CN114039109B - Additive for aqueous zinc ion battery electrolyte, aqueous zinc ion battery electrolyte and aqueous zinc ion battery - Google Patents
Additive for aqueous zinc ion battery electrolyte, aqueous zinc ion battery electrolyte and aqueous zinc ion battery Download PDFInfo
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- H—ELECTRICITY
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- H—ELECTRICITY
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses an additive for an aqueous zinc ion battery electrolyte, the aqueous zinc ion battery electrolyte and an aqueous zinc ion battery. The additive for the aqueous zinc ion battery electrolyte is water-soluble chitosan; the mass of the additive accounts for 0.1-10% of the total mass of the electrolyte. The additive provided by the invention can improve the interface environment between the electrolyte and the zinc cathode in the electrolyte, induce the ion concentration and electric field to be uniformly distributed near the zinc cathode, and effectively solve the problems of zinc dendrite, zinc corrosion and passivation of the zinc cathode, thereby improving the multiplying power performance and the cycle performance of the water-based zinc ion battery. In addition, the source of the additive provided by the invention is wide and environment-friendly.
Description
Technical Field
The invention relates to the field of aqueous zinc ion batteries, in particular to an additive for aqueous zinc ion battery electrolyte, aqueous zinc ion battery electrolyte and aqueous zinc ion battery.
Background
As an emerging energy storage battery, the water-based zinc ion battery has the advantages of high safety, low cost, environmental friendliness, high energy density, easiness in manufacturing and the like, and has wide application prospects in the fields of large-scale energy storage, wearable products and the like. However, the conventional aqueous electrolyte (zinc salt aqueous solution) adopted by the water-based zinc ion battery has the problem that zinc ion deposition/dissolution dynamic behaviors are not uniform and controllable, and uneven distribution of an electric field at one side of a zinc cathode can be caused, so that zinc dendrite formation and growth are caused. Meanwhile, a large amount of free flowing water exists in the traditional aqueous electrolyte, which can cause electrochemical side reaction and uncontrollable solid-liquid interface reaction on the surface of the zinc negative electrode, so that the passivation of the zinc negative electrode is caused, and the risk of corrosion of the zinc negative electrode can be increased. The problem of the zinc cathode can cause the reduction of coulomb efficiency and the excessively rapid capacity decay of the water-based zinc ion battery in the charge and discharge process, thereby influencing the multiplying power performance and the cycle performance of the battery, and severely restricting the development and the commercial application of the water-based zinc ion battery.
In order to solve the problems of dendrite, corrosion, passivation and other zinc cathodes, researchers have conducted a great deal of research work, mainly comprising two strategies of surface modification and electrolyte optimization of the zinc cathode. The surface modification of the zinc cathode mainly prevents the surface of the zinc cathode from being directly exposed in the electrolyte by establishing a buffer layer, thereby blocking the direct contact between the zinc cathode and the electrolyte and reducing the local exchange current density so as to promote the uniform deposition of zinc ions. However, the buffer layer often has non-uniformity problem, and can not completely isolate infiltration of electrolyte; in the reciprocating zinc deposition/stripping process, the volume of zinc metal is continuously changed, so that the buffer layer is gradually fallen off or damaged due to the fact that the buffer layer cannot bear the long-time volume change, and the protection effect of the zinc cathode is lost. From the practical point of view, electrolyte optimization is a simple, effective and easily implemented method of inhibiting dendrite formation and growth. The most common means of electrolyte optimization is the introduction of electrolyte additives. The electrolyte additive commonly used at present is mainly an organic polymer electrolyte additive, can be selectively adsorbed at a zinc deposition site, induces the ion concentration and the electric field near a zinc cathode to be uniformly distributed, further improves the interface environment between the zinc cathode and the electrolyte, avoids overgrowth of zinc dendrites, and can reduce corrosion and passivation of the zinc cathode. However, the traditional organic polymer electrolyte additive has high cost, and has potential safety hazards such as inflammability, toxicity and the like, so that the practical application of the additive in the field of large-scale energy storage is limited. Therefore, development of an electrolyte additive for an environment-friendly aqueous zinc ion battery is one of the current research hotspots.
