CN108075127B - Nickel-phosphorus-based sodium ion battery cathode composite material and preparation method and application thereof - Google Patents

Nickel-phosphorus-based sodium ion battery cathode composite material and preparation method and application thereof Download PDF

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CN108075127B
CN108075127B CN201711393781.5A CN201711393781A CN108075127B CN 108075127 B CN108075127 B CN 108075127B CN 201711393781 A CN201711393781 A CN 201711393781A CN 108075127 B CN108075127 B CN 108075127B
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ion battery
phosphorus
nickel
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based sodium
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CN108075127A (en
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刘宇杰
肖学章
陈立新
张依文
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Zhejiang University ZJU
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5805—Phosphides
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a nickel-phosphorus-based sodium-ion battery cathode composite material which is obtained by reducing graphene oxide loaded with a Ni-P active material, wherein the Ni-P active material is Ni3P and Ni2P2O7Two phases are formed. The invention also discloses a preparation method of the nickel-phosphorus-based sodium-ion battery cathode composite material, which comprises the following steps: (1) method for preparing nanorod NiNH by solvothermal method4PO4A precursor; (2) reacting NiNH4PO4Carrying out thermal reduction on the precursor to obtain a nano Ni-P material; (3) and compounding the nano Ni-P material and graphene oxide by a solvothermal method to obtain the nickel-phosphorus-based sodium-ion battery cathode composite material. The production process is easy to control and can be repeated, and is convenient for large-scale production. The composite material is used as a negative electrode material of a sodium ion battery for the first time, and has high initial discharge specific capacity, high charge specific capacity and good cycling stability.

Description

Nickel-phosphorus-based sodium ion battery cathode composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of material chemistry and electrochemistry, and particularly relates to a nickel-phosphorus-based sodium-ion battery cathode composite material, and a preparation method and application thereof.
Background
In recent years, sodium ion batteries have become a new research hotspot due to their many advantages. Currently, research on negative electrode materials of sodium ion batteries mainly focuses on carbon materials, conversion type metal oxides and sulfides, intercalation type metal oxides and polyanion compounds (such as phosphate), and P-orbital elements (simple substances, alloys, phosphorus and phosphide) in the following directions. The red phosphorus has the advantages of high theoretical capacity, low discharge voltage platform and the like, but the red phosphorus material has poor cycle performance, the capacity loss of the battery is rapid, and electrochemical modification is needed.
Alloying and nanocrystallization are two important ways for improving the electrochemical performance of the red phosphorus material, and the process of forming alloy by the red phosphorus and other metals is called alloying, so that the conductivity of the material can be improved, and the stability of the structure of the material is improved. The preparation of the alloy into nano particles is called nanocrystallization, and the specific surface area of the material can be increased and the difficulty of sodium ion deintercalation can be reduced by the method.
The existing Ni-P negative electrode materials and preparation methods thereof have more varieties and obvious defects, such as the paper "electric deposition of Ni" published in RSC Advances3P-Ni arrays on 3-D nickel foam as a high performance and lithium-ion batteries' preparation of Ni by chemical deposition method3P-Ni nano alloy, but the method has high requirements on the process and preparation conditions, and is difficult to apply on a large scale. It should be noted that, so far, there is no report about the use of Ni — P nano negative electrode material as the negative electrode of sodium ion battery. In U.S. patent "Hard Carbon Composite for Alkali Metal-ion batteries" published as US 2015/0270547 a1, the disclosed G-HC (graphene and Hard Carbon) Composite anode material has a specific sodium storage capacity of only-100 mAh/G at a current density of 100 mA/G; european patent publication No. WO 2016/137401A 1 entitled "SODIUM-ION BATTERYANODE" disclosing Na3Ti3O7The specific sodium storage capacity of the/C negative electrode material under the current density of 1C (88.9mA/g) is only 80 mAh/g; a paper "Carbon coated sodium-titanate nanoparticles as an advanced interaction for sodium-ion batteries" published in the Journal of Alloys and Compounds, which was prepared as Na2Ti3O7The reversible capacity of the/C composite material at a current density of 0.5C (155.5mA/g) is only 170 mAh/g. Therefore, in the prior art, the negative electrode material has the defects of low sodium storage specific capacity and reversible capacity.
Disclosure of Invention
The invention aims to overcome the defects of harsh synthesis conditions and more impurities in the product of the nickel-phosphorus electrode material, and provides a nickel-phosphorus-based sodium ion battery cathode composite material, a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
The nickel-phosphorus-based sodium-ion battery cathode composite material is obtained by reducing graphene oxide to load a Ni-P active material, wherein the Ni-P active material is Ni3p and Ni2P2O7Two phases are formed.
The material of the invention is Ni as the nickel-phosphorus-based active substance3P and Ni2P2O7The two-phase mixture has easily controlled and repeatable production process, is convenient for large-scale production, and has good sodium storage performance.
