CN113644326A - Water-based zinc ion battery and formation method - Google Patents
Water-based zinc ion battery and formation method Download PDFInfo
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- CN113644326A CN113644326A CN202111206876.8A CN202111206876A CN113644326A CN 113644326 A CN113644326 A CN 113644326A CN 202111206876 A CN202111206876 A CN 202111206876A CN 113644326 A CN113644326 A CN 113644326A
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- H—ELECTRICITY
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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Abstract
The invention relates to a water system zinc ion battery, which comprises a positive electrode, a negative electrode and electrolyte, wherein the negative electrode comprises a zinc-containing material, the electrolyte comprises conductive salt and water, the conductive salt comprises zinc salt, and the positive electrode comprises manganese-containing oxide; the manganese-containing oxide consists of a manganese element and an oxygen element; the valence state of the manganese element is lower than +4 valence; the aqueous zinc ion battery needs to be subjected to a formation step before use; the forming step comprises charging and discharging; after the formation step, the manganese oxide is gradually changed from an initial shape to a second shape; the second morphology is a sheet-like or microcrystalline sheet-like aggregate. By adjusting the electrolyte environment and the anode material, the contact interface between the anode material and the electrolyte can be improved, the converted morphology of the anode material can be regulated, the anode material is promoted to be converted into a nanosheet aggregate penetrating through the internal space of the electrode, the contact area between the anode material and the electrolyte is larger, the migration path of electrons is shorter, and the discharge capacity of the battery can be comprehensively improved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a water-based zinc ion battery and a formation method.
Background
The secondary battery is a battery which is widely applied at present and can be repeatedly charged and discharged, and the application of the secondary battery relates to a plurality of fields, wherein the lithium ion battery is most widely applied. However, due to the disadvantages of high cost, environmental unfriendliness, and insecurity associated with the use of organic electrolytes, it is not suitable for large-scale energy storage systems. A battery using a safe, low-cost aqueous electrolyte can accurately meet these requirements as compared with a non-aqueous battery. However, natural lithium storage is limited, and with the rapid development of lithium-related industries, the exhaustion of lithium comes sooner or later; in addition, the energy density of the water system lithium ion battery is lower due to the limitation of a narrower stable potential window of the aqueous solution, and the cathode material of the water system lithium ion battery has poor stability and short cycle life.
The zinc metal has high content in earth resources, large production scale, low cost and no toxicity; in addition, the zinc metal anode has higher theoretical capacity (820mAh.g) -1 ) Lower electrochemical potential (0.76V vs standard hydrogen electrode) and higher natural abundance, and the stability of zinc in water is very high due to the existence of hydrogen evolution overpotential. The water system zinc ion battery takes metal zinc with high theoretical capacity as a negative electrode, a zinc salt water solution as electrolyte, and a positive electrode material can be manganese oxide, vanadium oxide and a Prussian blue-like material, wherein the manganese oxide has the advantages of rich raw material reserves, no pollution, high specific capacity and the like, and has strong practicability.
Various low-valence manganese oxides have been disclosed as positive electrode materials of zinc ion batteries at present, but in the actual use process, the initial discharge capacity of the materials is low, and the stable charge and discharge performance of the materials can be achieved after multiple cycles; meanwhile, the electrical property of the existing low-price manganese anode material cannot be fully exerted, the actual discharge capacity is less than half of the theoretical capacity (about 300 mAh/g), the requirement of an energy storage device and a small electronic device on the energy density of the battery cannot be met, and the low-price manganese anode material is a main factor for restricting the further wide application of the water system zinc-manganese battery.
Disclosure of Invention
The invention provides a water system zinc ion battery and a formation method aiming at the defects of the prior art, wherein low-valence manganese-containing oxide (the valence of manganese element is lower than + 4) is adopted as a positive electrode material, and the electrical property of the positive electrode material is improved by adjusting the environment of electrolyte and charge-discharge parameters, so that the contact interface between the positive electrode material and the electrolyte can be improved in the charge-discharge cycle process of the positive electrode material; the shape of the anode material is regulated and controlled, the anode material is promoted to be converted into a nanosheet aggregate penetrating through the inner space of the electrode, the dissolution of manganese ions is reduced, the contact area of the anode material and an electrolyte is larger, the migration path of electrons is shorter, better electrochemical performance is shown, and the discharge capacity of the battery can be comprehensively improved; by adopting a specific formation mode, a positive electrode material and an electrolyte additive, the conversion rate of the low-price manganese positive electrode is improved, so that the cycle number required for reaching a stable stage during battery cycle is obviously reduced, and the specific capacity is obviously improved compared with a comparative example.
Alternatively, the manganese valence state being less than +4 means: the valence of the manganese element can be +1 valence, +2 valence, +3 valence or any other value lower than +4 valence.
According to an aspect of the present application, there is provided an aqueous zinc-ion battery including a positive electrode, a negative electrode, and an electrolytic solution, the negative electrode including a zinc-containing material; the electrolyte comprises a conductive salt and water, the conductive salt comprises a zinc salt, and the positive electrode comprises a manganese-containing oxide; the manganese-containing oxide consists of a manganese element and an oxygen element; the valence state of the manganese element is lower than +4 valence; the aqueous zinc ion battery needs to be subjected to a formation step before use; the forming step comprises charging and discharging; the charging voltage interval is 0-2.1V and comprises three stages; the first stage is as follows: when the charging voltage is not higher than 1.8V, constant current charging is adopted, and the multiplying power current is not higher than 0.2C; the second stage is as follows: the charging voltage is not lower than 1.8V, constant current charging is adopted, and the multiplying power current is not higher than 0.1C; in the third stage, constant voltage charging is adopted, the charging voltage is 1.9 to 2.1V, and the cut-off current value is 0.02C to 0.1C; in the formation step, the electrolyte further comprises a formation promoter; after the formation step, the manganese oxide is gradually changed from an initial shape to a second shape; the second morphology is a sheet-like or microcrystalline sheet-like aggregate.
