CN115172647A - Fatty acid zinc modified zinc metal negative electrode and preparation method and application thereof - Google Patents
Fatty acid zinc modified zinc metal negative electrode and preparation method and application thereof Download PDFInfo
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- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention discloses a fatty acid zinc modified zinc metal negative electrode and a preparation method and application thereof, wherein the preparation method of the fatty acid zinc modified zinc metal negative electrode comprises the following steps: step 1: dissolving fatty acid powder particles in an organic reagent, and stirring at normal temperature until the fatty acid powder particles are completely dissolved to obtain a fatty acid solution; step 2: and (3) placing the zinc sheet in a fatty acid solution, taking out after soaking reaction to obtain a modified zinc metal cathode, and drying the modified zinc metal cathode in an oven to obtain the fatty acid zinc modified zinc metal cathode. According to the invention, after the fatty acid is dissolved in the absolute ethyl alcohol, the metal zinc is added to carry out a chemical reaction, a fatty acid zinc modified layer is generated in situ on the surface of the zinc metal cathode, and desolvation is realized to a certain extent while zinc ions are induced to be uniformly and flatly deposited by utilizing the high ion conduction rate, the stronger hydrophobic property and the rapid zinc ion migration rate of the fatty acid zinc, so that the excellent effects of inhibiting hydrogen evolution corrosion and generating side reactions are realized.
Description
Technical Field
The invention relates to the technical field of water-based zinc ion batteries, in particular to a zinc fatty acid modified zinc metal negative electrode and a preparation method and application thereof.
Background
The zinc metal has the advantages of abundant reserves, low equilibrium potential, high hydrogen overpotential and high theoretical capacity (820 mA. H/g) in nature, the zinc has the highest energy in stable metal elements in aqueous solution, has quick kinetics, and has the advantages of low oxidation-reduction potential (-0.76V), environmental friendliness and the like. Zinc ion secondary batteries are currently the focus of research because zinc ions can carry more free charges during electrochemical reaction, theoretically having higher energy density than lithium ion batteries.
However, practical application thereof is hindered by various factors such as corrosion side reaction, hydrogen evolution, dendrite growth, and poor reversibility of the zinc negative electrode. The high-activity water molecules in the electrolyte are in direct contact with the zinc cathode, so that the electrode corrosion is inevitably caused, the hydrogen evolution reaction is accelerated, and the volume of the battery is expanded while the electrolyte is consumed. The rapid charge/discharge process can cause a large number of freely moving anions to accumulate around the zinc protrusions, thereby creating a non-uniform electric field that accelerates zinc dendrite growth, and the continuously growing dendrites can then puncture the separator causing a short circuit in the cell. The above problems cause the capacity attenuation of the battery, the reduction of coulombic efficiency and cycling stability, and the development and application of the water system zinc ion battery are seriously hindered.
To date, various strategies have been proposed to stabilize zinc metal anodes, including artificial interface layer construction (e.g., inorganic or organic interface layers), electrolyte engineering (i.e., additives, solid/quasi-solid and organic electrolytes), and electrode structural design (i.e., three-dimensional zinc current collector design and zinc with nanoporous structure). It should be noted, however, that most protective layers made on zinc anodes are based on slurry coating methods, which can result in poor adhesion, non-uniform coating, and some voids between the modified layer and the zinc surface. Furthermore, the slurry coating process always involves cumbersome handling of the synthetic binder (i.e. polyvinylidene fluoride) and toxic organic solvent (i.e. N-methyl pyrrolidone), which has potential negative environmental impact.
