CN108807961A - A kind of zinc-base cell negative electrode material and preparation method thereof - Google Patents
A kind of zinc-base cell negative electrode material and preparation method thereof Download PDFInfo
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- CN108807961A CN108807961A CN201810575861.0A CN201810575861A CN108807961A CN 108807961 A CN108807961 A CN 108807961A CN 201810575861 A CN201810575861 A CN 201810575861A CN 108807961 A CN108807961 A CN 108807961A
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of zinc-base cell negative electrode material and preparation method thereof, which includes zinc-base and the graphene for being supported on zinc-base surface, and preparation includes the following steps:(1) it after being surface-treated zinc-base, is placed in diluted acid and removes surface oxide layer, for use;(2) graphene oxide is placed in water, ultrasonic disperse obtains graphene oxide solution;(3) will treated that zinc-base is placed in graphene oxide solution reacts, then deionized water and electrolyte is used to impregnate to get the zinc-base cell negative electrode material respectively.Compared with prior art, negative material of the invention is 0.2 milliampere every square centimeter in current density, stablizes 150 circle of cycle in 0.5 mole every liter of zinc sulphate electrolyte, dendritic growth in cyclic process is effectively inhibited to pierce through diaphragm phenomenon;And preparation method is simple, is suitable for large-scale application.
Description
Technical field
The present invention relates to energy storage material fields, and in particular to a kind of zinc-base cell negative electrode material and preparation method thereof.
Background technology
Due to environmental pollution and energy shortage, new energy secondary cell has been paid close attention at people and the hot spot of research.Zinc
Base battery is a kind of very important energy storage device, because of the abundant reserves of metallic zinc and higher energy density, in tradition one
Occupy the prodigious market share in primary cell.Water system Zinc ion battery, the secondary cells such as zinc and air cell have higher energy close
Degree, environmental pollution is small, and battery process is simple with respect to organic battery system, cheap, while can effectively avoid existing business
The safety problems such as thermal runaway present in lithium battery, are widely paid close attention to.Water system Zinc ion battery remains branch at present
The problems such as crystalline substance, self discharge, volume expansion, coulombic efficiency, makes especially because the dendrite grown in cyclic process pierces through diaphragm
The problem of at battery short circuit, limits the further development of water system Zinc ion battery, therefore solves negative material dendritic growth and ask
Topic is particularly important, it may be said that negative material determine Zinc ion battery can commercialized development, therefore develop have it is excellent
The negative material of performance is to study one of problem the most key in zinc-base battery.
Invention content
It can effectively solve to bear it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of
The zinc-base cell negative electrode material and preparation method thereof of pole material dendritic growth problem.
The purpose of the present invention can be achieved through the following technical solutions:A kind of zinc-base cell negative electrode material, the cathode material
Material includes zinc-base and is supported on the graphene on zinc-base surface, wherein the thickness of graphene is 0.1~100 μm.The present invention is in zinc
Primary surface loads graphene, forms monolithic layer or few lamella, is not only effectively increased the contact area of zinc load and electrolyte,
And these monolithic layers or few lamella and finely dispersed graphene form one layer of physical buffer layer on zinc metal sheet surface, reduce
The volume change of negative material in cyclic process, battery remains able to normal charge and discharge after having recycled 300 hours, and change
Zinc metal sheet before property starts unstable having recycled 100 hours or so batteries, and it is thoroughly short-circuit to be recycled to 140 hours or so batteries, changes
Property after zinc load effective solution dendrite the problem of piercing through diaphragm.
The zinc-base is zine plate, zinc metal sheet or zinc foil.
A kind of preparation method of zinc-base cell negative electrode material as described above, includes the following steps:
(1) after being surface-treated zinc-base, surface oxide layer of going out is placed in diluted acid, for use;
(2) graphene oxide is placed in water, ultrasonic disperse obtains graphene oxide solution;
(3) will treated that zinc-base is placed in graphene oxide solution reacts, then use deionized water and electricity respectively
Liquid is solved to impregnate to get the zinc-base cell negative electrode material.