Optionally, the discharge is a constant current discharge; the discharge cut-off voltage is not higher than 0.8V, and the discharge multiplying power is not higher than 0.2C; the termination conditions of the formation step are as follows: let M n The specific discharge capacity of the nth cycle is shown, n is more than 1, | M n -M n-1 |/M n-1 ≤5%。
Alternatively, n is typically an integer greater than 1.
Optionally, the depth of discharge is 100%.
Optionally, a formation accelerator is added to the electrolyte before the formation step.
Optionally, the first stage is: and when the charging voltage is not higher than 1.8V, constant current charging is adopted, and the charging multiplying power is 0.02 to 0.2C.
Optionally, the charging voltage in the first stage is 0 to 1.8V.
Optionally, the lower charging voltage limit of the first stage is 0V, 0.1V, 0.2V, 0.3V, 0.4V, 0.5V, 0.6V, 0.7V, 0.8V, 0.9V, 1.0V, 1.1V, 1.2V, 1.3V, 1.4V, 1.5V, 1.6V, 1.7V, or a value between any two values; the upper limit is 0.1V, 0.2V, 0.3V, 0.4V, 0.5V, 0.6V, 0.7V, 0.8V, 0.9V, 1.0V, 1.1V, 1.2V, 1.3V, 1.4V, 1.5V, 1.6V, 1.7V, 1.8V, or a value between any two values.
Optionally, the charge rate of the first stage is 0.02C, 0.03C, 0.04C, 0.05C, 0.06C, 0.07C, 0.08C, 0.09C, 0.1C, 0.11C, 0.12C, 0.13C, 0.14C, 0.15C, 0.16C, 0.17C, 0.18C, 0.19C, 0.2C, or a number between any two values.
Optionally, the second stage is: the charging voltage is 1.8 to 2.1V, the charging is carried out by adopting a constant current, and the charging multiplying power is 0.02 to 0.1C.
Optionally, the lower limit of the charging voltage in the second stage is 1.8V, 1.85V, 1.9V, 1.95V, 2V, 2.05V, or a value between any two values; the upper limit is 1.85V, 1.9V, 1.95V, 2V, 2.05V, 2.1V, or a value between any two values.
Optionally, the charging voltage in the second stage is 1.8 to 1.9V, 1.8 to 1.95V, 1.8 to 2V, 1.8 to 2.05V, 1.8 to 2.1V, or any value between 1.8V and 1.9 to 2.1V.
Optionally, the charge rate of the second stage is 0.02C, 0.03C, 0.04C, 0.05C, 0.06C, 0.07C, 0.08C, 0.09C, 0.1C, or a number between any two numbers.
Optionally, the constant-current charging is staged charging, that is, the charging multiplying factors of the charging voltages in different ranges are different, and when the battery is formed through different charging multiplying factors and charging voltages, the cycle number can be reduced, and the maximum discharge capacity can be reached as soon as possible.
Optionally, the charging voltage in the third stage is any one of values from 1.9 to 2.1V.
Optionally, the charging voltage of the third stage is 1.9V, 1.95V, 1.98V, 2V, 2.05V, 2.1V, or a value between any two values.
Optionally, the off-current of the third stage is 0.02C, 0.03C, 0.04C, 0.05C, 0.06C, 0.07C, 0.08C, 0.09C, 0.1C, or a value between any two values.
Alternatively, the negative electrode of the aqueous zinc ion battery may be metal zinc or a zinc alloy, and the specific form is not limited, and zinc may be used only for the purpose of electron transfer. Therefore, the conductive salt must contain a zinc salt to satisfy the demand of the battery for zinc ions.
Optionally, the manganese-containing oxide is selected from at least one of manganese monoxide, manganese sesquioxide, and manganese tetraoxide.
Optionally, the mass content of the manganese-containing oxide in the positive electrode is 20% -95%.
Optionally, the mass content of zinc in the zinc-containing material is 40% -100%.
Optionally, the manganese-containing compound is present in the positive electrode at a mass content of 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or any point between any two values.
Preferably, the mass content of the manganese-containing compound in the positive electrode is 50% -95%.
Because the manganese element is an active substance of the positive electrode, the mass content of the manganese-containing compound in the positive electrode needs to be as large as possible so as to meet the requirement of higher capacitance and have better electrical properties.
Optionally, the zinc content of the zinc-containing material is 40%, 50%, 60%, 70%, 80%, 90%, 100%, or any point between any two values by mass.
Optionally, the concentration of zinc in the zinc salt in the electrolyte is 0.5-5 mol/L.
Optionally, the concentration of zinc in the zinc salt in the electrolyte is 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L or any value between any two values.
Optionally, the zinc salt is an important component in the electrolyte of the aqueous zinc ion battery, and the zinc salt mainly serves to provide enough zinc ions, so that the requirement of the chemical reaction between the positive electrode and the negative electrode of the battery on the zinc ions in the charging and discharging processes is met, and the ionic conductivity of the aqueous electrolyte is ensured. The addition of lithium salt, sodium salt and potassium salt can further improve the conductivity of the electrolyte; the total cation concentration of the conductive salt in the electrolyte is not lower than 1mol/L, and the zinc ion concentration is not lower than 0.5mol/L, so that the basic requirements of the battery on the conductivity and zinc ions required by electrochemical reaction are met.
Optionally, the formation promoter is an organic electrolyte salt, and the function of the formation promoter is mainly to improve the electrochemical performance, such as specific discharge capacity, cycle life and the like, of the low-valence manganese-containing oxide positive electrode material. The positive electrode material has no capacity in an initial state, can be discharged after being charged for the first time, has the condition that the specific capacity gradually rises in the initial circulation process, is called a formation stage when the specific discharge capacity of the positive electrode approaches or reaches the highest specific discharge capacity of the material, can go through 2-10 circulation times in the formation stage, and is converted into a flaky MnOOH junction after the formation is finishedMnO of structure or sheet shape 2 And (5) structure.
Optionally, the formation promoter is an ionic surfactant.
Optionally, the concentration of the formation promoter in the electrolyte is not less than 0.5mol/L.
Optionally, the concentration of the formation promoter in the electrolyte is 0.5-5 mol/L.
Optionally, the concentration of the formation promoter in the electrolyte is 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L or any value between any two values.
Optionally, the ionic surfactant is an anionic surfactant and/or a cationic surfactant.
The anionic surfactant and the cationic surfactant can play the roles, so that the specific discharge capacity of the positive electrode is improved; however, the deterioration of the cationic surfactant to the negative electrode is obvious, and the cationic surfactant needs to perform corresponding functions under acidic conditions, and the pH value needs to be less than 4.
Optionally, the cationic surfactant comprises at least one of cetyltrimethylammonium bromide, tetrabutylammonium bromide, polyquaternium-2, zinc acetate.
Optionally, the anionic surfactant is at least one of the compounds having the structure of formula I,
R-X-A formula I
Wherein X is a sulfonic group or a bissulfonylimido group; r is C containing substituent or not containing substituent a Alkyl or phenyl of (a); a is the number of carbon atoms contained in the alkyl or phenyl group; the value range of a is as follows: a is more than or equal to 1 and less than or equal to 16; a is at least one of zinc ion, sodium ion, potassium ion, lithium ion, magnesium ion and calcium ion.
The carboxylate anionic surfactant has poor hard water resistance, is easy to react with calcium ions and magnesium ions in water to generate precipitates, and is not beneficial to the conductive transmission of electrolyte. The sulfuric acid ester salt, which cannot be used for an acidic electrolyte, is hydrolyzed under acidic conditions. The sulfonic anionic surfactant has strong interfacial activity and can reduce the oil-water interfacial tension to below 10 to 3m N/m; and the raw materials have wide sources, the production process is simple, the cost is low, and the competitiveness is strong. In addition, when the anode material is converted into a layered structure, a liquid molecular layer can be formed on the surface of the anode material, and the migration of each ion is effectively controlled, so that the conversion of the anode material is more orderly carried out, and a sheet structure with smaller size is generated; meanwhile, the contact interface of the anode material and the electrolyte is increased, and the ion de-intercalation capability is improved.
Optionally, the substituent comprises a halogen element.
Alternatively, the substituent may be a mono-substituent, a di-substituent or a multi-substituent.
Optionally, the R-X is selected from at least one of dodecylbenzene sulfonate ion, perfluorobutyl sulfonate ion, trifluoromethanesulfonate ion, bis (trifluoromethanesulfonic acid) imide ion, methanesulfonate ion, and benzene sulfonate ion.
Optionally, the formation promoter comprises at least one of sodium dodecylbenzene sulfonate, sodium dodecylsulfonate, potassium perfluorobutylsulfonate, zinc trifluoromethanesulfonate, zinc methanesulfonate, potassium trifluoromethanesulfonate, sodium methanesulfonate, sodium trifluoromethanesulfonate, calcium methanesulfonate, magnesium trifluoromethanesulfonate, magnesium methanesulfonate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonate) imide, sodium benzoate, zinc benzenesulfonate, sodium benzenesulfonate.
Optionally, the anion of the formation promoter comprises at least one of dodecylbenzene sulfonate ion, acetate ion, dodecylsulfonate ion, perfluorobutyl sulfonate ion, trifluoromethane sulfonate ion, bis (trifluoromethane sulfonic acid) imide ion, methane sulfonate ion, benzoate ion, benzene sulfonate ion.
Optionally, the anion of the formation promoter is trifluoromethanesulfonate ion, methanesulfonate ion, bis (trifluoromethanesulfonic acid) iminate ion.
Optionally, the mass content of the ionic surfactant in the electrolyte is 0.02% -4%.
Optionally, the ionic surfactant is present in the electrolyte in an amount of 0.02%, 0.04%, 0.06%, 0.08%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, or any point between any two values.
Optionally, a has a value range of: a is more than or equal to 1 and less than or equal to 2, and the mass content of the ionic surfactant in the electrolyte is 0.5-4%.
Optionally, a has a value range of: a is more than 2 and less than or equal to 16, and the mass content of the ionic surfactant in the electrolyte is 0.02-0.5%.
Optionally, the conductive salt comprises an inorganic conductive salt and/or an organic conductive salt.
Optionally, the inorganic conductive salt comprises one or more of zinc sulfate, sodium sulfate, lithium sulfate, zinc sulfamate, sodium sulfamate and lithium sulfamate; the organic conductive salt comprises zinc trifluoromethanesulfonate, sodium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonate) imide, zinc methanesulfonate, sodium methanesulfonate, lithium methanesulfonate and potassium methanesulfonate.
Alternatively, the organic conductive salt of the conductive salt may be used as the formation promoter, i.e., an electrolyte using an organic conductive salt may not need an additional formation promoter.
Optionally, the conductive salt further comprises a water-soluble metal salt.
Optionally, the water-soluble metal salt is selected from one or more of lithium salt, sodium salt, potassium salt.
The concentration of the cations of the conductive salt in the electrolyte is 1-5 mol/L.
Optionally, the concentration of the cation of the conductive salt in the electrolyte is 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, or any value between any two values.
Optionally, the aqueous zinc-ion battery further includes a positive electrode sheet, a negative electrode sheet, and a separator.
Optionally, the positive electrode sheet comprises a positive electrode material, a conductive agent, a binder and a current collector; the negative plate comprises a negative electrode material, a conductive agent, a binder and a current collector; and sequentially stacking the positive plate, the diaphragm and the negative plate and adding the electrolyte to form the water-system zinc ion battery.
Optionally, the conductive agent includes a carbon black conductive agent and a graphite conductive agent.
Specifically, the Carbon black conductive agent is at least one selected from acetylene black, 350G, carbon fiber (VGCF), carbon Nanotubes (CNTs), ketjen black (ketjenblack ec300J, ketjenblackEC JD, carbon ECP600 JD); the graphite conductive agent is at least one selected from KS-6, KS-15, SFG-6 and SFG-15.
In the present application, the type of the conductive agent is not limited, and may be specifically selected according to the actual situation, and the selected type includes but is not limited to the above-described conductive agent, and is only for the purpose of collecting micro-current between the active materials and the current collector, so as to reduce the contact resistance of the electrode and accelerate the movement rate of electrons, and at the same time, effectively improve the migration rate of lithium ions in the electrode material, thereby improving the charging and discharging efficiency of the electrode.
Alternatively, the binder includes polyacrylic acid, polyacrylonitrile, polyvinylidene fluoride, polyacrylate, and the like. In the present application, the kind of the binder is not limited.
Optionally, the current collector comprises a metal foil. Including copper foil, aluminum foil, stainless steel foil, and the like. For collecting the current generated by the battery active materials so as to form a larger current output.
According to another aspect of the present application, there is provided a chemical conversion method for a zinc-ion battery, the method being as described in any of the above aqueous zinc-ion batteries.
Optionally, the formation method comprises charging and discharging; the charging voltage interval is 0 to 2.1V and comprises three stages; the first stage is as follows: when the charging voltage is not higher than 1.8V, constant current charging is adopted, and the multiplying power current is not higher than 0.2C; the second stage is as follows: when the charging voltage is not lower than 1.8V, constant current charging is adopted, and the multiplying power current is not higher than 0.1C; and in the third stage, constant-voltage charging is adopted, the charging voltage is 1.9-2.1V, and the cut-off current value is 0.02C-0.1C.
Optionally, the discharge is a constant current discharge; the discharge cut-off voltage is not higher than 0.8V, and the discharge multiplying power is not higher than 0.2C; the end conditions of the formation are as follows: let M n The specific discharge capacity of the nth cycle is shown, n is more than 1, | M n -M n-1 |/M n-1 ≤5%。
Optionally, the positive electrode material in the above-mentioned aqueous zinc ion battery to which the formation method is applied is a manganese oxide having a manganese valence of less than +4, specifically at least one of manganese monoxide, manganese sesquioxide, and manganese tetraoxide. Including but not limited to the aqueous zinc-ion battery of the present application.
Optionally, the first stage is: and when the charging voltage is not higher than 1.8V, constant current charging is adopted, and the charging multiplying power is 0.02 to 0.2C.
Optionally, the charging voltage in the first stage is 0 to 1.8V.
Optionally, the lower charging voltage limit of the first stage is 0V, 0.1V, 0.2V, 0.3V, 0.4V, 0.5V, 0.6V, 0.7V, 0.8V, 0.9V, 1.0V, 1.1V, 1.2V, 1.3V, 1.4V, 1.5V, 1.6V, 1.7V, or a value between any two values; the upper limit is 0.1V, 0.2V, 0.3V, 0.4V, 0.5V, 0.6V, 0.7V, 0.8V, 0.9V, 1.0V, 1.1V, 1.2V, 1.3V, 1.4V, 1.5V, 1.6V, 1.7V, 1.8V, or a value between any two values.
Optionally, the charge rate of the first stage is 0.02C, 0.03C, 0.04C, 0.05C, 0.06C, 0.07C, 0.08C, 0.09C, 0.1C, 0.11C, 0.12C, 0.13C, 0.14C, 0.15C, 0.16C, 0.17C, 0.18C, 0.19C, 0.2C, or a number between any two values.
Optionally, the second stage is: the charging voltage is 1.8 to 2.1V, the constant current charging is adopted, and the charging multiplying power is 0.02 to 0.1C.
Optionally, the lower limit of the charging voltage in the second stage is 1.8V, 1.85V, 1.9V, 1.95V, 2V, 2.05V, or a value between any two values; the upper limit is 1.85V, 1.9V, 1.95V, 2V, 2.05V, 2.1V, or a value between any two values.
Optionally, the charging voltage in the second stage is 1.8 to 1.9V, 1.8 to 1.95V, 1.8 to 2V, 1.8 to 2.05V, 1.8 to 2.1V, or any value between 1.8V and 1.9 to 2.1V.
Optionally, the charge rate of the second stage is 0.02C, 0.03C, 0.04C, 0.05C, 0.06C, 0.07C, 0.08C, 0.09C, 0.1C, or a number between any two numbers.
Optionally, when the charging voltage in the second stage is 1.8 to 1.9V, 1.8 to 1.95v, 1.8 to 2v, 1.8 to 2.05v, 1.8 to 2.1v, or any value between 1.8V and 1.9 to 2.1v, the charging rate is 0.02C, 0.03C, 0.04C, 0.05C, 0.06C, 0.07C, 0.08C, 0.09C, 0.1C, or any value between any two values.
Optionally, the constant-current charging is staged charging, that is, the charging multiplying factors of the charging voltages in different ranges are different, and when the battery is formed through different charging multiplying factors and charging voltages, the cycle number can be reduced, and the maximum discharge capacity can be reached as soon as possible.
Optionally, the charging voltage in the third stage is any one of values from 1.9 to 2.1V.
Optionally, the charging voltage of the third stage is 1.9V, 1.95V, 1.98V, 2V, 2.05V, 2.1V, or a value between any two values.
Optionally, the off-current of the third stage is 0.02C, 0.03C, 0.04C, 0.05C, 0.06C, 0.07C, 0.08C, 0.09C, 0.1C, or a value between any two values.
Optionally, the discharge rate is 0.1 to 0.2C.
Optionally, the depth of discharge is 100%.
Optionally, the formation termination conditions are: the ratio of the discharge capacity after the last charge-discharge cycle to the discharge capacity after the current charge-discharge cycle is not less than 95%, and the ratio of the discharge capacity after the last two charge-discharge cycles to the discharge capacity after the last charge-discharge cycle is not more than 95%.
The battery formation method can shorten the cycle times required by the formation stage, promote the positive electrode material to form a stable structure in the formation stage process, improve the discharge specific capacity of the positive electrode material, and further improve the overall performance of the water system zinc ions.
The invention has the following main beneficial effects:
(1) According to the application, a low-valence manganese-containing oxide (the valence of a manganese element is lower than + 4) is used as an anode material, and an electrolyte containing a formation promoter and a conductive salt is selected, so that the contact interface between the anode material and the electrolyte can be improved in the charge-discharge cycle process of the anode material; the shape of the positive electrode material is regulated and controlled, and the positive electrode material is promoted to be converted into a flaky or microcrystalline flaky aggregate penetrating through the inner space of the electrode, so that the contact area of the positive electrode material of the flaky or microcrystalline flaky aggregate and the electrolyte is larger, the migration path of electrons is shorter, better electrochemical performance is shown, and the discharge capacity of the battery can be comprehensively improved; in addition, other materials are not needed to be doped in the battery to maintain the structure of the anode material, so that the discharge capacity of the battery can be ensured to the maximum extent.
(2) The sulfonic group anionic surfactant is selected, when the anode material is converted into a sheet structure, a liquid molecular layer can be formed on the surface of the anode material, the chemical reaction potential barrier of a solid phase and a liquid phase is reduced, the conversion of the anode material is more orderly carried out, and a sheet or microcrystal sheet aggregate with smaller size is generated; meanwhile, the contact interface of the anode material and the electrolyte is changed, the influence of the aqueous solution on the anode material is reduced, and the solution of manganese ions is reduced, so that the collapse of the anode material structure is avoided, and the cycle performance and the specific capacity of the battery are improved.
(3) The method comprises the steps of charging and discharging in stages; the charging process comprises constant current charging and constant voltage charging, the constant current charging is divided into two stages, the charging multiplying power is not higher than 0.1C when the voltage range is not lower than 1.8, the constant voltage charging is carried out after the constant current charging is finished, and the discharging multiplying power is not higher than 0.2C, so that the cycle number can be reduced to reach the maximum discharging capacity as soon as possible, and the cycle number is reduced to 5 to 20 times when the battery is formed. And a smaller rate current or a lower voltage is adopted, so that the battery can be stably formed, the anode material is promoted to completely complete conversion, and the specific capacity of the battery can be obviously improved.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of an aqueous zinc ion battery positive electrode material before and after formation in example 1 of the present application; (a) SEM images before formation; (b) SEM pictures after 20 cycles.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the cathode material of the aqueous zinc-ion battery in example 2 of the present application before and after formation; (a) SEM images before formation; (b) SEM pictures after 20 cycles.
FIG. 3 is a Scanning Electron Microscope (SEM) image of the positive electrode material of the aqueous zinc-ion battery in comparative example 1; (a) SEM images before formation; (b) SEM pictures after 20 cycles.
FIG. 4 is a Scanning Electron Microscope (SEM) image of the positive electrode material of the aqueous zinc-ion battery in comparative example 2; (a) SEM images before formation; (b) SEM pictures after 20 cycles.
FIG. 5 is a graph of specific capacity of long-cycle discharge for example 1 and comparative examples 1, 2 and 3 of the present application; the abscissa is the cycle number, and the unit is times; the ordinate is specific discharge capacity in mAh.g -1 。
FIG. 6 is a graph of specific capacity for long-cycle discharge of example 2 of the present application; the abscissa is the cycle number, and the unit is times; the ordinate is specific discharge capacity in mAh.g -1 。
FIG. 7 is a graph of specific capacity for long-cycle discharge in example 3 of the present application; the abscissa is the cycle number, and the unit is times; the ordinate is specific discharge capacity in mAh.g -1 。
FIG. 8 is a graph of specific capacity for long-cycle discharge for example 4 of the present application and comparative example 4; the abscissa is the cycle number, and the unit is times; the ordinate is specific discharge capacity in mAh.g -1 。
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The reagents, materials and procedures used herein are those widely used in the corresponding fields and are generally available on the market.
Example 1
Weighing Mn in a mass ratio of 70 2 O 3 Acetylene black conductive agent, carbon nano tube and polyvinylidene fluoride (PVDF) binder, dissolving PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, and then uniformly grinding Mn 2 O 3 And acetylene black and carbon nanotubes are added into the solution, and stirring is continued to ensure that the slurry is uniformly mixed. And then uniformly coating the slurry on a stainless steel foil wafer (with the diameter of 12 mm), and drying in a vacuum oven at 100 ℃ to obtain the anode electrode plate.
The prepared positive electrode plate, a metal zinc plate and a glass fiber membrane are assembled into a zinc ion battery, and the electrolyte is a mixed aqueous solution of 0.01mol/L sodium dodecyl benzene sulfonate and 1.5mol/L zinc sulfate. The mass content of the sodium dodecyl benzene sulfonate in the electrolyte is 0.3 percent.
The formation method comprises the following steps: in the charging process, the multiplying current in a voltage range of 0 to 1.8V is 0.08C (the nominal specific capacity is 200 mAh/g), and the multiplying current in a voltage range of 1.8 to 2V is 0.03C; and after the constant-current charging is finished, constant-voltage charging is carried out, the voltage value of the constant-voltage charging is 1.98V, and the cut-off current is 0.02C.
In the discharging process, the discharging multiplying power is 0.1C, the cut-off voltage is 0.8V, and the discharging depth is 100%.
And after the formation is finished, performing cycle performance test by adopting 0.3C constant current charging and discharging, wherein the voltage range is 0.8-2V.
The morphology results before and after formation of the cathode material are shown in FIG. 1, and it can be seen that the cathode material Mn is before formation 2 O 3 Is granular, gaps exist among particles, and after 20 cycles, the appearance of the nano-particles is changed into nano-sheetsThe original particle form of the aggregate gradually disappears, and the reconstructed anode material eliminates the particle gap, so that the electron conductivity among the materials is enhanced, and the contact area between the materials and the electrolyte is increased.
As shown in fig. 5, the cycle performance of the positive electrode material of example 1 was such that the specific discharge capacity of the material gradually increased at the initial stage of the cycle and the discharge performance thereof became stable after the 8 th cycle, and therefore the formation stage was continued for 8 cycles, and the specific discharge capacity at the completion of the formation was 183.2mah.g -1 And the capacity is kept stable in the subsequent circulation, and the specific discharge capacity reaching the 50 th circulation is 171.6 mAh -1 The capacity retention rate was 93.6%.
Example 2
The sodium dodecylbenzenesulfonate in example 1 was changed to cetyltrimethylammonium chloride, and the procedure in example 1 was repeated.
As shown in fig. 2, after the conversion promoter is replaced, the positive electrode material also forms a morphology with nanosheet aggregates after 20 cycles, but compared with example 1, a part of unconverted positive electrode material is still visible, and the size of the nanosheets in the positive electrode material is larger than that in example 1, and when the size is larger, the contact area of the nanosheets with the electrolyte is reduced, so that the capacity exertion is influenced.
The cycle performance of the cathode material in example 2 is shown in fig. 6, and after 12 cycles of formation, the cathode material reaches the maximum specific discharge capacity of 168.8mAh.g -1 Slightly lower than example 1, however, the discharge capacity continued to decay after the 20 th cycle, reaching only 117.1mAh.g. at 50 cycles -1 The discharge specific capacity and the capacity retention rate are only 69%; since the positive electrode material of example 2 is also transformed similarly to example 1, and the law of the early cycle performance is similar, on the other hand, a large amount of zinc particles are found during the disassembly of the battery, it is presumed that the cationic surfactant affects the deposition morphology of the negative electrode, and promotes the zinc to fall off from the electrode surface, thereby causing the capacity attenuation of the battery. Therefore, it can be concluded that the formation promoter can promote the low-valence manganese oxide positive electrode material to be converted into a nanosheet aggregate structure, so as to improve the performance of the positive electrode material, but the formation promoter can also influence the performance of the positive electrode materialThe discharge performance of the cathode material can be improved by selecting a proper formation promoter for the zinc ion battery.
Example 3
Weighing Mn in a mass ratio of 50 3 O 4 Dissolving PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, adding uniformly ground MnO, acetylene black and the carbon nano tubes into the solution, and continuously stirring to ensure that the slurry is uniformly mixed. And then uniformly coating the slurry on a stainless steel foil wafer (with the diameter of 12 mm), and drying in a vacuum oven at 100 ℃ to obtain the anode electrode plate.
The prepared positive electrode plate, a metal zinc plate and a glass fiber membrane are assembled into a zinc ion battery, and the electrolyte is a mixed aqueous solution of 3.5mol/L lithium bis (trifluoromethanesulfonate) imide, 0.8mol/L zinc sulfate, 0.5mol/L lithium sulfamate and 0.5mol/L sodium sulfate. The mass content of the lithium bis (trifluoromethanesulfonate) imide in the electrolyte is 0.5%.
The formation method comprises the following steps: in the charging process, the multiplying power current in a voltage range of 0 to 1.8V is 0.1C (the nominal specific capacity is 200 mAh/g), the multiplying power current in a voltage range of 1.8 to 1.95V is 0.05C, constant-voltage charging is carried out after the constant-current charging is finished, the voltage value of the constant-voltage charging is 2.0V, and the cut-off current is 0.05C; in the discharging process, the discharging multiplying power is 0.15C, the cut-off voltage is 0.4V, and the discharging depth is 100%.
And after the formation is finished, performing cycle performance test by adopting 0.3C constant current charging and discharging, wherein the voltage range is 0.8-2V.
The cycle performance of the battery is shown in fig. 7, the formation of the battery in the 5 th cycle is completed, and the specific discharge capacity at the end of the formation is 165.5mah -1 The capacity showed a slight increase tendency during the subsequent cycle, and the specific discharge capacity at the 50 th cycle was 166.8mAh.g -1 The improvement is 1.3 mAh.g compared with the end of the formation -1 (ii) a The reason for this is that the transition process of the low-valence manganese-containing oxide is long-lasting, and the newly formed nanosheet aggregate gradually fills the inside of the electrode, further increasing the electron density of the materialAnd the conductivity is improved, so that the discharge performance of the material is improved in the later period of the cycle.
Example 4
Weighing MnO, acetylene black conductive agent, carbon nano tubes and polyvinylidene fluoride (PVDF) binder in a mass ratio of 80. And then uniformly coating the slurry on a stainless steel foil wafer (with the diameter of 12 mm), and drying in a vacuum oven at 100 ℃ to obtain the anode electrode plate.
The prepared positive electrode plate, a metal zinc plate and a glass fiber membrane are assembled into a zinc ion battery, electrolyte is a mixed aqueous solution of 1.5mol/L sodium trifluoromethanesulfonate, 0.8mol/L zinc sulfate and 0.5mol/L lithium sulfamate, and the pH of the electrolyte is adjusted to be 3.5. The mass content of the sodium trifluoromethanesulfonate in the electrolyte is 2%.
The formation method comprises the following steps: in the charging process, the multiplying current in a voltage range of 0 to 1.8V is 0.2C (the nominal specific capacity is 200 mAh/g), and the multiplying current in a voltage range of 1.8 to 1.9V is 0.02C; and after the constant-current charging is finished, constant-voltage charging is carried out, the voltage value of the constant-voltage charging is 1.9V, and the cutoff current is 0.02C.
In the discharging process, the discharging multiplying power is 0.1C, the cut-off voltage is 0.4V, and the discharging depth is 100%.
And after the formation is finished, performing cycle performance test by adopting 0.3C constant current charging and discharging, wherein the voltage range is 0.8-2V.