Therefore, it is very attractive to build a sustainable interface layer by an in-situ growth method. Recently, a zinc cathode modified by a Metal Organic Framework (MOF) is prepared through an in-situ zinc surface oxidation reaction and a coordination process, an organic zinc phosphate-silane composite passive film is constructed in situ to modify the zinc cathode, and the like, and a protective layer is generated in situ on the surface of the zinc cathode. The MOF layer is in close contact with the zinc foil, uniform charge distribution is presented in the galvanizing/stripping process, and the obtained MOF integrated zinc cathode presents high stability in deposition and stripping cycles; for example, the organic zinc phosphate-silane composite passive film in patent No. CN 113690401B has strong hydrophobicity, hydroxyethylidene diphosphonic acid (Hedp) with phosphate group is selected to establish a zinc-philic block through a formed zinc chelate, and the top hydrophobic group can effectively prevent H 2 O penetration to inhibit H 2 Precipitation and electrode corrosion, which provide a means to improve the stability of zinc anodes, it should be noted that such effective interfaces of zinc anodes still face the problems of complex manufacturing processes, high cost and limited mass production. Moreover, the use of organic phosphoric acid causes considerable environmental pollution, and the dense hydrophobic layer formed by using the strong hydrophobic organosilane and the zinc phosphate layer are uncontrollable in the hydrogen bond dehydration condensation process and have poor stability (1 mA cm) -2 ，1 mAh·cm -2 The lifetime under the test conditions of (2) is only 1200 h). There is a need for a sustainable and simple method to build a durable interface for zinc metal anodes.
Disclosure of Invention
In view of the defects, the invention provides a fatty acid zinc modified zinc metal cathode and a preparation method and application thereof, which utilize the characteristic that fatty acid is easily dissolved in an organic reagent and reacts with zinc metal to form a uniform fatty acid zinc protective layer, the fatty acid is dissolved in absolute ethyl alcohol and then added with metal zinc to carry out chemical reaction, a fatty acid zinc modified layer is generated on the surface of the zinc metal cathode in situ, and desolvation is realized to a certain extent while zinc ions are induced to be uniformly and flatly deposited by utilizing the high ion conduction rate, the stronger hydrophobic property and the rapid zinc ion migration rate of the fatty acid zinc, so that the excellent effects of inhibiting hydrogen evolution corrosion and generating side reactions are realized.
In order to achieve the aim, the invention provides a fatty acid zinc modified zinc metal negative electrode and a preparation method thereof, wherein the preparation method comprises the following steps:
step 1: dissolving fatty acid powder particles in an organic reagent, and stirring at normal temperature until the fatty acid powder particles are completely dissolved to obtain a fatty acid solution;
and 2, step: and (3) placing the zinc sheet in a fatty acid solution, taking out after soaking reaction to obtain a modified zinc metal cathode, and drying the modified zinc metal cathode in an oven to obtain the fatty acid zinc modified zinc metal cathode.
According to one aspect of the invention, the number of carbon atoms in the carbon chain of the fatty acid is greater than or equal to 6.
In accordance with one aspect of the present invention, the fatty acid is a saturated fatty acid, and the saturated fatty acid is any one of caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, pearlescent aliphatic acid, stearic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid, nervonic acid, cerotic acid, melissic acid and laccerotic acid.
According to one aspect of the present invention, the fatty acid is an unsaturated fatty acid, and the unsaturated fatty acid is any one of hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, myristoleic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, octadecenoic acid, oleic acid, linoleic acid, elaidic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, aconitic acid, docosapentaenoic acid, and docosahexaenoic acid.
In accordance with one aspect of the invention, the organic agent is one or more of methanol, ethanol, ethyl acetate, dimethylformamide, benzene, ethyl toluate, chloroform, carbon tetrachloride, benzene, and carbon disulfide.
According to one aspect of the invention, the fatty acid solution has a mass concentration of 2 to 24g/L.
According to one aspect of the invention, in the step 2, the soaking reaction time is 15-40h.
According to one aspect of the present invention, in the step 2, the specific drying parameters are: the temperature of the oven is 40-80 ℃ and the time is 0.3-5h.
Based on the same inventive concept, the invention also discloses a fatty acid zinc modified zinc metal negative electrode, and the fatty acid zinc modified zinc metal negative electrode is prepared by the preparation method of any one of the fatty acid zinc modified zinc metal negative electrodes.
