CN106229498B - Cathode material suitable for water-based metal ion battery and preparation method thereof - Google Patents

Cathode material suitable for water-based metal ion battery and preparation method thereof Download PDF

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CN106229498B
CN106229498B CN201610632608.5A CN201610632608A CN106229498B CN 106229498 B CN106229498 B CN 106229498B CN 201610632608 A CN201610632608 A CN 201610632608A CN 106229498 B CN106229498 B CN 106229498B
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bismuth oxide
aqueous
ion battery
water
electrode
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CN106229498A (en
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刘金平
左文华
朱伟华
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Wuhan University of Technology WUT
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G29/00Compounds of bismuth
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/36Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38Construction or manufacture
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a negative electrode material suitable for a water-system metal ion battery and a preparation method thereof, wherein the negative electrode material contains bismuth oxide, and the negative electrode material is a nano bismuth oxide array film, namely, the nano bismuth oxide array film is formed by directionally growing bismuth oxide nano sheets on a metal substrate, wherein the bismuth oxide nano sheets are vertically, uniformly and densely distributed on the metal substrate in an array shape, or the bismuth oxide nano sheets are obtained by uniformly mixing bismuth oxide powder, a conductive additive and a binder and then preparing a film on the metal substrate. The cathode material for an aqueous metal ion battery provided by the invention is applicable to a wide range of aqueous battery systems, including aqueous lithium ion batteries, aqueous sodium ion batteries, aqueous potassium ion batteries, aqueous magnesium ion batteries, aqueous calcium ion batteries, aqueous strontium ion batteries, aqueous barium ion batteries, aqueous aluminum ion batteries, and the like. And the water-based metal ion battery based on the cathode material has large capacity, good charge-discharge platform and high electrochemical reversibility.

Description

Cathode material suitable for water-based metal ion battery and preparation method thereof
Technical Field
The invention belongs to the technical field of water-based battery materials, and particularly relates to a negative electrode material suitable for a water-based metal ion battery and a preparation method thereof.
Background
Organic electrolyte lithium ion batteries have been widely studied and used in recent years thanks to outstanding electrochemical properties. However, the organic electrolyte has great potential safety hazard, relatively high price, high packaging requirement, slow lithium ion migration rate, high environmental pollution and other inherent defects. To solve these problems of organic electrolytes, Moli Energy corporation of canada (patent No. W095/20470) proposed the concept of aqueous lithium ion batteries using aqueous solutions as electrolytes, with the greenest, environmentally friendly, safest, and sustainable water as the solvent. On the basis, the university of Compound Dan (patent publication No. CN 101154745A) provides a carbon-coated intercalation compound based on LiTi2(PO4)3The aqueous lithium ion secondary battery of the core-shell structure cathode material further improves the comprehensive performance of the aqueous lithium ion battery.
The prior art research on water-based metal ion batteries has generally been conducted around lithium ion batteries. However, on the one hand, the natural lithium storage capacity is limited, and with the rapid development of lithium-related industries, the exhaustion of lithium comes sooner or later; on the other hand, negative electrode materials having excellent electrochemical performance are very rare even in a relatively mature aqueous lithium ion battery due to a relatively narrow stable potential window of an aqueous solution, and although known NASICON-type lithium titanium phosphate and sodium titanium phosphate have a good charge-discharge plateau, a suitable lithium deintercalation potential, and a relatively long cycle life, their capacity is very limited (<150 mAh/g). Therefore, new water-based battery systems, such as non-lithium ion batteries (e.g., sodium ion batteries, magnesium ion batteries, aluminum ion batteries, etc.), which may replace lithium ion batteries in the future, are gradually showing important scientific research and industrial application values. On the other hand, the number of negative electrode materials currently used in the field of aqueous metal ion batteries is relatively small, and the conventional negative electrode materials are generally used only for specific aqueous metal ion batteries, and therefore, it is necessary to study a negative electrode material that can be widely used for a plurality of aqueous metal ion batteries.