As shown in fig. 8, the battery was completed in the 7 th cycle, and the specific discharge capacity at the end of formation was 164.7mah.g -1 The capacity of the lithium ion battery shows a slight rising trend in the subsequent circulation process, and the specific discharge capacity of the 50 th circulation is 172.2mAh.g -1 The improvement is 7.5mAh.g compared with the improvement at the end of the formation -1 。
Comparative example 1
The procedure of example 1 was repeated except that sodium dodecylbenzenesulfonate in example 1 was removed.
Fig. 3 is scanning electron micrographs before and after the cycle of comparative example 1, and it is known from the morphologies of comparative example 1 and example 1 that, in the case where there is no formation promoter, the morphologies of the positive electrode material after the cycle of the two are different, as shown in fig. 1 and fig. 3, the positive electrode material in comparative example 1 still maintains the particle morphology after 20 cycles, unlike the initial state, the positive electrode material particles are aggregated into agglomerates, the gaps of the particles are locally reduced, and at the same time, it is found that the roughness of the material surface is increased, which is an expression that the low-valence manganese-containing oxide positive electrode material has been transformed, and the morphology transformation occurs only in a minute region of the material particle surface due to the absence of the formation promoter in the electrolyte, and does not further expand to the outside of the particle, and the nanosheet aggregate as in example 1 cannot be formed.
In terms of discharge performance, as shown in fig. 5 and table 1, the formation period of comparative example 1 is long, the formation stage is not finished until the 25 th cycle, and the performance stabilization period is entered, and the specific discharge capacity at the end of the formation is 136.6mah.g -1 The discharge performance is lower than that of the example 1, the discharge performance tends to be stable in subsequent cycles, and the specific discharge capacity of the 50 th cycle is 135.7 mAh.g -1 The capacity retention rate is 99.3%; as can be seen from the comparison of the cycle performance of example 1 with that of comparative example 1, the use of the formation promoter can reduce the formation completion period of the positive electrode material and improve the discharge performance of the material.
Comparative example 2
Mn in example 1 2 O 3 To MnO 2 Otherwise, the same procedure as in example 1 was repeated.
Comparative example 2 is different from example 1 in that the valence of Mn in the positive electrode material is +4 in a high valence state, and thus, discharge is performed after the completion of battery assembly, and fig. 4 is a scanning electron microscope image of the positive electrode material of comparative example 2 before and after 20 cycles, and MnO can be found 2 The positive electrode material has no obvious shape change before and after circulation, and is different from the embodiment 1 or the comparative example 1 due to MnO 2 No significant structural reorganization occurred at the early stage of the cycle, and no effect was exhibited by the formation promoter.
As can be seen from the discharge cycle performance graph of fig. 5, the positive electrode material of comparative example 2 was used in the first cycleThe ring shows higher specific discharge capacity which reaches 176.4 mAh -1 But continuously and rapidly decays in the subsequent circulation process, and the specific capacity of the material is only 68mAh.g after 50 times of circulation -1 The capacity retention was 38.9%, much lower than example 1, and lower than comparative example 1; although MnO is used 2 The cathode material can save the formation step of the battery, but the cycling stability is poor, and the using effect is inferior to that of the low-valence manganese cathode.
Comparative example 3
The same as example 1, but without formation step, the cycle performance test was carried out by directly adopting 0.3C constant current charging and discharging, and the voltage range was 0.8 to 2V.
The cycling performance is shown in fig. 5, and after the formation step was removed, the cell of comparative example 3 exhibited a slow capacity increase until the 45 th cycle reached its steady state performance with a specific capacity of 157mah -1 (ii) a The property of the low-valence manganese oxide causes that the material transformation rate is reduced under the condition of high current density, so that complete structure transformation can be realized and the highest performance state can be reached after more cycles, and the highest discharge specific capacity of the comparative example 3 is higher than that of the comparative example 1, thereby further showing that the formation promoter has the effect of improving the discharge performance of the material.
Comparative example 4
Weighing MnO, acetylene black conductive agent, carbon nano tubes and polyvinylidene fluoride (PVDF) binder in a mass ratio of 80. Then, the slurry is uniformly coated on a stainless steel foil wafer (with the diameter of 12 mm), and the stainless steel foil wafer is dried in a vacuum oven at 100 ℃ to obtain the anode electrode plate.
And assembling the prepared positive electrode plate, a metal zinc plate and a glass fiber membrane into a zinc ion battery, wherein the electrolyte is a mixed aqueous solution of 1.5mol/L zinc acetate, 0.8mol/L zinc sulfate and 0.5mol/L lithium sulfamate. The mass content of the zinc acetate in the electrolyte is 2%.
The procedure of example 4 was repeated except that the sodium trifluoromethanesulfonate of example 4 was changed to zinc acetate and the pH of the electrolyte was not adjusted.
Comparative example 4 cycling Performance As shown in FIG. 8, the discharge performance was at a lower level than that of example 4, but the number of cycles required for the formation was small, and the discharge rate after the 6 th cycle was in a stable discharge state and was 46.9mAh.g -1 The reason why 1/3 of example 4 is less is that zinc acetate as electrolyte increases the pH value of the electrolyte, and a higher pH value is not favorable for the performance of the manganese oxide positive electrode, but can maintain stable specific discharge capacity, and the specific discharge capacity at 50 th cycle is 48.6mAh.g -1 There is a slight upward trend. Even if the zinc acetate meets the structural conditions of the formation accelerant and the cycle number of the positive electrode material in the formation stage is reduced, the adverse effect on the battery performance is larger than the effect of the zinc acetate in the formation of manganese, so the selection of the formation accelerant needs to be compatible with the influence of the electrolyte environment on the positive and negative electrode materials of the battery.
Comparative example 5
The zinc sulfate in example 1 was changed to sodium sulfate, and the procedure was otherwise the same as in example 1.
The electrolyte of the comparative example does not contain zinc ions, and the electrochemical reaction of the zinc cathode needs the participation of the zinc ions, so that the comparative example 4 lacking the zinc ions is charged and discharged, and the specific discharge capacity is close to 0.
Comparative example 6
The electrolyte solution of example 1 was changed to acetonitrile instead of water, and the procedure of example 1 was otherwise the same.
The conversion reaction of the low-valence manganese requires the participation of water molecules, and as shown in the following formula, the electrolyte of the comparative example 6 does not contain water molecules, so that the low-valence manganese cannot be converted, the positive electrode material cannot be charged and discharged, and the specific discharge capacity of the positive electrode material is close to 0.
Charging reaction
2Mn 3 O 4 →Mn 5 O 8 +Mn 2+ +2e −
Mn 5 O 8 +xH 2 O→4MnO 2 ·xH 2 O+Mn 2+ +2e -
Discharge reaction
MnO 2 ·xH 2 O+H + +e − ⇔MnOOH+xH 2 O
In conclusion, the low-valence manganese-containing oxide (the valence of manganese element is lower than + 4) is used as the positive electrode material, the transformed morphology of the positive electrode material is regulated and controlled by adjusting the electrolyte environment, the positive electrode material is promoted to be transformed into a nano flaky morphology with smaller size, fine nano sheets form aggregates to be filled in the electrode, better electrochemical performance is shown, the discharge capacity and the circulation stability of the battery are improved, and the circulation frequency required by the positive electrode material to reach the discharge stable state is shortened.
It should be further noted that fig. 1~4 is the morphology diagrams before and after formation of the positive electrode materials of example 1, example 2, comparative example 1 and comparative example 2, respectively, and considering that the morphology of different cycle times may be different, the cycle period may be more thoroughly changed, so that it is convenient to compare by fixing one cycle time (i.e. 20 times); through comparison of the shapes before and after the same cycle number, the cathode material of the embodiment 1~2 of the application is completely converted into a sheet-shaped structure, while the comparative example 1~2 is still in an unconverted state or an incompletely converted state, and the effect of the formation promoter in the structure conversion of the cathode material is more highlighted. With reference to fig. 5, the difference between example 1 and comparative example 1 is more obvious, and compared with comparative example 1, the positive electrode material of example 1 not only has complete conversion, but also has improved corresponding specific discharge capacity, and further greatly reduces the cycle number required by the battery to reach a stable discharge state. In conclusion, the formation promoter can promote the structure transformation of the positive electrode material, improve the specific discharge capacity of the battery, reduce the cycle number and reach the maximum discharge capacity as soon as possible. However, it is clear that the technology of the present application can be completed within 10 cycles or so, whereas the cycle number of the comparative example needs to be 20+.
Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. An aqueous zinc ion battery comprising a positive electrode, a negative electrode and an electrolyte, the negative electrode comprising a zinc-containing material, the electrolyte comprising a conductive salt and water, the conductive salt comprising a zinc salt,
the positive electrode includes a manganese-containing oxide; the manganese-containing oxide consists of a manganese element and an oxygen element; the valence state of the manganese element is lower than +4 valence;
the aqueous zinc ion battery needs to be subjected to a formation step before use; the forming step comprises charging and discharging; the charging voltage interval is 0-2.1V and comprises three stages;
the first stage is as follows: when the charging voltage is not higher than 1.8V, constant current charging is adopted, and the multiplying power current is not higher than 0.2C; the second stage is as follows: when the charging voltage is not lower than 1.8V, constant current charging is adopted, and the multiplying power current is not higher than 0.1C; in the third stage, constant voltage charging is adopted, the charging voltage is 1.9 to 2.1V, and the cut-off current is 0.02C to 0.1C;
in the formation step, the electrolyte further comprises a formation promoter;
after the formation step, the manganese oxide is gradually changed from an initial shape to a second shape; the second morphology is a sheet-like or microcrystalline sheet-like aggregate.
2. The aqueous zinc-ion battery according to claim 1, characterized in that the discharge is a constant current discharge; the discharge cut-off voltage is not higher than 0.8V, and the discharge multiplying power is not higher than 0.2C;
the termination conditions of the formation step are as follows: let M n The specific discharge capacity of the nth cycle is shown, n is more than 1, | M n -M n-1 |/M n-1 ≤5%。
3. The aqueous zinc-ion battery according to claim 1, wherein the manganese-containing oxide is at least one selected from the group consisting of manganese monoxide, manganese sesquioxide, and manganese tetraoxide.
4. The aqueous zinc-ion battery according to claim 1, wherein the mass content of the manganese-containing oxide in the positive electrode is 20% to 95%.
5. The aqueous zinc ion battery according to claim 1, wherein the formation accelerator is an ionic surfactant;
the ionic surfactant is an anionic surfactant and/or a cationic surfactant.
6. The aqueous zinc-ion battery according to claim 5, wherein the anionic surfactant is at least one of compounds having a structure of formula I,
R-X-A formula I
Wherein X is a sulfonic group or a bissulfonylimido group; r is C with or without substituent a Alkyl or phenyl of (a); a is the number of carbon atoms contained in the alkyl or phenyl group; the value range of a is as follows: a is more than or equal to 1 and less than or equal to 16;
a is at least one of zinc ion, sodium ion, potassium ion, lithium ion, magnesium ion and calcium ion.
7. The aqueous zinc ion battery of claim 6, wherein R-X is selected from at least one of dodecylbenzene sulfonate ion, perfluorobutyl sulfonate ion, trifluoromethanesulfonate ion, bis (trifluoromethanesulfonic) imide ion, methanesulfonate ion, and benzenesulfonate ion.
8. The aqueous zinc ion battery of claim 6, wherein the ionic surfactant is present in the electrolyte in an amount of 0.02 to 4% by mass.
9. The aqueous zinc-ion battery according to claim 8, wherein a has a value in a range of: a is more than or equal to 1 and less than or equal to 2, and the mass content of the ionic surfactant in the electrolyte is 0.5-4%;
the value range of a is as follows: a is more than 2 and less than or equal to 16, and the mass content of the ionic surfactant in the electrolyte is 0.02-0.5%.
10. A method for forming a zinc-ion battery, characterized in that the method is as described in any one of claims 1 to 9.
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