CN115312685A - Protective layer of metal zinc cathode of water system zinc ion battery and preparation method of metal zinc cathode - Google Patents
Protective layer of metal zinc cathode of water system zinc ion battery and preparation method of metal zinc cathode Download PDFInfo
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- CN115312685A CN115312685A CN202211038450.0A CN202211038450A CN115312685A CN 115312685 A CN115312685 A CN 115312685A CN 202211038450 A CN202211038450 A CN 202211038450A CN 115312685 A CN115312685 A CN 115312685A
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- ion battery
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000011701 zinc Substances 0.000 title claims abstract description 104
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 104
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 57
- 239000002184 metal Substances 0.000 title claims abstract description 57
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000011241 protective layer Substances 0.000 title claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000011149 active material Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 23
- 239000006258 conductive agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000006255 coating slurry Substances 0.000 claims abstract description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000011253 protective coating Substances 0.000 claims abstract description 11
- 238000005520 cutting process Methods 0.000 claims abstract description 10
- 238000005096 rolling process Methods 0.000 claims abstract description 10
- 238000005341 cation exchange Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- 238000007790 scraping Methods 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 24
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003456 ion exchange resin Substances 0.000 claims description 15
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000005342 ion exchange Methods 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 5
- -1 polypropylene group Polymers 0.000 claims description 5
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 4
- 125000000101 thioether group Chemical group 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 239000013543 active substance Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000002161 passivation Methods 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CZLMUMZXIXSCFI-UHFFFAOYSA-N [Zn].[I] Chemical compound [Zn].[I] CZLMUMZXIXSCFI-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 2
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical compound [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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 invention discloses a protective layer of a metal zinc cathode of a water system zinc ion battery and a preparation method of the metal zinc cathode. The protective layer is mainly composed of 70-90% of active material, 5-15% of conductive agent and 5-15% of binder. Grinding and mixing the weighed active material, conductive agent and binder, adding N-methyl pyrrolidone or distilled water after mixing, and uniformly stirring to obtain protective coating slurry; and uniformly coating the obtained coating slurry on the metal zinc cathode, and then sequentially carrying out film scraping, drying, rolling and cutting processes to obtain the novel coating-protected metal zinc cathode of the water system zinc ion battery. The invention takes a cheap cation exchange material as an active substance of the metal zinc negative electrode protective layer to inhibit the growth and corrosion passivation of the dendritic crystal of the metal zinc negative electrode in the charge and discharge processes of the zinc ion battery, thereby greatly improving the cycle stability and the electrochemical performance of the battery.
Description
1. The technical field is as follows:
the invention belongs to the technical field of novel electrochemistry, and particularly relates to a protective layer of a metal zinc cathode of a water-based zinc ion battery and a preparation method of the metal zinc cathode.
2. Background art:
aqueous zinc ion secondary batteries (ZIBs) have recently received much attention due to their inherent characteristics of high safety, abundant and inexpensive resources, environmental friendliness, high energy density, and the like, and are considered to be one of strong competitors of next-generation new energy batteries. With metallic zinc (theoretical capacity: 820mAh g) -1 ) The ZIBs can meet the actual application requirements of different aspects by matching with different anode materials, such as manganese series materials (manganese dioxide), vanadium series materials (vanadium pentoxide), prussian blue analogues, organic compounds, halogen simple substances and the like. However, due to the uneven plating/stripping behavior of zinc ions during cycling, the negative electrodes of such batteries often have dendritic growth, which severely affects the service life of the battery. In addition, side reactions between the electrolyte and the negative electrode also cause irreversible corrosion of the zinc negative electrode, resulting in loss of active zinc and rapid degradation of battery performance.
