CN113611848A - Positive electrode material, preparation method thereof and zinc ion battery - Google Patents

Positive electrode material, preparation method thereof and zinc ion battery Download PDF

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CN113611848A
CN113611848A CN202110846087.4A CN202110846087A CN113611848A CN 113611848 A CN113611848 A CN 113611848A CN 202110846087 A CN202110846087 A CN 202110846087A CN 113611848 A CN113611848 A CN 113611848A
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zinc
positive electrode
electrode material
battery
salt
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钱瑶
罗云峰
陈璞
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Ruihai Bo (Changzhou) Energy Technology Co.,Ltd.
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

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Abstract

The invention discloses a positive electrode material, a preparation method thereof and a zinc ion battery. The stability of the manganese-based material can be obviously improved by doping at least one of Ti element and Al element in the manganese-based material, so that the dissolution and the structural collapse of the anode material in the zinc ion battery can be effectively inhibited, the electronic structure and the conductivity of the anode material can be optimized by doping, and the specific capacity and the cycle performance of the zinc ion battery can be further improved.

Description

Positive electrode material, preparation method thereof and zinc ion battery
Technical Field
The invention belongs to the field of batteries, and particularly relates to a positive electrode material, a preparation method thereof and a zinc ion battery.
Background
Manganese based (e.g. MnO)2) In zinc secondary batteries, an aqueous electrolyte, for example H, is often used2O as a solvent and then a metal salt electrolyte is added. The water system electrolyte has the advantages of no toxicity, no harm, no flammability, low cost, low requirement on production environment and the like. However, the use of aqueous electrolytes has the following drawbacks: 1. the dissolution phenomenon of the active substance is very obvious; 2. side reactions are more, and a gas evolution phenomenon exists, so that a battery system is unstable; 3. the voltage window is low: the voltage window of the water-based battery cannot be too high due to the decomposition voltage of water. The use of organic electrolytes also has the following disadvantages: 1. the gram capacity of the anode material is insufficient; 2. in the process of falling Zn ions, the structural stability of the positive active material is insufficient, resulting in insufficient cycle stability.
Therefore, the existing zinc ion secondary battery is in need of improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a positive electrode material, a method for preparing the same, and a zinc ion battery, in which at least one of Ti and Al is doped into a manganese-based material, so that the stability of the manganese-based material can be significantly improved, thereby effectively inhibiting the dissolution and structural collapse of the positive electrode material in the zinc ion battery, and the electronic structure and conductivity of the positive electrode material can be optimized by doping, thereby improving the specific capacity and cycle performance of the zinc ion battery.
In one aspect of the invention, a positive electrode material is provided. According to an embodiment of the present invention, the positive electrode material is a manganese-based material doped with a metal element, wherein the doped metal element includes at least one of Ti and Al.
According to the positive electrode material provided by the embodiment of the invention, at least one of Ti element and Al element is doped in the manganese-based material, so that the stability of the manganese-based material can be obviously improved, the dissolution and the structural collapse of the positive electrode material in the zinc ion battery can be effectively inhibited, the electronic structure and the conductivity of the positive electrode material can be optimized through doping, and the specific capacity and the cycle performance of the zinc ion battery can be further improved.
In addition, the positive electrode material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the manganese-based material comprises MnO2。
In some embodiments of the invention, the mass proportion of the doped metal element is 1-10% based on the mass of the cathode material. This can significantly improve the stability of the manganese-based material.
In a second aspect of the present invention, the present invention provides a method for preparing the above-mentioned positive electrode material. According to an embodiment of the invention, the method comprises:
(1) mixing a manganese salt solution with a doping metal salt to obtain a mixed solution, wherein the doping metal salt comprises an aluminum-containing salt or/and a titanium-containing salt;
(2) mixing the mixed solution with persulfate;
(3) and (3) washing and drying the liquid obtained in the step (2) after the reaction so as to obtain the cathode material.
According to the method for preparing the cathode material, the manganese salt solution and the doped metal salt are mixed and then react with the persulfate, and the obtained reaction solution is washed and dried, namely at least one of Ti element and Al element is doped in the manganese-based material, so that the stability of the manganese-based material can be obviously improved, the dissolution and the structural collapse of the cathode material in the zinc ion battery can be effectively inhibited, the electronic structure and the conductivity of the cathode material can be optimized through doping, and the specific capacity and the cycle performance of the zinc ion battery can be improved.
In addition, the method for preparing the cathode material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the molar ratio of the manganese salt solution to the doping metal-containing salt and the persulfate salt is (25-128): (1-5): (25-128). This can improve the stability of the positive electrode material.
