CN115911592A - Zinc ion battery electrolyte containing carbon dots and preparation method and application thereof - Google Patents
Zinc ion battery electrolyte containing carbon dots and preparation method and application thereof Download PDFInfo
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- CN115911592A CN115911592A CN202211613634.5A CN202211613634A CN115911592A CN 115911592 A CN115911592 A CN 115911592A CN 202211613634 A CN202211613634 A CN 202211613634A CN 115911592 A CN115911592 A CN 115911592A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 120
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 76
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910001868 water Inorganic materials 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 150000003751 zinc Chemical class 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 150000003384 small molecules Chemical class 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- MAGFQRLKWCCTQJ-UHFFFAOYSA-M 4-ethenylbenzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-M 0.000 claims abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 8
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- -1 lithium poly (4-styrenesulfonate) salt Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
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- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011592 zinc chloride Substances 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011701 zinc Substances 0.000 abstract description 82
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 79
- 229910052725 zinc Inorganic materials 0.000 abstract description 74
- 210000001787 dendrite Anatomy 0.000 abstract description 23
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- 239000008151 electrolyte solution Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
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- VCPQWWKLNIMKND-UHFFFAOYSA-L zinc hydroxy sulfate Chemical compound [Zn++].OOS([O-])(=O)=O.OOS([O-])(=O)=O VCPQWWKLNIMKND-UHFFFAOYSA-L 0.000 description 2
- 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 2
- 208000032953 Device battery issue Diseases 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- KSHPUQQHKKJVIO-UHFFFAOYSA-N [Na].[Zn] Chemical compound [Na].[Zn] KSHPUQQHKKJVIO-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a zinc ion battery electrolyte containing carbon dots, a preparation method and application thereof, wherein the electrolyte comprises soluble zinc salt, deionized water, an organic solvent and carbon dots, and the concentration of the carbon dots is 0.2-2.0 g/L; the preparation method of the carbon dots comprises the following steps: dissolving lithium poly (4-styrenesulfonate) and citric acid in water to obtain a mixed solution; evaporating the solvent of the mixed solution with water until dry powder is obtained; reacting the powder under the protection of inert atmosphere, wherein the reaction temperature is 180-240 ℃; after the reaction is finished, dissolving the mixture in water, and dialyzing to remove small molecules and ions; then freeze-drying the solution from which the small molecules and ions are removed to obtain the carbon dots; the electrolyte can effectively inhibit the generation of zinc dendrites and improve the rate capability and cycle performance of the zinc ion battery.
Description
Technical Field
The invention relates to the technical field of zinc ion batteries, in particular to a zinc ion battery electrolyte containing carbon points and a preparation method and application thereof.
Background
People's day of fossil energy shortage and environmental pollutionThe method has the advantages of greatly stimulating the exploration of sustainable energy integration. Although lithium ion batteries have become the main energy storage technology for portable electronic products and mobile electric vehicles, the application of large-scale energy storage is hindered by the long-standing potential safety problem and insufficient lithium resources. Rechargeable aqueous zinc batteries are considered to be a promising alternative due to their inherent safety, low cost and simple technology. Furthermore, high capacity (820 mAh/g and 5855 Ah/cm) 3 ) The advantages of low equilibrium potential (-0.762V vs SHE), high ionic conductivity (> 1S/m) and the like make the material stand out in an energy storage system.
However, poor cycling stability and fast capacity fade due to parasitic reactions, dendrite growth and dead zinc still hinder further development of zinc-ion batteries. Zn 2+ Poor Hydrogen Evolution Reactions (HER) from the decomposition of active water in the solvolysis layer may affect the Zn deposition process, leading to porous electrode deposition morphology and initiating Zn corrosion, producing OH - Which in turn leads to localized deposition of insulation byproducts. Most disconcerting is that uncontrolled growth of dendrites due to non-uniform charge concentration and fewer nucleation sites will increase the contact exposure of the zinc anode and electrolyte quality inspection, which inevitably exacerbates parasitic reactions, producing inactive "dead zinc", which can seriously affect the cycling stability of the zinc electrode. Therefore, reducing water activity and homogenizing nucleation sites are of great significance for building a robust electrode/electrolyte interface.
