CN112614992B - Nickel composite positive electrode material of water-based zinc-nickel battery and preparation method of nickel composite positive electrode material - Google Patents

Nickel composite positive electrode material of water-based zinc-nickel battery and preparation method of nickel composite positive electrode material Download PDF

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CN112614992B
CN112614992B CN202011438756.6A CN202011438756A CN112614992B CN 112614992 B CN112614992 B CN 112614992B CN 202011438756 A CN202011438756 A CN 202011438756A CN 112614992 B CN112614992 B CN 112614992B
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nickel
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孙小华
黄延清
陈善华
刘秋恒
李鸣
赵大福
周琳翔
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China Three Gorges University CTGU
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Abstract

The invention discloses a preparation method of a nickel composite positive electrode material of a water system zinc-nickel battery with excellent performance. The preparation method of the material is a two-step hydrothermal method, wherein in the first step, a certain amount of selenium powder and sodium borohydride are added into deionized water, then the obtained solution is transferred into a hydrothermal kettle, and a three-dimensional substrate material is added into the solution to carry out hydrothermal reaction; and in the second step of hydrothermal treatment, a certain amount of thiourea and nickel nitrate are added into deionized water, then the mixed solution is transferred into a hydrothermal kettle, and the three-dimensional substrate material obtained in the first step is added into the solution. After the reaction is cooled, the three-dimensional base material is washed a plurality of times and dried. To obtain the flaky petaloid nickelous diselenide/nickel hydroxide which uniformly grows on the three-dimensional substrate material. The prepared material is used for the anode material of the water system zinc-nickel battery, has high specific capacity and good cycling stability, and is mild in reaction condition, simple in process and suitable for large-scale production.

Description

Nickel composite positive electrode material of water-based zinc-nickel battery and preparation method of nickel composite positive electrode material
Technical Field
The invention relates to the technical field of energy storage, in particular to a water system zinc-nickel battery, and specifically provides a nickel composite cathode material and a preparation method thereof.
Background
The zinc-nickel battery has the characteristics of high specific energy of the zinc-silver battery and long service life of the cadmium-nickel battery. The specific energy can reach 50-80Wh/Kg, the specific power can exceed 200W/Kg, the working temperature range is wide, and the working temperature can be between 20 ℃ below zero and 60 ℃. The source of the raw materials is not problematic, and the cost is low. And the pollution is not caused, and the power supply is an environment-friendly chemical power supply. At present, the charging cycle life of the battery can reach about 600 weeks, and great capital and technical force are invested abroad for development, so that the zinc-nickel battery is tried to be industrialized to replace lead-acid batteries, cadmium-nickel batteries and other chemical power supplies which cause serious environmental pollution. When the dendritic crystal and deformation of the zinc electrode of the zinc-nickel battery are discharged, the zinc electrode generates zinc oxide and zinc hydroxide, and a large amount of the products are dissolved in strong base electrolyte; during charging, most of the zincate is not deposited on the porous zinc electrode due to the solubility of the product, but around the electrolyte and in the separator, which makes the transfer process of the zinc electrode difficult and forms dendritic deposits on the outer surface and some points of the zinc electrode. The dendrites have no adhesion and easily pierce the membrane. In addition, the zincate has a higher density and tends to sink; with the progress of charge-discharge circulation, the upper part of the electrode is consumed, a large amount of zinc is deposited on the lower part of the electrode, so that the electrode is deformed, the effective area is reduced due to the electrode deformation, the discharge rate is reduced, and the battery capacity is influenced.
Disclosure of Invention
The invention aims to prepare a water-based zinc-nickel battery with excellent performance, and solve the problem of the cycle life of the conventional zinc-nickel battery.
In order to solve the technical problems, the invention adopts the following technical scheme: an aqueous zinc-nickel battery with excellent performance comprises a nickel-containing positive electrode material, a zinc negative electrode material, an electrolyte solution and a diaphragm.
The cathode material comprises any one of nickel selenide, nickelous diselenide or nickelous diselenide/nickel hydroxide.
The anode material can also be nickel disulfide/nickel hydroxide.
