CN115710734A - 220 preferred orientation copper material, preparation thereof and application thereof in metal cathode and metal battery - Google Patents

Abstract

The invention belongs to the field of metal battery cathode materials, and particularly relates to a 220 preferred orientation copper material, wherein the relative texture coefficient of a Cu (220) crystal face is more than or equal to 75%. The invention also provides the preparation and application of the copper material, and also provides a zinc cathode based on the copper material composite, and the preparation and application thereof. The invention provides a copper material with a 220 crystal face texture coefficient of more than or equal to 75%, and the 220 preferred orientation material is found to have excellent metal reversible deposition/stripping performance, thereby being beneficial to improving the electrochemical performance of a metal cathode.

Description

220 preferred orientation copper material, preparation thereof and application thereof in metal cathode and metal battery

Technical Field

The invention belongs to the field of metal negative current collector materials, and particularly relates to the field of metal negative electrodes.

Background

The water system zinc ion battery taking zinc metal as the cathode has the advantages of safety, environmental protection, considerable energy density and the like, and is expected to replace the lithium ion battery in a large-scale energy storage system, so that the problems of resources, safety and the like of the lithium ion battery are solved. However, the practical application of zinc foil cathodes is limited because it suffers from zinc dendrites and zinc foil perforation problems due to irregular zinc deposition/stripping during cycling. The problem of perforation of the electrode can be essentially solved by using an inert current collector, but zinc dendrites are induced due to the non-uniformity of the substrate surface and the low zinc deposition activity. The problems of activity and heterogeneity of the substrate surface can be relieved by regulating the crystal plane orientation of the substrate surface. For example, a planar graphene decorative layer may achieve dense zinc deposition by inducing epitaxial growth of Zn (001), and copper nanowires with Cu (111) crystal face exposure may promote uniform growth of zinc and nucleation. In addition, commercially expensive Cu (100) single crystals can also be used to suppress the generation of zinc dendrites. However, the prospects for graphene, copper nanowires and copper single crystals for low-cost aqueous zinc-ion batteries are severely limited because of their high cost. Therefore, there is a need to develop more efficient and less costly conditioning strategies for current collector materials.

Electrolytic copper foil is a widely used commercial current collector material due to its mature manufacturing technology and acceptable cost. Selective crystal face exposure during copper foil electrolysis has proven to be easy to achieve and can be integrated into existing copper foil manufacture. Thus, the preparation of specially oriented copper foil by electrolysis may be a promising practical method. Unfortunately, the copper electrolysis process may expose multiple crystal planes such as (111), (200), (220), and (311), etc., whose zinc deposition activity has not been fully studied, nor can it be determined which crystal plane is most active. If the most active crystal plane is identified, zinc deposition can be efficiently tuned by selectively exposing that crystal plane. Therefore, the production of copper current collector materials with high active crystal face exposure by electrolytic methods is very important to improve the reversibility of zinc deposition/exfoliation of the current collector.

Disclosure of Invention

The first objective of the invention is to provide a copper material with 220 preferred orientation, aiming at providing a material with excellent reversible deposition/stripping property of metal (such as metal zinc) and improved electrochemical performance of the prepared metal cathode.

The second objective of the invention is to provide a preparation method of the copper material with the 220 preferred orientation, and to provide a copper material which can prepare a copper material with a high 220 texture coefficient and can improve the electrochemical performance of a metal negative electrode.

The third purpose of the invention is to provide the application of the copper material with the preferred orientation of 220 as a current collector for inducing the reversible deposition/stripping of metals such as metal zinc and preparing a metal zinc cathode.

The fourth purpose of the invention is to provide a composite zinc negative electrode for depositing zinc metal on a copper material with a preferred orientation of 220, which aims to improve the reversible deposition/stripping of zinc of the zinc negative electrode and improve the electrochemical stability.

The fifth purpose of the invention is to provide a preparation method of the composite zinc negative electrode and application of the composite zinc negative electrode in a battery.

The sixth purpose of the invention is to provide a metal zinc battery containing the composite zinc negative electrode.