In order to solve the above problems, researchers try to improve the cycle stability of the zinc negative electrode by inhibiting the growth of dendrites through methods such as zinc surface coating, electrolyte optimization, current collector modification, and novel separator development. The electrolyte is used as an important component of the battery, and other components provide a migration path of zinc ions to determine the electrochemical window of the system. The optimization of the electrolyte composition has significant application advantages: and (1) the operation is simple. Because the water system electrolyte is stable in the air, the additive can be directly added in the atmospheric environment; and (2) the cost is low. The content of the required additives is generally very small, the sources are wide, and the selectivity is strong; and (3) the effect is obvious. The additive is regarded as 'vitamin' in the electrolyte, although the content is small, the effect is not negligible, and the additive has a great improvement effect on the cycle performance of the battery.
Therefore, it is one of the keys to construct a high-performance zinc ion battery by developing an electrolyte capable of simultaneously suppressing dendrite growth and interfacial side reactions.
However, the current modification of the electrolyte of the zinc ion battery has no obvious improvement effect on improving the cycling stability of the zinc anode, and cannot meet the requirement of practical application.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides the zinc ion battery electrolyte, the electrolyte contains specific carbon points as additives, the carbon points and zinc ions have stronger interaction and can be preferentially adsorbed on the surface of an electrode to serve as nucleation sites, so that the nucleation overpotential is effectively reduced, the uniform zinc deposition is guided, and the growth of dendritic crystals is inhibited; and the electronegative functional group on the surface of the carbon dot can form a hydrogen bond network with a solvent to inhibit a side reaction in which water participates, so that the rate capability and the cycle performance of the zinc ion battery are improved.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a zinc ion battery electrolyte containing carbon dots comprises soluble zinc salt, deionized water, an organic solvent and carbon dots, wherein the concentration of the carbon dots is 0.2-2.0 g/L; the preparation method of the carbon dots comprises the following steps:
s1, dissolving lithium poly (4-styrenesulfonate) and citric acid in water to obtain a mixed solution;
s2, gasifying the solvent water of the mixed solution until dry powder is obtained;
s3, reacting the powder under the protection of inert atmosphere, wherein the reaction temperature is 180-240 ℃;
s4, after the reaction is finished, dissolving the mixture in water, and dialyzing to remove small molecules and ions; and then freeze-drying after removing small molecules and ions to obtain the carbon dots.
In some embodiments, the mass ratio of the lithium poly (4-styrenesulfonate) salt to citric acid is 1:1.5 to 3; preferably, the mass ratio of the two is 1:2.
in some embodiments, the reaction temperature is 200 to 220 ℃ and the reaction time is 2 to 4 hours; preferably, the reaction temperature is 200 and the reaction time is 2h.
In some embodiments, the soluble zinc salt is present at a concentration of 0.5 to 5mol/L.
In some embodiments, in step S2, the drying temperature is 100 ℃ and the drying time is 24h.
In some embodiments, the method for preparing the carbon dots comprises the steps of:
s1, dissolving lithium salt of poly (4-styrene sulfonate) and citric acid in water to obtain a mixed solution;
s2, gasifying the solvent water of the mixed solution until dry powder is obtained;
s3, reacting the powder under the protection of inert atmosphere, wherein the reaction temperature is 180-240 ℃;
s4, after the reaction is finished, dissolving the mixture in water, and dialyzing the mixture in a dialysis bag for 2-5 d to remove small molecules and ions; and then, freeze-drying the solution from which the small molecules and ions are removed to obtain the carbon dots.
In some embodiments, the concentration of the soluble zinc salt is 0.5 to 5mol/L.
In some embodiments, the volume ratio of the deionized water to the organic solvent is 8:2.
in some embodiments, the soluble zinc salt is at least one of zinc sulfate, zinc chloride, zinc triflate, zinc nitrate.
In some embodiments, the organic solvent is one of acetone, ethanol, dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, acetonitrile, and ethylene carbonate.
The invention also provides a preparation method of the zinc ion battery electrolyte, which comprises the following steps:
and uniformly mixing the soluble zinc salt, deionized water, an organic solvent and carbon dots to obtain the zinc ion battery electrolyte.
The invention also provides a zinc ion battery, which comprises the zinc ion battery electrolyte of any one of the embodiments.
In some embodiments, the zinc-ion battery further comprises a cathode, an anode, and a separator.
In some embodiments, the positive electrode includes a positive active material that is manganese dioxide and/or sodium vanadate.