The method is one of effective ways for realizing the high-stability zinc cathode by constructing the functional coating on the surface of the zinc. For example: 1. the invention patent application of CN114005949A discloses a zinc battery cathode protected by a hydrophobic layer and a preparation method thereof; 2. the invention patent application of CN113363410B discloses a preparation method and application of an in-situ fast-growing multifunctional zinc cathode protective layer; 3. the invention patent application of CN113097496A discloses a zinc cathode with a composite nanofiber protective layer, and preparation and application thereof. Although these methods solve the above-mentioned zinc negative electrode problems to some extent, they still have the problems of complicated preparation process, high cost, environmental unfriendliness, high energy consumption, etc. (such as using heavy metal salts, electrospinning, high temperature calcination), and are not conducive to the further industrialization of ZIBs. Therefore, finding a simple, cheap and environment-friendly material to prepare the functional coating capable of simultaneously inhibiting dendritic growth of the zinc cathode and electrode corrosion has important practical significance.
3. The invention content is as follows:
the technical problem to be solved by the invention is as follows: the invention provides a protective layer of a metal zinc cathode of a water system zinc ion battery and a preparation method of the metal zinc cathode, aiming at the problems that the water system zinc ion battery cathode is poor in stability, dendritic crystal growth and corrosion are easy to occur in the circulating process and the like.
In order to solve the problems, the invention adopts the technical scheme that:
the invention provides a protective layer of a metal zinc cathode of a water system zinc ion battery, which comprises the following raw materials, by weight, 70-90% of an active material, 5-15% of a conductive agent and 5-15% of a binder.
According to the protective layer of the metal zinc cathode of the water-based zinc ion battery, the binder in the step a is at least one of polyvinylidene fluoride, sodium carboxymethylcellulose and polyacrylic acid;
the conductive agent is at least one of Super P, carbon black, acetylene black, graphite, graphene oxide and carbon nano tubes;
the active material is any one of polyphenylene sulfide group strong acid ion exchange fiber, polyphenylene sulfide group strong acid ion exchange resin, polyacrylonitrile group weak acid ion exchange fiber, polyacrylonitrile group weak acid ion exchange resin, polystyrene group strong acid ion exchange resin, polystyrene group weak acid ion exchange resin, polypropylene group strong acid ion exchange fiber, polypropylene group strong acid ion exchange resin, polyacrylic group weak acid ion exchange resin and cation exchange membrane.
In addition, a method for preparing a metal zinc negative electrode of an aqueous zinc ion battery using the above protective layer is provided, the preparation method comprising the steps of:
a. weighing the active material, the conductive agent and the binder according to the raw material proportion of the protective layer;
b. grinding and mixing the weighed active material, conductive agent and binder, adding N-methyl pyrrolidone or distilled water after mixing, and uniformly stirring to obtain protective coating slurry;
c. and c, uniformly coating the coating slurry obtained in the step b on a metal zinc cathode, and then sequentially carrying out film scraping, drying, rolling and cutting processes to obtain the novel coating-protected metal zinc cathode of the water system zinc ion battery.
According to the method for preparing the metal zinc cathode of the water-based zinc ion battery, in the step b, the addition amount of the N-methyl pyrrolidone or the distilled water accounts for 10-30% of the total mass of the three materials.
According to the method for preparing the metal zinc cathode of the water system zinc ion battery, the drying conditions in the step c are as follows: vacuum drying at 50-80 deg.c for 12-24 hr to obtain the final thickness of the coating of 20-500 micron.
According to the method for preparing the metal zinc cathode of the water system zinc ion battery, the metal zinc cathode is any one of a galvanized carbon material, a galvanized alloy, a zinc foil, a zinc alloy foil, zinc powder and zinc alloy powder.
The invention adopts cation exchange material as active substance of the metal zinc negative electrode protective coating, then the active substance is ground and mixed with conductive agent and binder according to a certain proportion, N-methyl pyrrolidone or water is added for size mixing, the mixture is coated on the zinc negative electrode, and the negative electrode sheet with proper size is obtained after drying, rolling and cutting. Then, a proper diaphragm and electrolyte with a certain concentration are adopted, the positive plate and the diaphragm are placed, a certain amount of electrolyte is dripped, then the negative plate, the gasket, the elastic sheet and the negative plate are placed, and the battery is sealed by a battery packaging machine. For the soft package battery, a similar method is adopted, namely a positive plate, a diaphragm and a negative plate are stacked in a sandwich mode, then nickel and aluminum tabs are respectively added to the positive plate and the negative plate, and then the positive plate and the negative plate are packaged by an aluminum-plastic film.
