CN110867579A - Water-based zinc ion battery and preparation method and application thereof - Google Patents

Water-based zinc ion battery and preparation method and application thereof Download PDF

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CN110867579A
CN110867579A CN201911146515.1A CN201911146515A CN110867579A CN 110867579 A CN110867579 A CN 110867579A CN 201911146515 A CN201911146515 A CN 201911146515A CN 110867579 A CN110867579 A CN 110867579A
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water
zinc
positive electrode
mixed solution
battery
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CN110867579B (en
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侯之国
董梦飞
宋忠诚
张雪倩
熊亚丽
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Jiangsu University of Technology
Jiangsu Institute of Technology
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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
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M10/38—Construction or manufacture
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a water system zinc ion battery and a preparation method and application thereof. According to the invention, the carbon material and the birnessite are compounded in situ, so that the prepared battery can inhibit the dissolution of Mn as a positive electrode material, and the urea modified electrolyte can inhibit the generation of dead zinc and zinc dendrites, thereby prolonging the cycle life of the battery; the nylon net or the positive current collector of the nylon net can reduce the cost and improve the energy density of the battery, and the conductive adhesive bonding busbar can prolong the service life of the battery. The method is suitable for pilot scale production; the battery can be used as a power battery of the electric bicycle.

Description

Water-based zinc ion battery and preparation method and application thereof
Technical Field
The invention relates to the technical field of batteries, in particular to a water-based zinc ion battery and a preparation method and application thereof.
Background
Due to the demand for energy storage batteries for electric bicycles, different energy storage batteries are being investigated as power batteries for electric bicycles. The water system zinc ion battery is a candidate with application prospect in the field due to the factors of abundant raw material sources, environmental friendliness, high energy density, low price and the like.
The anode material of the traditional zinc ion battery generally adopts MnO2The negative electrode material adopts a metal zinc sheet, and the battery is a primary battery which can not be charged when being used up, so that the battery can not be used as a power battery of the electric bicycle.
Jun Liu (Nature Energy,2016,1(5):16039.) et al reported α -MnO2Can reversibly de-intercalate zinc ions in zinc sulfate weakly acidic electrolyte, can provide 300mAh/g capacity when matched with a zinc powder negative electrode into a full cell, and is used for 5000 cycle life α -MnO2Has excellent cycle stability and is a very excellent choice for the positive electrode material of the zinc ion battery. However, Mn is dissolved seriously in the charging and discharging processes of the materials, so that the cycle life of the battery is shortened, and the self-discharge is high. In addition, a large amount of dead zinc is formed in the zinc powder cathode in the circulating process, the service life of the battery is seriously shortened, and even zinc dendrite is generated to cause short circuit failure of the battery.
Wang et al (electrochemical Acta,2018,272:154-160.) report that birnessite as the positive electrode material of zinc ion batteries has a large interlayer distance, and zinc ions can be rapidly deintercalated, showing excellent cycle performance and rate capability. However, the problems of Mn dissolution of electrode materials, zinc dendrite generation of zinc cathodes and the like still exist in the battery cycling process.
Disclosure of Invention
In order to solve the technical problems that Mn is dissolved in an electrode material and zinc dendrites are generated on a zinc cathode, the water system zinc ion battery and the preparation method and application thereof are provided. The water system zinc ion battery provided by the invention is a birnessite/carbon-metal zinc powder system zinc ion battery, a carbon composite birnessite anode material is synthesized by adopting a coprecipitation reaction, a slurry drawing method is adopted to prepare an anode pole piece and a cathode pole piece, a battery cell is further prepared by a winding method, an electrode pole piece and a busbar are bonded by a conductive adhesive bonding method, and a zinc ion-urea-water mixed solution is taken as an electrolyte, so that the whole battery is assembled.
In order to achieve the purpose, the invention is realized by the following technical scheme:
an aqueous zinc ion battery includes a positive electrode, a negative electrode, an electrolyte, and a separator provided between the positive electrode and the negative electrode;
the electrolyte comprises an electrolyte, a positive electrode and a negative electrode, wherein the positive electrode is made of birnessite/carbon composite material, the negative electrode is made of metal zinc powder, the electrolyte comprises solute and solvent, the solvent is water, and the solute is water-soluble zinc salt and urea; the mass ratio of the positive electrode active material to the negative electrode active material is (1-10): 1.
Further, the carbon material in the birnessite/carbon composite material as the active substance of the positive electrode is one or more of graphene, carbon nano tubes, graphite and acetylene black, and the carbon material accounts for 1-20 wt% of the composite material;
the preparation method of the birnessite/carbon composite material comprises the following steps: dissolving manganese salt and a carbon material in partial water and carrying out ultrasonic treatment to obtain a mixed solution A; dissolving an alkali source and an oxidant in part of water to obtain a mixed solution B; and dropwise adding the mixed solution B into the mixed solution A under the stirring condition, aging for 12-24 h, repeatedly washing with water and ethanol after suction filtration, and drying at 50 ℃ for 12-24 h to obtain the birnessite/carbon composite material. The aging can increase the crystallinity of the product and increase the cycle life of the battery; in the drying process, the temperature cannot exceed 50 ℃, otherwise, the product loses crystal water, and the specific capacity of the battery is reduced.