Disclosure of Invention
The invention aims to solve the technical problem of providing a negative electrode material which has large capacity, long cycle life and good charge-discharge platform and is suitable for various water-system metal ion battery systems and a preparation method thereof aiming at the defects in the prior art.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
provided is a negative electrode material suitable for an aqueous metal ion battery, which contains bismuth oxide.
According to the scheme, the negative electrode material is a nano bismuth oxide array film, and is formed by directionally growing bismuth oxide nano-sheets on a metal substrate, wherein the bismuth oxide nano-sheets are vertically, uniformly and densely distributed on the metal substrate and are in an array shape.
Preferably, the metal substrate is a titanium sheet.
Preferably, the thickness of the bismuth oxide nano-sheet is 10-30 nm.
According to the scheme, the preparation method of the nano bismuth oxide array film comprises the following steps: and (3) placing the titanium sheet with clean surface into a bismuth-containing precursor solution prepared by using ethylene glycol and acetone as a mixed solvent, and carrying out hydrothermal reaction to obtain the cathode material suitable for the water-based metal ion battery.
Preferably, the concentration of bismuth nitrate pentahydrate in the bismuth-containing precursor solution is 0.03-0.04 g/mL.
According to the scheme, the negative electrode material is prepared by uniformly mixing bismuth oxide powder, a conductive additive and a binder and then preparing a film on a metal substrate.
According to the scheme, the preparation method of the cathode material comprises the following steps:
1) preparing bismuth oxide powder: preparing a bismuth-containing precursor solution by using ethylene glycol and acetone as a mixed solvent, and carrying out hydrothermal reaction and post-treatment on the bismuth-containing precursor solution to obtain bismuth oxide powder;
2) adding bismuth oxide powder, a conductive additive and a binder into a solvent, fully ball-milling to obtain slurry, uniformly coating the obtained slurry on a titanium sheet, drying, and then pressing by using a tablet press to obtain the cathode material suitable for the water-based metal ion battery.
Preferably, the volume ratio of the ethylene glycol to the acetone is 1: 1-2.
According to the scheme, the bismuth-containing precursor solution is obtained by dissolving bismuth nitrate pentahydrate in a mixed solvent; the hydrothermal reaction temperature is 120-180 ℃, and the reaction time is 3-8 h.
According to the scheme, the conductive additive is carbon black, graphene or carbon nano tubes, the binder is polyvinylidene fluoride or polytetrafluoroethylene, the mass ratio of bismuth oxide powder to the negative electrode material is 60-80%, the mass ratio of the conductive additive to the negative electrode material is 5-20%, and the mass ratio of the binder to the negative electrode material is 5-20%.
The invention also provides an aqueous metal ion battery, which comprises a positive electrode, a negative electrode and an electrolyte, wherein the negative electrode contains the negative electrode material.
According to the scheme, the water-based metal ion battery comprises one or more mixed water-based ion batteries of a water-based lithium ion battery, a water-based sodium ion battery, a water-based potassium ion battery, a water-based magnesium ion battery, a water-based calcium ion battery, a water-based strontium ion battery, a water-based barium ion battery and a water-based aluminum ion battery.
According to the scheme, the electrolyte is one or more of soluble sulfate, nitrate and chloride mixed aqueous solution.
Preferably, the electrolyte of the aqueous metal-ion battery is an aqueous solution of one or more of lithium sulfate, lithium chloride, lithium nitrate, sodium sulfate, sodium chloride, sodium nitrate, potassium sulfate, potassium chloride, potassium nitrate, magnesium chloride, magnesium nitrate, calcium chloride, calcium nitrate, strontium chloride, strontium nitrate, barium chloride, barium nitrate, and aluminum nitrate, and the aqueous solution has a pH of 2.0 to 8.0 and a cation concentration of 0.5 to 10 mol/L.
According to the scheme, the positive electrode is obtained by adding a conductive agent and a binder into a positive electrode material and then uniformly coating the conductive agent and the binder on a current collector.