220, the relative texture coefficient of the Cu (220) crystal face is more than or equal to 75 percent.

The invention provides a copper material with a 220 crystal face texture coefficient of more than or equal to 75%, and the 220 preferred orientation material is found to have excellent metal reversible deposition/stripping performance, which is beneficial to improving the electrochemical performance of the prepared metal cathode.

The invention innovatively researches and discovers that the 220 preferred orientation and the metal deposition activity have positive correlation, and the improvement of the relative texture coefficient of a (220) crystal face is beneficial to improving the metal deposition activity and is beneficial to unexpectedly improving the electrochemical performance of a metal cathode.

In the present invention, the relative texture coefficient [ TC (220) ] of the (220) crystal plane accounts for the ratio [ TC (220) ] of the total Texture Coefficient (TC) of the (111), the (200), the (220) and the (311) crystal planes of the copper layer.

Preferably, the relative texture coefficient of the Cu (220) crystal face is more than or equal to 85 percent; more preferably 90%. Research shows that the copper material with the preferable Cu (220) crystal face contributes to further improving the reversible deposition/stripping of metal and the electrochemical performance of the prepared metal cathode.

Preferably, the copper material is a copper planar material (such as copper foil).

The invention also provides a preparation method of the copper material with the 220 preferred orientation, which comprises the steps of taking copper as an anode and a deposition substrate as a cathode, and carrying out electroplating treatment in a copper plating solution to obtain the copper material with the 220 preferred orientation;

the copper plating solution is an aqueous solution in which copper sulfate, sulfuric acid, a compound shown in the formula 1 and alkali metal chloride are dissolved; wherein, cuSO ₄ The concentration is 100-250gL ^-1 ；H ₂ SO ₄ The concentration of (A) is 50-120gL ^-1 (ii) a The compound of formula 1 is 0.05-0.2gL ^-1 (ii) a The concentration of alkali chloride is 0.1-0.4gL ^-1 ；

N is 1 to 6; m is H, na or K;

the current density of electroplating treatment is 100-200mAcm ^-2 。

The invention innovatively discovers that the copper material which has high 220 texture coefficient, excellent reversible metal deposition/stripping and improved metal negative electrode electrochemical performance can realize synergy and can unexpectedly induce 220 orientation by the combined control of the components, the component proportion and the current density of the copper plating solution.

In the invention, the alkali metal chloride is at least one of sodium chloride and potassium chloride.

Preferably, in the formula 1, n is 2 to 4, preferably 3; and M is Na or K.

In the present invention, the combined control of the components, component ratios, and current density of the plating solution is critical to the synergistic induction of 220 orientation.

Preferably, in the electroplating bath, cuSO ₄ The concentration is 150-200 gL ^-1 ；H ₂ SO ₄ The concentration of (A) is 80-100gL ^-1 (ii) a The compound of formula 1 is 0.1-0.2gL ^-1 (ii) a The concentration of alkali chloride is 0.1-0.4gL ^-1 。

In the present invention, the concentrations of the components of the plating solution refer to the measured concentrations of the ingredients.

Preferably, the plating solution is a solution consisting of copper sulfate, sulfuric acid, the compound of formula 1, an alkali metal chloride and water in the stated amounts.

Preferably, the current density of the electroplating treatment is 100-120mAcm ^-2 ；

Preferably, the electroplating treatment time is 6-10 min; preferably 8 to 10min.

In the present invention, the deposition substrate electrode may be any inert conductive substrate, such as stainless steel or titanium foil.

The invention also provides application of the copper material with the preferred orientation of 220, which is used as a current collector for preparing a metal battery.

The invention is preferably applied to the preparation of a composite metal negative electrode (a metal negative electrode with the current collector) of a metal battery by taking the current collector as the current collector and inducing metal to be uniformly deposited.

The innovative research of the invention finds that positive correlation exists between 220 orientation and metal deposition, the 220 texture coefficient is improved, the deposition activity of the metal is improved, and the electrochemical performance of the cathode after the metal deposition is improved.