In some embodiments, the positive electrode further comprises a current collector; mixing the positive active material, a binder and a conductive agent to prepare positive slurry, and coating the positive slurry on the surface of the current collector to prepare the positive electrode; the negative electrode is zinc foil; the diaphragm is made of glass fiber.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the specific soluble carbon points are added into the electrolyte of the zinc ion battery, so that the effect of regulating the electrolyte to stabilize the zinc cathode is achieved; wherein, the carbon dots are novel zero-dimensional nano materials, the surfaces of the carbon dots contain rich zinc-philic oxygen-containing functional groups (zinc-philic hydroxyl, carboxyl and sulfonic group), the carbon dots can be preferentially adsorbed on the surface of a zinc cathode under the action of an electric field, and the electronegative carbon dots can repel SO through electrostatic action 4 2- Due to the reconstruction of a hydrogen bond network, the direct contact between free water and a zinc cathode can be reduced, so that the hydrogen evolution reaction and the corrosion reaction which are participated by water are inhibited; meanwhile, the carbon points in the electrolyte can reduce the over potential and interface impedance of nucleation by virtue of stronger binding energy of the carbon points and zinc ions, improve reaction kinetics, and can be used as nucleation sites to continuously adjust zinc ion flow to guide the zinc ions to be uniformly deposited on the surface of the zinc cathode, thereby effectively inhibiting the generation of zinc dendrites or dendrites. The electrolyte modified by specific carbon points greatly enhances the cycling stability of the zinc cathode, and further obviously improves the rate capability and the cycling performance of the water system zinc ion battery.
Compared with the common zinc salt electrolyte, the electrolyte provided by the invention has higher conductivity, promotes charge transfer of zinc ions, effectively inhibits the dissolution of a positive electrode material, reduces the corrosion and hydrogen evolution rate of a zinc negative electrode, effectively inhibits the formation and growth of zinc dendrites, and greatly improves the safety performance and cycle performance of a zinc ion battery. In addition, the electrolyte can prolong the service life of the zinc ion battery under the condition of ensuring the use safety of the zinc ion battery, so that the zinc ion battery meets the technical requirement of electrochemical energy storage, and has wide application prospect.
In addition, the carbon dots provided by the invention have the advantages of easily available raw materials, low cost, low toxicity, safety, simple preparation method, small addition amount and obvious effect.
Drawings
FIG. 1 is a transmission electron micrograph (a) of a carbon dot obtained in example 1 of the present invention, and an infrared spectrum (b) of the carbon dot; (c) Graphs (d) are Zeta potential for different solutions and ionic conductivity for different electrolytes, respectively;
in fig. 2, (a) is a scanning electron microscope image of a zinc negative electrode of a zinc symmetrical battery using the reference electrolyte obtained in comparative example 1 as an electrolyte in application example 1 after different cycles of charge and discharge cycles; (b) The figure is a scanning electron microscope image of a zinc negative electrode of a zinc symmetrical battery which adopts the electrolyte obtained in the embodiment 2 as the electrolyte in the application example 1 after different circles of charge and discharge cycles;
fig. 3 (a) is a tafel plot of a zinc negative electrode after cycling in a zinc symmetric battery using the control electrolyte in comparative example 1 and the electrolyte 1 in example 2 as electrolytes, respectively, in application example 1; (b) The figure is an XRD spectrogram of a zinc cathode of the zinc symmetric battery after 100 cycles of charge-discharge cycle; (c) The graph shows the LSV curve (c) in the voltage range of-2.0-1.0V; (d) the graph is an LSV curve under the voltage range of 1.5-2.5V;
FIG. 4 is a graph (a) and a graph (b) of 1mAcm for an aqueous zinc ion symmetric battery using the comparative electrolyte in comparative example 1 and the electrolyte 1 in example 2 as electrolytes in application example 2, respectively -2 And 5mAcm -2 Voltage-time curve at current density of (a); (c) is an alternating current impedance diagram before the zinc symmetrical battery is cycled; (d) The sum is shown at 1.0mAcm -2 Nucleation overpotential at current density;
fig. 5 is a graph (a) and a graph (b) showing voltage-time curves at different current densities for an aqueous zinc ion symmetric battery using the comparative electrolyte in comparative example 1 and the electrolyte 1 in example 2 as electrolytes in application example 2, respectively;
fig. 6 is a graph showing cycle performance at 2A/g and 5A/g current density of an aqueous zinc ion battery of application example 2 using the control electrolyte of comparative example 1 and the first electrolyte of example 2 as the electrolyte;
fig. 7 is a rate performance curve obtained by performing charge and discharge cycles under different conditions in an aqueous zinc-ion battery using the comparative electrolyte in comparative example 1 and the electrolyte 1 in example 2 as electrolytes, respectively, in application example 2.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms than those specifically described herein, and it will be apparent to those skilled in the art that many more modifications are possible without departing from the spirit and scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the following examples, unless otherwise specified, all the means used are conventional in the art.
