CN114094035A - Preparation method of high-cycle-stability aluminum-zinc alloy coating of cathode of secondary zinc battery - Google Patents
Preparation method of high-cycle-stability aluminum-zinc alloy coating of cathode of secondary zinc battery Download PDFInfo
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Abstract
A preparation method of a high-cycle stable secondary zinc battery cathode aluminum-zinc alloy coating relates to a zinc ion battery. By utilizing a magnetron co-sputtering technology and adjusting the sputtering power of the two metal targets, the aluminum content of the aluminum-zinc alloy coating is accurately controlled, an aluminum site forms a compact oxide film in an aqueous solution to generate an electrostatic shielding effect, the aggregation of zinc ions is inhibited, and then the zinc ions are converted into uniform deposition on the surface of a negative electrode, and the cycle performance of the zinc negative electrode is improved. The aluminum-zinc alloy coating containing different metal component proportions is deposited on a zinc electrode substrate by co-sputtering aluminum and zinc metal targets, controlling the sputtering power of the two targets and accurately regulating and controlling the aluminum-zinc component proportions, so that the aluminum-zinc alloy coating of the cathode of the secondary zinc battery with high cycle stability is obtained. When the aluminum content of the aluminum-zinc coating is 30 percent, the prepared aluminum-zinc coating zinc cathode is at 1mA cm ‑2 ，1mAh cm ‑2 Has long cycle life of more than 4000h under the test condition.
Description
Technical Field
The invention relates to a zinc ion battery, belongs to the field of novel chemical power sources, and particularly relates to a preparation method of a high-cycle stable secondary zinc battery cathode aluminum-zinc alloy coating.
Background
Secondary batteries, such as lithium ion batteries, have become an essential energy storage carrier in daily life. The method is seen from mobile terminals, transportation and large-scale energy storage everywhere. However, the organic electrolyte used in the lithium ion battery is toxic and flammable, and has a great potential safety hazard, and a great number of cases about the fire and explosion of the lithium ion battery are present. Meanwhile, the scarcity of lithium resources and high cost further promote people to find green, environment-friendly, safe, reliable, cheap and easily available secondary metal batteries.
Zinc attracts people's attention as a metal which is green, environment-friendly, cheap and easily available, easy to process and form and difficult to spontaneously combust. However, zinc metal is easily subjected to dendrite short circuit, corrosion passivation, hydrogen evolution expansion and the like in the cyclic charge and discharge process under the alkaline or acidic electrolyte condition, so that the zinc metal cannot be applied to the secondary battery market on a large scale. A great deal of researchers have been led to zinc ion deposition behavior by using mechanisms such as electric field induction, selective functional coating, change of zinc ion solvation structure and electrolyte concentration, and the like, so as to inhibit the occurrence of dendrite and corrosion. The oxide and metal conductive coatings in the functional coating have certain mechanical strength, so that the diffusion of zinc ions can be accelerated, and the surface volume change and serious zinc substrate corrosion can be inhibited. However, as the cycle progresses it remains difficult to remove the effects of the dendrites, which eventually can still break through the membrane. 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 and controllable structure 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 ion battery. The alloy film prepared by magnetron sputtering has the advantages of controllable structure, uniform film layer composition, stable quality and the like, and is used for preparing various alloy films in large scale. The aluminum-zinc alloy coating prepared by magnetron co-sputtering is used for zinc electrode protection, and 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 high-cycle-stability secondary zinc battery cathode aluminum-zinc alloy coating, which is used for guiding zinc to be uniformly deposited on the surface of the secondary zinc battery cathode aluminum-zinc alloy coating and has high cycle stability.
The invention utilizes the magnetron co-sputtering technology, and accurately controls the aluminum content of the aluminum-zinc alloy coating by adjusting the sputtering power of two metal targets, and the specific method comprises the following steps:
1) Heating the chamber and the sample stage, and vacuumizing the chamber by using a mechanical pump and a molecular pump; introducing Ar gas, and removing zinc oxide impurities on the surface of the zinc foil by using an ion source cleaning technology;
2) Introducing Ar gas, co-sputtering aluminum and zinc metal targets, adjusting the power of the two targets to change the content of aluminum in the alloy coating, and depositing the zinc-aluminum alloy coating on the surface of the zinc foil cleaned by the ion source;
3) And heating the obtained zinc foil modified by the zinc-aluminum coating to obtain the component-adjustable aluminum-zinc alloy coating for the zinc battery cathode.