Furthermore, the power of the ultrasonic treatment is 100W, and the treatment time is 30 min; the stirring speed is 2000 rpm; the speed of dropwise adding the mixed solution B into the mixed solution A is 1 mL/min;
the manganese salt is one of manganese sulfate, manganese nitrate and manganese acetate; the alkali source is sodium hydroxide or ammonia water; the oxidant is 30 wt% of hydrogen peroxide; the molar ratio of the manganese salt, the alkali source and the oxidant is (0.1-1): 1-10, preferably (0.1-0.5): 0.1-0.6): 1-5; the molar concentration of the manganese salt in the mixed solution A is 0.1-2 mol/L, the molar concentration of the alkali source in the mixed solution B is 0.1-2 mol/L, and the molar concentration of the oxidant in the mixed solution B is 1-6 mol/L.
Further, the positive electrode comprises a positive electrode current collector and a positive electrode film attached to the positive electrode current collector, the positive electrode current collector is a nylon net or a nylon net, and the positive electrode film comprises birnessite/carbon composite material, conductive carbon powder and a binder according to the mass ratio of (75-95) to (1-25) to (1-15), preferably (85-95) to (4-15) to (2-7), and further preferably (90-95) to (4-5) to (2-5); the negative electrode comprises a negative electrode current collector and a negative electrode film attached to the negative electrode current collector, the negative electrode current collector is a punched stainless steel band, and the negative electrode film comprises metallic zinc powder, conductive carbon powder and a binder which are prepared according to the mass ratio of (75-95): (1-25): 1-15), preferably the mass ratio of (85-95): 4-15): 2-7, and further preferably the mass ratio of (90-95): 4-5): 2-5.
Furthermore, the conductive carbon powder is one or more of acetylene black, carbon nano tubes, graphite and active carbon; the binder is prepared from sodium carboxymethylcellulose and styrene butadiene rubber emulsion according to the mass ratio of (1-5) to 1.
Further, the water-soluble zinc salt in the electrolyte is zinc sulfate; the molar ratio of the water-soluble zinc salt to the water to the urea is (0.1-2) to (1-20) to (1-8), and preferably (1-2) to (10-20) to (2-6).
The invention also provides a preparation method of the water-based zinc ion battery, which comprises the following steps:
(1) preparing a positive pole piece: uniformly mixing the birnessite/carbon composite material as the positive active material with conductive carbon powder and a binder, uniformly coating the mixture on a positive current collector by adopting a slurry drawing method, and drying to obtain a positive electrode film attached to the positive current collector, wherein the positive electrode film is used as a positive electrode piece; the positive current collector is a nylon net or a nylon net;
(2) preparing a negative pole piece: uniformly mixing a negative active material metal zinc powder, conductive carbon powder and a binder, uniformly coating the mixture on a negative current collector by adopting a slurry drawing method, and drying to obtain a negative electrode film attached to the negative current collector, wherein the negative electrode film is used as a negative electrode plate; the negative current collector is a punched stainless steel band;
(3) preparing an electric core: rolling the positive pole piece in the step (1) and the negative pole piece in the step (2) into a cylindrical battery cell through a winding process; bonding circular busbars at two ends of a cylindrical battery cell by conductive adhesives, forming a positive busbar and a negative busbar at two ends of the cylindrical battery cell, coating conductive adhesives on the surfaces of the positive busbar and the negative busbar close to the battery cell respectively, and then pressing the conductive adhesives on two ends of the battery cell to bond the positive busbar and the negative busbar with the battery cell;
(4) assembling the battery: and (3) placing the battery cell bonded with the busbar in the step (3) in a stainless steel cylinder, welding a negative busbar with a stainless steel shell, rolling a groove, adding zinc sulfate-urea-water mixed electrolyte, connecting a positive busbar with a sealing cover by using a stainless steel sheet, and sealing the sealing cover to obtain the water-based zinc ion battery.
Further, the preparation method of the birnessite/carbon composite material as the positive electrode active substance in the step (1) comprises the following steps: dissolving manganese salt and a carbon material in partial water and carrying out ultrasonic treatment to obtain a mixed solution A; dissolving an alkali source and an oxidant in part of water to obtain a mixed solution B; dropwise adding the mixed solution B into the mixed solution A under the stirring condition, aging for 12-24 h, repeatedly washing with water and ethanol after suction filtration, and drying at 50 ℃ for 12-24 h to obtain a positive active substance birnessite/carbon composite material;
the power of ultrasonic treatment is 100W, and the treatment time is 30 min; the stirring speed is 2000 rpm; the speed of dropwise adding the mixed solution B into the mixed solution A is 1 mL/min; the manganese salt is one of manganese sulfate, manganese nitrate and manganese acetate; the alkali source is sodium hydroxide or ammonia water; the oxidant is hydrogen peroxide with the concentration of 30 wt%; the molar ratio of the manganese salt, the alkali source and the oxidant is (0.1-1): 1-10, preferably (0.1-0.5): 0.1-0.6): 1-5, the molar concentration of the manganese salt in the mixed solution A is 0.1-2 mol/L, the molar concentration of the alkali source in the mixed solution B is 0.1-2 mol/L, and the molar concentration of the oxidant in the mixed solution B is 1-6 mol/L;
the carbon material is one or a combination of more of graphene, carbon nano tubes, graphite, acetylene black and the like, and accounts for 1-20 wt% of the composite material.