Based on the same inventive concept, the invention also discloses a zinc fatty acid modified zinc metal cathode obtained by the preparation method of any one of the zinc fatty acid modified zinc metal cathodes or an application of the zinc fatty acid modified zinc metal cathode, and the zinc fatty acid modified zinc metal cathode is assembled into a symmetrical battery; or the fatty acid zinc modified zinc metal negative electrode and a commercial current collector are assembled into a half-cell; or modifying the zinc fatty acid zinc into a zinc metal negative electrode, CNT/MnO 2 、V 2 O 5 Or prussian blue is used as the anode, and the water-based zinc ion battery is obtained by assembling.
The invention has the beneficial effects that:
(1) The invention selects cheap and easily obtained and environment-friendly fatty acid, utilizes the fatty acid to be easily dissolved in an organic reagent and reacts with zinc metal to generate a fatty acid zinc modified zinc metal cathode, and utilizes the reaction of a carboxyl terminal of the fatty acid with the zinc to generate a layer of uniform fatty acid zinc in situ, wherein the carbonyl group of the fatty acid zinc is an excellent electron-donating group, so that the high ion conduction rate can be realized, the obstruction of zinc deposition is reduced, and the uniform deposition of zinc ions is guided; and long carbon chains (the number of carbon atoms in the carbon chain is more than or equal to 6) which are arranged in an outward orientation have excellent hydrophobicity, and can exclude water molecules to inhibit side reactions such as hydrogen evolution corrosion and the like. The zinc aliphatate enhances the zinc affinity and brings the desolvation effect, regulates and controls the electric field distribution on the surface of the zinc cathode, and protects the zinc metal cathode to realize long-cycle stability.
The modified layer on the surface of the zinc metal cathode modified by the fatty acid zinc has stronger water molecule capacity, is suitable for transportation and storage and long-cycle stable use of commercial zinc sheets, improves the electrochemical performance and cycle stability of the zinc cathode, and effectively improves the performance of a water system zinc ion battery because the cycle of a symmetrical battery exceeds 2000h and the cycle of a full battery exceeds 2700 cycles.
Drawings
Fig. 1 is an SEM image of a zinc fatty acid zinc-modified zinc metal negative electrode obtained in example 1 of the present invention;
FIG. 2 is an SEM image of an unmodified commercial zinc sheet;
FIG. 3 is an electrodynamic polarization curve of a fatty acid zinc modified zinc metal negative electrode and an unmodified commercial zinc sheet in 2M zinc sulfate aqueous solution obtained in example 1 of the present invention;
FIG. 4 (a) is a contact angle test chart of unmodified commercial zinc sheets of the present invention in 2M aqueous zinc sulfate solution; fig. 4 (b) is a contact angle test chart of the fatty acid zinc modified zinc metal negative electrode obtained in example 1 of the present invention in a 2M zinc sulfate aqueous solution;
fig. 5 is a linear sweep voltammetry curve of a fatty acid zinc modified zinc metal negative electrode and an unmodified commercial zinc sheet in 2M sodium sulfate aqueous solution obtained in example 1 of the present invention;
FIG. 6 shows that the symmetric cell with the zinc-modified zinc metal cathode of fatty acid zinc obtained in example 1 and the unmodified commercial zinc sheet assembled separately is 1 mA cm -2 A time-voltage comparison graph for carrying out a cycle stability test for each 1h of continuous charging and discharging under the current density;
FIG. 7 shows that the symmetric cell with the zinc-modified zinc metal cathode of fatty acid zinc obtained in example 1 and the unmodified commercial zinc sheet assembled separately is 1 mA cm -2 Time-voltage comparison graph of cycle stability test is carried out for 0.5h each of continuous charging and discharging under the current density;
FIG. 8 shows that the zinc fatty acid modified zinc metal cathode and the unmodified commercial zinc sheet obtained in example 1 of the present invention are respectively matched with V 2 O 5 Specific capacity and efficiency plots of the assembled full cell cycle;
