CN111682268B - Aqueous zinc ion battery compound gel electrolyte and preparation method and application thereof - Google Patents
Aqueous zinc ion battery compound gel electrolyte and preparation method and application thereof Download PDFInfo
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a water system zinc ion battery compound gel electrolyte, a preparation method and application thereof. The preparation method is that lignin derivative and inorganic nano particles are added into aqueous phase electrolyte in sequence, and the mixture is fully stirred and then is stood for a certain time, thus obtaining uniform and stable compound gel electrolyte. The compound gel electrolyte provided by the invention is safer than the aqueous phase electrolyte; the water-based zinc ion battery using the compound gel electrolyte provided by the invention has better multiplying power and cycle performance; the lignin derivative provided by the invention has wide sources, is renewable and low in price, and the provided inorganic nano particles can be produced in large scale. Therefore, the water-based zinc ion battery using the compound gel electrolyte prepared by the invention meets the technical requirements of zinc ion energy storage of high capacity, high energy density, long service life and environmental friendliness, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of water-based zinc ion batteries, and particularly relates to a water-based zinc ion battery compound gel electrolyte, a preparation method thereof and a water-based zinc ion battery based on the compound gel electrolyte.
Background
The theoretical volume specific capacity and the theoretical mass specific capacity of the metal zinc are respectively up to 5854mAh & cm -3 And 819 mAh.g -1 And Zn/Zn 2+ The lower standard electrode potential (-0.76 Vvs standard hydrogen electrode) makes rechargeable aqueous zinc-ion batteries the subject of hot spot research in numerous secondary batteries. Wherein, the mixed aqueous solution of water-soluble zinc salt and water-soluble manganese salt is taken as electrolyte, and metallic zinc is taken as negative electrodeThe rechargeable water-based zinc ion battery (ReAZIB) is regarded as one of the secondary batteries with very competitive power in the fields of large-scale energy storage, portable electric tools, wearable electronic equipment and the like in the future because of wide sources of electrode materials, low price, no toxicity, high specific capacity, high safety of electrolyte and environmental protection.
However, in the ordinary aqueous electrolyte (mixed aqueous solution of water-soluble zinc salt and water-soluble manganese salt), zn 2+ The electrochemical deposition/stripping behavior on the zinc anode surface is disordered and the process is uncontrollable, so that zinc dendrites are very easy to grow on the zinc anode surface, thereby greatly reducing the cycle performance of the ReAZIB. Gel electrolyte prepared by adding polymers such as xanthan gum, gelatin or polyvinyl alcohol into aqueous electrolyte can effectively inhibit formation and growth of zinc dendrite, but can cause great reduction of ionic conductivity of the electrolyte, which inevitably leads to capacity loss and rate performance reduction of a battery. Zn/LiMn reported in aqueous system 2 O 4 In the secondary battery, an aqueous electrolyte (Li 2 SO 4 And ZnSO 4 The mixed aqueous solution of the zinc dendrites is added with the gel electrolyte formed by the gas phase nano silicon dioxide, so that the formation and growth of the zinc dendrites can be effectively inhibited, and the higher ionic conductivity can be maintained; but hydroxyl groups (-OH) on the surface of the fumed silica particles release H + Thereby increasing the corrosion of the electrolyte to the zinc cathode, and leading to the gel electrolyte having no obvious effect of improving the cycle performance of the battery. In addition, no research report on application of the gas phase nano silica-based gel electrolyte to the ReAZIB exists at present.
Lignin is a natural renewable amorphous polymer with a three-dimensional network structure and rich functional groups, has the characteristics of an amphiphilic structure and natural properties of antibiosis, antioxidation, corrosion inhibition and the like, and can be used as a high molecular surfactant, a functional material and the like, thereby having great potential application value in the fields of construction, agriculture, energy sources and the like. However, the structure is complex and physical or chemical isomerism is very easy to occur, so that less than 5% of industrial lignin produced annually worldwide is commercialized and utilized, and the rest is directly combusted or is buried as garbage, so that potential application value of the lignin is not excavated, and huge resource waste and serious environmental pollution are caused. Therefore, development of lignin-based high value-added chemicals, development of high value-added application fields of lignin-based chemicals, and the like are particularly important.