Preferably, the metal is at least one of lithium, zinc and sodium; preferably zinc metal.

In a preferred application, the metal negative electrode is assembled to form a metal battery; for example, a lithium metal battery, a zinc metal battery, or the like may be used.

The invention also provides a composite zinc cathode, which comprises the 220 preferred orientation copper material; and metal zinc compounded on the surface of the zinc alloy.

In the invention, the copper material with the preferred orientation of 220 is used as a current collector, which is beneficial to inducing the deposition of metal zinc, so that the composite zinc cathode material can show excellent electrochemical performance.

In the invention, the copper material with the preferred orientation of 220 is used as a current collector, and metal zinc can be deposited on the current collector based on the existing method to obtain the composite zinc cathode. For example, the composite zinc cathode can be prepared by electrochemical deposition.

The invention also provides a preparation method of the composite zinc cathode, which is to electrodeposit metal zinc on the copper material with the preferred orientation of 220 to prepare the composite zinc cathode.

The preferred electrodeposition steps are: the zinc anode is used, the copper material with the preferred orientation of 220 is used as a cathode, and electrodeposition is carried out in zinc plating solution containing zinc salt to prepare the zinc-plated zinc alloy;

preferably, the zinc salt is a water-soluble zinc salt, and further preferably ZnSO ₄ 、ZnCl ₂ 、Zn (CH ₃ COO) ₂ And zinc trifluoromethanesulfonate. The concentration of the zinc salt is not particularly limited, and may be, for example, 0.5 to 5M.

Preferably, it isThe current density of electrodeposition is 1mAcm ^-2 -50mAcm ^-2 。

In the present invention, the content of the metallic zinc can be adjusted based on the existing knowledge and the application requirements, for example, can be 1-10 mAhcm ^-2 。

The invention also provides application of the composite zinc cathode, and a zinc metal battery is obtained by assembling the composite zinc cathode.

In the invention, the composite zinc cathode can be used as a cathode, and can be assembled with conventional electrical components and structures such as a cathode, a diaphragm and the like to form a battery taking zinc metal as the cathode.

The invention also provides a zinc metal battery which comprises the composite zinc cathode.

The novel metal battery of the invention can be well known in other parts and structures except for the composite zinc cathode of the invention. For example, the zinc metal battery is at least one of a zinc-manganese battery, a zinc-polyaniline battery, a zinc vanadate battery and a zinc ion battery capacitor.

Electrochemical testing and topography showed that these Cu (220) highly preferred current collectors have highly reversible zinc deposition/exfoliation behavior while exhibiting dendrite-free zinc deposition topography. Assembling Zn [ l ] MnO ₂ Full cell testing indicates that the optimized copper current collector can still have a capacity retention rate of 93.9% after 640 battery cycles, while the commonly commercialized electrolytic copper foil current collector has a capacity retention rate of only 44.2%.

Compared with the prior art, the invention has the following advantages:

(1) The invention provides a copper material with a high 220 texture coefficient rate, and researches show that the orientation content of 220 has positive correlation with metal reversible deposition/stripping.

The invention firstly uses an optical microscope combined with an electron back scattering diffraction technology and an energy spectrometer to prove that the Cu (220) crystal face has higher zinc deposition activity than the Cu (111), the Cu (200) and the Cu (311), thereby realizing high Cu (220) crystal face exposure and being beneficial to improving the overall activity of the electrode. For example, the copper foil with (220) relative texture coefficient more than or equal to 75% can realize highly reversible zinc deposition/stripping behavior by using the high-activity copper foil, and the method for regulating and controlling the crystal plane orientation of the copper foil by electrolysis has huge application prospect on the current collector of the lithium metal battery.

(2) The copper material can unexpectedly obtain (220) the copper material with the relative texture coefficient more than or equal to 75 percent through the combined control of the electroplating solution components, the component proportion, the current density and other processes, and the copper material can unexpectedly show excellent induced metal reversible deposition/stripping performance and excellent electrochemical performance.

