CN105720236B - A kind of sodium-ion battery cathode nickel foam self-supporting sheet Ni3P/C composite materials and preparation method thereof - Google Patents
A kind of sodium-ion battery cathode nickel foam self-supporting sheet Ni3P/C composite materials and preparation method thereof Download PDFInfo
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- CN105720236B CN105720236B CN201610186251.2A CN201610186251A CN105720236B CN 105720236 B CN105720236 B CN 105720236B CN 201610186251 A CN201610186251 A CN 201610186251A CN 105720236 B CN105720236 B CN 105720236B
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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 kind of sodium-ion battery cathode nickel foam self-supporting sheet Ni3P/C composite materials and preparation method thereof.The sheet Ni in the composite material3P is equably grown in nickel foam, and C films are equably wrapped in Ni3On P.The preparation method of the composite material is:Using nickel compound as raw material, using hydro-thermal method in its uniformly long last layer hydroxide flake nickel.Then using sodium hypophosphite as phosphorus source, 2 hours are kept the temperature at 300 DEG C, prepares nickel foam self-supporting sheet Ni3P materials.Carbon coating finally is carried out to it, prepares nickel foam self-supporting sheet Ni3P/C composite materials.The Ni of the present invention3Sodium-ion battery cathode prepared by P/C composite materials has excellent specific capacity, high rate performance and stable circulation performance.The method of the present invention simple possible, raw material sources are wide, suitable for industrialized production.
Description
Technical field
Preparation and application field the invention belongs to energy and material, and in particular to a kind of sodium-ion battery cathode with nickel foam from
Support sheet Ni3P/C composite materials and preparation method thereof.
Background technology
Lithium ion battery is widely used in mobile phone, notebook, shifting because of its energy density height and the advantages that have extended cycle life
Dynamic power supply, electric vehicle and hybrid vehicle etc..But lithium resource reserves are limited, on a large scale should for lithium ion battery
With lithium resource shortage and rapid rise of price seriously will hinder lithium ion battery further to develop.Since sodium and lithium belong to same main group member
Element, they have similar physics and chemical property, and sodium-ion battery has caused more and more interest in recent years.And relative to lithium
Resource, sodium resource storage capacity is very big, abundance, and price is relatively cheap so that sodium-ion battery be expected to future substitution lithium from
Sub- battery and be widely used in the fields such as mobile power and extensive energy storage.Due to Na+Radius it is larger, make it in stratiform knot
It is not easy embedded in structure graphite and deviates from, the graphite with good embedding lithium ability is not suitable as sodium-ion battery cathode material
Material.Therefore, negative material is the key that sodium-ion battery development.
One alternative solution of sodium-ion battery cathode is using black phosphorus, and theoretical discharge capacity when generating sodium phosphide is
2596mAh/g.But larger volume expansion can occur when being moved to phosphorus cathode for sodium ion, cause system unstable.Relative to
It is elemental phosphorous, nickel phosphide(Ni3P)Anode material of lithium-ion battery also has very high specific capacity.But nickel phosphide electronic conduction
For rate than relatively low, this seriously affects its high rate performance.In addition, since sodium ion Chin-Shih enters Ni3Volume expansion caused by after P, also easily
Lead to its structural instability and special capacity fade.It is to overcome one of effective way of the above problem that surface modification, which is considered as,.Cause
This, the present invention coats one layer of good carbon of nano-level conducting in phosphatization nickel surface(C)Film, this can not only improve the electronics of material
Electric conductivity, and can nickel phosphide volume expansion during buffer cycles, so as to improve Ni3P anode material of lithium-ion batteries
Multiplying power and stable circulation performance.
Invention content
A kind of specific capacity of present invention offer is high, high rate performance is excellent, good cycling stability sodium-ion battery cathode bubble
Foam nickel self-supporting sheet Ni3P/C composite materials and preparation method thereof.
Sodium-ion battery cathode of the present invention nickel foam self-supporting sheet Ni3The preparation method of P/C composite materials
It is divided into three steps:First, nickel foam self-supporting Ni (OH) is prepared using hydro-thermal method2.Then, it is phosphorus source using sodium hypophosphite
By nickel foam self-supporting Ni (OH)2Phosphatization prepares nickel foam self-supporting Ni3P negative materials.Finally, using organic carbon source to bubble
Foam nickel self-supporting Ni3P carries out carbon coating, prepares nickel foam self-supporting Ni3P/C negative materials.In terms of mass fraction:Sodium ion
Cell negative electrode material nickel foam self-supporting Ni3Mass fraction shared by carbon film is 5-20% in P/C composite materials.
