CN115566150A - Neutral or weakly acidic system water system zinc ion battery positive electrode material and preparation method and application thereof - Google Patents

Neutral or weakly acidic system water system zinc ion battery positive electrode material and preparation method and application thereof Download PDF

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CN115566150A
CN115566150A CN202110745904.7A CN202110745904A CN115566150A CN 115566150 A CN115566150 A CN 115566150A CN 202110745904 A CN202110745904 A CN 202110745904A CN 115566150 A CN115566150 A CN 115566150A
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positive electrode
manganese
zinc ion
ion battery
bismuth
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傅洋
田毅
倪珂帆
于春雨
陈璞
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Ruihai Bo Changzhou Energy Technology Co ltd
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Priority to PCT/CN2022/098188 priority patent/WO2023273835A1/en
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • 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
    • 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

Abstract

The invention discloses a neutral or weakly acidic system water system zinc ion battery anode material and a preparation method and application thereof, wherein the anode material comprises Bi x Mn y‑x O z And manganese-containing compound, bi x Mn y‑x O z Distributed on the surface of manganese-containing compound, wherein, 0<y/z≤1,0<x is less than or equal to y. Therefore, the positive electrode material is stable in structure, and can be applied to a zinc ion battery to solve the problem of poor cycle performance of the zinc ion battery, so that the zinc ion battery with good electrochemical performance, high specific capacity and excellent cycle performance is obtained.

Description

Neutral or weakly acidic system water system zinc ion battery positive electrode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of zinc ion batteries, and particularly relates to a neutral or weakly acidic system water system zinc ion battery positive electrode material, and a preparation method and application thereof.
Background
With the popularization of portable electronic devices such as computers, mobile phones and tablets and the rapid development of green and environment-friendly electric automobiles, people have increasingly large demands on secondary batteries, and lithium ion batteries are also exposed to some defects as secondary batteries with the most extensive applications: the price of lithium resources rises year by year due to shortage of the lithium resources, lithium dendrite is easy to form on a negative electrode to cause short circuit, organic electrolyte is flammable, and certain potential safety hazards exist. Compared with lithium, zinc has more abundant resources and lower cost, and the water system zinc ion battery eliminates the danger of fire, explosion and the like possibly caused by organic electrolyte. In addition, 2 electrons are transferred in the oxidation-reduction process of zinc ions, so that the zinc ion has higher theoretical capacity.
Most of the positive electrode materials for neutral or weakly acidic aqueous zinc ion batteries reported so far use manganese dioxide not coated with a Bi compound as the positive electrode material for aqueous zinc ion batteries. MnO 2 The + 4-valent Mn in the positive electrode material is easily reduced to + 2-valent Mn, so that the positive electrode material is dissolved in the electrolyte, resulting in deterioration of cycle performance.
Therefore, the existing neutral or weakly acidic system water-based zinc ion battery positive electrode material needs to be improved.
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, the invention aims to provide a neutral or weakly acidic system water system zinc ion battery positive electrode material, and a preparation method and application thereof.
In one aspect of the invention, the invention provides a neutral or weakly acidic system water system zinc ion battery positive electrode material. According to an embodiment of the present invention, the positive electrode material comprises Bi x Mn y-x O z And manganese-containing compound, bi x Mn y-x O z Is distributed on the surface of the manganese-containing compound, wherein, 0<y/z≤1,0<x≤y。
The cathode material comprises Bi x Mn y-x O z And manganese-containing compound, bi x Mn y-x O z Distributed on the surface of manganese-containing compound, wherein, 0<y/z≤1,0<x is less than or equal to y. When x = y, bi x Mn y-x O z Being oxides of bismuth, i.e. Bi x Mn y-x O z The electrolyte comprises bismuth oxide and/or bismuth-manganese oxide, wherein the bismuth oxide isolates a manganese-containing compound from the electrolyte, so that the occurrence of side reaction between the electrolyte and the manganese-containing compound is reduced, and the bismuth-manganese oxide enables the structure of the anode material to be more stable in the charge-discharge process, thereby improving the cycle performance of the battery core. In the method, an in-situ combination mode is adopted, and the Bi element is uniformly distributed on the surface of primary particles of the manganese-containing compound in the process of synthesizing the manganese-containing compound; if the oxide of bismuth is directly mixed with the manganese-containing compound or the manganese-containing compound is directly doped with Bi, bi is mainly distributed on the surface of secondary particles and is difficult to be uniformly distributed, and intermolecular acting force is much worse than in-situ combination, so that Bi is easy to migrate to a negative electrode and loses the protection effect on the positive electrode in the charge and discharge processes of the material. The positive electrode material can be applied to a neutral or weakly acidic system water system zinc ion battery, and solves the problem of poor cycle performance of the zinc ion battery, so that the zinc ion battery with good electrochemical performance, high specific capacity and excellent cycle performance is obtained.
