CN116826194A - High-performance zinc-based water-based electrolyte and application thereof - Google Patents
High-performance zinc-based water-based electrolyte and application thereof Download PDFInfo
- Publication number
- CN116826194A CN116826194A CN202310497779.1A CN202310497779A CN116826194A CN 116826194 A CN116826194 A CN 116826194A CN 202310497779 A CN202310497779 A CN 202310497779A CN 116826194 A CN116826194 A CN 116826194A
- Authority
- CN
- China
- Prior art keywords
- zinc
- electrolyte
- performance
- aqueous electrolyte
- based aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000011701 zinc Substances 0.000 title claims abstract description 81
- 239000003792 electrolyte Substances 0.000 title claims abstract description 76
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229920002678 cellulose Polymers 0.000 claims abstract description 53
- 239000001913 cellulose Substances 0.000 claims abstract description 53
- 150000003751 zinc Chemical class 0.000 claims abstract description 20
- 239000003990 capacitor Substances 0.000 claims abstract description 11
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 27
- 239000002159 nanocrystal Substances 0.000 claims description 15
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 5
- 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 claims description 5
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 32
- 230000000996 additive effect Effects 0.000 abstract description 28
- 210000001787 dendrite Anatomy 0.000 abstract description 11
- 238000007086 side reaction Methods 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 231100000956 nontoxicity Toxicity 0.000 abstract description 4
- 210000004027 cell Anatomy 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 230000008021 deposition Effects 0.000 description 12
- 238000004146 energy storage Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 6
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000007614 solvation Methods 0.000 description 5
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- VCPQWWKLNIMKND-UHFFFAOYSA-L zinc hydroxy sulfate Chemical compound [Zn++].OOS([O-])(=O)=O.OOS([O-])(=O)=O VCPQWWKLNIMKND-UHFFFAOYSA-L 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- 239000002000 Electrolyte additive Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 3
- 239000004312 hexamethylene tetramine Substances 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 238000004807 desolvation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000003071 parasitic effect Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 241000744472 Cinna Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a high-performance zinc-based water-based electrolyte and application thereof. The electrolyte comprises water, zinc salt and cellulose nanocrystalline. The zinc-based water-based electrolyte has the characteristics of no toxicity, environmental protection, high safety and low additive cost, and can guide zinc to be uniformly deposited, inhibit zinc dendrite growth and inhibit side reaction after being used for batteries and capacitors, thereby greatly improving the charge and discharge efficiency and the cycle stability of the batteries and the capacitors.
Description
Technical Field
The invention relates to an electrolyte and application thereof, in particular to a high-performance zinc-based water-based electrolyte and application thereof.
Background
Compared with lithium metal, zinc metal has the characteristics of abundant reserves, low cost, no toxicity and easy processing, and zinc metal has the advantages of high theoretical specific capacity and low electrochemical oxidation-reduction potential in a water system energy storage system. The water-based zinc-based energy storage device is outstanding in a plurality of electrochemical energy storage systems, has wide application prospect in the fields of large-scale distributed energy storage, intelligent equipment, wearable products and the like, and is considered as a candidate system most likely to become a lithium ion battery.
However, in the long-term electrochemical reaction of the zinc metal electrode, the zinc metal electrode is limited by nonuniform deposition and side reaction of zinc ions in the traditional water-based zinc salt electrolyte, so that the coulomb efficiency of the water-based zinc-based energy storage device is reduced, the zinc utilization rate is reduced and the capacity attenuation is too fast in the charge and discharge process; even causing device shorting and expansion cracking; this severely hampers the large-scale development and multi-functional commercial application of aqueous zinc-based energy storage devices.
In order to solve the key scientific problems of zinc ion non-uniform deposition and side reaction, researchers have adopted various strategies such as adjusting electrode structure, optimizing diaphragm design, constructing interface protection, etc. However, these strategies are difficult to effectively alleviate uneven deposition of zinc in the deposition/stripping process, and have complicated preparation process, high technical requirements, and difficult to realize industrial application. In contrast, from the practical application point of view, the method for inhibiting zinc ion non-uniform deposition and side reaction is simple, efficient, low-cost and easy to realize by introducing the high-performance additive into the electrolyte, and is a key technical method for solving the problem of zinc metal electrode interface.