Metal zinc metal sheet is placed in graphene aqueous solution, since there are potential differences to make graphene oxide on zinc metal sheet surface for the two
Electrostatic Absorption occurs, and electron exchange occurs, that is, redox reaction occurs so that metallic zinc lose electronics become zinc from
Son, surface of graphene oxide functional group obtain electronics and graphene oxide are reduced.
The surface treatment includes the following steps:Zinc-base is placed in acetone soln, is cleaned by ultrasonic, then successively with anhydrous second
Alcohol and deionized water rinse surface.Aforesaid operations can be by the organic pollutant removal on zinc-base surface.
The diluted acid includes dilute hydrochloric acid, dilute sulfuric acid, hydrofluoric acid or acetic acid, and the mass concentration of the diluted acid is 1%~3%.
It impregnates, the oxide layer on zinc-base surface can be removed so that zinc-base surface exhibits go out stronger reproducibility in diluted acid.
Residence time of the zinc-base in diluted acid is 1~10s.
A concentration of 0.01~3g/L of the graphene oxide solution.Hummers can be used in the graphene oxide of the present invention
Graphite is prepared by method by multistep oxidation, commercial oxidation graphene can also be used to be made through overactivation.It is specific as follows:
1 prepares intercalated graphite:Crystalline flake graphite (32 mesh) is put into the concentrated sulfuric acid and concentrated nitric acid mixed solution (volume ratio 3/1),
About 12 hours are stood, filtering clean with deionized water, abundant washing, 120 DEG C of dryings about 12 hours.
2 prepare thermal expansion graphite:Tube furnace is warming up to 1050 DEG C, intercalated graphite is placed in magnetic boat and is sent into tube furnace
It expands about 10 seconds (black solid volume is not until expansion in magnetic boat).
3 prepare pre-oxidation graphite:3 grams of intercalated graphites, 3 grams of potassium peroxydisulfates, 3 gram of five oxidation are separately added into three-necked flask
Two phosphorus, 250 milliliters of concentrated sulfuric acids are to slowly warm up to 80 DEG C after stirring evenly, keep the temperature 5 hours, ice is poured slowly into after being cooled to room temperature
Aqueous mixtures, stirring to heat release it is complete after, filtering, fully washed with deionized water.120 DEG C of dryings 12 hours.
4 prepare graphite oxide:Be separately added into three-necked flask 3 grams pre-oxidation graphite, 250 milliliters of concentrated sulfuric acids, at room temperature
After stirring evenly, three-necked flask is placed in ice-water bath, 15 grams of potassium permanganate are then slowly added in three-necked flask, wait for Gao Meng
Sour potassium is added completely into recession and removes ice-water bath, and 35 DEG C are to slowly warm up to after stirring one hour at room temperature, reacts 2 hours.Reaction terminates
Reaction solution is poured into a large amount of mixture of ice and water afterwards, stirring to resulting exothermic solution it is complete after, be added 40 milliliters of hydrogen peroxide.It is collected by centrifugation
Precipitation washs precipitation for several times (with sulfate radical-free ion in saturation barium chloride detection solution) with 10 dilute hydrochloric acid, then
It is washed with deionized neutral to solution journey.Collect bottom oxide graphite.
The time of the reaction is 0.1~10h.
The electrolyte is 0.5~3M zinc sulfate solutions.After zinc metal sheet stands a period of time in graphene solution, table
Face is adsorbed with one layer of redox graphene, and adsorption is had the zinc metal sheet of redox graphene in water after reaction completion
Immersion has removed the non-redox graphene in surface layer, then impregnates in the electrolytic solution, electrolyte is allowed fully to infiltrate zinc metal sheet surface layer stone
Black alkene film prevents the water existing for graphene film interlayer in being subsequently assembled into cell process from concentration of electrolyte being caused to reduce.