In addition, the neutral or weakly acidic system water system zinc ion battery positive electrode material according to the above embodiment of the present invention may further have the following additional technical features:
according to some embodiments of the invention, the manganese-containing compound comprises MnO 2 、MnO，Mn 2 O 3 And Mn 3 O 4 At least one of (a).
According to some embodiments of the present invention, the molar ratio of the Bi element to the Mn element in the positive electrode material is between 0 and 1, excluding the endpoint 0.
In a second aspect of the invention, the invention provides a method for preparing the above-mentioned positive electrode material. According to an embodiment of the invention, the method comprises:
(1) Mixing the manganese-containing material, the bismuth-containing compound and water with stirring, and then drying to obtain a precursor;
(2) And sintering the precursor to obtain the cathode material.
According to the method for preparing the cathode material, the manganese-containing material, the bismuth-containing compound and water are mixed with stirring, the bismuth-containing compound is uniformly dispersed in the water and coated on the surface of the manganese-containing material, and a part of the bismuth-containing compound reacts with the manganese-containing material, namely, the bismuth element in the bismuth-containing compound replaces the manganese element in the crystal lattice of the manganese-containing material to generate bismuth-manganese oxide, so that the structure of the cathode material is more stable in the charge and discharge processes, the cycle performance of a battery cell is improved, and a precursor is obtained after drying; then sintering the obtained precursor, wherein the bismuth-containing compound which is not reacted with the manganese-containing material is converted into Bi which is difficult to dissolve in water 2 O 3 The manganese-containing material is isolated from the electrolyte, so that the occurrence of side reaction between the electrolyte and the manganese-containing material is reduced, and the cycle performance of the battery cell is improved. The method is applied to the neutral or acidic system water system zinc ion battery for the first time, the problem of uneven distribution of the coating is solved through a solution method, the coating proportion is controllable, the preparation process is simple, the raw material cost is low, and the method can be applied to large-scale industrial production. In addition, the prepared cathode material contains bismuth on the surface, so that the cathode material is more stable in structure in the charging and discharging processes, and when the cathode material is applied to a zinc ion battery, the electrochemical performance, specific capacity and cycle performance of the battery can be improved.
In some embodiments of the present invention, in step (1), the stirring time is 1min to 100h. Thus, the coating of the positive electrode material is uniformly distributed.
In some embodiments of the present invention, in step (1), the molar ratio of the Bi element in the bismuth-containing compound to the Mn element in the manganese-containing material is between 0 and 1, excluding endpoint 0. Thus, the proportion of the coating is controllable.
In some embodiments of the invention, the manganese-containing material comprises MnO 2 、MnO，Mn 2 O 3 And Mn 3 O 4 At least one of (a).
In some implementations of the inventionIn one embodiment, the bismuth-containing compound comprises Bi 2 O 3 、Bi(NO 3 ) 3 Bismuth subnitrate, bi 2 (SO 4 ) 3 、BiCl 3 、Bi(CH 3 COO) 3 Bismuth subcarbonate and Bi 2 (C 2 O 4 ) 3 At least one of (a).
In some embodiments of the invention, in the step (2), the sintering temperature is 50-900 ℃ and the sintering time is 1 min-30 h.
In a third aspect of the present invention, the present invention provides a positive electrode sheet. According to the embodiment of the invention, the positive pole piece is provided with the positive pole material or the positive pole material prepared by the method. Therefore, the cathode pole piece is assembled into a neutral or weakly acidic system water system zinc ion battery, and the electrochemical performance, specific capacity and cycle performance of the battery can be improved.