fig. 9 is a time-voltage diagram of a cycle stability test of a symmetrical battery assembled with a fatty acid zinc modified zinc metal negative electrode and an unmodified commercial zinc sheet respectively obtained in example 2 of the present invention;
fig. 10 is a time-voltage diagram of a cycle stability test of a symmetrical battery assembled with a fatty acid zinc modified zinc metal negative electrode and an unmodified commercial zinc sheet respectively obtained in example 3 of the present invention;
fig. 11 is a time-voltage diagram of a cycle stability test of a symmetrical battery assembled with a fatty acid zinc modified zinc metal negative electrode and an unmodified commercial zinc sheet respectively obtained in example 4 of the present invention;
fig. 12 is a time-voltage diagram of a cycle stability test of a symmetrical battery in which a zinc fatty acid modified zinc metal negative electrode obtained in comparative example 1 of the present invention and an unmodified commercial zinc sheet were separately assembled;
fig. 13 is a time-voltage diagram of a cycle stability test of a symmetrical battery in which a zinc fatty acid modified zinc metal negative electrode obtained in comparative example 2 of the present invention and an unmodified commercial zinc sheet were separately assembled;
fig. 14 is a time-voltage diagram of a cycle stability test of a symmetrical battery in which a zinc fatty acid modified zinc metal negative electrode obtained in comparative example 3 of the present invention and an unmodified commercial zinc sheet were separately assembled;
fig. 15 is a time-voltage diagram of a cycle stability test of a symmetrical battery in which a fatty acid zinc modified zinc metal negative electrode obtained in comparative example 4 of the present invention and an unmodified commercial zinc sheet were separately assembled.
Detailed Description
In order that the invention may be more readily understood, reference is now made to the following examples which are intended to illustrate the invention. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention, and it should be understood that the described examples are only a portion of the examples of the present invention, rather than the entire scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Unless otherwise defined, the terms used hereinafter are consistent with the meaning understood by those skilled in the art; unless otherwise indicated, all materials, reagents, equipment referred to herein may be purchased from commercial sources or prepared by well-known methods.
The full cell in the specific embodiment of the present application is an aqueous zinc ion cell, and the electrolyte of the full cell is 2M zinc sulfate aqueous solution.
"Bar Zn" in the figures of the present application denotes unmodified commercial zinc flakes; "SA @ Zn" in the drawings of the present application represents zinc stearate modified zinc metal negative electrodes; in the attached figures of the application, "SA @ Zn-12h" represents a zinc stearate modified zinc metal negative electrode obtained by soaking for 12 h; in the attached drawings of the application, "SA @ Zn-48h" represents zinc stearate modified zinc metal negative electrode obtained with the soaking reaction time of 48 h; "la @ zn" in the drawings of the present application represents zinc laurate-modified zinc metal negative electrode; "AA @ Zn" in the attached drawings of the application represents zinc arachidate modified zinc metal negative electrode; "OA @ Zn" in the drawings of the application represents zinc metal negative electrode modified by zinc octadecenoate; "PA @ Zn" in the drawings of the application represents zinc propionate modified zinc metal cathode; in the attached drawings of the application, "CA @ Zn" represents zinc crotonate modified zinc metal negative electrode; here, the abscissa and the ordinate of the small graph in fig. 6 are the same as the ordinate, and therefore, the abscissa and the ordinate of the small graph are omitted.
Example 1
Firstly, preparing a zinc metal wafer to be modified: taking a commercial zinc sheet with a certain area and a thickness of 0.1mm, then punching the commercial zinc sheet into a circular sheet with the diameter of 16mm by using a punching machine, then pressing the surface of the punched zinc sheet to be flat by using a weight, sequentially ultrasonically cleaning the flattened zinc sheet for 10 minutes by using ultrapure water and ethanol, and then drying the flattened zinc sheet in a vacuum oven at 30 ℃ for later use.