The invention reasonably modifies lignin which is rich in source, low in price and nontoxic, and then adds the lignin and gas phase nano particles into the aqueous phase electrolyte to prepare the compound gel electrolyte which has the function of inhibiting zinc dendrite and has low corrosiveness to a zinc cathode, thereby improving the multiplying power performance and the cycle performance of the ReAZIB. The invention can provide a new thought for the construction of the electrolyte of the high-performance rechargeable water system zinc ion battery, and simultaneously opens up a new application field for the high-value utilization of lignin resources.
Disclosure of Invention
In order to improve the comprehensive performance of the water-based zinc ion battery, the primary aim of the invention is to provide the compound gel electrolyte of the water-based zinc ion battery.
The invention also aims to provide a water-based zinc ion battery based on the compound gel electrolyte.
The aim of the invention is achieved by the following scheme:
the compound gel electrolyte of the water-based zinc ion battery is characterized by being prepared by uniformly mixing lignin derivatives, inorganic nano particles and aqueous electrolyte.
The lignin derivative comprises one or more of hydroxylation, amination and quaternization products obtained by taking alkali lignin, enzymolysis lignin, organic solvent lignin or steam explosion lignin as raw materials and introducing hydroxyl, amino and quaternary ammonium radical functional groups through chemical reaction.
The lignin derivatives are preferably hydroxylated alkali lignin, hydroxylated enzymatic lignin, quaternized alkali lignin and quaternized enzymatic lignin.
The inorganic nano particles comprise one or more of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide and nano zinc oxide.
The inorganic nano particles are preferably nano silicon dioxide and nano titanium dioxide.
The mass of the lignin derivative accounts for 0.1-50% of the mass of the inorganic nano particles.
The mass of the lignin derivative is preferably 5-30% of the mass of the inorganic nanoparticles.
The total mass of the lignin derivative and the inorganic nano particles accounts for 2% -20% of the mass of the aqueous electrolyte.
The ratio of the total mass of the lignin derivative and the inorganic nano particles to the mass of the aqueous electrolyte is preferably 3-10%.
The aqueous phase electrolyte is prepared by mixing and dissolving water-soluble zinc salt and water-soluble manganese salt.
The water-soluble zinc salt comprises one or more of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate and zinc trifluoromethane sulfonate; the water-soluble manganese salt comprises one or more of manganese sulfate, manganese chloride, manganese nitrate, manganese acetate and manganese trifluoromethane sulfonate.
The water-soluble zinc salt is preferably zinc sulfate and zinc trifluoromethane sulfonate; the water-soluble manganese salt is manganese sulfate and manganese trifluoromethane sulfonate.
The concentration of the water-soluble zinc salt in the aqueous phase electrolyte is 0.1-10 mol/L, and the concentration of the water-soluble manganese salt is 0-1.5 mol/L.
The concentration of the water-soluble zinc salt is preferably 1-5 mol/L, and the concentration of the water-soluble manganese salt is preferably 0-1 mol/L.
The preparation method of the water system zinc ion battery compound gel electrolyte is characterized in that lignin derivatives and inorganic nano particles are sequentially added into the water phase electrolyte, and the water system zinc ion battery compound gel electrolyte is obtained after full stirring and standing.
The invention also provides a water-based zinc ion battery containing the compound gel electrolyte.
The water-based zinc ion battery comprises a battery shell, a pole core and electrolyte, wherein the pole core and the electrolyte are sealed in the battery shell, the pole core comprises a positive plate capable of reacting with zinc ions, a zinc negative electrode and a diaphragm positioned between the positive plate and the negative electrode, and the electrolyte is the compound gel electrolyte.
The mechanism of the invention is as follows:
according to the invention, the compound gel electrolyte is applied to the water-based zinc ion battery, so that the risk of electrolyte leakage can be reduced, the safety of the battery can be improved, and the rate performance and the cycle performance of the battery can be obviously improved. Compared with the aqueous electrolyte, the compound gel electrolyte has the advantages that the free flowing water is extremely small, so that the leakage of the electrolyte is not easy to occur in the aqueous zinc ion battery, and the safety is greatly improved; gel electrolyte formed by singly adding inorganic nano particles has the capability of improving the multiplying power performance and the cycle performance of a water system zinc ion battery, but hydroxyl functional groups on the surfaces of the inorganic nano particles release H + The zinc cathode is corroded and weighted, so that the improvement effect of the inorganic nanoparticle gel electrolyte on the multiplying power performance and the cycle performance of the water system zinc ion battery is not obvious; when the lignin derivative and the inorganic nano particles are added simultaneously, the lignin derivative not only can be adsorbed on the surfaces of the inorganic nano particles to prevent the hydroxyl groups on the surfaces from releasing H + Can be adsorbed on the surface of the zinc cathode, thus preventing the corrosion of the zinc cathode and inhibiting the formation of zinc dendrites by regulating and controlling the uniform deposition and dissolution of zinc ions on the surface of the zinc cathode, thereby greatly improving the rate capability and the cycle performance of the water-based zinc ion battery.