The terms "comprises," "comprising," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental raw materials used in the examples of the present invention are all commercially available products.
Example 1
A preparation method of carbon dots specifically comprises the following steps:
p1, preparation of a dispersion liquid:
dissolving 1.921g of lithium poly (4-styrenesulfonate) salt and 3.842g of citric acid in 100mL of water, stirring at room temperature for 30min, and then performing ultrasonic treatment for 15min to obtain a uniform mixed solution;
p2, solvent gasification:
putting the mixed solution into an oven at 100 ℃ to gasify the solvent water until dry powder is obtained, taking out the powder, and naturally cooling the powder to room temperature;
p3, high-temperature pyrolysis:
putting the cooled product in a tubular furnace for pyrolysis under the protection of argon atmosphere, wherein the reaction temperature is 200 ℃; the reaction time is 2h; naturally cooling to room temperature after reaction;
p4, dialysis:
dissolving the solid obtained in the step P3 in solvent water, and putting the obtained solution into a dialysis bag for dialysis for 3d;
p5, freeze drying:
and D, putting the solution obtained in the step P4 into a refrigerator to be frozen into ice, and then putting the ice into a freeze dryer to be dried for 3d to finally obtain the light yellow fluffy carbon dots.
Taking a proper amount of the carbon dots obtained in the embodiment, adding a proper amount of absolute ethyl alcohol, performing ultrasonic treatment for 30min to prepare a transmission sample, and observing a microstructure, wherein the result is shown in a (a) diagram of fig. 1; as can be seen from the graph (a) of fig. 1, the carbon dots are uniformly dispersed and the particle size is below 10nm, indicating that the carbon dots have been successfully prepared.
The obtained infrared spectrum of the carbon point is shown in FIG. 1 (b); as can be seen from fig. 1 (b), the carbon dots contain rich oxygen-containing functional groups (zinc-philic hydroxyl, carboxyl and sulfonic), can be used as nucleation sites to capture zinc ions in the electrolyte, reduce nucleation overpotential, and induce uniform nucleation of zinc, so as to realize tight deposition of zinc and inhibit dendritic crystal generation.
As can be seen from the graph (c) of fig. 1, which shows the Zeta potential of the carbon dot in aqueous solution of-28.8 mV, the carbon dot surface is electronegative and thus can bind with positively charged zinc ions; the carbon dots are added into zinc sulfate electrolyte to find that the Zeta potential is positive shifted, and the surface carbon dots adsorb zinc ions.
As shown in fig. 1 (d), the ion conductivity of different electrolytes is shown, and it can be seen from fig. 1 (d), as the content of the organic solvent Dimethylformamide (DMF) is gradually increased, the ion conductivity of the electrolyte is gradually reduced, because the introduction of the organic solvent can be more tightly combined with zinc ions, and the solvation structure of the zinc ions is changed, which is not beneficial to the migration of the zinc ions. It is worth noting that after the carbon dots are added, the ionic conductivity of the electrolyte is remarkably improved, because the nano-sized carbon dots can adsorb a large amount of zinc ions to promote zinc ion migration, and oxygen-containing functional groups on the surfaces of the carbon dots can reconstruct a hydrogen bond network with a solvent to inhibit the formation of zinc ion-solvent clusters.
Example 2
Preparing electrolyte:
25mg of carbon dots and 28.75g of zinc sulfate heptahydrate are weighed out and dissolved in a suitable amount of solvent (V) H2O :V DMF = 8:2), the solution was completely dissolved by stirring for 20min, and then transferred to a 50mL volumetric flask, and the solvent was added to the flask to a constant volume, thereby obtaining an electrolytic solution 1.