In the step 1), the Ar gas is introduced, and the specific conditions of the ion source cleaning technology may be: the flow rate of Ar gas was set to 15sccm, the pressure in the chamber was adjusted to 0.4Pa, the cathode voltage was set to 40V, the anode voltage was set to 70V, and the bias voltage was-200V. The ion source cleaning time is 10-15 min.
In the step 2), the specific conditions of introducing Ar gas and co-sputtering the aluminum and zinc metal target materials are as follows: introducing Ar gas, wherein the total gas flow is 60sccm; adjusting the power of an aluminum metal target material to 100-200W, adjusting the power of a zinc target material to 100-200W, maintaining the sputtering pressure at 2.0Pa and the sputtering time at 30min;
the thickness of the zinc-aluminum alloy coating is 0.8-1.5 mu m;
the content of the aluminum element is 20 to 40 percent under different sputtering powers.
In step 3), the pair is obtainedThe specific conditions for the heat treatment of the zinc foil modified by the zinc-aluminum coating can be as follows: introducing 30sccm of N into the chamber 2 Gas and 30sccm of Ar mixed gas, wherein the substrate temperature is set to be 120 ℃, the chamber temperature is 150 ℃, and the heat treatment time is 30min.
Compared with the prior art, the invention has the following outstanding advantages:
1. according to the invention, the aluminum-zinc alloy coating with controllable structure and adjustable components is prepared, the aluminum sites form a compact oxide film in an aqueous solution to generate an electrostatic shielding effect, the aluminum-zinc coating can effectively inhibit dendritic crystal generation, corrosion and other problems by utilizing the electrostatic shielding effect of an aluminum oxide insulating shell layer on the surface of aluminum, the electrostatic shielding strength of the surface of an electrode is controlled by adjusting the content of aluminum, and the cycle life and electrochemical performance of a zinc cathode are greatly improved.
2. The invention uses the aluminum-zinc alloy coating for zinc cathode protection, and realizes the preparation of high-performance zinc cathode. The electrostatic shielding effect generated by the alumina sites can effectively avoid the aggregation effect of zinc ions, thereby guiding the zinc ions to be uniformly deposited on the surface of the aluminum-zinc alloy coating. Under the condition that the sputtering power of aluminum and zinc is 150W and 150W respectively, the aluminum content in the prepared aluminum-zinc alloy coating is 30 percent, and the zinc cathode protected by the aluminum-zinc alloy coating has high cycle stability. In a symmetrical cell, the test current density was 1.0mA cm -2 And meanwhile, the zinc electrode realizes stable circulation for more than 4000 hours, and realizes the circulation capacity of more than 1700 times in the zinc-manganese dioxide secondary battery.
Drawings
FIG. 1 is an XRD spectrum of an aluminum zinc coating.
Fig. 2 is a SEM topography of comparative and example zinc foils after 50h cycling in a symmetric cell.
FIG. 3 is the overpotential map for deposition of the comparative example and the example.
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 positive and negative of a symmetrical cellAt extreme time of 1.0mA 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 appended 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 a person skilled in the art could make some insubstantial modifications and adaptations to the present invention based on the contents of the present invention.
Comparative example 1
1. Blank zinc cathode preparation
The thickness of the film is 0.2mm, 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 30 ℃ for 5min.
2. Preparation of manganese dioxide electrode
0.7g of manganese dioxide powder, 0.2g of acetylene black and 0.1g of polyvinylidene fluoride (PVDF) powder were mixed uniformly, 2.5mL of N-methylpyrrolidone (NMP) solution was added, and the mixture was magnetically stirred for 24 hours to disperse the active substance.
3. Adopting SEM to observe blank zinc foil structure
Fig. 2 (a) is an SEM surface topography of a blank zinc foil before charging and discharging in a symmetrical cell. The surface of the zinc foil is smooth before reaction, and no obvious corrosion pits or other impurities appear. Assembling blank zinc foil into symmetrical battery at 1.0mA cm -2 After 50h of cycling at the current density of (c), it can be seen from the graph of fig. 2 (b) that a large amount of by-products and protruding plate-like dendrites are formed.