The invention can make the rechargeable water system zinc ion battery into button, column, sheet and soft package structures by using the prepared metal zinc cathode.
The invention has the following positive beneficial effects:
1. the invention covers a uniform and cheap ion exchange layer, namely the protective layer of the invention, on the surface of the zinc metal cathode by a simple coating method. The ion exchange layer can adsorb metal ions in the solution through strong electrostatic interaction force between active groups (such as carboxyl and sulfonic acid) loaded on the ion exchange layer and zinc ions, guide the zinc ions to be uniformly deposited, regulate and control the activity of the zinc ions, and realize the inhibition of the growth of zinc dendrites. In addition, the active groups can form a hydrogen bond network with free water while changing the solvation structure of metal ions, so that the corrosion of water to zinc is inhibited, and the electrochemical performance and the cycle life of the battery are effectively improved.
2. According to the technical scheme, the cheap cation exchange material is used as the active substance of the metal zinc negative electrode protective layer to inhibit the growth and corrosion passivation of the dendritic crystal of the metal zinc negative electrode in the charging and discharging processes of the zinc ion battery, so that the cycle stability and the electrochemical performance of the battery are greatly improved.
3. The water-based zinc battery prepared by the technical scheme of the invention has long cycle life and stable performance.
4. The cation exchange material adopted in the technical scheme of the invention has wide industrial basis, has the characteristics of abundant resources, low price, environmental protection and the like, and can meet the requirement of large-scale production.
5. The technical scheme of the invention provides a concept of taking a cation exchange material as a metal zinc cathode protective layer of a water system zinc ion battery, and the zinc cathode with excellent stability can be obtained only by coating a commercialized cation exchange material on the surface of the zinc cathode, so that the high-performance water system zinc battery is realized.
6. The water-based zinc battery prepared by the technical scheme of the invention is safe and reliable, and the zinc symmetrical battery prepared by the water-based zinc battery is 1mA cm -2 (1mAh cm -2 ) The cycle life under the current density can reach 1400h; the zinc-iodine battery prepared by the method is 3.2A g -1 Current densities (calculated on the active material basis) can be maintained over 6000 cycles with capacity retention as high as 90.2%.
In conclusion, the zinc battery prepared by taking the cation exchange material as the metal zinc cathode protective coating has obvious technical progress, and is expected to accelerate the industrialization process of the zinc battery.
4. Description of the drawings:
fig. 1 is a schematic representation of a coated zinc anode and pouch cell made using the protective layer described in example 7.
Fig. 2 is a graph of long cycle performance of a zinc-iodine cell made using the protective layer described in example 7.
Fig. 3 is a graph of long cycle performance of a zinc symmetric cell prepared using the protective layer described in example 8.
Figure 4 is a graph of the long cycle performance of a zinc bromine battery prepared using the protective layer described in example 9.
Fig. 5 is a graph of long cycle performance for a zinc symmetric cell prepared using the protective layer described in example 10.
Fig. 6 is an SEM image of a coated or uncoated zinc negative electrode prepared using example 11 after cycling 100 cycles.
Figure 7 is a graph of the plating/stripping cycle performance of a zinc-copper half cell prepared using the protective layer described in example 12.
5. The specific implementation mode is as follows:
the invention is further illustrated by the following examples, which do not limit the scope of the invention.
Example 1:
the protective layer of the metal zinc cathode of the water system zinc ion battery is prepared from 85% of polyphenylene sulfide-based strong acid ion exchange fiber, 5% of Super P and 10% of polyvinylidene fluoride by weight percentage.
Example 2:
the protective layer of the metal zinc cathode of the water system zinc ion battery is prepared from 80 weight percent of polyacrylonitrile-based weak acid ion exchange fiber, 5 weight percent of carbon black and 15 weight percent of polyvinylidene fluoride.
Example 3:
the protective layer of the metal zinc cathode of the water system zinc ion battery is characterized in that the protective layer comprises 80 weight percent of polystyrene-based weak acid ion exchange resin, 10 weight percent of carbon nano tubes and 10 weight percent of polyvinylidene fluoride.
