CN116154147A - Zinc metal anode material modified based on ion/electron double-conductor interface film, preparation and application thereof - Google Patents

Zinc metal anode material modified based on ion/electron double-conductor interface film, preparation and application thereof Download PDF

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CN116154147A
CN116154147A CN202211623772.1A CN202211623772A CN116154147A CN 116154147 A CN116154147 A CN 116154147A CN 202211623772 A CN202211623772 A CN 202211623772A CN 116154147 A CN116154147 A CN 116154147A
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ion
zinc
interface film
conductor interface
negative electrode
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谢嫚
周佳辉
吴锋
夏信德
孙文彬
刘安妮
颉琛
杨可晴
梅杨
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Guangzhou Great Power Energy & Technology Co ltd
He'nan Penghui Power Supply Co ltd
Zhuhai Penghui Energy Co ltd
Beijing Institute of Technology BIT
Chongqing Innovation Center of Beijing University of Technology
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Guangzhou Great Power Energy & Technology Co ltd
He'nan Penghui Power Supply Co ltd
Zhuhai Penghui Energy Co ltd
Beijing Institute of Technology BIT
Chongqing Innovation Center of Beijing University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention relates to a zinc metal anode material modified based on an ion/electron double-conductor interface film, and preparation and application thereof, and belongs to the technical field of zinc ion batteries. The zinc metal negative electrode material modified based on the ion/electron double-conductor interface film is a zinc metal material with the surface containing the ion/electron double-conductor interface film; wherein the ion/electron double-conductor interface film is made of doped conductive material and Zn (CF) 3 SO 3 ) 2 The polymer film has an ionic conductivity of 0.1 to 0.8S/m and an electronic conductivity of 0.01 to 0.1S/m. The cathode material has the capability of cooperatively transmitting ions and electrons, endows the interfacial film with rich nucleation sites, can guide zinc ions to nucleate,the cathode material is beneficial to the deposition of metallic zinc, inhibits the growth of zinc dendrite, reduces the polarization of an electrode, can show excellent electrochemical performance when being applied to a water-based zinc ion battery, has simple preparation process, is environment-friendly, is easy to popularize, and has good application prospect in the field of the water-based zinc ion battery.

Description

Zinc metal anode material modified based on ion/electron double-conductor interface film, preparation and application thereof
Technical Field
The invention relates to a zinc metal anode material modified based on an ion/electron double-conductor interface film, and preparation and application thereof, and belongs to the technical field of zinc ion batteries.
Background
With the continuous development of society, the utility model is highly safe and stableCertain, low cost, environmentally friendly electrochemical energy storage systems are receiving increasing attention. Zinc is an inexpensive, abundant metal with a high volumetric capacity (5855 mAh cm -3 ) And a lower redox potential (-0.76V versus standard hydrogen electrode). Based on the advantages of zinc metal cathodes themselves, aqueous zinc ion batteries are one of the popular candidates for next generation energy storage devices. In recent years, various aqueous zinc-based batteries, e.g. Zn-MnO 2 、Zn-V 2 O 5 、Zn-LiMn 2 O 4 Systems and the like have been widely studied and have made significant progress. However, deposition due to non-uniform nucleation of zinc negative electrodes tends to dendritic growth, and severe hydrogen corrosion under thermodynamic driving, which results in unstable interfaces of zinc metal during cycling, severely hampering large-scale application of aqueous zinc ion batteries.
The effective artificial interface film can avoid direct contact between electrolyte and zinc metal, regulate and control nucleation of zinc and release (HER) of hydrogen, thereby realizing zinc metal cathode with long cycle life. Therefore, researchers have designed a variety of artificial modification films on the surface of metal anodes. Based on the type of material, it can be largely classified into Electron Conductive (EC) and Ion Conductive (IC) interface films. The higher electron conductivity of the EC film causes a rapid local current distribution at the electrode surface, inhibiting dendrite formation, but unbalanced electron/ion conductivity can cause zinc deposition over the EC film, resulting in failure of interfacial film protection. The IC film makes zinc metal in the electrode the only electronic conductor, ensures that zinc deposition starts from the metal surface, simultaneously allows zinc ions to be transmitted inside the film, and preferentially regulates nucleation sites of zinc. However, zinc deposition/extraction is accompanied by a change in the volume of the negative electrode, which causes deterioration of interface contact between the IC interface film and zinc metal, resulting in breakage of electron transport of the composite electrode, poor rate performance, and failure of the battery. Therefore, the novel artificial interface membrane is explored to design and synthesize, balance the ion/electron transmission rate and clarify the internal action mechanism, and has high guiding significance and application universality for the subsequent zinc anode interface modification and the construction of the high-magnification water-based zinc ion battery.