Further, the mass ratio of the birnessite/carbon composite material, the conductive carbon powder and the binder in the positive electrode film in the step (1) is (75-95): 1-25): 1-15, preferably (85-95): 4-15): 2-7, and more preferably (90-95): 4-5): 2-5; in the step (2), the mass ratio of the metallic zinc powder, the conductive carbon powder and the binder in the negative electrode film is (75-95): 1-25): 1-15), preferably (85-95): 4-15): 2-7, and more preferably (90-95): 4-5): 2-5;
the conductive carbon powder is one or more of acetylene black, carbon nano tubes, graphite and active carbon; the binder is prepared from sodium carboxymethylcellulose and styrene butadiene rubber emulsion according to the mass ratio of (1-5) to 1.
Further, the length of the positive pole piece or the negative pole piece is 0.1 m-2 m, the width is 0.01 m-0.2 m, and the preferred length is 0.8 m-1.8 m, and the preferred width is 0.05 m-0.15 m; in the step (3), the conductive adhesive is one or more of conductive silver paste, conductive electro-ink adhesive, conductive copper adhesive and the like.
The invention finally provides an application of the water-based zinc ion battery in a power battery of an electric bicycle.
Experiments prove that the carbon material and the birnessite are compounded, and the high conductivity of the carbon material can greatly improve the conductivity of the cathode material, so that the rate capability of the battery can be improved; in addition, the high specific surface area of the carbon material can greatly adsorb Mn ions and prevent the manganese ions from being dissolved in electrolyte, so that the cycle life of the battery is prolonged, and therefore, the carbon material and the birnessite are compounded by a coprecipitation method, so that the rate performance and the cycle life of the water-based zinc ion battery can be prolonged;
the nylon net or the nylon net is adopted to replace the traditional stainless steel or foamed nickel anode current collector, the production cost of the battery can be greatly reduced, and the weight of the battery is greatly reduced and the energy density of the battery is greatly improved because the density of the nylon net or the nylon net is far lower than that of metal;
the winding process is adopted to manufacture the battery, so that the problem of volume effect of the water system zinc ion battery in the charging and discharging process can be greatly relieved, and the service life of the battery can be further prolonged;
the mode of bonding the pole piece and the bus bar by the conductive adhesive can solve the problem of corrosion of a welding part caused by traditional resistance welding or laser welding, and the service life of the battery is greatly prolonged;
the urea is added into the electrolyte, so that on one hand, the generation of dead zinc such as zinc hydroxide or zinc oxide on the surface of the negative electrode can be reduced by the coordination of the urea and zinc ions, and the cycle life and the coulombic efficiency of the battery are improved; on the other hand, the coordination of the urea and the zinc ions is beneficial to more uniformly reducing the zinc ions into metal zinc, thereby preventing the generation of zinc dendrite and preventing the short circuit of the battery.
The beneficial technical effects are as follows:
(1) the carbon composite birnessite is used as a positive electrode material, zinc powder is used as a negative electrode material, zinc sulfate is dissolved in water and urea to form a mixed solution which is used as an electrolyte to assemble the full cell, the cycle life of the cell is long, Mn dissolution can be greatly inhibited, zinc dendrite is basically not formed at the zinc negative electrode, the cycle life of a model cell can reach more than 1000 times, the cost is lower than 0.3 yuan/watt hour, the energy density reaches 60-100 watt hour/kg, the rate capability reaches 5C, and the full cell is very suitable for a power cell of an electric bicycle;
the carbon material and the birnessite are compounded, so that the conductivity of the positive electrode material can be improved, and the dissolution of manganese ions can be inhibited, so that the cycle life of the battery is prolonged.
(2) The urea is added into the electrolyte, ① urea molecules and zinc ions in the electrolyte form a complex, the probability of reaction between water molecules and metal zinc is reduced in the charging and discharging process, so that the generation of zinc hydroxide and zinc oxide is reduced, the generation of dead zinc is inhibited, ② metal zinc dendrite is mainly caused by uneven reduction of the zinc ions on the surface of a negative electrode, the urea molecules and the zinc ions in the electrolyte form a complex, on one hand, the generation of the dead zinc is reduced, the surface of the electrode has no passivation point, the zinc ions can be uniformly reduced on the surface of the whole electrode, on the other hand, the complex formed by the urea and the zinc ions can more uniformly and slowly generate metal zinc reducing substances in the charging process, and the generation of the zinc dendrite is greatly inhibited in two aspects.
(3) The current collector of the positive electrode of the traditional water-based battery adopts expensive materials such as nickel foam, 304 stainless steel or graphite paper, so that the manufacturing cost of the water-based battery is high, and the industrialization progress of the water-based battery is seriously hindered. In addition, the traditional positive electrode current collector foamed nickel or 304 stainless steel current collector and battery tab connection mode is welding, and the welding part is easy to corrode, so that the battery capacity is attenuated, and even the battery capacity is failed. The positive current collector adopts the nylon or the nylon net as the positive current collector, and the cost of the nylon net or the nylon net is far lower than that of the foamed nickel and 304 stainless steel, so that the cost of the battery can be further reduced; in addition, the connection mode of the positive pole piece and the pole lug is bonded by adopting a corrosion-resistant high-conductivity conductive adhesive, so that the corrosion problem of the joint of the pole lug and the pole piece can be prevented, and the service life of the battery is further prolonged.
Drawings
Fig. 1 is an X-ray diffraction pattern of birnessite/carbon composite produced in example 1.
Fig. 2 is a scanning electron microscope image of the birnessite/carbon composite material prepared in example 1.
Fig. 3 is a raman spectrum of the birnessite/carbon composite material prepared in example 1.
FIG. 4 is a schematic diagram of the positive electrode plate and the negative electrode plate obtained in step (1) of example 4.