Compared with prior art, beneficial effects of the present invention are embodied in following several respects:
(1) negative material of the invention is 0.2 milliampere of every square centimeter, 0.5 mole every liter of zinc sulfate in current density
Stablize 150 circle of cycle in electrolyte, dendritic growth in cyclic process is effectively inhibited to pierce through diaphragm phenomenon;
(2) preparation method of the invention is simple, is suitable for large-scale application.
Description of the drawings
Fig. 1 is the front and back infrared spectrogram of graphene oxide reduction;
Fig. 2 is cross-sectional scans electron microscope of the graphene after zinc surface absorption;
Fig. 3 is graphene film sectional view scanning electron microscope (SEM) photograph after ten circle of cycle;
Fig. 4 is that current density is 0.2mA/cm2, charge/discharge capacity 0.2mAh/cm2Charge and discharge discharge cycles curve.
Specific implementation mode
It elaborates below to the embodiment of the present invention, the present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
A kind of preparation method of zinc ion secondary battery cathode material, includes the following steps:
(1) pretreatment of metallic zinc:The zinc metal sheet that thickness is 0.3 millimeter is cut into the big sequin of 16 mm dias, is placed in third
In ketone, it is cleaned by ultrasonic 30 minutes, then uses absolute ethyl alcohol successively, deionized water cleaning removes zinc metal sheet surface and oil contaminant, then uses concentration
For 1% 10 seconds removal zinc metal sheet surface oxide layers of alkene salt acid soak, then rinsed with deionized water, dried for standby;
(2) graphene oxide solution is prepared:Using the crystalline flake graphite of 32 mesh as raw material, graphite oxide is prepared using hummers,
It after eccentric cleaning, collects graphite oxide in centrifuge tube and is freeze-dried, graphite oxide 0.1g additions 1L is obtained after weighing drying
Deionized water obtains the uniform graphene oxide water solution of color by stirring and ultrasound stripping.
(3) graphene oxide in zinc metal sheet surface reduction and adsorbs:It is molten it will to be put into graphene oxide by pretreated zinc metal sheet
In liquid, taken out after standing 30 minutes.
(4) electrode pre-processes:Zinc metal sheet after reaction is taken out, first impregnates 5 seconds in deionized water, is subsequently placed at 0.5M/L
It is impregnated 5 seconds in sulfuric acid zinc point solution liquid, then directly dresses up button cell and carry out electro-chemical test.
Fig. 1 is that 1 zinc metal sheet of embodiment is placed in absorption and redox graphene film in graphene oxide water solution, with oxidation
Graphene infrared absorpting light spectra, from figure I can be seen that absorption peak dies down between carbon oxygen after reduction, illustrates on zinc metal sheet surface
Redox graphene surface layer oxygen-containing functional group is reduced, and graphene oxide is reduced.
Fig. 2 is 1 zinc metal sheet surface layer redox graphene scanning electron microscope sectional view after natural drying of embodiment, from figure
It can be seen that graphene sheet layer is in the uniform sequential stacking of stratiform.
Fig. 3 is embodiment 1, is modified with the zinc metal sheet of redox graphene film in the sectional view after 10 circle cycles, from figure
In it can be found that have equally distributed metallic zinc among graphene film after 10 circle cycles, illustrate in cycle charge-discharge mistake
Deposition dissolution occurs between graphene layer for metallic gold in journey.
It in current density is 0.2mA/cm that Fig. 4, which is 1 gained cathode of embodiment,2, charge/discharge capacity 0.2mAh/cm2Charge and discharge
Discharge cycles curve.Therefrom it will be seen that the negative material that is prepared of the present embodiment performance base after charge and discharge 300 times again
Originally it remains unchanged, far superior to pure Zn negative materials.