The mass ratio of the Ni-P active material to the reduced graphene oxide is 100: and 5-25, gradually improving the electrochemical performance of the composite material along with the improvement of the reduced graphene oxide ratio, and after the reduced graphene oxide ratio is increased to a certain value, continuously increasing the reduced graphene oxide ratio is unfavorable for the electrochemical performance of the composite material.
The invention also provides a preparation method of the nickel-phosphorus-based sodium-ion battery cathode composite material, which comprises the following steps: (1) method for preparing nanorod NiNH by solvothermal method4PO4a precursor; (2) reacting NiNH4PO4Carrying out thermal reduction on the precursor to obtain a nano Ni-P material; (3) and compounding the nano Ni-P material and graphene oxide by a solvothermal method to obtain the Ni-P @ RGO electrode material, namely the nickel-phosphorus-based sodium-ion battery cathode composite material.
Further, step (1) includes: weighing a certain amount of NiCl2·6H2O and NaH2PO4·2H2Dissolving O in water, sequentially adding ethylene glycol, DMF and Na2CO3Finally, adding ammonia water, stirring uniformly, and reacting at 160-200 ℃ for 16-20 h to prepare nano-rod-shaped NiNH4PO4And (3) precursor.
wherein NiCl2·6H2O、NaH2PO4·2H2O and Na2CO3the feeding molar ratio of (1): 0.5-2: 0.5 to 2, wherein NiCl2·6H2O and NaH2PO4·2H2The molar ratio of O fed will affect the molar ratio of Ni and P elements in the solvent to NiNH formed4PO4The crystal structure of the precursor has certain influence, and the two raw materials and Na2CO3Will influence the pH of the solution and further influence the NiNH4PO4The precipitation process of the precursor in the hydrothermal process is NiNH4PO4the yield of the precursor has an influence.
in the step (1), the adding volume ratio of water, glycol, DMF and ammonia water is 4: 1: 0.5-2: 0.5-1, in the reaction system in the step (1), water and ethylene glycol mainly play a role of a solvent, DMF can control the microscopic morphology of a precursor, the addition amount of DMF is increased to a certain degree, and the synthesized NiNH4PO4The shape of the precursor is changed into a nano rod shape, and the ammonia water plays a role in providing NH4 +The amount of the compound (A) also affects the NiNH4PO4The yield of the precursor is high, and in addition, the ammonia can dissolve NiCl2·6H2O and Na2CO3Ni produced by reaction2CO3The addition amount of the Ni can be increased to a certain ratio to completely dissolve Ni2CO3So that the solution appears lake blue clear.
Preferably, in the step (1), stirring is carried out for 60-120 min before reaction, and the stirring time can influence the distribution condition of DMF in the mixed solution, and further influence NiNH in the step (1)4PO4the precursor is in a micro shape, and the precursor is converted into a nano rod shape after being stirred for a certain time.
The NiNH4PO4The precursor is of a rod-shaped structure, and the diameter of the precursor is 50-100 nm.
Further, the step (2) comprises: NiNH obtained in the step (1)4PO4Putting the precursor into a tube furnace, and introducing H2Heating the mixed gas of Ar and the mixed gas to 600-700 ℃ at the heating rate of 1-5 ℃/min, and preserving the temperature for 2-8 hours to obtain the nano Ni-P material, wherein the sintering temperature can influence the phase of a formed product after sintering, and when the reaction temperature is lower than 500 ℃, the reaction product is a single phase Ni2P2O7And when the reaction temperature is higher than 800 ℃, the reaction product is converted into pure Ni2And (4) P phase.
Wherein, said H2In a mixed gas of Ar and H2Accounting for 5 to 20 percent of the total volume of the mixed gas; the flow rate of the mixed gas is 20-50 ml/min.
The nano Ni-P material is in a granular structure, and the particle size distribution range is 50-200 nm.
Further, step (3) includes: and (3) mixing the nano Ni-P material obtained in the step (2) with graphene oxide, adding ethanol, uniformly stirring, reacting for 5-20 h at 100-200 ℃, and performing post-treatment to obtain a Ni-P @ RGO electrode material, namely the nickel-phosphorus-based sodium ion battery cathode composite material.
Wherein the feeding ratio of the nano Ni-P material to the graphene oxide to the ethanol is 100 mg: 5-25 mg: 40 ml.
The invention also discloses application of the nickel-phosphorus-based sodium ion battery cathode composite material in a sodium ion battery. The composite material Ni-P @ RGO is used as a negative electrode material of a sodium ion battery for the first time, and has high initial discharge specific capacity, high charge specific capacity and good cycling stability.
Under the conditions that the charging and discharging interval is 0.005V-3V and the discharging current density is 100mA/g, the initial discharging specific capacity of the nickel-phosphorus-based sodium ion battery negative electrode composite material is 360-650 mAh/g, the charging specific capacity is 180-310 mAh/g, and the reversible specific capacity is kept to be 90-210 mAh/g after 50 cycles.