The water-soluble chitosan is a chitosan derivative prepared by the chemical modification reaction of chitosan, and has good solubility and thickening property. The electrolyte additive can reduce the activity of free water in the water-based electrolyte, and effectively inhibit electrochemical side reactions and uncontrollable solid-liquid interface reactions on the surface of the zinc negative electrode, thereby relieving the problems of zinc corrosion and zinc negative electrode passivation. Meanwhile, the molecular chain of the water-soluble chitosan also contains a large number of hydroxyl and amine functional groups, and the functional groups have certain complexing capacity with zinc ions, so that the uniform distribution of the concentration of ions and an electric field near the zinc cathode is expected to be induced by the complexing action between the water-soluble chitosan and the zinc ions, so that the zinc ions are uniformly deposited and dissolved out on the surface of the zinc cathode, and the growth of zinc dendrites is effectively inhibited. In addition, the water-soluble chitosan has wide sources, low price, environmental protection and large-scale production, and has important significance for constructing the water-based zinc ion battery with high performance and low cost.
Disclosure of Invention
Aiming at the defects of the prior art, the primary aim of the invention is to provide an additive for the electrolyte of the water system zinc ion battery, which has low cost, safety, environmental protection and easy scale preparation, can effectively inhibit the growth of zinc dendrites, effectively solve the problems of zinc corrosion, passivation of zinc cathode and the like, and has great significance in improving the electrochemical performance, stability and commercial application potential of the water system zinc ion battery.
Another object of the present invention is to provide an aqueous zinc-ion battery electrolyte capable of improving the rate performance and cycle performance of an aqueous zinc-ion battery.
It is still another object of the present invention to provide an aqueous zinc-ion battery which is superior in rate performance and cycle performance.
The invention aims at realizing the following technical scheme:
an additive for an aqueous zinc ion battery electrolyte, characterized in that the additive is water-soluble chitosan; the mass of the additive accounts for 0.1-10% of the total mass of the electrolyte.
The mass fraction of the additive accounting for the total mass of the electrolyte is preferably 1-6%.
The water-soluble chitosan comprises one or more of chitosan quaternary ammonium salt, chitosan hydrochloride, chitosan sulfate, chitosan nitrate, chitosan lactate and chitosan acetate.
The water-soluble chitosan is preferably at least one of chitosan quaternary ammonium salt, chitosan hydrochloride, chitosan sulfate and chitosan lactate.
The aqueous zinc ion battery electrolyte is characterized by comprising zinc salt, manganese salt, water and the additive for the aqueous zinc ion battery electrolyte.
The zinc salt comprises one or more of zinc sulfate, zinc bromide, zinc nitrate, zinc chloride and zinc triflate; the concentration of zinc salt is 0.2-12 mol/L.
The zinc salt is preferably zinc sulfate or zinc chloride; the concentration of the zinc salt is preferably 1-8 mol/L.
The manganese salt comprises one or more of manganese sulfate, manganese bromide, manganese nitrate, manganese chloride and manganese triflate; the concentration of the manganese salt is 0.01-3.5 mol/L.
The manganese salt is preferably manganese sulfate and manganese chloride; the concentration of the manganese salt is preferably 0.1 to 2.5mol/L.
The pH value of the aqueous zinc ion battery electrolyte is 3-7.
The pH value of the aqueous zinc ion battery electrolyte is preferably 4-6.
The invention also provides a water-based zinc ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and the water-based zinc ion battery electrolyte.
The mechanism of the invention is as follows:
the invention uses water-soluble chitosan as electrolyte additive to be applied to water-based zinc ion battery, which can effectively solve the problems of zinc dendrite, zinc corrosion and zinc cathode passivation, thereby remarkably improving the multiplying power performance and cycle performance of the battery. The water-soluble chitosan molecule contains a large number of hydroxyl and amine functional groups, the functional groups have certain complexing capacity on zinc ions in the electrolyte, and the complexing action between the hydroxyl and amine functional groups can be utilized to induce the uniform distribution of the concentration of ions and the electric field near the zinc cathode, so that the uniform deposition and dissolution of the zinc ions on the surface of the zinc cathode can be effectively regulated, and the formation and growth of zinc dendrites can be inhibited. In addition, the water-soluble chitosan has the physical characteristic of thickening, can reduce the activity of free water in electrolyte, and reduce electrochemical side reactions and uncontrollable solid-liquid interface reactions on the surface of a zinc negative electrode, thereby effectively solving the problems of zinc corrosion, passivation of the zinc negative electrode and the like.