However, the existing electrolyte additives have the problems of high price, inflammability, toxicity and the like, and in the circulating process, even if the stability of a zinc metal electrode interface is enhanced, the internal resistance of an energy storage system is often increased, long-term heavy-current charge and discharge are difficult to realize, and the application of the electrolyte additives in a large scale is limited. For example:
in Hexamethylenetetramine additive with zincophilic head and hydrophobictail for realizing ultra-stable Zn anode, xingxing Gu et al, it is reported that the stability problem of zinc anode is solved by adding hexamethylenetetramine having a zinc-philic end and a water-repellent end as additives, but hexamethylenetetramine itself has low toxicity and can decompose toxic nitrogen oxide gas by heating, which causes a risk of drastically reduced safety to intrinsically safe aqueous electrolytes.
The article "zinc-phobic electrolyte implements highly reversible zinc ion cells" published by the university of North lake Wang Hao reports that a method of modifying the surface free energy by introducing Succinonitrile (SN) molecules into the electrolyte was used to construct a zinc-phobic electrolyte. The electrolyte with zinc being hydrophobic in nature can reduce the affinity of zinc metal to the electrolyte and prevent hydrogen evolution reaction caused by interfacial waterShould and corrosion occur. Thus, compared with the conventional electrolyte (2 MZnSO 4 ) In contrast, SN electrolyte (2 MZnSO 4 +0.5gL -1 SN) not only reduces corrosion of Zn metal, but also changes the growth trend of Zinc Hydroxysulfate (ZHS) and achieves a flat, high Zn formed from horizontally stacked ZHS 2+ SEI of flux (H-SEI). The H-SEI prevents further corrosion of Zn and inhibits dendrite growth compared to the usual vertically grown ZHS forming SEI (V-SEI). But the additive Succinonitrile (SN) is harmful to the environment and has certain toxicity.
North Da Shao Yuanlong researchers&Su Dacheng the article by the Tao professor, "modulating the inner Helmholtz plane with a high donor additive to achieve efficient anode reversibility in aqueous zinc ion batteries" states that the performance of Aqueous Zinc Ion Batteries (AZIBs) is highly dependent on the Inner Helmholtz Plane (IHP) chemistry. The notorious parasitic reactions involving Hydrogen Evolution (HER) and Zn dendrites all result from the abundance of free H within active IHP 2 O and random Zn deposition. A general high Donor Number (DN) additive pyridine (Py) is reported in the paper in an amount of only 1vol.% (Py-to-H) 2 O volume ratio) for modulating molecular distribution within the IHP. But the additive pyridine itself is a toxic substance.
The article 'trimethyl phosphate (TMP) for regulating and controlling zinc ion solvation structure to realize wide-temperature-range zinc ion energy storage' published by Shenzhen university Miao-nationality task group indicates that the method successfully inhibits the occurrence of negative dendrite and side reaction and simultaneously inhibits the dissolution of positive active materials by adding a strategy for regulating the zinc ion solvation structure of trimethyl phosphate (TMP), thereby improving the overall performance of the zinc ion battery. However, the additive trimethyl phosphate (TMP) therein is still a toxic and flammable organic substance.
The cellulose nanocrystalline is a nanoscale cellulose extracted from natural fibers, and has the advantages of good biocompatibility, high safety, low cost and the like. Although Nanocellulose has been reported to be used in zinc-based hydrogel electrolytes for inhibiting dendrite growth, its effect is not ideal, as in document nanocellose-Carboxymethylcellulose Electrolyte for Stable, high-RThe preparation of nanocellulose-carboxymethylcellulose (CMC) hydrogel electrolytes has been reported by ate Zinc-Ion Batteries, lin Xu et al to greatly improve cycle performance and higher Zn 2+ Conductivity, but its current density is 50mA cm -2 The area capacity is only 4mAh cm -2 . The cellulose nanocrystals are used in zinc-based aqueous electrolyte to solve the above technical problems in zinc-based aqueous electrolyte, and have not been reported at present.