Compared with the prior art, the method has the following beneficial effects:
(1) The material of the invention is Ni as the nickel-phosphorus-based active substance3P and Ni2P2O7The two-phase mixture has easily controlled and repeatable production process and is convenient for large-scale production.
(2) The composite material Ni-P @ RGO is used as a negative electrode material of a sodium ion battery for the first time, and has high initial discharge specific capacity, high charge specific capacity and good cycling stability.
Drawings
FIG. 1 shows a nano-rod-shaped NiNH4PO4scanning electron microscope pictures of the precursor;
FIG. 2 is a scanning electron microscope image of the nano Ni-P material;
FIG. 3 is an X-ray diffraction pattern of a Ni-P @ RGO electrode material;
FIG. 4 is a scanning electron microscope photograph of the Ni-P @ RGO electrode material;
FIG. 5 is a first charge and discharge curve of the Ni-P @ RGO electrode material prepared in example 1;
FIG. 6 is a plot of the constant current charge-discharge cycle performance of the Ni-P @ RGO electrode material prepared in example 1;
FIG. 7 is a plot of the constant current charge-discharge cycle performance of the Ni-P @ RGO electrode material prepared in example 2;
FIG. 8 is a plot of the constant current charge-discharge cycle performance of the Ni-P @ RGO electrode material prepared in example 3;
FIG. 9 is a plot of the constant current charge-discharge cycle performance of the Ni-P @ RGO electrode material prepared in example 4;
FIG. 10 is a plot of the constant current charge-discharge cycle performance of the Ni-P @ RGO electrode material prepared in example 5;
FIG. 11 is a NiNH prepared in comparative example 14PO4Scanning electron microscopy of the precursor;
FIG. 12 is an X-ray diffraction pattern of the Ni-P material prepared in comparative example 1;
FIG. 13 is a graph of constant current charge-discharge cycle performance of the Ni-P material prepared in comparative example 1;
FIG. 14 is an X-ray diffraction pattern of the Ni-P material prepared in comparative example 2;
FIG. 15 is a graph of constant current charge-discharge cycle performance of the Ni-P material prepared in comparative example 2.
Detailed Description
The following examples further illustrate the present invention in conjunction with the drawings of the specification, but the present invention is not limited to the scope described below.
Example 1
The preparation method of the nickel-phosphorus-based sodium-ion battery cathode composite material comprises the following steps:
(1) 1426mg of powdered NiCl were mixed2·6H2O and 1248mg of crystalline NaH2PO4·2H2O dissolved in 40ml deionized water and started to strengthStirring, 10ml of ethylene glycol and 10ml of DMF are then added thereto, and after 5 minutes 530mg of Na are added2CO3immediately followed by addition of 7ml of NH3·H2And O, stirring for 2 hours, adding the mixed solution into the reaction kettle, sealing, and then preserving heat at 180 ℃ for 16 hours. Centrifugally cleaning the obtained product for 3 times at 12000r/min with ethanol and deionized water, drying at 110 deg.C for 8 hr to obtain NiNH in nano rod shape4PO4And (3) precursor.
The obtained NiNH4PO4The picture of the precursor scanning electron microscope is shown in figure 1, and the sample is rod-shaped and has the diameter of 50-100 nm.
(2) putting the product dried in the step (1) into a porcelain boat, putting the porcelain boat into a tube furnace, and introducing H210% of H2and vacuumizing and cleaning for three times by using a/Ar mixed gas. Adjusting the gas flow to 30ml/min, heating to 600 ℃ at the heating rate of 2 ℃/min, and then preserving the heat for 5h to obtain the nano Ni-P material.
The scanning electron microscope picture of the obtained nano-granular Ni-P material is shown in figure 2, and the particle size distribution range of the particles is 50-200 nm.
(3) Adding 100mg of nano Ni-P material and 20mg of Graphene Oxide (GO) into 40ml of absolute ethyl alcohol, stirring strongly for 6h, pouring the mixed suspension into a reaction kettle, and preserving heat at 120 ℃ for 12 h. After the reaction is finished, centrifugally cleaning and drying the product to obtain the Ni-P @ RGO electrode material, namely the nickel-phosphorus-based sodium ion battery cathode composite material.
The preparation process of the Graphene Oxide (GO) is as follows:
3g of graphite was added to 360ml of concentrated sulfuric acid H2SO4Then 40ml of concentrated phosphoric acid H are added3PO4After stirring for 8h, 18g of potassium permanganate KMnO is weighed4The mixed solution was slowly poured in, followed by heating in a water bath at 50 ℃ for 12 h. And after the reaction is finished, adding water into the turbid liquid, centrifuging, and freeze-drying to obtain Graphene Oxide (GO).