Drawings

FIG. 1a is an optical micrograph of a large grain copper foil without zinc deposition;

FIG. 1b is a reverse pole figure obtained from electron back-scattering diffraction testing of large grain copper foil without zinc deposition;

FIG. 1c is a graph of confidence indices from electron back-scattering diffraction of large grain copper foil without zinc deposition;

FIG. 1d is an optical microscope image of a large grain copper foil after a small amount of zinc deposition;

FIG. 1e is an electron backscatter image after zinc deposition;

FIG. 1f is a reverse polarity view after deposition of zinc;

FIG. 1g is a confidence index image after zinc deposition;

FIG. 1h shows the orientation of the distribution of elements at two locations after zinc deposition;

FIG. 2a is a scanning electron microscope image of an electrolytically prepared Cu (220) preferentially oriented copper foil (designated P-Cu (220));

FIG. 2b, c is an electron photograph and XRD spectrum of the corresponding copper foil;

FIG. 2d is a reverse polarity diagram of P-Cu (220);

FIG. 3 is a scanning electron microscope image of the surface and cross-section of commercial electrolytic copper foil (designated C-Cu) and P-Cu (220) copper foils;

FIG. 4a is a Cyclic Voltammogram (CV) for a Zn | | Cu half cell;

FIG. 4b, c are the nucleation overpotential curves and results obtained from the three-electrode test;

FIG. 4d is C-Cu deposition 4mAhcm ^-2 Scanning electron microscope images of the zinc;

FIGS. 4e-f are 4mAhcm for P-Cu (220) deposition, respectively ^-2 Images of the zinc-containing laser confocal microscope and scanning electron microscope;

FIG. 5 shows P-Cu (220) and C-Cu deposition of 2mAhcm ^-2 Scanning electron microscope images of the zinc;

FIG. 6 is a graph of cycling performance of P-Cu (220) and C-Cu assembled half cells with zinc and symmetric cells;

FIG. 7a is a scanning electron microscope image of zinc after 50 cycles on P-Cu (220) and C-Cu;

FIG. 7b shows P-Cu (220) and C-Cu after zinc plating with MnO ₂ Results of cycle testing after assembling the positive electrode with the full cell.

Detailed Description

The technical solutions of the present invention are further described below with reference to the embodiments, but the present invention is not limited thereto, and all modifications or equivalent substitutions that do not depart from the spirit and scope of the technical solutions of the present invention should be included in the scope of the present invention.

In the following cases, unless otherwise stated, the compounds of formula 1 in the electroplating bath are all referred to as formula 1-A:

in the following cases, the process for depositing metallic zinc on a copper current collector is, except where specifically stated:

taking metallic zinc as an anode and copper foil materials in different cases as a cathode, and carrying out electrodeposition in a 1M zinc sulfate solution, wherein the deposition content of zinc on the copper foil is 4mAhcm ^-2 。

Example 1

In order to prove that the Cu (220) crystal face has high zinc deposition activity, the invention uses a copper foil with large crystal grain size and random crystal orientation as a research object because the copper foil has good crystal face identification, and the large crystal grain copper foil can be prepared by annealing a common copper foil at 700 ℃ for 2h and then is subjected to annealing at the temperature of 700 DEG C5mAcm ^-2 Depositing 20s of zinc at the current density, then carrying out optical microscope observation and electron back scattering diffraction test, simultaneously using an energy spectrometer to represent the content of the zinc deposited on the related crystal grains, and finally specifying the crystal face with the highest zinc deposition activity.