Fig. 5 is a diagram of a cylindrical cell obtained by the winding method in step (3) of example 4.
Fig. 6 is a diagram showing the positive electrode bus bar and the negative electrode bus bar and their bonded positive electrode tab and negative electrode tab in step (3) of example 4.
Fig. 7 is a diagram of a battery in which a cell is assembled into a stainless steel cylindrical case and a positive insulating gasket is attached in step (4) of example 4.
Fig. 8 is a diagram of a battery after a negative electrode bus bar and a battery case are welded and rolled in step (4) of example 4.
Fig. 9 is a view showing the positive electrode bus bar and the upper battery cover in step (4) of example 4 after they are connected.
FIG. 10 is a diagram of a final product of the aqueous zinc-ion battery obtained by injecting the electrolyte in example 4.
Fig. 11 is a charge/discharge plateau curve of the aqueous zinc ion full cell obtained in example 4 at 0.1C.
Fig. 12 is a performance graph of the aqueous zinc ion all-cell prepared in example 4 at different charge and discharge rates.
Fig. 13 is a graph showing the long cycle life at 1C rate of the aqueous zinc ion full cell prepared in example 4.
Fig. 14 is a graph of cycle life at 1C rate and a graph of rate performance for the cell made in comparative example 1.
Fig. 15 is a graph of the cycle life at 1C rate for the cell made in comparative example 2.
Fig. 16 is a graph of discharge capacity and cycle life at 0.1C rate for the cell made in comparative example 3.
Detailed Description
The invention is further described below with reference to the figures and specific examples, without limiting the scope of the invention.
Example 1
Preparing a birnessite/carbon composite material serving as a positive electrode active substance:
2.265g of anhydrous manganese sulfate is dissolved in 50 ml of water, 200 mg of carbon nano tube is added, and ultrasonic dispersion is carried out for 30 minutes under the power of 100W, so as to obtain mixed liquor A; 2.16 g of sodium hydroxide is dissolved in 90 ml of water, and 10 ml of hydrogen peroxide (30 wt%) is added to obtain a mixed solution B; and (2) dissolving the B into the A at a stirring speed of 2000rpm, dropwise adding the B into the A at a speed of 1mL/min, aging for 24h, performing suction filtration, sequentially washing water, ethanol, water and ethanol, performing suction filtration for half an hour, transferring to a 50 ℃ oven, and drying for 24h to obtain the birnessite/carbon composite material, wherein the carbon nano tubes account for 10 wt% of the birnessite/carbon composite material.
X-ray powder diffractometer was used to perform X-ray diffraction analysis on the birnessite/carbon composite material of this example, and the spectrogram is shown in fig. 1, and as can be seen from fig. 1, there are clearly visible diffraction peaks in the spectrogram, and all diffraction peaks can be indicated by (JCPDS 23-1046) birnessite in a layered form.
The microscopic morphology of the birnessite/carbon composite material of the present example was observed by using a scanning electron microscope, and an SEM image is shown in fig. 2, and it can be seen from fig. 2 that the birnessite prepared in the present example is lamellar, and the carbon nanotubes are coated therein.
The birnessite/carbon composite material of the embodiment was subjected to raman spectroscopy, and the spectrum is shown in fig. 3, and it can be seen from fig. 3 that the D peak and the G peak are both raman characteristic peaks of the C atom crystal, and are respectively 1300cm in size-1And 1580cm-1Nearby; the D peak represents a defect of the C atom lattice, and the G peak represents a C atom sp2And (3) carrying out hybrid in-plane stretching vibration, wherein Raman spectrum shows that the carbon material exists in the composite material.
Example 2
Preparing a birnessite/carbon composite material serving as a positive electrode active substance:
dissolving 12.55g of manganese nitrate tetrahydrate in 50 ml of water, adding 100 mg of graphene, and performing ultrasonic dispersion for 30 minutes at the power of 100W to obtain a mixed solution A; dissolving 3.85mL of ammonia water in 90 mL of water, and adding 15.3 mL of hydrogen peroxide (30 wt%) to obtain a mixed solution B; dropwise adding the mixed solution B into the mixed solution A at a speed of 1mL/min under stirring at 2000rpm, aging for 20h, performing suction filtration, sequentially washing water, ethanol, water and ethanol, performing suction filtration for half an hour, transferring to a 50 ℃ oven, and drying for 20h to obtain the birnessite/carbon composite material, wherein the graphene accounts for 1 wt% of the birnessite/carbon composite material.
Example 3
Preparing a birnessite/carbon composite material serving as a positive electrode active substance:
6.1273g of manganese acetate is dissolved in 50 ml of water, 1 g of graphite is added, and ultrasonic dispersion is carried out for 30 minutes under the power of 100W, so as to obtain a mixed solution A; dissolving 2.80 g of sodium hydroxide in 90 ml of water, and adding 12.3 ml of hydrogen peroxide (30 wt%) to obtain a mixed solution B; and (2) dissolving the B into the A under stirring at 2000rpm, dropwise adding the B into the A at a speed of 1mL/min, aging for 16h, performing suction filtration, sequentially washing water, ethanol, water and ethanol, performing suction filtration for half an hour, transferring to a 50 ℃ oven, and drying for 18h to obtain the birnessite/carbon composite material, wherein the graphite accounts for 20 wt% of the birnessite/carbon composite material.
Example 4
The preparation method of the water system zinc ion battery comprises the following steps:
(1) preparing a positive pole piece: dispersing the birnessite/carbon composite material prepared in the example 1 of the positive active substance in water (the mass fraction of water is 10-30%) in a mass ratio of 92:3:2:0.5:2.5, stirring for 5 hours to form uniform slurry, pulling the slurry on a slurry pulling device by using a 80-mesh 20-centimeter wide positive current collector-nylon net or nylon net as a load, drying at 60 ℃ to prepare a positive electrode film, drying, and rolling on a roller press, wherein the compaction density reaches 2.9 g/cubic centimeter, the load is 1000 g/square meter, and the positive electrode sheet is obtained by slitting on a slitting machine, wherein each width is 8 centimeters and each length is 1.5 meters;
(2) preparing a negative pole piece: dispersing a negative active material metal zinc powder, a carbon nano tube, acetylene black, sodium carboxymethylcellulose and styrene butadiene rubber emulsion (50 wt%) in water according to a mass ratio of 92:3:2:0.5:2.5 (the mass fraction of the water is 10-30%), stirring for 5 hours to form uniform slurry, carrying out slurry drawing on a slurry drawing device by using a punched steel belt with the width of 8 centimeters as a negative current collector, drying at 60 ℃ to prepare a negative electrode film, carrying out rolling on a roller press after drying, wherein the compaction density reaches 4.9 grams/cubic centimeter, the loading capacity is 250 grams/square meter, slitting on a slitting machine, and each width is 8 centimeters and the length is 1.65 meters to obtain a negative electrode piece;
the mass ratio of the positive electrode active material to the negative electrode active material was about 3.64: 1;
the physical diagrams of the positive pole piece and the negative pole piece are shown in FIG. 4;
(3) preparing an electric core: winding the positive pole piece and the negative pole piece on a winding machine by adopting a winding method, wherein the diaphragm is made of non-woven fabric or polypropylene, the diaphragm is positioned between the positive pole piece and the negative pole piece, the winding process is in an interlaced mode, the diameter of a winding core is 0.5 cm, the first circle of the winding core is the negative pole piece, then the positive pole piece is wound, the outermost layer of the winding layer is the negative pole, a base band of the positive pole piece extends 1 mm from the diaphragm to serve as a positive pole lug, a base band of the negative pole piece extends 1 mm from the diaphragm to serve as a negative pole lug, and the prepared battery cell is cylindrical and; a physical diagram of the cylindrical cell is shown in fig. 5;
bonding the two ends of the cylindrical battery cell with the circular busbars by adopting conductive silver adhesive, and forming a positive busbar and a negative busbar at the two ends of the cylindrical battery cell;
uniformly coating conductive copper adhesive with the thickness of 1 mm on one surface of the negative busbar close to the battery cell, and then tightly pressing the conductive copper adhesive on a negative electrode tab of the battery cell; uniformly coating 1 mm-thick conductive ink adhesive on one surface of the positive busbar close to the battery cell, then tightly pressing the positive busbar on a positive lug of the battery cell, tightly pressing and solidifying the positive busbar and the negative busbar for 1 night, and tightly bonding the positive busbar and the negative busbar with the positive lug and the negative lug of the battery cell; the battery core object bonded with the busbar is shown in fig. 6;
(4) assembling the battery: placing the battery core bonded with the bus bar in the step (3) into a stainless steel cylinder with the cathode facing downwards, and sleeving a round insulating gasket on the upper part of the anode bus bar to prevent the anode bus bar from contacting with a battery shell to cause short circuit of the battery, as shown in fig. 7;
welding a negative bus bar and a stainless steel shell together in a resistance welding mode, specifically, welding a long copper nail with the diameter of 3 mm by penetrating into the bottom of a battery, and then grooving on a grooving machine, wherein the distance between a grooving opening and the upper edge of the battery shell is 8 mm, and the depth of the grooving is 3 mm, as shown in fig. 8;
connecting the positive electrode bus bar and the upper cover of the battery together by laser welding through a 304 stainless steel conductive strip, as shown in fig. 9;
then vacuumizing the water-based zinc ion battery, injecting 20 ml of electrolyte (the molar ratio of zinc sulfate to water to urea is 1:14:4), soaking the electrolyte overnight in vacuum, and sealing the water-based zinc ion battery on a sealing machine to obtain the assembled complete water-based zinc ion battery, wherein the material object diagram is shown in fig. 10.
The aqueous zinc ion battery prepared in this example was subjected to a charge/discharge test at a rate of 0.1C (1000 milliamp current density) between 1 volt and 1.8 volts, and was subjected to a charge/discharge test at a rate of 0.1C, 0.5C, 1C, 5C (1C ═ 1 amp) between 1 volt and 1.8 volts, respectively; the battery cycle life was tested at 1C rate.
Fig. 11 is a charge/discharge plateau curve of the aqueous zinc ion battery of this example at 0.1C, where the battery capacity reaches 10 ampere-hour, the voltage plateau reaches 1.3V, and the battery energy density reaches 60 watt-hours/kg.
Fig. 12 shows the charge/discharge capacity of the aqueous zinc ion battery of this example at different rates, and the battery capacity reached 5 ampere-hours at a high rate of 5C.
Fig. 13 shows the cycle life of the aqueous zinc-ion battery of this example at 1C rate, and the capacity retention of the aqueous zinc-ion battery of this example after 1000 cycles was as high as 90%.
Comparative example 1:
the positive electrode active material of this comparative example is different from example 1 in that no carbon material is added, and the specific preparation method is as follows:
the method for synthesizing the birnessite in the embodiment 1 is changed into the following steps: 2.265g of anhydrous manganese sulfate is dissolved in 50 ml of water to obtain a solution A; 2.16 g of sodium hydroxide is dissolved in 90 ml of water, and 10 ml of hydrogen peroxide (30 wt%) is added to obtain a mixed solution B; dropwise adding the mixed solution B into the solution A while stirring, aging for 24h, performing suction filtration, sequentially washing water, ethanol, water and ethanol, performing suction filtration for half an hour, transferring to a 50-degree oven, and drying for 24h to obtain the birnessite.
The aqueous zinc-ion battery of this comparative example was prepared in the same manner as in example 4, except that the positive electrode active material was birnessite of this comparative example.
The aqueous zinc-ion battery prepared in this comparative example was subjected to a cycle life test at a 1C rate of 1 v to 1.8 v, and a charge-discharge test at a 0.1C, 0.5C, 1C, 5C (1C ═ 1 ampere) rate of 1 v to 1.8 v, respectively.
Fig. 14 shows the cycle life of the battery of comparative example 1 at 1C, the capacity of the battery decayed by 75% after 100 charges and discharges, and the capacity of the battery reached only 1 ampere-hour at 5C rate.
This comparative example demonstrates that the compounding of the carbon material of example 1 of the present invention can improve the conductivity of the positive electrode material and suppress the dissolution of Mn ions in the electrolyte, and can not only improve the rate performance of an aqueous zinc ion battery but also increase the cycle life of the battery.
Comparative example 2:
the aqueous zinc ion battery of this comparative example was prepared in the same manner as in example 4, except that the electrolyte in this comparative example was a 1mol/l aqueous solution of zinc sulfate, and no urea was added.
The water system zinc ion battery prepared by the comparative example is subjected to cycle life test at 1C multiplying power between 1 volt and 1.8 volts.
FIG. 15 shows the cycle life of the comparative example cell at 1C, with capacity fading to half of the initial capacity after 5 partial cell charges and discharges; in addition, a part of the batteries are charged and discharged for about 5 times, and then short circuit occurs.
The comparative example shows that the urea is added into the electrolyte, so that the generation of dead zinc such as zinc hydroxide or zinc oxide on the surface of the negative electrode can be reduced by the coordination of the urea and zinc ions, and the cycle life and the coulombic efficiency of the battery are improved; on the other hand, the coordination of the urea and the zinc ions is beneficial to more uniformly reducing the zinc ions into metal zinc, thereby preventing the generation of zinc dendrite and preventing the short circuit of the battery.
Comparative example 3:
the aqueous zinc-ion battery of this comparative example was prepared in the same manner as in example 4, except that the positive electrode current collector in step (1) was replaced with a 20 μm thick 304 stainless steel strip. And (4) welding the positive electrode tab and the positive bus bar by resistance welding, and welding the negative electrode tab and the negative bus bar by resistance welding.
The aqueous zinc ion battery prepared by the comparative example is subjected to battery discharge capacity and cycle life tests at 0.1C rate between 1 volt and 1.8 volts.
Fig. 16 is a graph showing the capacity and cycle life of the battery of this comparative example at 0.1C rate, using 304 stainless steel bands as the positive electrode current collector, the capacity of the battery was only 8 ampere-hours, but the weight of the battery was 30% heavier than that obtained in example 4, resulting in a battery energy density of only 40 watt-hours/kg, which is much lower than that of the battery using a nylon mesh or a nylon mesh. In addition, the capacity of the battery is attenuated by 70% after 10 times of circulation, and the battery disassembly result shows that the welding part of the pole piece and the bus bar is seriously corroded.
Experimental results show that the carbon composite birnessite anode material is prepared by a coprecipitation method, metal zinc powder is used as a cathode material, and a zinc sulfate-water-urea mixed solution is used as an electrolyte to assemble the whole battery. The full battery has the advantages of high energy density (up to 60-100 watt-hour/kg), good cycle stability (the service life can reach 1000 times), excellent rate performance, low cost of the electrode material synthesis method, environmental friendliness, safe, nontoxic, stable, pollution-free and low-price electrolyte, simple and easy assembly method, environmental friendliness and no pollution, and provides possibility for the practical application of the water system zinc ion battery in the aspect of the power battery of the electric bicycle by assembling the battery through slurry drawing, winding and the busbar bonding method of the conductive adhesive.
Some embodiments of the invention synthesize the carbon composite birnessite by a coprecipitation method to be used as a positive electrode material, and a zinc sulfate aqueous urea solution is used as an electrolyte to assemble a full battery. The battery system can still stabilize the capacity at 9.5 ampere hours after being cycled for 1000 times at the rate of 1C, and shows excellent rate performance. Compared with zinc ion batteries reported in literatures, the zinc ion battery has the advantages of high cycling stability, simple synthesis and cheap and wide raw materials, and effectively solves the problems of high cost, short service life and low energy density of the water-based zinc ion battery as a power battery of an electric bicycle.
The invention provides a method for preparing a carbon composite birnessite anode material by coprecipitation, and application of a full battery system assembled by using the material prepared by the method as anode and cathode active substances of a battery in the aspect of an electric bicycle power battery. The preparation method is simple, the raw materials are low in price, the assembled battery system has relatively high energy density and excellent cycle performance, and the problems of short service life, high cost and low charging and discharging speed of the zinc ion battery as a power battery element in the aspect of electric bicycles can be effectively solved.