The X-ray diffraction pattern of the obtained Ni-P @ RGO electrode material is shown in figure 3, and analysis can obtain that the Ni-P material in the sample is made of Ni3P and Ni2P2O7Two phase compositioncomposition analysis showed that Ni3P and Ni2P2O7The mass ratio of the two phases was about 70: 30. The scanning electron microscope picture of the Ni-P @ RGO electrode material is shown in FIG. 4, and it can be clearly seen that nano Ni-P particles are loaded on the wrinkled layer of the reduced graphene oxide.
The electrode plate manufacturing and assembling process of the sodium ion half cell is as follows:
(1) mixing a Ni-P @ RGO electrode material, conductive Carbon Black (CB) and sodium alginate according to a mass ratio of 70: 15: 15, weighed and placed in an agate mortar for grinding for 20 minutes, then deionized water is added dropwise thereto and grinding is continued until a slurry of moderate viscosity is formed, and then the slurry is uniformly coated on a copper foil. After standing in air for 8h, the pieces were cut and placed in a vacuum oven and dried at 60 ℃ for 6 h.
(2) Under Ar protective atmosphere, the electrode slice dried in the step (1) is used as a positive electrode, a sodium slice is cut as a negative electrode, a glass fiber GF/C is used as a diaphragm, and the electrolyte is 1M NaClO4With the addition of 10% of FEC as additive to the electrolyte, EC/DMC (1:1 vol%) of (C). And (4) completing half-cell assembly and pressure sealing according to the sequence of the positive electrode shell, the positive electrode, the diaphragm, the negative electrode and the negative electrode shell.
After the assembly of the half-cell of the sodium-ion cell button is finished, constant-current charge-discharge test is carried out on the half-cell, the charge-discharge interval is 0.005-3V, the charge-discharge current density is 100mA/g, the first three charge-discharge curves of the Ni-P @ RGO electrode material are shown in figure 5, the first discharge capacity is 610mAh/g, and the first charge capacity is 303.1 mAh/g. As shown in FIG. 6, the reversible capacity of the Ni-P @ RGO electrode material remained at 200.1mAh/g after 50 cycles.
Example 2
The preparation method of the nickel-phosphorus-based sodium-ion battery cathode composite material comprises the following steps:
(1) 1426mg of powdered NiCl were mixed2·6H2O and 748.8mg of crystalline NaH2PO4·2H2O was dissolved in 40ml of deionized water and vigorous stirring was started, then 10ml of ethylene glycol and 10ml of DMF were added thereto, 954mg of Na was added after 5 minutes2CO3Immediately followed by addition of 7ml of NH3·H2And O, stirring for 2 hours. Adding the mixed solution into the reaction kettle, sealing, and then preserving the temperature at 180 ℃ for 18 h. Centrifugally cleaning the obtained product for 3 times at 12000r/min with ethanol and deionized water, drying at 110 deg.C for 8 hr to obtain NiNH in nano rod shape4PO4And (3) precursor.
(2) Putting the dried product in the step (1) into a porcelain boat, putting the porcelain boat into a tube furnace, and introducing H210% of H2and vacuumizing and cleaning for three times by using a/Ar mixed gas. Adjusting the gas flow to 40ml/min, heating to 700 ℃ at the heating rate of 5 ℃/min, and then preserving the heat for 5h to obtain the nano Ni-P material.
(3) Adding 100mg of Ni-P material and 20mg of graphene oxide into 40ml of absolute ethyl alcohol, stirring strongly for 6h, pouring the mixed suspension into a reaction kettle, and preserving heat for 15h at 140 ℃. After the reaction is finished, centrifugally cleaning and drying the product to obtain the Ni-P @ RGO electrode material, namely the nickel-phosphorus-based sodium ion battery cathode composite material.
The preparation process of the graphene oxide is as follows:
Adding 4g of graphite into 360ml of concentrated sulfuric acid H2SO4Then 50ml of concentrated phosphoric acid H are added3PO4After stirring for 10h, 20g of potassium permanganate KMnO was weighed4The mixed solution was slowly poured in, followed by heating in a water bath at 50 ℃ for 12 h. And after the reaction is finished, adding water into the turbid liquid, centrifuging, and freeze-drying to obtain the graphene oxide.
The electrode plate manufacturing and assembling process of the sodium ion half cell is as follows:
(1) Mixing an electrode material of Ni-P @ RGO, conductive carbon black and sodium alginate in a mass ratio of 70: 15: 15, weighed and placed in an agate mortar for grinding for 20 minutes, then deionized water is added dropwise thereto and grinding is continued until a slurry of moderate viscosity is formed, and then the slurry is uniformly coated on a copper foil. After standing in air for 8h, the pieces were cut and placed in a vacuum oven and dried at 60 ℃ for 6 h.