As shown in fig. 1d, when a certain amount of zinc is deposited on the copper foil, a distinct difference in gloss appears on the surface of the copper foil, as some crystal grains show distinct metallic gloss, and some crystal faces do not undergo zinc deposition, which is in sharp contrast to the copper foil of fig. 1a, which does not undergo zinc deposition. It was found that, as shown in fig. 1b, c, the copper foil without zinc deposition had a strong backscatter diffraction signal and no black noise occurred, while the copper foil after zinc deposition had a significant black noise concentration as shown in fig. 1e, f, g, which resulted from zinc preferentially deposited on the copper foil, and the spectrometer also demonstrated the conclusion that the zinc signal was more significant on the grains with the black noise concentration in fig. 1e, and then the backscatter diffraction orientation technique was used to indicate that these crystal planes prone to zinc deposition were Cu (220) crystal planes and zinc was rarely deposited on Cu (111), cu (200) and Cu (311), which was the first demonstrated by the present invention: the Cu (220) crystal plane has higher zinc deposition activity than Cu (111), cu (200) and Cu (311). The maximum exposure of the crystal face of the Cu (220) is beneficial to improving the overall electrochemical activity of the substrate, and considering the problems of strength of the copper foil and the like, the Cu (220) has excellent electrochemical performance when the texture coefficient is more than or equal to 75%.

Example 2

Based on the mature electrolytic copper foil technology at present, the invention adopts the electrolytic method capable of large-scale production to prepare the copper foil with the preferred orientation of Cu (220) and has the following specific preparation process and method, and electroplating is carried out by using electroplating liquid with the following components: cuSO ₄ 200gL ^-1 ，H ₂ SO ₄ 80gL ^-1 Of the formula 1-A0.1gL ^-1 ， NaCl0.2gL ^-1 . Using 120mAcm ^-2 Electroplating the current density on the cathode of the stainless steel sheet for 10min to obtain the copper foil with the thickness of about 24 microns, wherein the anode used for electroplating is pure copper foil. Such asAs shown in fig. 2a, the surface of the prepared copper foil was composed of polyhedrons having a size of about 4 μm. As shown in fig. 2b, the copper foil can be prepared in a laboratory on a small scale and has a significant difference in gloss compared to a commercial electrolytic copper foil (such commercial copper foil is designated as C-Cu, and the manufacturer is noded ltd).

As shown in fig. 2C, XRD testing revealed that the major diffraction peak of the copper foil produced by this electrolytic process was Cu (220), which was calculated to have a relative texture coefficient as high as 95% (this copper foil is designated as highly preferred oriented Cu (220) foil, abbreviated as P-Cu (220)), whereas the relative texture coefficient of the (220) crystal plane of the conventional commercial electrolytic copper foil (this copper foil is designated as C-Cu) was only 67.7%. As shown in fig. 2d, P-Cu (220) has a strong (220) texture, indicating that its surface is highly exposed to the Cu (220) crystal plane. Fig. 3 shows that this electrolytically prepared copper foil has a significant roughness difference from the commercial copper foil, but their thicknesses do not differ much.

Copper foils with different Cu (220) texture coefficients were prepared using different electrolyte formulations as shown in table 1.

TABLE 1 relative texture coefficients of Cu (220) crystallographic planes of copper foils prepared using different baths and electrolysis parameters

Example 3

In order to further explore the zinc deposition performance of the P-Cu (220) copper foil, the assembled battery of the invention uses the zinc foil as a counter electrode and the P-Cu (220) and the C-Cu as working electrodes to carry out CV test, as shown in FIG. 4a, the P-Cu (220) can be found to have higher zinc deposition/stripping reversibility and extremely low nucleation overpotential. By using the copper foil as a working electrode, the zinc foil as a counter electrode and the Ag/AgCl as a reference electrode to accurately test the nucleation overpotentials of different copper foils, as shown in FIG. 4b, C, the P-Cu (220) has lower nucleation overpotentials in a wide current density range compared with the C-Cu, and further shows that the preferential property of the Cu (220) crystal face can significantly improve the activity of the electrodeAnd (4) sex. 4d-f, depositing 4mAhcm on the copper foil ^-2 As a result of scanning electron microscopy, it was found that P-Cu (220) enables dense and uniform zinc deposition without zinc dendrite generation, whereas C-Cu generates significant zinc dendrites due to low electrode activity.

As shown in FIG. 5, further tests were performed at 5mAcm ^-2 Current density deposition of 2mAhcm ^-2 The scanning electron microscope of the zinc of (2) shows that the P-Cu (220) has a dense zinc deposition. This further demonstrates that the Cu (220) crystal plane is the active crystal plane for zinc deposition.