Disclosure of Invention
Aiming at the defects of the prior interface film, the invention provides a zinc metal anode material modified based on an ion/electron double-conductor interface film, and preparation and application thereof, adopts doped conductive material and Zn (CF) 3 SO 3 ) 2 The polymer film of (2) is used as an interface film, has the capability of cooperatively transmitting ions and electrons, endows the interface film with rich nucleation sites, can guide zinc ions to go into nuclei, is favorable for depositing metallic zinc, inhibits the growth of zinc dendrites, reduces the polarization of electrodes, and is favorable for improving the electrochemical performance of a battery when the zinc metal anode material modified based on the ion/electron double-conductor interface film is applied to a water-based zinc ion battery; the zinc metal anode material based on the ion/electron double-conductor interface film modification has simple preparation process, is green and environment-friendly, and is easy to popularize.
The aim of the invention is achieved by the following technical scheme.
The zinc metal negative electrode material modified based on the ion/electron double-conductor interface film is a zinc metal material with the surface containing the ion/electron double-conductor interface film;
the ion/electron double-conductor interface film is made of doped conductive material and Zn (CF) 3 SO 3 ) 2 The polymer film has an ionic conductivity of 0.1 to 0.8S/m and an electronic conductivity of 0.01 to 0.1S/m.
Preferably, the conductive material is MXene (preferably Ti 3 C 2 T x Or Ti (Ti) 3 AlC 2 ) The polymer is one or more of polyvinyl alcohol, polyethylene glycol, polyethylene oxide and poly (vinylidene fluoride-co-hexafluoropropylene). Accordingly, conductive material, zn (CF 3 SO 3 ) 2 More preferably, the mass ratio of the polymers is 1: (1-3): (3-8).
Preferably, the zinc-containing metal material is a zinc foil or a zinc alloy foil.
Preferably, the thickness of the ion/electron double conductor interface film is 200nm to 40 μm.
The preparation method of the zinc metal anode material based on ion/electron double-conductor interface film modification comprises the following steps:
(1) Conductive material, zn (CF) 3 SO 3 ) 2 Mixing the polymer and water, and heating and stirring to obtain a thick slurry;
(2) And (3) coating the slurry prepared in the step (1) on the surface of the zinc-containing metal material, freezing, thawing, and repeating the freezing-thawing operation for 3-5 times to obtain the zinc-containing metal negative electrode material modified based on the ion/electron double-conductor interface film.
Preferably, in step (1), the concentration of the conductive material in the slurry is 1 to 5mg/mL.
Preferably, in step (1), the slurry is stirred to a viscous slurry at 60 to 90 ℃.
Preferably, in the step (2), the temperature of each freezing is-40 to-20 ℃ and the freezing time is 30min to 24h, and the temperature of each thawing is 20 to 40 ℃ and the thawing time is 2 to 24h.
The zinc metal negative electrode material modified based on the ion/electron double-conductor interface film is used as a negative electrode to be applied to a water-based zinc ion battery.
The beneficial effects are that:
(1) The ion/electron double-conductor interface film has higher ion conductivity and electron conductivity, can enable local current on the surface of an electrode to be rapidly distributed, inhibit dendrite formation, ensure that zinc is deposited from the surface of metal, allow zinc ions to be transmitted in the film, preferentially regulate and control nucleation sites of zinc, avoid the phenomenon that zinc is deposited above the film due to unbalanced electron/ion conductivity when a single electron conducting film is used, and simultaneously avoid the problem that the electrode multiplying power performance is poor due to single ion conductivity, and the battery is invalid.
(2) In the ion/electron double-conductor interface film, the conductive material can be in valence bond connection with hydrogen bonds in the polymer, so that the solubility of the material is improved, and the electron conductivity of the interface film is promoted; the addition of zinc salt provides a transport path for zinc ions and provides a channel for ion transport. In addition, the conductive material and the polymer form a layered porous structure, so that zinc salt can be uniformly and firmly dispersed in the whole film, and the addition of the zinc salt strengthens the bonding strength of the conductive material and the polymer, and the zinc salt and the polymer cooperate to promote the passage of high-speed ionic/electronic double conductors.
(3) According to the invention, a conductive material with higher metering is introduced as an additive component of the interface film, so that the electronic conductivity of the interface film is effectively improved; in addition, the preferred zinc salt concentration activates the ion transport path of the interfacial film, promoting the interfacial transport rate of zinc ions.
(4) In the preparation process of the ion/electron double-conductor interface film, repeated freezing-thawing cycle treatment is carried out, and the formed ice crystals mainly form a porous structure in the interface film, so that the abundant pores can effectively improve the ion/electron transmission rate.
(5) The zinc metal anode material modified based on the ion/electron double-conductor interface film is applied to a water-based zinc ion battery as an anode material, has excellent electrochemical performance, is simple in preparation process, is environment-friendly and easy to popularize, and has a good application prospect in the field of water-based zinc ion batteries.