Compared with the prior art, the invention has the following advantages:
the electrolyte additive provided by the invention is beneficial to improving the interface environment between the electrolyte and the zinc cathode, and promoting the uniform deposition and dissolution of zinc ions on the surface of the zinc cathode, thereby effectively inhibiting the formation and overgrowth of zinc dendrites; the electrolyte additive has good water solubility and thickening property, can reduce the activity of free water in the electrolyte, and inhibit the occurrence of side reactions on the surface of the zinc negative electrode, thereby effectively relieving the corrosion and passivation of the zinc negative electrode; therefore, the electrolyte of the aqueous zinc ion battery electrolyte additive provided by the invention can obviously improve the rate performance and the cycle performance of the aqueous zinc ion battery. In addition, the electrolyte additive provided by the invention is low in price, wide in source and environment-friendly, and is favorable for developing the water-based zinc ion battery electrolyte and the water-based zinc ion battery with excellent performance, safety, environment friendliness and low cost.
Drawings
Fig. 1 (a) and (b) are graphs of the rate performance and cycle performance of aqueous zinc ion batteries using the test electrolyte and the reference electrolyte, respectively, of example 1.
Fig. 2 (a) and (b) are graphs of the rate performance and cycle performance of aqueous zinc ion batteries using the test electrolyte and the reference electrolyte, respectively, of example 2.
Fig. 3 (a) and (b) are graphs of the rate performance and cycle performance of aqueous zinc ion batteries using the test electrolyte and the reference electrolyte, respectively, of example 3.
Fig. 4 (a) and (b) are graphs of the rate performance and cycle performance of aqueous zinc ion batteries using the test electrolyte and the reference electrolyte, respectively, of example 4.
Fig. 5 (a) and (b) are graphs of rate performance and cycle performance of aqueous zinc ion batteries using the test electrolyte and the reference electrolyte of comparative example 1, respectively.
Fig. 6 (a) and (b) are graphs of rate performance and cycle performance of aqueous zinc ion batteries using the test electrolyte and the reference electrolyte of comparative example 2, respectively.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
Example 1
1. Configuration of test electrolyte and aqueous zinc ion battery assembly based thereon:
sequentially adding 1g of chitosan quaternary ammonium salt and 1g of chitosan hydrochloride into a water phase electrolyte of 2mol/L zinc sulfate and 0.2mol/L manganese sulfate with the total mass of 98g, fully stirring until the chitosan quaternary ammonium salt and the chitosan hydrochloride are completely dissolved, then adjusting the pH value of the mixed aqueous solution to be 4.5, and standing to obtain the water system zinc ion battery electrolyte.
And placing the graphite paper gasket in the positive electrode shell, sequentially placing the positive electrode plate and the diaphragm, dripping electrolyte until the diaphragm is completely wetted, sequentially placing the negative electrode plate (zinc plate), the stainless steel gasket, the elastic sheet and the negative electrode shell, and then placing the negative electrode plate, the stainless steel gasket, the elastic sheet and the negative electrode shell in a static press for static pressure sealing to obtain the water-based zinc ion battery.
2. Configuration of reference electrolyte and aqueous zinc ion battery assembly based thereon:
sequentially adding zinc sulfate and manganese sulfate into deionized water, fully stirring until the zinc sulfate and the manganese sulfate are completely dissolved, preparing a 2mol/L zinc sulfate and 0.2mol/L manganese sulfate aqueous electrolyte with the total mass of 100g, and then adjusting the pH value of the aqueous electrolyte to 4.5 to obtain the reference electrolyte. The assembly process of the aqueous zinc-ion battery using the reference electrolyte is the same as above.