(2) In Ar protective atmosphere, the electrode slice dried in the step (1) is used as a positive electrode, a sodium slice is cut at present and used as a negative electrode, a glass fiber GF/C is used as a diaphragm, and an electrolyte is used1M NaClO4With the addition of 10% of FEC as additive to the electrolyte, EC/DMC (1:1 vol%) of (C). And (4) completing half-cell assembly and pressure sealing according to the sequence of the positive electrode shell, the positive electrode, the diaphragm, the negative electrode and the negative electrode shell. And (3) carrying out cycle performance test on the prepared battery, wherein the charge-discharge interval is 0.005-3V, the test current density is 100mA/g, the test result is shown in figure 7, the first discharge capacity is 517.7mAh/g, the first charge capacity is 251.7mAh/g, and the reversible capacity of the Ni-P @ RGO electrode material is 168.5mAh/g after 50 cycles.
Example 3
The preparation method of the nickel-phosphorus-based sodium-ion battery cathode composite material comprises the following steps:
(1) 1426mg of powdered NiCl were mixed2·6H2O and 1684.8mg of crystalline NaH2PO4·2H2O was dissolved in 40ml of deionized water and vigorous stirring was started, then 10ml of ethylene glycol and 10ml of DMF were added thereto, and after 5 minutes 763.2mg of Na was added2CO3Immediately followed by addition of 8ml of NH3·H2And O, stirring for 2 hours. Adding the mixed solution into a reaction kettle, sealing, and then preserving heat at 180 ℃ for 20 hours. Centrifugally cleaning the obtained product for 3 times at 12000r/min with alcohol and deionized water, drying at 110 deg.C for 8 hr to obtain NiNH in nano rod shape4PO4And (3) precursor.
(2) Putting the dried product in the step (1) into a porcelain boat, putting the porcelain boat into a tube furnace, and introducing H with the hydrogen volume ratio of 10%2and vacuumizing and cleaning for three times by using a/Ar mixed gas. Adjusting the gas flow to 50ml/min, heating to 600 ℃ at the heating rate of 5 ℃/min, and then preserving the heat for 5h to obtain the nano Ni-P material.
(3) Adding 100mg of Ni-P material and 20mg of graphene oxide into 40ml of absolute ethyl alcohol, stirring strongly for 6h, pouring the mixed suspension into a reaction kettle, and preserving heat at 120 ℃ for 12 h. After the reaction is finished, centrifugally cleaning and drying the product to obtain the Ni-P @ RGO electrode material, namely the nickel-phosphorus-based sodium ion battery cathode composite material.
the preparation process of the graphene oxide is as follows:
3g of graphite was added to 480ml of concentrated sulfuric acid H2SO4Then 30ml of H are added3PO4After stirring for 12h, 18g of potassium permanganate KMnO is weighed4The mixed solution was slowly poured in, followed by heating in a water bath at 60 ℃ for 12 h. And after the reaction is finished, adding water into the turbid liquid, centrifuging, and freeze-drying to obtain the graphene oxide.
the electrode plate manufacturing and assembling process of the sodium ion half cell is as follows:
(1) Mixing a Ni-P @ RGO electrode material, conductive carbon black and sodium alginate in a mass ratio of 70: 15: 15, weighed and placed in an agate mortar for grinding for 20 minutes, then deionized water is added dropwise thereto and grinding is continued until a slurry of moderate viscosity is formed, and then the slurry is uniformly coated on a copper foil. After standing in air for 8h, the pieces were cut and placed in a vacuum oven and dried at 60 ℃ for 6 h.
(2) Under Ar protective atmosphere, the electrode slice dried in the step (1) is used as a positive electrode, a sodium slice is cut as a negative electrode, a glass fiber GF/C is used as a diaphragm, and the electrolyte is 1M NaClO4With the addition of 10% of FEC as additive to the electrolyte, EC/DMC (1:1 vol%) of (C). And (4) completing half-cell assembly and pressure sealing according to the sequence of the positive electrode shell, the positive electrode, the diaphragm, the negative electrode and the negative electrode shell. The prepared battery is subjected to cycle performance test, the charging and discharging interval is 0.005-3V, the test current density is 100mA/g, and the result is shown in figure 8. The first discharge capacity is 488.7mAh/g, the first charge capacity is 242.5mAh/g, and the reversible capacity of the Ni-P @ RGO electrode material is 163.6mAh/g after 50 cycles.
Example 4
The preparation method of the nickel-phosphorus-based sodium-ion battery cathode composite material comprises the following steps:
(1) 1426mg of powdered NiCl were mixed2·6H2O and 1248mg of crystalline NaH2PO4·2H2o was dissolved in 40ml of deionized water and vigorous stirring was started, then 10ml of ethylene glycol and 20ml of DMF were added thereto, and after 5 minutes 530mg of Na was added2CO3Followed by addition of 10ml of NH3·H2And O, stirring for 2 hours. Adding the mixed solution into a reaction kettle, sealing, and then preserving heat at 180 ℃ for 20 hours. Will be provided withCentrifugally cleaning the obtained product for 3 times at 12000r/min with alcohol and deionized water, drying at 110 deg.C for 8 hr to obtain nanometer rod-shaped NiNH4PO4And (3) precursor.