The general formula of the nickel selenide is NiSe, the nickel selenide is rod-shaped nanometer, and the length of the nickel selenide is 100-500 nm; the above-mentionedThe nickel diselenide/nickel hydroxide is a composite material of nickel diselenide and nickel hydroxide, and the general formula is Ni 3 Se 2 /Ni(OH) 2 The shape is a flaky petal shape, and the particle size is 100-500 nm.
The general formula of the nickel disulfide/nickel hydroxide is Ni 3 S 2 /Ni(OH) 2 The shape is flaky, and the width is 200-1000 nm.
According to the product and the structural general formula of the product, the invention also provides a preparation method of the nickel composite cathode material, which comprises the following steps: adding sodium borohydride and selenium powder into the ionized water, wherein the molar ratio of the sodium borohydride to the selenium powder is 1.2-1.6: 1, continuously stirring after mixing to form uniform precursor solution; then transferring the precursor solution containing the selenium element to a hydrothermal kettle, and adding foamed nickel (1X 1-4X 4 cm) 2 ) And carrying out hydrothermal reaction for 10-15h at the temperature of 120-150 ℃ after sealing to obtain NiSe, namely the nickel composite anode material, wherein the NiSe is rod-shaped nano and has a length of 100-500 nm.
Preferably, the preparation method of the nickel composite cathode material comprises the steps of placing the NiSe prepared in the step A into a mixed aqueous solution of nickel nitrate and thiourea, standing for 1-3 days, and carrying out hydrothermal reaction at the temperature of 100-130 ℃ for 18-25h to obtain the nickel composite cathode material Ni 3 Se 2 /Ni(OH) 2 Wherein the molar ratio of the nickel nitrate to the thiourea is 1-2: 1; prepared Ni 3 Se 2 /Ni(OH) 2 The shape is a flaky petal shape, and the particle size is 100-500 nm. .
With respect to the above Ni 3 Se 2 /Ni(OH) 2 The invention also provides a nickel disulfide/nickel hydroxide (Ni) 3 S 2 /Ni(OH) 2 ) The preparation method specifically comprises the following steps:
placing the foamed nickel in a mixed aqueous solution of nickel nitrate and thiourea, standing for 1-3 days, then completely transferring the foamed nickel to a hydrothermal kettle, carrying out hydrothermal reaction at the temperature of 100 ℃ and 130 ℃ for 18-25h, wherein the product after the hydrothermal reaction is Ni 3 S 2 /Ni(OH) 2 . The molar ratio of the nickel nitrate to the thiourea is 1-2: 1,prepared Ni 3 S 2 /Ni(OH) 2 The shape is flaky, and the width is 200-1000 nm.
The technical scheme of the invention is that the water-system zinc-nickel battery is composed of the nickel composite anode material prepared by the method, a zinc cathode material, water-system electrolyte and a diaphragm.
The electrolyte is potassium hydroxide and zinc salt solution, the concentration of the potassium hydroxide solution is 0.1-10 mol/L, and the zinc salt is added: zinc chloride, zinc acetate, zinc oxide, zinc nitrate, or the like, at a concentration of 0.01 to 1 mol/L.
The zinc negative electrode material matrix is active substance mainly containing zinc element, such as zinc powder, zinc foil, and zinc sheet. The thickness of the material is 1-10 mm.
The membrane should be at least one of a pulp-coated paper membrane, a hydrophilic Ni-Zn membrane, an NKK membrane, a glass fiber membrane, a sulfonated membrane, a dust-free paper membrane, a porous polyolefin membrane and filter paper.
The alloy obtained by adopting the technical scheme of the invention comprises NiSe and Ni 3 Se 2 /Ni(OH) 2 、Ni 3 S 2 /Ni(OH) 2 The composite anode material is prepared by applying a nickel selenide composite material or a nickel sulfide composite material to the research of a battery for the first time, and the anode is a rod-shaped nano composite material which is synthesized on a three-dimensional substrate by a one-step hydrothermal method and uniformly grows, and has a larger specific surface area. The material has rich raw materials, good stability and high specific capacity, thereby showing excellent electrochemical performance. The composite material disclosed by the invention has extremely high capacity, and the oxidation peak-to-peak current density of the CV test under the swept number of 20mv/s is 154mA/cm 2 The corresponding potential is 0.755V, and the reduction peak-to-peak current density is 170mA/cm 2 The corresponding potential was 0.152V. The charge and discharge effect is high.