Example 3
Preparing electrolyte:
15mg of carbon dots and 18.94g of zinc nitrate were weighed out and dissolved in an appropriate amount of solvent (V) H2O :V DMF = 8:2), the solution was completely dissolved by stirring for 20min, and then transferred to a 50mL volumetric flask, and the solvent was added to the flask to a constant volume, thereby obtaining an electrolytic solution 2.
Comparative example 1
Preparing electrolyte:
28.75g of zinc sulfate heptahydrate are weighed and dissolved in a proper amount of solvent (V) H2O :V DMF = 8:2), stirring for 20min to completely dissolve, transferring to a 50mL volumetric flask, and adding a solvent to a constant volume to obtain a control electrolyte.
Application example 1
Preparing a zinc symmetrical battery:
at room temperature, the electrolyte, the metal zinc foil anode and cathode and the glass fiber diaphragm of the examples 2-3 and the comparative example 1 are respectively used for completing button cell assembly in the air; wherein the zinc foil has a thickness of 50 μm.
Application example 2
Preparing a zinc ion full battery:
button cell assembly was completed in air with the electrolytes of examples 2-3 and comparative example 1, respectively, metal zinc foil negative electrode, sodium vanadate positive electrode, and glass fiber separator at room temperature.
Wherein:
the preparation process of sodium vanadate comprises the following steps:
weigh 0.724g V 2 O 5 And 0.588g of Na 3 C 6 H 5 O 7 ·2H 2 Adding O into 60mL of deionized water, and stirring vigorously for 30min; and then transferring the mixed solution into a reaction kettle, reacting for 48 hours at 160 ℃, naturally cooling to room temperature, washing the product with ethanol and deionized water respectively, and finally drying for 10 hours in a vacuum drying oven at 100 ℃ to obtain the positive electrode material sodium vanadate.
The preparation process of the sodium vanadate anode comprises the following steps:
according to the mass ratio of 7:2:1 weighing 70mg of sodium vanadate, 20mg of SuperP and 10mg of PVDF respectively into an agate mortar, uniformly stirring, then dripping NMP into the mortar, stirring the mixture, grinding the mixture for 5min to uniform slurry, uniformly coating the mixture on the surface of a stainless steel net with the diameter of 12mm by using a scraper, and then putting the stainless steel net into a vacuum drying oven for standing for 12 hours at the temperature of 80 ℃.
Performance test
The prepared symmetrical battery is subjected to cycle performance test by using the Xinwei electrochemical test system, and the current density of the symmetrical battery is 1-10 mA/cm 2 (ii) a The cycle performance of the zinc ion full cell is tested by using a Xinwei electrochemical testing system, and the voltage range of the zinc-sodium vanadate cell is as follows: 0.2-1.5V, and current density of 0.2-5A/g 1 。
After the battery in application example 1 was assembled and left standing for 2 hours, the battery was set at 1mA/cm 2 Current density of 1mAh/cm 2 At capacity of (2), performing charge-discharge cycle, after the cycle, disassembling the button cell, and using waterAnd ethanol cleaning, preparing a sample of the zinc cathode, carrying out scanning electron microscope shooting and XRD test, and carrying out corrosion test on the zinc cathode at a sweep rate of 1mV/s relative to an open circuit potential of-0.3 mV by using a three-electrode test system (zinc foil as a working electrode, stainless steel mesh as a counter electrode and AgCl/Ag as a reference electrode), wherein the results are shown in figures 2-3.
