CN105720236A - Foamed nickel self-supported flake-shaped Ni3P/C composite material for sodium ion battery negative electrode and preparation method for composite material - Google Patents
Foamed nickel self-supported flake-shaped Ni3P/C composite material for sodium ion battery negative electrode and preparation method for composite material Download PDFInfo
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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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- 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 foamed nickel self-supported flake-shaped Ni3P/C composite material for a sodium ion battery negative electrode and a preparation method for the composite material. According to the composite material, the flake-shaped Ni3P is uniformly growing on the foamed nickel; and the Ni3P is uniformly coated with a C film. The preparation method for the composite material comprises the steps of taking a nickel compound as the raw material, and uniformly growing a flake-shaped nickel hydroxide layer on the surface of the nickel compound through a hydrothermal method; then taking sodium hypophosphite as a phosphorus source, and performing thermal insulation at a temperature of 300 DEG C for 2h to prepare the foamed nickel self-supported flake-shaped Ni3P material; and finally, performing carbon coating on the foamed nickel self-supported flake-shaped Ni3P material to obtain the foamed nickel self-supported flake-shaped Ni3P/C composite material. The sodium ion battery prepared from the Ni3P/C composite material prepared by the invention has excellent specific capacity, rate capability and stable cycling performance; and in addition, the preparation method is simple and feasible, wide in raw material resources and suitable for industrial production.
Description
Technical field
The invention belongs to the preparation of energy and material and application, be specifically related to a kind of sodium-ion battery negative pole nickel foam self-supporting lamellar Ni3P/C composite and preparation method thereof.
Background technology
Lithium ion battery, because of advantages such as its energy density are high and has extended cycle life, is widely used in mobile phone, notebook, portable power source, electric automobile and hybrid vehicle etc..But, lithium resource reserves are limited, along with the large-scale application of lithium ion battery, lithium resource shortage and rapid rise of price, will seriously hinder lithium ion battery to develop further.Owing to sodium and lithium belong to same major element, they have similar physics and chemical property, and sodium-ion battery has caused increasing interest in recent years.And relative to lithium resource, sodium resource storage capacity is very big, and abundance, price comparison is cheap so that sodium-ion battery is expected to replace lithium ion battery in future and be widely used in the field such as portable power source and extensive energy storage.Due to Na+Radius bigger so that it is be not easy in layer structure graphite embed and deviate from, the graphite with good embedding lithium ability is not suitable as anode material of lithium-ion battery.Therefore, negative material is the key of sodium-ion battery development.
One replacement scheme of sodium-ion battery negative pole is to adopt black phosphorus, and theoretical discharge capacity when generating sodium phosphide is 2596mAh/g.But, can there is bigger volumetric expansion when moving to phosphorus negative pole in sodium ion, cause that system is unstable.Relative to elemental phosphorous, nickel phosphide (Ni3P) anode material of lithium-ion battery also has very high specific capacity.But, nickel phosphide electronic conductivity is relatively low, and this has a strong impact on its high rate performance.Further, since sodium ion enters Ni3The volumetric expansion caused after P, is also easily caused its structural instability and special capacity fade.Surface modification is considered as be one of effective way overcoming the problems referred to above.Therefore, the present invention is at one layer of nano-level conducting good carbon (C) film of nickel phosphide Surface coating, and this not only can improve the electron conduction of material, and can nickel phosphide volumetric expansion in buffer cycles process, thus improving Ni3The multiplying power of P anode material of lithium-ion battery and stable circulation performance.
Summary of the invention
The present invention provides the sodium-ion battery negative pole nickel foam self-supporting lamellar Ni of a kind of specific capacity height, high rate performance excellence, good cycling stability3P/C composite and preparation method thereof.
Sodium-ion battery negative pole nickel foam self-supporting lamellar Ni of the present invention3The preparation method of P/C composite is divided into three steps: first, utilizes hydro-thermal method to prepare nickel foam self-supporting Ni (OH)2.Then, utilize sodium hypophosphite for phosphorus source by nickel foam self-supporting Ni (OH)2Phosphatization, prepares nickel foam self-supporting Ni3P negative material.Finally, utilize organic carbon source to nickel foam self-supporting Ni3P carries out carbon cladding, prepares nickel foam self-supporting Ni3P/C negative material.In mass fraction: anode material of lithium-ion battery nickel foam self-supporting Ni3In P/C composite, mass fraction shared by carbon film is 5-20%.
The purpose of the present invention is achieved through the following technical solutions.