In some embodiments of the invention, compared with the existing solid phase reaction, hydrothermal synthesis and other technologies, the required reaction temperature is lower and the method is simple in the aspect of the synthesis method. In general, the raw materials used in the invention have low price, the preparation process is simple and environment-friendly, the large-scale production is facilitated, and the key problem of the macro-production of the carbon composite birnessite material is effectively solved.
The obtained material is used for assembling the full cell, the assembling process is simple, and the material is green and pollution-free; the assembled full battery has high energy density, excellent rate performance and good cycle stability, and provides possibility for the application of the zinc ion battery in power batteries.
The method has mild reaction conditions, is environment-friendly, is beneficial to pilot scale experiment, and has no substantial difficulty in scale-up production. When a full battery is assembled by using the two materials of the invention as the positive electrode active material and the negative electrode active material, higher energy density and excellent cycle stability are shown. Can be used as a power battery of the electric bicycle.
The above embodiments clearly and specifically describe the technical solutions of the present invention. It is to be understood that the described embodiments are merely a few, and not all, embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention.

Claims (10)

1. An aqueous zinc ion battery comprising a positive electrode, a negative electrode, an electrolyte, and a separator provided between the positive electrode and the negative electrode,
the electrolyte comprises an electrolyte, a positive electrode and a negative electrode, wherein the positive electrode is made of birnessite/carbon composite material, the negative electrode is made of metal zinc powder, the electrolyte comprises solute and solvent, the solvent is water, and the solute is water-soluble zinc salt and urea; the mass ratio of the positive electrode active material to the negative electrode active material is (1-10): 1.
2. The aqueous zinc-ion battery of claim 1, wherein the carbon material in the birnessite/carbon composite material as the active material of the positive electrode is one or more of graphene, carbon nanotubes, graphite and acetylene black, and the carbon material accounts for 1-20 wt% of the birnessite/carbon composite material;
the preparation method of the birnessite/carbon composite material comprises the following steps: dissolving manganese salt and a carbon material in partial water and carrying out ultrasonic treatment to obtain a mixed solution A; dissolving an alkali source and an oxidant in part of water to obtain a mixed solution B; and dropwise adding the mixed solution B into the mixed solution A under the stirring condition, aging for 12-24 h, repeatedly washing with water and ethanol after suction filtration, and drying at 50 ℃ for 12-24 h to obtain the birnessite/carbon composite material.
3. The aqueous zinc-ion battery according to claim 2, wherein the power of the ultrasonic treatment is 100W, and the treatment time is 30 min; the stirring speed is 2000 rpm; the speed of dropwise adding the mixed solution B into the mixed solution A is 1 mL/min;
the manganese salt is one of manganese sulfate, manganese nitrate and manganese acetate; the alkali source is sodium hydroxide or ammonia water; the oxidant is 30 wt% of hydrogen peroxide; the molar ratio of the manganese salt, the alkali source and the oxidant is (0.1-1): 1-10; the molar concentration of the manganese salt in the mixed solution A is 0.1-2 mol/L, the molar concentration of the alkali source in the mixed solution B is 0.1-2 mol/L, and the molar concentration of the oxidant in the mixed solution B is 1-6 mol/L.
4. The water-based zinc ion battery of claim 1, wherein the positive electrode comprises a positive electrode current collector and a positive electrode film attached to the positive electrode current collector, the positive electrode current collector is a nylon net or a nylon net, and the positive electrode film comprises birnessite/carbon composite material, conductive carbon powder and a binder in a mass ratio of (75-95) to (1-25) to (1-15);
the negative electrode comprises a negative current collector and a negative electrode film attached to the negative current collector, the negative current collector is a punched stainless steel band, and the negative electrode film comprises metal zinc powder, conductive carbon powder and a binder which are prepared according to a mass ratio of (75-95): (1-25): 1-15;
the conductive carbon powder is one or more of acetylene black, carbon nano tubes, graphite and active carbon;
the binder is prepared from sodium carboxymethylcellulose and styrene butadiene rubber emulsion according to the mass ratio of (1-5) to 1.
5. The aqueous zinc ion battery of claim 1, wherein the solute water-soluble zinc salt in the electrolyte is zinc sulfate, and the molar ratio of the water-soluble zinc salt, water and urea is (0.1-2): (1-20): (1-8).
6. A method for producing an aqueous zinc-ion battery according to any one of claims 1 to 5, characterized by comprising the steps of:
(1) preparing a positive pole piece: uniformly mixing the birnessite/carbon composite material as the positive active material with conductive carbon powder and a binder, uniformly coating the mixture on a positive current collector by adopting a slurry drawing method, and drying to obtain a positive electrode film attached to the positive current collector, wherein the positive electrode film is used as a positive electrode piece; the positive current collector is a nylon net or a nylon net;
(2) preparing a negative pole piece: uniformly mixing a negative active material metal zinc powder, conductive carbon powder and a binder, uniformly coating the mixture on a negative current collector by adopting a slurry drawing method, and drying to obtain a negative electrode film attached to the negative current collector, wherein the negative electrode film is used as a negative electrode plate; the negative current collector is a punched stainless steel band;
(3) preparing an electric core: rolling the positive pole piece in the step (1) and the negative pole piece in the step (2) into a cylindrical battery cell through a winding process; bonding circular busbars at two ends of a cylindrical battery cell by conductive adhesives, forming a positive busbar and a negative busbar at two ends of the cylindrical battery cell, coating conductive adhesives on the surfaces of the positive busbar and the negative busbar close to the battery cell respectively, and then pressing the conductive adhesives on two ends of the battery cell to bond the positive busbar and the negative busbar with the battery cell;
(4) assembling the battery: and (3) placing the battery cell bonded with the busbar in the step (3) in a stainless steel cylinder, welding a negative busbar with a stainless steel shell, rolling a groove, adding zinc sulfate-urea-water mixed electrolyte, connecting a positive busbar with a sealing cover by using a stainless steel sheet, and sealing the sealing cover to obtain the water-based zinc ion battery.
