CN108630458B - Aqueous electrolyte and application thereof - Google Patents
Aqueous electrolyte and application thereof Download PDFInfo
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- CN108630458B CN108630458B CN201710166271.8A CN201710166271A CN108630458B CN 108630458 B CN108630458 B CN 108630458B CN 201710166271 A CN201710166271 A CN 201710166271A CN 108630458 B CN108630458 B CN 108630458B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
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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
- 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
- H01M2300/0005—Acid electrolytes
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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 application discloses an aqueous electrolyte and application thereof. The aqueous electrolyte contains 40-85% of potassium acetate by total weight. According to the water system electrolyte, the high-concentration potassium acetate is added into the water system electrolyte, so that almost all water molecules are hydrated with potassium ions, the water molecules are tightly connected with the potassium ions through Van der Waals force, and the electrolysis of the water molecules on the surface of an electrode is inhibited, so that the decomposition voltage is improved, the service life and the capacity retention rate of an electrochemical energy storage device are improved, the electrochemical performance of the electrochemical energy storage device is greatly improved, and the water system electrolyte has great significance for research and application in the water system energy storage field.
Description
Technical Field
The application relates to the field of electrochemical energy storage, in particular to a water-based electrolyte and application thereof.
Background
With the development of socio-economy, people have higher and higher demands for energy. However, chemical energy is continuously exhausted, and people develop and utilize renewable energy sources such as wind energy, water energy and solar energy more and more widely. Therefore, energy storage technology and industry are highly regarded by various countries, and research and development of various novel electrochemical energy storage technologies are rapid. Secondary batteries, electrochemical supercapacitors, fuel cells, and the like are now mainly used as chemical power sources. The electrochemical energy storage is divided into an organic system and a water system according to the electrolyte, namely the adopted electrolyte is organic electrolyte and aqueous electrolyte. The chemical power source of the organic system has the problems of safety, high cost and great environmental pollution due to the use of organic electrolyte, and the future development is limited. The existing water-system secondary batteries include traditional lead-acid storage batteries, nickel-hydrogen batteries, zinc-manganese batteries, zinc-nickel batteries, lead-carbon super-capacitor batteries, and water-system lithium ion batteries (international patent No. W095/21470) proposed by Moli Energy corporation, canada, etc.; the water system super capacitor comprises a high-energy nickel-carbon super capacitor, a water system lithium ion super capacitor and the like.
However, in the aqueous electrolyte, since the decomposition voltage of water is only 1.23V, when the voltage is raised to a certain potential, hydrogen evolution and oxygen evolution reactions occur. Because of the low decomposition voltage of water, when some water system chemical power supplies work under a higher voltage, the service life is reduced very quickly, and the capacity is reduced completely only after dozens or hundreds of charge-discharge cycles, so that the development of water system energy storage with low price, safety and environmental protection is greatly limited.
Disclosure of Invention
The purpose of the present application is to provide a novel aqueous electrolyte and its use.
The following technical scheme is adopted in the application:
the application discloses an aqueous electrolyte, which contains 40-85% of potassium acetate by total weight.
The aqueous electrolyte solution of the present invention may be an aqueous solution of potassium acetate as it is, or may contain other conventional electrolytes or additives. The high-concentration potassium acetate is added into the water system electrolyte, potassium ions are hydrated and solvated, a large number of water molecules are consumed, almost all water molecules in the solution are used for hydrating with the potassium ions due to the high-concentration potassium acetate, and the water molecules are closely connected with the potassium ions through Van der Waals force, so that the electrolysis of the water molecules on the surface of an electrode is inhibited, and the decomposition voltage is improved; further, the problems of high life-span reduction rate, low capacity retention rate and the like caused by low water decomposition voltage in the aqueous electrolyte are solved.
Preferably, the aqueous electrolyte solution of the present application further contains an electrolyte other than potassium acetate, and the electrolyte is a sulfate, a nitrate, an acetate, a chloride, or a hydroxide of at least one of an alkali metal, an alkaline earth metal, a rare earth metal, aluminum, and zinc.