Implementation column 2
(1) pretreatment of metallic zinc:The zinc metal sheet that thickness is 0.2 millimeter is cut into the big sequin of 15 mm dias, is placed in third
In ketone, it is cleaned by ultrasonic 30 minutes, then uses absolute ethyl alcohol successively, deionized water cleaning removes zinc metal sheet surface and oil contaminant, then uses concentration
For 1% 10 seconds removal zinc metal sheet surface oxide layers of alkene salt acid soak, then rinsed with deionized water, dried for standby
(2) graphene oxide solution is prepared:Using the crystalline flake graphite of 64 mesh as raw material, graphite oxide is prepared using hummers,
It after eccentric cleaning, collects graphite oxide in centrifuge tube and is freeze-dried, weigh the graphite oxide 0.5g after drying and 1L is added
Deionized water obtains the uniform graphene oxide water solution of color by stirring and ultrasound stripping.
(3) graphene oxide in zinc metal sheet surface reduction and adsorbs:It is molten it will to be put into graphene oxide by pretreated zinc metal sheet
In liquid, taken out after standing 50 minutes.
(4) electrode pre-processes:Zinc metal sheet after reaction is taken out, first impregnates 10 seconds in deionized water, is subsequently placed at 0.5M/
It is impregnated 5 seconds in L sulfuric acid zinc point solution liquid, then directly dresses up button cell and carry out electro-chemical test.
Verified, the prepared gained negative material of the present embodiment effectively inhibits dendritic growth in cyclic process to pierce through diaphragm
Phenomenon, service life are long.
Embodiment 3
(1) pretreatment of metallic zinc:The zinc metal sheet that thickness is 0.1 millimeter is cut into the big sequin of 15 mm dias, is placed in third
In ketone, it is cleaned by ultrasonic 50 minutes, then uses absolute ethyl alcohol successively, deionized water cleaning removes zinc metal sheet surface and oil contaminant, then uses concentration
For 3% 5 seconds removal zinc metal sheet surface oxide layers of alkene salt acid soak, then rinsed with deionized water, dried for standby
(2) graphene oxide solution is prepared:Using the crystalline flake graphite of 128 mesh as raw material, oxidation stone is prepared using hummers
Ink is collected graphite oxide in centrifuge tube and is freeze-dried after eccentric cleaning, weighs the graphite oxide 2g after drying and 1L is added
Deionized water obtains the uniform graphene oxide water solution of color by stirring and ultrasound stripping.
(3) graphene oxide in zinc metal sheet surface reduction and adsorbs:It is molten it will to be put into graphene oxide by pretreated zinc metal sheet
In liquid, standing is taken out after twenty minutes.
(4) electrode pre-processes:Zinc metal sheet after reaction is taken out, first impregnates 10 seconds in deionized water, is subsequently placed at 1M/L
It is impregnated 5 seconds in sulfuric acid zinc point solution liquid, then directly dresses up button cell and carry out electro-chemical test.
Verified, the prepared gained negative material of the present embodiment effectively inhibits dendritic growth in cyclic process to pierce through diaphragm
Phenomenon, service life are long.
Embodiment 4
(1) pretreatment of metallic zinc:The zinc metal sheet that thickness is 0.1 millimeter is cut into the big sequin of 15 mm dias, is placed in third
In ketone, it is cleaned by ultrasonic 30 minutes, then uses absolute ethyl alcohol successively, deionized water cleaning removes zinc metal sheet surface and oil contaminant, then uses concentration
For 2% 5 seconds removal zinc metal sheet surface oxide layers of alkene salt acid soak, then rinsed with deionized water, dried for standby
(2) graphene oxide solution is prepared:Using the crystalline flake graphite of 128 mesh as raw material, oxidation stone is prepared using hummers
Ink is collected graphite oxide in centrifuge tube and is freeze-dried after eccentric cleaning, weighs the graphite oxide 3g after drying and 1L is added
Deionized water obtains the uniform graphene oxide water solution of color by stirring and ultrasound stripping.