Example 4

The coulombic efficiency and cycle life of Zn | | Cu half cells were tested using zinc foil as the counter electrode, copper foil (commercial copper foil and 220 copper foil with 95% texture coefficient) as the working electrode, and zinc acetate solution as the electrolyte, and as can be seen from fig. 6a, P-Cu (220) has high coulombic efficiency and can be cycled over 1100 times without short circuit and reduced coulombic efficiency, while C-Cu has low coulombic efficiency and short circuit occurs after the 67 th cycle, indicating that this highly preferred orientation copper foil has its 15 times cycle life compared to ordinary copper foil. Using zinc-plated 4mAhcm ^-2 The copper foil of (2) was used as a negative electrode, and its rate capability was tested.

As shown in fig. 6b, P-Cu (220) may exhibit longer cycle life and smoother voltage hysteresis, indicating that P-Cu (220) has more excellent electrochemical performance. The morphology of the zinc deposition on these copper foils was further tested and as shown in fig. 7a, the zinc deposition on P-Cu (220) was still dense, while the zinc deposition on C-Cu showed a pronounced dendritic morphology. To further verify the utility of this copper foil, we used a galvanized copper foil as the negative electrode, a commercial MnO ₂ The material is used as a positive electrode, glass fiber is used as a diaphragm, zinc acetate solution is used as electrolyte, and a CR-2025 button type zinc ion full cell is assembled for testing, wherein MnO is added ₂ The positive plate is made of conductive carbon black: polytetrafluoroethylene binder: mnO ₂ Is 1:1:8, wherein MnO is ₂ The supported amount of the active material (2) was 5mgcm ^-2 . Such asThe full cell test data of fig. 7b shows that the galvanized P-Cu (220) negative electrode can cycle 640 times at 20% depth of discharge and maintain 93.9% capacity retention, while the galvanized C-Cu only has 44.2% capacity retention after 640 cycles, further demonstrating the utility of this preferred oriented copper foil.

Copper foil with different Cu (220) preferred orientation prepared from example 2, after galvanization, with MnO ₂ The positive electrode was assembled into a full cell and tested, and their capacity retention rates are shown in table 2 (640 cycles), which fully demonstrates that (220) copper foil with texture coefficient of 75% or more has more excellent electrochemical performance.

Table 2 electrochemical performance exhibited by assembled full cells using copper foils of different texture coefficients as current collectors

As can be seen from table 2, the material with high 220 orientation prepared by the present invention has excellent electrochemical performance.

Example 5

In order to prove the superiority of the copper current collector material with the texture coefficient more than or equal to 75% in the lithium metal battery, a button battery with 2015 is assembled for testing, a lithium iron phosphate material containing lithium ions is used as a positive electrode material, a positive electrode plate is prepared by coating, and positive electrode slurry is prepared by conductive carbon: PVDF binder: lithium iron phosphate is equal to 1:1:8, and then drying the mixture in vacuum at 80 ℃ for 12 hours; the negative electrode material used no active lithium metal, but only a copper current collector as the negative electrode (this battery is called a non-negative electrode lithium metal battery, the active material of the negative electrode is derived from lithium metal deposited by first charge, which can better prove the deposition stripping reversibility of the current collector), a polypropylene film as the diaphragm, and a commercial lithium metal battery electrolyte containing 2% of lithium nitrate purchased from multiple reagents as the electrolyte for the full battery. The assembled cells were tested using the copper foils numbered 4, 9, 11 of example 2 with a commercial copper foil C-Cu. The specific first capacity and capacity retention after 50 cycles are shown in table 3: the method proves that the deposition/stripping reversibility of the copper current collector can be obviously improved by realizing that the Cu (220) texture coefficient is more than or equal to 75 percent.