3. Electrochemical performance test:
the water-based zinc ion batteries using the test electrolyte and the reference electrolyte are subjected to multiplying power charge and discharge and constant current charge and discharge tests respectively, the set multiplying power is 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g, and the set constant current density is 1.5A/g.
4. Analysis of results:
as can be seen from the rate performance test of fig. 1 (a), the specific discharge capacities of the aqueous zinc ion battery using the test electrolyte at the current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g are all significantly higher than those of the aqueous zinc ion battery using the reference electrolyte, indicating that the battery using the test electrolyte has excellent rate performance; as can be seen from the cycle performance test of fig. 1 (b), after 2800 times of constant current charge and discharge at a current density of 1.5A/g, the specific discharge capacity of the battery using the test electrolyte was 153.2mAh/g, which is much higher than that of the battery using the reference electrolyte by 48.1mAh/g, and the cycle stability of the battery using the test electrolyte during 2800 times of constant current charge and discharge was significantly higher than that of the battery using the reference electrolyte. This is mainly because the test electrolyte of this example can achieve full coverage of nucleation sites and dendrite-free growth compared to the reference electrolyte. In addition, the activity of free water in the electrolyte is extremely low, and the electrochemical side reaction on the surface of the zinc negative electrode is effectively inhibited, so that the corrosion and passivation of the zinc negative electrode are relieved. Therefore, the aqueous zinc ion battery using the test electrolyte has excellent rate performance and cycle performance.
Example 2
1. Configuration of test electrolyte and aqueous zinc ion battery assembly based thereon:
adding 1g of chitosan lactate, 1g of chitosan sulfate and 3g of chitosan hydrochloride into an aqueous electrolyte with the total mass of 95g of 2mol/L zinc chloride, 1mol/L zinc sulfate, 0.3mol/L manganese chloride and 0.5mol/L manganese sulfate, fully stirring until the chitosan lactate, the chitosan sulfate and the chitosan hydrochloride are completely dissolved, then adjusting the pH value of the mixed aqueous solution to be 5.0, and standing to obtain the aqueous zinc ion battery electrolyte.
And placing the graphite paper gasket in the positive electrode shell, sequentially placing the positive electrode plate and the diaphragm, dripping electrolyte until the diaphragm is completely wetted, sequentially placing the negative electrode plate (zinc plate), the stainless steel gasket, the elastic sheet and the negative electrode shell, and then placing the negative electrode plate, the stainless steel gasket, the elastic sheet and the negative electrode shell in a static press for static pressure sealing to obtain the water-based zinc ion battery.
2. Configuration of reference electrolyte and aqueous zinc ion battery assembly based thereon:
sequentially adding zinc chloride, zinc sulfate, manganese chloride and manganese sulfate into deionized water, fully stirring until the zinc chloride, the zinc sulfate, the manganese chloride and the manganese sulfate are completely dissolved, preparing 2mol/L zinc chloride, 1mol/L zinc sulfate, 0.3mol/L manganese chloride and 0.5mol/L manganese sulfate aqueous electrolyte with the total mass of 100g, and then regulating the pH value of the aqueous electrolyte to 5.0 to obtain the reference electrolyte. The assembly process of the aqueous zinc-ion battery using the reference electrolyte is the same as above.
3. Electrochemical performance test:
the water-based zinc ion batteries using the test electrolyte and the reference electrolyte are subjected to multiplying power charge and discharge and constant current charge and discharge tests respectively, the set multiplying power is 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g, and the set constant current density is 1.5A/g.