Preferably, the aqueous electrolyte further comprises additives including an acid or an alkali for adjusting the pH of the electrolyte, and a metal oxide for adjusting the viscosity of the electrolyte, the metal oxide including but not limited to porous SiO 2 Or porous Al 2 O 3 。
It is understood that the key point of the aqueous electrolyte of the present application is that high-concentration potassium acetate is used, and the aqueous electrolyte may contain only potassium acetate, or may contain other conventionally used electrolytes and additives.
Preferably, the pH of the aqueous electrolyte solution of the present invention is 3 to 12.
The PH of the electrolyte solution is preferably neutral in general, and the PH of the electrolyte solution of the present invention is preferably 3 to 12 because the PH can be selected appropriately according to the specific aqueous battery system to be used.
The application further discloses the application of the water-based electrolyte in an electrochemical energy storage device.
In another aspect, the present application discloses an electrochemical energy storage device using the aqueous electrolyte of the present application, wherein the electrochemical energy storage device is an aqueous secondary battery or an aqueous electrochemical supercapacitor, or an organic combination of the two.
Preferably, the water-based secondary battery includes, but is not limited to, at least one of a lithium ion battery, a sodium ion battery, a magnesium ion battery, and a zinc ion battery.
The water system electrolyte is researched for the electrochemical energy storage device, so that the decomposition voltage of water is improved, the service life and the capacity retention rate of the electrochemical energy storage device are further improved, and a foundation is laid for the popularization and application of the electrochemical energy storage device.
The beneficial effect of this application lies in:
according to the water system electrolyte, high-concentration potassium acetate is added into the water system electrolyte, so that almost all water molecules are hydrated with potassium ions, the water molecules are tightly connected with the potassium ions through Van der Waals force, and the electrolysis of the water molecules on the surface of an electrode is inhibited, so that the decomposition voltage is improved, the capacity retention rate and the service life of an electrochemical energy storage device are improved, the electrochemical performance of the electrochemical energy storage device is greatly improved, and the water system electrolyte has great significance for research and application in the water system energy storage field.
Drawings
FIG. 1 is a plot of cyclic voltammetry scans of two different concentrations of potassium acetate electrolyte in one example of the present application, where the solid curve is high concentration potassium acetate electrolyte and the dashed curve is low concentration potassium acetate electrolyte;
FIG. 2 is a cycle test chart of an electrochemical energy storage device using an aqueous electrolyte according to example two of the present application;
fig. 3 is a cycle test chart of a hybrid supercapacitor using an aqueous electrolyte solution according to example three of the present application.
Detailed Description
In the course of research and experiments on an aqueous electrolyte, the inventors of the present application found that by adding potassium acetate to the aqueous electrolyte, water molecules can be hydrated and solvated, and that when the potassium ion concentration reaches a certain level, almost all water molecules in the solution hydrate with it, and the water molecules and potassium ions are closely connected by van der waals force, so that electrolysis of water molecules on the electrode surface can be effectively inhibited, and the decomposition voltage can be increased. Based on this finding, the inventors of the present application have proposed a novel aqueous electrolyte, i.e., an aqueous electrolyte of the present application containing 40% to 85% by weight of potassium acetate based on the total weight. Subsequent researches show that only potassium acetate can be independently adopted in the water-based electrolyte, namely, a potassium acetate aqueous solution is independently adopted as the electrolyte; it is also possible to add thereto conventionally used electrolytes and additives. The specific use condition may be determined according to different use requirements, and is not specifically limited herein.
The present application will be described in further detail with reference to specific examples. The following examples are merely illustrative of the present application and should not be construed as limiting the present application.