0.79g of stearic acid was weighed out and added to a beaker containing 100mL of absolute ethanol and stirred to be sufficiently dissolved, thereby obtaining a stearic acid solution. And soaking the dried zinc sheet into a stearic acid solution for 24h, taking out the zinc sheet, absorbing the redundant residual solution on the surface of the zinc sheet by using dust-free cloth, putting the zinc sheet into a 60 ℃ oven, drying for 1-2h, taking out, and cooling to room temperature to obtain the fatty acid zinc modified zinc metal cathode.
In the embodiment, taking cheap and stable stearic acid in fatty acid as an example, the generated reaction is shown as follows, stearic acid powder is dissolved in absolute ethyl alcohol, the obtained stearic acid solution and a zinc metal negative electrode generate a chemical reaction, the surface of a zinc sheet is etched, zinc stearate is generated in situ on the surface of the zinc sheet, a carboxyl zinc-philic end of the zinc stearate is tightly combined with a substrate, a uniform zinc stearate modified layer is formed with a carbon chain end facing outwards, and the zinc negative electrode after the reaction and etching is quickly dried to form the stable saturated zinc stearate modified zinc metal negative electrode.
Example 2
This example was conducted in a similar parallel experiment to example 1, in which the fatty acid was lauric acid, and the other preparation method was exactly the same as example 1, to obtain a zinc-fatty acid zinc-modified zinc metal negative electrode.
Example 3
In this example, a similar parallel experiment was performed as in example 1, in which the fatty acid was arachidic acid, and the other preparation methods were exactly the same as in example 1, to obtain a zinc-modified zinc metal negative electrode.
Example 4
This example was conducted in a similar parallel experiment as example 1, in which the fatty acid was octadecenoic acid and the other preparation methods were exactly the same as example 1, to obtain a zinc metal negative electrode modified with fatty acid zinc.
Comparative example 1
Comparative example 1 a similar parallel test was performed as in example 1, in which the reaction time was 12 hours, and the other preparation methods were exactly the same as in example 1, to obtain a fatty acid zinc-modified zinc metal negative electrode.
Comparative example 2
This comparative example was subjected to a similar parallel test as comparative example 1, in which the reaction time was 48 hours, and the other preparation methods were completely the same as example 1, to obtain a fatty acid zinc-modified zinc metal negative electrode.
Comparative example 3
This comparative example was conducted in a similar parallel test as example 1, in which the fatty acid was propionic acid, and the other preparation methods were exactly the same as example 1, to obtain a fatty acid zinc-modified zinc metal negative electrode.
Comparative example 4
A similar parallel test was performed as in example 1, where the fatty acid was crotonic acid, and the other preparation methods were the same as in example 1, to obtain a zinc metal negative electrode modified with fatty acid zinc.
And (4) performance testing:
the microstructure representation of the zinc metal cathode modified by the fatty acid zinc in the embodiment 1 and the commercial zinc sheet is carried out by adopting a scanning electron microscope, specifically detailed SEM images in figures 1 and 2 are shown, and the comparison with figure 2 shows that a compact and uniform zinc stearate modified layer is obviously formed on the surface of the zinc metal cathode modified by the fatty acid zinc in the embodiment 1, so that the stable zinc deposition, the hydrogen evolution inhibition and other side reactions in the long-circulating process of the battery can be favorably carried out.
When the zinc fatty acid modified zinc metal negative electrode obtained in example 1 and a commercial zinc sheet were subjected to an electrodynamic polarization curve measurement in a 2M zinc sulfate aqueous solution, as shown in fig. 3, the corrosion current of the zinc fatty acid modified zinc metal negative electrode obtained in this example was significantly reduced. As shown in fig. 4, the contact angle between the commercial zinc sheet and the modified zinc metal negative electrode to the 2M zinc sulfate aqueous solution shows that the fatty acid zinc modified layer in example 1 of the present invention has a strong hydrophobic ability, which is beneficial to the modified zinc negative electrode to inhibit hydrogen evolution corrosion. As shown in fig. 5, when the modified zinc metal negative electrode of example 1 and the unmodified commercial zinc sheet are subjected to a linear sweep voltammetry test, the zinc stearate modified zinc metal negative electrode of example 1 of the present invention has a higher hydrogen evolution potential, which indicates that the modified zinc metal negative electrode of example 1 of the present invention has a stronger hydrogen evolution inhibition capability.