4. Deposition overpotential test
Fig. 3 is a zinc-stainless steel half cell deposition overpotential test. The blank zinc foil is used as a negative electrode, and the stainless steel net is used as a positive electrode. At 1.0mA cm -2 ，1.0mAh cm -2 Conditions and 2mol/L ZnSO 4 In (3) performing a deposition test. The overpotential for deposition of the blank zinc foil can be seen to be 110mV. Proving that the deposition process needs to overcome the larger nucleation energy.
5.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. The test parameters are set as constant current charging and constant current discharging, the upper limit charging voltage is 1900mV, and the lower limit discharging voltage is 800mV. 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 that the capacity of the zinc-manganese battery rapidly decays within 20 cycles when the blank zinc foil is used as the negative electrode. When the blank zinc foil is used as the negative electrode, the specific discharge capacity of the battery after charging and discharging for nearly 500 circles is about 20mAhg -1 。
6.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 a cathode and an anode. The electrolyte used is 2mol/L ZnSO 4 Solution 150. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 1.0mA cm -2 . Fig. 5 demonstrates the effective cycle time of the bare zinc foil at the current densities described above, about 180 hours, and it can be seen that the uncoated protected blank failed in a relatively short period of time.
Example 1
1. Pretreatment of substrate
(1) The thickness of the film is 0.2mm, 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 30 ℃ for 5min.
(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 matrix for 10min by using a Hall ion source. Ar gas is introduced, and the specific conditions of ion source cleaning are as follows: the flow rate of Ar gas was set to 15sccm, the pressure in the chamber was adjusted to 0.4Pa, the cathode voltage was set to 40V, and the anode voltage was set to 70V. The bias voltage was-200V. The ion source cleaning time was 10min.
2. Preparation of aluminum-zinc alloy coating
Heating the chamber and the sample stage to 120 deg.C, and vacuumizing the chamber to 1.0 × 10 or less with a mechanical pump and a molecular pump - 2 Pa; introducing Ar gas, setting the flow rate to be 50sccm, and adjusting the deposition pressure in the chamber to be 1.0Pa; adjusting the power of the aluminum and silver metal target materials to 200W and 100W respectively, and carrying out pre-sputtering for 5 min; after the pre-sputtering is finished, regulating the flow of Ar gas to 60sccm; the power of the aluminum and zinc metal target materials is adjusted to 200W and 100W, the sputtering pressure is maintained at 2.0Pa, and the sputtering time is 30min. A pure aluminum coating was produced with a thickness of about 1.5 μm. N at 30sccm 2 Gas and 30sccm of Ar mixed gas atmosphere. The substrate temperature was set at 120 ℃ and the chamber temperature was 150 ℃. The heat treatment time is 30min. And heating the zinc foil coated with the zinc-aluminum alloy. The aluminum content in the aluminum-zinc coating is 40 percent.
3. Preparation of manganese dioxide electrode
0.7g of manganese dioxide powder, 0.2g of acetylene black and 0.1g of polyvinylidene fluoride (PVDF) powder were mixed uniformly, 2.5mL of N-methylpyrrolidone (NMP) solution was added, and the mixture was magnetically stirred for 24 hours to disperse the active substance.
4. Characterization of the phase structure of the Al-Zn alloy coating by XRD
And (3) depositing an aluminum zinc film on the silicon substrate under the condition consistent with the step 2. FIG. 1 is an XRD spectrum of an aluminum-zinc thin film, which shows that aluminum particles are mainly composed of (111) and (200) crystal planes.
5. Adopt SEM to observe zinc foil structure
And (c) in fig. 2 is an SEM surface topography of the zinc foil prepared in step 2 before being used in a symmetrical battery for charging and discharging, and the zinc foil has a flat surface and is uniformly covered with aluminum zinc particles. The graph (d) in fig. 2 shows that the surface appearance of zinc is uniform after the zinc reacts on the aluminum-zinc coating with the aluminum content of 40% for 50h, and zinc ions can not be sufficiently diffused for a long time due to the strong electrostatic shielding effect of the coating and are deposited on the existing zinc crystal nuclei, so that the zinc ions penetrate through the aluminum coating.