7. The method for preparing an aqueous zinc-ion battery according to claim 6, wherein the method for preparing the birnessite/carbon composite material as the positive electrode active material in the step (1) comprises: dissolving manganese salt and a carbon material in partial water and carrying out ultrasonic treatment to obtain a mixed solution A; dissolving an alkali source and an oxidant in part of water to obtain a mixed solution B; dropwise adding the mixed solution B into the mixed solution A under the stirring condition, aging for 12-24 h, repeatedly washing with water and ethanol after suction filtration, and drying at 50 ℃ for 12-24 h to obtain a positive active substance birnessite/carbon composite material;
the power of ultrasonic treatment is 100W, and the treatment time is 30 min; the stirring speed is 2000 rpm; the speed of dropwise adding the mixed solution B into the mixed solution A is 1 mL/min; the manganese salt is one of manganese sulfate, manganese nitrate and manganese acetate; the alkali source is sodium hydroxide or ammonia water; the oxidant is hydrogen peroxide with the concentration of 30 wt%; the molar ratio of the manganese salt to the alkali source to the oxidant is (0.1-1): 1-10, the molar concentration of the manganese salt in the mixed solution A is 0.1-2 mol/L, the molar concentration of the alkali source in the mixed solution B is 0.1-2 mol/L, and the molar concentration of the oxidant in the mixed solution B is 1-6 mol/L;
the carbon material is one or a combination of more of graphene, carbon nano tubes, graphite, acetylene black and the like, and accounts for 1-20 wt% of the composite material.
8. The method for preparing an aqueous zinc ion battery according to claim 6, wherein the mass ratio of the birnessite/carbon composite material, the conductive carbon powder and the binder in the positive electrode film in the step (1) is (75-95): 1-25): 1-15; in the step (2), the mass ratio of the metallic zinc powder, the conductive carbon powder and the binder in the negative electrode film is (75-95): (1-25): 1-15);
the conductive carbon powder is one or more of acetylene black, carbon nano tubes, graphite and active carbon;
the binder is prepared from sodium carboxymethylcellulose and styrene butadiene rubber emulsion according to the mass ratio of (1-5) to 1.
9. The method for preparing the aqueous zinc-ion battery according to claim 6, wherein the length of the positive electrode plate and the negative electrode plate is 0.1-2 m, and the width of the positive electrode plate and the negative electrode plate is 0.01-0.2 m; in the step (3), the conductive adhesive is one or more of conductive silver paste, conductive electro-ink adhesive, conductive copper adhesive and the like.
10. Use of the aqueous zinc-ion battery according to any one of claims 1 to 5 in a power battery for an electric bicycle.
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CN114357813A (en) * 2022-03-21 2022-04-15 中北大学南通智能光机电研究院 Simulation method for dendritic crystal growth condition of zinc ion battery
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CN112086694A (en) * 2020-09-18 2020-12-15 浙江浙能中科储能科技有限公司 Aqueous electrolyte for improving reversibility of neutral zinc-manganese battery and preparation method thereof
CN112599865B (en) * 2020-12-10 2022-04-26 浙江浙能中科储能科技有限公司 Neutral chargeable zinc ion battery based on large-area-capacity manganese-free positive electrode and preparation method thereof
CN112599865A (en) * 2020-12-10 2021-04-02 浙江浙能中科储能科技有限公司 Neutral chargeable zinc ion battery based on large-area-capacity manganese-free positive electrode and preparation method thereof
CN112803083A (en) * 2021-02-08 2021-05-14 江苏师范大学 Zinc ion battery containing zinc complex
CN113078372A (en) * 2021-04-09 2021-07-06 江苏大学 Zinc ion solid electrolyte, application thereof in quasi-solid zinc ion battery and preparation method thereof
CN114388901A (en) * 2021-12-06 2022-04-22 华中科技大学 Aqueous zinc ion battery electrolyte and battery
CN114357813A (en) * 2022-03-21 2022-04-15 中北大学南通智能光机电研究院 Simulation method for dendritic crystal growth condition of zinc ion battery
CN114744362A (en) * 2022-04-28 2022-07-12 江苏理工学院 Functional diaphragm for improving stability of metal zinc cathode and preparation method thereof
CN114744362B (en) * 2022-04-28 2023-09-22 江苏理工学院 Functional diaphragm for improving stability of metallic zinc negative electrode and preparation method thereof
CN115084636A (en) * 2022-08-03 2022-09-20 西安交通大学 Composite modified electrolyte for improving stability of water-based zinc ion battery and preparation method thereof
CN115084636B (en) * 2022-08-03 2023-08-18 西安交通大学 Composite modified electrolyte for improving stability of water-based zinc ion battery and preparation method thereof
CN116062795A (en) * 2023-03-09 2023-05-05 浙江师范大学 Preparation method, product and application of doped birnessite nanometer flower ball
CN116062795B (en) * 2023-03-09 2024-01-30 浙江师范大学 Preparation method, product and application of doped birnessite nanometer flower ball

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