(2) Putting the dried product in the step (1) into a porcelain boat, putting the porcelain boat into a tube furnace, and introducing H210% of H2And vacuumizing and cleaning for three times by using a/Ar mixed gas. Adjusting the gas flow to 50ml/min, heating to 600 ℃ at the heating rate of 5 ℃/min, and then preserving the heat for 5h to obtain the nano Ni-P material.
(3) Adding 100mg of Ni-P material and 25mg of graphene oxide into 40ml of absolute ethyl alcohol, stirring strongly for 6h, pouring the mixed suspension into a reaction kettle, and preserving heat at 120 ℃ for 12 h. After the reaction is finished, centrifugally cleaning and drying the product to obtain the Ni-P @ RGO electrode material, namely the nickel-phosphorus-based sodium ion battery cathode composite material.
the preparation process of the graphene oxide is as follows:
3g of graphite is added to 480ml of concentrated sulfuric acid H2SO4Then 30ml of H are added3PO4After stirring for 12h, 18g of potassium permanganate KMnO is weighed4The mixed solution was slowly poured in, followed by heating in a water bath at 60 ℃ for 12 h. And after the reaction is finished, adding water into the turbid liquid, centrifuging, and freeze-drying to obtain the graphene oxide.
The electrode plate manufacturing and assembling process of the sodium ion half cell is as follows:
(1) Mixing a Ni-P @ RGO electrode material, conductive carbon black and sodium alginate in a mass ratio of 70: 15: 15, weighed and placed in an agate mortar for grinding for 20 minutes, then deionized water is added dropwise thereto and grinding is continued until a slurry of moderate viscosity is formed, and then the slurry is uniformly coated on a copper foil. After standing in air for 8h, the pieces were cut and placed in a vacuum oven and dried at 60 ℃ for 6 h.
(2) Under Ar protective atmosphere, the electrode slice dried in the step (1) is used as a positive electrode, a sodium slice is cut as a negative electrode, a glass fiber GF/C is used as a diaphragm, and the electrolyte is 1M NaClO4With the addition of 10% of FEC as additive to the electrolyte, EC/DMC (1:1 vol%) of (C). According to the positive electrode shell, the positive electrode, the diaphragm and the negative electrodeAnd the sequence of the negative electrode shell completes half cell assembly and pressure sealing. The prepared battery is subjected to cycle performance test, the charging and discharging interval is 0.005-3V, the test current density is 100mA/g), and the result is shown in FIG. 9, the first discharge capacity is 465mAh/g, the first charge capacity is 230.5mAh/g, and the reversible capacity of the Ni-P @ RGO electrode material is 152.6mAh/g after 50 cycles.
Example 5
The preparation method of the nickel-phosphorus-based sodium-ion battery cathode composite material comprises the following steps:
(1) 1426mg of powdered NiCl were mixed2·6H2O and 1248mg of crystalline NaH2PO4·2H2O was dissolved in 40ml of deionized water and vigorous stirring was started, then 10ml of ethylene glycol and 10ml of DMF were added thereto, and after 5 minutes 530mg of Na was added2CO3followed by addition of 10ml of NH3·H2And O, stirring for 2 hours. Adding the mixed solution into a reaction kettle, sealing, and then preserving heat at 180 ℃ for 20 hours. Centrifugally cleaning the obtained product for 3 times at 12000r/min with alcohol and deionized water, drying at 110 deg.C for 8 hr to obtain NiNH in nano rod shape4PO4and (3) precursor.
(2) Putting the dried product in the step (1) into a porcelain boat, putting the porcelain boat into a tube furnace, and introducing H210% of H2And vacuumizing and cleaning for three times by using a/Ar mixed gas. Adjusting the gas flow to 50ml/min, heating to 600 ℃ at the heating rate of 5 ℃/min, and then preserving the heat for 5h to obtain the nano Ni-P material.
(3) Adding 100mg of Ni-P material and 5mg of graphene oxide into 40ml of absolute ethyl alcohol, stirring strongly for 6h, pouring the mixed suspension into a reaction kettle, and preserving heat at 120 ℃ for 12 h. After the reaction is finished, centrifugally cleaning and drying the product to obtain the Ni-P @ RGO electrode material, namely the nickel-phosphorus-based sodium ion battery cathode composite material.
The preparation process of the graphene oxide is as follows:
3g of graphite is added to 480ml of concentrated sulfuric acid H2SO4Then 30ml of H are added3PO4after stirring for 12h, 18g of potassium permanganate KMnO is weighed4The mixed solution was slowly poured in, followed by heating in a water bath at 60 ℃ for 12 h. And after the reaction is finished, adding water into the turbid liquid, centrifuging, and freeze-drying to obtain the graphene oxide.
the electrode plate manufacturing and assembling process of the sodium ion half cell is as follows:
(1) Mixing a Ni-P @ RGO electrode material, conductive carbon black and sodium alginate in a mass ratio of 70: 15: 15, weighed and placed in an agate mortar for grinding for 20 minutes, then deionized water is added dropwise thereto and grinding is continued until a slurry of moderate viscosity is formed, and then the slurry is uniformly coated on a copper foil. After standing in air for 8h, the pieces were cut and placed in a vacuum oven and dried at 60 ℃ for 6 h.