Example 4:
the protective layer of the metal zinc cathode of the water system zinc ion battery is characterized in that the protective layer comprises 80 weight percent of polystyrene-based strong acid ion exchange resin (D001), 5 weight percent of graphene and 15 weight percent of sodium carboxymethylcellulose.
Example 5:
the protective layer of the metal zinc cathode of the water system zinc ion battery is characterized in that the protective layer comprises, by weight, 85% of polypropylene-based strong acid ion exchange fiber, 5% of acetylene black and 10% of polyacrylic acid.
Example 6:
the protective layer of the metal zinc cathode of the water system zinc ion battery is prepared from 75% of polystyrene-based strong acid ion exchange resin (D001), 15% of graphite and 10% of polyvinylidene fluoride by weight percentage.
Example 7:
a method for preparing a metal zinc anode of an aqueous zinc ion battery by using the protective layer described in example 1, the method comprises the following detailed steps:
a. weighing an active material, a conductive agent and a binder according to the raw material proportion of the protective layer in the embodiment 1;
b. grinding and mixing the weighed active material, the conductive agent and the binder, adding N-methyl pyrrolidone accounting for 30 percent of the total weight of the three raw materials after mixing, and uniformly stirring to obtain protective coating slurry;
c. c, uniformly coating the coating slurry obtained in the step b on the surface of the zinc foil negative electrode, wherein the thickness is 80-100 mu m; and then vacuum drying is carried out for 24h at 60 ℃, rolling and cutting are carried out, and the metal zinc cathode of the water system zinc ion battery protected by the novel coating with proper size is obtained (the coating zinc cathode and the soft package battery are shown in the attached figure 1).
To prepare the obtained zinc cathode and 2mol/L ZnSO 4 Zinc symmetrical button cell assembled by aqueous solution and glass fiber diaphragm and arranged at 1mA cm -2 (1mAh cm -2 ) The cycle life can reach 800h under the current density; under the same conditions, the zinc cathode and the iodine cathode assembled battery prepared by the method are subjected to charge-discharge cycle test3.2A g -1 At current densities (calculated based on iodine active species) it was possible to maintain over 6000 cycles with capacity retention as high as 90.2% (as shown in figure 2).
Example 8:
a method of making a metal zinc negative electrode for an aqueous zinc ion battery using the protective layer described in example 2, the method comprising the steps of:
a. weighing an active material, a conductive agent and a binder according to the raw material proportion of the protective layer in the embodiment 2;
b. grinding and mixing the weighed active material, the conductive agent and the binder, adding N-methyl pyrrolidone accounting for 15 percent of the total weight of the three raw materials after mixing, and uniformly stirring to obtain protective coating slurry;
c. uniformly coating the coating slurry obtained in the step b on the surface of a zinc foil negative electrode, wherein the thickness of the coating slurry is 100-120 mu m; and then vacuum drying is carried out for 24 hours at the temperature of 50 ℃, rolling and cutting are carried out, and the metal zinc cathode of the water system zinc ion battery protected by the novel coating with proper size is obtained.
To prepare the obtained zinc cathode and 2mol/L ZnSO 4 Zinc symmetrical button cell assembled by water solution and filter paper at 1mA cm -2 (1mAh cm -2 ) The cycle life can reach 600h (as shown in figure 3) under the current density; under the same conditions, the battery assembled by the zinc cathode and the manganese dioxide cathode prepared in the above way is subjected to charge-discharge cycle test, and the charge-discharge cycle test is carried out at 1A g -1 Over 1000 cycles can be maintained at current densities (calculated on an active material basis) and capacity retention rates as high as 80.5%.
Example 9:
a method for preparing a metal zinc cathode of an aqueous zinc ion battery by using the protective layer in example 3, which comprises the following steps:
a. weighing an active material, a conductive agent and a binder according to the raw material proportion of the protective layer in the embodiment 3;
b. grinding and mixing the weighed active material, the conductive agent and the binder, adding N-methylpyrrolidone accounting for 20 percent of the total weight of the three raw materials after mixing, and uniformly stirring to obtain protective coating slurry;
c. c, uniformly coating the coating slurry obtained in the step b on the surface of the zinc foil negative electrode, wherein the thickness is 20-40 mu m; and then vacuum drying is carried out for 24 hours at 50 ℃, rolling and cutting are carried out, and the metal zinc cathode of the water system zinc ion battery protected by the novel coating with proper size is obtained.