The modified zinc metal anodes obtained in example 1 were assembled into symmetrical cells for electrochemical performance testing and compared with commercial zinc sheets, the results are shown in FIG. 6 at 1 mA. Cm -2 The current density of the zinc oxide is continuously charged and discharged for 1 hour, and the cycling stability is tested, so that the modified zinc metal cathode obtained in the embodiment 1 of the invention has excellent cycling performance which is 1 mA cm -2 The stable circulation of the current is more than or equal to 1800h under the current density; as shown in FIG. 7, the value is 1 mA. Cm -2 The current density of the lithium ion battery is continuously charged and discharged for 0.5h respectively, the stable circulation is more than or equal to 2000h, and the excellent stability is shown. The modified zinc metal negative electrode obtained in example 1 was mixed with V 2 O 5 Assembling the positive pole piece into a full cell for electrochemical performance test, and using commercial zincFor comparison, the results are shown in FIG. 8, which shows that the ratio of the total weight of the tablets is 5A · g -1 The charge and discharge test is carried out under the current density of (1), and the stable circulation exceeds 2700 circles.
The modified zinc metal anodes obtained in examples 2, 3 and 4 were assembled into a symmetrical cell and subjected to electrochemical performance test, and the results are shown in fig. 9, 10 and 11, where 1 mA cm -2 Under the test condition of continuous charging and discharging for 1 hour under the current density, the cycle duration is respectively longer than 1100 hours, 1200 hours and 1100 hours, and similar to the result in the example 1, no matter the zinc fatty acid is saturated zinc fatty acid or unsaturated zinc fatty acid, the carbonyl group which is conductive and hydrophilic and the long carbon chain which is hydrophobic play an ideal role, so that the zinc fatty acid modified zinc metal cathode has excellent cycle performance.
The modified zinc metal cathodes obtained in comparative examples 1, 2, 3 and 4 were assembled into symmetrical batteries respectively for electrochemical performance tests, and the results are shown in fig. 12, 13, 14 and 15, the electrochemical performance of the symmetrical batteries of the modified zinc metal cathodes prepared in each comparative example is significantly reduced, because the reaction time of comparative example 1 is insufficient, the amount of the generated fatty acid zinc is small and uneven, and the hydrophobic ability and the structural stability of the modified layer are significantly reduced; the comparative example 2 is that the reaction time is too long, the generated fatty acid zinc is too much, the zinc substrate is seriously etched, the conductivity of the modified zinc cathode is reduced, and the cycle stability of the modified zinc cathode is influenced; similarly, in comparative examples 3 and 4, propionic acid and crotonic acid have strong acidity and react with a zinc substrate violently, so that the corrosion is serious, the hydrophobic effect is not obvious due to the short carbon chain, and the generated fatty acid zinc cannot be stably connected with the substrate zinc, so that the fatty acid zinc is easy to fall off in the circulation process, and the circulation stability is poor.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (7)
1. The preparation method of the fatty acid zinc modified zinc metal negative electrode is characterized by comprising the following steps:
step 1: dissolving fatty acid powder particles in an organic reagent, and stirring at normal temperature until the fatty acid powder particles are completely dissolved to obtain a fatty acid solution;
and 2, step: placing the zinc sheet in a fatty acid solution, taking out after soaking reaction to obtain a modified zinc metal cathode, and drying the modified zinc metal cathode in an oven to obtain a fatty acid zinc modified zinc metal cathode;
wherein the fatty acid is a saturated fatty acid or an unsaturated fatty acid; the number of carbon atoms in the carbon chain of the fatty acid is more than or equal to 6; the organic reagent is one or more of methanol, ethanol, ethyl acetate, dimethylformamide, benzene, toluene ethyl ether, chloroform, carbon tetrachloride, benzene and carbon disulfide; the mass concentration of the fatty acid solution is 2-24g/L.