Drawings
Fig. 1 is a Surface Electron Microscope (SEM) image of the anode material 10 prepared in example 1.
Fig. 2 is a cross-sectional electron microscopic view of the anode material 10 prepared in example 1.
FIG. 3 is a graph of the assembled battery of example 1 at a current density of 20mA/cm 2 The capacity is 1mAh/cm 2 Graph of cyclic performance at that time.
FIG. 4 is a graph of the assembled battery of example 1 at a current density of 20mA/cm 2 The capacity is 1mAh/cm 2 Surface scanning electron microscopy of the negative electrode after 100 weeks of lower cycle.
Fig. 5 is a comparative graph of the long cycle performance test of the assembled battery of example 1 versus the assembled battery of comparative example 1 at a 0.5C rate.
Fig. 6 is a surface scanning electron microscope image of the negative electrode of the assembled full cell of example 1 after 100 weeks of cycling.
FIG. 7 is an electrical representation of the assembled battery of comparative example 1The flow density was 20mA/cm 2 The capacity is 1mAh/cm 2 Graph of cyclic performance at that time.
FIG. 8 is a graph showing the current density of the assembled battery of comparative example 1 at 20mA/cm 2 The capacity is 1mAh/cm 2 Surface scanning electron microscopy of the negative electrode after 100 weeks of lower cycle.
Fig. 9 is a surface scanning electron microscope image of the negative electrode of the assembled full cell of comparative example 1 after 100 weeks of cycle.
Detailed Description
The present invention will be further described with reference to the following detailed description, wherein the processes are conventional, and wherein the starting materials are commercially available from the open market, unless otherwise specified.
In the following examples and comparative examples:
SEM characterization: the microscopic morphology of the sample is observed by a field emission scanning electron microscope (Hitachi SU-7), and the accelerating voltage is 5.0kV;
ion conductivity test: assembling the stainless steel-interface film-stainless steel type blocking electrode, passing the AC impedance test, and selecting the frequency range from 10 to 10 5 Hz, ac amplitude 5mV; measuring the thickness of the interface film, the resistance value and the contact area of the stainless steel electrode, and calculating to obtain the ionic conductivity of the interface film;
electron conductivity test: assembling a stainless steel-interface film-stainless steel type blocking electrode, applying a 1V polarization voltage on the testing electrode, and recording the change curve of the current along with time; only electrons in the electrode can continuously pass through, and the steady-state current, the polarization voltage, the interface film thickness and the area are recorded, so that the electron conductivity can be obtained through calculation;
assembly of CR2032 battery: the anode material prepared in the example or the comparative example was used as an anode and a cathode, glass fiber was used as a separator, and the solute of the electrolyte was 2M zinc trifluoromethane sulfonate Zn (CF 3 SO 3 ) 2 The solvent of the electrolyte is deionized water, and the paired batteries are assembled; the anode material prepared in example or comparative example was used as anode, liMn 2 O 4 The electrolyte was 1M Zn (CF 3 SO 3 ) 2 2M lithium sulfate Li 2 SO 4 The solvent of the electrolyte is deionized water, and the full battery is assembled;
electrochemical performance test: electrochemical performance testing was performed on CR2032 cells using the Land system and test data was recorded using software.
Example 1
(1) 10mg of Ti 3 C 2 T x And 20mg Zn (CF) 3 SO 3 ) 2 Adding the mixture into 10mL of deionized water, uniformly stirring and mixing, adding 50mg of polyvinyl alcohol, heating to 80 ℃ and stirring to form viscous slurry;
(2) After the slurry is scraped on the surface of zinc foil by using a scraper, the zinc foil is frozen for 6 hours at the temperature of minus 20 ℃ and then thawed for 12 hours at the temperature of 30 ℃, and the freezing-thawing operation is repeated for three times, so that the zinc metal negative electrode material modified by the ion/electron double-conductor interface film is obtained and is simply called as a negative electrode material 10.
The negative electrode material 10 prepared in this example was subjected to microscopic morphology characterization, and the surface SEM image of fig. 1 shows that the interfacial film on the surface of the composite material is completely coated without obvious wrinkles; the cross-sectional SEM image of fig. 2 shows that the interfacial film is tightly covered on the surface of the zinc foil, and the thickness of the interfacial film is about 15 μm.
The ionic conductivity of the interfacial film in the anode material 10 was found to be 0.4S/m and the electronic conductivity was found to be 0.04S/m.
The negative electrode material 10 prepared in this example was assembled as a positive electrode and a negative electrode into a CR2032 pair battery, and the cycle performance was tested. As can be seen from the test results of FIG. 3, the current density was 20mA/cm 2 With a capacity of 1mAh/cm 2 In the case of the negative electrode, the voltage curve is still flat after more than 1000 hours, the overpotential is only 33mV, and the overpotential is small without obvious fluctuation.