(2) under Ar protective atmosphere, the electrode slice dried in the step (1) is used as a positive electrode, a sodium slice is cut as a negative electrode, a glass fiber GF/C is used as a diaphragm, and the electrolyte is 1M NaClO4With the addition of 10% of FEC as additive to the electrolyte, EC/DMC (1:1 vol%) of (C). And (4) completing half-cell assembly and pressure sealing according to the sequence of the positive electrode shell, the positive electrode, the diaphragm, the negative electrode and the negative electrode shell. The prepared battery is subjected to cycle performance test, the charge-discharge interval is 0.005-3V, the test current density is 100mA/g, the result is shown in figure 10, the first discharge capacity is 366.2mAh/g, the first charge capacity is 188.5mAh/g, and the reversible capacity of the Ni-P @ RGO electrode material is 92.6mAh/g after 50 cycles.
Comparative example 1
the preparation method of the cathode material of the nickel-phosphorus-based sodium-ion battery in the comparative example specifically comprises the following steps:
(1) 1426mg of powdered NiCl were mixed2·6H2O and 1248mg of crystalline NaH2PO4·2H2O was dissolved in 40ml of deionized water and vigorous stirring was started, then 10ml of ethylene glycol and 5ml of DMF were added thereto, and after 5 minutes 530mg of Na was added2CO3Followed by addition of 10ml of NH3·H2And O, stirring for 5 min. Adding the mixed solution into a reaction kettle, sealing, and then preserving heat at 180 ℃ for 20 hours. Centrifugally cleaning the obtained product for 3 times at 12000r/min with alcohol and deionized water, drying at 110 deg.C for 8 hr to obtain non-nanorod NiNH4PO4the precursor, its micro-topography is shown in fig. 11.
(2) Putting the dried product in the step (1) into a porcelain boat, putting the porcelain boat into a tube furnace, and introducing H210% of H2And vacuumizing and cleaning for three times by using a/Ar mixed gas. Adjusting the gas flow to 30ml/min, heating to 500 ℃ at the heating rate of 2 ℃/min, and then preserving the heat for 5h to obtain the Ni-P material with the phase of pure Ni2P2O7The X-ray diffraction pattern is shown in FIG. 12.
The electrode plate manufacturing and assembling process of the sodium ion half cell is as follows:
(1) Mixing Ni-P electrode material, conductive carbon black and sodium alginate according to a mass ratio of 70: 15: 15, weighed and placed in an agate mortar for grinding for 20 minutes, then deionized water is added dropwise thereto and grinding is continued until a slurry of moderate viscosity is formed, and then the slurry is uniformly coated on a copper foil. After standing in air for 8h, the pieces were cut and placed in a vacuum oven and dried at 60 ℃ for 6 h.
(2) Under Ar protective atmosphere, the electrode slice dried in the step (1) is used as a positive electrode, a sodium slice is cut as a negative electrode, a glass fiber GF/C is used as a diaphragm, and the electrolyte is 1M NaClO4With the addition of 10% of FEC as additive to the electrolyte, EC/DMC (1:1 vol%) of (C). And (4) completing half-cell assembly and pressure sealing according to the sequence of the positive electrode shell, the positive electrode, the diaphragm, the negative electrode and the negative electrode shell. The prepared battery is subjected to cycle performance test, the charge-discharge interval is 0.005-3V, the test current density is 100mA/g, the result is shown in figure 13, the first discharge capacity is 437.4mAh/g, the first charge capacity is 235mAh/g, and the reversible capacity of the Ni-P electrode material is only 57.5mAh/g after 50 cycles.
Comparative example 2
The preparation method of the cathode material of the nickel-phosphorus-based sodium-ion battery in the comparative example specifically comprises the following steps:
(1) 1426mg of powdered NiCl were mixed2·6H2O and 1248mg of crystalline NaH2PO4·2H2O was dissolved in 40ml of deionized water and vigorous stirring was started, then 10ml of ethylene glycol and 5ml of DMF were added thereto, and after 5 minutes 530mg of Na was added2CO3Followed by addition of 10ml of NH3·H2And O, stirring for 5 min. Adding the mixed solution into a reaction kettle, sealing, and then preserving heat at 180 ℃ for 20 hours. Centrifugally cleaning the obtained product for 3 times at 12000r/min with alcohol and deionized water, drying at 110 deg.C for 8 hr to obtain non-nanorod NiNH4PO4And (3) precursor.