Compared with the prior art, the invention has the following advantages:
compared with the aqueous electrolyte, the compound gel electrolyte prepared by adding the lignin derivative and the inorganic nano particles into the aqueous electrolyte simultaneously has little free flowing water, so that leakage of the electrolyte can be effectively avoided, and the safety performance of the water-based zinc ion battery is improved; compared with a single inorganic nanoparticle gel electrolyte, the compound gel electrolyte has all the advantages of the single inorganic nanoparticle gel electrolyte, and simultaneously lignin derivatives are adsorbed on the surface of a zinc anode, and can also prevent H released by hydroxyl (-OH) on the surface of inorganic nanoparticles + Corrosion to zinc cathode and further congeals with inorganic nano-particlesGlue network cooperative regulation and control Zn 2+ Uniformly depositing and dissolving out on the surface of the zinc cathode to effectively inhibit zinc dendrite formation, thereby greatly improving the multiplying power and cycle performance of the battery.
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 the following 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:
preparing a total of 93g of a mixed aqueous solution of 2mol/L zinc sulfate and 0.2mol/L manganese sulfate, adding 0.5g of hydroxylated alkali lignin and 0.5g of hydroxylated enzymolysis lignin, fully stirring until the hydroxylated alkali lignin and the hydroxylated enzymolysis lignin are completely dissolved, and then adding 6g of gas phase nano SiO 2 And (3) fully stirring and standing the powder to obtain the compound gel electrolyte.
And assembling the positive plate, the zinc negative electrode, the diaphragm between the positive electrode and the negative electrode and the compound gel electrolyte which can react with zinc ions into a battery shell to obtain the gel-type water-based zinc ion battery.
2. Configuration of reference electrolyte and aqueous zinc ion battery assembly based thereon:
preparing a total of 93g of mixed aqueous solution of 2mol/L zinc sulfate and 0.2mol/L manganese sulfate, and adding 6g of gas phase nano SiO 2 And (3) fully stirring and standing the powder to obtain the reference aqueous phase gel electrolyte, wherein the assembly process of the aqueous zinc ion battery using the reference electrolyte is the same as that described above.
3. Electrochemical performance test:
and performing multiplying power charge and discharge and constant current charge and discharge tests on the water-based zinc ion battery using the test electrolyte and the reference electrolyte respectively, wherein 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 fig. 1 (a), at current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g, 5A/g, the specific capacities of the aqueous zinc-ion cells using the test electrolyte were all significantly higher than those of the aqueous zinc-ion cells using the reference electrolyte; as can be seen from fig. 1 (b), the initial specific capacity of the aqueous zinc-ion battery using the test electrolyte is up to 240mAh/g at a current density of 1.5A/g, which is much higher than the initial specific capacity of 200mAh/g of the aqueous zinc-ion battery using the reference electrolyte, and after 1400 times of charge and discharge at this current density, the specific capacity is still much higher than that of the aqueous zinc-ion battery using the reference electrolyte. This is mainly because, compared with the reference electrolyte, the compound gel electrolyte of the embodiment has stronger capability of inhibiting zinc dendrite formation and growth and weaker corrosiveness to the zinc cathode, so that the multiplying power and the cycle performance of the water-based zinc ion battery can be greatly improved.
Example 2
1. Configuration of test electrolyte and water-based zinc ion battery assembly:
preparing 92g of mixed aqueous solution of 2.5mol/L zinc trifluoromethane sulfonate and 0.1mol/L manganese trifluoromethane sulfonate, adding 0.5g of aminated alkali lignin, 0.4g of quaternized alkali lignin and 0.3g of quaternary ammoniumStirring ammonification enzymatic hydrolysis lignin and 0.3g of hydroxylation organic solvent lignin fully until the ammonification alkali lignin, the quaternization enzymatic hydrolysis lignin and the hydroxylation organic solvent lignin are completely dissolved, and then adding 6.5g of gas phase nano TiO 2 And (3) fully stirring and standing the powder to obtain the compound gel electrolyte.
And assembling the positive plate, the zinc negative electrode, the diaphragm between the positive electrode and the negative electrode and the compound gel electrolyte which can react with zinc ions into a battery shell to obtain the gel-type water-based zinc ion battery.