Table 3 electrochemical performance exhibited by non-negative lithium metal full cell assembled using copper foils of different texture coefficients as current collectors

In conclusion, the method provided by the invention can be used for unexpectedly obtaining the 220 preferred orientation material, and moreover, the 220 preferred orientation material has an excellent reversible induced metal deposition/stripping effect, and when the material is applied to a metal battery, the electrochemical performance of the metal battery can be obviously improved.

The specific embodiments are merely illustrative of the present application and not restrictive, and those skilled in the art who review this disclosure may make modifications to the embodiments as required without any inventive contribution, but fall within the scope of the claims of the present application.

Claims (10)

1.220 preferentially oriented copper material, which is characterized in that the relative texture coefficient of a Cu (220) crystal face is more than or equal to 75 percent.

2. The preferentially oriented copper material of claim 1, wherein the relative texture coefficient of the Cu (220) crystal plane is greater than or equal to 85%; the copper material is a copper plane material.

3. The method for preparing the 220 preferred orientation copper material according to claim 1 or 2, characterized in that the copper is used as an anode and a deposition substrate is used as a cathode to carry out electroplating treatment in a copper plating solution to obtain the 220 preferred orientation copper material;

the copper plating solution is an aqueous solution in which copper sulfate, sulfuric acid, a compound shown in a formula 1 and alkali metal chloride are dissolved; wherein, cuSO ₄ The concentration is 100-250gL ^-1 ；H ₂ SO ₄ The concentration of (A) is 50-120gL ^-1 (ii) a The compound of formula 1 is 0.05-0.2gL ^-1 (ii) a The concentration of alkali chloride is 0.1-0.4gL ^-1 ；

N is 1 to 6; m is H, na or K;

the current density of electroplating treatment is 100-200mAcm ^-2 。

4. The method of claim 3 wherein the copper material having a preferred orientation of 220 is produced by,

CuSO ₄ the concentration is 150-200 gL ^-1 ；

H ₂ SO ₄ The concentration of (A) is 80-100gL ^-1 ；

The compound of formula 1 is 0.1-0.2gL ^-1 ；

The concentration of alkali chloride is 0.1-0.4gL ^-1 ；

The electroplating solution is a solution consisting of copper sulfate, sulfuric acid, a compound shown in the formula 1, alkali metal chloride and water in the content ratio;

the current density of the electroplating treatment is 100-120mAcm ^-2 ；

The electroplating treatment time is 6-10 min.

5. Use of a 220 preferred orientation copper material according to any of claims 1-2 or a 220 preferred orientation copper material produced by a production process according to any of claims 3-4 as a current collector for the production of a metal battery.

6. The use according to claim 5 as a current collector for the induced deposition of metals for the preparation of composite metal negative electrodes for metal batteries;

the metal is at least one of lithium, zinc and sodium;

the metal battery is a metal zinc battery.

7. A composite zinc negative electrode, characterized by comprising the 220 preferred-orientation copper material according to any one of claims 1 to 2 or the 220 preferred-orientation copper material produced by the production method according to any one of claims 3 to 4; and metal zinc compounded on the surface of the zinc alloy.

8. The preparation method of the composite zinc negative electrode of claim 7, characterized in that metal zinc is electrodeposited on the copper material with the preferred orientation of 220 by adopting an electrochemical deposition mode to prepare the composite zinc negative electrode:

the electrodeposition steps are: taking a zinc anode and the copper material with the preferred orientation of 220 as a cathode, and carrying out electrodeposition in zinc plating solution containing zinc salt to prepare the zinc-based alloy material;

the zinc salt is water-soluble zinc salt, and is further preferably ZnSO ₄ 、ZnCl ₂ 、Zn(CH ₃ COO) ₂ At least one of zinc trifluoromethanesulfonate;

the current density of the electrodeposition is 1mAcm ^-2 -50mAcm ^-2 。

9. Use of a composite zinc anode according to claim 7, characterised in that it is assembled to obtain a zinc metal battery;

the zinc metal battery is at least one of a zinc-manganese battery, a zinc-polyaniline battery, a zinc vanadate battery and a zinc ion battery capacitor.

10. A zinc metal battery comprising the composite zinc negative electrode of claim 7.

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