In some embodiments of the invention, in the step (2), the mixed solution and the persulfate are stirred at 70-100 ℃ for 5-12 h with stirring. This can improve the stability of the positive electrode material.
In a third aspect of the invention, a zinc-ion battery is provided. According to an embodiment of the invention, the zinc-ion battery comprises:
the positive electrode is prepared from the positive electrode material or the positive electrode material obtained by the method;
a negative electrode comprising metallic zinc and/or a zinc-containing compound;
an electrolyte comprising an organic solvent and a zinc-containing ionic salt.
According to the zinc ion battery provided by the embodiment of the invention, the positive electrode is prepared by adopting the positive electrode material with excellent stability, the dissolution and the structural collapse of the positive electrode material in the zinc ion battery can be effectively inhibited, the electronic structure and the conductivity of the positive electrode material can be optimized by doping, and the specific capacity and the cycle performance of the zinc ion battery can be further improved.
In addition, the zinc-ion battery according to the above embodiment of the invention may also have the following additional technical features:
in some embodiments of the invention, the organic solvent comprises at least one of N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and diglyme.
In some embodiments of the invention, the zinc-containing ionic salt comprises at least one of zinc chloride, zinc tetrafluoroborate, zinc perchlorate, zinc trifluoromethanesulfonate, zinc sulfate, zinc nitrate, zinc oxalate, zinc benzenesulfonate, zinc p-toluenesulfonate, and zinc isooctanoate.
In some embodiments of the invention, the electrolyte further comprises at least one of dimethyl carbonate, ethylene carbonate, propylene carbonate, trimethyl phosphate, and triethyl phosphate.
In some embodiments of the present invention, the electrolyte further includes a second ion, and the second ion includes at least one of a sodium ion, a potassium ion, a lithium ion, and a magnesium ion.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic flow chart of a method for preparing a cathode material according to an embodiment of the present invention;
FIG. 2 is a cycle performance curve of the battery in example 1;
fig. 3 is SEM images of the positive electrode material before and after the test in example 1;
fig. 4 is an XRD pattern of the positive electrode material before and after the test in example 1;
fig. 5 is an EDS diagram of the positive electrode material before the test in example 1;
FIG. 6 is a cycle performance curve of the battery in example 7;
fig. 7 is a cycle performance curve of the battery in the comparative example.
Detailed Description
The following detailed description of the embodiments of the present invention is intended to be illustrative, and not to be construed as limiting the invention.
In one aspect of the invention, a positive electrode material is provided. According to an embodiment of the present invention, the positive electrode material is a manganese-based material doped with a metal element, wherein the doped metal element includes at least one of Ti and Al. The inventor finds that the stability of the manganese-based material can be remarkably improved by doping at least one of the Ti element and the Al element in the manganese-based material, so that the dissolution and the structural collapse of the positive electrode material in the zinc ion battery can be effectively inhibited, the electronic structure and the conductivity of the positive electrode material can be optimized by doping, and the specific capacity and the cycle performance of the zinc ion battery can be improved.
Further, the manganese-based material includes MnO2Based on the mass of the anode material, the mass ratio of the doped metal elements is 1-10%, and the inventor finds that the doped metal elements in the range can uniformly and partially replace Mn atoms, so that the structural stability of the anode material is improved to a great extent, the cycling stability of the battery is improved, and the insertion and the extraction of Zn ions in the material are facilitated. Preferably, the doped metal element is Ti element, and Ti (IV) and Mn (IV) have the same valence state, similar ionic radius and coordination structure, so as to facilitate the doping of the Ti element in the manganese-based material. According to a specific embodiment of the invention, the doped metal element simultaneously comprises a Ti element and an Al element, and the molar ratio of the Ti element to the Al element is (1-10): (1 to 10)). The inventor finds that excessive doping can lead to the reduction of the capacity of the active material because the doped metal does not generate valence state change in the charging and discharging processes; if the content of the doped metal is insufficient, the supporting effect on the active material structure is insufficient, resulting in insufficient material cycle stability. Therefore, the material circulation stability can be improved while the capacity of the active material is ensured by adopting the doping amount.
In a second aspect of the present invention, the present invention provides a method for preparing the above-mentioned positive electrode material. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: mixing manganese salt solution with doped metal salt
In the step, a manganese salt solution is mixed with a doped metal salt to obtain a mixed solution, wherein the doped metal salt comprises an aluminum-containing salt or/and a titanium-containing salt. Further, the manganese salt solution includes at least one of manganese sulfate, manganese acetate, manganese nitrate, manganese chloride, and the like, the titanium-containing salt includes at least one of titanyl sulfate, titanium tetrachloride, and tetrabutyl titanate, and the aluminum salt includes at least one of aluminum sulfate, aluminum acetate, aluminum nitrate, and aluminum chloride.