The anode material 10 prepared in this example was used as a positive electrode and a negative electrode to form a CR2032 pair battery having a current density of 20mA/cm 2 With a capacity of 1mAh/cm 2 After the battery is disassembled after the cycle of 100 weeks, the microscopic morphology of the cathode after the cycle of 100 weeks is observed, and the surface of the cathode is clear and flat without obvious dendrite growth, as shown in figure 4。
The anode material 10 prepared in this example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled, and long cycle performance test was performed at a rate of 0.5C (1c=148 mAh/g). As can be seen from the test results of fig. 5, the full cell assembled using the anode material 10 exhibited excellent cycling stability, and the capacity was still able to be maintained at 64mAh/g after 440 weeks of cycling.
The anode material 10 prepared in this example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled, cycled at a rate of 0.5C for 100 weeks, after which the full cell was disassembled, and the negative electrode microstructure after 100 weeks of cycling was observed, and the surface was found to be flat, and zinc was uniformly deposited, as shown in fig. 6.
Example 2
Except that the polyvinyl alcohol in step (1) of example 1 was replaced with polyethylene oxide, and the other conditions and steps were the same as in example 1, a zinc metal negative electrode material modified with an ion/electron double conductor interface film was obtained in the same manner as in example 1, abbreviated as negative electrode material 20.
The negative electrode material 20 prepared in this example was subjected to microscopic morphological characterization, and according to the characterization result, the surface of the zinc foil was coated with an interfacial film having a thickness of about 15 μm, and the surface was flat and ordered.
The ionic conductivity of the interfacial film in the anode material 20 was found to be 0.3S/m and the electronic conductivity was found to be 0.04S/m.
The negative electrode material 20 prepared in this example was assembled as a positive electrode and a negative electrode into a CR2032 pair battery, and the cycle performance was tested. As a result of the test, it was found that the current density was 20mA/cm 2 With a capacity of 1mAh/cm 2 In the case of the negative electrode, the voltage curve is still flat after more than 800 hours, the overpotential is only 35mV, and the overpotential is small without obvious fluctuation.
The anode material 20 prepared in this example was used as the positive and negative electrodes to prepare a CR2032 pair battery having a current density of 20mA/cm 2 With a capacity of 1mAh/cm 2 After the battery was disassembled after 100 weeks of cycle, the microscopic morphology of the negative electrode after 100 weeks of cycle was observed, and foundThe surface of the material is clear and smooth, and no obvious dendrite growth exists.
The anode material 20 prepared in this example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled, and long cycle performance test was performed at a rate of 0.5C. From the test results, it was found that the full cell assembled with the negative electrode material 20 exhibited excellent cycle stability, and the capacity remained at 69mAh/g after 400 weeks of cycle.
The anode material 20 prepared in this example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled, cycled at a rate of 0.5C for 100 weeks, and then the full cell was disassembled, and the negative electrode microscopic morphology after 100 weeks of cycling was observed, and it was found that the surface was flat and zinc was deposited uniformly.
Example 3
On the basis of example 1, only Ti in step (1) of example 1 3 C 2 T x The mass was adjusted to 20mg, and the zinc metal negative electrode material modified with an ion/electron double-conductor interface film was obtained in the same manner as in example 1, except for the conditions and steps, which were abbreviated as negative electrode material 11.
The negative electrode material 11 prepared in this example was subjected to microscopic morphology characterization, and according to the characterization result, the surface of the zinc foil was coated with an interfacial film having a thickness of about 15 μm, and the surface was flat and ordered.
The ionic conductivity of the interfacial film in the negative electrode material 11 was found to be 0.5S/m and the electronic conductivity was found to be 0.08S/m.
The negative electrode material 11 prepared in this example was assembled as a positive electrode and a negative electrode into a CR2032 pair battery, and the cycle performance was tested. As a result of the test, it was found that the current density was 20mA/cm 2 With a capacity of 1mAh/cm 2 In the case of the negative electrode, the voltage curve is still flat after more than 1000 hours, the overpotential is only 40mV, and the overpotential is small and has no obvious fluctuation.
The anode material 11 prepared in this example was used as a positive electrode and a negative electrode to prepare a CR2032 pair battery having a current density of 20mA/cm 2 With a capacity of 1mAh/cm 2 After the battery was disassembled after 100 weeks of cycle, the negative electrode after 100 weeks of cycle was observedMicroscopic morphology, the surface of which is clear and smooth, and no obvious dendrite growth is found.
The anode material 11 prepared in this example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled, and long cycle performance test was performed at a rate of 0.5C. From the test results, it was found that the full cell assembled with the negative electrode material 11 exhibited excellent cycle stability, and the capacity remained at 59mAh/g after 400 weeks of cycle.
The anode material 11 prepared in this example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled, cycled at a rate of 0.5C for 100 weeks, and then the full cell was disassembled, and the negative electrode microscopic morphology after 100 weeks of cycling was observed, and it was found that the surface was flat and zinc was deposited uniformly.