Example one
The aqueous electrolyte of the present example specifically consists of water, potassium acetate, and lithium acetate, and the preparation method thereof is as follows:
the aqueous electrolyte of this example was obtained by weighing the components in a weight ratio of water/potassium acetate/lithium acetate =1.5/7.5/1 and dissolving the components in water. Wherein, the potassium acetate accounts for 75 percent of the total mass fraction.
In addition, an aqueous electrolyte with a low potassium acetate concentration was prepared as a comparison, specifically, each component was weighed in a weight ratio of water/potassium acetate/lithium acetate =8/1/1 and dissolved in water, to obtain an aqueous electrolyte with a potassium acetate concentration of 10% by mass as a comparison.
The aqueous electrolyte prepared in the example was subjected to cyclic voltammetry curve testing using three-electrode cyclic voltammetry, where the working and counter electrodes were Pt electrodes, the reference electrode was a saturated calomel electrode, the scan voltage was-1.5V, and the scan rate was 5mv/s. The test results are shown in fig. 1, in which the solid line curve is the aqueous electrolyte with high potassium acetate concentration, and the dotted line curve is the aqueous electrolyte with low potassium acetate concentration; the results showed that the aqueous electrolyte with high potassium acetate concentration was almost a coincident straight line between-1.2V and 1.0V, indicating that it was electrochemically stable at this point and almost no decomposition reaction of water occurred; the aqueous electrolyte with low potassium acetate concentration has obvious hydrogen evolution and oxygen evolution reactions at-1V and 0.8V, and the electrochemical stability window of the aqueous electrolyte adopting high-concentration potassium acetate is 2.2V, which is obviously better than that of the common aqueous electrolyte adopting low-concentration potassium acetate, and the electrochemical stability window of the aqueous electrolyte adopting low-concentration potassium acetate is less than 1.8V.
The aqueous electrolyte of this example was used in an aqueous lithium ion battery, and the positive electrode was a commercially available spinel LiMn 2 O 4 The negative electrode is LiTi 2 (PO 4 ) 3 Mixing the positive electrode and the negative electrode according to the weight ratio of active material/acetylene black/PTFE =80/10/10 to prepare slurry, coating the slurry on a stainless steel mesh, and drying to prepare the electrode. The battery was then assembled using a separator of a commercial nickel-metal hydride battery, the electrolyte being the aqueous electrolyte of this example.
The capacity retention ratio of the lithium ion battery using the aqueous electrolyte of this example was measured, specifically, the capacity retention ratio was measured for 2000 cycles of charge and discharge at a voltage range of 0 to 1.8V and a current density of 200 mA/g. The result shows that the capacity retention rate is 95% after 2000 cycles, which indicates that the aqueous lithium ion battery adopting the aqueous electrolyte has long cycle life.
Example two
The aqueous electrolyte of the embodiment specifically comprises water, potassium acetate and lithium acetate, and the preparation method comprises the following steps:
the components were weighed out in a weight ratio of water/potassium acetate/lithium acetate =1/7/1, and dissolved in water to obtain an aqueous electrolyte solution of this example. Wherein, the potassium acetate accounts for 77.8 percent of the total mass fraction.
The cyclic voltammetry test of the electrolyte of this example was carried out using the same method and conditions as in example one, and the results showed that the anodic oxygen evolution potential was 1.0V (vs. sce), the cathodic hydrogen evolution potential was-1.2V (vs. sce), and the voltage window reached 2.2V.
The aqueous electrolyte of this example was used in an aqueous lithium ion battery, and the positive electrode was a commercial spinel LiMn 2 O 4 The negative electrode is LiTi 2 (PO 4 ) 3 Mixing the positive electrode and the negative electrode according to the weight ratio of active material/acetylene black/PTFE =80/10/10 to prepare slurry, coating the slurry on a stainless steel mesh, and drying to prepare the electrode. And then assembled into a battery, and the separator used was that of a commercial nickel-metal hydride battery, i.e., the aqueous electrolyte of this example.