To prepare the obtained zinc cathode and 2mol/L ZnSO 4 Zinc symmetrical button cell assembled by aqueous solution and glass fiber diaphragm and arranged at 1mA cm -2 (1mAh cm -2 ) The cycle life can reach 900h under the current density; under the same conditions, the zinc cathode and bromine cathode assembled battery prepared in the above way is subjected to charge-discharge cycle test, and the charge-discharge cycle test is carried out on the zinc cathode and bromine cathode assembled battery which is 1Ag -1 The current density (calculated based on bromine active) can be maintained over 650 cycles without capacity degradation (as shown in figure 4).
Example 10:
a method for preparing a metal zinc negative electrode of an aqueous zinc ion battery using the protective layer described in example 4, the method comprising the following detailed steps:
a. weighing an active material, a conductive agent and a binder according to the raw material proportion of the protective layer in the embodiment 4;
b. grinding and mixing the weighed active material, the conductive agent and the binder, adding N-methylpyrrolidone accounting for 25% of the total weight of the three raw materials after mixing, and uniformly stirring to obtain protective coating slurry;
c. uniformly coating the coating slurry obtained in the step b on the surface of a zinc foil negative electrode, wherein the thickness of the coating slurry is 450-500 mu m; and then vacuum drying is carried out for 24 hours at the temperature of 60 ℃, rolling and cutting are carried out, and the metal zinc cathode of the water system zinc ion battery protected by the novel coating with proper size is obtained.
To prepare the obtained zinc cathode and 2mol/L ZnSO 4 Zinc symmetrical button cell assembled by aqueous solution and glass fiber diaphragm and arranged at 1mA cm -2 (1mAh cm -2 ) The cycle life can reach 1400h (as shown in figure 5) under the current density. Under the same conditions, the battery assembled by the zinc cathode and the manganese dioxide cathode prepared in the above way is subjected to charge-discharge cycle test, and the charge-discharge cycle test is carried out, wherein the charge-discharge cycle test is carried out, and the charge-discharge cycle test is carried out at 1A g -1 Over 1000 cycles can be maintained at current densities (calculated on an active material basis) with capacity retention as high as 82.2%.
Example 11:
a method of making a metal zinc negative electrode for an aqueous zinc ion battery using the protective layer described in example 5, the method comprising the steps of:
a. weighing an active material, a conductive agent and a binder according to the raw material proportion of the protective layer in the embodiment 5;
b. grinding and mixing the weighed active material, the conductive agent and the binder, adding N-methyl pyrrolidone accounting for 15 percent of the total weight of the three raw materials after mixing, and uniformly stirring to obtain protective coating slurry;
c. uniformly coating the coating slurry obtained in the step b on the surface of a zinc foil negative electrode, wherein the thickness of the coating slurry is 90-110 microns; and then vacuum drying is carried out for 24 hours at the temperature of 50 ℃, rolling and cutting are carried out, and the metal zinc cathode of the water system zinc ion battery protected by the novel coating with proper size is obtained.
Assembling a zinc symmetrical button cell by using the prepared zinc cathode, 1mol/L zinc trifluoromethanesulfonate aqueous solution and a glass fiber diaphragm at 2mA cm -2 (1mAh cm -2 ) Under the current density, the cycle life can reach 500h, and the SEM image after 100 cycles of the cycle has no obvious dendrite (as shown in figure 6); under the same conditions, the charge-discharge cycle test of the zinc cathode and bromine cathode assembled battery prepared by the method is carried out, and the charge-discharge cycle test is carried out and is carried out at 2A g -1 Over 500 cycles can be maintained at current densities (calculated based on bromine active species) and capacity retention rates as high as 94.2%.