The purpose of the present invention is achieved through the following technical solutions.
A kind of sodium-ion battery cathode nickel foam self-supporting sheet Ni3The preparation method of P/C composite materials, including following
Step:
1)Nickel foam is ultrasonic in the sodium hydrate aqueous solution of 0.5-2mol/L, absolute ethyl alcohol and deionized water successively
0.5-1 hours;
2)It weighs nickel salt dissolving in deionized water, is configured to the nickel salt solution of a concentration of 0.5-2mol/L;
3)Surfactant is added in into step 2)In gained nickel salt solution, stir 0.5-1 hours, obtain mixed at 50-80 DEG C
Close solution;
4)By step 3)Gained mixed solution is placed in autoclave, and step 1)The nickel foam handled well is put into
In autoclave, 5-24 hours are kept the temperature at 100-200 DEG C;
5)It treats reaction kettle cooled to room temperature, takes out nickel foam, ultrasound 0.5-1 is small in deionized water and ethyl alcohol respectively
When, at 80-120 DEG C dry 4 ~ 12 hours to get to nickel foam self-supporting Ni (OH)2;
6)It weighs sodium hypophosphite and adds in step 5 for phosphorus source)Gained nickel foam self-supporting Ni (OH)2In, under an argon atmosphere
300-600 DEG C is sintered 3-10 hours, you can obtains nickel foam self-supporting Ni3P materials;
7)By step 6)Prepared nickel foam self-supporting Ni3P materials are placed in 0.1-2mol/L organic carbon source aqueous solutions
It is 1-3 hours, then 4 ~ 12 hours dry at 80-120 DEG C, it calcines 5-12 hours for 300-500 DEG C under an argon atmosphere, you can
To nickel foam self-supporting Ni3P/C composite materials.
Further, the nickel salt described in step 2) is one or more of nickel nitrate, nickel sulfate and nickel acetate.
Further, the surfactant described in step 3) is hexamethylenetetramine, PEG, PVP, Span and Tween system
One or more of row, the dosage of surfactant are the 5~20% of nickel salt quality..
Further, step 3) the surfactant additive amount is 2-10g.
Further, the sodium hypophosphite addition quality described in step 6) is 0.5-5g.
Further, step 6) is to be warming up to 300-600 DEG C with the heating rate of 1-5 DEG C/min to calcine 3-10 hours.
Further, the organic carbon source described in step 7) is in glucose, sucrose, tartaric acid, starch and citric acid
It is one or more of.
Further, the dosage of the step 7) organic carbon source is the 5~20% of nickel salt quality.
Further, step 7) is to be warming up to 300-500 DEG C with the heating rate of 1-5 DEG C/min to calcine 5-12 hours.
A kind of nickel foam self-supporting sheet Ni of sodium-ion battery cathode as made from above-mentioned preparation method3P/C composite woods
Material, the sheet Ni in the composite material3For P/C homoepitaxials in nickel foam, carbon film is uniformly coated on Ni3P surfaces, Ni3P pieces
Thickness for 20-100 nanometer, the content of carbon is 5 ~ 20wt.% in composite material.
Compared with prior art, the invention has the advantages that and technique effect:
1st, nickel foam self-supporting sheet Ni of the invention3Battery performance made of P/C composite materials is excellent, has higher
Specific capacity, excellent high rate performance and cycle performance.
2nd, nickel foam self-supporting sheet Ni of the invention3The preparation method simple possible of P/C composite materials, raw material sources
Extensively, suitable for industrialized production.
Description of the drawings
Fig. 1 is nickel foam self-supporting Ni (OH) made from embodiment 12Material and nickel foam self-supporting Ni3P/C composite woods
The XRD spectrum of material.
Fig. 2 is nickel foam self-supporting Ni (OH) made from embodiment 12The SEM figures of material.
Fig. 3 is nickel foam self-supporting Ni made from embodiment 13The SEM figures of P/C composite materials.
Fig. 4 is nickel foam self-supporting Ni made from embodiment 13For the first time charge and discharges of the P/C as sodium-ion battery cathode material
Electric curve.
Fig. 5 is nickel foam self-supporting Ni made from embodiment 13High rate performances of the P/C as sodium-ion battery cathode material
Curve.
Fig. 6 is nickel foam self-supporting Ni made from embodiment 13P/C is as sodium-ion battery cathode material in 100 mAg-1The specific volume spirogram of 50 times is recycled under current density.
Fig. 7 is nickel foam self-supporting Ni made from embodiment 13P/C is as sodium-ion battery cathode material in 500 mAg-1The specific volume spirogram of 100 times is recycled under current density.
Specific embodiment
The present invention may be better understood in following embodiment, but the present invention is not limited to following embodiment.
Embodiment 1
1. by 2*4cm nickel foams are ultrasonic in 0.5mol/L sodium hydrate aqueous solutions, absolute ethyl alcohol and deionized water successively
0.5 hour.
2. weighing 2.91 g nickel nitrates to be dissolved in 20 mL deionized waters, the salt for being configured to a concentration of 0.5mol/L is molten
Liquid.
3. 2.0g hexamethylenetetramines are added in above-mentioned salting liquid, stirred 0.5 hour at 50 DEG C, obtain mixed solution.
4. above-mentioned mixed solution is placed in autoclave, and the nickel foam handled well is placed in autoclave,
24 hours are kept the temperature at 100 DEG C.
5. treating autoclave cooled to room temperature, nickel foam is taken out, it is ultrasonic in deionized water and ethyl alcohol respectively
It is 0.5 hour, then 12 hours dry at 80 DEG C, you can to obtain nickel foam self-supporting Ni (OH)2。
6. weigh 1.0g sodium hypophosphites adds in above-mentioned nickel foam self-supporting Ni (OH) for phosphorus source2In,Under an argon atmosphere with 1
DEG C/heating rate of min is warming up to 300 DEG C and is sintered 10 hours, you can obtain nickel foam self-supporting Ni3P materials.
7. by above-mentioned prepared nickel foam self-supporting Ni3P materials are placed 1 hour in 0.1mol/L glucose solutions,
Then it is 12 hours dry at 80 DEG C, 300 DEG C are warming up to the heating rate of 1 DEG C/min calcine 12 hours under an argon atmosphere,
It can obtain nickel foam self-supporting Ni3P/C composite materials.
Nickel foam self-supporting Ni obtained by the present embodiment3The XRD spectrums of P/C composite materials is as shown in Figure 1, can be with from figure
Find out nickel foam self-supporting Ni3There are two kinds of object phases of metal simple-substance nickel and nickel phosphide in P/C composite materials.Made from the present embodiment
Nickel foam self-supporting Ni (OH)2The SEM figures of material are as shown in Figure 2.Nickel foam self-supporting Ni obtained by the present embodiment3P/C composite woods
The SEM of material is as shown in figure 3, sheet Ni as seen from Figure 33P/C is uniformly raw in foam web.
The nickel foam self-supporting Ni that will be prepared3P/C composite materials are cut into a diameter of 1.2cm positive plates, with lithium metal
For piece as cathode, polypropylene is diaphragm and NaPF6For electrolyte, assembled in the glove box full of argon gas and obtain CR2032 type knobs
Detain experimental cell.This experimental cell carries out first charge-discharge, the cyclic curve of gained with the multiplying power of 50mA/g between 0.01-3.0V
As shown in Figure 4.The battery that gained is implemented is subjected to high rate performance test, high rate performance curve is as shown in Figure 5.Gained is implemented
Battery respectively multiplying power be 100mAg-1And 500mAg-150 and 100 loop tests are carried out under current density, gained
Cyclic curve is as shown in Figures 6 and 7.
As shown in Figure 5,1 gained nickel foam self-supporting Ni of embodiment3P/C composite negative pole materials are in 50mAg-1With 500
mA·g-1Charge specific capacity is respectively 620 and 352mAh/g under current density.It will be appreciated from fig. 6 that 1 gained nickel foam of embodiment is propped up certainly
Support Ni3P/C composite negative pole materials are in 100mAg-1Initial discharge specific capacity is 501.5 mAh/g under current density, by 50 times
After cycle, specific discharge capacity is 440.7 mAh/g, and specific capacity conservation rate is 87.9%.As shown in Figure 7, in 500 mAg-1Electricity
Its initial discharge specific capacity is 351.1 mAh/g under current density, after 100 cycles, specific discharge capacity 231.2
MAh/g, specific capacity conservation rate are about 65.9%.It can be seen from the above result that gained is used as sodium-ion battery cathode nickel foam self-supporting
Ni3P/C composite materials have excellent specific capacity, high rate performance and stable circulation performance.