Example 4
Based on example 1, only Zn (CF) in step (1) of example 1 3 SO 3 ) 2 The mass was adjusted to 30mg, and the zinc metal negative electrode material modified with an ion/electron double-conductor interface film, abbreviated as negative electrode material 12, was obtained in the same manner as in example 1 under the same conditions and procedures.
The negative electrode material 12 prepared in this example was subjected to microscopic morphology characterization, and according to the characterization result, the surface of the zinc foil was coated with an interfacial film having a thickness of about 15 μm, and the surface was flat and ordered.
The ionic conductivity of the interfacial film in the negative electrode material 12 was found to be 0.6S/m and the electronic conductivity was found to be 0.05S/m.
The negative electrode material 12 prepared in this example was assembled as a positive electrode and a negative electrode into a CR2032 pair battery, and the cycle performance was tested. As a result of the test, it was found that the current density was 20mA/cm 2 With a capacity of 1mAh/cm 2 In the case of the negative electrode, the voltage curve is still flat after more than 1000 hours, the overpotential is only 50mV, and the overpotential is small and has no obvious fluctuation.
The anode material 12 prepared in this example was used as positive and negative electrodes to prepare a CR2032 pair battery having a current density of 20mA/cm 2 With a capacity of 1mAh/cm 2 Is circulated for 100 weeks, and then the battery is disassembled to observe the circulationThe microscopic morphology of the cathode after 100 weeks of the ring is found that the surface of the cathode is clear and smooth, and no obvious dendrite growth exists.
The anode material 12 prepared in this example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled, and long cycle performance test was performed at a rate of 0.5C. From the test results, it was found that the full cell assembled with the negative electrode material 12 exhibited excellent cycle stability, and the capacity remained at 62mAh/g after 400 weeks of cycle.
The anode material 12 prepared in this example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled, cycled at a rate of 0.5C for 100 weeks, and then the full cell was disassembled, and the negative electrode microscopic morphology after 100 weeks of cycling was observed, and it was found that the surface was flat and zinc was deposited uniformly.
Example 5
Except that the mass of polyvinyl alcohol in the step (1) of example 1 was adjusted to 80mg based on the example 1, the other conditions and steps were the same as in the example 1, and a zinc metal negative electrode material modified with an ion/electron double conductor interface film was obtained in the same manner, abbreviated as negative electrode material 13.
The negative electrode material 13 prepared in this example was subjected to microscopic morphology characterization, and according to the characterization result, the surface of the zinc foil was coated with an interfacial film having a thickness of about 30 μm, and the surface was flat and ordered.
The ionic conductivity of the interfacial film in the negative electrode material 13 was 0.2S/m and the electronic conductivity was 0.02S/m, as calculated by test.
The negative electrode material 13 prepared in this example was used as a positive electrode and a negative electrode to be assembled into a CR2032 pair battery, and the cycle performance was tested. As a result of the test, it was found that the current density was 20mA/cm 2 With a capacity of 1mAh/cm 2 In the case of the negative electrode, the voltage curve is still flat after more than 1000 hours, the overpotential is only 50mV, and the overpotential is small and has no obvious fluctuation.
The anode material 13 prepared in this example was used as the positive and negative electrodes to prepare a CR2032 pair battery having a current density of 20mA/cm 2 With a capacity of 1mAh/cm 2 After 100 weeks of cycling, the battery was disassembled and the cycling 100 was observedThe microscopic morphology of the cathode after the circumference shows that the surface of the cathode is clear and smooth, and no obvious dendrite growth exists.
The anode material 13 prepared in this example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled, and long cycle performance test was performed at a rate of 0.5C. From the test results, it was found that the full cell assembled with the negative electrode material 13 exhibited excellent cycle stability, and the capacity was maintained at 58mAh/g after 400 weeks of cycle.
The anode material 13 prepared in this example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled, cycled at a rate of 0.5C for 100 weeks, and then the full cell was disassembled, and the negative electrode microscopic morphology after 100 weeks of cycling was observed, and it was found that the surface was flat and zinc was deposited uniformly.
Example 6
Except that the freezing time in the step (2) of example 1 was adjusted to 12 hours in addition to example 1, the conditions and steps were the same as in example 1, and a zinc metal negative electrode material modified with an ion/electron double conductor interface film was obtained in the same manner, which was abbreviated as negative electrode material 14.
The negative electrode material 14 prepared in this example was subjected to microscopic morphological characterization, and according to the characterization result, the surface of the zinc foil was coated with an interfacial film having a thickness of about 15 μm, and the surface was flat and ordered.
The ionic conductivity of the interfacial film in the anode material 14 was found to be 0.45S/m and the electronic conductivity was found to be 0.043S/m.