Example 12:
a method of making a metal zinc negative electrode for an aqueous zinc ion battery using the protective layer described in example 6, the method comprising the steps of:
a. weighing the active material, the conductive agent and the binder according to the raw material proportion of the protective layer in the embodiment 6;
b. grinding and mixing the weighed active material, the conductive agent and the binder, adding N-methylpyrrolidone accounting for 30% of the total weight of the three raw materials after mixing, and uniformly stirring to obtain protective coating slurry;
c. uniformly coating the coating slurry obtained in the step b on the surface of a zinc foil negative electrode, wherein the thickness of the coating slurry is 60-80 microns; and then vacuum drying is carried out for 24 hours at the temperature of 60 ℃, rolling and cutting are carried out, and the metal zinc cathode of the water system zinc ion battery protected by the novel coating with proper size is obtained.
Assembling a zinc symmetrical button cell by using the prepared zinc cathode, 2mol/L zinc trifluoromethanesulfonate aqueous solution and filter paper, wherein the zinc symmetrical button cell is 1mA cm in length -2 (1mAh cm -2 ) The cycle life can reach 1200h under the current density, and the assembled zinc-copper half cell is tested in an electroplating/stripping cycle at 1mA cm -2 (1mAh cm -2 ) The average coulombic efficiency after 50 cycles of current density cycling was as high as 98.9% (as shown in figure 7). Under the same condition, the battery assembled by the zinc cathode and the vanadium pentoxide anode prepared by the method is subjected to charge-discharge cycle test, and the charge-discharge cycle test is carried out at 1A g -1 Over 500 cycles can be maintained at current densities (calculated on an active material basis) and capacity retention rates as high as 76.9%.
Claims (6)
1. A protective layer of a metal zinc negative electrode of a water system zinc ion battery is characterized in that: the protective layer comprises, by weight, 70-90% of active material, 5-15% of conductive agent and 5-15% of binder.
2. The protective layer for a metal zinc negative electrode of an aqueous zinc ion battery according to claim 1, characterized in that: the binder is at least one of polyvinylidene fluoride, sodium carboxymethylcellulose and polyacrylic acid;
the conductive agent is at least one of Super P, carbon black, acetylene black, graphite, graphene oxide and carbon nano tubes;
the active material is any one of polyphenylene sulfide group strong acid ion exchange fiber, polyphenylene sulfide group strong acid ion exchange resin, polyacrylonitrile group weak acid ion exchange fiber, polyacrylonitrile group weak acid ion exchange resin, polystyrene group strong acid ion exchange resin, polystyrene group weak acid ion exchange resin, polypropylene group strong acid ion exchange fiber, polypropylene group strong acid ion exchange resin, polyacrylic group weak acid ion exchange resin and cation exchange membrane.
3. A method of making a metal zinc anode for an aqueous zinc ion battery using the protective layer of claim 1, the method comprising the steps of:
a. weighing the active material, the conductive agent and the binder according to the raw material proportion of the protective layer in claim 1;
b. grinding and mixing the weighed active material, the conductive agent and the binder, adding N-methyl pyrrolidone or distilled water after mixing, and uniformly stirring to obtain protective coating slurry;
c. and c, uniformly coating the coating slurry obtained in the step b on the metal zinc cathode, and then sequentially carrying out film scraping, drying, rolling and cutting processes to obtain the novel coating-protected metal zinc cathode of the water-based zinc ion battery.
4. The method of making an aqueous zinc ion battery metal zinc anode of claim 3, characterized in that: in the step b, the adding amount of the N-methyl pyrrolidone or the distilled water accounts for 10-30% of the total mass of the three materials.
5. The method of preparing an aqueous zinc ion battery metal zinc anode of claim 3, wherein the drying conditions in step c are: vacuum drying at 50-80 deg.c for 12-24 hr to obtain the final thickness of the coating of 20-500 micron.
6. The method of making an aqueous zinc ion battery metal zinc anode of claim 3, characterized in that: the metal zinc cathode is any one of a zinc-plated carbon material, a zinc-plated alloy, a zinc foil, a zinc alloy foil, zinc powder and zinc alloy powder.
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