S200: mixing the mixed solution with persulfate
In the step, the mixed solution obtained in the step S100 and persulfate are stirred for 5-12 hours at 70-100 ℃ with stirring, and precipitation is generated. Further, the persulfate includes at least one of potassium persulfate, ammonium persulfate, and sodium persulfate.
According to an embodiment of the invention, the molar ratio of the manganese salt solution to the doped metal salt and persulfate is (25-128): (1-5): (25-128). The inventor finds that excessive doping can lead to the reduction of the capacity of the active material because the doped metal does not generate valence state change in the charging and discharging processes; if the content of the doped metal is insufficient, the supporting effect on the active material structure is insufficient, resulting in insufficient material cycle stability. Therefore, the mixing proportion of the composite material can ensure the capacity of the active material and improve the cycling stability of the material.
S300: washing and drying the reacted liquid obtained in the step S200
In this step, the reaction solution obtained in step S200 is subjected to solid-liquid separation to obtain a precipitate, and the precipitate is washed several times and then vacuum-dried to obtain the positive electrode material. It should be noted that the specific operations of washing and vacuum drying are routine operations in the art, and those skilled in the art can select the operations according to actual needs, and will not be described herein again.
According to the method for preparing the cathode material, the manganese salt solution and the doped metal salt are mixed and then react with the persulfate, and the obtained reaction solution is washed and dried, namely at least one of Ti element and Al element is doped in the manganese-based material, so that the stability of the manganese-based material can be obviously improved, the dissolution and the structural collapse of the cathode material in the zinc ion battery can be effectively inhibited, the electronic structure and the conductivity of the cathode material can be optimized through doping, and the specific capacity and the cycle performance of the zinc ion battery can be improved. It should be noted that the features and advantages described above for the positive electrode material are also applicable to the method for preparing the positive electrode material, and are not described in detail here.
In a third aspect of the invention, a zinc-ion battery is provided. According to an embodiment of the invention, the zinc ion battery comprises a positive electrode, a negative electrode, an electrolyte and a diaphragm, wherein the positive electrode is prepared from the positive electrode material described above or the positive electrode material obtained by the method. The inventor finds that the positive electrode is prepared by adopting the positive electrode material with excellent stability, can effectively inhibit the dissolution and the structural collapse of the positive electrode material in the zinc ion battery, can optimize the electronic structure and the conductivity of the positive electrode material by doping, and can further improve the specific capacity and the cycle performance of the zinc ion battery.
According to an embodiment of the invention, the negative electrode comprises metallic zinc and/or a zinc-containing compound, the electrolyte comprises an organic solvent and a zinc-containing ionic salt, wherein the organic solvent comprises at least one of N, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO) and diglyme (G2), preferably DMF; the zinc-containing ionic salt includes at least one of zinc chloride, zinc tetrafluoroborate, zinc perchlorate, zinc trifluoromethanesulfonate, zinc sulfate, zinc nitrate, zinc oxalate, zinc benzenesulfonate, zinc p-toluenesulfonate and zinc isooctoate, preferably the zinc-containing ionic salt is zinc trifluoromethanesulfonate, and the concentration of the zinc-containing ionic salt in the electrolyte is 0.1mol/L to a saturation concentration, preferably 0.25 mol/L.
According to an embodiment of the present invention, the electrolyte may further include at least one of dimethyl carbonate, ethylene carbonate, propylene carbonate, trimethyl phosphate, and triethyl phosphate. According to still another embodiment of the present invention, the electrolyte further includes a second ion, wherein the second ion includes at least one of a sodium ion, a potassium ion, a lithium ion, and a magnesium ion.
According to the embodiment of the invention, the separator is one or more of AGM glass fiber membrane, sulfonated separator, PP membrane, PE membrane, non-woven fabric or modified separator modified by compound.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
The method for preparing the cathode material comprises the following steps:
1. adding 32mmol ammonium persulfate ((NH)4)2S2O8) Dissolving in 25ml water to obtain uniform solution A;
2. adding 32mmol of MnSO4Dissolving in 25ml deionized water, and adding 2mmol titanyl sulfate to obtain solution B;
3. dropwise adding the solution B into the solution A with stirring, heating to 80 ℃, and reacting for 6 hours with vigorous stirring to obtain a reacted solution;
4. centrifugally washing the precipitate obtained after the solid-liquid separation of the reacted solution for a plurality of times, and then drying the precipitate in vacuum for 12 hours to obtain the manganese-based material (MnO) doped with titanium element2-Ti)。
Assembling the battery: in MnO2Ti as the positive electrode, zinc foil as the negative electrode and AGM diaphragm as the diaphragm. Electrolyte solution: n, N-Dimethylformamide (DMF) as an organic solventThe zinc trifluoromethanesulfonate is zinc salt, and is dissolved in DMF, Zn2+The concentration was 0.25 mol/L.
And (3) testing the battery: in an environment of 25 ℃, the battery is discharged firstly under the current density of 50mA/g and the voltage range of 0.8-1.9V, the initial specific capacity is 192.7mAh/g, the capacity is kept at 120.1mAh/g after 20 circles, the capacity is kept at 124.2mAh/g after 400 circles, compared with 20 circles, the capacity of the battery is basically kept unchanged, and the cycle performance curve is shown in figure 2. SEM images of the positive electrode material before and after the test are shown in fig. 3, and it can be seen that the structure of the positive electrode material before and after the test is substantially stable. XRD of the positive electrode material before and after the test is shown in figure 4, and the positive electrode material after the test has no impurity. The EDS of the positive electrode material before the test is shown in fig. 5, and it can be seen that the Ti element is uniformly distributed in the positive electrode material.
The battery is amplified to 5Ah capacity level, and the gas production condition of the battery is detected by adopting a drainage method: no gas was collected.
Example 2
The method for preparing the cathode material comprises the following steps:
1. dissolving 32mmol of potassium persulfate in 25ml of water to obtain a uniform solution A;
2. dissolving 32mmol of manganese acetate in 25ml of deionized water, and adding 2mmol of titanium tetrachloride to obtain a solution B;
3. dropwise adding the solution B into the solution A with stirring, heating to 70 ℃, and reacting for 8 hours with vigorous stirring to obtain a reacted solution;
4. centrifugally washing the precipitate obtained after the solid-liquid separation of the reacted solution for a plurality of times, and then drying the precipitate in vacuum for 12 hours to obtain the manganese-based material (MnO) doped with titanium element2-Ti)。
Assembling the battery: in MnO2Ti as the positive electrode, zinc foil as the negative electrode and AGM diaphragm as the diaphragm. Electrolyte solution: n-methylpyrrolidone (NMP) is used as an organic solvent, zinc chloride is used as a zinc salt, and the zinc chloride is dissolved in the NMP until the zinc chloride is saturated.
And (3) testing the battery: in an environment of 25 ℃, the battery is discharged firstly under the current density of 50mA/g and the voltage range of 0.8-1.9V, the initial specific capacity is 155mAh/g, the capacity is kept to be 114.9mAh/g after 20 circles, the capacity is kept to be 104mAh/g after 400 circles, and compared with 20 circles, the capacity of the battery is basically kept unchanged. From the SEM images of the positive electrode material before and after the test, it can be seen that the structure of the positive electrode material before and after the test is substantially stable. The XRD of the anode material before and after the test shows that the anode material after the test has no impurity. The EDS of the positive electrode material before the test shows that the Ti element is uniformly distributed in the positive electrode material.
The battery is amplified to 5Ah capacity level, and the gas production condition of the battery is detected by adopting a drainage method: no gas was collected.
Example 3
The method for preparing the cathode material comprises the following steps:
1. dissolving 64mmol of sodium persulfate in 50ml of water to obtain a uniform solution A;
2. dissolving 64mmol of manganese nitrate in 50ml of deionized water, and adding 4mmol of tetrabutyl titanate to obtain a solution B;
3. dropwise adding the solution B into the solution A with stirring, heating to 90 ℃, and carrying out vigorous stirring reaction for 10 hours to obtain a reacted solution;
4. centrifugally washing the precipitate obtained after the solid-liquid separation of the reacted solution for a plurality of times, and then drying the precipitate in vacuum for 12 hours to obtain the manganese-based material (MnO) doped with titanium element2-Ti)。
Assembling the battery: in MnO2Ti as the positive electrode, zinc foil as the negative electrode and AGM diaphragm as the diaphragm. Electrolyte solution: dimethyl sulfoxide (DMSO) is used as an organic solvent, zinc tetrafluoroborate is used as zinc salt, the zinc tetrafluoroborate is dissolved in DMSO, and Zn is added2+The concentration was 0.25 mol/L.
And (3) testing the battery: in an environment of 25 ℃, the battery is discharged firstly under the current density of 50mA/g and the voltage range of 0.8-1.9V, the initial specific capacity is 140.4mAh/g, the capacity is kept to be 117.3mAh/g after 20 circles, the capacity is kept to be 105.7mAh/g after 400 circles, and compared with 20 circles, the capacity of the battery is basically kept unchanged. From the SEM images of the positive electrode material before and after the test, it can be seen that the structure of the positive electrode material before and after the test is substantially stable. The XRD of the anode material before and after the test shows that the anode material after the test has no impurity. The EDS of the positive electrode material before the test shows that the Ti element is uniformly distributed in the positive electrode material.
The battery is amplified to 5Ah capacity level, and the gas production condition of the battery is detected by adopting a drainage method: no gas was collected.
Example 4
The method for preparing the cathode material comprises the following steps:
1. dissolving 32mmol of sodium persulfate in 5ml of water to obtain a uniform solution A;
2. dissolving 32mmol of manganese chloride in 5ml of deionized water, and adding 2mmol of titanyl sulfate to obtain a solution B;
3. dropwise adding the solution B into the solution A with stirring, heating to 100 ℃, and reacting for 5 hours with vigorous stirring to obtain a reacted solution;
4. centrifugally washing the precipitate obtained after the solid-liquid separation of the reacted solution for a plurality of times, and then drying the precipitate in vacuum for 12 hours to obtain the manganese-based material (MnO) doped with titanium element2-Ti)。
Assembling the battery: in MnO2Ti as the positive electrode, zinc foil as the negative electrode and AGM diaphragm as the diaphragm. Electrolyte solution: diethylene glycol dimethyl ether (G2) as organic solvent, zinc benzene sulfonate as zinc salt, dissolving zinc benzene sulfonate in diethylene glycol dimethyl ether (G2), Zn2+The concentration was 0.25 mol/L.
And (3) testing the battery: in an environment of 25 ℃, the battery is discharged firstly under the current density of 50mA/g and the voltage range of 0.8-1.9V, the initial specific capacity is 175.8mAh/g, the capacity is kept to be 126.7mAh/g after 20 circles, the capacity is kept to be 101.8mAh/g after 400 circles, and compared with 20 circles, the capacity retention rate is about 80.3%. From the SEM images of the positive electrode material before and after the test, it can be seen that the structure of the positive electrode material before and after the test is substantially stable. The XRD of the anode material before and after the test shows that the anode material after the test has no impurity. The EDS of the positive electrode material before the test shows that the Ti element is uniformly distributed in the positive electrode material.
The battery is amplified to 5Ah capacity level, and the gas production condition of the battery is detected by adopting a drainage method: no gas was collected.
Example 5
The method for preparing the cathode material was the same as in example 4;
assembling the battery: in MnO2-Ti as positive electrode, zinc foilAs a negative electrode, the separator is an AGM separator. Electrolyte solution: diglyme (G2) and dimethyl carbonate as organic solvent, zinc benzene sulfonate as zinc salt, dissolving zinc benzene sulfonate in organic solvent until saturation, and sodium ion as second ion.
And (3) testing the battery: in an environment of 25 ℃, the battery is discharged firstly under the current density of 50mA/g and the voltage range of 0.8-1.9V, the initial specific capacity is 157.8mAh/g, the capacity is kept to be 107.7mAh/g after 20 circles, the capacity is kept to be 107.2mAh/g after 400 circles, and compared with 20 circles, the battery capacity is basically kept unchanged. From the SEM images of the positive electrode material before and after the test, it can be seen that the structure of the positive electrode material before and after the test is substantially stable. The XRD of the anode material before and after the test shows that the anode material after the test has no impurity. The EDS of the positive electrode material before the test shows that the Ti element is uniformly distributed in the positive electrode material.
The battery is amplified to 5Ah capacity level, and the gas production condition of the battery is detected by adopting a drainage method: no gas was collected.
Example 6
The method for preparing the cathode material was the same as in example 4;
assembling the battery: in MnO2Ti as the positive electrode, zinc foil as the negative electrode and AGM diaphragm as the diaphragm. Electrolyte solution: n, N-Dimethylformamide (DMF) and ethylene carbonate are used as organic solvent, zinc isooctanoate is used as zinc salt, the zinc isooctanoate is dissolved in the organic solvent, Zn2+The concentration is 0.25mol/L, and potassium ions are taken as second ions.
And (3) testing the battery: in an environment of 25 ℃, the battery is discharged firstly under the current density of 50mA/g and the voltage range of 0.8-1.9V, the initial specific capacity is 150.6mAh/g, the capacity is kept at 120.4mAh/g after 20 circles, the capacity is kept at 113.5mAh/g after 400 circles, and compared with 20 circles, the capacity of the battery is basically kept unchanged. From the SEM images of the positive electrode material before and after the test, it can be seen that the structure of the positive electrode material before and after the test is substantially stable. The XRD of the anode material before and after the test shows that the anode material after the test has no impurity. The EDS of the positive electrode material before the test shows that the Ti element is uniformly distributed in the positive electrode material.
The battery is amplified to 5Ah capacity level, and the gas production condition of the battery is detected by adopting a drainage method: no gas was collected.
Example 7
The method for preparing the cathode material comprises the following steps:
1. adding 32mmol ammonium persulfate ((NH)4)2S2O8) Dissolving in 25ml water to obtain uniform solution A;
2. adding 32mmol of MnSO4Dissolving in 25ml of deionized water, and adding 2mmol of aluminum sulfate to obtain a solution B;
3. dropwise adding the solution B into the solution A with stirring, heating to 80 ℃, and reacting for 6 hours with vigorous stirring to obtain a reacted solution;
4. centrifuging and washing the precipitate after solid-liquid separation of the reacted solution for multiple times, and vacuum drying for 12h to obtain the manganese-based material (MnO) doped with aluminum element2-Al)。
Assembling the battery: in MnO2-Al as the anode, zinc foil as the cathode, and AGM as the separator. Electrolyte solution: n, N-Dimethylformamide (DMF) is taken as an organic solvent, zinc trifluoromethanesulfonate is taken as zinc salt, the zinc trifluoromethanesulfonate is dissolved in the DMF, and Zn2+The concentration was 0.25 mol/L.
And (3) testing the battery: in an environment of 25 ℃, the battery is discharged firstly under the current density of 50mA/g and the voltage range of 0.8-1.9V, the initial specific capacity is 172.7mAh/g, the capacity is kept at 115.6mAh/g after 20 circles, the capacity is kept at 96.4mAh/g after 300 circles, compared with the capacity at the 20 th circle, the capacity retention rate is 83.4%, and the cycle performance curve is shown in fig. 6.
Example 8
The method for preparing the cathode material comprises the following steps:
1. dissolving 32mmol of potassium persulfate in 25ml of water to obtain a uniform solution A;
2. dissolving 32mmol of manganese nitrate in 25ml of deionized water, and adding 1.5mmol of aluminum acetate to obtain a solution B;
3. dropwise adding the solution B into the solution A with stirring, heating to 100 ℃, and reacting for 5 hours with vigorous stirring to obtain a reacted solution;
4. centrifugally washing the precipitate obtained after solid-liquid separation of the reacted liquid for many times, and then vacuum drying12h to obtain manganese-based material (MnO) doped with aluminum element2-Al)。
Assembling the battery: in MnO2-Al as the anode, zinc foil as the cathode, and AGM as the separator. Electrolyte solution: n, N-Dimethylformamide (DMF) is taken as an organic solvent, zinc trifluoromethanesulfonate is taken as zinc salt, the zinc trifluoromethanesulfonate is dissolved in the organic solvent, and Zn2+The concentration was 0.25 mol/L.
And (3) testing the battery: in an environment of 25 ℃, the battery is discharged firstly under the current density of 50mA/g and the voltage range of 0.8-1.9V, the initial specific capacity is 145.7mAh/g, the capacity is kept to be 117.5mAh/g after 20 circles, the capacity is kept to be 95.5mAh/g after 400 circles, and compared with 20 circles, the capacity retention rate is 81.3% compared with the 20 th circle. From the SEM images of the positive electrode material before and after the test, it can be seen that the structure of the positive electrode material before and after the test is substantially stable. The XRD of the anode material before and after the test shows that the anode material after the test has no impurity. The EDS of the anode material before the test shows that the Al element is uniformly distributed in the anode material.
The battery is amplified to 5Ah capacity level, and the gas production condition of the battery is detected by adopting a drainage method: no gas was collected.
Example 9
The method for preparing the cathode material comprises the following steps:
1. dissolving 25mmol of sodium persulfate in 30ml of water to obtain a uniform solution A;
2. dissolving 25mmol of manganese acetate in 30ml of deionized water, and adding 3mmol of aluminum nitrate to obtain a solution B;
3. dropwise adding the solution B into the solution A with stirring, heating to 80 ℃, and reacting for 9 hours with vigorous stirring to obtain a reacted solution;
4. centrifuging and washing the precipitate after solid-liquid separation of the reacted solution for multiple times, and then drying in vacuum for 12h to obtain the manganese-based material (MnO) doped with aluminum element2-Al)。
Assembling the battery: in MnO2-Al as the anode, zinc foil as the cathode, and AGM as the separator. Electrolyte solution: n, N-Dimethylformamide (DMF) and triethyl phosphate are used as organic solvents, zinc p-toluenesulfonate is used as a zinc salt, and the zinc p-toluenesulfonate is dissolvedIn an organic solvent, Zn2+The concentration was 0.3mol/L, and lithium ions were used as the second ions.
And (3) testing the battery: in an environment of 25 ℃, the battery is discharged firstly under the current density of 50mA/g and the voltage range of 0.8-1.9V, the initial specific capacity is 150.2mAh/g, the capacity is kept to be 113.5mAh/g after 20 circles, the capacity is kept to be 95.3mAh/g after 400 circles, and compared with 20 circles, the capacity retention rate is 84.0% compared with 20 th circles. From the SEM images of the positive electrode material before and after the test, it can be seen that the structure of the positive electrode material before and after the test is substantially stable. The XRD of the anode material before and after the test shows that the anode material after the test has no impurity. The EDS of the anode material before the test shows that the Al element is uniformly distributed in the anode material.
The battery is amplified to 5Ah capacity level, and the gas production condition of the battery is detected by adopting a drainage method: no gas was collected.
Example 10
The method for preparing the cathode material comprises the following steps:
1. dissolving 40mmol of sodium persulfate in 25ml of water to obtain a uniform solution A;
2. dissolving 40mmol of manganese nitrate in 25ml of deionized water, and adding 3mmol of aluminum chloride to obtain a solution B;
3. dropwise adding the solution B into the solution A with stirring, heating to 90 ℃, and reacting for 11 hours with vigorous stirring to obtain a reacted solution;
4. centrifuging and washing the precipitate after solid-liquid separation of the reacted solution for multiple times, and then drying in vacuum for 12h to obtain the manganese-based material (MnO) doped with aluminum element2-Al)。
Assembling the battery: in MnO2-Al as the anode, zinc foil as the cathode, and AGM as the separator. Electrolyte solution: n, N-Dimethylformamide (DMF) and trimethyl phosphate are used as organic solvents, zinc perchlorate is used as zinc salt, the zinc perchlorate is dissolved in the organic solvents until saturation is achieved, and magnesium ions are used as second ions.
And (3) testing the battery: in an environment of 25 ℃, the battery discharges firstly under the current density of 50mA/g and the voltage range of 0.8-1.9V, the initial specific capacity is 141.6mAh/g, the capacity is kept at 110.3mAh/g after 20 circles, the capacity is kept at 92.5mAh/g after 400 circles, and compared with 20 circles, the capacity retention rate is 83.9%. From the SEM images of the positive electrode material before and after the test, it can be seen that the structure of the positive electrode material before and after the test is substantially stable. The XRD of the anode material before and after the test shows that the anode material after the test has no impurity. The EDS of the anode material before the test shows that the Al element is uniformly distributed in the anode material.
The battery is amplified to 5Ah capacity level, and the gas production condition of the battery is detected by adopting a drainage method: no gas was collected.
Example 11 (doping with both Al and Ti)
The method for preparing the cathode material comprises the following steps:
1. dissolving 32mmol of sodium persulfate in 25ml of water to obtain a uniform solution A;
2. dissolving 32mmol of manganese nitrate in 25ml of deionized water, and adding 1.5mmol of sulfated aluminum and 1.0mmol of titanyl sulfate to obtain a solution B;
3. dropwise adding the solution B into the solution A with stirring, heating to 90 ℃, and reacting for 11 hours with vigorous stirring to obtain a reacted solution;
4. centrifuging and washing the precipitate after solid-liquid separation of the reacted solution for multiple times, and then drying in vacuum for 12h to obtain the manganese-based material (MnO) doped with aluminum element2-Al/Ti)。
Assembling the battery: in MnO2-Al/Ti as the anode, zinc foil as the cathode and AGM as the diaphragm. Electrolyte solution: n, N-Dimethylformamide (DMF) is taken as an organic solvent, zinc trifluoromethanesulfonate is taken as zinc salt, the zinc trifluoromethanesulfonate is dissolved in the organic solvent, and Zn2+The concentration was 0.25 mol/L.
And (3) testing the battery: in an environment of 25 ℃, the battery is discharged firstly under the current density of 50mA/g and the voltage range of 0.8-1.9V, the initial specific capacity is 153.4mAh/g, the capacity is kept at 122.5mAh/g after 20 circles, the capacity is kept at 117.6mAh/g after 400 circles, and compared with 20 circles, the battery capacity is basically kept unchanged. From the SEM images of the positive electrode material before and after the test, it can be seen that the structure of the positive electrode material before and after the test is substantially stable. The XRD of the anode material before and after the test shows that the anode material after the test has no impurity. The EDS of the positive electrode material before the test shows that Al and Ti elements are uniformly distributed in the positive electrode material.
The battery is amplified to 5Ah capacity level, and the gas production condition of the battery is detected by adopting a drainage method: no gas was collected.
Comparative example
The method for preparing the cathode material comprises the following steps:
1. dissolving 10g of PEG-1500 in 25ml of water with the temperature of 60 ℃ to obtain a uniform solution A;
2. with stirring, 0.8g of KMnO4Dissolving in 25ml of deionized water, dropwise adding the solution A, and heating to 80 ℃ for reaction for 6 hours to obtain a reacted solution;
3. centrifugally washing the precipitate after solid-liquid separation of the reacted solution for multiple times, and then vacuum drying for 12h to obtain manganese-based material (MnO)2)。
Assembling the battery: in MnO2The anode is made of zinc foil, the cathode is made of zinc foil, and the diaphragm is an AGM diaphragm. Electrolyte solution: n, N-Dimethylformamide (DMF) is taken as a solvent, zinc trifluoromethanesulfonate is taken as zinc salt, the zinc trifluoromethanesulfonate is dissolved in the DMF, and Zn2+The concentration was 0.25 mol/L.
And (3) testing the battery: in an environment of 25 ℃, the initial discharge specific capacity of the battery under the current density of 50mA/g is 22.3mAh/g, the capacity is increased to 65.6mAh/g after 30 circles, the capacity is declined to 45.1mAh/g after 200 circles, the capacity and the cycle performance of the battery are not good, and the cycle performance curve is shown in figure 7.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A positive electrode material, characterized in that the positive electrode material is a manganese-based material doped with a metal element, wherein the doped metal element includes at least one of Ti and Al.
2. The positive electrode material of claim 1, wherein the manganese-based material comprises MnO2。
3. The positive electrode material according to claim 1 or 2, wherein the mass proportion of the doped metal element is 1 to 10% based on the mass of the positive electrode material.
4. A method for producing the positive electrode material according to any one of claims 1 to 3, comprising:
(1) mixing a manganese salt solution with a doping metal salt to obtain a mixed solution, wherein the doping metal salt comprises an aluminum-containing salt or/and a titanium-containing salt;
(2) mixing the mixed solution with persulfate;
(3) and (3) washing and drying the liquid obtained in the step (2) after the reaction so as to obtain the cathode material.
5. The method according to claim 4, wherein the molar ratio of the manganese salt solution to the doping metal salt and the persulfate salt is (25-128): (1-5): (25-128).
6. The method according to claim 4, wherein in the step (2), the mixed solution and the persulfate are stirred at 70 to 100 ℃ for 5 to 12 hours with stirring.
7. A zinc-ion battery, comprising:
a positive electrode prepared from the positive electrode material according to any one of claims 1 to 3 or the positive electrode material obtained by the method according to any one of claims 4 to 6;
a negative electrode comprising metallic zinc and/or a zinc-containing compound;
an electrolyte comprising an organic solvent and a zinc-containing ionic salt.
8. The zinc-ion battery of claim 7, wherein the organic solvent comprises at least one of N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and diglyme.
9. The zinc-ion battery of claim 7 or 8, wherein the zinc-containing ionic salt comprises at least one of zinc chloride, zinc tetrafluoroborate, zinc perchlorate, zinc trifluoromethanesulfonate, zinc sulfate, zinc nitrate, zinc oxalate, zinc benzenesulfonate, zinc p-toluenesulfonate, and zinc isooctanoate.
10. The zinc ion battery of claim 9, wherein the electrolyte further comprises at least one of dimethyl carbonate, ethylene carbonate, propylene carbonate, trimethyl phosphate, and triethyl phosphate;
optionally, the electrolyte further comprises a second ion comprising at least one of sodium ion, potassium ion, lithium ion, and magnesium ion.
CN202110846087.4A 2021-07-26 2021-07-26 Positive electrode material, preparation method thereof and zinc ion battery Pending CN113611848A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114408976A (en) * 2022-01-11 2022-04-29 成都大学 High-performance alpha-MnO2Al nanorod and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114408976A (en) * 2022-01-11 2022-04-29 成都大学 High-performance alpha-MnO2Al nanorod and preparation method and application thereof
CN114408976B (en) * 2022-01-11 2023-09-22 成都大学 High-performance alpha-MnO 2 Al nano rod and preparation method and application thereof

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