Wherein:
fig. 2 (a) is an SEM photograph of the zinc negative electrode of the coin cell using the comparative electrolyte as the electrolyte in comparative example 1, from which it can be seen that the Zn surface becomes rough after 25 cycles, and a small cavity can be observed; after 50 cycles, there may be more and more dendrites piercing the fiberglass membrane, further causing a large amount of glass fibers to adhere to the Zn anode surface and accumulating partially broken dead zinc; when the cycle times were increased to 100, the formation of dead zinc was further accelerated by crazy growth of dendrites, and as the contact area of the electrolyte with the electrode increased, a large amount of black nonconductive by-products accumulated on the zinc anode surface, indicating severe electrochemical corrosion of the zinc electrode, which could hinder charge transfer and even puncture the separator, leading to poor cycle stability and even cell failure. Fig. 2 (b) is an SEM photograph of a zinc negative electrode of a coin cell using the electrolyte 1 of example 2 as an electrolyte, from which it can be seen that there is almost no zinc dendrite on the Zn deposition layer during the cycle and the surface becomes smoother, indicating that CDs can guide uniform Zn deposition to suppress the growth of dendrite because the sulfonic acid group on the surface of CDs increases the nucleation site. After 50 cycles, the zinc surface can still keep a smooth texture without dendrites. Even after 200 hours of circulation, the deposited zinc plate is parallel to the substrate, the zinc surface is compact and uniform, and no obvious dendrite and by-product are formed. The results of fig. 2 are compared and analyzed, and it can be seen that the carbon dots can effectively inhibit the formation of zinc dendrites as an electrolyte additive, greatly reducing the risk of the dendrites piercing the separator, thereby improving the stability and cycle life of the zinc cathode.
FIG. 3 (a) is a Tafel plot showing the corrosion test results of a zinc negative electrode in a three-electrode system, from which it can be seen that the button cell using the electrolyte 1 of example 2 as the electrolyteThe corrosion rate of the zinc cathode is 0.535mAcm -2 Much lower than the corrosion rate (0.956 mAcm) of the zinc negative electrode of the coin cell using the control electrolyte of comparative example 1 as electrolyte -2 ) As can be seen from the results of comparing and analyzing the graph (a) in fig. 3, the carbon dots can reduce the corrosion rate of the zinc negative electrode and improve the coulomb efficiency of the zinc negative electrode. Fig. 3 (b) is an XRD spectrogram of the zinc cathode after cycling in the coin cell, from which it can be seen that, in the XRD spectrogram of the zinc cathode of the coin cell using the comparative electrolyte in comparative example 1 as the electrolyte, there is a very obvious peak of by-product zinc hydroxy sulfate at about 9 °, in the XRD spectrogram of the zinc cathode of the coin cell using the electrolyte 1 in example 2 as the electrolyte, the intensity of the peak at 9 ° (by-product zinc hydroxy sulfate) is not obvious, and the result of comparing and analyzing fig. 3 (b) shows that electronegative carbon dots can be adsorbed on the surface of the zinc cathode to form an inert protective layer to repel the sulfuric acid more close to the ions, which can effectively inhibit the generation of by-products; and abundant oxygen-containing functional groups can be used for reconstructing a hydrogen bond network with a solvent to inhibit the reaction activity of water, so that the cycle life of the zinc cathode is prolonged. Linear Sweep Voltammetry (LSV) further revealed the inhibitory effect of interfacial adsorbed functional CDs on HER. To avoid interference of the zinc deposition reaction, 1mol L of zinc is used -1 Na 2 SO 4 Substituted by 2mol L -1 ZnSO 4 And (3) an electrolyte. As shown in the graph (c) of fig. 3, the increase rate of the cathodic current density of the electrolyte 1 in example 2 is much slower than that of the control electrolyte in comparative example 1, and there is a larger overpotential, further indicating that CDs can reduce HER activity. At the same time, LSV scan curves of 1.5-2.5V were also tested (see FIG. 3 (d) for results). It is thus seen that the addition of CDs can inhibit the decomposition of water, reduce the current density and thus broaden the voltage window of the electrolyte.
In conclusion, the carbon dots contain rich oxygen-containing functional groups and can coordinate with zinc ions, so that the zinc ion flow is adjusted, and the uniform deposition of zinc is guided; meanwhile, the carbon dots can be adsorbed on the surface of the zinc cathode to form a functional protective layer, so that direct contact between water and the zinc cathode is reduced, the stability of the zinc cathode is improved, and the cycle life of the zinc cathode is greatly prolonged.
The water-based zinc ion symmetrical battery is assembled by respectively adopting the electrolyte 1 in the application example 2 and the control electrolyte in the comparative example 1 as electrolytes, 50-micron zinc foils as positive and negative electrodes, glass fibers as a diaphragm and a CR2016 type battery case in the application example 2, and the electrochemical test is carried out after the assembly is finished and the battery is kept still for 2 hours.