A kind of sodium-ion battery negative pole nickel foam self-supporting lamellar Ni3The preparation method of P/C composite, comprises the following steps:
1) by nickel foam successively in the sodium hydrate aqueous solution of 0.5-2mol/L, dehydrated alcohol and deionized water for ultrasonic 0.5-1 hour；
2) weigh nickel salt to dissolve in deionized water, be configured to the nickel salt solution that concentration is 0.5-2mol/L；
3) surfactant is added step 2) in gained nickel salt solution, stir 0.5-1 hour at 50-80 DEG C, obtain mixed solution；
4) step 3) gained mixed solution is placed in autoclave, and the nickel foam that step 1) is handled well is put in autoclave, at 100-200 DEG C, be incubated 5-24 hour；
5) question response still naturally cools to room temperature, takes out nickel foam, in deionized water and ethanol ultrasonic 0.5-1 hour respectively, at 80-120 DEG C dry 4 ~ 12 hours, namely obtains nickel foam self-supporting Ni (OH)2；
6) weighing sodium hypophosphite is that phosphorus source adds step 5) gained nickel foam self-supporting Ni (OH)2In, 300-600 DEG C sinters 3-10 hour under an argon atmosphere, can obtain nickel foam self-supporting Ni3P material；
7) by nickel foam self-supporting Ni prepared by step 6)3P material is placed 1-3 hour in 0.1-2mol/L organic carbon source aqueous solution, then dries 4 ~ 12 hours at 80-120 DEG C, calcines 5-12 hour for 300-500 DEG C under an argon atmosphere, can obtain nickel foam self-supporting Ni3P/C composite.
Further, step 2) described in nickel salt be one or more in nickel nitrate, nickel sulfate and nickel acetate.
Further, step 3) described in surfactant be one or more in hexamethylenetetramine, PEG, PVP, Span and Tween series, the consumption of surfactant is the 5～20% of nickel salt quality..
Further, step 3) described surfactant addition is 2-10g.
Further, step 6) described in sodium hypophosphite add quality be 0.5-5g.
Further, step 6) it is be warmed up to 300-600 DEG C with the heating rate of 1-5 DEG C/min to calcine 3-10 hour.
Further, step 7) described in organic carbon source be one or more in glucose, sucrose, tartaric acid, starch and citric acid.
Further, step 7) described organic carbon source consumption is nickel salt quality 5～20%.
Further, step 7) it is be warmed up to 300-500 DEG C with the heating rate of 1-5 DEG C/min to calcine 5-12 hour.
A kind of sodium-ion battery negative pole nickel foam self-supporting lamellar Ni prepared by above-mentioned preparation method3P/C composite, lamellar Ni in this composite3P/C homoepitaxial is in nickel foam, and carbon film is uniformly coated on Ni3P surface, Ni3The thickness of P sheet is 20-100 nanometer, and in composite, the content of carbon is 5 ~ 20wt.%.
Compared with prior art, the invention have the advantages that and technique effect:
1, the nickel foam self-supporting lamellar Ni of the present invention3The battery performance that P/C composite is made is excellent, has high specific capacity, excellent high rate performance and cycle performance.
2, the nickel foam self-supporting lamellar Ni of the present invention3The preparation method simple possible of P/C composite, raw material sources are wide, production suitable for industrialized.
Accompanying drawing explanation
Fig. 1 is the nickel foam self-supporting Ni (OH) that embodiment 1 prepares2Material and nickel foam self-supporting Ni3The XRD figure spectrum of P/C composite.
Fig. 2 is the nickel foam self-supporting Ni (OH) that embodiment 1 prepares2The SEM figure of material.
Fig. 3 is the nickel foam self-supporting Ni that embodiment 1 prepares3The SEM figure of P/C composite.
Fig. 4 is the nickel foam self-supporting Ni that embodiment 1 prepares3P/C is as the first charge-discharge curve of sodium-ion battery negative pole material.
Fig. 5 is the nickel foam self-supporting Ni that embodiment 1 prepares3P/C is as the high rate performance curve of sodium-ion battery negative pole material.
Fig. 6 is the nickel foam self-supporting Ni that embodiment 1 prepares3P/C as sodium-ion battery negative pole material at 100mA g-1The specific volume spirogram of 50 times is circulated under electric current density.
Fig. 7 is the nickel foam self-supporting Ni that embodiment 1 prepares3P/C as sodium-ion battery negative pole material at 500mA g-1The specific volume spirogram of 100 times is circulated under electric current density.