6. Deposition overpotential test
Fig. 3 is a zinc-stainless steel half cell deposition overpotential test. Will be plated as prepared in step 2The zinc foil and the stainless steel of the coating are respectively used as a negative electrode and a positive electrode. At 1.0mA cm -2 ，1.0mAh cm -2 Conditions and 2mol/L ZnSO 4 In the deposition test. The overpotential for deposition of the blank zinc foil is 105mV as can be seen from the figure. It is proved that the deposition process needs to overcome larger nucleation energy, and the pure aluminum coating hinders the normal diffusion of zinc ions.
7.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 1900mV, and the lower limit discharging voltage is 800mV. 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 short circuit of the zinc-manganese battery fails after the zinc-manganese battery is cycled for about 515 times. And the capacity is improved compared with the battery consisting of a blank zinc electrode.
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 150. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 1.0mA cm -2 . Fig. 5 demonstrates that the effective cycle time of the zinc foil produced in step 2 at the current densities described above is about 600 hours, and it can be seen that the coating improves the performance of the cell.
Example 2
1. Pretreatment of substrate
(1) The thickness of the mixture is 0.2mm, 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 30 ℃ for 5min.
(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 matrix for 10min by using a Hall ion source. Ar gas is introduced, and the specific conditions of ion source cleaning are as follows: the flow rate of Ar gas was set to 15sccm, the pressure in the chamber was adjusted to 0.4Pa, the cathode voltage was set to 40V, and the anode voltage was set to 70V. The bias voltage was-200V. The ion source cleaning time was 10min.
2. Preparation of aluminum-zinc alloy coating
Heating the chamber and the sample stage to 120 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 50sccm, and adjusting the deposition pressure in the chamber to 1.0Pa; adjusting the power of the aluminum and silver metal target materials to 200W and 100W respectively, and carrying out pre-sputtering for 5 min; after the pre-sputtering is finished, adjusting the flow of Ar gas to 60sccm; the power of the aluminum and zinc metal targets is adjusted to 200 and 200W, the sputtering pressure is maintained at 2.0Pa, and the sputtering time is 30min. A pure aluminum coating was produced with a thickness of about 1.2 μm. N at 30sccm 2 Gas and Ar of 30 sccm. The substrate temperature was set at 120 ℃ and the chamber temperature was 150 ℃. The heat treatment time is 30min. And heating the zinc foil coated with the zinc-aluminum alloy. The aluminum content in the aluminum-zinc coating is 35 percent.
3. Preparation of manganese dioxide electrode
0.7g of manganese dioxide powder, 0.2g of acetylene black and 0.1g of polyvinylidene fluoride (PVDF) powder were mixed uniformly, 2.5mL of N-methylpyrrolidone (NMP) solution was added, and the mixture was magnetically stirred for 24 hours to disperse the active substance.
4. Characterization of the phase structure of the Al-Zn alloy coating by XRD
And (3) depositing an aluminum zinc film on the silicon substrate under the condition consistent with the step 2. Fig. 1 is an XRD spectrum of the aluminum-zinc film, which shows that the coating is composed of elemental aluminum and elemental zinc particles. Zinc is mainly based on (100) and (101) crystal planes.
5. Observing zinc foil structure by SEM
And (e) in fig. 2 is an SEM surface topography of the zinc foil prepared in step 2 before being used in a symmetrical battery for charging and discharging, and the surface of the zinc foil is relatively flat and uniformly covered with aluminum zinc particles. The graph (f) in fig. 2 shows that the surface appearance of zinc is still relatively flat after the zinc reacts on the coating for 50 hours, and the zinc ions are deposited on the surface of the aluminum zinc coating more smoothly due to the reduction of the electrostatic shielding effect.
6. Deposition overpotential test
Fig. 3 is a zinc-stainless steel half cell deposition overpotential test. And (3) respectively taking the zinc foil and the stainless steel plated with the coating prepared in the step (2) as a negative electrode and a positive electrode. At 1.0mA cm -2 ，1.0mAh cm -2 Conditions and 2mol/L ZnSO 4 In (3) performing a deposition test. The overpotential for deposition of the blank zinc foil is 96mV as can be seen from the figure.