2. Configuration of reference electrolyte and aqueous zinc ion battery assembly based thereon:
preparing 92g of 2.5mol/L zinc trifluoromethane sulfonate and 0.1mol/L manganese trifluoromethane sulfonate base sample aqueous electrolyte, and adding 6.5g of gas phase nano TiO 2 And (3) fully stirring the powder, and standing to obtain the reference aqueous phase gel electrolyte. The assembly process of the aqueous zinc-ion battery using the reference electrolyte is the same as above.
3. Electrochemical performance test:
and performing multiplying power charge and discharge and constant current charge and discharge tests on the water-based zinc ion battery using the test electrolyte and the reference electrolyte respectively, wherein 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 fig. 2 (a), at current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g, 5A/g, the specific capacities of the aqueous zinc-ion cells using the test electrolyte were all significantly higher than those of the aqueous zinc-ion cells using the reference electrolyte; as can be seen from fig. 2 (b), the initial specific capacity of the aqueous zinc-ion battery using the test electrolyte is up to 250mAh/g at a current density of 1.5A/g, which is much higher than the initial specific capacity of 190mAh/g of the aqueous zinc-ion battery using the reference electrolyte, and after 1400 times of charge and discharge at this current density, the specific capacity is still much higher than that of the aqueous zinc-ion battery using the reference electrolyte. This is mainly because, compared with the reference electrolyte, the compound gel electrolyte of the embodiment has stronger capability of inhibiting zinc dendrite formation and growth and weaker corrosiveness to the zinc cathode, so that the multiplying power and the cycle performance of the water-based zinc ion battery can be greatly improved.
Example 3
1. Configuration of test electrolyte and water-based zinc ion battery assembly:
preparing 91g of mixed aqueous solution of 1mol/L zinc chloride and 0.1mol/L manganese chloride, adding 0.4g of hydroxylated steam explosion lignin, 0.3g of amination steam explosion lignin and 0.3g of quaternized steam explosion lignin, fully stirring until the hydroxylated steam explosion lignin, the amination steam explosion lignin and the quaternized steam explosion lignin are completely dissolved, and adding 8g of gas phase nano SiO (silicon dioxide) 2 And (3) fully stirring and standing the powder to obtain the compound gel electrolyte.
2. Reference electrolyte preparation and water-based zinc ion battery assembly:
preparing 91g of mixed aqueous solution of 1mol/L zinc chloride and 0.1mol/L manganese chloride, and adding 8g of gas phase nano SiO 2 And (3) fully stirring and standing the powder to obtain the reference aqueous phase gel electrolyte, wherein the assembly process of the aqueous zinc ion battery using the reference electrolyte is the same as that described above.
3. Electrochemical performance test:
and performing multiplying power charge and discharge and constant current charge and discharge tests on the water system zinc ion battery using the test electrolyte and the reference electrolyte respectively, wherein 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 fig. 3 (a), at current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g, 5A/g, the specific capacities of the aqueous zinc-ion cells using the test electrolyte were all significantly higher than those of the aqueous zinc-ion cells using the reference electrolyte; as can be seen from fig. 3 (b), the initial specific capacity of the aqueous zinc-ion battery using the test electrolyte is up to 240mAh/g at a current density of 1.5A/g, which is much higher than the initial specific capacity of 160mAh/g of the aqueous zinc-ion battery using the reference electrolyte, and after 1400 times of charge and discharge at this current density, the specific capacity is still much higher than that of the aqueous zinc-ion battery using the reference electrolyte. This is mainly because, compared with the reference electrolyte, the compound gel electrolyte of the embodiment has stronger capability of inhibiting zinc dendrite formation and growth and weaker corrosiveness to the zinc cathode, so that the multiplying power and the cycle performance of the water-based zinc ion battery can be greatly improved.
Example 4
1. Configuration of test electrolyte and water-based zinc ion battery assembly:
preparing 94g of mixed aqueous solution of 1.5mol/L zinc nitrate, 1mol/L zinc acetate, 0.2mol/L manganese nitrate and 0.3mol/L manganese acetate, adding 0.2g of quaternized alkali lignin, 0.3g of hydroxylation enzymatic hydrolysis lignin, 0.3. 0.3g of amination organic solvent lignin and 0.2g of quaternized organic solvent lignin, fully stirring until the quaternized alkali lignin, the hydroxylation enzymatic hydrolysis lignin, the amination organic solvent lignin and the quaternized organic solvent lignin are fully stirred, and then adding 5g of gas phase nano TiO 2 And (3) fully stirring and standing the powder to obtain the compound gel electrolyte.