The negative electrode material 14 prepared in this example was assembled as a positive electrode and a negative electrode into a CR2032 pair battery, and the cycle performance was tested. As a result of the test, it was found that the current density was 20mA/cm 2 With a capacity of 1mAh/cm 2 In the case of the negative electrode, the voltage curve is still flat after more than 1000 hours, the overpotential is only 52mV, and the overpotential is small and has no obvious fluctuation.
The anode material 14 prepared in this example was used as the positive and negative electrodes to prepare a CR2032 pair battery having a current density of 20mA/cm 2 With a capacity of 1mAh/cm 2 After the battery was disassembled after 100 weeks of cycle, the negative electrode after 100 weeks of cycle was observedMicroscopic morphology, the surface of which is clear and smooth, and no obvious dendrite growth is found.
The anode material 14 prepared in this example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled, and long cycle performance test was performed at a rate of 0.5C. From the test results, it was found that the full cell assembled with the anode material 14 exhibited excellent cycle stability, and the capacity remained at 62mAh/g after 400 weeks of cycle.
The anode material 14 prepared in this example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled, cycled at a rate of 0.5C for 100 weeks, and then the full cell was disassembled, and the negative electrode microscopic morphology after 100 weeks of cycling was observed, and it was found that the surface was flat and zinc was deposited uniformly.
Comparative example 1
Pure zinc foil is used as positive and negative electrodes to be assembled into a CR2032 pair battery, and the cycle performance test is carried out. As can be seen from the test results of FIG. 7, the current density was 20mA/cm 2 With a capacity of 1mAh/cm 2 In the case of pure zinc foil, the problem of a pronounced short circuit occurs only after cycling for less than 500 hours, and the overpotential is as high as 70mV.
Pure zinc foil is used as positive and negative electrodes to be assembled into a CR2032 pair battery, and the current density is 20mA/cm 2 With a capacity of 1mAh/cm 2 After the cycle was disassembled for 100 weeks, the microscopic morphology of the pure zinc foil negative electrode after 100 weeks of the cycle was observed, and the surface morphology was found to be rugged, and a large amount of inactive zinc dendrites were present, as shown in fig. 8.
Pure zinc foil is used as a negative electrode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled, and long cycle performance test was performed at a rate of 0.5C. From the test results of FIG. 5, it can be seen that the capacity of the pure zinc foil anode decays rapidly after 180 weeks of cycling, with only 4mAh/g remaining after 200 weeks of cycling.
Pure zinc foil is used as a negative electrode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled, circulated at a rate of 0.5C for 100 weeks, then the full cell was disassembled, the microscopic morphology of the pure zinc foil negative electrode after 100 weeks of circulation was observed, a large amount of corrosion of the surface thereof was found,as shown in fig. 9.
Comparative example 2
(1) 10mg of Ti 3 C 2 T x Adding the mixture into 10mL of deionized water, uniformly stirring and mixing, adding 50mg of polyvinyl alcohol, heating to 80 ℃ and stirring to form viscous slurry;
(2) After the slurry is scraped on the surface of the zinc foil by using a scraper, the zinc foil is frozen for 6 hours at the temperature of minus 20 ℃ and then thawed for 12 hours at the temperature of 30 ℃, and the freezing-thawing operation is repeated for three times, so that the zinc metal anode material decorated by the interface film is obtained and is abbreviated as an anode material 30.
The negative electrode material 30 prepared in this comparative example was subjected to microscopic morphological characterization, and according to the characterization result, the surface of the zinc foil was coated with an interfacial film having a thickness of about 15 μm.
The ionic conductivity of the interfacial film in the anode material 30 was found to be 2×10 by test calculation -8 S/m, the electron conductivity was 0.035S/m.
The negative electrode material 30 prepared in this comparative example was assembled as a positive electrode and a negative electrode into a CR2032 pair battery, and the cycle performance was tested. At a current density of 20mA/cm 2 With a capacity of 1mAh/cm 2 In the case of (2), the voltage of the negative electrode shows significant fluctuation after exceeding 200 hours, and the battery is damaged.
The negative electrode material 30 prepared in this comparative example was assembled as a positive electrode and a negative electrode into a CR2032 pair battery having a current density of 20mA/cm 2 With a capacity of 1mAh/cm 2 After the cycle was completed for 100 weeks, the battery was disassembled, and the microscopic morphology of the negative electrode after the cycle was observed for 100 weeks, and the surface was found to exhibit remarkable dendrite growth.
The anode material 30 prepared in this comparative example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full battery was assembled, and a long cycle performance test was performed at a rate of 0.5C (1c=148 mAh/g), and the capacity of the full battery remained only 23mAh/g after 400 weeks of cycle.
The anode material 30 prepared in this comparative example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled, cycled at a rate of 0.5C for 100 weeks, and then the full cell was disassembled, and the PM@Zn negative electrode was observed after 100 weeks of cycleThe appearance is observed, and the surface of the material is uneven, so that obvious corrosion and dendrite growth are shown.