In a fourth aspect of the invention, the invention provides a neutral or weakly acidic system water system zinc ion battery. According to an embodiment of the invention, the battery is provided with the positive pole piece. Therefore, the zinc ion battery has good electrochemical performance, high specific capacity and high cycle performance.
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 an SEM image of the cathode material prepared in example 1;
fig. 3 is an EDS diagram of the cathode material prepared in example 1;
fig. 4 is a graph comparing cycle performance of the positive electrode materials prepared in examples 1 to 2 and comparative example 1.
Detailed Description
The embodiments described below with reference to the accompanying drawings are illustrative and intended to explain the present invention and should not be construed as limiting the present invention.
In a first aspect of the invention, the invention provides a neutral or weakly acidic system water system zinc ion battery positive electrode material. According to an embodiment of the present invention, the positive electrode material comprises Bi x Mn y-x O z And manganese-containing compounds, bi x Mn y-x O z Distributed on the surface of manganese-containing compound, wherein, 0<y/z≤1,0<x≤y。
The inventors found that the positive electrode material of the present application includes Bi x Mn y-x O z And manganese-containing compounds, bi x Mn y-x O z Distributed on the surface of the manganese-containing compound, wherein 0<y/z≤1,0<x is less than or equal to y. When x = y, bi x Mn y-x O z Being oxides of bismuth, i.e. Bi x Mn y-x O z The electrolyte comprises bismuth oxide and/or bismuth manganese oxide, wherein the bismuth oxide isolates a manganese-containing compound from the electrolyte, so that the occurrence of side reactions between the electrolyte and the manganese-containing compound is reduced, and the bismuth manganese oxide enables the structure of the positive electrode material to be more stable in the charge-discharge process, thereby improving the cycle performance of the battery cell. In the method, an in-situ combination mode is adopted, and the Bi element is uniformly distributed on the surface of primary particles of the manganese-containing compound in the process of synthesizing the manganese-containing compound; if the bismuth oxide is directly mixed with the manganese-containing compound or the manganese-containing compound is directly doped with Bi, bi is mainly distributed on the surface of secondary particles and is difficult to be uniformly distributed, and intermolecular acting force is much poorer than that of in-situ combination, so that Bi is easy to migrate to a negative electrode and loses the protection effect on the positive electrode in the charge-discharge process of the material. The positive electrode material can be applied to a neutral or weakly acidic system water system zinc ion battery, and solves the problem of poor cycle performance of the zinc ion battery, so that the zinc ion battery with good electrochemical performance, high specific capacity and excellent cycle performance is obtained.
It is noted that the specific type of manganese-containing compound, e.g., manganese-containing compound including MnO, can be selected by those skilled in the art according to actual needs 2 、MnO，Mn 2 O 3 And Mn 3 O 4 At least one of (a).
Further, the molar ratio of the Bi element to the Mn element in the positive electrode material is between 0 and 1, excluding the endpoint 0. The inventors found that if the molar ratio is too large, the gram capacity of the cell is severely reduced because Mn, as an active material, proceeds and loses electrons to provide the gram capacity in the bismuth manganese oxide, while the Bi element does not provide or provides less gram capacity. Therefore, the gram capacity of the battery cell can be prevented from being reduced while the battery cell cycle performance is improved by adopting the molar ratio.
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 the manganese-containing material, bismuth-containing compound and water with stirring, and drying
In the step, the manganese-containing material is dispersed in water with stirring (e.g., magnetic stirring), then the bismuth-containing compound is added, and the precursor can be obtained after the mixture is continuously stirred for a period of time and dried. The inventor finds that the bismuth-containing compound uniformly coats the manganese-containing material in water, and a part of the bismuth-containing compound reacts with the manganese-containing material, namely, the bismuth element in the bismuth-containing compound replaces the manganese element in the manganese-containing material lattice to generate bismuth-manganese oxide, and the bismuth-manganese oxide enables the structure of the positive electrode material to be more stable in the charging and discharging processes, so that the cycle performance of the battery cell is improved. It should be noted that the specific types of the manganese-containing material and the bismuth-containing compound are not particularly limited, and can be selected by those skilled in the art according to the actual needs, for example, the manganese-containing material includes MnO 2 、MnO，Mn 2 O 3 And Mn 3 O 4 At least one of; the bismuth-containing compound comprises Bi 2 O 3 、Bi(NO 3 ) 3 Basic bismuth nitrate and Bi 2 (SO 4 ) 3 、BiCl 3 、Bi(CH 3 COO) 3 Bismuth subcarbonate and Bi 2 (C 2 O 4 ) 3 At least one of (a).