Disclosure of Invention
The invention aims to provide a high-performance zinc-based aqueous electrolyte and application thereof. The zinc-based water-based electrolyte has the characteristics of no toxicity, environmental protection, high safety and low additive cost, and can guide zinc to be uniformly deposited, inhibit zinc dendrite growth and inhibit side reaction after being used for batteries and capacitors, thereby greatly improving the charge and discharge efficiency and the cycle stability of the batteries and the capacitors.
The technical scheme of the invention is as follows: a high-performance zinc-based aqueous electrolyte comprises water, zinc salt and cellulose nanocrystals.
The concentration of zinc salt in the high-performance zinc-based water-based electrolyte is 0.5-15mol/L.
The concentration of zinc salt in the high-performance zinc-based water-based electrolyte is 3-8mol/L.
In the high-performance zinc-based aqueous electrolyte, the mass ratio of the cellulose nanocrystalline to the zinc salt is 0.1:100-15:100.
In the high-performance zinc-based aqueous electrolyte, the mass ratio of the cellulose nanocrystalline to the zinc salt is 5:100-10:100.
The zinc salt is one or a combination of any more of zinc sulfate, zinc trifluoromethane sulfonate, zinc nitrate, zinc chloride or zinc acetate.
The application of the high-performance zinc-based aqueous electrolyte in a zinc ion battery.
The use of a zinc-based aqueous electrolyte according to the foregoing high performance in zinc ion capacitors.
A zinc ion battery comprising the foregoing high-performance zinc-based aqueous electrolyte.
A zinc ion capacitor comprising the foregoing high-performance zinc-based aqueous electrolyte.
The beneficial effects of the invention are that
1. According to the electrolyte provided by the invention, through the additive cellulose nanocrystalline, a large number of hydroxyl groups can be formed between the additive cellulose nanocrystalline and water molecules, so that a large number of hydrogen bonds can be formed, solvated shell layers of hydrated zinc ions are damaged, the number of active water molecules is reduced, side reactions can be effectively reduced, and uniform deposition of zinc ions can be promoted. The method fundamentally damages the tip effect in the deposition process, inhibits the formation of dendrites and side reactions, reduces hydrogen evolution and corrosion, has obvious inhibition effect on corrosion and passivation reaction on the surface of the zinc metal negative electrode, and improves the deposition/stripping efficiency of the zinc metal negative electrode.
2. In the electrolyte provided by the invention, the cellulose nanocrystalline has good self-assembly characteristic, can form a self-adaptive structure on the surface, has the effect of weakening local stress of an interface, and can be adsorbed on the surface of a zinc metal electrode and in-situ adsorbed to form a water-stable and self-repairing protective film. The cellulose nanocrystalline-based protective film not only shows strong zinc ion affinity to promote uniform zinc deposition, but also has good insulating property to inhibit parasitic reaction, so that a dendrite-free zinc metal electrode is obtained, and the cycle life of the zinc metal electrode is prolonged, which is not possessed by a cellulose hydrogel electrolyte.
3. The electrolyte provided by the invention adopts cellulose nanocrystalline as an electrolyte additive for the first time, has a strong adsorption effect and improves a solvation structure with zinc ions in the electrolyte, and has the dual effects of promoting zinc uniform deposition by forming a cellulose nanocrystalline base protective film on the surface of a zinc metal electrode in situ. The method can solve the problems of hydrogen evolution, corrosion, passivation, dendrite and the like of the zinc metal electrode in the water-based electrolyte, and improve the charge-discharge efficiency, the cycling stability and other electrochemical properties of the battery. The invention is characterized in thatAfter the electrolyte is assembled into the zinc symmetrical battery, the current density is 50mA cm -2 The time-area capacity can reach 50mAh cm -2 And has good cycle stability.
4. The electrolyte provided by the invention has the remarkable advantages of low price, safety, environmental protection, no pollution, simple preparation method, wide application range and the like. Has great application prospect and research value in the field of water-based zinc-based energy storage systems and other potential new energy batteries. The aqueous zinc-based energy storage system electrolyte provided by the invention can improve the cycle stability and the service life of the aqueous zinc ion battery and the aqueous zinc ion capacitor.
In conclusion, the zinc-based aqueous electrolyte has the advantages of no toxicity, environmental protection, high safety and low additive cost, and can guide zinc to be uniformly deposited, inhibit zinc dendrite growth and prevent side reaction after being used for batteries and capacitors, thereby greatly improving the charge and discharge efficiency and the cycle stability of the batteries and the capacitors.