Drawings
Fig. 1 is a morphology chart of nickel selenide prepared in example 1.
Figure 2 is a topographical view of the nickel disulfide/nickel hydroxide material prepared in example 2.
Fig. 3 is a morphology chart obtained by preparing nickel diselenide/nickel hydroxide obtained in example 3.
FIG. 4 is a graph showing CV comparison results from electrochemical tests performed on materials prepared in examples 1, 2 and 3.
FIG. 5 shows 5mA/cm of nickel selenide prepared in example 1 2 And (4) charge-discharge cycle stability.
FIG. 6 shows the nickel disulfide/nickel hydroxide solution prepared in example 2 at 5mA/cm 2 And (4) charge-discharge cycle stability.
FIG. 7 shows the nickel diselenide/nickel hydroxide solution prepared in example 3 at 5mA/cm 2 And (4) charge-discharge cycle stability.
FIG. 8 is a CV comparison graph of electrochemical tests performed on the materials assembled in examples 1 and 2, the materials assembled in examples 1 and 3, and the materials assembled in examples 2 and 3, respectively.
Detailed Description
The invention will be further described below with reference to the drawings and specific examples, to which, however, embodiments of the invention are not restricted.
Example 1
(1) Foam nickel pretreatment
Cutting foamed nickel to 2 × 4cm 2 And then washed with deionized water. Preparing 1mol/L hydrochloric acid, and soaking the cleaned and dried foamed nickel in the hydrochloric acid for 10min to remove oxides. Then transferring the mixture into 100mL of deionized water containing 1.5g of NaOH (5min), and then carrying out ultrasonic treatment for 5min and drying the mixture to obtain the finished product.
(2) Preparation of nickel selenide material
Firstly, adding 1.6mmol of sodium borohydride and 0.75mmol of selenium powder into 30mL of ionized water, and continuously stirring for 30min to form a precursor solution containing selenium. Then transferring the precursor solution containing selenium into a hydrothermal kettle, and adding the precursor solution into the 2 x 4cm treated in the step (1) 2 And (3) placing the foamed nickel obliquely and immersing the foamed nickel, sealing the foamed nickel, putting the sealed foamed nickel into an air-blowing drying oven for hydrothermal treatment, wherein the hydrothermal temperature is 130 ℃, the hydrothermal time is 12 hours, and then cooling the foamed nickel to the room temperature. Finally, taking out the foamed nickel from the reaction solution cooled to room temperature, washing impurities which can be remained on the surface of the foamed nickel for many times by using deionized water and absolute ethyl alcohol, and placing the cleaned foamed nickel in vacuum for dryingAnd keeping the temperature for 8h in the box at 60 ℃ to obtain NiSe, as shown in figure 1. The obtained nickel selenide is of a rod-shaped nano structure, the diameter of the nano rod is 100-300nm, and the length of the nano rod is 100-500 nm.
Electrochemical CV test was tested as follows: cutting into 1 × 1cm 2 Nickel selenide is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a carbon rod is used as a counter electrode, CV test is carried out on an electrochemical workstation, the scan number during the test is 20mv/s, as shown in figure 4, the peak current density of an oxidation peak is 120mA/cm through the test 2 The corresponding potential is 0.705V: the reduction peak current density was 110mA/cm 2 The corresponding potential was 0.245V.
The materials were assembled into a battery as follows: the specific process is as follows, the nickel selenide prepared in the example (2) is cut into 1X 1cm 2 As a positive electrode, the Zn sheet was cut into 2X 2cm pieces 2 As a negative electrode, 6mol/L KOH +0.2mmol/L ZnCl is prepared 2 The mixed solution is used as a battery electrolyte. Then, a blue-ray battery testing system is used for carrying out constant current charging and discharging tests, the testing voltage is 1.9-0.6V, and the current density is 5mA/cm 2 . As shown in fig. 5, the first charge-discharge specific capacities are: 0.673mAh/cm 2 ，0.539mAh/cm 2 . Has obvious charge and discharge platform. The charging and discharging specific capacities after 1300 times of circulation are respectively 0.539mAh/cm 2 ，0.349mAh/cm 2 The specific discharge capacity retention value was 64.75%.