At 1mA/cm 2 Current density of 1mAh/cm 2 The voltage-time curve obtained by performing a charge-discharge cycle at the capacity of (a) is shown in fig. 4. As can be seen from the graph (a) of fig. 4, in the aqueous zinc ion symmetric cell using the control electrolyte of comparative example 1 as the electrolyte, after 500h of cycling, the polarization of the zinc negative electrode increases due to severe interfacial side reactions and zinc dendrite formation, and after 800h of cycling, the continued dendrite growth causes the separator to be pierced, resulting in cell failure; the water-based zinc ion symmetric battery using the electrolyte 1 in the embodiment 2 as the electrolyte can stably circulate for more than 4000 hours, which shows that dendrites and side reactions can be reduced under the action of carbon points, so that the circulation stability of the zinc cathode is greatly improved, and the circulation life is prolonged; further, as shown in FIG. 4 (b), the concentration of the compound is 5mA/cm 2 High current density and 5mAh cm -2 The water-based zinc ion symmetrical battery using the electrolyte 1 in the embodiment 2 as the electrolyte can still continuously and stably work for more than 1000 hours under the high area capacity, is obviously superior to the cycle life of the water-based zinc ion symmetrical battery using the comparison electrolyte in the comparison embodiment 1 as the electrolyte, and has lower polarization potential.
FIG. 4 (c) is an AC impedance diagram before the circulation of the zinc symmetrical battery, and it can be seen from the diagram of FIG. 4 (c) that the charge transfer resistance of the water-based zinc ion symmetrical battery using the electrolyte 1 in the example 2 as the electrolyte is significantly lower than that of the water-based zinc ion symmetrical battery using the comparative electrolyte in the comparative example 1, indicating that the addition of carbon dots can reduce the interfacial impedance and increase the Zn 2+ The conductivity of the electrolyte is beneficial to improving the interface reaction kinetics, thereby improving the electrochemical performance of the battery. FIG. 4 (d) is a graph of a symmetrical cell at 1mA/cm 2 The voltage-time curve under current, as can be seen from the graph (d) of FIG. 4, the nucleation overpotential of the electrolyte solution 1 in example 2 is only 38.8mV compared with the comparative electrolyte in comparative example 1, the electrolyte shows a large initial nucleation overpotential of 52.5mV, and the surface carbon dots and zinc ions have stronger interaction and can be used as nucleation sites to anchor the zinc ions and guide uniform zinc deposition to inhibit dendritic crystal growth.
At 1-10mAcm -2 The charge-discharge cycle was performed at the current density of (a), and the voltage-time curve obtained is shown in fig. 5. As can be seen from the graph (a) of fig. 5, in the aqueous zinc ion symmetric battery using the electrolyte solution 1 in example 2 as the electrolyte solution, the polarization potential of the zinc negative electrode gradually increases with the gradual increase of the current density, and the polarization potentials are all lower than the polarization potential of the zinc negative electrode in the aqueous zinc ion symmetric battery using the control electrolyte solution in comparative example 1 as the electrolyte solution.
Most importantly, as shown in FIG. 5 (a), when the current density returns to 2mA cm -2 The aqueous zinc ion symmetric battery using the electrolyte 1 of example 2 as an electrolyte can still normally operate for more than 400 hours, while the aqueous zinc ion symmetric battery using the control electrolyte without carbon dots of comparative example 1 as an electrolyte can be short-circuited after 160 hours of cycle to cause battery failure (as shown in (b) of fig. 5), which is caused by large interfacial resistance and severe zinc dendrite growth, which indicates that the aqueous zinc ion symmetric battery using the electrolyte 1 of example 2 as an electrolyte has more excellent rate capability and can be applied to different conditions.
The cycle performance obtained by performing charge-discharge cycles at a voltage interval of 0.2-1.5V and a current density of 2A/g is shown in FIG. 6 (a). As can be seen from the graph (a) of fig. 6, the aqueous zinc ion full cell using the electrolyte 1 in the example 2 as the electrolyte still has a specific discharge capacity of 187.8mAh/g after 1000 cycles, and the capacity retention rate is 77.3%, whereas the aqueous zinc ion full cell using the control electrolyte without carbon dots in the comparative example 1 as the electrolyte has a specific discharge capacity of only 147.8mAh/g and a capacity retention rate of only 61.3% after 1000 cycles, which is because the coulomb efficiency of the zinc cathode is reduced due to the complex side reaction of the zinc cathode and the formation of dendrites, thereby causing the discharge capacity of the full cell to be rapidly attenuated. As can be seen from the diagram (b) of figure 6,the aqueous zinc ion full cell prepared by using the electrolyte 1 of the example 2 as an electrolyte at a current density of 5A/g still has 119.2mAh g after 5000 cycles of circulation -1 The discharge specific capacity of the electrolyte is 95.8mAh g, and the capacity of the water-system zinc ion full battery prepared by taking the reference electrolyte of the comparative example 1 as the electrolyte is only 95.8mAh g after 4500 cycles of circulation -1 And the battery fails due to the continuous growth of dendrites.