Comparative example 3
(1) 20mg Zn (CF) 3 SO 3 ) 2 Adding the mixture into 10mL of deionized water, uniformly stirring and mixing, adding 50mg of polyvinyl alcohol, heating to 80 ℃ and stirring to form viscous slurry;
(2) After the slurry is scraped on the surface of the zinc foil by using a scraper, the zinc foil is frozen for 6 hours at the temperature of minus 20 ℃ and then thawed for 12 hours at the temperature of 30 ℃, and the freezing-thawing operation is repeated for three times, so that the zinc metal anode material decorated by the interface film is obtained and is abbreviated as an anode material 40.
The negative electrode material 40 prepared in this comparative example was subjected to microscopic morphological characterization, and according to the characterization result, the surface of the zinc foil was coated with an interfacial film having a thickness of about 15 μm.
The ionic conductivity of the interfacial film in the anode material 40 was found to be 0.38S/m and the electronic conductivity was found to be 3X 10 -9 S/m。
The negative electrode material 40 prepared in this comparative example was assembled as a positive electrode and a negative electrode into a CR2032 pair battery, and the cycle performance was tested. At a current density of 20mA/cm 2 With a capacity of 1mAh/cm 2 In the case of (2), the voltage of the negative electrode shows significant fluctuation after more than 180 hours, and the battery is damaged.
The negative electrode material 40 prepared in this comparative example was assembled as a positive electrode and a negative electrode into a CR2032 pair battery having a current density of 20mA/cm 2 With a capacity of 1mAh/cm 2 After the cycle was completed for 100 weeks, the battery was disassembled, and the microscopic morphology of the negative electrode after the cycle was observed for 100 weeks, and the surface was found to exhibit remarkable dendrite growth.
The anode material 40 prepared in this comparative example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full battery was assembled, and a long cycle performance test was performed at a rate of 0.5C (1c=148 mAh/g), and the capacity of the full battery remained only 25mAh/g after 400 weeks of cycle.
The anode material 40 prepared in this comparative example was used as an anode, liMn 2 O 4 As a positive electrode, a CR2032 full cell was assembled and cycled at a rate of 0.5C of 10And after 0 weeks, the full battery is disassembled, the microscopic morphology of the cathode after 100 weeks of circulation is observed, and the surface of the cathode is uneven, so that obvious corrosion and dendrite growth are shown.
Comparative example 4
On the basis of example 1, only Ti in step (1) of example 1 3 C 2 T x The mass was adjusted to 200mg and Zn (CF) 3 SO 3 ) 2 The mass was adjusted to 100mg, and the other conditions and steps were the same as in example 1, to obtain an interface film-modified zinc metal negative electrode material, abbreviated as negative electrode material 15.
The negative electrode material 15 prepared in this comparative example was subjected to microscopic morphological characterization, and according to the characterization result, the surface of the zinc foil was coated with an interfacial film having a thickness of about 30 μm.
The ionic conductivity of the interfacial film in the negative electrode material 15 was found to be 4×10 by test calculation -4 S/m, electron conductivity of 3X 10 -6 S/m, the result indicates that excessive Ti is added 3 C 2 T x And Zn (CF) 3 SO 3 ) 2 The whole structure of the interface film is damaged, and the transmission rate of the double conductors is obviously reduced.
The negative electrode material 15 prepared in this comparative example was assembled as a positive electrode and a negative electrode into a CR2032 pair battery, and the cycle performance was tested. At a current density of 20mA/cm 2 With a capacity of 1mAh/cm 2 In the case of (2), the voltage of the negative electrode shows significant fluctuation after more than 40 hours, and the battery is damaged.
The negative electrode material 15 prepared in this comparative example was assembled as a positive electrode and a negative electrode into a CR2032 pair battery having a current density of 20mA/cm 2 With a capacity of 1mAh/cm 2 After the cycle was completed for 100 weeks, the battery was disassembled, and the microscopic morphology of the negative electrode after the cycle was observed for 100 weeks, and the surface was found to exhibit remarkable dendrite growth.
The anode material 15 prepared in this comparative example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full battery was assembled, and a long cycle performance test was performed at a rate of 0.5C (1c=148 mAh/g), and the capacity of the full battery remained only 15mAh/g after 100 weeks of cycle.
The book is put intoComparative example negative electrode material 15 as a negative electrode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled, cycled at a rate of 0.5C for 100 weeks, after which the full cell was disassembled, and the negative electrode microscopic morphology after 100 weeks of cycling was observed, and the surface roughness was found to exhibit significant corrosion and dendrite growth.
Comparative example 5
Except that the freeze-thaw process was removed and air-dried at normal room temperature, the process was carried out in the same manner as in example 1 except that the interface film-modified zinc metal anode material, abbreviated as anode material 16, was obtained in the same manner as in example 1.