4. Analysis of results:
as can be seen from the rate performance test of fig. 2 (a), the specific discharge capacities of the aqueous zinc ion battery using the test electrolyte at the current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g are all significantly higher than those of the aqueous zinc ion battery using the reference electrolyte, indicating that the battery using the test electrolyte has excellent rate performance; as can be seen from the cycle performance test of fig. 2 (b), after 2800 times of constant current charge and discharge at a current density of 1.5A/g, the specific discharge capacity of the battery using the test electrolyte was 100.1mAh/g, which is much higher than that of the battery using the reference electrolyte by 47.9mAh/g, and the cycle stability of the battery using the test electrolyte during 2800 times of constant current charge and discharge was significantly higher than that of the battery using the reference electrolyte. This is mainly because the test electrolyte of this example can achieve full coverage of nucleation sites and dendrite-free growth compared to the reference electrolyte. In addition, the activity of free water in the electrolyte is extremely low, and the electrochemical side reaction on the surface of the zinc negative electrode is effectively inhibited, so that the corrosion and passivation of the zinc negative electrode are relieved. Therefore, the aqueous zinc ion battery using the test electrolyte has excellent rate performance and cycle performance.
Example 3
1. Configuration of test electrolyte and assembly of water-filled zinc-manganese battery based on the same:
adding 1g of chitosan sulfate, 2g of chitosan quaternary ammonium salt, 2g of chitosan nitrate and 1g of chitosan lactate into aqueous electrolyte of which the total mass is 94g of 1.8mol/L zinc bromide, 1.2mol/L zinc nitrate, 1.4mol/L zinc triflate, 0.3mol/L manganese bromide, 0.5mol/L manganese nitrate and 0.7mol/L manganese triflate, fully stirring until the chitosan sulfate, the chitosan quaternary ammonium salt, the chitosan nitrate and the chitosan lactate are completely dissolved, then adjusting the pH value of the mixed aqueous solution to be 4.8, and standing to obtain the aqueous zinc ion battery electrolyte.
And placing the graphite paper gasket in the positive electrode shell, sequentially placing the positive electrode plate and the diaphragm, dripping electrolyte until the diaphragm is completely wetted, sequentially placing the negative electrode plate (zinc plate), the stainless steel gasket, the elastic sheet and the negative electrode shell, and then placing the negative electrode plate, the stainless steel gasket, the elastic sheet and the negative electrode shell in a static press for static pressure sealing to obtain the water-based zinc ion battery.
2. Configuration of reference electrolyte and aqueous zinc ion battery assembly based thereon:
sequentially adding zinc bromide, zinc nitrate, zinc triflate, manganese bromide, manganese nitrate and manganese triflate into solvent water, fully stirring until the zinc bromide, the zinc nitrate, the zinc triflate, the manganese bromide, the manganese nitrate and the manganese triflate are completely dissolved, preparing 1.8mol/L zinc bromide, 1.2mol/L zinc nitrate, 1.4mol/L zinc triflate, 0.3mol/L manganese bromide, 0.5mol/L manganese nitrate and 0.7mol/L manganese triflate aqueous phase electrolyte with the total mass of 100g, and then adjusting the pH value of the aqueous phase electrolyte to 4.3 to obtain the reference electrolyte. The assembly process of the aqueous zinc-ion battery using the reference electrolyte is the same as above.
3. Electrochemical performance test:
the water-based zinc ion batteries using the test electrolyte and the reference electrolyte are subjected to multiplying power charge and discharge and constant current charge and discharge tests respectively, the set multiplying power is 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g, and the set constant current density is 1.5A/g.
4. Analysis of results:
as can be seen from the rate performance test of fig. 3 (a), the specific discharge capacities of the aqueous zinc ion battery using the test electrolyte at the current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g are all significantly higher than those of the aqueous zinc ion battery using the reference electrolyte, indicating that the battery using the test electrolyte has excellent rate performance; as can be seen from the cycle performance test of fig. 3 (b), after 2800 times of constant current charge and discharge at a current density of 1.5A/g, the specific discharge capacity of the battery using the test electrolyte was 83.6mAh/g, which is much higher than that of the battery using the reference electrolyte by 43.3mAh/g, and the cycle stability of the battery using the test electrolyte during 2800 times of constant current charge and discharge was significantly higher than that of the battery using the reference electrolyte. This is mainly because the test electrolyte of this example can achieve full coverage of nucleation sites and dendrite-free growth compared to the reference electrolyte. In addition, the activity of free water in the electrolyte is extremely low, and the electrochemical side reaction on the surface of the zinc negative electrode is effectively inhibited, so that the corrosion and passivation of the zinc negative electrode are relieved. Therefore, the aqueous zinc ion battery using the test electrolyte has excellent rate performance and cycle performance.