Embodiment 2
1. by 2*4cm nickel foams successively ultrasonic 1 in 2mol/L sodium hydrate aqueous solutions, absolute ethyl alcohol and deionized water
Hour.
2. weighing 10.52 g nickel sulfates to be dissolved in 20 mL deionized waters, it is configured to a concentration of 2mol/L salting liquids.
3. the PEG of 1.0g is added in above-mentioned salting liquid, stirred 1 hour at 80 DEG C, obtain mixed solution.
4. above-mentioned mixed solution is placed in autoclave, and above-mentioned nickel foam of handling well is put into reaction under high pressure
In kettle, 5 hours are kept the temperature at 200 DEG C.
5. treating autoclave cooled to room temperature, nickel foam is taken out, respectively the ultrasound 1 in deionized water and ethyl alcohol
Hour, it is 4 hours dry at 120 DEG C, you can to obtain nickel foam self-supporting Ni (OH)2。
6. weigh 2.0g sodium hypophosphites adds in above-mentioned nickel foam self-supporting Ni (OH) for phosphorus source2In, under an argon atmosphere with
The heating rate of 5 DEG C/min is warming up to 600 DEG C and is sintered 3 hours, you can obtains nickel foam self-supporting Ni3P materials.
7. by above-mentioned prepared nickel foam self-supporting Ni3P materials are placed 3 hours in 2mol/L sucrose solutions, Ran Hou
It is 4 hours dry at 120 DEG C, 500 DEG C are warming up to the heating rate of 5 DEG C/min under an argon atmosphere and calcined 5 hours, you can obtain
Nickel foam self-supporting Ni3P/C composite materials.
To the nickel foam self-supporting Ni of 2 gained of embodiment3The preparation of P/C composite material cathode and chemical property analysis:
The nickel foam self-supporting Ni that will be prepared3P/C composite materials are cut into a diameter of 1.2cm positive plates, in anaerobism glove box with
Metallic sodium piece is to electrode, is assembled into CR2025 button cells.At 25 DEG C, exist with the multiplying power of 100mA/g and in 500mA/g
200 charge and discharge cycles, nickel foam self-supporting Ni are carried out between 0.01-3.0V3P/C composite materials capacity retention ratio is high, it is shown that
Excellent chemical property.
Embodiment 3
It is 1. 2*4cm nickel foams is ultrasonic in 1.2mol/L sodium hydrate aqueous solutions, absolute ethyl alcohol and deionized water successively
0.7 hour.
2. weighing 6.23g nickel acetates to be dissolved in 20mL deionized waters, it is configured to the salting liquid of a concentration of 1.25mol/L.
3. ten dihydroxy sodium sulfonates of 3.0g are added in above-mentioned salting liquid, stir 1.3 hours, must mix molten at 65 DEG C
Liquid.
4. above-mentioned mixed solution is placed in autoclave, and above-mentioned nickel foam of handling well is put into reaction under high pressure
In kettle, 14.5 hours are kept the temperature at 150 DEG C.
5. treating autoclave cooled to room temperature, nickel foam is taken out, it is ultrasonic in deionized water and ethyl alcohol respectively
It is 0.7 hour, 8 hours dry at 100 DEG C, you can to obtain nickel foam self-supporting Ni (OH)2。
6. weigh 3.0g sodium hypophosphites adds in above-mentioned nickel foam self-supporting Ni (OH) for phosphorus source2In, under an argon atmosphere with
The heating rate of 3.5 DEG C/min is warming up to 450 DEG C and is sintered 6.5 hours, you can obtains nickel foam self-supporting Ni3P materials.
7. by above-mentioned prepared nickel foam self-supporting Ni3P materials place 2 hours in 1.05mol/L starch solutions, so
It is 8 hours dry at 100 DEG C afterwards, 400 DEG C are warming up to the heating rate of 3.5 DEG C/min calcine 8.5 hours under an argon atmosphere,
It can obtain nickel foam self-supporting Ni3P/C composite materials.
To the nickel foam self-supporting Ni of 3 gained of embodiment3The preparation of P/C composite material cathode and chemical property analysis:
The nickel foam self-supporting Ni that will be prepared3P/C composite materials are cut into a diameter of 1.2cm positive plates, in anaerobism glove box with
Metallic sodium piece is to electrode, is assembled into CR2025 button cells.At 25 DEG C, exist with the multiplying power of 100mA/g and in 500mA/g
200 charge and discharge cycles, nickel foam self-supporting Ni are carried out between 0.01-3.0V3P/C composite materials capacity retention ratio is high, it is shown that
Excellent chemical property.
Embodiment 4
It is 1. 2*4cm nickel foams is ultrasonic in 1.5mol/L sodium hydrate aqueous solutions, absolute ethyl alcohol and deionized water successively
0.6 hour.
2. weighing the dissolving of 6.98g nickel nitrates in deionized water, it is configured to the salting liquid of a concentration of 1.2mol/L.
3. the PVP of 3.5g is added in above-mentioned salting liquid, stirred 1 hour at 80 DEG C, obtain mixed solution.
4. above-mentioned mixed solution is placed in autoclave, and above-mentioned nickel foam of handling well is put into reaction under high pressure
In kettle, 20 hours are kept the temperature at 100 DEG C.
5. treating autoclave cooled to room temperature, nickel foam is taken out, respectively the ultrasound 1 in deionized water and ethyl alcohol
Hour, it is 12 hours dry at 120 DEG C, you can to obtain nickel foam self-supporting Ni (OH)2。
6. the sodium hypophosphite for weighing 4.0g adds in above-mentioned nickel foam self-supporting Ni (OH) for phosphorus source2In, under an argon atmosphere
450 DEG C are warming up to the heating rate of 3.5 DEG C/min to be sintered 2 hours, you can obtain nickel foam self-supporting Ni3P materials.
7. by above-mentioned prepared nickel foam self-supporting Ni3P materials place 1 hour in 0.5mol/L tartaric acid solutions, so
Afterwards dry 12 hours at 120 DEG C, 350 DEG C are warming up to the heating rate of 1 DEG C/min under an argon atmosphere and calcine 3 hours, i.e.,
It can obtain nickel foam self-supporting Ni3P/C materials.
To the nickel foam self-supporting Ni of 4 gained of embodiment3The preparation of P/C composite material cathode and chemical property analysis:
The nickel foam self-supporting Ni that will be prepared3P/C composite materials are cut into a diameter of 1.2cm positive plates, in anaerobism glove box with
Metallic sodium piece is to electrode, is assembled into CR2025 button cells.At 25 DEG C, exist with the multiplying power of 100mA/g and in 500mA/g
200 charge and discharge cycles, nickel foam self-supporting Ni are carried out between 0.01-3.0V3P/C composite materials capacity retention ratio is high, it is shown that
Excellent chemical property.
Embodiment 5
It is 1. 2*4cm nickel foams is ultrasonic in 2.0mol/L sodium hydrate aqueous solutions, absolute ethyl alcohol and deionized water successively
0.7 hour.
2. weighing the dissolving of 6.83g nickel sulfates in deionized water, it is configured to the salting liquid of a concentration of 1.3mol/L.
3. the Tween80 of 4.0g is added in above-mentioned salting liquid, stirred 1 hour at 80 DEG C, obtain mixed solution.
4. above-mentioned mixed solution is placed in autoclave, and above-mentioned nickel foam of handling well is placed reaction under high pressure
In kettle, 15 hours are kept the temperature at 120 DEG C.
5. treating that autoclave naturally cools to room temperature, nickel foam is taken out, respectively the ultrasound 1 in deionized water and ethyl alcohol
Hour, it is 12 hours dry at 120 DEG C, you can to obtain nickel foam self-supporting Ni (OH)2。
6. weigh 5.0g sodium hypophosphites adds in above-mentioned nickel foam self-supporting Ni (OH) for phosphorus source2In, under an argon atmosphere with
The heating rate of 5 DEG C/min is warming up to 500 DEG C and is sintered 2 hours, you can obtains nickel foam self-supporting Ni3P materials.