2. Reference electrolyte preparation and water-based zinc ion battery assembly:
preparing 94g of mixed aqueous solution of 1.5mol/L zinc nitrate, 1mol/L zinc acetate, 0.2mol/L manganese nitrate and 0.3mol/L manganese acetate, and adding 5g of gas phase nano TiO 2 And (3) fully stirring the powder, and standing to obtain the reference aqueous phase gel electrolyte. The assembly process of the aqueous zinc-ion battery using the reference electrolyte is the same as above.
3. Electrochemical performance test:
and performing multiplying power charge and discharge and constant current charge and discharge tests on the water-based zinc ion battery using the test electrolyte and the reference electrolyte respectively, wherein 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 fig. 4 (a), at current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g, 5A/g, the specific capacities of the aqueous zinc-ion cells using the test electrolyte were all significantly higher than those of the aqueous zinc-ion cells using the reference electrolyte; as can be seen from fig. 4 (b), the initial specific capacity of the aqueous zinc-ion battery using the test electrolyte at a current density of 1.5A/g is up to 220mAh/g, which is much higher than the initial specific capacity 165mAh/g of the aqueous zinc-ion battery using the reference electrolyte, and after 1400 times of charge and discharge at this current density, the specific capacity is still much higher than that of the aqueous zinc-ion battery using the reference electrolyte. This is mainly because, compared with the reference electrolyte, the compound gel electrolyte of the embodiment has stronger capability of inhibiting zinc dendrite formation and growth and weaker corrosiveness to the zinc cathode, so that the multiplying power and the cycle performance of the water-based zinc ion battery can be greatly improved.
Comparative example 1
1. Configuration of test electrolyte and water-based zinc ion battery assembly:
preparing 98g of a mixed aqueous solution of 2mol/L zinc sulfate and 0.2mol/L manganese sulfate, adding 0.05g of hydroxylated alkali lignin, 0.05g of quaternized enzymolysis lignin and 0.1g of hydroxylated steam explosion lignin, fully stirring until the hydroxylated alkali lignin, the quaternized enzymolysis lignin and the hydroxylated steam explosion lignin are completely dissolved, and then adding 1.6g of gas phase nano SiO 2 And (3) fully stirring and standing the powder to obtain the compound gel electrolyte.
And assembling the positive plate, the diaphragm, the compound gel electrolyte and the zinc negative electrode which can react with zinc ions into a battery shell to obtain the compound gel water-based zinc ion battery.
2. Reference electrolyte preparation and water-based zinc ion battery assembly:
preparing 98g of a basic aqueous phase electrolyte of 2mol/L zinc sulfate and 0.2mol/L manganese sulfate, and adding 1.6. 1.6g gas phase nano SiO 2 And (3) fully stirring the powder, and standing to obtain the reference aqueous phase gel electrolyte. The assembly process of the aqueous zinc ion battery using the reference electrolyte is the same as above.
3. Electrochemical performance test:
and performing multiplying power charge and discharge and constant current charge and discharge tests on the water-based zinc ion battery using the test electrolyte and the reference electrolyte respectively, wherein 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 fig. 5 (a), at current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g, 5A/g, the specific capacities of the aqueous zinc-ion cells using the test electrolyte were all significantly lower than those of the aqueous zinc-ion cells using the reference electrolyte; as can be seen from fig. 5 (b), the initial specific capacity of the aqueous zinc-ion battery using the test electrolyte at a current density of 1.5A/g was 100mAh/g, which is far lower than the initial specific capacity of 220mAh/g of the aqueous zinc-ion battery using the reference electrolyte, and after 1400 times of charge and discharge at this current density, the specific capacity was still lower than that of the aqueous zinc-ion battery using the reference electrolyte. This shows that when the total mass of lignin derivative and inorganic nanoparticles is less than 2% of the mass of aqueous electrolyte, the gel structure of the compound gel electrolyte is unstable, resulting in that the compound gel electrolyte does not have the ability to inhibit the formation and growth of zinc dendrites, thereby significantly reducing the rate and cycle performance of the aqueous zinc ion battery.