The multiplying power performance curve obtained by performing charge-discharge circulation under the conditions that the voltage interval is 0.2-1.5V and the current density is 0.2-4A/g is shown in figure 7. As can be seen from fig. 7, as the current density gradually increased, the capacity of the aqueous zinc ion full cell using the control electrolyte without carbon dots in comparative example 1 as the electrolyte rapidly declined, the capacity declined to 91.1mAh/g at a current density of 4A/g, and when the current density returned to 0.5A/g, the capacity was only 257.2mAh/g; the aqueous zinc ion symmetric battery using the electrolyte 1 in the embodiment 2 as the electrolyte still has a discharge specific capacity of 128.8mAh/g at a current density of 4A/g, and still has a capacity as high as 274.5mAh/g at a current density of 0.5A/g, because the carbon dots can inhibit the growth of dendrites and relieve the interface side reaction, the cycling stability of the zinc cathode is improved, and the purpose of improving the full-electric power of Chi Xing is achieved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The zinc ion battery electrolyte containing the carbon dots is characterized by comprising soluble zinc salt, deionized water, an organic solvent and the carbon dots, wherein the concentration of the carbon dots is 0.2-2.0 g/L; the preparation method of the carbon dots comprises the following steps:
s1, dissolving lithium poly (4-styrenesulfonate) and citric acid in water to obtain a mixed solution;
s2, gasifying the solvent water of the mixed solution until dry powder is obtained;
s3, reacting the powder under the protection of inert atmosphere, wherein the reaction temperature is 180-240 ℃;
s4, after the reaction is finished, dissolving the mixture in water, and dialyzing to remove small molecules and ions; and then freeze-drying the solution from which the small molecules and ions are removed to obtain the carbon dots.
2. The carbon dot-containing zinc ion battery electrolyte of claim 1, wherein the mass ratio of the lithium poly (4-styrenesulfonate) salt to citric acid is 1:1.5 to 3.
3. The electrolyte for zinc-ion batteries containing carbon dots according to claim 1, characterized in that the reaction temperature is 200-220 ℃ and the reaction time is 2-4 h.
4. The carbon dot containing zinc ion battery electrolyte of any one of claims 1-3, wherein the concentration of the soluble zinc salt is 0.5 to 5mol/L.
5. The carbon dot containing zinc ion battery electrolyte of any one of claims 1-3, wherein the volume ratio of the deionized water to the organic solvent is 8:2.
6. the carbon dot containing zinc ion battery electrolyte of any one of claims 1-3, wherein the soluble zinc salt is at least one of zinc sulfate, zinc chloride, zinc triflate, zinc nitrate; and/or the organic solvent is one of acetone, ethanol, dimethylformamide, N-methyl pyrrolidone, dimethyl sulfoxide, acetonitrile and ethylene carbonate.
7. The method of making the carbonaceous zinc ion battery electrolyte of claims 1-6 comprising the steps of:
and uniformly mixing the soluble zinc salt, deionized water, an organic solvent and carbon dots to obtain the zinc ion battery electrolyte.
8. A zinc ion battery comprising the electrolyte of any one of claims 1 to 7.
9. The zinc-ion battery of claim 8, further comprising a positive electrode, a negative electrode, and a separator.
10. The zinc-ion battery of claim 9, wherein the positive electrode comprises a positive active material that is manganese dioxide and/or sodium vanadate.
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| CN111509306A (en) * | 2020-04-26 | 2020-08-07 | 河北大学 | Electrolyte for rechargeable zinc ion battery, preparation method of electrolyte and rechargeable zinc ion battery |
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| CN111509306A (en) * | 2020-04-26 | 2020-08-07 | 河北大学 | Electrolyte for rechargeable zinc ion battery, preparation method of electrolyte and rechargeable zinc ion battery |
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