7. by above-mentioned prepared nickel foam self-supporting Ni3P materials are placed in 0.8mol/L citric acid solutions 1 hour,
It is 12 hours dry at 120 DEG C, 350 DEG C are warming up to the heating rate of 1 DEG C/min calcine 3 hours under an argon atmosphere, you can
To nickel foam self-supporting Ni3P/C materials.
To the nickel foam self-supporting Ni of 5 gained of embodiment3The preparation of P/C composite material cathode and chemical property analysis:
The nickel foam self-supporting Ni that will be prepared3P/C composite materials are cut into a diameter of 1.2cm positive plates, in anaerobism glove box with
Metallic sodium piece is to electrode, is assembled into CR2025 button cells.At 25 DEG C, exist with the multiplying power of 100mA/g and in 500mA/g
200 charge and discharge cycles, nickel foam self-supporting Ni are carried out between 0.01-3.0V3P/C composite materials capacity retention ratio is high, it is shown that
Excellent chemical property.
Claims (8)
1. a kind of sodium-ion battery cathode nickel foam self-supporting sheet Ni3The preparation method of P/C composite materials, which is characterized in that
Include the following steps:
1)The ultrasound 0.5-1 in the sodium hydrate aqueous solution of 0.5-2mol/L, absolute ethyl alcohol and deionized water successively by nickel foam
Hour;
2)It weighs nickel salt dissolving in deionized water, is configured to the nickel salt solution of a concentration of 0.5-2mol/L;
3)Surfactant is added in into step 2)In gained nickel salt solution, stir 0.5-1 hours, must mix molten at 50-80 DEG C
Liquid;
4)By step 3)Gained mixed solution is placed in autoclave, and step 1)The nickel foam handled well is put into high pressure
In reaction kettle, 5-24 hours are kept the temperature at 100-200 DEG C;
5)It treats reaction kettle cooled to room temperature, takes out nickel foam, respectively ultrasound 0.5-1 hours in deionized water and ethyl alcohol,
At 80-120 DEG C dry 4 ~ 12 hours to get to nickel foam self-supporting Ni (OH)2;
6)It weighs sodium hypophosphite and adds in step 5 for phosphorus source)Gained nickel foam self-supporting Ni (OH)2In, under an argon atmosphere with 1-5
DEG C/heating rate of min is warming up to 300-600 DEG C of calcining 3-10 hours to get to nickel foam self-supporting Ni3P materials;
7)By step 6)Prepared nickel foam self-supporting Ni3It is small that P materials place 1-3 in 0.1-2 mol/L organic carbon source aqueous solutions
When, it is then 4 ~ 12 hours dry at 80-120 DEG C, 300- is warming up to the heating rate of 1-5 DEG C/min under an argon atmosphere
500 DEG C of calcinings 5-12 hours are to get to nickel foam self-supporting Ni3P/C composite materials.
2. preparation method according to claim 1, which is characterized in that the nickel salt described in step 2) is nickel nitrate, sulfuric acid
One or more of nickel and nickel acetate.
3. preparation method according to claim 1, which is characterized in that the surfactant described in step 3) is six first
One or more of urotropine, PEG, PVP, Span and Tween series, the dosage of surfactant for nickel salt quality 5~
20%。
4. preparation method according to claim 1, which is characterized in that step 3) the surfactant additive amount is 2-
10g。
5. preparation method according to claim 1, which is characterized in that the sodium hypophosphite described in step 6) adds quality and is
0.5-5g。
6. preparation method according to claim 1, which is characterized in that organic carbon source described in step 7) is glucose,
One or more of sucrose, tartaric acid, starch and citric acid.
7. preparation method according to claim 1, which is characterized in that the dosage of the step 7) organic carbon source is nickel salt
The 5~20% of quality.
8. a kind of sodium-ion battery cathode nickel foam self-supporting as made from claim 1-7 any one of them preparation methods
Sheet Ni3P/C composite materials, which is characterized in that the sheet Ni in the composite material3P/C homoepitaxials are in nickel foam, carbon film
It is uniformly coated on Ni3P surfaces, Ni3The thickness of P pieces is 20-100 nanometers, and the content of carbon is 5 ~ 20wt.% in composite material.
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