CN117831964A - Hydrophilic corrosion-resistant LaPO 4 Preparation method and application of interface layer modified zinc metal anode - Google Patents
Hydrophilic corrosion-resistant LaPO 4 Preparation method and application of interface layer modified zinc metal anode Download PDFInfo
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Abstract
The invention discloses a hydrophilic corrosion-resistant LaPO 4 Preparation method and application of interface layer modified zinc metal anode, aiming at the problems of hydrogen evolution and zinc corrosion side reaction, serious and uncontrollable zinc dendrite growth caused by zinc and electrolyte in water-based electrolyte of pure zinc metal anode, hydrophilic corrosion-resistant LaPO is adopted 4 And the interface layer is modified to improve the comprehensive electrochemical performance of the zinc anode. Spherical LaPO 4 LaPO of particle composition 4 The interface layer has excellent hydrophilicity and rich porosity, can play the role of a reservoir, inhibit the activity of water in the zinc anode interface electrolyte, and weaken the reactivity of water and a zinc anode, thereby inhibiting electrochemical hydrogen evolution and zinc corrosion side reactions of the zinc anode interface. Furthermore, laPO 4 The interface can also inhibit two-dimensional diffusion of zinc ions at the interface, induce uniform zinc deposition, avoid zinc dendrite generation and realize development of long-cycle-life zinc anode.
Description
Technical Field
The invention belongs to the technical field of water-based zinc ion batteries and zinc ion capacitors, and relates to hydrophilic corrosion-resistant LaPO 4 Zinc metal anode modified by interface layer (LaPO) 4 Zn) and its preparation method and application.
Background
Zinc-based aqueous energy storage systems such as zinc ion batteries and zinc ion capacitors have attracted considerable attention from researchers due to their high safety, abundant resources, high specific capacity, and the like. The metallic zinc negative electrode is the negative electrode material with the most commercialized prospect in the field of zinc ion batteries or zinc ion capacitors, and has high theoretical capacity (820 mAh g −1 ) Low electrochemical oxidation-reduction potential, abundant resources, convenient assembly and the like. However, the problems of serious interface side reactions (hydrogen evolution reaction, zinc metal corrosion) and uncontrollable dendrite growth and the like of the zinc metal negative electrode in the water-based electrolyte still prevent the practical application of the zinc negative electrode and the water-based energy storage device. Uncontrolled zinc dendrite growth on zinc metal surfaces, for example, can lead to the generation of "dead zinc" which, in severe cases, can puncture the separator causing shorting and failure of the cell. Current researchers have proposed electrolyte composition optimization,The interface modification and zinc metal structure optimization peak strategy are used for solving the problems of the zinc cathode. However, the technical problem of side reaction and dendrite control of the zinc cathode interface is not solved effectively.
In order to prevent dendrites from penetrating the separator and inhibit side reactions at the zinc anode interface, researchers have now proposed some effective interface protection layer modification strategies to reduce the occurrence of interface side reactions and inhibit dendrite growth and its damage to the separator. For example, some organic polymer materials (such as PAN, PVDF and the like) are directly coated on the surface of the zinc cathode, so as to improve the comprehensive electrochemical performance of the zinc cathode. For example, the patent CN114864913a generates zinc fluoride or cerium fluoride layer on the zinc surface in situ, which can induce zinc to deposit uniformly while inhibiting side reaction, and avoid dendrite generation. Although some research progress has been made in this area, there are also problems with existing modification strategies. For example, the interfacial layer of the hydrophobic organic polymer material may inhibit side reactions, but may affect the wetting of the electrolyte, resulting in slow migration of zinc ions. In addition, swelling phenomenon can occur when a single organic polymer material is soaked in electrolyte for a long time, so that the interface protection layer is unstable. While in-situ grown inorganic interface layers have better mechanical strength and can optimize uniformity of zinc deposition, in-situ grown coatings are generally thinner, have limited inhibition effect on electrochemical hydrogen evolution, and have poor volume adaptability. Therefore, an interface protection layer which can be stable in aqueous solution for a long time and has better mechanical strength is sought, and the interface protection layer can inhibit the technology of coating some inorganic nano materials on the surface of a zinc anode in the prior art of zinc and water in electrolyte, for example, a preparation method of porous vermiculite nano sheets acting on the zinc anode in patent CN116443887A, wherein vermiculite is dispersed in water, and simultaneously mechanical stirring and ultrasonic crushing are carried out to obtain a suspension containing vermiculite sheets; carrying out solid-liquid separation on the suspension to obtain a supernatant; and freeze-drying the supernatant to obtain the porous vermiculite nano sheet. Although the zinc cathode can be protected to a certain extent by the multi-layer or multi-layer atomic pore canal, the zinc cathode has no larger internal specific surface area and can not control dendrite deposition electroplated on the surface of the zinc cathode, and the migration number of zinc ions is limited, and the preparation method and the performance improvement of the zinc cathode still need to be improved.