Drawings
FIG. 1 is an electron photograph showing the results of comparative examples and example 1 of the present invention, in which the electrolyte containing and not containing the cellulose nanocrystalline additive was left for 20 days, and the dispersibility was verified by using the Tyndall effect. 1M ZnSO of 0.5wt% cellulose nanocrystals can be clearly seen 4 Under the irradiation of laser, the solution electrolyte presents the Tyndall effect, which proves that the cellulose nanocrystalline is in ZnSO 4 The dispersion is uniform in the solution and the dispersibility is good.
Fig. 2 is an SEM image of the electrolyte obtained in comparative example and example 1 of the present invention after soaking zinc foil for 15 days with and without cellulose nanocrystalline additive. Compared with the solution without cellulose nanocrystalline additive, the surface of the zinc foil is rugged; when the zinc foil is soaked in the additive containing cellulose nanocrystals, the surface of the zinc foil is extremely uniform and flat, which proves that the additive can be preferentially adsorbed on the surface of the zinc foil, thereby reducing ZnSO 4 Corrosion of zinc foil by the solution.
FIG. 3 shows the current flow of assembled zinc symmetrical cells with and without cellulose nanocrystalline additives for the electrolytes obtained in comparative example and example 1 of the present inventionDensity of 1mA cm -2 The area capacity is 1mAh cm -2 Long cycle performance plots below. When the electrolyte contains the cellulose nanocrystalline additive, the zinc symmetrical battery shows more excellent stability in circulation, the stable circulation is more than 1100 hours, the service life is greatly prolonged, and the long-circulation stability of the battery is effectively improved.
FIG. 4 shows the assembled zinc symmetrical cell at a current density of 1mA cm with and without the cellulose nanocrystalline additive according to the electrolyte obtained in comparative example and example 1 of the present invention -2 The area capacity is 1mAh cm -2 SEM images after 20 cycles of long cycle. It is evident that 1M ZnSO without cellulose nanocrystalline additive was observed 4 A large amount of dendrite on the surface of the solution electrolyte grows to form a sharp cone shape; while 1M ZnSO containing cellulose nanocrystalline additive 4 The surface of the solution electrolyte is relatively flat, no obvious dendrite growth condition exists, and the cellulose nanocrystalline additive is proved to be capable of guiding zinc ions to be uniformly deposited on the surface of the zinc electrode.
Fig. 5 is a graph showing the rate performance of assembled zinc symmetrical cells at different current densities for the electrolyte obtained in example 1 of the present invention with a cellulose nanocrystalline additive. It can be obviously observed that the symmetrical battery containing the cellulose nanocrystalline additive has different current densities (1-40 mA cm) -2 ) The cellulose nanocrystalline additive has good multiplying power performance and reversibility, and proves that the cellulose nanocrystalline additive can effectively regulate zinc ion deposition, guide zinc solvation migration and desolvation transformation.
FIG. 6 shows the assembled zinc symmetrical cell at a current density of 50mA cm with and without the cellulose nanocrystalline additive for the electrolytes obtained in comparative example and example 1 of the present invention -2 The area capacity is 50mAh cm -2 Long cycle performance plots below. It is evident that 1M ZnSO containing cellulose nanocrystalline additives was observed 4 Solution electrolyte zinc symmetrical cells have a stable cycle of over 900 hours, far exceeding 1M ZnSO without cellulose nanocrystalline additives 4 And (3) a solution electrolyte. The addition of cellulose nanocrystalline can effectively change solvation structure and guide uniform deposition of zinc ions; at the same time, can promote zinc ionsMigration kinetics and achieving a rapid desolvation reaction.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
Embodiments of the invention
The experimental methods used in the examples below are conventional, unless otherwise specified.
Reagents, materials, and the like used in the examples described below are commercially available unless otherwise specified.
In the following examples, the Cinna cell test system was used for testing the cell performance, the polished zinc foil in the following examples was used as positive electrode and negative electrode, the glass fiber membrane was used as diaphragm, and the electrolyte was 1MZnSO containing cellulose nanocrystalline additive 4 The solution was assembled into a button cell CR2032 in an air atmosphere and tested for electrochemical stability at constant current density and constant time.