7.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 1900mV, and the lower limit discharging voltage is 800mV. 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 short circuit of the zinc-manganese battery fails after about 1500 cycles. And the capacity is improved compared with the full battery consisting of a blank zinc electrode.
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 150. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 1.0mA cm -2 . Fig. 5 demonstrates that the effective cycle time of the zinc foil produced in step 2 at the current density described above is about 2000 hours, and it can be seen that the coating improves the performance of the cell.
Example 3
1. Pretreatment of substrate
(1) The thickness of the mixture is 0.2mm, and the area is 1.32cm 2 The zinc foil is polished by 2000-mesh abrasive paper, then is ultrasonically cleaned by acetone, ethanol and deionized water in sequence, and is placed in a vacuum oven at 30 DEG COven drying for 5min.
(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 matrix for 10min by using a Hall ion source. Introducing Ar gas, wherein the specific conditions for cleaning the ion source are as follows: the flow rate of Ar gas was set to 15sccm, the pressure in the chamber was adjusted to 0.4Pa, the cathode voltage was set to 40V, and the anode voltage was set to 70V. The bias voltage was-200V. The ion source cleaning time was 10min.
2. Preparation of aluminum-zinc alloy coating
Heating the chamber and the sample stage to 120 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 50sccm, and adjusting the deposition pressure in the chamber to 1.0Pa; adjusting the power of the aluminum and silver metal target materials to 200 and 100W respectively, and carrying out pre-sputtering for 5 min; after the pre-sputtering is finished, adjusting the flow of Ar gas to 60sccm; the power of the aluminum and zinc metal targets is adjusted to 150 and 150W, the sputtering pressure is maintained at 2.0Pa, and the sputtering time is 30min. A pure aluminum coating was produced with a thickness of about 1.0 μm. N at 30sccm 2 Gas and Ar of 30 sccm. The substrate temperature was set at 120 ℃ and the chamber temperature was 150 ℃. The heat treatment time is 30min. And heating the zinc foil coated with the zinc-aluminum alloy. The aluminum content in the aluminum-zinc coating is 30 percent.
3. Preparation of manganese dioxide electrode
0.7g of manganese dioxide powder, 0.2g of acetylene black and 0.1g of polyvinylidene fluoride (PVDF) powder were mixed uniformly, 2.5mL of N-methylpyrrolidone (NMP) solution was added, and the mixture was magnetically stirred for 24 hours to disperse the active substance.
4. Characterization of the phase structure of the Al-Zn alloy coating by XRD
And (3) depositing an aluminum film on the silicon substrate under the condition consistent with the step 2. Fig. 1 is an XRD spectrum of an al-zn thin film, showing that the characteristic peaks of zn are enhanced as the al content decreases, but still consist of two elemental metals without forming a significant alloy.
5. Observing zinc foil structure by SEM
In fig. 2, (i) is an SEM surface topography of the zinc foil prepared in step 2 before being used in a symmetrical battery for charging and discharging, and the surface of the zinc foil is relatively flat and uniformly covered with aluminum zinc particles. The graph (j) in fig. 2 shows that the surface appearance of zinc is very flat after the zinc reacts on the coating for 50 hours, and the fact that the aluminum zinc coating with the aluminum content of 30% has a moderate electrostatic shielding effect is proved, and the aggregation of zinc ions and the generation of dendrites can be avoided.
6. Deposition overpotential test
Fig. 3 is a zinc-stainless steel half cell deposition overpotential test. And (3) respectively taking the zinc foil and the stainless steel plated with the coating prepared in the step (2) as a negative electrode and a positive electrode. At 1.0mA cm -2 ，1.0mAh cm -2 Conditions and 2mol/L ZnSO 4 In (3) performing a deposition test. The deposition overpotential of the blank zinc foil can be seen to be 30mV. The nucleation energy required to be overcome in the deposition process is proved to be obviously reduced, and the charge transfer and the ion diffusion are facilitated.
7.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 1900mV, and the lower limit discharging voltage is 800mV. 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 cycle performance of the zinc-manganese battery is further improved to 1700 times.
8.Zn-Zn symmetrical battery performance test
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 positive and negative electrodes. The electrolyte used is 2mol/L ZnSO 4 Solution 150. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 1.0mA cm -2 . Fig. 5 demonstrates that the effective cycle time of the zinc foil produced in step 2 at the current density described above is greater than 4000 hours, and it can be seen that the coating significantly improves the performance of the cell.
Example 4
1. Pretreatment of substrate
(1) The thickness of the film is 0.2mm, 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 30 ℃ for 5min.
(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 matrix for 10min by using a Hall ion source. Introducing Ar gas, wherein the specific conditions for cleaning the ion source are as follows: the flow rate of Ar gas was set to 15sccm, the pressure in the chamber was adjusted to 0.4Pa, the cathode voltage was set to 40V, and the anode voltage was set to 70V. The bias voltage was-200V. The ion source cleaning time was 10min.
2. Preparation of aluminum-zinc alloy coating
Heating the chamber and the sample stage to 120 deg.C, and vacuumizing the chamber to 1.0 × 10 or less with a mechanical pump and a molecular pump - 2 Pa; introducing Ar gas, setting the flow rate to be 50sccm, and adjusting the deposition pressure in the chamber to 1.0Pa; adjusting the power of the aluminum and silver metal target materials to 200 and 100W respectively, and carrying out pre-sputtering for 5 min; after the pre-sputtering is finished, regulating the flow of Ar gas to 60sccm; the power of the aluminum and zinc metal target materials is adjusted to 100 and 100W, the sputtering pressure is maintained at 2.0Pa, and the sputtering time is 30min. A pure aluminum coating was produced with a thickness of about 0.8 μm. N at 30sccm 2 Gas and 30sccm of Ar mixed gas atmosphere. The substrate temperature was set at 120 ℃ and the chamber temperature was 150 ℃. The heat treatment time is 30min. And heating the zinc foil coated with the zinc-aluminum alloy. The aluminum content in the aluminum-zinc coating is 20 percent.
3. Preparation of manganese dioxide electrode
0.7g of manganese dioxide powder, 0.2g of acetylene black and 0.1g of polyvinylidene fluoride (PVDF) powder were mixed uniformly, 2.5mL of N-methylpyrrolidone (NMP) solution was added, and the mixture was magnetically stirred for 24 hours to disperse the active substance.
4. Characterization of Al-Zn alloy coating phase structure by XRD
And (3) depositing an aluminum film on the silicon substrate under the condition consistent with the step 2. FIG. 1 is an XRD spectrum of an aluminum zinc film, and the intensity of an aluminum peak is reduced along with the further reduction of the aluminum content.
5. Observing zinc foil structure by SEM
And (c) in fig. 2, the surface appearance image of the SEM before the zinc foil prepared in step 2 is used for charging and discharging in a symmetrical battery, and the surface of the zinc foil is relatively flat and is uniformly covered by the aluminum zinc particles. FIG. 2 (d) shows that the surface morphology of the zinc layer after 50h reaction on the coating layer is greatly changed, and the electrostatic shielding strength of the coating layer is weakened due to the reduction of the aluminum content, so that zinc ions can not be sufficiently diffused and can be transferred to the deposition on the existing zinc crystal nucleus, and the membrane is pierced.
6. Deposition overpotential test
Fig. 3 is a zinc-stainless steel half cell deposition overpotential test. And (3) respectively taking the zinc foil and the stainless steel plated with the coating prepared in the step (2) as a negative electrode and a positive electrode. At 1.0mA cm -2 ，1.0mAh cm -2 Conditions and 2mol/L ZnSO 4 In (3) performing a deposition test. The deposition overpotential of the blank zinc foil can be seen to be 70mV.
7.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 was used as positive and negative electrode 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 1900mV, and the lower limit discharging voltage is 800mV.
8.Zn-Zn symmetrical battery performance test
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 positive and negative electrodes. The electrolyte used is 2mol/L ZnSO 4 The solution was 150. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 1.0mA cm -2 . Fig. 5 demonstrates that the effective cycle time of the zinc foil produced in step 2 at the current density described above is about 1100 hours, and it can be seen that the coating, although improving the performance of the cell, does not perform as well as the zinc anode due to the reduced aluminum content as the aluminum-zinc coating at 30% aluminum content.