Disclosure of Invention
Aiming at the technical problems of the existing zinc anode coating in the aspects of simultaneously realizing uniform zinc deposition, inhibiting zinc anode interface side reaction, accelerating interface zinc ion migration and the like, the invention provides a hydrophilic corrosion-resistant LaPO 4 Preparation method of interface layer modified zinc metal anode and nanosphere LaPO 4 The particles are used as a main material to form hydrophilic LaPO on the surface of the zinc anode 4 The interface protective layer is used for realizing uniform zinc deposition so as to realize development of the dendrite-free zinc anode, and can also inhibit electrochemical hydrogen evolution and zinc corrosion side reaction of water and the zinc anode in the interface electrolyte, thereby improving the cycling stability of the zinc anode.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
as a first aspect of the present invention, there is provided the hydrophilic corrosion-resistant LaPO 4 The preparation method of the interface layer modified zinc metal anode comprises the following steps: taking (NH) 4 ) 3 PO 4 Dissolving the powder in water to obtain (NH) 4 ) 3 PO 4 Aqueous solution in which (NH) 4 ) 3 PO 4 The mass ratio of the water to the water is 1:2.5-10; taking La (NO) 3 ) 3 ·6H 2 Dissolving O in water to obtain La (NO) 3 ) 3 Aqueous solution in which La (NO 3 ) 3 ·6H 2 The mass ratio of O to water is 1:1-5; control (NH) 4 ) 3 PO 4 Aqueous solution and La (NO) 3 ) 3 The volume ratio of the aqueous solution is 0.5-2:1. Will (NH) 4 ) 3 PO 4 Dripping the aqueous solution into La (NO) 3 ) 3 In the aqueous solution, heating and stirring at 30-90 ℃ until the mixed solution becomes turbid. After centrifugal washing, the obtained material is dried for 12 to 48 hours at 50 to 90 ℃ to obtain LaPO 4 And (3) powder. Taking a binder and LaPO with the mass ratio of 1:3-10 4 Placing the powder in a mortar, adding an appropriate amount of organic solvent (N-dimethylpyrrolidone) per 1g based on the total mass of binder and LaPO45-20, mL, grinding to make the slurry uniform, and then coating the slurry on the surface of the zinc sheet. Finally, drying the zinc sheet coated by the coating at 30-90 ℃ for 8-48 hours, wherein the thickness of the dried coating is 30-90 mu m to obtain LaPO 4 and/Zn metal anode, namely hydrophilic corrosion-resistant LaPO4 interface layer modified zinc metal anode.
As a second aspect of the invention, the present application also provides LaPO 4 Zinc ion capacitor prepared by Zn metal anode.
The negative electrode of the zinc ion capacitor is LaPO 4 The Zn metal electrode, the anode is a carbon material electrode, and the electrolyte is zinc sulfate aqueous solution.
The carbon material electrode comprises a coating layer and a conductive substrate, wherein the components of the coating layer are carbon materials and binders, and the concentration of the zinc sulfate aqueous solution is 0.5-5 mol/L.
The carbon material is one or two of active carbon, acetylene black and carbon nano tube; the binder is one of PVDF and PTFE; the conductive substrate is one of titanium foil, stainless steel net and carbon cloth.
The invention has the following beneficial effects:
1. the zinc ions have stronger solvation effect in the zinc sulfate electrolyte, and the stronger acting force of the zinc ions and water molecules can lead to difficult migration of the zinc ions at the interface of the pure zinc anode, thus leading to poor dynamic migration behavior of the zinc ions at the interface of the zinc anode and uncontrollable zinc deposition behavior. In addition, the pure zinc interface has the problems of side reactions between zinc and water, such as electrochemical hydrogen evolution, zinc corrosion and the like. The side reaction of the pure zinc anode may deteriorate the efficiency of zinc plating/stripping and the cycling stability of the zinc anode. LaPO in the present invention 4 The zinc anode has excellent hydrophilicity, and can play a role of a reservoir at the interface of the zinc anode, so that the reactivity of water can be weakened, the side reaction between the water and the edge of zinc can be inhibited, and the separation of zinc ions from water molecules can be facilitated, and the interface migration of the zinc ions can be accelerated. Furthermore, laPO 4 The self-made water-based paint has better structural stability in water, can play a long-term interface protection role in the long-term electrochemical circulation process. The invention adopts the nanometer spherical LaPO 4 An interfacial protection layer assembled from particles, which can be mentionedThe zinc ion desolvation of zinc ions is accelerated by the rich zinc ion transmission channels, and zinc deposition behaviors of zinc electrode interfaces can be optimized. Thus, laPO 4 Zn has the advantages of uniform zinc deposition, weakened electrochemical hydrogen evolution reaction and the like, thereby realizing the development of zinc cathodes and zinc ion batteries with long cycle life.
2. The invention constructs LaPO on the zinc electrode 4 An interface protection layer which can avoid direct contact between the zinc cathode and the electrolyte and can realize zinc deposition to occur in LaPO 4 And the damage of uncontrollable zinc dendrites to the diaphragm is avoided between the zinc plate, and the circulation stability of the zinc anode is improved.
3. LaPO prepared by the invention 4 The Zn anode can effectively inhibit zinc dendrite growth, and the comparison with a comparison sample (blank pure zinc anode) shows that the LaPO prepared by the invention 4 The Zn anode has flat electrode surfaces before and after the reaction, no vertical dendrite is found, more vertical dendrite appears after the blank pure zinc anode is reacted, the anode surface is broken, as shown in figure 1, the LaPO is proved 4 The Zn anode can realize the function of zinc-free dendrite growth.
4. LaPO prepared by the invention 4 The Zn anode has excellent multiplying power performance and cycle stability. As shown in FIG. 3, at 2 mA cm -2 ，1 mAh cm -2 Next, the blank pure Zn// Zn symmetric cell had a sudden dip in polarization voltage when cycled to 50 h, a phenomenon resulting from cell damage caused by cell shorting. Under the same test conditions, the LaPO of the invention 4 After 700 h cycles,/Zn still exhibits a stable polarization voltage curve, exhibiting excellent cycling stability. As can be seen from the rate capability of FIG. 2, when the switching current density is from 1 to 10 mA cm -2 In this case, a sharp voltage short circuit phenomenon occurs in the pure zinc symmetrical battery. Whereas LaPO 4 Zn switching current density from 1 to 10 mA cm -2 It still showed smooth and even changes when measured from 10 mA cm -2 Is switched back to 1 mA cm -2 At the time of LaPO 4 The Zn symmetric battery still maintains stable polarization voltage and shows excellent rate performance.
5. LaPO prepared by the invention 4 Zn has a higher degree ofGood migration behavior of zinc ions as shown in FIG. 4, laPO prepared by testing the present invention 4 CA curve of Zn and pure zinc shows that LaPO 4 Zn contributes to three-dimensional diffusion of zinc ions, whereas pure zinc tends more to two-dimensional diffusion. It is known that three-dimensional diffusion of zinc ions will help to achieve uniform zinc deposition, avoiding zinc dendrite formation.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows LaPO prepared in example 1 of the present invention 4 A comparison chart of electron micrographs before and after the reaction of the modified metal zinc anode and the comparison pure zinc anode under the same scale; wherein (a) is a scanning electron microscope image of a pure zinc electrode before reaction; (b) As LaPO before reaction 4 Scanning electron microscope image of Zn electrode; (c) scanning electron microscope pictures of the pure zinc electrode after the reaction; (d) To be reacted LaPO 4 Scanning electron microscope image of Zn electrode.
FIG. 2 shows pure zinc, laPO in example 1 of the present invention 4 Zn symmetric cell at 1 mAh cm -2 And (3) a ratio performance graph under plating capacity.
FIG. 3 shows pure zinc, laPO in example 1 of the present invention 4 The Zn symmetric battery has a capacity of 2 mA cm -2 、1 mAh cm -2 Long cycle performance plot under test conditions.
FIG. 4 shows pure zinc, laPO, of example 1 of the present invention 4 CA test result diagram of Zn electrode.
FIG. 5 shows pure zinc, laPO in example 1 of the present invention 4 Zinc ion migration number of Zn electrode.
FIG. 6 shows LaPO prepared in example 1 of the present invention 4 Zn/AC and comparative example Zn/AC Zinc ion capacitor at the same current density (200 mA g -1 -2000 mA g -1 ) Multiple of the lower testRate performance graph.
FIG. 7 shows LaPO in example 1 of the present invention 4 Long cycle performance of the/Zn// AC versus the control group Zn// AC capacitors.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1
This example is a hydrophilic corrosion resistant LaPO 4 Zinc metal anode modified by interface layer (nanometer particle LaPO) 4 Zn metal negative electrode) is prepared by the following steps:
(1) Take 15 g (NH) 4 ) 3 PO 4 Dissolved in 105g of water ((NH) 4 ) 3 PO 4 The mass ratio of the water to the water is 1:7), stirring, and ultrasonic dispersing until (NH) 4 ) 3 PO 4 All dissolved (solution a).
(2) 40 g La (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, (La (NO) 3 ) 3 ·6H 2 The mass ratio of O to water is 1:2.5, and stirring and ultrasonic dispersing are carried out until La (NO 3 ) 3 The solution was completely dissolved (solution B).
(3) 100mL of solution A was continuously titrated into 100mL of solution B ((NH) 4 ) 3 PO 4 Aqueous solution and La (NO) 3 ) 3 The volume ratio of the aqueous solution is 1:1), the dripping process is carried out under stirring at 60 ℃, and then the product is dried at 70 ℃ for 24 hours after centrifugal washing, thus obtaining the LaPO 4 And (3) powder.
(4) 54 mg LaPO is taken 4 6mgPVDF (binder and LaPO) 4 The mass ratio of (1:9), 0.6 mLN-dimethyl pyrrolidone is mixed and ground uniformly to form coating slurry, then a scraper with the size of 150 mu m coats the slurry on the surface of a zinc sheet, and then the zinc sheet is dried for 24 hours at the temperature of 70 ℃ to obtain LaPO 4 Zn metal anode, i.e. hydrophilic corrosion-resistant LaPO 4 The zinc metal anode is decorated to the interface layer, and the thickness of coating is 60 mu m.
(5) The LaPO is prepared by 4 Zn is used as a negative electrode, a 2mol/L zinc sulfate aqueous solution is used as an electrolyte, activated carbon and acetylene black are coated on a titanium foil under the action of PVDF to obtain a carbon material electrode which is used as a positive electrode, and a zinc ion capacitor is assembled and tested for performance.
Example 2
This example is a hydrophilic corrosion resistant LaPO 4 Zinc metal anode modified by interface layer (nanometer particle LaPO) 4 Zn metal negative electrode) is prepared by the following steps:
(1) 40 to g (NH) 4 ) 3 PO 4 Dissolved in 100g of water ((NH) 4 ) 3 PO 4 The mass ratio of the water to the water is 1:2.5), stirring, and ultrasonic dispersing until (NH) 4 ) 3 PO 4 All dissolved (solution a).
(2) 100g La (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, (La (NO) 3 ) 3 ·6H 2 The mass ratio of O to water is 1:1, and stirring and ultrasonic dispersing are carried out until La (NO 3 ) 3 The solution was completely dissolved (solution B).
(3) 50mL of solution A was continuously titrated into 100mL of solution B ((NH) 4 ) 3 PO 4 Aqueous solution and La (NO) 3 ) 3 The volume ratio of the aqueous solution is 0.5:1), the dripping process is carried out under stirring at 30 ℃, and then the product is dried at 50 ℃ for 8 hours after centrifugal washing, thus obtaining the LaPO 4 And (3) powder.
(4) 54 mg LaPO is taken 4 18mgPVDF (binder and LaPO) 4 The mass ratio of (1:3), 0.36-mLN-dimethyl pyrrolidone is mixed and ground uniformly to form coating slurry, then a 150 mu m scraper coats the slurry on the surface of a zinc sheet, and then the zinc sheet is dried for 48 hours at 90 ℃ to obtain LaPO 4 Zn metal anode, i.e. hydrophilic corrosion-resistant LaPO 4 The zinc metal anode is decorated to the interface layer, and the thickness of coating is 90 mu m.
(5) The LaPO is prepared by 4 Zn is negative electrode, 0.5mol/LThe zinc sulfate aqueous solution is used as electrolyte, the carbon material electrode obtained by coating activated carbon on the titanium foil under the action of PVDF is used as an anode, and the zinc ion capacitor is assembled and tested for performance.
Example 3
This example is a hydrophilic corrosion resistant LaPO 4 Zinc metal anode modified by interface layer (nanometer particle LaPO) 4 Zn metal negative electrode) is prepared by the following steps:
(1) Take 10 g (NH) 4 ) 3 PO 4 Dissolved in 100g of water ((NH) 4 ) 3 PO 4 The mass ratio of the water to the water is 1:10), stirring, and performing ultrasonic dispersion until (NH) 4 ) 3 PO 4 All dissolved (solution a).
(2) 20 g La (NO) 3 ) 3 ·6H 2 O was dissolved in 100mL of water, (La (NO) 3 ) 3 ·6H 2 O and water in a mass ratio of 1:5, stirring, and performing ultrasonic dispersion until La (NO 3 ) 3 The solution was completely dissolved (solution B).
(3) 100mL of solution A was continuously titrated into 50mL of solution B ((NH) 4 ) 3 PO 4 Aqueous solution and La (NO) 3 ) 3 The volume ratio of the aqueous solution is 2:1), the dripping process is carried out under stirring at 90 ℃, and then the product is dried at 90 ℃ for 8 hours after centrifugal washing, thus obtaining the LaPO 4 And (3) powder.
(4) 100 mg LaPO is taken 4 1mgPVDF (binder and LaPO) 4 The mass ratio of (1:10), 2.02 mLN-dimethyl pyrrolidone is mixed and ground uniformly to form coating slurry, then a scraper with the size of 100 mu m coats the slurry on the surface of a zinc sheet, and then the zinc sheet is dried for 40 hours at the temperature of 30 ℃ to obtain LaPO 4 Zn metal anode, i.e. hydrophilic corrosion-resistant LaPO 4 The zinc metal anode is decorated to the interface layer, and the thickness of coating is 30 mu m.
(5) The LaPO is prepared by 4 Zn is used as a negative electrode, a 5mol/L zinc sulfate aqueous solution is used as an electrolyte, a carbon material electrode obtained by coating a carbon nano tube on a stainless steel net under the action of PTFE is used as a positive electrode, and a zinc ion capacitor is assembled and tested for performance.
Example 4
This example is a hydrophilic corrosion resistant LaPO 4 Zinc metal anode modified by interface layer (nanometer particle LaPO) 4 Zn metal negative electrode) is prepared by the following steps:
(1) Take 20 g (NH) 4 ) 3 PO 4 Dissolved in 100g of water ((NH) 4 ) 3 PO 4 The mass ratio of the water to the water is 1:5), stirring, and ultrasonic dispersing until (NH) 4 ) 3 PO 4 All dissolved (solution a).
(2) 20 g La (NO) 3 ) 3 ·6H 2 O was dissolved in 60mL of water, (La (NO) 3 ) 3 ·6H 2 The mass ratio of O to water is 1:3, and stirring and ultrasonic dispersing are carried out until La (NO 3 ) 3 The solution was completely dissolved (solution B).
(3) 50mL of solution A was continuously titrated into 50mL of solution B ((NH) 4 ) 3 PO 4 Aqueous solution and La (NO) 3 ) 3 The volume ratio of the aqueous solution is 1:1), the dripping process is carried out under stirring at 70 ℃, and then the product is dried at 60 ℃ for 20h after centrifugal washing, thus obtaining the LaPO 4 And (3) powder.
(4) 100 mg LaPO is taken 4 10mgPVDF+10mgPTFE (adhesive and LaPO) 4 The mass ratio of (1:5), 1.2-mLN-dimethyl pyrrolidone is mixed and ground uniformly to form coating slurry, then a 200 mu m scraper coats the slurry on the surface of a zinc sheet, and then the zinc sheet is dried for 24 hours at 70 ℃ to obtain LaPO 4 Zn metal anode, i.e. hydrophilic corrosion-resistant LaPO 4 The zinc metal anode is decorated by the interface layer, and the thickness of the coating layer is 70 mu m.
(5) The LaPO is prepared by 4 Zn is used as a negative electrode, a 3mol/L zinc sulfate aqueous solution is used as an electrolyte, a carbon material electrode obtained by coating carbon nano tubes and acetylene black on carbon cloth under the action of PVDF is used as a positive electrode, and a zinc ion capacitor is assembled and tested for performance.
Examples of the effects
LaPO prepared in examples 1 to 4 4 After the Zn metal cathode is assembled into a symmetrical battery and a zinc ion capacitor, electrochemical performance test is carried out, and the test is as follows:
1. assembly and testing of Zn// Zn symmetric cells
LaPO prepared in example 1 4 Cutting Zn metal cathode into 8 mm diameter disc, using glass fiber as diaphragm, using 2M ZnSO 4 The solution is electrolyte, a metal gasket and an elastic sheet are used as filling materials, the CR-2032 button cell is assembled and packaged by a packaging machine, and then the electrochemical performance test is carried out after standing for 7 h. Zinc deposition/stripping performance was tested on a blue charge-discharge tester using a constant current method to characterize its cycle performance and polarization potential, and the results are shown in fig. 2 and 3. The same assembly method is used for assembling the comparative Zn// Zn symmetric cell. LaPO compared to a pure Zn// Zn symmetric cell 4 /Zn//LaPO 4 The Zn symmetric battery shows more excellent cycle stability and better rate performance at the display site.
Test LaPO 4 SEM comparison of Zn and pure zinc electrodes before and after zinc plating/stripping, the results are shown in fig. 1. Fig. 1 (a) is an SEM picture of a pure Zn electrode before reaction; (b) As LaPO before reaction 4 SEM picture of Zn; (c) SEM pictures of the pure Zn electrode after the reaction; (d) To be reacted LaPO 4 SEM pictures of Zn. From (a) and (b), it was found that the surface of the comparative sample of pure Zn before the reaction was relatively flat, and from (b), the prepared LaPO was found 4 The surface morphology of Zn is formed by uniformly stacking nano particles; from (c), it is known that the surface of the blank pure Zn is uneven after reaction, and many dendrite byproducts in a vertical shape appear, and the dendrite can puncture the separator to damage the battery under severe conditions. However, from (d), it is known that the nanoparticles LaPO 4 The surface of the electrode plate keeps the original uniformly distributed morphology of the nano particles after Zn circulation, and zinc dendrite deposition does not exist on the surface. From this, laPO 4 The growth of zinc dendrites can be inhibited after modification, and the generation of upright zinc dendrites is avoided.
2. CA and zinc ion migration transport test
LaPO prepared in example 1 4 The Zn electrode plate is subjected to CA and negative electrode zinc ion migration number test, and the LaPO is characterized 4 The Zn pole piece has excellent performance of enhancing ion diffusion kinetics during zinc ion deposition, as shown in figures 4 and 5. From the CA chart of FIG. 4, laPO is known 4 Zn realizes zinc ion very quicklyWhile the two-dimensional diffusion process of zinc ions of pure Zn is long. Longer two-dimensional diffusion tends to result in dendrite growth. The migration number of zinc ions in FIG. 4 indicates LaPO 4 The Zn electrode has higher migration number of zinc ions, which means LaPO 4 The interfacial layer accelerates migration of zinc ions.
3. Zinc// active carbon full cell assembly
LaPO prepared in example 1 4 Cutting Zn metal cathode into 8 mm diameter disc, coating active carbon, acetylene black and binder (PVDF) on titanium foil according to mass ratio of 7:2:1, vacuum drying at 70deg.C, cutting into 8 mm diameter electrode sheet, and controlling active load at 1-1.5 mg/cm -2 And serves as a positive electrode. Glass fiber is used as a diaphragm, and 2M ZnSO is used as a diaphragm 4 The solution is electrolyte, a metal gasket and an elastic sheet are used as filling materials, the CR-2032 button cell is assembled and packaged by a packaging machine, and then the electrochemical performance test is carried out after standing for 7 h. The same assembly method was used to assemble the comparative Zn// AC zinc ion capacitor.
4. Electrochemical performance test analysis
FIGS. 2 and 3 show LaPO prepared in example 1 of the present invention 4 /Zn//LaPO 4 Performance comparison of Zn versus comparative Zn// Zn symmetric cells. As can be seen from FIG. 3, the temperature is 2 mA cm -2 When the Zn// Zn cell is cycled to 30 h, the polarization voltage curve is suddenly dropped by a cliff, which is indicative of a short circuit to the symmetrical cell. In contrast, laPO 4 The symmetrical cell of/Zn still exhibits a stable polarization voltage curve after 700 h cycles, exhibiting excellent cycling stability. As can be seen from fig. 2, when the current density is switched, the polarization voltage of the pure zinc electrode is suddenly changed or short-circuited. In contrast, for LaPO 4 Zn, when the switching current density is from 1 to 10 mA cm -2 When the polarization curve of the light source is changed smoothly, the polarization curve of the light source is changed smoothly. When it is from 10 mA cm -2 Is switched back to 1 mA cm -2 At the time of LaPO 4 The Zn symmetric cell still maintains stable polarization voltage, which indicates LaPO 4 Zn has excellent rate performance.
FIG. 6 shows LaPO prepared in example 1 of the present invention 4 Zn// AC and comparative Zn// AC Zinc ion capacitors at different current densities (200 mA g -1 -1000 mA g -1 ) Is a charge-discharge rate performance graph of (a). As can be seen from FIG. 6, at 1000 mA g -1 LaPO at high current density of (2) 4 The Zn/AC capacitor can also reach 50mAh g -1 Specific capacity of 200 mA g -1 Can be recovered to 59 mAh g -1 This is clearly superior to the performance of Zn// AC zinc ion capacitors. This benefits from LaPO 4 Higher zinc ion migration number and no dendrite growth characteristics.
FIG. 7 shows LaPO prepared in example 1 of the present invention 4 Long cycle performance comparative plots of Zn// AC and comparative Zn// AC zinc ion capacitors. As can be seen from FIG. 7, it was experimentally verified that at a current density of 1A/g, laPO 4 The first 2000 specific capacity of Zn/AC can reach 50mAh g -1 42 mAh g compared to pure zinc -1 Has higher specific capacity. In addition, the material can still keep up to 55 mAh g after 10000 times of circulation -1 And cycle efficiency as high as 99.58% or more, exhibits excellent capacity retention and cycle life.