The positive electrode material in the present invention is a material based on a redox reaction, and specifically may be a mixed oxide or a conductive polymer of one or more of Mn, Co, Ni, Fe and other oxides into which lithium, sodium, potassium, magnesium, calcium, strontium, barium and aluminum ions can be inserted, or a positive electrode material based on a redox reaction.
The current collectors of the positive and negative electrodes in the present invention may be carbon materials, metallic nickel, metallic titanium, stainless steel foil, etc., or porous mesh substrates.
The novel electrode material of the water-based rechargeable battery is a breakthrough in the field of water-based metal ion batteries, and is suitable for the preparation processes of various electrodes, such as film coating, slurry drawing, film pressing and the like.
The nano bismuth oxide array film or bismuth oxide powder electrode prepared by the invention is used for preparing the water system metal ion battery, and the energy density (78Wh kg) of the obtained water system metal ion battery system-1) Is higher than most of water-based metal ion batteries (less than or equal to 50Wh kg)-1) And the bismuth oxide water system metal ion battery has a good charging and discharging platform, so that the battery can have stable output voltage.
The invention has the beneficial effects that: the invention provides a novel cathode material of an aqueous metal ion battery, which is applicable to a wide aqueous battery system and comprises an aqueous lithium ion battery, an aqueous sodium ion battery, an aqueous potassium ion battery, an aqueous magnesium ion battery, an aqueous calcium ion battery, an aqueous strontium ion battery, an aqueous barium ion battery, an aqueous aluminum ion battery and the like. And the water-based metal ion battery based on the cathode material has large capacity, good charge-discharge platform and high electrochemical reversibility.
Drawings
FIG. 1 is an X-ray diffraction pattern of a nano-bismuth oxide array film prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope topography of the nano bismuth oxide array film prepared in example 1;
FIG. 3 is the constant current charge and discharge curve of the nano bismuth oxide array film prepared in example 1 in 18 solutions;
FIG. 4 is a graph showing the cycle and charge/discharge of the negative electrode material prepared from bismuth oxide powder in a sodium nitrate solution in example 2;
fig. 5 is a charge and discharge curve of the battery prepared in example 4;
fig. 6 is a discharge curve of the battery prepared in example 5 at different current densities.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention is further described in detail below with reference to the accompanying drawings, but the present invention is not limited to the following embodiments.
The reagents and materials in the following examples are commercially available unless otherwise specified.
Example 1
Preparing a negative electrode material suitable for an aqueous metal ion battery: stirring 0.6g of bismuth nitrate pentahydrate, 6mL of ethylene glycol and 12mL of acetone for 30 minutes to obtain a bismuth-containing precursor solution, putting a cleaned titanium sheet with the thickness of 50 microns into the bismuth-containing precursor solution, placing the titanium sheet into a 20mL polytetrafluoroethylene inner container, then putting the inner container into a hydrothermal reaction kettle, sealing, carrying out hydrothermal reaction for 5 hours at 160 ℃, then stopping heating and cooling to room temperature, washing the residual solution on the surface of a sample with ethanol and deionized water, and growing a layer of bismuth oxide film on the surface of a titanium sheet current collector, namely the cathode material suitable for the water-based metal ion battery. The X-ray diffraction spectrum of the bismuth oxide film is shown in figure 1, the scanning electron microscope image of the bismuth oxide film on the surface of the negative electrode material is shown in figure 2, the obtained negative electrode material is a nano bismuth oxide array film and is formed by directionally growing bismuth oxide nano-sheets on a titanium sheet, the thickness of the bismuth oxide nano-sheets is 10-12nm, and the bismuth oxide nano-sheets are vertically, uniformly and densely distributed on a metal substrate and are in an array shape.
The anode material prepared in this example was tested for its redox reversibility in different aqueous solutions:
1. the cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is 0.5mol/L lithium sulfate solution, and the pH value is 7.08. The bismuth oxide discharge capacity was 320mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 248mAh/g at a charge-discharge current density of 0.5A/g.
2. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is 0.5mol/L sodium sulfate solution, and the pH value is 7.16. The discharge capacity of bismuth oxide was 322mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 278mAh/g at a charge-discharge current density of 0.5A/g.
3. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is 0.5mol/L potassium sulfate solution, and the pH value is 6.90. The discharge capacity of bismuth oxide was 234mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 232mAh/g at a charge-discharge current density of 0.5A/g.
4. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is 1mol/L lithium chloride solution, and the pH value is 7.03. The discharge capacity of bismuth oxide was 183mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 234mAh/g at a charge-discharge current density of 0.5A/g.
5. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is 1mol/L sodium chloride solution, and the pH value is 7.06. The discharge capacity of bismuth oxide was 324mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 157mAh/g at a charge-discharge current density of 0.5A/g.
6. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is 1mol/L potassium chloride solution, and the pH value is 6.91. The discharge capacity of bismuth oxide was 342mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 248mAh/g at a charge-discharge current density of 0.5A/g.
7. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is 1mol/L lithium nitrate solution, and the pH value is 7.41. The discharge capacity of bismuth oxide was 214mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 278mAh/g at a charge-discharge current density of 0.5A/g.
8. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is 1mol/L sodium nitrate solution, and the pH value is 7.26. The discharge capacity of bismuth oxide was 235mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 255mAh/g at a charge-discharge current density of 0.5A/g.
9. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is 1mol/L potassium nitrate solution, and the pH value is 7.10. The discharge capacity of the bismuth oxide was 317mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 186mAh/g at a charge-discharge current density of 0.5A/g.
10. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is a 1mol/L magnesium chloride solution, and the pH value is 7.03. The discharge capacity of the bismuth oxide was 223mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 228mAh/g at a charge-discharge current density of 0.5A/g.
11. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is a 1mol/L magnesium nitrate solution, and the pH value is 6.62. The discharge capacity of bismuth oxide was 84mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 156mAh/g at a charge-discharge current density of 0.5A/g.
12. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is 1mol/L calcium chloride solution, and the pH value is 7.52. The discharge capacity of bismuth oxide was 321mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 356mAh/g at a charge-discharge current density of 0.5A/g.
13. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is 1mol/L calcium nitrate solution, and the pH value is 7.23. The discharge capacity of bismuth oxide was 188mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 187mAh/g at a charge-discharge current density of 0.5A/g.
14. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is 1mol/L strontium chloride solution, and the pH value is 7.00. The discharge capacity of bismuth oxide was 104mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 106mAh/g at a charge-discharge current density of 0.5A/g.
15. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is a 1mol/L strontium nitrate solution, and the pH value is 7.41. The discharge capacity of bismuth oxide was 177mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 164mAh/g at a charge-discharge current density of 0.5A/g.
16. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is 1mol/L barium chloride solution, and the pH value is 7.27. The discharge capacity of bismuth oxide was 331mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 165mAh/g at a charge-discharge current density of 0.5A/g.
17. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is a saturated barium nitrate solution, and the pH value is 7.46. The discharge capacity of bismuth oxide was 194mAh/g at a sweep rate of 1 mV/s. The discharge capacity of bismuth oxide was 258mAh/g at a charge-discharge current density of 0.5A/g.
18. The cathode material is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, the electrolyte is 1mol/L aluminum nitrate solution, and the pH value is 2.58. The discharge capacity of bismuth oxide was 171mAh/g at a charge-discharge current density of 0.5A/g.
The pH values of the above 18 solutions, the discharge capacities of the cyclic voltammetry test and the constant current charge and discharge test are shown in table 1, and the constant current charge and discharge curves of the various solutions are shown in fig. 3, which illustrates that the negative electrode material prepared in this example is suitable for an aqueous lithium ion battery, an aqueous sodium ion battery, an aqueous potassium ion battery, an aqueous magnesium ion battery, an aqueous calcium ion battery, an aqueous strontium ion battery, an aqueous barium ion battery and an aqueous aluminum ion battery, and has a high capacity and a good charge and discharge platform.
TABLE 1 pH of different solutions and Cyclic Voltammetry (CV) and constant current Charge and Discharge (CD) capacities of negative electrode materials in different electrolytes
Example 2
Preparing a negative electrode material suitable for an aqueous metal ion battery:
1) preparing bismuth oxide powder: stirring 0.6g of bismuth nitrate pentahydrate, 6mL of ethylene glycol and 12mL of acetone for 30 minutes, then placing the mixture into a 20mL polytetrafluoroethylene inner container, then placing the inner container into a hydrothermal reaction kettle, sealing, carrying out hydrothermal reaction for 5 hours at 160 ℃, then stopping heating and cooling to room temperature, stirring and cleaning a sample in a centrifuge by using ethanol and deionized water, and drying to obtain nano bismuth oxide powder;
2) preparing a negative electrode material: adding nano bismuth oxide powder, carbon black and polyvinylidene fluoride (PVDF) into an N-methylpyrrolidone solvent according to the mass ratio of 8:1:1, carrying out ball milling for 10 hours to obtain slurry, then uniformly coating the obtained slurry on a thin titanium sheet with the thickness of 8 microns, drying for 10 hours at 120 ℃ under a vacuum condition, and finally pressing for 5 minutes at 10MPa by using a tablet press, wherein the mass of an active material per square centimeter is about 5mg, so as to obtain the negative electrode material (bismuth oxide powder electrode) suitable for the water system metal ion battery.
The electrochemical performance of the negative electrode material obtained in this example in a sodium nitrate solution was tested:
the bismuth oxide powder electrode is used as a working electrode, a metal platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, an electrolyte is a 1mol/L sodium nitrate solution, the cycle performance and the charge-discharge curve of the cathode material are shown in figure 4, wherein A is the charge-discharge current density of 2mA/cm2The following cycle chart shows that the capacity of bismuth oxide is 1.45mAh/cm2After 50 cycles, the capacity retention rate of the bismuth oxide is 82%; b is the current density of 6.5mA/cm2The cycle chart below shows that the capacity of bismuth oxide is maintained at 0.6mAh/cm2The capacity retention rate is 80.5 percent after 140 cycles; c is the charging and discharging current density of 2mA/cm respectively2And 6.5mA/cm2The constant current charge-discharge curve chart shows that the bismuth oxide powder electrode has good charge-discharge platform and excellent charge-discharge rate performance.
Example 3
Preparing a negative electrode material suitable for an aqueous metal ion battery: stirring 0.6g of bismuth nitrate pentahydrate, 6mL of ethylene glycol and 6mL of acetone for 30 minutes to obtain a bismuth-containing precursor solution, putting a cleaned titanium sheet into the bismuth-containing precursor solution, placing the bismuth-containing precursor solution into a 20mL polytetrafluoroethylene inner container, then placing the inner container into a hydrothermal reaction kettle, sealing, carrying out hydrothermal reaction for 8 hours at the temperature of 120 ℃, then stopping heating and cooling to room temperature, washing the residual solution on the surface of a sample with ethanol and deionized water, and growing a layer of bismuth oxide film on the surface of a titanium sheet current collector, namely the cathode material suitable for the water-based metal ion battery. Scanning electron microscope images of the bismuth oxide film on the surface of the cathode material show that the morphology of the obtained nano bismuth oxide array film is similar to that of the nano bismuth oxide array film obtained in the embodiment 1.
Example 4
Assembly and electrochemical performance testing of aqueous lithium ion batteries based on the negative electrode material and lithium manganate electrode prepared in example 1.