Comparative example 2
1. Configuration of test electrolyte and aqueous zinc ion battery assembly based thereon:
preparing 90g of mixed aqueous solution of 2mol/L zinc trifluoromethane sulfonate and 0.2mol/L manganese trifluoromethane sulfonate, adding 2g of hydroxylated alkali lignin, 1g of hydroxylated enzymolysis lignin, 1g of quaternized alkali lignin and 1g of quaternized enzymolysis lignin, fully stirring until the hydroxylated alkali lignin, hydroxylated enzymolysis lignin, quaternized alkali lignin and quaternized enzymolysis lignin are completely dissolved, and adding 15g of gas phase nano SiO (silicon dioxide) 2 And (3) fully stirring and standing the powder to obtain the compound gel electrolyte.
And assembling the positive plate, the diaphragm, the compound gel electrolyte and the zinc negative electrode which can react with zinc ions into a battery shell to obtain the compound gel water-based zinc ion battery.
2. Configuration of reference electrolyte and aqueous zinc ion battery assembly based thereon:
preparing 90g of mixed aqueous solution of 2mol/L zinc trifluoromethane sulfonate and 0.2mol/L manganese trifluoromethane sulfonate, and adding 15g of gas phase nano SiO 2 Fully stirring and standing the powder to obtainReference aqueous gel electrolyte. The assembly process of the aqueous zinc-ion battery using the reference electrolyte is the same as above.
3. Electrochemical performance test:
and performing multiplying power charge and discharge and constant current charge and discharge tests on the water-based zinc ion battery using the test electrolyte and the reference electrolyte respectively, wherein 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 fig. 6 (a), at current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g, 5A/g, the specific capacities of the aqueous zinc-ion cells using the test electrolyte were all significantly lower than those of the aqueous zinc-ion cells using the reference electrolyte; as can be seen from fig. 6 (b), the initial specific capacity at a current density of 1.5A/g is 180mAh/g, which is lower than the initial specific capacity of 200mAh/g of the aqueous zinc-ion battery using the reference electrolyte, and after 1400 times of charge and discharge at this current density, the specific capacity is still much lower than that of the aqueous zinc-ion battery using the reference electrolyte. This shows that when the total mass of lignin derivative and inorganic nano particles is higher than 20% of the mass of aqueous electrolyte, the ionic conductivity of the compound gel electrolyte is greatly reduced, the ability of inhibiting zinc dendrite formation and growth is weakened, and the corrosiveness to zinc cathode is enhanced, thereby leading to significant reduction of the multiplying power and cycle performance of the aqueous 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 (4)
1. A water system zinc ion battery compound gel electrolyte is characterized in that: the compound gel electrolyte is prepared by uniformly mixing lignin derivatives, inorganic nano particles and aqueous electrolyte; the lignin derivative comprises one or more of hydroxylation, amination and quaternization products obtained by taking alkali lignin, enzymolysis lignin, organic solvent lignin or steam explosion lignin as raw materials and introducing hydroxyl, amino and quaternary ammonium radical functional groups through chemical reaction; the mass of the lignin derivative accounts for 0.1-50% of the mass of the inorganic nano-particles; the total mass of the lignin derivative and the inorganic nano particles accounts for 2-20% of the mass of the aqueous electrolyte; the aqueous phase electrolyte is prepared by mixing and dissolving water-soluble zinc salt and water-soluble manganese salt; completely dissolving lignin derivatives in aqueous electrolyte, adding inorganic nano particles, stirring and standing; the inorganic nano particles comprise one or more of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide and nano zinc oxide.
2. The aqueous zinc ion battery compound gel electrolyte according to claim 1, wherein: the water-soluble zinc salt comprises one or more of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate and zinc trifluoromethane sulfonate; the water-soluble manganese salt comprises one or more of manganese sulfate, manganese chloride, manganese nitrate, manganese acetate and manganese trifluoromethane sulfonate.
3. The aqueous zinc ion battery compound gel electrolyte according to claim 1, wherein: the concentration of the water-soluble zinc salt in the aqueous electrolyte is 0.1-10 mol/L, and the concentration of the water-soluble manganese salt is 0-1.5 mol/L.
4. An aqueous zinc ion battery comprising the aqueous zinc ion battery complex gel electrolyte according to any one of claims 1 to 3.
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| JP7113995B1 (en) * | 2022-06-01 | 2022-08-05 | 住友精化株式会社 | Electrodes for lithium ion batteries and lithium ion batteries |
| CN114976299A (en) * | 2022-07-12 | 2022-08-30 | 中南大学 | Wet sand electrolyte for water-based zinc ion battery, preparation method of wet sand electrolyte and water-based zinc ion battery |
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