(3) graphene oxide in zinc metal sheet surface reduction and adsorbs:It is molten it will to be put into graphene oxide by pretreated zinc metal sheet
In liquid, standing is taken out after twenty minutes.
(4) electrode pre-processes:Zinc metal sheet after reaction is taken out, first impregnates 10 seconds in deionized water, is subsequently placed at 1M/L
It is impregnated 5 seconds in sulfuric acid zinc point solution liquid, then directly dresses up button cell and carry out electro-chemical test.
Verified, the prepared gained negative material of the present embodiment effectively inhibits dendritic growth in cyclic process to pierce through diaphragm
Phenomenon, service life are long.
Embodiment 5
(1) pretreatment of metallic zinc:The zinc metal sheet that thickness is 0.1 millimeter is cut into the big sequin of 15 mm dias, is placed in third
In ketone, it is cleaned by ultrasonic 30 minutes, then uses absolute ethyl alcohol successively, deionized water cleaning removes zinc metal sheet surface and oil contaminant, then uses concentration
For 2% 5 seconds removal zinc metal sheet surface oxide layers of alkene salt acid soak, then rinsed with deionized water, dried for standby
(2) graphene oxide solution is prepared:Commercial graphite alkene and potassium hydroxide are pressed 1:2~1:5 than row mixed grinding, so
Mixture is put under nitrogen atmosphere afterwards and keeps the temperature 3 hours for 600~900 degree, then neutrality is washed till with 1M alkene hydrochloric acid, is weighed after dry
1g graphene dispersions obtain the uniform graphene oxide water solution of color in 1L water, by stirring and ultrasound stripping.
(3) graphene oxide in zinc metal sheet surface reduction and adsorbs:It is molten it will to be put into graphene oxide by pretreated zinc metal sheet
In liquid, standing is taken out after twenty minutes.
(4) electrode pre-processes:Zinc metal sheet after reaction is taken out, first impregnates 10 seconds in deionized water, is subsequently placed at 1M/L
It is impregnated 5 seconds in sulfuric acid zinc point solution liquid, then directly dresses up button cell and carry out electro-chemical test.
Verified, the prepared gained negative material of the present embodiment effectively inhibits dendritic growth in cyclic process to pierce through diaphragm
Phenomenon, service life are long.
Embodiment 6
(1) pretreatment of metallic zinc:The zinc metal sheet that thickness is 0.2 millimeter is cut into the big sequin of 15 mm dias, is placed in third
In ketone, it is cleaned by ultrasonic 40 minutes, then uses absolute ethyl alcohol successively, deionized water cleaning removes zinc metal sheet surface and oil contaminant, then uses concentration
For 2% 5 seconds removal zinc metal sheet surface oxide layers of alkene salt acid soak, then rinsed with deionized water, dried for standby
(2) graphene oxide solution is prepared:Commercial graphite alkene and potassium hydroxide are pressed 1:2~1:5 than row mixed grinding, so
Mixture is put under nitrogen atmosphere afterwards and keeps the temperature 3 hours for 600~900 degree, then neutrality is washed till with 1M alkene hydrochloric acid, is weighed after dry
0.5g graphene dispersions obtain the uniform graphene oxide water solution of color in 1L water, by stirring and ultrasound stripping.
(3) graphene oxide in zinc metal sheet surface reduction and adsorbs:It is molten it will to be put into graphene oxide by pretreated zinc metal sheet
In liquid, standing is taken out after ten minutes.
(4) electrode pre-processes:Zinc metal sheet after reaction is taken out, first impregnates 10 seconds in deionized water, is subsequently placed at 1M/L
It is impregnated 5 seconds in sulfuric acid zinc point solution liquid, then directly dresses up button cell and carry out electro-chemical test.
Verified, the prepared gained negative material of the present embodiment effectively inhibits dendritic growth in cyclic process to pierce through diaphragm
Phenomenon, service life are long.