The capacity retention ratio of the lithium ion battery using the aqueous electrolyte of this example was measured, specifically, the capacity retention ratio was measured for 2000 cycles of charge and discharge at a voltage range of 0 to 1.8V and a current density of 200 mA/g. The test result is shown in fig. 2, and the result shows that the capacity retention rate exceeds 90% after 2000 cycles, which indicates that the aqueous lithium ion battery adopting the aqueous electrolyte has long cycle life.
EXAMPLE III
The aqueous electrolyte of the present example specifically consists of water, potassium acetate, and lithium sulfate, and the preparation method thereof is as follows:
the components were weighed out in a weight ratio of water/potassium acetate/lithium sulfate =1/6/1, and dissolved in water to obtain an aqueous electrolyte solution of this example. Wherein, the potassium acetate accounts for 75 percent of the total mass fraction.
The cyclic voltammetry test of the electrolyte of this example was carried out using the same method and conditions as in example one, and the results showed that the anodic oxygen evolution potential was 1.0V (vs. sce), the cathodic hydrogen evolution potential was-1.2V (vs. sce), and the voltage window reached 2.2V.
The aqueous electrolyte of this example was used in an aqueous lithium-ion hybrid supercapacitor, and the positive electrode was a commercial spinel LiMn 2 O 4 The cathode active material is active carbon, the anode and the cathode are mixed according to the weight ratio of the active material/super-P/PTFE =85/8/7 to prepare slurry, the slurry is coated on a stainless steel mesh, and the electrode is prepared by drying. Then, a lithium ion hybrid supercapacitor was assembled using a separator of a commercial nickel-metal hydride battery, and the electrolyte was an aqueous electrolyte of this example.
The capacity retention rate of the lithium ion hybrid supercapacitor adopting the embodiment is measured, specifically, the lithium ion hybrid supercapacitor is charged and discharged under the voltage range of 0-2.0V, the current density is 1000mA/g, and the capacity retention rate of 20000 cycles is tested. The test result is shown in fig. 3, and the result shows that the capacity retention rate hardly decays after 20000 cycles, so that the excellent cycle stability can be maintained under the working voltage of 2.0V, and the electrochemical stability window of the electrolyte can reach 2.2V.
Example four
The aqueous electrolyte of this example specifically comprised water, potassium acetate and an additive Al 2 O 3 Namely, in this example, only the aqueous solution of potassium acetate is used as the electrolyte, and the preparation method is as follows:
water/potassium acetate/Al in the weight ratio 2 O 3 Weighing each component according to a ratio of =0.95/4/0.05, dissolving potassium acetate in water, adding Al 2 O 3 The aqueous electrolyte of this example was obtained by uniformly dispersing the powder. Wherein, the potassium acetate accounts for 80 percent of the total mass fraction.
The electrolyte of this example was subjected to cyclic voltammetry tests using the same method and conditions as in example one, and the results showed that the anodic oxygen evolution potential was 1.0V (vs. sce), the cathodic hydrogen evolution potential was-1.2V (vs. sce), and the voltage window reached 2.2V.
The electrolyte of the example is used in an aqueous hybrid supercapacitor, and the positive electrode active material is MnO 2 The cathode active material is active carbon, the anode and the cathode are mixed into slurry according to the weight ratio of the active material/acetylene black/PTFE =80/10/10, the slurry is coated on a stainless steel net, and the electrode is manufactured by drying. Then assembling water system MnO 2 The separator used in the hybrid supercapacitor was that of a commercial nickel-metal hydride battery, and the electrolyte was an aqueous electrolyte in this example.
The capacity retention rate of the water system hybrid supercapacitor adopting the embodiment is measured, specifically, the capacitor is charged and discharged under the voltage range of 0-2.0V, the current density is 1000mA/g, and the capacity retention rate of 10000 cycles of the capacitor is tested. The result shows that the capacity retention rate is 95% after 10000 cycles, the hybrid supercapacitor can still keep long cycle life when being charged and discharged under high working voltage, and the electrochemical stability window of the electrolyte reaches 2.2V, which is far higher than the decomposition potential of water.
EXAMPLE five
The aqueous electrolyte of the embodiment specifically comprises water, potassium acetate and sodium sulfate, and the preparation method comprises the following steps:
the components were weighed out in a weight ratio of water/potassium acetate/sodium sulfate =2/6/1, and dissolved in water to obtain an aqueous electrolyte solution of this example. Wherein, the potassium acetate accounts for 66.7 percent of the total mass fraction.
The electrolyte of this example was subjected to cyclic voltammetry tests using the same method and conditions as in example one, and the results showed that the anodic oxygen evolution potential was 0.9V (vs. sce), the cathodic hydrogen evolution potential was-1.1V (vs. sce), and the voltage window reached 2.1V.
The aqueous electrolyte of this example was used in an aqueous sodium ion battery, and the positive electrode active material was Na 3 V 2 (PO 4 ) 3 The negative active material is NaTi 2 (PO 4 ) 3 Mixing the positive electrode and the negative electrode into slurry according to the weight ratio of active material/acetylene black/KS-6/PTFE =85/6/4/5, coating the slurry on a stainless steel mesh, and drying to manufacture the electrode. Then assembling water system sodium ionsThe battery used was a separator glass fiber separator, and the electrolyte was the aqueous electrolyte of this example.
The voltage interval of the charge and discharge of the aqueous sodium ion battery is 0.4-1.6V, the average discharge voltage of the aqueous sodium ion battery is close to 1.2V, and the overall capacity retention rate of the aqueous sodium ion battery is 90% after the aqueous sodium ion battery is cycled at 5 ℃ for 500.
EXAMPLE six
The aqueous electrolyte of the present example was prepared by adding potassium acetate in an amount of 60% by weight based on the total weight of sodium acetate as an electrolyte, as follows:
the aqueous electrolyte of this example was prepared by weighing the components in the weight ratio of water to potassium acetate to sodium acetate =1. Wherein, the potassium acetate accounts for 60 percent of the total mass fraction.
The electrolyte of this example was subjected to cyclic voltammetry tests using the same method and conditions as in example one, and the results showed that the anodic oxygen evolution potential was 0.95V (vs. sce), the cathodic hydrogen evolution potential was-1.1V (vs. sce), and the voltage window reached 2.1V.
The aqueous electrolyte of this example was used in an aqueous sodium ion battery, and the positive electrode active material was NaTi 2 (PO 4 ) 3 The negative electrode active material is Na 0.44 MnO 2 Mixing the positive electrode and the negative electrode into slurry according to the weight ratio of active material/acetylene black/KS-6/PTFE =85/6/4/5, coating the slurry on a stainless steel mesh, and drying to manufacture the electrode. Then, an aqueous sodium ion battery was assembled using a separator glass fiber separator, and the electrolyte was the aqueous electrolyte of this example.
The aqueous sodium ion battery is charged and discharged, the voltage interval is 0.5-1.5V, and the capacity retention ratio is 90% after 1000 times of charging and discharging circulation at 5C.
EXAMPLE seven
The aqueous electrolyte of the embodiment specifically comprises water, potassium acetate and sodium sulfate, and the preparation method comprises the following steps:
the components were weighed out in a weight ratio of water/potassium acetate/sodium sulfate =2/7/1, and dissolved in water to obtain an aqueous electrolyte solution of this example. Wherein, the potassium acetate accounts for 70 percent of the total mass fraction.
The cyclic voltammetry test of the electrolyte of this example was carried out using the same method and conditions as in example one, and the results showed that the anodic oxygen evolution potential was 1.05V (vs. sce), the cathodic hydrogen evolution potential was-1.2V (vs. sce), and the voltage window reached 2.1V.
The aqueous electrolyte of this example was used in an aqueous sodium ion battery, and the positive electrode active material was NaTi 2 (PO 4 ) 3 The negative active material is Na 0.44 MnO 2 Mixing the positive electrode and the negative electrode into slurry according to the weight ratio of active material/acetylene black/KS-6/PTFE =85/6/4/5, coating the slurry on a stainless steel mesh, and drying to manufacture the electrode. Then, an aqueous sodium ion battery was assembled using a separator glass fiber separator, and the electrolyte was the aqueous electrolyte of this example.
The aqueous sodium ion battery is charged and discharged, the voltage range is 0.5-1.5V, and the capacity retention ratio is 91 percent after 1000 times of charging and discharging circulation at 5C.
Example eight
The aqueous electrolyte of this example specifically contains water, potassium acetate, lithium sulfate and an additive SiO 2 The preparation method comprises the following steps:
according to the weight ratio of water/potassium acetate/lithium sulfate/SiO 2 The components were weighed out in a proportion of 1/8/0.98/0.02, dissolved in water, and stirred uniformly to obtain the aqueous electrolyte solution of this example. Wherein, the potassium acetate accounts for 80 percent of the total mass fraction.
The electrolyte of this example was subjected to cyclic voltammetry tests using the same method and conditions as in example one, and the results showed that the anodic oxygen evolution potential was 1.1V (vs. sce), the cathodic hydrogen evolution potential was-1.25V (vs. sce), and the voltage window reached 2.2V.
The aqueous electrolyte of this example was used in an aqueous lithium ion battery, and the positive electrode active material was LiTi 2 (PO 4 ) 3 The negative active material is LiMn 2 O 4 Mixing the positive and negative electrodes according to the weight ratio of active material/acetylene black/PTFE =80/10/10 to prepare slurry, and mixingCoating on stainless steel net, and oven drying to obtain electrode. Then, a water-based lithium ion battery was assembled, and the separator used in the commercial nickel-metal hydride battery was the water-based electrolyte in this example.
The lithium ion battery is charged and discharged, the voltage interval is 1-2V, and the capacity retention rate is 90% after 2000 times of charging and discharging circulation at 5C.
Example nine
The aqueous electrolyte of the present example specifically consists of water, potassium acetate, and zinc nitrate, and the preparation method thereof is as follows:
the components were weighed out in a weight ratio of water/potassium acetate/zinc nitrate =1/8.5/0.5, and dissolved in water to obtain an aqueous electrolyte solution of this example. Wherein, the potassium acetate accounts for 85 percent of the total mass fraction.
The cyclic voltammetry test of the electrolyte of this example using the same method and conditions as in example one showed that the anodic oxygen evolution potential was 1.0V (vs. sce), the cathodic hydrogen evolution potential was-1.25V (vs. sce) and the voltage window reached 2.25V.
The aqueous electrolyte of this example was used in an aqueous zinc ion battery, and Zn was used as a positive electrode, and Na was used as a negative electrode active material 3 V 2 (PO 4 ) 3 The negative electrode is mixed according to the weight ratio of active material/acetylene black/PTFE =80/10/10 to prepare slurry, and the slurry is coated on a stainless steel mesh and dried to prepare the electrode. Then, an aqueous zinc ion battery was assembled, and a separator of a commercial nickel-metal hydride battery was used as the separator, and the electrolyte was the aqueous electrolyte of this example.
When the zinc ion battery is charged and discharged, the voltage interval is 0.8-1.8V, and the capacity retention rate is 82% after 200 times of charging and discharging circulation at 3C.
Example ten
The aqueous electrolyte of the present example specifically contains water, potassium acetate, and lithium hydroxide, and the preparation method thereof is as follows:
the components were weighed out in a weight ratio of water/potassium acetate/lithium hydroxide =1/6/0.2, and dissolved in water to obtain an aqueous electrolyte solution of this example. Wherein, the potassium acetate accounts for 83.3 percent of the total mass fraction.