(2) Putting the dried product in the step (1) into a porcelain boat, putting the porcelain boat into a tube furnace, and introducing H220% of H2And vacuumizing and cleaning for three times by using a/Ar mixed gas. Adjusting the gas flow to 50ml/min, heating to 600 ℃ at the heating rate of 5 ℃/min, heating to 800 ℃ at the heating rate of 2 ℃/min, and then preserving heat for 5h to obtain the nano Ni-P material, wherein the phase is pure-phase Ni2P, its X-ray diffraction pattern is shown in FIG. 14.
The electrode plate manufacturing and assembling process of the sodium ion half cell is as follows:
(1) mixing Ni-P electrode material, conductive carbon black and sodium alginate according to a mass ratio of 70: 15: 15, weighed and placed in an agate mortar for grinding for 20 minutes, then deionized water is added dropwise thereto and grinding is continued until a slurry of moderate viscosity is formed, and then the slurry is uniformly coated on a copper foil. After standing in air for 8h, the pieces were cut and placed in a vacuum oven and dried at 60 ℃ for 6 h.
(2) Under Ar protective atmosphere, the electrode slice dried in the step (1) is used as a positive electrode, a sodium slice is cut as a negative electrode, a glass fiber GF/C is used as a diaphragm, and the electrolyte is 1M NaClO4With the addition of 10% of FEC as additive to the electrolyte, EC/DMC (1:1 vol%) of (C). And (4) completing half-cell assembly and pressure sealing according to the sequence of the positive electrode shell, the positive electrode, the diaphragm, the negative electrode and the negative electrode shell. The prepared battery is subjected to cycle performance test, the charging and discharging interval is 0.005-3V, the test current density is 100mA/g, and the result is shown in figure 15, the first discharging capacity is 161.6mAh/g, the first charging capacity is 47.2mAh/g, and the reversible capacity of the Ni-P electrode material is only 39.4mAh/g after 50 cycles.

Claims (9)

1. The nickel-phosphorus-based sodium ion battery cathode composite material is characterized in thatThen, the material is obtained by loading a Ni-P active material on reduced graphene oxide, wherein the Ni-P active material is made of Ni3P and Ni2P2O7two phases are formed;
The preparation method of the nickel-phosphorus-based sodium-ion battery cathode composite material comprises the following steps: (1) method for preparing nanorod NiNH by solvothermal method4PO4A precursor; (2) reacting NiNH4PO4carrying out thermal reduction on the precursor to obtain a nano Ni-P material; (3) and compounding the nano Ni-P material and graphene oxide by a solvothermal method to obtain the Ni-P @ RGO electrode material, namely the nickel-phosphorus-based sodium-ion battery cathode composite material.
2. The negative electrode composite material of the nickel-phosphorus-based sodium-ion battery of claim 1, wherein the mass ratio of the Ni-P active material to the reduced graphene oxide is 100: 5 to 25.
3. The negative electrode composite material of the nickel-phosphorus-based sodium-ion battery as claimed in claim 1, wherein the step (1) comprises: weighing a certain amount of NiCl2·6H2O and NaH2PO4·2H2Dissolving O in water, sequentially adding ethylene glycol, DMF and Na2CO3Finally, adding ammonia water, stirring uniformly, and reacting at 160-200 ℃ for 16-20 h to prepare nano-rod-shaped NiNH4PO4And (3) precursor.
4. the nickel-phosphorus-based sodium-ion battery negative electrode composite material of claim 3, wherein NiCl2·6H2O、NaH2PO4·2H2O and Na2CO3the feeding molar ratio of (1): 0.5-2: 0.5 to 2.
5. The cathode composite material of the nickel-phosphorus-based sodium-ion battery as claimed in claim 3, wherein in the step (1), the adding volume ratio of water, glycol, DMF and ammonia water is 4: 1: 0.5-2: 0.5 to 1.
6. The negative electrode composite material for the nickel-phosphorus-based sodium-ion battery as claimed in claim 3, wherein in the step (1), the mixture is stirred for 60-120 min before reaction.
7. The negative electrode composite material of the nickel-phosphorus-based sodium-ion battery as claimed in claim 1, wherein the step (2) comprises: NiNH obtained in the step (1)4PO4Putting the precursor into a tube furnace, and introducing H2And heating the mixed gas of Ar and the mixed gas to 600-700 ℃ at the heating rate of 1-5 ℃/min, and preserving the heat for 2-8 hours to obtain the nano Ni-P material.
8. The negative electrode composite material of the nickel-phosphorus-based sodium-ion battery as claimed in claim 1, wherein the step (3) comprises: and (3) mixing the nano Ni-P material obtained in the step (2) with graphene oxide, adding ethanol, uniformly stirring, reacting for 5-20 h at 100-200 ℃, and performing post-treatment to obtain a Ni-P @ RGO electrode material, namely the nickel-phosphorus-based sodium ion battery cathode composite material.
9. Use of the nickel phosphorus based sodium ion battery negative electrode composite material according to claim 1 in a sodium ion battery.
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