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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
zinc
base
negative electrode
electrode material
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810575861.0A
Other languages
Chinese (zh)
Inventor
刘海梅
夏奥林
徐群杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai University of Electric Power
University of Shanghai for Science and Technology
Original Assignee
Shanghai University of Electric Power
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai University of Electric Power filed Critical Shanghai University of Electric Power
Priority to CN201810575861.0A priority Critical patent/CN108807961A/en
Publication of CN108807961A publication Critical patent/CN108807961A/en
Pending legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42Alloys based on zinc
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy 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

A kind of zinc-base cell negative electrode material and preparation method thereof
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.
CN201810575861.0A 2018-06-06 2018-06-06 A kind of zinc-base cell negative electrode material and preparation method thereof Pending CN108807961A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810575861.0A CN108807961A (en) 2018-06-06 2018-06-06 A kind of zinc-base cell negative electrode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810575861.0A CN108807961A (en) 2018-06-06 2018-06-06 A kind of zinc-base cell negative electrode material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN108807961A true CN108807961A (en) 2018-11-13

Family

ID=64087199

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810575861.0A Pending CN108807961A (en) 2018-06-06 2018-06-06 A kind of zinc-base cell negative electrode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108807961A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103265022A (en) * 2013-06-03 2013-08-28 北京理工大学 Method for spontaneously depositing three-dimensional graphene on conductive substrate
CN107473261A (en) * 2017-09-01 2017-12-15 北京化工大学 A kind of preparation method of zinc oxide/redox graphene composite
CN107634192A (en) * 2017-08-23 2018-01-26 北京航空航天大学 A kind of zinc-base negative electrode battery material and preparation method thereof
KR20180022402A (en) * 2016-08-24 2018-03-06 울산과학기술원 Negative electrode active material for rechargable battery, method for manufacturing the same, and rechargable battery including the same
CN107768741A (en) * 2017-09-18 2018-03-06 中国科学院青岛生物能源与过程研究所 Eutectic electrolyte and its application in secondary zinc battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103265022A (en) * 2013-06-03 2013-08-28 北京理工大学 Method for spontaneously depositing three-dimensional graphene on conductive substrate
KR20180022402A (en) * 2016-08-24 2018-03-06 울산과학기술원 Negative electrode active material for rechargable battery, method for manufacturing the same, and rechargable battery including the same
CN107634192A (en) * 2017-08-23 2018-01-26 北京航空航天大学 A kind of zinc-base negative electrode battery material and preparation method thereof
CN107473261A (en) * 2017-09-01 2017-12-15 北京化工大学 A kind of preparation method of zinc oxide/redox graphene composite
CN107768741A (en) * 2017-09-18 2018-03-06 中国科学院青岛生物能源与过程研究所 Eutectic electrolyte and its application in secondary zinc battery

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN113363410B (en) * 2021-05-27 2022-04-12 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
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

Similar Documents

Publication Publication Date Title
CN108807961A (en) A kind of zinc-base cell negative electrode material and preparation method thereof
US11728489B2 (en) Three-dimensional current collector for metal secondary battery anode, its preparation and application
CN104393283B (en) Nano crystalline CoO-graphene composite material as well as preparation and application thereof
CN110299530A (en) A kind of ZIF-67 base cobalt molybdenum oxide hollow Nano cage/graphene composite material and the preparation method and application thereof
CN104009236B (en) A kind of metatitanic acid lithium mesoporous single crystals nano particle/redox graphene matrix material and its preparation method and application
CN109148877A (en) Rechargeable zinc-manganese battery and preparation method thereof
CN103531817A (en) Three-dimensional copper nanowire array current collector for lithium ion battery and production method of three-dimensional copper nanowire array current collector
CN104167540A (en) Negative electrode active material and preparation method thereof and lithium ion battery
CN105870426A (en) V2O5 nanowire paper for energy storage device electrodes and preparation method
CN109360740A (en) Porous carbon nanosheet of a kind of two dimension N doping and preparation method thereof
CN106340633A (en) Composite nano material for high performance lithium ion battery and preparation method thereof
CN106099077B (en) Carbon/ferriferrous oxide composite material preparation method, lithium ion battery
CN108123141A (en) A kind of three-dimensional porous foams grapheme material and its application
CN108878812A (en) One kind loading SnO in stainless (steel) wire2/SnS2The preparation method and application of nanometer sheet kalium ion battery anode material
CN111430672B (en) Preparation method and application of silicon dioxide/carbon cloth self-supporting electrode material
CN113270577A (en) Aqueous zinc ion battery and positive electrode material
CN106450356A (en) Anode material of Sn-containing electrocatalyst and preparation method thereof
CN109904390A (en) A kind of preparation method of lithium metal/nickel plating carbon cloth composite negative pole
CN110311117A (en) A kind of MoS2The double salt ion cell positive materials of@EG magnesium-lithium and its construction method
CN113782710A (en) High-performance chargeable and dischargeable aqueous zinc-iodine battery and preparation method thereof
CN111082162B (en) Aqueous sodium ion battery
CN108987123A (en) A kind of manganese dioxide-expanded graphite-cotton fiber tri compound electrochemical capacitance electrode material and preparation method thereof
CN112928343A (en) Water system copper ion battery suitable for large-scale energy storage application
CN102437334A (en) Microwave hydrothermal synthesizing method for carbon nanotube/LiFePO4 lithium ion battery anode material
CN105679548B (en) A kind of electrode plates and preparation method thereof for graphene-based supercapacitor

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20181113

RJ01 Rejection of invention patent application after publication