Example 2
Preparation of nickel disulfide/nickel hydroxide material
Adding 0.08mmol of nickel nitrate and 0.055mmol of thiourea into 25mL of deionized water, continuously stirring for 15min, placing the foamed nickel obtained in the step (1) in the embodiment 1 into the mixed solution, standing for 1 day, then completely transferring the foamed nickel into a hydrothermal kettle, carrying out hydrothermal reaction for 20h at the temperature of 120 ℃, taking out the foamed nickel after the reaction is finished, washing the foamed nickel with deionized water or ethanol for multiple times, and continuously drying the foamed nickel in a vacuum drying box at the temperature of 60 ℃ for 10h to obtain Ni 3 S 2 /Ni(OH) 2 . The shape is sheet, the width is 200-1000 nm, and the drawing is shown in figure 2.
Using a method as described in example 1Methods test CV and assembled batteries. As shown in FIG. 4, the oxidation peak to peak current density of the CV test at 20mv/s scan was 100mA/cm 2 The corresponding potential is 0.75V, and the reduction peak-to-peak current density is 121mA/cm 2 The corresponding potential was 0.213V. As shown in FIG. 6, the cells were assembled at 5mA/cm on a blue test system 2 The specific capacities of the first charge and discharge under the constant current density are respectively as follows: 0.609mAh/cm 2 ，0.6mAh/cm 2 . After 1200 times of circulation, the charging and discharging specific capacities are respectively 0.262mAh/cm 2 ，0.26mAh/cm 2 . The specific discharge capacity retention value was 43.3%.
Example 3
Preparation of nickel diselenide/nickel hydroxide material
Adding 0.08mmol of nickel nitrate and 0.055mmol of thiourea into 25mL of deionized water, continuously stirring for 15min, placing the nickel selenide subjected to hydrothermal reaction in the step (2) in the embodiment 1 in a mixed solution, standing for 1 day, transferring to a hydrothermal kettle, sealing, carrying out hydrothermal reaction at 120 ℃ for 20h, cooling to room temperature after the hydrothermal reaction, washing the obtained product with deionized water and absolute ethyl alcohol for multiple times, and continuously drying in a vacuum drying oven at 60 ℃ for 10h to obtain the Ni 3 Se 2 /Ni(OH) 2 The grown composite material is of a flaky petal-shaped structure, and the particle size is 100-500 nm. As shown in fig. 3. The CV and assembled cell were tested using the method as shown in example 1. As shown in FIG. 4, the oxidation peak to peak current density of the CV test at 20mv/s scan was 154mA/cm 2 The corresponding potential is 0.755V, and the reduction peak-to-peak current density is 170mA/cm 2 The corresponding potential was 0.152V. As shown in FIG. 7, the cells were assembled at 5mA/cm on a blue test system 2 The specific capacities of the first charge and discharge under the constant current density are respectively as follows: 0.642mAh/cm 2 ，0.655mAh/cm 2 . After 1300 times of circulation, the charging and discharging specific capacities are respectively 0.54mAh/cm 2 ，0.537mAh/cm 2 . The specific discharge capacity retention value was 81.7%. The cycle stability is excellent. The redox peak current density of the sample obtained in example 3 after electrochemical test CV is higher than that measured in examples 1 and 2, and the material and the zinc sheet are assembled into the battery to obtain the initial charge-discharge specific capacity and the charge-discharge ratio after 1300 cyclesThe capacity is higher than that tested in examples 1 and 2, which shows that the specific capacity of the battery is larger and the stability is better.
In order to verify the feasibility and excellent performance of the formula, low-molar-weight nickel nitrate and thiourea (0.01 mmol of nickel nitrate and 0.02mmol of thiourea) are adopted in example 3, and the peak current densities of electrochemical CV redox of products obtained by reaction are respectively as follows according to the test method in example 1: 111.2mA/cm 2 ，110.4mA/cm 2 . The high molar amount of nickel nitrate and thiourea (0.1 mmol of nickel nitrate and 0.1mmol of thiourea) are adopted, and the products obtained by the reaction are tested according to the test method of the embodiment 1, and the peak current densities of the oxidation reduction of the electrochemical CV are respectively as follows: 79.7mA/cm 2 ，69.2mA/cm 2 . The results show that the above electrochemical properties are inferior to those measured for the formulation used in example 3.