Claims (9)
1. a kind of zinc-base cell negative electrode material, which is characterized in that the negative material includes zinc-base and is supported on zinc-base surface
Graphene, wherein the thickness of graphene is 0.1~100 μm.
2. a kind of zinc-base cell negative electrode material according to claim 1, which is characterized in that the zinc-base is zine plate, zinc
Piece or zinc foil.
3. a kind of preparation method of zinc-base cell negative electrode material as claimed in claim 1 or 2, which is characterized in that including following step
Suddenly:
(1) it after being surface-treated zinc-base, is placed in diluted acid and removes surface oxide layer, for use;
(2) graphene oxide is placed in water, ultrasonic disperse obtains graphene oxide solution;
(3) will treated that zinc-base is placed in graphene oxide solution reacts, then use deionized water and electrolyte respectively
It impregnates to get the zinc-base cell negative electrode material.
4. a kind of preparation method of zinc-base cell negative electrode material according to claim 3, which is characterized in that at the surface
Reason includes the following steps:Zinc-base is placed in acetone soln, is cleaned by ultrasonic, then absolute ethyl alcohol and deionized water is used to rinse table successively
Face.
5. a kind of preparation method of zinc-base cell negative electrode material according to claim 3, which is characterized in that the diluted acid packet
Dilute hydrochloric acid, dilute sulfuric acid, hydrofluoric acid or acetic acid are included, the mass concentration of the diluted acid is 1%~3%.
6. a kind of preparation method of zinc-base cell negative electrode material according to claim 5, which is characterized in that the zinc-base exists
Residence time in diluted acid is 1~10s.
7. a kind of preparation method of zinc-base cell negative electrode material according to claim 3, which is characterized in that the oxidation stone
A concentration of 0.01~3g/L of black alkene solution.
8. a kind of preparation method of zinc-base cell negative electrode material according to claim 3, which is characterized in that the reaction
Time is 0.1~10h.
9. a kind of preparation method of zinc-base cell negative electrode material according to claim 3, which is characterized in that the electrolyte
For 0.5~3M zinc sulfate solutions.
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Cited By (6)
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CN112582578A (en) * | 2020-12-28 | 2021-03-30 | 安阳师范学院 | Zinc cathode with protective layer and preparation method and application thereof |
CN113363410A (en) * | 2021-05-27 | 2021-09-07 | 哈尔滨工业大学 | Preparation method and application of in-situ fast-growth multifunctional zinc cathode protective layer |
CN113410452A (en) * | 2021-06-17 | 2021-09-17 | 中国科学技术大学 | Modified zinc cathode and preparation method and application thereof |
CN113725392A (en) * | 2021-09-09 | 2021-11-30 | 郑州大学 | Interface modified metal zinc cathode and preparation method thereof |
CN113871620A (en) * | 2021-08-19 | 2021-12-31 | 北京理工大学 | Ultrathin interface modified zinc metal negative electrode material, and preparation and application thereof |
CN116885303A (en) * | 2023-07-26 | 2023-10-13 | 长春理工大学 | Multifunctional phase interface protective layer for negative electrode of water-based zinc ion battery and preparation method thereof |
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CN113871620A (en) * | 2021-08-19 | 2021-12-31 | 北京理工大学 | Ultrathin interface modified zinc metal negative electrode material, and preparation and application thereof |
CN113725392A (en) * | 2021-09-09 | 2021-11-30 | 郑州大学 | Interface modified metal zinc cathode and preparation method thereof |
CN113725392B (en) * | 2021-09-09 | 2023-02-21 | 郑州大学 | Interface modified metal zinc cathode and preparation method thereof |
CN116885303A (en) * | 2023-07-26 | 2023-10-13 | 长春理工大学 | Multifunctional phase interface protective layer for negative electrode of water-based zinc ion battery and preparation method thereof |
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