Comparative example
2.8756g of zinc sulfate heptahydrate and proper amount of deionized water are fixed in a volumetric flask of 10mL, and are fully dissolved at room temperature to obtain 1MZnSO 4 A solution. With 1MZnSO 4 The solution is electrolyte, zinc foil is an anode and a cathode, a glass fiber membrane is a diaphragm, and the button cell CR2032 is assembled in an air atmosphere for electrochemical stability test.
Example 1
The cellulose nanocrystals (0.0144 g), zinc sulfate heptahydrate (2.8756 g) and a proper amount of deionized water are fixed in a volumetric flask (10 mL), and are fully dissolved at room temperature to obtain the cellulose nanocrystals (0.5 wt.%), 1MZnSO 4 A solution. ZnSO in 0.5wt% cellulose nanocrystals 4 The solution is electrolyte, zinc foil is an anode and a cathode, a glass fiber membrane is a diaphragm, and the button cell CR2032 is assembled in an air atmosphere for electrochemical stability test.
Example 2
The cellulose nanocrystalline 0.2908g, zinc trifluoromethane sulfonate 14.5412g and proper deionized water are fixed in a volumetric flask of 10mL, and are fully dissolved at room temperatureSolution, 4M (CF) of 2.0wt% cellulose nanocrystalline was obtained 3 SO 3 ) 2 Zn solution. (CF) at 2.0wt% cellulose nanocrystals 3 SO 3 ) 2 Zn solution is electrolyte, zinc foil is positive electrode and negative electrode, glass fiber membrane is diaphragm, and CR2032 button cell is assembled in air atmosphere.
Example 3
0.6981g of cellulose nanocrystals, 5.7512g of zinc sulfate heptahydrate, 2.9749g of zinc nitrate hexahydrate and a proper amount of deionized water are fixed in a 10mL volumetric flask, and are fully dissolved at room temperature to obtain a 3M zinc salt mixed solution of 8.0wt% of cellulose nanocrystals. 8.0wt% of zinc salt mixed solution of cellulose nanocrystalline is used as electrolyte, zinc foil is used as an anode and a cathode, a glass fiber membrane is used as a diaphragm, and the CR2032 button cell is assembled in an air atmosphere.
Example 4
0.7417g of cellulose nanocrystals, 2.8756g of zinc sulfate heptahydrate, 1.8177g of zinc trifluoromethane sulfonate, 1.4875g of zinc nitrate hexahydrate and a proper amount of deionized water are fixed in a 10mL volumetric flask, and are fully dissolved at room temperature to obtain a 2M zinc salt mixed solution of 12.0wt% of cellulose nanocrystals. The button cell of CR2032 is assembled in air atmosphere by taking a zinc salt mixed solution of 12.0wt% cellulose nanocrystalline as electrolyte, zinc foil as anode and cathode, and glass fiber membrane as diaphragm.
Example 5
0.3813g cellulose nanocrystals, 0.9088g zinc trifluoromethane sulfonate, 0.7437g zinc nitrate hexahydrate, 0.3408g zinc chloride, 0.5487g zinc acetate and a proper amount of deionized water are fixed in a 10mL volumetric flask, and are fully dissolved at room temperature to obtain a 1M zinc salt mixed solution of 15.0wt% cellulose nanocrystals. The button cell of CR2032 is assembled in air atmosphere by taking 15.0wt% of zinc salt mixed solution of cellulose nanocrystalline as electrolyte, zinc foil as anode and cathode, and glass fiber membrane as diaphragm.
While the invention has been described with reference to the preferred embodiments, it should be understood that the invention is not limited to the embodiments described above, but is intended to cover modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. A high-performance zinc-based aqueous electrolyte is characterized in that: including water, zinc salts, and cellulose nanocrystals.
2. The high-performance zinc-based aqueous electrolyte according to claim 1, wherein: in the electrolyte, the concentration of zinc salt is 0.5-15mol/L.
3. The high-performance zinc-based aqueous electrolyte according to claim 2, wherein: in the electrolyte, the concentration of zinc salt is 3-8mol/L.