The negative electrode material 16 prepared in this comparative example was subjected to microscopic morphological characterization, and according to the characterization result, the surface of the zinc foil was coated with an interfacial film having a thickness of about 10 μm, and significant curling occurred on the surface.
The ionic conductivity of the interfacial film in the anode material 16 was found to be 4×10 by test calculation -4 S/m, electron conductivity of 5X 10 -6 S/m。
The negative electrode material 16 prepared in this comparative example was assembled as a positive electrode and a negative electrode into a CR2032 pair battery, and the cycle performance was tested. At a current density of 20mA/cm 2 With a capacity of 1mAh/cm 2 In the case of (2), the voltage of the negative electrode showed significant fluctuation after more than 50 hours, and the battery was damaged.
The negative electrode material 16 prepared in this comparative example was assembled as a positive electrode and a negative electrode into a CR2032 pair battery having a current density of 20mA/cm 2 With a capacity of 1mAh/cm 2 After the cycle was completed for 100 weeks, the battery was disassembled, and the microscopic morphology of the negative electrode after the cycle was observed for 100 weeks, and the surface was found to exhibit remarkable dendrite growth.
The anode material 16 prepared in this comparative example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full battery was assembled, and a long cycle performance test was performed at a rate of 0.5C (1c=148 mAh/g), and the capacity of the full battery remained only 23mAh/g after 100 weeks of cycle.
The anode material 16 prepared in this comparative example was used as an anode, liMn 2 O 4 As the positive electrode, a CR2032 full cell was assembled at 0And 5C, circulating for 100 weeks at a multiplying power, then disassembling the full battery, observing the microscopic morphology of the cathode after 100 weeks of circulation, and finding that the surface of the cathode is uneven and obvious corrosion and dendrite growth are presented.
In summary, the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The zinc metal anode material based on ion/electron double-conductor interface film modification is characterized in that: is a zinc-containing metal material with an ion/electron double-conductor interface film on the surface;
wherein the ion/electron double-conductor interface film is made of doped conductive material and Zn (CF) 3 SO 3 ) 2 The polymer film has an ionic conductivity of 0.1 to 0.8S/m and an electronic conductivity of 0.01 to 0.1S/m.
2. The zinc metal anode material based on ion/electron double-conductor interface film modification according to claim 1, wherein: the conductive material is MXene, reduced graphene oxide or heteroatom doped graphene, and the polymer is one or more of polyvinyl alcohol, polyethylene glycol, polyethylene oxide and poly (vinylidene fluoride-co-hexafluoropropylene).
3. The zinc metal anode material based on ion/electron double-conductor interface film modification according to claim 2, wherein: MXene is selected from Ti 3 C 2 T x Or Ti (Ti) 3 AlC 2 。
4. The zinc metal anode material based on ion/electron double-conductor interface film modification according to claim 2, wherein: conductive material, zn (CF) 3 SO 3 ) 2 The mass ratio of the polymer is 1: (1-3): (3-8).
5. The zinc metal anode material based on the modification of an ion/electron double conductor interface film according to any one of claims 1 to 4, characterized in that: the thickness of the ion/electron double-conductor interface film is 200 nm-40 mu m.
6. The method for producing a zinc metal anode material based on ion/electron double conductor interface film modification according to any one of claims 1 to 5, characterized in that: the method comprises the following steps:
(1) Conductive material, zn (CF) 3 SO 3 ) 2 Mixing the polymer and water, and heating and stirring to obtain a thick slurry;
(2) And (3) coating the slurry prepared in the step (1) on the surface of the zinc-containing metal material, freezing, thawing, and repeating the freezing-thawing operation for 3-5 times to obtain the zinc-containing metal negative electrode material modified based on the ion/electron double-conductor interface film.
7. The method for preparing the zinc metal anode material modified based on the ion/electron double-conductor interface film according to claim 6, which is characterized in that: in the step (1), the concentration of the conductive material in the slurry is 1-5 mg/mL.
8. The method for preparing the zinc metal anode material modified based on the ion/electron double-conductor interface film according to claim 6, which is characterized in that: in step (1), stirring is carried out at 60-90 ℃ to obtain thick slurry.
9. The method for preparing the zinc metal anode material modified based on the ion/electron double-conductor interface film according to claim 6, which is characterized in that: in the step (2), the temperature of each freezing is-40 to-20 ℃ and the freezing time is 30min to 24h, and the temperature of each thawing is 20 to 40 ℃ and the thawing time is 2 to 24h.
10. The zinc metal negative electrode material modified based on an ion/electron double conductor interface film according to any one of claims 1 to 5, applied as a negative electrode in an aqueous zinc ion battery.
CN202211623772.1A 2022-12-16 2022-12-16 Zinc metal anode material modified based on ion/electron double-conductor interface film, preparation and application thereof Pending CN116154147A (en)

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