The electrolyte of this example was subjected to cyclic voltammetry tests using the same method and conditions as in example one, and the results showed that the anodic oxygen evolution potential was 0.95V (vs. sce), the cathodic hydrogen evolution potential was-1.3V (vs. sce), and the voltage window reached 2.2V.
The aqueous electrolyte of this example was used in an activated carbon (abbreviation AC)// AC symmetrical supercapacitor. The symmetrical super capacitor is charged and discharged, the voltage interval is 0-1.8V, and the capacity retention rate of 50C after 10000 times of charge and discharge circulation is 95%.
EXAMPLE eleven
The aqueous electrolyte of the embodiment specifically comprises water, potassium acetate, lithium sulfate and sulfuric acid, and the preparation method comprises the following steps:
the components were weighed out in a weight ratio of water/potassium acetate/lithium sulfate/sulfuric acid =1/6/1/0.06, and dissolved in water to obtain an aqueous electrolyte solution of this example. Wherein, the potassium acetate accounts for 74.9 percent of the total mass fraction.
The electrolyte of this example was subjected to cyclic voltammetry tests using the same method and conditions as in example one, and the results showed that the anodic oxygen evolution potential was 1.15V (vs. sce), the cathodic hydrogen evolution potential was-1.15V (vs. sce), and the voltage window reached 2.2V.
The aqueous electrolyte of this example was used in an aqueous lithium ion battery, and the positive electrode active material was LiTi 2 (PO 4 ) 3 The negative active material is LiMn 2 O 4 Mixing the positive electrode and the negative electrode according to the weight ratio of active material/acetylene black/PTFE =80/10/10 to prepare slurry, coating the slurry on a stainless steel mesh, and drying to prepare the electrode. Then, a water-based lithium ion battery was assembled, and the separator used in the commercial nickel-metal hydride battery was the water-based electrolyte in this example.
The lithium ion battery is charged and discharged, the voltage interval is 1-2V, and the capacity retention ratio is 86% after 2000 times of charging and discharging circulation at 5C.
Example twelve
The aqueous electrolyte of the embodiment specifically comprises water, potassium acetate and magnesium nitrate, namely the embodiment only adopts a potassium acetate aqueous solution as the electrolyte, and the preparation method comprises the following steps:
the aqueous electrolyte of this example was obtained by weighing each component at a weight ratio of water/potassium acetate/magnesium nitrate =2/2/1 and dissolving potassium acetate and magnesium nitrate in water. Wherein, the potassium acetate accounts for 40 percent of the total mass fraction.
The electrolyte of this example was subjected to cyclic voltammetry tests using the same method and conditions as in example one, and the results showed that the anodic oxygen evolution potential was 0.85V (vs. sce), the cathodic hydrogen evolution potential was-1.05V (vs. sce), and the voltage window reached 1.9V.
The electrolyte of this example was used in an aqueous magnesium ion battery, and the positive electrode active material was MnO 2 The cathode active material is active carbon, the anode and the cathode are mixed into slurry according to the weight ratio of the active material/acetylene black/PTFE =80/10/10, the slurry is coated on a stainless steel net, and the electrode is manufactured by drying. Then, an aqueous magnesium ion battery was assembled using a commercial nonwoven fabric separator as a separator, and the electrolyte was the aqueous electrolyte of this example.
The capacity retention rate of the aqueous magnesium ion battery adopting the embodiment is measured, specifically, the battery is charged and discharged under the voltage range of 0-1.8V, the current density is 1000mA/g, and the capacity retention rate of 10000 cycles is tested. The results showed that the capacity retention rate was 80% after 10000 cycles.
The foregoing is a more detailed description of the present application in connection with specific embodiments thereof, and it is not intended that the present application be limited to the specific embodiments thereof. For those skilled in the art to which the present application pertains, several simple deductions or substitutions may be made without departing from the concept of the present application, and all should be considered as belonging to the protection scope of the present application.
Claims (6)
1. An aqueous electrolyte characterized in that: the water system electrolyte contains 66.7-85% of potassium acetate by total weight; the pH value of the aqueous electrolyte is 3 to 12.