Example 5
1. Pretreatment of substrate
(1) The thickness of the film is 0.2mm, 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 30 ℃ for 5min.
(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 matrix for 10min by using a Hall ion source. Introducing Ar gas, wherein the specific conditions for cleaning the ion source are as follows: the flow rate of Ar gas was set to 15sccm, the pressure in the chamber was adjusted to 0.4Pa, the cathode voltage was set to 40V, and the anode voltage was set to 70V. The bias voltage was-200V. The ion source cleaning time was 10min.
2. Preparation of aluminum-zinc alloy coating
Heating the chamber and the sample stage to 120 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 50sccm, and adjusting the deposition pressure in the chamber to 1.0Pa; adjusting the power of the aluminum and silver metal target materials to 200W and 100W respectively, and carrying out pre-sputtering for 5 min; after the pre-sputtering is finished, regulating the flow of Ar gas to 60sccm; the power of the aluminum and zinc metal targets is adjusted to 100 and 200W, the sputtering pressure is maintained at 2.0Pa, and the sputtering time is 30min. And obtaining the pure aluminum coating. N at 30sccm 2 Gas and 30sccm of Ar mixed gas atmosphere. The substrate temperature was set at 120 ℃ and the chamber temperature was 150 ℃. The heat treatment time is 30min. And heating the zinc foil coated with the zinc-aluminum alloy.
3. Preparation of manganese dioxide electrode
0.7g of manganese dioxide powder, 0.2g of acetylene black and 0.1g of polyvinylidene fluoride (PVDF) powder were mixed uniformly, 2.5mL of N-methylpyrrolidone (NMP) solution was added, and the mixture was magnetically stirred for 24 hours to disperse the active substance.
4. Characterization of the phase structure of the Al-Zn alloy coating by XRD
5. Observing zinc foil structure by SEM
6. Deposition overpotential test
And (3) respectively taking the zinc foil and the stainless steel plated with the coating prepared in the step (2) as a negative electrode and a positive electrode. At 1.0mA cm -2 ，1.0mAh cm -2 Conditions and 2mol/L ZnSO 4 In the deposition test.
7.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 1900mV, and the lower limit discharging voltage is 800mV.
8.Zn-Zn symmetrical battery performance test
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 The solution was 150. Mu.L. The test parameters are set as constant current charging and constant current discharging, and the current density is 1.0mA cm -2 。
Example 6
1. Pretreatment of substrate
(1) The thickness of the mixture is 0.2mm, 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 30 ℃ for 5min.
(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 matrix for 10min by using a Hall ion source. Introducing Ar gas, wherein the specific conditions for cleaning the ion source are as follows: the flow rate of Ar gas was set to 15sccm, the pressure in the chamber was adjusted to 0.4Pa, the cathode voltage was set to 40V, and the anode voltage was set to 70V. The bias voltage was-200V. The ion source cleaning time was 10min.
2. Preparation of aluminum-zinc alloy coating
Heating the chamber and the sample stage to 120 deg.C, and vacuumizing the chamber to 1.0 × 10 or less with a mechanical pump and a molecular pump - 2 Pa; introducing Ar gas, setting the flow rate at 50sccm, and adjusting the deposition pressure in the chamberForce to 1.0Pa; adjusting the power of the aluminum and silver metal target materials to 200 and 100W respectively, and carrying out pre-sputtering for 5 min; after the pre-sputtering is finished, adjusting the flow of Ar gas to 60sccm; the aluminum and zinc metal target powers were adjusted to 175 and 175W, the sputtering pressure was maintained at 2.0Pa, and the sputtering time was 30min. And obtaining the pure aluminum coating. N at 30sccm 2 Gas and 30sccm of Ar mixed gas atmosphere. The substrate temperature was set at 120 ℃ and the chamber temperature was 150 ℃. The heat treatment time is 30min. And heating the zinc foil coated with the zinc-aluminum alloy.