Example 4
1. Configuration of test electrolyte and aqueous zinc ion battery assembly based thereon:
adding 3g of chitosan lactate into aqueous electrolyte of 1.3mol/L zinc sulfate, 1.5mol/L zinc chloride, 1.2mol/L zinc bromide, 1.7mol/L zinc nitrate, 1.3mol/L zinc triflate, 0.15mol/L manganese sulfate, 0.25mol/L manganese chloride, 0.5mol/L manganese bromide, 0.8mol/L manganese nitrate and 0.5mol/L manganese triflate, fully stirring until the chitosan lactate is completely dissolved, then adjusting the pH value of the mixed aqueous solution to 4.0, and standing to obtain the aqueous zinc ion battery electrolyte.
And placing the graphite paper gasket in the positive electrode shell, sequentially placing the positive electrode plate and the diaphragm, dripping electrolyte until the diaphragm is completely wetted, sequentially placing the negative electrode plate (zinc plate), the stainless steel gasket, the elastic sheet and the negative electrode shell, and then placing the negative electrode plate, the stainless steel gasket, the elastic sheet and the negative electrode shell in a static press for static pressure sealing to obtain the water-based zinc ion battery.
2. Configuration of reference electrolyte and aqueous zinc ion battery assembly based thereon:
sequentially adding zinc sulfate, zinc chloride, zinc bromide, zinc nitrate, zinc triflate, manganese sulfate, manganese chloride, manganese bromide, manganese nitrate and manganese triflate into solvent water, fully stirring until the zinc sulfate, zinc chloride, zinc bromide, zinc nitrate, zinc triflate, manganese sulfate, manganese chloride, manganese bromide, manganese nitrate and manganese triflate are completely dissolved, preparing 1.3mol/L zinc sulfate, 1.5mol/L zinc chloride, 1.2mol/L zinc bromide, 1.7mol/L zinc nitrate, 1.3mol/L zinc triflate, 0.15mol/L manganese sulfate, 0.25mol/L manganese chloride, 0.5mol/L manganese bromide, 0.8mol/L manganese nitrate and 0.5mol/L manganese triflate aqueous electrolyte with the total mass of 100g, and then adjusting the pH value of the aqueous electrolyte to 4.0 to obtain the reference electrolyte. The assembly process of the aqueous zinc-ion battery using the reference electrolyte is the same as above.
3. Electrochemical performance test:
the water-based zinc ion batteries using the test electrolyte and the reference electrolyte are subjected to multiplying power charge and discharge and constant current charge and discharge tests respectively, the set multiplying power is 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g, and the set constant current density is 1.5A/g.
4. Analysis of results:
as can be seen from the rate performance test of fig. 4 (a), the specific discharge capacities of the aqueous zinc ion battery using the test electrolyte at the current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g are all significantly higher than those of the aqueous zinc ion battery using the reference electrolyte, indicating that the battery using the test electrolyte has excellent rate performance; as can be seen from the cycle performance test of fig. 4 (b), after 2800 times of constant current charge and discharge at a current density of 1.5A/g, the specific discharge capacity of the battery using the test electrolyte was 101.6mAh/g, which is much higher than that of the battery using the reference electrolyte by 60.2mAh/g, and the cycle stability of the battery using the test electrolyte during 2800 times of constant current charge and discharge was significantly higher than that of the battery using the reference electrolyte. This is mainly because the test electrolyte of this example can achieve full coverage of nucleation sites and dendrite-free growth compared to the reference electrolyte. In addition, the activity of free water in the electrolyte is extremely low, and the electrochemical side reaction on the surface of the zinc negative electrode is effectively inhibited, so that the corrosion and passivation of the zinc negative electrode are relieved. Therefore, the aqueous zinc ion battery using the test electrolyte has excellent rate performance and cycle performance.