2. The method for preparing a zinc fatty acid modified zinc metal negative electrode according to claim 1, wherein the saturated fatty acid is any one of caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, pearlescent fatty acid, stearic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid, nervonic acid, cerotic acid, melissic acid, and lacca acid.
3. The method for preparing a zinc metal negative electrode modified by fatty acid zinc according to claim 1, wherein the unsaturated fatty acid is any one of hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, myristoleic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, octadecenoic acid, oleic acid, linoleic acid, elaidic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, aconitic acid, docosapentaenoic acid, and docosahexaenoic acid.
4. The method for preparing the zinc fatty acid modified zinc metal negative electrode as claimed in claim 1, wherein in the step 2, the soaking reaction time is 15-40h.
5. The method for preparing the zinc fatty acid modified zinc metal negative electrode according to claim 1, wherein in the step 2, the specific drying parameters are as follows: the temperature of the oven is 40-80 ℃ and the time is 0.3-5h.
6. A zinc fatty acid zinc modified zinc metal negative electrode, characterized in that the zinc fatty acid zinc modified zinc metal negative electrode is prepared by the method for preparing the zinc fatty acid zinc modified zinc metal negative electrode according to any one of claims 1 to 5.
7. An application of the zinc fatty acid zinc modified zinc metal negative electrode obtained by the preparation method of the zinc fatty acid zinc modified zinc metal negative electrode of any one of claims 1 to 5 or the zinc fatty acid zinc modified zinc metal negative electrode of claim 9, characterized in that the zinc fatty acid zinc modified zinc metal negative electrode is assembled into a symmetrical battery; or the fatty acid zinc modified zinc metal negative electrode and a commercial current collector are assembled into a half-cell; or modifying the zinc fatty acid zinc into a zinc metal negative electrode, CNT/MnO 2 、V 2 O 5 Or prussian blue is used as the anode, and the water-based zinc ion battery is obtained by assembling.
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| CN1744355A (en) * | 2005-09-28 | 2006-03-08 | 浙江工业大学 | Negative material of a kind of alkaline secondary zinc electrode and preparation method thereof |
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| KR20190097781A (en) * | 2018-02-13 | 2019-08-21 | 전남대학교산학협력단 | Zinc secondary battery having an alkali metal vanadium oxide electrode |
| CN113097496A (en) * | 2021-02-25 | 2021-07-09 | 东华大学 | Zinc cathode with composite nanofiber protective layer and preparation and application thereof |
| CN113937341A (en) * | 2021-09-09 | 2022-01-14 | 复旦大学 | Metal zinc secondary battery |
| CN114613933A (en) * | 2022-03-20 | 2022-06-10 | 青岛科技大学 | Porous CeO2Zinc cathode coating design and aqueous zinc ion battery |
| CN114824278A (en) * | 2022-05-24 | 2022-07-29 | 北京大学深圳研究生院 | SEI film reaction liquid, modification method of zinc negative electrode and modified zinc negative electrode |
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| JP2007273407A (en) * | 2006-03-31 | 2007-10-18 | Matsushita Electric Ind Co Ltd | Alkaline battery |
| KR20190097781A (en) * | 2018-02-13 | 2019-08-21 | 전남대학교산학협력단 | Zinc secondary battery having an alkali metal vanadium oxide electrode |
| CN113097496A (en) * | 2021-02-25 | 2021-07-09 | 东华大学 | Zinc cathode with composite nanofiber protective layer and preparation and application thereof |
| CN113937341A (en) * | 2021-09-09 | 2022-01-14 | 复旦大学 | Metal zinc secondary battery |
| CN114613933A (en) * | 2022-03-20 | 2022-06-10 | 青岛科技大学 | Porous CeO2Zinc cathode coating design and aqueous zinc ion battery |
| CN114824278A (en) * | 2022-05-24 | 2022-07-29 | 北京大学深圳研究生院 | SEI film reaction liquid, modification method of zinc negative electrode and modified zinc negative electrode |
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