Table 1 comparison of pure zinc performance for examples 1-4 and the comparison
Table 1 shows the comparison of the pure zinc properties of examples 1-4 with the comparison sample, and it can be seen from Table 1 that the comparison sample Zn// AC zinc ion capacitor has a cycle life of only 3000 cycles and a specific capacity of less than 40 mAh g at 2000 cycles -1 The method comprises the steps of carrying out a first treatment on the surface of the LaPO in example 1 4 The coating thickness of the zinc anode interface protective layer for the Zn// AC zinc ion capacitor is 60 mu m, the capacitor can be circulated to 18000 circles, and the specific capacity can reach 49.79 mAh g when 2000 circles -1 The method comprises the steps of carrying out a first treatment on the surface of the LaPO in example 2 4 The coating thickness of the zinc cathode interface protective layer for the Zn// AC capacitor is increased to 90 mu m, the increase of the coating thickness leads to the increase of the cycle life of the device, but the interface coating is too thick to influence the dynamics of zinc ion migration, so that the specific capacity is reduced to 45mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the LaPO in example 3 4 The coating thickness of the zinc anode interface protective layer for Zn// CNT is 30 mu m, and the specific capacity of the assembled capacitor device reaches 50mAh g -1 The cycle life is 12000 cycles; laPO in example 4 4 The thickness of the zinc anode interface protective layer for Zn// CNT is increased to 70 mu m, the cycle life of the device can reach 17000 circles, and the specific capacity is 48.5mAh g -1 。
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. Hydrophilic corrosion-resistant LaPO 4 The preparation method of the interface layer modified zinc metal anode is characterized by comprising the following steps:
(1) Will (NH) 4 ) 3 PO 4 The aqueous solution was added dropwise to La (NO) 3 ) 3 Heating and stirring the aqueous solution until the solution is turbid, and then centrifugally washing and drying the aqueous solution to obtain LaPO 4 A powder;
(2) LaPO of step (1) 4 Mixing and grinding the powder and the binder under the action of an organic solvent to obtain slurry, and then coating the slurry on the surface of a zinc sheet to form LaPO 4 Coating, and drying to obtain LaPO 4 Zn metal anode, i.e. hydrophilic corrosion-resistant LaPO 4 And zinc metal anode with interface layer modified.
2. The hydrophilic corrosion resistant LaPO of claim 1 4 The preparation method of the interface layer modified zinc metal anode is characterized by comprising the following steps: in the step (1) (NH) 4 ) 3 PO 4 In aqueous solution (NH) 4 ) 3 PO 4 The mass ratio of the water to the water is 1:2.5-10, la (NO 3 ) 3 La (NO) in aqueous solution 3 ) 3 ·6H 2 The mass ratio of O to water is 1:1-5; wherein (NH) 4 ) 3 PO 4 Aqueous solution and La (NO) 3 ) 3 The volume ratio of the aqueous solution is 0.5-2:1.
3. A hydrophilic corrosion resistant LaPO according to claim 2 4 The preparation method of the interface layer modified zinc metal anode is characterized by comprising the following steps: the heating and stirring conditions in the step (1) are that the temperature is 30-90 ℃, the drying conditions are that the temperature is 50-90 ℃ and the time is 12-48h.
4. A hydrophilic corrosion resistant LaPO according to claim 3 4 The preparation method of the interface layer modified zinc metal anode is characterized by comprising the following steps: the binder in the step (2) is one or two of PVDF or PTFE, and the binder and LaPO 4 The mass ratio of (3) is 1:3-10.
5. The hydrophilic corrosion resistant LaPO of claim 4 4 The preparation method of the interface layer modified zinc metal anode is characterized by comprising the following steps: the organic solvent in the step (2) is N-dimethyl pyrrolidone, and the organic solvent is prepared from a binder and LaPO 4 5-20. 20 mL of organic solvent is added per 1g of the total mass.
6. The hydrophilic corrosion resistant LaPO of claim 5 4 The preparation method of the interface layer modified zinc metal anode is characterized by comprising the following steps: and (3) drying in the step (2) at the temperature of 30-90 ℃ for 8-48 hours, wherein the thickness of the dried coating layer is 30-90 mu m.
7. LaPO (LaPO) 4 A Zn metal anode characterized in that: the LaPO 4 A Zn metal anode prepared by the method of any one of claims 1-6.
8. Use of LaPO according to claim 7 4 The zinc ion capacitor prepared by the Zn metal anode is characterized in that: the negative electrode of the zinc ion capacitor is LaPO 4 and/Zn, wherein the anode is a carbon material electrode, and the electrolyte is zinc sulfate aqueous solution.
9. The LaPO of claim 8 4 The zinc ion capacitor prepared by the Zn metal anode is characterized in that: the carbon material electrode comprises a coating layerAnd a conductive substrate, wherein the components of the coating layer are carbon materials and binders, and the concentration of the zinc sulfate aqueous solution is 0.5-5 mol/L.
10. The LaPO of claim 9 4 The zinc ion capacitor prepared by the Zn metal anode is characterized in that: the carbon material is one or two of active carbon, acetylene black and carbon nano tubes; the binder is PVDF and/or PTFE; the conductive substrate is one of titanium foil, stainless steel net and carbon cloth.
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