Comparative example 1
1. Configuration of test electrolyte and aqueous zinc ion battery assembly based thereon:
adding 0.01g of chitosan quaternary ammonium salt and 0.01g of chitosan hydrochloride into aqueous electrolyte of 0.01mol/L zinc sulfate, 0.02mol/L zinc nitrate, 0.1mol/L manganese sulfate and 1.6mol/L manganese nitrate with the total mass of 99.98g, fully stirring until the chitosan quaternary ammonium salt and the chitosan hydrochloride are completely dissolved, then adjusting the pH value of the mixed aqueous solution to be 4.5, and standing to obtain the aqueous zinc ion battery electrolyte.
And placing the graphite paper gasket in the positive electrode shell, sequentially placing the positive electrode plate and the diaphragm, dripping electrolyte until the diaphragm is completely wetted, sequentially placing the negative electrode plate (zinc plate), the stainless steel gasket, the elastic sheet and the negative electrode shell, and then placing the negative electrode plate, the stainless steel gasket, the elastic sheet and the negative electrode shell in a static press for static pressure sealing to obtain the water-based zinc ion battery.
2. Configuration of reference electrolyte and aqueous zinc ion battery assembly based thereon:
sequentially adding zinc sulfate, zinc nitrate, manganese sulfate and manganese nitrate into solvent water, fully stirring until the zinc sulfate, the zinc nitrate, the manganese sulfate and the manganese nitrate are completely dissolved, preparing an aqueous phase electrolyte of 0.01mol/L zinc sulfate, 0.02mol/L zinc nitrate, 0.1mol/L manganese sulfate and 1.6mol/L manganese nitrate with the total mass of 100g, and then regulating the pH value of the aqueous phase electrolyte to be 4.5 to obtain the reference electrolyte. The assembly process of the aqueous zinc-ion battery using the reference electrolyte is the same as above.
3. Electrochemical performance test:
the water-based zinc ion batteries using the test electrolyte and the reference electrolyte are subjected to multiplying power charge and discharge and constant current charge and discharge tests respectively, the set multiplying power is 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g, and the set constant current density is 1.5A/g.
4. Analysis of results:
as can be seen from the rate performance test of fig. 5 (a), the specific discharge capacities of the aqueous zinc ion battery using the test electrolyte at the current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g were all significantly lower than those of the aqueous zinc ion battery using the reference electrolyte, indicating that the battery using the test electrolyte had poor rate performance; as can be seen from the cycle performance test of fig. 5 (b), after 2800 times of constant current charge and discharge at a current density of 1.5A/g, the specific discharge capacity of the battery using the test electrolyte was 65.4mAh/g, which was 75.3mAh/g lower than that of the battery using the reference electrolyte, and the cycle stability of the battery using the test electrolyte was significantly lower than that of the battery using the reference electrolyte during 2800 times of constant current charge and discharge. This is mainly because when the mass fraction of the water-soluble chitosan in the total mass of the electrolyte is less than 0.1% and the concentration of the zinc salt is less than 0.2mol/L, the test electrolyte of this example cannot completely achieve full coverage of the favorable nucleation sites, resulting in overgrowth of zinc dendrites. In addition, the electrolyte promotes the increase of electrochemical side reactions on the surface of the zinc cathode, thereby increasing the corrosion and passivation of the zinc cathode and further weakening the rate capability and the cycle capability of the water-based zinc ion battery.
Comparative example 2
1. Configuration of test electrolyte and aqueous zinc ion battery assembly based thereon:
adding 2g of chitosan lactate, 2g of chitosan nitrate, 2g of chitosan quaternary ammonium salt and 5g of chitosan sulfate into aqueous electrolyte of 5mol/L zinc triflate, 4mol/L zinc chloride, 4mol/L zinc nitrate, 1mol/L manganese triflate, 0.5mol/L manganese chloride and 0.6mol/L manganese nitrate with the total mass of 89g, fully stirring until the chitosan lactate, the chitosan nitrate, the chitosan quaternary ammonium salt and the chitosan sulfate are completely dissolved, then adjusting the pH value of the mixed aqueous solution to be 4.6, and standing to obtain the aqueous zinc ion battery electrolyte.