4. A high-performance zinc-based aqueous electrolyte according to any one of claims 1 to 3, characterized in that: in the electrolyte, the mass ratio of the cellulose nanocrystalline to the zinc salt is 0.1:100-15:100.
5. The high-performance zinc-based aqueous electrolyte according to claim 4, wherein: in the electrolyte, the mass ratio of the cellulose nanocrystalline to the zinc salt is 5:100-10:100.
6. The high-performance zinc-based aqueous electrolyte according to claim 1, wherein: the zinc salt is one or a combination of any more of zinc sulfate, zinc trifluoromethane sulfonate, zinc nitrate, zinc chloride or zinc acetate.
7. Use of the high-performance zinc-based aqueous electrolyte according to any one of claims 1 to 6 in a zinc ion battery.
8. Use of the high-performance zinc-based aqueous electrolyte according to any one of claims 1 to 6 in zinc ion capacitors.
9. A zinc ion battery comprising the high performance zinc-based aqueous electrolyte of any one of claims 1-6.
10. A zinc ion capacitor comprising the high-performance zinc-based aqueous electrolyte of any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310497779.1A CN116826194A (en) | 2023-05-05 | 2023-05-05 | High-performance zinc-based water-based electrolyte and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310497779.1A CN116826194A (en) | 2023-05-05 | 2023-05-05 | High-performance zinc-based water-based electrolyte and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116826194A true CN116826194A (en) | 2023-09-29 |
Family
ID=88115631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310497779.1A Pending CN116826194A (en) | 2023-05-05 | 2023-05-05 | High-performance zinc-based water-based electrolyte and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116826194A (en) |
-
2023
- 2023-05-05 CN CN202310497779.1A patent/CN116826194A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110416549B (en) | Metal zinc cathode with uniform mesoporous structure coating and preparation method and application thereof | |
| CN111362254A (en) | Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material | |
| CN105870502B (en) | A kind of electrolysis additive and its application | |
| CN111600036A (en) | Three-dimensional porous copper oxide modified copper foil for lithium metal battery current collector and preparation method and application thereof | |
| Liu et al. | Toward long‐life aqueous zinc ion batteries by constructing stable zinc anodes | |
| CN112635698B (en) | Negative pole piece of zinc secondary battery and preparation method and application thereof | |
| CN110790248A (en) | Iron-doped cobalt phosphide microsphere electrode material with flower-like structure and preparation method and application thereof | |
| CN104112871B (en) | For the surface modification method of lithium secondary battery positive active material | |
| CN117080584A (en) | Maltitol-containing aqueous zinc ion electrolyte additive and application thereof | |
| CN105118979B (en) | Lithium titanate material and preparation method thereof, the electrode plates using it, battery | |
| CN116111208A (en) | Aqueous zinc ion battery electrolyte and aqueous zinc ion battery containing same | |
| CN116826194A (en) | High-performance zinc-based water-based electrolyte and application thereof | |
| CN115051047A (en) | Electrolyte additive for water-based zinc ion battery and application thereof | |
| CN114927772A (en) | Electrolyte additive, application thereof, electrolyte and water-based zinc ion battery | |
| KR102549303B1 (en) | Surface treatment method of electrode, surface-treated electrode and Zinc-Manganese dioxide(Zn-MnO2) secondary battery including the same | |
| CN113764830A (en) | Ion selective functional diaphragm and preparation method and application thereof | |
| CN118040093A (en) | Dynamically-protected zinc-based water-based electrolyte and application thereof | |
| Shi et al. | Research progress of interface protective layer materials in zinc anode | |
| CN115275399B (en) | Electrolyte and aqueous zinc ion battery using same | |
| CN114520302B (en) | Aqueous metal battery and modified anode thereof | |
| CN115360356B (en) | Modified lithium cladding structure and preparation method and application thereof | |
| CN115966783A (en) | Aqueous zinc ion battery electrolyte and application thereof | |
| CN116995298A (en) | Lithium metal battery electrolyte capable of improving battery cycle performance and preparation method thereof | |
| CN117458001A (en) | Application of 1-ethyl-3-methylimidazole trifluoromethane sulfonate as electrolyte cosolvent in water-based zinc ion battery | |
| CN117613512A (en) | Rare earth oxide modified glass fiber diaphragm and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |