CN114843431A - Zinc metal negative electrode with aminosilane polymer protective layer and preparation method thereof - Google Patents
Zinc metal negative electrode with aminosilane polymer protective layer and preparation method thereof Download PDFInfo
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- CN114843431A CN114843431A CN202210550780.1A CN202210550780A CN114843431A CN 114843431 A CN114843431 A CN 114843431A CN 202210550780 A CN202210550780 A CN 202210550780A CN 114843431 A CN114843431 A CN 114843431A
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 227
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 114
- 239000011701 zinc Substances 0.000 title claims abstract description 114
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229920000642 polymer Polymers 0.000 title claims abstract description 109
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 75
- 239000002184 metal Substances 0.000 title claims abstract description 75
- 239000011241 protective layer Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 32
- 239000010410 layer Substances 0.000 claims abstract description 61
- 230000004048 modification Effects 0.000 claims abstract description 31
- 238000012986 modification Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 109
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 75
- 239000011259 mixed solution Substances 0.000 claims description 69
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 17
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 15
- 238000007598 dipping method Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- UBVMBXTYMSRUDX-UHFFFAOYSA-N n-prop-2-enyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCC=C UBVMBXTYMSRUDX-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 7
- TZZGHGKTHXIOMN-UHFFFAOYSA-N 3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCC[Si](OC)(OC)OC TZZGHGKTHXIOMN-UHFFFAOYSA-N 0.000 claims description 7
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 7
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 7
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 7
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 7
- UNVFWCQQWZUPLB-UHFFFAOYSA-N 3-[dimethoxy(pentan-3-yloxy)silyl]propan-1-amine Chemical compound CCC(CC)O[Si](OC)(OC)CCCN UNVFWCQQWZUPLB-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 208000005156 Dehydration Diseases 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims description 3
- 229920001558 organosilicon polymer Polymers 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- QIOYHIUHPGORLS-UHFFFAOYSA-N n,n-dimethyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(C)C QIOYHIUHPGORLS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910018557 Si O Inorganic materials 0.000 claims 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 1
- 210000001787 dendrite Anatomy 0.000 abstract description 16
- 238000000151 deposition Methods 0.000 abstract description 16
- 230000008021 deposition Effects 0.000 abstract description 16
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 14
- 230000001351 cycling effect Effects 0.000 abstract description 10
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
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- 238000000576 coating method Methods 0.000 description 43
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- 238000001878 scanning electron micrograph Methods 0.000 description 8
- BTXFTCVNWMNXKH-UHFFFAOYSA-N NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC Chemical compound NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC BTXFTCVNWMNXKH-UHFFFAOYSA-N 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000003751 zinc Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
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- 238000004146 energy storage Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- -1 siloxane chains Chemical group 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of electrochemical power supplies, and particularly relates to a zinc metal cathode with an aminosilane polymer protective layer. Compared with the prior art, the method has the advantages that the aminosilane polymer modification layer is formed on the zinc foil in situ, so that the compatibility of the zinc cathode and an electrolyte interface can be well improved, the deposition behavior of zinc ions is optimized, and the formation of zinc dendrites is inhibited, so that the safety and the cycling stability of the zinc cathode are improved. The aminosilane polymer protective layer is simple in preparation method, easy in raw material obtaining, suitable for large-scale production and high in practicability.
Description
Technical Field
The invention belongs to the technical field of electrochemical power supplies, and particularly relates to a zinc metal cathode with an aminosilane polymer protective layer and a preparation method thereof.
Technical Field
With the rapid development of the portable energy storage industry and the new energy electric automobile industry, people increasingly demand electrochemical energy storage devices with high energy density, long cycle life, high safety and low cost, and the traditional lithium ion batteries are gradually difficult to meet the demands. The water system zinc metal secondary battery is a secondary battery directly using metal zinc as a negative electrode, and has the advantages of simple and convenient operation, safety, environmental protection, low cost, high energy density and the like, so that people pay extensive attention to the water system zinc metal secondary battery.
Specifically, in the case of manufacturing a zinc metal secondary battery, a commercial zinc foil is directly used as a negative electrode and an aqueous electrolyte solution is used as an electrolyte solution, so that the zinc metal secondary battery has the advantages of simplicity and convenience in operation, safety, environmental friendliness, low cost and the like. The zinc metal negative electrode has higher specific capacity (820 mAh g) -1 ) The zinc metal secondary battery has extremely high energy density, is far higher than the traditional lithium ion battery, and is expected to be used as a next-generation green energy storage device in the fields of portable equipment, electric automobiles and the like.
However, zinc metal anodes currently suffer from a number of problems, one of which is that zinc ions tend to form dendrites during deposition. When zinc ions are deposited on the surface of commercial zinc foil, due to low electrode surface flatness and sharp-end deposition effects, subsequently deposited zinc is preferentially deposited at the deposited sites, and zinc dendrites are formed. The growth of dendrites can cause internal short circuit of the battery, and potential safety hazards are brought. The formation of zinc dendrites also results in zinc waste, which severely shortens battery life. Therefore, the application of zinc secondary batteries must overcome the dendrite problem.
The zinc deposition process is closely related to the interface between the zinc cathode and the electrolyte, so in order to solve the problem of dendrite, the interface modification is carried out to optimize the deposition behavior of zinc, which is one of the main strategies, and the proper coating is constructed to promote the uniform deposition of zinc and inhibit the generation of dendrite.
Methods for preparing protective layers on the surfaces of water-based metals have been reported, but many coatings are complex in preparation method, use easy-to-corrode, toxic and harmful solvents, and cannot meet the requirements for safety and environmental protection of water-based batteries. For example, in order to prepare a graphene oxide-based protective layer (for example, patent documents CN114171726A and CN 113871620A), highly corrosive hazardous chemicals such as concentrated hydrochloric acid and concentrated sulfuric acid are used to prepare a graphene oxide raw material; the process of introducing alloy coatings (such as patent documents CN113871624A and CN113782702A) on the surface is complex and tedious, and large-scale production cannot be realized; the conventional surface coating method often needs additional addition of a binder, and the surface coating is difficult to ensure the thickness uniformity; in-situ deposition or sputtering surface modification often requires complex, expensive equipment. Therefore, it is urgently needed to develop a zinc metal surface modification method with strong operability, low cost, adjustable coating thickness and high coating stability so as to adapt to the applicable conditions of a water system zinc metal battery.
In view of the above, the present invention provides a zinc metal negative electrode with an aminosilane polymer protective layer, which can solve the dendrite problem in a zinc metal secondary battery, and the preparation method thereof adopts a simple dipping method to form an aminosilane polymer protective layer on the surface of zinc metal to inhibit the formation of zinc dendrite. When the amino silane polymer protective layer is adopted, due to the high affinity characteristic of amino functional groups to zinc ions and the space induction effect of siloxane chains, the oriented diffusion and deposition of metal ions are induced to form a uniform and compact metal deposition layer, so that the generation of zinc dendrites is effectively inhibited.
Disclosure of Invention
One of the objects of the present invention is: based on the problems that the conventional zinc cathode modification method is complicated, large-scale production cannot be realized and the like, the invention provides the simple and low-cost aminosilane polymer modified zinc cathode and the preparation method thereof. The aminosilane polymer protective layer is simple in preparation method, high in coating uniformity, good in electrochemical stability, easy in raw material obtaining, suitable for large-scale production and high in practicability. The zinc cathode modified by the aminosilane polymer layer, which is prepared by the invention, has excellent cycling stability as a secondary zinc battery cathode, and has huge application prospect in zinc ion batteries, zinc ion capacitors, zinc-air batteries and other fields relating to metal zinc sheets.
In order to achieve the purpose, the invention adopts the following technical scheme:
a zinc metal negative electrode having an aminosilane polymer protective layer comprising a zinc foil and a uniform, dense aminosilane polymer protective layer formed in situ on a surface of the zinc foil.
As an improvement of the zinc metal negative electrode with the amino silane polymer protective layer, the concrete components of the polymer protective layer are organic silicon polymer containing amino functional groups; the organosilicon polymer containing amino functional groups is specifically a gamma-aminopropyltriethoxysilane polymer, a gamma-aminopropyltrimethoxysilane polymer, a gamma-aminopropylmethyldiethoxysilane polymer, a gamma-diethylenetriaminepropylmethyldimethoxysilane polymer, an N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane polymer, an N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane polymer, an N- (beta-aminoethyl) -gamma-aminopropylmethyldiethoxysilane polymer, an N- (beta-aminoethyl) -gamma-aminopropylmethyl-dimethoxysilane polymer, an N-N diethylaminopropyltrimethoxysilane polymer, an N-N dimethylaminopropyltrimethoxysilane polymer, 3- (N-allylamino) propyltrimethoxysilane, anilinomethyltriethoxysilane, and bis (3-trimethoxysilylpropyl) amine.
Another object of the invention is to provide a method for preparing a zinc metal negative electrode having an aminosilane polymer protective layer, comprising at least the steps of:
firstly, dissolving aminosilane in a first solvent containing water, and uniformly stirring to obtain a silanol mixed solution; aminosilane hydrolyzes to silanol in the presence of water.
Secondly, dipping the polished zinc foil into the silanol mixed liquid obtained in the first step to form a modification layer on the surface of the zinc foil, so as to obtain the zinc foil containing the modification layer;
and thirdly, fully washing and drying the zinc foil containing the modification layer obtained in the second step by using a second solvent, heating for dehydration, hydrolyzing silanol and then carrying out polycondensation to obtain the zinc cathode with the aminosilane polymer modification layer.
Taking gamma-aminopropyltriethoxysilane as an example, the reaction involved is shown by the following chemical reaction equation:
wherein, the reaction equation (1) is that aminosiloxane is hydrolyzed into aminosilicol, the reaction equation (2) is that aminosilicol reacts with the surface of the zinc foil, and the reaction equation (3) is that aminosilane modified on the surface of the zinc foil further performs polycondensation with the silanol to form an aminosilane polymer modification layer.
As an improvement in the method of making the zinc metal negative electrode of the present invention having a protective layer of an aminosilane polymer, the aminosilane is a siloxane containing at least one amino group and having the molecular structure Y-R-Si (OR) 3 (wherein Y is an organic functional group having at least one amino group, and Si-OR is a siloxy group); the aminosilane is specifically gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-diethylenetriaminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldiethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyl-dimethoxysilane, N-diethylaminopropyltrimethoxysilane, N-dimethylaminopropyltrimethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, at least one of aniline methyl triethoxy silane and bis (3-trimethoxysilylpropyl) amine.
As an improvement of the preparation method of the zinc metal negative electrode with the amino silane polymer protective layer, the volume ratio of the amino silane to the first solvent is (1-40): (60-99).
As an improvement of the preparation method of the zinc metal negative electrode with the amino silane polymer protective layer, the first solvent further contains an organic alcohol solvent, the volume ratio of the organic alcohol solvent to water is 20:1-1:5, and the organic alcohol solvent is specifically at least one of methanol, ethanol, isopropanol and ethylene glycol. The addition of alcohol can regulate the degree of hydrolysis of the aminosilane.
As an improvement of the preparation method of the zinc metal negative electrode with the amino silane polymer protective layer, the dipping time in the second step is 1-200 h, and the dipping temperature is 20-40 ℃.
As an improvement of the preparation method of the zinc metal cathode with the amino silane polymer protective layer, the drying method after the dipping treatment is natural air drying, the temperature of the heating dehydration treatment is 50-150 ℃, and the duration time is 1-6 h. Through the heating treatment for 1-6 h, the aminosilane can be further dehydrated and condensed to form a compact and uniform polymer modification layer.
As an improvement of the preparation method of the zinc metal negative electrode with the amino silane polymer protective layer, in the third step, the second solvent is at least one of methanol, ethanol, isopropanol and ethylene glycol.
The zinc negative electrode of the present invention can be used in a zinc ion battery, a zinc ion capacitor or a zinc-gas battery.
According to the invention, the amino silane polymer modification layer is designed, rich amino functional groups can be used as zinc ion capture sites, and cross-linked silica chains can provide nanopores so as to uniform zinc ion flow and effectively realize the inhibition effect on zinc dendritic crystal growth. According to the invention, a uniform and compact aminosilane polymer modification layer is formed on the surface of the zinc metal through simple dipping treatment.
Compared with the prior art, the aminosilane polymer modification layer solves the problem of dendrite of the zinc negative electrode, optimizes the zinc ion deposition behavior and realizes the zinc negative electrode without dendrite. The coating has the advantages of high uniformity, good stability and low thickness, and meanwhile, the preparation method is simple, the cost is low, and the industrialization is easy to realize. The symmetrical battery assembled by the zinc cathode modified by the amino silane polymer layer can stably circulate for 2950 h, and has excellent circulation stability.
The zinc secondary battery adopting the modified zinc cathode has the characteristics of high safety, long service life and high energy density.
Compared with the prior art, the invention has the following advantages:
firstly, the method has mild conditions, simple operation and green and pollution-free preparation process, and can realize uniform coating of the modification layer on the surface of the zinc cathode by utilizing simple dipping treatment so as to regulate and control the migration and deposition of zinc ions and obviously improve the cycling stability of the electrode.
Secondly, the method can realize the accurate regulation and control of the thickness of the coating, and the thickness and the structure of the coating can be regulated and controlled by changing the type, the concentration and the dipping time of the dipping solution so as to adapt to the transmission of zinc ions under different charging and discharging conditions.
According to the invention, through simple dipping treatment, an aminosilane polymer modification layer is formed on the surface of zinc metal or a current collector, so that the compatibility of a zinc cathode and an electrolyte interface can be well improved, the deposition behavior of zinc ions is optimized, and the formation of zinc dendrites is inhibited, thereby improving the safety and the cycling stability of the zinc cathode. The aminosilane polymer protective layer is simple in preparation method, easy in raw material obtaining, suitable for large-scale production and high in practicability.
Drawings
Fig. 1 is a scanning electron micrograph of a zinc negative electrode obtained in example 1.
Fig. 2 is a graph of cycle performance of the zinc negative electrode of example 1 assembled into a symmetrical cell.
Fig. 3 is a scanning electron micrograph and a spectrum analysis of the zinc negative electrode obtained in example 2.
FIG. 4 shows the zinc negative electrode deposition of 5 mAh cm obtained in example 2 -2 Plain scanning electron micrographs of zinc.
FIG. 5 shows the deposition of 10 mAh cm on the zinc negative electrode obtained in example 2 -2 Cross-sectional scanning electron micrographs of zinc.
Fig. 6 is a graph of cycle performance of the zinc negative electrode obtained in example 2 assembled into a symmetrical battery.
Fig. 7 is a graph showing cycle performance of the zinc negative electrode obtained in example 2 after the zinc negative electrode is assembled into a full cell.
FIG. 8 shows that the bare zinc negative electrode of comparative example 1 has a load of 5 mAh cm -2 Plain scanning electron micrographs of zinc.
Fig. 9 is a graph showing the cycling stability performance of the bare zinc anode of comparative example 1.
Detailed Description
The technical solutions of the present invention are described below with specific examples, but the scope of the present invention is not limited thereto.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available.
Example 1
The embodiment provides a water-based zinc negative electrode based on an aminosilane polymer modification layer, wherein the aminosilane polymer modification layer with good adhesion uniformly grows on the surface of a zinc foil. Wherein the aminosilane is gamma-aminopropyltriethoxysilane.
The preparation method comprises the following steps:
step one, putting 40 mL of gamma-aminopropyltriethoxysilane and 60 mL of mixed solution of methanol and water (the volume ratio of the methanol to the water is 5: 1) into a 150 mL beaker, and stirring for 30min to uniformly mix the mixture to obtain silanol mixed solution;
and step two, cleaning the zinc foil (about 100 mu m) polished by 1000-mesh sand paper by using distilled water and ethanol in sequence, airing, soaking in the silanol mixed solution in the step one, and soaking for 1h at normal temperature.
Step three, taking out the zinc foil from the mixed solution, sequentially cleaning the surface of the zinc foil by using methanol, water and ethanol, and then naturally drying the zinc foil; and (3) placing the dried zinc foil in a blast oven, maintaining the heating at 120 ℃ for 2 h, dehydrating the coating to form a compact coating, and obtaining the zinc foil which is the metal zinc cathode modified with the gamma-aminopropyltriethoxysilane polymer protective layer.
The SEM image of the gamma-aminopropyltriethoxysilane modifying layer prepared in example 1 is shown in fig. 1, and it can be seen from fig. 1 that: the surface finishing layer is uniformly attached to the bottom surface of the zinc substrate.
The symmetrical battery cycling stability of the zinc negative electrode modified with the aminosilane polymer layer prepared in example 1 is shown in fig. 2, and it can be seen from fig. 2 that: the metal zinc cathode modified with the gamma-aminopropyltriethoxysilane polymer protective layer has good cycling stability.
Example 2
The embodiment provides an aqueous metal negative electrode based on an aminosilane polymer modification layer, wherein the aminosilane polymer modification layer with good adhesion is uniformly grown on the surface of a zinc foil. Wherein the aminosilane is gamma-aminopropyltriethoxysilane.
The preparation method comprises the following steps:
step one, putting 40 mL of gamma-aminopropyltriethoxysilane and 60 mL of mixed solution of methanol and water (the volume ratio of the methanol to the water is 5: 1) into a 150 mL beaker, and stirring for 30min to uniformly mix the mixture to obtain silanol mixed solution;
and step two, cleaning the zinc foil (about 100 mu m) polished by 1000-mesh sand paper by using distilled water and ethanol in sequence, airing, soaking in the silanol mixed solution in the step one, and soaking for 4 hours at the temperature of 30 ℃.
Step three, taking out the zinc foil from the mixed solution, sequentially cleaning the surface of the zinc foil by using methanol, water and ethanol, and then naturally drying the zinc foil; and (3) placing the dried zinc foil in a blast oven, maintaining the heating at 120 ℃ for 3 h, dehydrating the coating to form a compact coating, and obtaining the zinc foil which is the metal zinc cathode modified with the gamma-aminopropyltriethoxysilane polymer protective layer.
The SEM image of the gamma-aminopropyltriethoxysilane modifying layer prepared in example 2 is shown in fig. 3, and it can be seen from fig. 3 that: the zinc negative electrode surface modification layer coating is uniformly attached to the zinc base surface.
The morphology of the gamma-aminopropyltriethoxysilane-modified zinc cathode after deposition is shown in fig. 4 and 5, and it can be clearly seen from the scanning electron microscope picture in fig. 3 and the cross-sectional scanning electron microscope photograph in fig. 4 that the zinc deposition layer deposited on the metal surface modified with the aminosilane polymer protective layer is uniformly and densely deposited without vertically-grown zinc dendrites.
The cycling stability of the symmetric battery of the gamma-aminopropyltriethoxysilane polymer modified zinc negative electrode prepared in example 2 is shown in fig. 6, and can be seen from fig. 6: the zinc cathode modified with the aminosilane polymer layer has very good cycling stability.
The full cell cycle stability of the aminosilane polymer-modified metallic zinc negative electrode prepared in example 2 is shown in fig. 7, and can be seen from fig. 7: the metal zinc cathode modified with the amino silane polymer protective layer has stable full-battery cycle stability and capacity retention rate.
Example 3
This example provides an aqueous metal negative electrode based on an aminosilane polymer-modified layer, which has a good adhesion of the aminosilane polymer layer uniformly grown on the surface of a zinc foil. Wherein the aminosilane is gamma-ethylenediamine propyl trimethoxy silane.
The preparation method comprises the following steps:
step one, placing 30 mL of gamma-ethylenediamine propyl trimethoxy silane and 70 mL of mixed solution of isopropanol and water (the volume ratio of the isopropanol to the water is 5: 2) in a 150 mL beaker, and stirring for 30min to uniformly mix the materials to obtain silanol mixed solution;
and step two, cleaning the zinc foil (about 100 mu m) polished by 1000-mesh sand paper by using distilled water and ethanol in sequence, airing, soaking in the silanol mixed solution in the step one, and soaking for 8 hours at 35 ℃.
Thirdly, taking out the zinc foil from the mixed solution, sequentially cleaning the surface of the zinc foil by using isopropanol, water and ethanol, and then naturally drying the zinc foil; and (3) placing the dried zinc foil in a blast oven, maintaining the heating at 110 ℃ for 2 h, and dehydrating the coating to form a compact coating, thus obtaining the metal zinc cathode modified with the gamma-ethylenediamine propyl trimethoxy silane polymer protective layer.
Example 4
This example provides an aqueous metal negative electrode based on an aminosilane polymer-modified layer, which has a good adhesion of the aminosilane polymer layer uniformly grown on the surface of the zinc foil. Wherein the aminosilane is gamma-aminopropyltrimethoxysilane.