3. Preparation of manganese dioxide electrode
0.7g of manganese dioxide powder, 0.2g of acetylene black and 0.1g of polyvinylidene fluoride (PVDF) powder were mixed uniformly, 2.5mL of N-methylpyrrolidone (NMP) solution was added, and the mixture was magnetically stirred for 24 hours to disperse the active.
4. Characterization of the phase structure of the Al-Zn alloy coating by XRD
5. Observing zinc foil structure by SEM
6. Deposition overpotential test
And (3) respectively taking the zinc foil and the stainless steel plated with the coating prepared in the step (2) as a negative electrode and a positive electrode. At 1.0mA cm -2 ，1.0mAh cm -2 Conditions and 2mol/L ZnSO 4 In the deposition test.
7.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 1900mV, and the lower limit discharging voltage is 800mV.
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 150. Mu.L. Setting the test parameters to constant currentCharging and constant current discharging with current density of 1.0mA cm -2 。
The invention deposits the aluminum-zinc alloy coating on the zinc electrode substrate by a magnetron co-sputtering method to obtain the cathode of the secondary zinc battery. The sputtering power of the two targets is controlled to regulate the content of aluminum and zinc elements, so that the electrostatic shielding strength of the surface of the electrode is changed, the uniform nucleation growth of zinc metal is guided, and the generation of dendritic crystals is inhibited. The aluminum zinc 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 aluminum-zinc alloy layer has excellent cycle life and full battery performance.
The above-described embodiments are merely preferred embodiments of the present invention, and should not be considered as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (6)
1. A preparation method of a high-cycle stable secondary zinc battery cathode aluminum zinc alloy coating is characterized by comprising the following steps:
1) Heating the chamber and the sample stage, and vacuumizing the chamber by using a mechanical pump and a molecular pump; introducing Ar gas, and removing zinc oxide impurities on the surface of the zinc foil by using an ion source cleaning technology;
2) Introducing Ar gas, co-sputtering aluminum and zinc metal targets, adjusting the power of the two targets to change the content of an aluminum element in the alloy coating, and depositing the zinc-aluminum alloy coating on the surface of the zinc foil cleaned by the ion source;
3) And heating the obtained zinc foil modified by the zinc-aluminum coating to obtain the component-adjustable aluminum-zinc alloy coating for the zinc battery cathode.
2. The method for preparing the aluminum-zinc alloy coating of the negative electrode of the high-cycle stable secondary zinc battery as claimed in claim 1, wherein in the step 1), ar gas is introduced, and the specific conditions of the ion source cleaning technology are as follows: setting the flow rate of Ar gas to be 15sccm, adjusting the pressure in the chamber to be 0.4Pa, setting the cathode voltage to be 40V, setting the anode voltage to be 70V and biasing to be-200V; the ion source cleaning time is 10-15 min.
3. The method for preparing the aluminum-zinc alloy coating of the negative electrode of the high-cycle-stability secondary zinc battery as claimed in claim 1, wherein in the step 2), the specific conditions for introducing Ar gas and co-sputtering the aluminum and zinc metal targets are as follows: introducing Ar gas, wherein the total flow of the gas is 60sccm; the power of the aluminum metal target material is adjusted to 100-200W, the power of the zinc target material is adjusted to 100-200W, the sputtering pressure is maintained at 2.0Pa, and the sputtering time is 30min.
4. The method for preparing the aluminum-zinc alloy coating of the negative electrode of the secondary zinc battery with high cycle stability as claimed in claim 1, wherein in the step 2), the thickness of the aluminum-zinc alloy coating is 0.8 to 1.5 μm.
5. The method for preparing the aluminum-zinc alloy coating of the negative electrode of the secondary zinc battery with high cycle stability as claimed in claim 1, wherein in the step 2), the content of the aluminum element is 20 to 40 percent under different sputtering powers.
6. The method for preparing the aluminum-zinc alloy coating of the negative electrode of the secondary zinc battery with high cycle stability as claimed in claim 1, wherein in the step 3), the specific conditions for performing the heat treatment on the obtained zinc foil modified by the zinc-aluminum coating are as follows: introducing 30sccm of N into the chamber 2 Gas and 30sccm of Ar mixed gas, wherein the substrate temperature is set to be 120 ℃, the chamber temperature is 150 ℃, and the heat treatment time is 30min.
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