学物理研究所 Zinc-based battery negative electrode and preparation and application thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114540752A (en) * 2022-03-02 2022-05-27 西安工业大学 Fuel cell metal polar plate with conductive corrosion-resistant coating and preparation method thereof
CN114540752B (en) * 2022-03-02 2023-10-03 西安工业大学 Fuel cell metal polar plate with conductive corrosion-resistant coating and preparation method thereof
CN114566608A (en) * 2022-03-14 2022-05-31 郑州大学 Silver-zinc alloy coating with zinc sheet as substrate and preparation method thereof
CN114824229A (en) * 2022-05-23 2022-07-29 厦门大学 Preparation method of high-performance secondary zinc battery cathode silver-doped aluminum nitride coating
CN114824229B (en) * 2022-05-23 2024-05-28 厦门大学 Preparation method of silver-doped aluminum nitride coating of secondary zinc battery negative electrode

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