2. The aqueous electrolyte of claim 1, wherein: the aqueous electrolyte further contains an electrolyte other than the potassium acetate, and the electrolyte is a sulfate, a nitrate, an acetate, a chloride or a hydroxide of at least one of an alkali metal, an alkaline earth metal, a rare earth metal, aluminum and zinc.
3. The aqueous electrolyte according to claim 1 or 2, characterized in that: the aqueous electrolyte also contains additives, the additives comprise acid or alkali for adjusting the pH value of the electrolyte and metal oxide for adjusting the viscosity of the electrolyte, and the metal oxide comprises porous SiO 2 Or porous Al 2 O 3 。
4. Use of an aqueous electrolyte according to any of claims 1-3 in an electrochemical energy storage device.
5. An electrochemical energy storage device using the aqueous electrolyte according to any one of claims 1 to 3, which is an aqueous secondary battery or an aqueous electrochemical supercapacitor, or an organic combination of both.
6. An electrochemical energy storage device as in claim 5, wherein: the aqueous secondary battery includes at least one of a lithium ion battery, a sodium ion battery, a magnesium ion battery, and a zinc ion battery.
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| JP6939307B2 (en) * | 2017-09-19 | 2021-09-22 | トヨタ自動車株式会社 | Method for manufacturing water-based lithium-ion secondary battery, negative electrode active material composite, and method for manufacturing water-based lithium-ion secondary battery |
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| CN111725002A (en) * | 2019-03-19 | 2020-09-29 | 南京工业大学 | Water system alkaline electrolyte and application thereof, zinc-based hybrid supercapacitor and preparation method thereof |
| CN110060882B (en) * | 2019-05-24 | 2021-09-07 | 中国科学院理化技术研究所 | Aqueous electrolyte and application thereof |
| CN110060883B (en) * | 2019-05-24 | 2021-05-14 | 中国科学院理化技术研究所 | Aqueous electrolyte and application thereof |
| CN110120309B (en) * | 2019-05-24 | 2021-06-29 | 中国科学院理化技术研究所 | Aqueous electrolyte and application thereof |
| CN110690060B (en) * | 2019-09-29 | 2020-11-20 | 北京科技大学 | Electrolyte for improving working voltage of aqueous electrochemical capacitor |
| CN110655114B (en) * | 2019-10-09 | 2021-09-24 | 东北大学 | Method for improving voltage of zinc ion battery |
| CN111463524B (en) * | 2020-03-16 | 2021-11-05 | 中南大学 | Alkaline water-based electrolyte for aluminum-air battery and application thereof |
| CN111900496A (en) * | 2020-06-12 | 2020-11-06 | 北京大学深圳研究生院 | Electrolyte for water-based zinc ion battery and application thereof |
| CN111900497A (en) * | 2020-06-12 | 2020-11-06 | 北京大学深圳研究生院 | Aqueous zinc ion battery electrolyte and application thereof |
| CN114552072A (en) * | 2020-11-25 | 2022-05-27 | 中国科学院大连化学物理研究所 | Aqueous magnesium battery electrolyte |
| CN112599892A (en) * | 2020-12-02 | 2021-04-02 | 南京航空航天大学 | High-stability gel electrolyte for zinc-air battery and preparation method thereof |
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| CN101241802A (en) * | 2008-03-13 | 2008-08-13 | 复旦大学 | A non symmetric water natrium/kalium ion battery capacitor |
| CN102253105B (en) * | 2011-06-15 | 2013-09-25 | 郑州炜盛电子科技有限公司 | Electrochemical sensor |
| CN103219551A (en) * | 2013-03-27 | 2013-07-24 | 恩力能源科技（南通）有限公司 | Water-system alkali metal ion power storage device |
| CN103545578B (en) * | 2013-09-30 | 2016-03-02 | 刘甲祥 | A kind of electrolyte of magnesium air cell |
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