Detailed description of the invention
Following example can be more fully understood that the present invention, but the present invention is not limited to following example.
Embodiment 1
1. by 2*4cm nickel foam is successively in 0.5mol/L sodium hydrate aqueous solution, dehydrated alcohol and deionized water for ultrasonic 0.5 hour.
2. weigh 2.91g nickel nitrate to be dissolved in 20mL deionized water, be configured to the saline solution that concentration is 0.5mol/L.
3. 2.0g hexamethylenetetramine is added in above-mentioned saline solution, stir 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, at 100 DEG C, be incubated 24 hours.
5. treat that autoclave naturally cools to room temperature, take out nickel foam, in deionized water and ethanol ultrasonic 0.5 hour respectively, then at 80 DEG C dry 12 hours, nickel foam self-supporting Ni (OH) can be obtained2。
6. weighing 1.0g sodium hypophosphite is that phosphorus source adds above-mentioned nickel foam self-supporting Ni (OH)2In,It is warmed up to 300 DEG C with the heating rate of 1 DEG C/min under an argon atmosphere to sinter 10 hours, nickel foam self-supporting Ni can be obtained3P material.
7. by above-mentioned prepared nickel foam self-supporting Ni3P material is placed 1 hour in 0.1mol/L glucose solution, then dries 12 hours at 80 DEG C, is warmed up to 300 DEG C with the heating rate of 1 DEG C/min under an argon atmosphere and calcines 12 hours, can obtain nickel foam self-supporting Ni3P/C composite.
The nickel foam self-supporting Ni of the present embodiment gained3The XRD figure spectrum of P/C composite is as it is shown in figure 1, as can be seen from the figure nickel foam self-supporting Ni3P/C composite exists metal simple-substance nickel and two kinds of thing phases of nickel phosphide.The nickel foam self-supporting Ni (OH) that the present embodiment prepares2The SEM of material schemes as shown in Figure 2.The nickel foam self-supporting Ni of the present embodiment gained3The SEM of P/C composite is as it is shown on figure 3, lamellar Ni as seen from Figure 33P/C uniformly gives birth in foam web.
The nickel foam self-supporting Ni that will prepare3It is 1.2cm positive plate that P/C composite is cut into diameter, and using metal lithium sheet as negative pole, polypropylene is barrier film and NaPF6For electrolyte, in the glove box of full argon, assembling obtains CR2032 type button experimental cell.This experimental cell carries out first charge-discharge with the multiplying power of 50mA/g between 0.01-3.0V, and the cyclic curve of gained is as shown in Figure 4.The battery that gained is implemented is carried out high rate performance test, and its high rate performance curve is as shown in Figure 5.The battery implemented by gained is 100mA g in multiplying power respectively-1With 500mA g-1Carrying out 50 and 100 loop tests under electric current density, the cyclic curve of gained is as shown in Figures 6 and 7.
As shown in Figure 5, embodiment 1 gained nickel foam self-supporting Ni3P/C composite negative pole material is at 50mA g-1With 500mA g-1Charge specific capacity respectively 620 and 352mAh/g under electric current density.It will be appreciated from fig. 6 that embodiment 1 gained nickel foam self-supporting Ni3P/C composite negative pole material is at 100mA g-1Under electric current density, initial discharge specific capacity is 501.5mAh/g, and after 50 times circulate, its specific discharge capacity is 440.7mAh/g, and specific capacity conservation rate is 87.9%.As shown in Figure 7, at 500mA g-1Under electric current density, its initial discharge specific capacity is 351.1mAh/g, and after 100 times circulate, its specific discharge capacity is 231.2mAh/g, and specific capacity conservation rate is about 65.9%.By result above it can be seen that gained is used as sodium-ion battery negative pole nickel foam self-supporting Ni3P/C composite has the specific capacity of excellence, high rate performance and stable circulation performance.
Embodiment 2
1. by 2*4cm nickel foam successively in 2mol/L sodium hydrate aqueous solution, dehydrated alcohol and deionized water for ultrasonic 1 hour.
2. weighing 10.52g nickel sulfate to be dissolved in 20mL deionized water, being configured to concentration is 2mol/L saline solution.
3. the PEG of 1.0g is added in above-mentioned saline solution, stir 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 in autoclave, at 200 DEG C, be incubated 5 hours.