Example 4
Preparation of nickel selenide-nickelous disulfide/nickel hydroxide material
To further demonstrate the superior performance of nickel diselenide/hydroxide in example 3, the nickel selenide in example 1 was now combined with the nickel disulfide/hydroxide in example 2 by 1X 0.5cm 2 Nickel selenide and 1 x 0.5cm 2 The combined nickel disulfide/nickel hydroxide electrode material was subjected to electrochemical CV testing as in example 1 and the CV redox peak current densities were measured to be 117mA/cm each at 20mv/s sweep as shown in FIG. 8 2 ，96.2mA/cm 2 The results show that the above electrochemical properties are inferior to those measured for the formulation used in example 3.
Example 5
Preparation of nickel selenide-nickelous diselenide/nickel hydroxide material
To further demonstrate the superior performance of nickel diselenide/hydroxide in example 3, the nickel selenide in example 1 was now combined with the nickel diselenide/hydroxide in example 3 at 1 × 0.5cm 2 Nickel selenide and 1 x 0.5cm 2 The nickel diselenide/nickel hydroxide composite electrode material was subjected to electrochemical CV testing as in example 1 and the CV redox peak current densities thereof were found to be 149mA/cm, respectively, at 20mv/s scan as shown in FIG. 8 2 ，143mA/cm 2 The results show that the above electrochemical properties are inferior to those measured for the formulation used in example 3.
Example 6
Preparation of nickel disulfide/nickel hydroxide-nickel diselenide/nickel hydroxide material
To further demonstrate the superior performance of nickel diselenide/hydroxide in example 3, nickel disulfide/hydroxide in example 2 was combined with nickel diselenide/hydroxide in example 3 at 1X 0.5cm 2 Trinickel disulfide/nickel hydroxide and 1 x 0.5cm 2 The nickel diselenide/nickel hydroxide composite electrode material was subjected to electrochemical CV testing as in example 1 and the CV redox peak current densities thereof were measured to be 151mA/cm, respectively, at 20mv/s scan as shown in FIG. 8 2 ，147mA/cm 2 The results show that the above electrochemical properties are inferior to those measured for the formulation used in example 3.

Claims (3)

1. The preparation method of the nickel composite positive electrode material of the water system zinc-nickel battery is characterized by comprising the following steps:
step (1): adding sodium borohydride and selenium powder into deionized water, mixing and continuously stirring for 10-60min to form a precursor solution containing selenium; transferring the precursor solution containing selenium into a hydrothermal kettle, adding nickel foam, sealing, and carrying out hydrothermal reaction at the temperature of 120-150 ℃ for 10-15h to obtain a product NiSe after the hydrothermal reaction;
step (2): putting the NiSe prepared in the step (1) into a mixed aqueous solution of nickel nitrate and thiourea, standing for 1-3 days, then completely transferring into a hydrothermal kettle, carrying out hydrothermal reaction at 100-130 ℃ for 18-25h, wherein the product after the hydrothermal reaction is Ni 3 Se 2 /Ni(OH) 2 (ii) a Said Ni 3 Se 2 /Ni(OH) 2 Is a composite material of nickelous diselenide and nickel hydroxide, and the general formula is Ni 3 Se 2 /Ni(OH) 2 The shape is a flaky petal shape, and the particle size is 100-500 nm.
2. The preparation method of the nickel composite positive electrode material of the water-based zinc-nickel battery as claimed in claim 1, wherein the molar ratio of the sodium borohydride to the selenium powder is 1.2-1.6: 1; the molar ratio of the nickel nitrate to the thiourea is 1-2: 1.
3. the method for preparing the nickel composite positive electrode material of the water-based zinc-nickel battery according to claim 1, wherein the molar ratio of nickel nitrate to thiourea is 1-2: 1.
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