The preparation method comprises the following steps:
step one, putting 10 mL of gamma-aminopropyltrimethoxysilane, 90 mL of mixed solution of ethanol and water (the volume ratio of the ethanol to the water is 1: 5) into a 150 mL beaker, and stirring for 30min to uniformly mix the materials to obtain silanol mixed solution;
and step two, cleaning the zinc foil (about 100 mu m) polished by 1000-mesh sand paper by using distilled water and ethanol in sequence, airing, soaking in the silanol mixed solution in the step one, and soaking for 20 hours at 25 ℃.
Thirdly, taking out the zinc foil from the mixed solution, cleaning the surface of the zinc foil by using ethanol, water and ethanol in sequence, and then naturally drying the zinc foil; and (3) placing the dried zinc foil in a blast oven, maintaining the heating at 120 ℃ for 4 h, and dehydrating the coating to form a compact coating, thus obtaining the metal zinc cathode modified with the gamma-aminopropyltrimethoxysilane polymer protective layer.
Example 5
This example provides an aqueous metal negative electrode based on an aminosilane polymer-modified layer, which has a good adhesion of the aminosilane polymer layer uniformly grown on the surface of a zinc foil. Wherein the aminosilane is gamma-aminopropyl methyl diethoxy silane.
The preparation method comprises the following steps:
step one, placing 5 mL of gamma-aminopropyl methyl diethoxy silane and 95 mL of mixed solution of glycol and water (the volume ratio of the glycol to the water is 1: 2) in a 150 mL beaker, and stirring for 30min to uniformly mix the materials to obtain a silanol mixed solution;
and step two, cleaning the zinc foil (about 100 mu m) polished by 1000-mesh sand paper by using distilled water and ethanol in sequence, airing, soaking in the silanol mixed solution in the step one, and soaking for 50 hours at 40 ℃.
Thirdly, taking out the zinc foil from the mixed solution, sequentially cleaning the surface of the zinc foil by using glycol, water and ethanol, and naturally drying the zinc foil; and (3) placing the dried zinc foil in a blast oven, maintaining heating at 50 ℃ for 6 h, and dehydrating the coating to form a compact coating, thus obtaining the metal zinc cathode modified with the gamma-aminopropyl methyl diethoxy silane polymer protective layer.
Example 6
This example provides an aqueous metal negative electrode based on an aminosilane polymer-modified layer, which has a good adhesion of the aminosilane polymer layer uniformly grown on the surface of a zinc foil. Wherein, the aminosilane is N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane.
The preparation method comprises the following steps:
step one, 2 mL of N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, 98 mL of a mixed solution of methanol and water (the volume ratio of the methanol to the water is 1: 5) are placed in a 150 mL beaker, and are stirred for 30min to be uniformly mixed, so that a silanol mixed solution is obtained;
and step two, cleaning the zinc foil (about 100 mu m) polished by 1000-mesh sand paper by using distilled water and ethanol in sequence, airing, soaking in the silanol mixed solution in the step one, and soaking for 100 hours at the temperature of 20 ℃.
Step three, taking out the zinc foil from the mixed solution, sequentially cleaning the surface of the zinc foil by using methanol, water and ethanol, and then naturally drying the zinc foil; and (3) placing the dried zinc foil in a blast oven, maintaining heating at 80 ℃ for 4 h, and dehydrating the coating to form a compact coating, thus obtaining the metal zinc cathode modified with the N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane polymer protective layer.
Example 7
This example provides an aqueous metal negative electrode based on an aminosilane polymer-modified layer, which has a good adhesion of the aminosilane polymer layer uniformly grown on the surface of a zinc foil. Wherein, the aminosilane is N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane.
The preparation method comprises the following steps:
step one, 1 mL of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and 99 mL of mixed solution of water (the volume ratio of isopropanol to water is 1: 4) are put into a 150 mL beaker and stirred for 30min to be uniformly mixed, so that silanol mixed solution is obtained;
and step two, cleaning the zinc foil (about 100 mu m) polished by 1000-mesh sand paper by using distilled water and ethanol in sequence, airing, soaking in the silanol mixed solution in the step one, and soaking for 80 hours at 35 ℃.
Thirdly, taking out the zinc foil from the mixed solution, sequentially cleaning the surface of the zinc foil by using isopropanol, water and ethanol, and then naturally drying the zinc foil; and (3) placing the dried zinc foil in a blast oven, maintaining heating at 90 ℃ for 4 h, and dehydrating the coating to form a compact coating, thus obtaining the metal zinc cathode modified with the N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane polymer protective layer.
Example 8
This example provides an aqueous metal negative electrode based on an aminosilane polymer-modified layer, which has a good adhesion of the aminosilane polymer layer uniformly grown on the surface of a zinc foil. Wherein, the aminosilane is N- (beta-aminoethyl) -gamma-aminopropyl methyl diethoxy silane.
The preparation method comprises the following steps:
step one, taking 10 mL of N- (beta-aminoethyl) -gamma-aminopropyl methyl diethoxy silane and 90 mL of mixed solution of methanol and water (the volume ratio of the methanol to the water is 1: 1) and placing the mixed solution and the water in a 150 mL beaker, and stirring for 30min to uniformly mix the mixed solution to obtain silanol mixed solution;
and step two, cleaning the zinc foil (about 100 mu m) polished by 1000-mesh sand paper by using distilled water and ethanol in sequence, airing, soaking in the silanol mixed solution in the step one, and soaking for 25 hours at the temperature of 24 ℃.
Step three, taking out the zinc foil from the mixed solution, sequentially cleaning the surface of the zinc foil by using methanol, water and ethanol, and then naturally drying the zinc foil; and (3) placing the dried zinc foil in a blast oven, maintaining the heating at 100 ℃ for 2 h, and dehydrating the coating to form a compact coating, thus obtaining the metal zinc cathode modified with the N- (beta-aminoethyl) -gamma-aminopropyl methyl diethoxy silane polymer protective layer.
Example 9
This example provides an aqueous metal negative electrode based on an aminosilane polymer-modified layer, which has a good adhesion of the aminosilane polymer layer uniformly grown on the surface of a zinc foil. Wherein, the aminosilane is N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
The preparation method comprises the following steps:
step one, taking 15 mL of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 85 mL of mixed solution of ethanol and water (the volume ratio of the ethanol to the water is 2: 1) and placing the mixed solution into a 150 mL beaker, and stirring for 30min to uniformly mix the mixed solution to obtain silanol mixed solution;
and step two, cleaning the zinc foil (about 100 mu m) polished by 1000-mesh sand paper by using distilled water and ethanol in sequence, airing, soaking in the silanol mixed solution in the step one, and soaking for 40 hours at 35 ℃.
Thirdly, taking out the zinc foil from the mixed solution, cleaning the surface of the zinc foil by using ethanol, water and ethanol in sequence, and then naturally drying the zinc foil; and (3) placing the dried zinc foil in a blast oven, maintaining heating at 60 ℃ for 6 h, and dehydrating the coating to form a compact coating, thus obtaining the metal zinc cathode modified with the N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane polymer protective layer.
Example 10
This example provides an aqueous metal negative electrode based on an aminosilane polymer-modified layer, which has a good adhesion of the aminosilane polymer layer uniformly grown on the surface of a zinc foil. Wherein the aminosilane is N-N diethylaminopropyl trimethoxy silane.
The preparation method comprises the following steps:
step one, taking 5 mL of N-N diethyl aminopropyl trimethoxy silane and 95 mL of mixed solution of ethylene glycol and water (the volume ratio of the ethylene glycol to the water is 1: 3) and placing the mixed solution into a 150 mL beaker, and stirring for 30min to uniformly mix the mixed solution to obtain silanol mixed solution;
and step two, cleaning the zinc foil (about 100 mu m) polished by 1000-mesh sand paper by using distilled water and ethanol in sequence, airing, soaking in the silanol mixed solution in the step one, and soaking for 50 hours at 35 ℃.
Thirdly, taking out the zinc foil from the mixed solution, sequentially cleaning the surface of the zinc foil by using glycol, water and ethanol, and naturally drying the zinc foil; and (3) placing the dried zinc foil in a blast oven, maintaining the heating at 100 ℃ for 2 h, and dehydrating the coating to form a compact coating, thus obtaining the metal zinc cathode modified with the N-N diethylaminopropyl trimethoxy silane polymer protective layer.
Example 11
This example provides an aqueous metal negative electrode based on an aminosilane polymer-modified layer, which has a good adhesion of the aminosilane polymer layer uniformly grown on the surface of a zinc foil. Wherein the aminosilane is 3- (N-allylamino) propyl trimethoxy silane.
The preparation method comprises the following steps:
step one, taking 5 mL of 3- (N-allylamino) propyl trimethoxy silane, placing 95 mL of mixed solution of ethanol and water (the volume ratio of the ethanol to the water is 4: 1) in a 150 mL beaker, and stirring for 30min to uniformly mix the mixed solution to obtain silanol mixed solution;
and step two, cleaning the zinc foil (about 100 mu m) polished by 1000-mesh sand paper by using distilled water and ethanol in sequence, airing, soaking in the silanol mixed solution in the step one, and soaking for 10 hours at the temperature of 30 ℃.
Thirdly, taking out the zinc foil from the mixed solution, cleaning the surface of the zinc foil by using ethanol, water and ethanol in sequence, and then naturally drying the zinc foil; and (3) placing the dried zinc foil in a blast oven, maintaining the heating at 110 ℃ for 2 h, and dehydrating the coating to form a compact coating, thereby obtaining the metal zinc cathode modified with the 3- (N-allylamino) propyl trimethoxy silane polymer protective layer.
Example 12
This example provides an aqueous metal negative electrode based on an aminosilane polymer-modified layer, which has a good adhesion of the aminosilane polymer layer uniformly grown on the surface of a zinc foil. Wherein the aminosilane is 3- (N-allylamino) propyl trimethoxy silane.
The preparation method comprises the following steps:
step one, placing 10 mL of 3- (N-allylamino) propyl trimethoxy silane, 90 mL of mixed solution of ethylene glycol and water (the volume ratio of ethanol to water is 10: 1) in a 150 mL beaker, and stirring for 30min to uniformly mix the materials to obtain silanol mixed solution;
and step two, cleaning the zinc foil (about 100 mu m) polished by 1000-mesh sand paper by distilled water and ethanol in sequence, airing, soaking in the silanol mixed solution in the step one, and soaking for 8 hours at the temperature of 30 ℃.
Thirdly, taking out the zinc foil from the mixed solution, cleaning the surface of the zinc foil by using ethanol, water and ethanol in sequence, and then naturally drying the zinc foil; and (3) placing the dried zinc foil in a blast oven, maintaining the heating for 2 hours at the temperature of 100 ℃, and dehydrating the coating to form a compact coating, thereby obtaining the metal zinc cathode modified with the 3- (N-allylamino) propyl trimethoxy silane polymer protective layer.
Example 13
The embodiment provides an aqueous metal negative electrode based on an aminosilane polymer modification layer, wherein the aminosilane polymer modification layer with good adhesion is uniformly grown on the surface of a zinc foil. Wherein the aminosilane is aniline methyl triethoxysilane.
The preparation method comprises the following steps:
step one, placing 30 mL of aniline methyl triethoxysilane, 70 mL of mixed solution of isopropanol and water (the volume ratio of the isopropanol to the water is 13: 1) in a 150 mL beaker, and stirring for 30min to uniformly mix the mixture to obtain silanol mixed solution;
and step two, cleaning the zinc foil (about 100 mu m) polished by 1000-mesh sand paper by using distilled water and ethanol in sequence, airing, soaking in the silanol mixed solution in the step one, and soaking for 40 hours at the temperature of 30 ℃.
Thirdly, taking out the zinc foil from the mixed solution, sequentially cleaning the surface of the zinc foil by using isopropanol, water and ethanol, and then naturally drying the zinc foil; and (3) placing the dried zinc foil in a blast oven, maintaining the heating at 120 ℃ for 2 h, and dehydrating the coating to form a compact coating, thus obtaining the metal zinc cathode modified with aniline methyl triethoxysilane and a polymer protective layer.
Example 14
The embodiment provides an aqueous metal negative electrode based on an aminosilane polymer modification layer, wherein the aminosilane polymer modification layer with good adhesion is uniformly grown on the surface of a zinc foil. Wherein the aminosilane is aniline methyl triethoxysilane.
The preparation method comprises the following steps:
step one, putting 10 mL of aniline methyl triethoxysilane, 90 mL of mixed solution of methanol and water (the volume ratio of the methanol to the water is 10: 1) into a 150 mL beaker, and stirring for 30min to uniformly mix the solution to obtain silanol mixed solution;
and step two, cleaning the zinc foil (about 100 mu m) polished by 1000-mesh sand paper by using distilled water and ethanol in sequence, airing, soaking in the silanol mixed solution in the step one, and soaking for 50 hours at the temperature of 30 ℃.
Step three, taking out the zinc foil from the mixed solution, sequentially cleaning the surface of the zinc foil by using methanol, water and ethanol, and then naturally drying the zinc foil; and (3) placing the dried zinc foil in a blast oven, maintaining the heating at 110 ℃ for 2 h, and dehydrating the coating to form a compact coating, thus obtaining the metal zinc cathode modified with the aniline methyl triethoxysilane polymer protective layer.
Example 15
This example provides an aqueous metal negative electrode based on an aminosilane polymer-modified layer, which has a good adhesion of the aminosilane polymer layer uniformly grown on the surface of a zinc foil. Wherein the aminosilane is bis (3-trimethoxysilylpropyl) amine.
The preparation method comprises the following steps:
step one, 5 mL of bis (3-trimethoxysilylpropyl) amine and 95 mL of mixed solution of ethanol and water (the volume ratio of the ethanol to the water is 10: 1) are placed in a 150 mL beaker and stirred for 30min to be uniformly mixed, and then silanol mixed solution is obtained;
and step two, cleaning the zinc foil (about 100 mu m) polished by 1000-mesh sand paper by using distilled water and ethanol in sequence, airing, soaking in the silanol mixed solution in the step one, and soaking for 20 hours at the temperature of 30 ℃.
Thirdly, taking out the zinc foil from the mixed solution, cleaning the surface of the zinc foil by using ethanol, water and ethanol in sequence, and then naturally drying the zinc foil; and (3) placing the dried zinc foil in a blast oven, maintaining the heating for h at the temperature of 100 ℃, and dehydrating the coating to form a compact coating, thereby obtaining the metal zinc cathode modified with the bis (3-trimethoxysilylpropyl) amine polymer protective layer.
Comparative example 1
Comparative example 1 is a zinc foil after sanding, specifically a zinc foil (about 100 μm) after sanding with 1000 mesh sand paper, washed with distilled water and ethanol in this order, and dried to be used as a zinc negative electrode.
FIG. 8 shows that the bare zinc negative electrode is loaded with 5 mAh cm -2 Planar scanning electron micrographs of zinc, the cycling stability of the pure zinc foil symmetrical cell is shown in fig. 9, which can be seen in fig. 9: the unmodified zinc cathode has very poor cycle stability, and short circuit occurs quickly in deposition/extraction cycles.
In conclusion, when the aminosilane polymer layer is used as a surface modification layer of a water-based metal negative electrode, uniform deposition of metal can be induced, and formation of zinc dendrite is greatly inhibited, so that the safety and the service life of the water-based zinc metal negative electrode are remarkably improved. The aminosilane polymer layer serving as the zinc cathode surface modification layer is simple in preparation method, easy in raw material obtaining and suitable for large-scale production. Therefore, the zinc cathode modified by the aminosilane polymer layer adopted by the invention can be used as a high-safety and high-energy-density energy storage device and has a good application prospect.
Variations and modifications to the above-described embodiments may become apparent to those skilled in the art to which the invention pertains, upon review of the foregoing disclosure and guidance. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and modifications and variations of the present invention are also intended to fall within the scope of the appended claims.
Claims (10)
1. A zinc metal negative electrode having a protective layer of an aminosilane polymer, comprising: comprises a zinc foil and a uniform and compact aminosilane polymer protective layer formed in situ on the surface of the zinc foil.
2. The zinc metal negative electrode having an aminosilane polymer protective layer of claim 1, wherein: the specific component of the aminosilane polymer protective layer is an organosilicon polymer containing amino functional groups.
3. The zinc metal negative electrode having an aminosilane polymer protective layer of claim 1, wherein: the aminosilane polymer protective layer is specifically a gamma-aminopropyltriethoxysilane polymer, a gamma-aminopropyltrimethoxysilane polymer, a gamma-aminopropylmethyldiethoxysilane polymer, a gamma-diethylenetriaminopropylmethyldimethoxysilane polymer, an N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane polymer, an N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane polymer, an N- (beta-aminoethyl) -gamma-aminopropylmethyldiethoxysilane polymer, an N- (beta-aminoethyl) -gamma-aminopropylmethyl-dimethoxysilane polymer, an N-N diethylaminopropyltrimethoxysilane polymer, an N-N dimethylaminopropyltrimethoxysilane polymer, 3- (N-allylamino) propyltrimethoxysilane, anilinomethyltriethoxysilane, and bis (3-trimethoxysilylpropyl) amine.
4. A method for preparing a zinc metal negative electrode with an aminosilane polymer protective layer, comprising at least the steps of:
firstly, dissolving aminosilane in a first solvent containing water, and uniformly stirring to obtain a silanol mixed solution;
secondly, dipping the zinc foil into the silanol mixed liquid obtained in the first step to form a modification layer on the surface of the zinc foil, so as to obtain the zinc foil containing the modification layer;
and thirdly, fully washing and drying the zinc foil containing the modification layer obtained in the second step by using a second solvent, and then heating and dehydrating to obtain the zinc cathode with the aminosilane polymer modification layer.
5. The method of making a zinc metal negative electrode with an aminosilane polymer protective layer of claim 4, comprising: the aminosilane is siloxane containing at least one amino group, and the molecular structure of the aminosilane is Y-R-Si (OR) 3 (wherein Y is an organic functional group containing an amino group, and Si-O is a siloxy group); the aminosilane is specifically gamma-aminopropyltriethoxysilane, gamma-aminopropylTrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-diethylenetriaminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldiethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyl-dimethoxysilane, N-diethylaminopropyltrimethoxysilane, N-dimethylaminopropyltrimethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, anilinomethyltriethoxysilane, bis (3-trimethoxysilylpropyl) amine.
6. The method of making a zinc metal negative electrode with an aminosilane polymer protective layer of claim 4, comprising: the volume ratio of the aminosilane to the first solvent is (1-40): (60-99).
7. The method of making a zinc metal negative electrode with an aminosilane polymer protective layer of claim 4, comprising: the first solvent also contains an organic alcohol solvent, the volume ratio of the organic alcohol solvent to water is 20:1-1:5, and the organic alcohol solvent is specifically at least one of methanol, ethanol, isopropanol and ethylene glycol.
8. The method of making a zinc metal negative electrode with an aminosilane polymer protective layer of claim 4, comprising: the zinc foil in the second step is polished, the dipping time in the second step is 1-200 h, and the dipping temperature is 20-40 ℃.
9. The method of making a zinc metal negative electrode with an aminosilane polymer protective layer of claim 4, comprising: the drying method after the dipping treatment is natural air drying, the temperature of the heating dehydration treatment is 50-150 ℃, and the duration time is 1-6 h.
10. The method of making a zinc metal negative electrode with an aminosilane polymer protective layer of claim 4, comprising: and thirdly, the second solvent is at least one of methanol, ethanol, isopropanol and glycol.
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| CN104927650A (en) * | 2015-06-15 | 2015-09-23 | 北京化工大学 | Preparation method of functional coating |
| CN109546100A (en) * | 2018-10-16 | 2019-03-29 | 中航锂电（洛阳）有限公司 | A kind of silicon-carbon composite film electrode and lithium ion battery |
| CN113690401A (en) * | 2021-10-26 | 2021-11-23 | 中南大学 | Zinc phosphate-silane composite passive film modified zinc metal negative electrode and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104927650A (en) * | 2015-06-15 | 2015-09-23 | 北京化工大学 | Preparation method of functional coating |
| CN109546100A (en) * | 2018-10-16 | 2019-03-29 | 中航锂电（洛阳）有限公司 | A kind of silicon-carbon composite film electrode and lithium ion battery |
| CN113690401A (en) * | 2021-10-26 | 2021-11-23 | 中南大学 | Zinc phosphate-silane composite passive film modified zinc metal negative electrode and preparation method and application thereof |
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