Further, the stirring time is 1min to 100 hours, preferably 1 hour to 8 hours. The inventor finds that if the stirring time is too long, other side reactions can be caused; if the stirring time is too short, the reaction does not occur sufficiently due to insufficient contact between different substances, and the materials are not mixed uniformly. From this, adopt the churning time of this application can make the material misce bene, and the reaction is abundant, can avoid the emergence of side reaction simultaneously.
Furthermore, the molar ratio of the Bi element in the bismuth-containing compound to the Mn element in the manganese-containing material is between 0 and 1, and the endpoint is not 0. The inventors found that if the molar ratio is too large, the gram capacity of the cell is severely reduced because Mn, as an active material, proceeds and loses electrons to provide the gram capacity in the bismuth manganese oxide, while the Bi element does not provide or provides less gram capacity. Therefore, the gram capacity of the battery cell can be prevented from being reduced while the battery cell cycle performance is improved by adopting the molar ratio.
S200: sintering the precursor
In the step, the precursor is sintered to obtain the cathode material. In particular, the sintering process may be performed in a box furnace. The inventors have found that the sintering process converts bismuth-containing compounds in the coating that have not reacted with the manganese-containing material to Bi that is poorly soluble in water 2 O 3 The manganese-containing material is isolated from the electrolyte, so that the occurrence of side reaction between the electrolyte and the manganese-containing material is reduced, and the cycle performance of the battery cell is improved. Further, the sintering temperature is 50-900 ℃, preferably 300-470 ℃, and the time is 1 min-30 h, preferably 1 h-8 h. The inventors have found that if the temperature is too low, the reaction temperature at which the Bi salt is not sufficiently decomposed is not reached, and the reaction to form Bi cannot proceed sufficiently 2 O 3 Or bismuth manganese oxide; if the temperature is too high, phase change of the material can occur. Meanwhile, if the time is too long, the phase change of the material can be caused; if the time is too short, the reaction may not sufficiently occur. Therefore, the sintering conditions of the method can fully react, and can avoid phase change of materials.
The inventors have found that by concomitant stirringMixing the manganese-containing material, the bismuth-containing compound and water, uniformly dispersing the bismuth-containing compound in the water, coating the bismuth-containing compound on the surface of the manganese-containing material, and reacting a part of the bismuth-containing compound with the manganese-containing material, namely replacing the manganese element in the crystal lattice of the manganese-containing material with the bismuth element in the bismuth-containing compound to generate bismuth-manganese oxide, so that the structure of the positive electrode material is more stable in the charging and discharging process, the cycle performance of the battery cell is improved, and a precursor is obtained after drying; then sintering the obtained precursor, wherein the bismuth-containing compound which is not reacted with the manganese-containing material is converted into Bi which is difficult to dissolve in water 2 O 3 The manganese-containing material is isolated from the electrolyte, so that the occurrence of side reaction between the electrolyte and the manganese-containing material is reduced, and the cycle performance of the battery cell is improved. The method is applied to the neutral or acidic system water system zinc ion battery for the first time, the problem of uneven distribution of the coating is solved through a solution method, the coating proportion is controllable, the preparation process is simple, the raw material cost is low, and the method can be applied to large-scale industrial production. In addition, the prepared positive electrode material coating layer contains bismuth, so that the positive electrode material is more stable in structure in the charging and discharging processes, and when the positive electrode material coating layer is applied to a zinc ion battery, the electrochemical performance, specific capacity and cycle performance of the battery can be improved.
In a third aspect of the present invention, the present invention provides a positive electrode plate. According to the embodiment of the invention, the positive pole piece is provided with the positive pole material or the positive pole material prepared by the method. Therefore, the cathode pole piece is assembled into a neutral or weakly acidic system water system zinc ion battery, and the electrochemical performance, specific capacity and cycle performance of the battery can be improved.
In addition, the mixing ratio of the positive electrode material, the conductive agent and the binder, the specific types of the conductive agent, the binder and the base film, and the like in the process of preparing the positive electrode plate are all conventional settings in the field, for example, the conductive agent is acetylene black; the binder is CMC and/or SBR; the base film is a conductive PE film, and meanwhile, the characteristics and advantages described for the positive electrode material and the preparation method thereof are also applicable to the positive electrode piece, and are not described again here.
In a fourth aspect of the invention, the invention provides a neutral or weakly acidic system water system zinc ion battery. According to an embodiment of the invention, the battery is provided with the positive pole piece. Therefore, the zinc ion battery has good electrochemical performance, high specific capacity and high cycle performance.
In addition, the specific types of the negative electrode plate and the separator in the above battery assembling process are conventional in the art, for example, the negative electrode plate is zinc foil or zinc powder; the diaphragm is an AGM diaphragm, in addition, the electrolyte is a neutral or weakly acidic system, and meanwhile, the characteristics and the advantages described for the positive pole piece are also applicable to the zinc ion battery, and are not described again.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to one skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
(1) With MnSO 4 Preparing solution A with the concentration of 0.5mol/L and the total volume of 500ml as raw materials. With Na 2 CO 3 Preparing solution B as raw material with concentration of 0.5mol/L and total volume of 500ml.
(2) Adding the A and B solutions into a 2L beaker at the same speed, performing magnetic stirring for 2h, washing the material with distilled water for 3 times, and drying at 70 ℃ to obtain MnCO 3 And (3) powder.
(3) Mixing MnCO 3 And putting the powder into a box furnace for heat treatment, wherein the sintering temperature is 410 ℃, and the sintering time is 4h.
(4) After the mixture is cooled to room temperature, the material is taken out and ground by an agate mortar to obtain MnO 2 。
(5) MnO of 2 Dispersed in water and magnetically stirred, followed by addition of Bi (NO) in a Bi/Mn ratio of 0.04 3 ) 3 And magnetically stirring for 3h, and then drying.
(6) And (3) sintering the dried material in a box-type furnace at 465 ℃ for 4h.
(7) After the anode material is cooled to room temperature, the material is taken out and ground by an agate mortar to obtain a well-coated anode material (the coating layer comprises Bi) 2 O 3 And Bi x Mn y-x O z ，0＜x≤1，y＝1，z＝2)。
(8) Manufacturing a battery positive pole piece: and (3) preparing a positive electrode material: acetylene black: CMC: SBR =80, 3, and then the uniformly stirred positive electrode slurry was uniformly applied to a conductive PE film and dried at room temperature.
(9) Assembling the battery: ( And (3) positive electrode: the positive electrode material prepared in the above way; negative electrode: a zinc powder negative electrode is prepared by adopting a copper mesh current collector slurry drawing method; diaphragm: an AGM separator; electrolyte solution: the concentration of the aqueous solution is 1.8mol/L zinc sulfate and 0.2mol/L manganese sulfate )
And (3) fully soaking the AGM diaphragm in liquid electrolyte, and then combining the prepared positive electrode material and the prepared negative electrode Zn powder to assemble the battery.
(10) And (3) testing the battery: the surface density of the positive pole piece is 20mg/cm 2 The highest specific capacity of the zinc ion battery under the current density of 50mA/g is 200mAh/g under the environment of 25 ℃, the zinc ion battery circulates for 200 circles under the current density of 125mA/g, and the capacity retention rate is 93%. The test results of the positive electrode material SEM and the EDS are respectively shown in figures 2 and 3, the material sphericity is high and the morphology is regular from figure 2, the particle size of the secondary particles is about 4 micrometers, and the Bi element is uniformly distributed in the material from figure 3; the cell cycling performance is shown in figure 4.
Example 2
The same procedure as in example 1 was repeated except that the negative electrode was replaced with a zinc foil. The SEM test result of the obtained cathode material shows that the material has high sphericity and regular appearance, the secondary particle size is about 4 microns, and the EDS test result shows that the Bi element is uniformly distributed in the material.
(11) And (3) testing the battery: the highest specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 203mAh/g, the zinc ion battery is circulated for 200 circles under the current density of 125mA/g, and the capacity retention rate is 82%. The cell cycling performance is shown in figure 4.
Example 3
The molar ratio Bi/Mn was changed to 0.06.
The coated anode material (the coating layer comprises Bi) is prepared 2 O 3 And Bi x Mn y-x O z 0 < x ≦ 1, y =1, z = 2). From the SEM test result of the obtained cathode material, the material is spherical particles, the appearance is regular, the particle size of secondary particles is about 4 micrometers, and from the EDS test result, bi element is very uniformly distributed in the material, and the Bi/Mn ratio is close to 0.06
And (3) testing the battery: the highest specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 203mAh/g, the zinc ion battery is circulated for 200 circles under the current density of 125mA/g, and the capacity retention rate is 90%.
Example 4
Adding Bi (NO) 3 ) 3 By replacing with Bi (CH) 3 COO) 3 Otherwise, the same procedure as in example 1 was repeated.
Preparing the coated positive electrode material (the coating layer comprises Bi) 2 O 3 And Bi x Mn y-x O z 0 < x ≦ 1, y =1, z = 2). According to the SEM test result of the obtained cathode material, the material is spherical particles, the shape is regular, the particle size of the secondary particles is about 4 microns, and the distribution of Bi element in the material is very uniform according to the EDS test result.
And (3) testing the battery: the highest specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 214mAh/g, the zinc ion battery is circulated for 180 circles under the current density of 125mA/g, and the capacity retention rate is 95%.
Example 5
Adding Bi (NO) 3 ) 3 The procedure is as in example 1 except that bismuth subcarbonate is used instead.
Preparing the coated positive electrode material (the coating layer comprises Bi) 2 O 3 And Bi x Mn y-x O z 0 < x ≦ 1, y =1, z = 2). As can be seen from the SEM test result of the obtained cathode material, the material is spherical particles with regular appearance, the grain diameter of the secondary particles is about 4 microns, and the secondary particles are obtained from the spherical particlesThe EDS test result shows that the Bi element is distributed in the material very uniformly.
And (3) testing the battery: the highest specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 210mAh/g, the zinc ion battery is circulated for 230 circles under the current density of 125mA/g, and the capacity retention rate is 85%.
Example 6
Adding Bi (NO) 3 ) 3 By changing to Bi 2 O 3 Otherwise, the same procedure as in example 1 was repeated.
The coated anode material (the coating layer comprises Bi) is prepared 2 O 3 And Bi x Mn y-x O z 0 < x ≦ 1, y =1, z = 2). According to the SEM test result of the obtained cathode material, the material is spherical particles, the appearance is regular, the particle size of secondary particles is about 4 micrometers, and the distribution of Bi elements in the material is very uniform according to the EDS test result.
And (3) testing the battery: the highest specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 212mAh/g, the zinc ion battery is circulated for 130 circles under the current density of 125mA/g, and the capacity retention rate is 83%.
Example 7
MnO of 2 By changing to Mn 2 O 3 Otherwise, the same procedure as in example 1 was repeated.
Preparing the coated positive electrode material (the coating layer comprises Bi) 2 O 3 And Bi x Mn y-x O z 0 < x ≦ 2, y =2, z = 3). The SEM test result of the obtained cathode material shows that the material is spherical particles and has regular appearance, and the EDS test result shows that the Bi element is very uniformly distributed in the material.
And (3) testing the battery: the highest specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 122mAh/g, the zinc ion battery is circulated for 230 circles under the current density of 125mA/g, and the capacity retention rate is 95%.
Example 8
MnO of 2 By changing to Mn 3 O 4 Otherwise, the same procedure as in example 1 was repeated.
Preparing the coated positive electrode material (the coating layer comprises Bi) 2 O 3 And Bi x Mn y-x O z 0 < x ≦ 3, y =3, z = 4). The SEM test result of the obtained cathode material shows that the material is spherical particles and has regular appearance, and the EDS test result shows that the Bi element is very uniformly distributed in the material.
And (3) testing the battery: the maximum specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 92mAh/g, the zinc ion battery is circulated for 300 circles under the current density of 125mA/g, and the capacity retention rate is 92%.
Example 9
The molar ratio Bi/Mn was changed to 0.5.
Preparing the coated positive electrode material (the coating layer comprises Bi) 2 O 3 And Bi x Mn y-x O z 0 < x ≦ 1, y =1, z = 2). The SEM test result of the obtained cathode material shows that the material is spherical particles and has regular appearance, and the EDS test result shows that the Bi element is very uniformly distributed in the material.
And (3) testing the battery: the highest specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 136mAh/g, the zinc ion battery is circulated for 280 circles under the current density of 125mA/g, and the capacity retention rate is 93%.
Example 10
The molar ratio Bi/Mn was changed to 0.95.
Preparing the coated positive electrode material (the coating layer comprises Bi) 2 O 3 And Bi x Mn y-x O z 0 < x ≦ 1, y =1, z = 2). The SEM test result of the obtained cathode material shows that the material is spherical particles and has regular appearance, and the EDS test result shows that the Bi element is very uniformly distributed in the material.
And (3) testing the battery: the highest specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 45mAh/g, 685 cycles are circulated under the current density of 125mA/g, and the capacity retention rate is 95%.
Example 11
Adding Bi (NO) 3 ) 3 By replacing with Bi 2 (SO 4 ) 3 The molar ratio Bi/Mn was changed to 0.75.
Preparing the coated positive electrode material (the coating layer comprises Bi) 2 O 3 And Bi x Mn y-x O z 0 < x ≦ 1, y =1, z = 2). The SEM test result of the obtained cathode material shows that the material is spherical particles and has regular appearance, and the EDS test result shows that the Bi element is very uniformly distributed in the material.
And (3) testing the battery: the maximum specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 122mAh/g, the zinc ion battery circulates 462 circles under the current density of 125mA/g, and the capacity retention rate is 90%.
Example 12
Adding Bi (NO) 3 ) 3 Is replaced by BiCl 3 The molar ratio Bi/Mn was changed to 0.25.
The coated anode material (the coating layer comprises Bi) is prepared 2 O 3 And Bi x Mn y-x O z 0 < x ≦ 1, y =1, z = 2). The SEM test result of the obtained cathode material shows that the material is spherical particles and has regular appearance, and the EDS test result shows that the Bi element is very uniformly distributed in the material.
And (3) testing the battery: the highest specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 168mAh/g, the zinc ion battery is circulated for 280 circles under the current density of 125mA/g, and the capacity retention rate is 82%.
Example 13
The sintering temperature was changed to 300 ℃ and the sintering time was changed to 8 hours, as in example 1.
Preparing the coated positive electrode material (the coating layer comprises Bi) 2 O 3 And Bi x Mn y-x O z 0 < x ≦ 1, y =1, z = 2). The SEM test result of the obtained cathode material shows that the material is spherical particles and has regular appearance, and the EDS test result shows that the Bi element is very uniformly distributed in the material.
And (3) testing the battery: the maximum specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 192mAh/g, the zinc ion battery can be circulated for 125 circles under the current density of 125mA/g, and the capacity retention rate is 81%.
Example 14
The sintering temperature was changed to 50 ℃ and the sintering time to 30 hours, as in example 1.
The coated anode material (the coating layer comprises Bi) is prepared 2 O 3 And Bi x Mn y-x O z 0 < x ≦ 1, y =1, z = 2). The SEM test result of the obtained cathode material shows that the material is spherical particles and has regular appearance, and the EDS test result shows that the Bi element is very uniformly distributed in the material.
And (3) testing the battery: the highest specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 210mAh/g, the zinc ion battery is circulated for 100 circles under the current density of 125mA/g, and the capacity retention rate is 75%.
Example 15
The sintering temperature was changed to 900 ℃ and the sintering time was changed to 10min, as in example 1.
Preparing the coated positive electrode material (the coating layer comprises Bi) 2 O 3 And Bi x Mn y-x O z 0 < x ≦ 1, y =1, z = 2). The SEM test result of the obtained cathode material shows that the material is spherical particles and has regular appearance, and the EDS test result shows that the Bi element is very uniformly distributed in the material.
And (3) testing the battery: the maximum specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 65mAh/g, the zinc ion battery is circulated for 300 circles under the current density of 125mA/g, and the capacity retention rate is 95%.
Comparative example 1
Synthesis of MnO with uncoated Bi element 2 The subsequent processes of making the battery pole piece and assembling the cell are the same as in example 1.
And (3) testing the battery: the maximum specific capacity of the zinc ion battery under the current density of 50mA/g at 25 ℃ is 230mAh/g, the zinc ion battery is circulated for 70 circles under the current density of 125mA/g, and the capacity retention rate is 63%. The cell cycling performance is shown in figure 4.
Comparative example 2
Directly adding Bi in the homogenate process of preparing the anode plate 2 O 3 With MnO 2 The procedure for mixing, then making the battery pole pieces and assembling the battery was the same as in example 1.
And (3) testing the battery: the maximum specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 223mAh/g, the zinc ion battery circulates 85 circles under the current density of 125mA/g, and the capacity retention rate is 70%.
Comparative example 3
The anode material is replaced by Bi 0.2 Mn 0.8 O 2 The subsequent process of making the battery pole piece and assembling the battery is the same as example 1.
And (3) testing the battery: the maximum specific capacity of the zinc ion battery under the current density of 50mA/g at the temperature of 25 ℃ is 223mAh/g, the zinc ion battery is circulated for 85 circles under the current density of 125mA/g, and the capacity retention rate is 70%.
In the description of the specification, reference to the description of "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like means 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. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, 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. The neutral or weakly acidic system water system zinc ion battery positive electrode material is characterized by comprising Bi x Mn y-x O z And manganese-containing compound, bi x Mn y-x O z Is distributed on the surface of the manganese-containing compound, wherein, 0<y/z≤1，0<x≤y。
2. The positive electrode material as claimed in claim 1, wherein the manganese-containing compound comprises MnO 2 、MnO，Mn 2 O 3 And Mn 3 O 4 At least one of (a).
3. The positive electrode material according to claim 1, wherein a molar ratio of the Bi element to the Mn element in the positive electrode material is between 0 and 1, excluding an endpoint of 0.
4. A method for producing the positive electrode material according to any one of claims 1 to 3, comprising:
(1) Mixing a manganese-containing material, a bismuth-containing compound and water with stirring, and then drying to obtain a precursor;
(2) And sintering the precursor to obtain the cathode material.
5. The method according to claim 4, wherein in the step (1), the stirring time is 1min to 100h.
6. The method of claim 4, wherein in step (1), the molar ratio of the element Bi in the bismuth-containing compound to the element Mn in the manganese-containing material is between 0 and 1, excluding the endpoint 0.
7. The method of claim 4, wherein the manganese-containing material comprises MnO 2 、MnO，Mn 2 O 3 And Mn 3 O 4 At least one of;
optionally, the bismuth-containing compound comprises Bi 2 O 3 、Bi(NO 3 ) 3 Bismuth subnitrate, bi 2 (SO 4 ) 3 、BiCl 3 、Bi(CH 3 COO) 3 Bismuth subcarbonate and Bi 2 (C 2 O 4 ) 3 At least one of (a).
8. The method according to claim 4, wherein in the step (2), the sintering temperature is 50-900 ℃ and the sintering time is 1 min-30 h.
9. A positive electrode sheet, characterized by comprising the positive electrode material according to any one of claims 1 to 3 or the positive electrode material produced by the method according to any one of claims 4 to 8.
10. A neutral or weakly acidic system aqueous zinc ion battery, characterized by comprising the positive electrode sheet according to claim 9.
CN202110745904.7A 2021-07-01 2021-07-01 Neutral or weakly acidic system water system zinc ion battery positive electrode material and preparation method and application thereof Pending CN115566150A (en)

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JPS6079679A (en) * 1983-09-29 1985-05-07 フオ−ド　モ−タ−　カンパニ− Rechargeable manganese dioxide/zinc battery
CN102013526B (en) * 2009-09-08 2012-08-29 清华大学深圳研究生院 Rechargeable zinc ion battery
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