Preparing a lithium manganate electrode: adding lithium manganate powder, carbon black and PVDF into an N-methylpyrrolidone solvent in a ratio of 8:1:1, carrying out ball milling for 10 hours to obtain slurry, uniformly coating the slurry on a thin titanium sheet with the thickness of 8 microns, drying for 10 hours at 120 ℃ under a vacuum condition, and finally pressing for 5 minutes at 10MPa by using a tablet press to obtain the lithium manganate electrode.
The negative electrode material prepared in example 1 was used as a negative electrode, the lithium manganate electrode was used as a positive electrode, and the battery was assembled by cutting and matching according to specifications, the separator used was a commercially available nickel-hydrogen battery separator, the electrolyte was a mixed lithium ion solution (lithium sulfate and lithium chloride solutions were mixed in a volume ratio of 1:2, and the lithium ion concentration was kept at 1mol/L), the charge and discharge curve of the battery was as shown in fig. 5, and in a 0-2.2V operating range, the charge and discharge current was 172mA/g, the discharge capacity of the entire battery was 78.9mAh/g, and the discharge plateau was about 1V. The capacity retention ratio of the battery after 50 cycles is 60% under the current density of 250mAh/g of charge and discharge current.
Example 5
Assembly and electrochemical performance testing of aqueous lithium ion batteries based on bismuth oxide powder electrodes and lithium manganate electrodes prepared in example 2.
The bismuth oxide powder electrode prepared in example 2 is used as a negative electrode, the lithium manganate electrode prepared in example 4 is used as a positive electrode, and the battery is assembled by cutting and matching according to specifications, the adopted diaphragm is a commercially available nickel-metal hydride battery diaphragm, the electrolyte is a mixed lithium ion solution (lithium sulfate and lithium chloride solution are mixed according to a volume ratio of 1:2, and the lithium ion concentration is kept to be 1mol/L), the discharge curves of the battery under different current densities are shown in FIG. 6, when the charging and discharging current is increased by 2, 5, 10 and 50 times from 0.025A/g in a 0-2.2V working interval, the capacity of the battery is 90%, 74.7%, 66.1% and 35.75% of the capacity under the condition of 0.025A/g respectively, when the current density is increased by 100 times and is increased from 0.025A/g to 2.5A/g, the capacity retention ratio is 26.7%, the discharge capacity of the battery is 78.9mAh/g, and when the charging and discharging current is at a current density of 250mAh/g, the capacity retention after 100 cycles was 68.3%.
It should be understood that the above-mentioned embodiments are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.

Claims (1)

1. An aqueous metal-ion battery having a composition comprising a positive electrode, a negative electrode, and an electrolyte, characterized in that: the negative electrode is a nano bismuth oxide array film and is formed by directionally growing bismuth oxide nano-sheets on a metal substrate, and the bismuth oxide nano-sheets are vertically, uniformly and densely distributed on the metal substrate and are in an array shape;
the preparation method of the nano bismuth oxide array film comprises the following steps: placing a titanium sheet with a clean surface in a bismuth-containing precursor solution prepared by using ethylene glycol and acetone as a mixed solvent, and carrying out hydrothermal reaction to obtain a negative electrode material suitable for a water-based metal ion battery;
the volume ratio of the ethylene glycol to the acetone is 1: 1-2;
the bismuth-containing precursor solution is obtained by dissolving bismuth nitrate pentahydrate in a mixed solvent; the hydrothermal reaction temperature is 120-180 ℃, and the reaction time is 3-8 h;
the water-system metal ion battery is one of a water-system lithium ion battery or a water-system sodium ion battery;
the electrolyte of the water-based lithium ion battery is one or more than two aqueous solutions of lithium sulfate, lithium chloride and lithium nitrate, the pH value of the aqueous solution is 2.0-8.0, and the cation concentration is 0.5-10 mol/L;
the electrolyte of the water system sodium ion battery is one or more than two aqueous solutions of sodium sulfate, sodium chloride and sodium nitrate, the pH value of the aqueous solution is 2.0-8.0, and the cation concentration is 0.5-10 mol/L.
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