And placing the graphite paper gasket in the positive electrode shell, sequentially placing the positive electrode plate and the diaphragm, dripping electrolyte until the diaphragm is completely wetted, sequentially placing the negative electrode plate (zinc plate), the stainless steel gasket, the elastic sheet and the negative electrode shell, and then placing the negative electrode plate, the stainless steel gasket, the elastic sheet and the negative electrode shell in a static press for static pressure sealing to obtain the water-based zinc ion battery.
2. Configuration of reference electrolyte and aqueous zinc ion battery assembly based thereon:
and (3) completely dissolving zinc triflate, zinc chloride, zinc nitrate, manganese triflate, manganese chloride and manganese nitrate, preparing 5mol/L zinc triflate, 4mol/L zinc chloride, 4mol/L zinc nitrate, 1mol/L manganese triflate, 0.5mol/L manganese chloride and 0.6mol/L manganese nitrate aqueous electrolyte with the total mass of 100g, and then regulating the pH value of the aqueous electrolyte to be 4.6 to obtain the reference electrolyte. The assembly process of the aqueous zinc-ion battery using the reference electrolyte is the same as above.
3. Electrochemical performance test:
the water-based zinc ion batteries using the test electrolyte and the reference electrolyte are subjected to multiplying power charge and discharge and constant current charge and discharge tests respectively, the set multiplying power is 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g, and the set constant current density is 1.5A/g.
4. Analysis of results:
as can be seen from the rate performance test of fig. 6 (a), the specific discharge capacities of the aqueous zinc ion battery using the test electrolyte at the current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g were all significantly lower than those of the aqueous zinc ion battery using the reference electrolyte, indicating that the battery using the test electrolyte had poor rate performance; as can be seen from the cycle performance test of fig. 6 (b), after 2800 times of constant current charge and discharge at a current density of 1.5A/g, the specific discharge capacity of the battery using the test electrolyte was 63.1mAh/g, which was lower than that of the battery using the reference electrolyte by 70.4mAh/g, and the cycle stability of the battery using the test electrolyte during 2800 times of constant current charge and discharge was significantly lower than that of the battery using the reference electrolyte. This is mainly because the test electrolyte of this example cannot fully achieve full coverage of the favorable nucleation sites when the mass fraction of water-soluble chitosan to the total mass of the electrolyte is higher than 10% and the concentration of zinc salt is higher than 12mol/L, resulting in overgrowth of zinc dendrites. In addition, the electrolyte promotes the increase of electrochemical side reactions on the surface of the zinc cathode, thereby increasing the corrosion and passivation of the zinc cathode and further weakening the rate capability and the cycle capability of the water-based zinc ion battery.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (6)
1. An aqueous zinc ion battery electrolyte, which is characterized in that: comprises zinc salt, manganese salt, water and additives; the additive is water-soluble chitosan; the mass of the additive accounts for 0.1-10% of the total mass of the electrolyte.
2. The aqueous zinc-ion battery electrolyte according to claim 1, wherein: the water-soluble chitosan comprises one or more of chitosan quaternary ammonium salt, chitosan hydrochloride, chitosan sulfate, chitosan nitrate, chitosan lactate and chitosan acetate.
3. The aqueous zinc-ion battery electrolyte according to claim 1, wherein: the zinc salt comprises one or more of zinc sulfate, zinc bromide, zinc nitrate, zinc chloride and zinc triflate; the concentration of zinc salt is 0.2-12 mol/L.
4. The aqueous zinc-ion battery electrolyte according to claim 1, wherein: the manganese salt comprises one or more of manganese sulfate, manganese bromide, manganese nitrate, manganese chloride and manganese triflate; the concentration of the manganese salt is 0.01-3.5 mol/L.
5. The aqueous zinc-ion battery electrolyte according to claim 1, wherein: the pH value of the aqueous zinc ion battery electrolyte is 3-7.
6. A water-based zinc ion battery, characterized in that: comprising a positive electrode, a negative electrode, a separator and the aqueous zinc-ion battery electrolyte according to any one of claims 1 to 5.
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