5. treat that autoclave naturally cools to room temperature, take out nickel foam, in deionized water and ethanol ultrasonic 1 hour respectively, at 120 DEG C dry 4 hours, nickel foam self-supporting Ni (OH) can be obtained2。
6. weighing 2.0g sodium hypophosphite is that phosphorus source adds above-mentioned nickel foam self-supporting Ni (OH)2In, it is warmed up to 600 DEG C with the heating rate of 5 DEG C/min under an argon atmosphere and sinters 3 hours, nickel foam self-supporting Ni can be obtained3P material.
7. by above-mentioned prepared nickel foam self-supporting Ni3P material is placed 3 hours in 2mol/L sucrose solution, then dries 4 hours at 120 DEG C, is warmed up to 500 DEG C with the heating rate of 5 DEG C/min under an argon atmosphere and calcines 5 hours, can obtain nickel foam self-supporting Ni3P/C composite.
Nickel foam self-supporting Ni to embodiment 2 gained3The preparation of P/C composite negative pole and chemical property analysis: the nickel foam self-supporting Ni that will prepare3It is 1.2cm positive plate that P/C composite is cut into diameter, with metallic sodium sheet for electrode, being assembled into CR2025 button cell in anaerobism glove box.At 25 DEG C, between 0.01-3.0V, carry out 200 charge and discharge cycles, nickel foam self-supporting Ni with the multiplying power of 100mA/g with at 500mA/g3P/C composite capability retention is high, it is shown that excellent chemical property.
Embodiment 3
1. by 2*4cm nickel foam successively in 1.2mol/L sodium hydrate aqueous solution, dehydrated alcohol and deionized water for ultrasonic 0.7 hour.
2. weigh 6.23g nickel acetate to be dissolved in 20mL deionized water, be configured to the saline solution that concentration is 1.25mol/L.
3. 3.0g ten dihydroxy sodium sulfonate is added in above-mentioned saline solution, stir 1.3 hours at 65 DEG C, obtain mixed solution.
4. above-mentioned mixed solution is placed in autoclave, and above-mentioned nickel foam of handling well is put in autoclave, at 150 DEG C, be incubated 14.5 hours.
5. treat that autoclave naturally cools to room temperature, take out nickel foam, in deionized water and ethanol ultrasonic 0.7 hour respectively, at 100 DEG C dry 8 hours, nickel foam self-supporting Ni (OH) can be obtained2。
6. weighing 3.0g sodium hypophosphite is that phosphorus source adds above-mentioned nickel foam self-supporting Ni (OH)2In, it is warmed up to 450 DEG C with the heating rate of 3.5 DEG C/min under an argon atmosphere and sinters 6.5 hours, nickel foam self-supporting Ni can be obtained3P material.
7. by above-mentioned prepared nickel foam self-supporting Ni3P material is placed 2 hours in 1.05mol/L starch solution, then dries 8 hours at 100 DEG C, is warmed up to 400 DEG C with the heating rate of 3.5 DEG C/min under an argon atmosphere and calcines 8.5 hours, can obtain nickel foam self-supporting Ni3P/C composite.
Nickel foam self-supporting Ni to embodiment 3 gained3The preparation of P/C composite negative pole and chemical property analysis: the nickel foam self-supporting Ni that will prepare3It is 1.2cm positive plate that P/C composite is cut into diameter, with metallic sodium sheet for electrode, being assembled into CR2025 button cell in anaerobism glove box.At 25 DEG C, between 0.01-3.0V, carry out 200 charge and discharge cycles, nickel foam self-supporting Ni with the multiplying power of 100mA/g with at 500mA/g3P/C composite capability retention is high, it is shown that excellent chemical property.
Embodiment 4
1. by 2*4cm nickel foam successively in 1.5mol/L sodium hydrate aqueous solution, dehydrated alcohol and deionized water for ultrasonic 0.6 hour.
2. weigh 6.98g nickel nitrate to dissolve in deionized water, be configured to the saline solution that concentration is 1.2mol/L.
3. the PVP of 3.5g is added in above-mentioned saline solution, stir 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 in autoclave, at 100 DEG C, be incubated 20 hours.
5. treat that autoclave naturally cools to room temperature, take out nickel foam, in deionized water and ethanol ultrasonic 1 hour respectively, at 120 DEG C dry 12 hours, nickel foam self-supporting Ni (OH) can be obtained2。
6. the sodium hypophosphite weighing 4.0g is that phosphorus source adds above-mentioned nickel foam self-supporting Ni (OH)2In, it is warmed up to 450 DEG C with the heating rate of 3.5 DEG C/min under an argon atmosphere and sinters 2 hours, nickel foam self-supporting Ni can be obtained3P material.
7. by above-mentioned prepared nickel foam self-supporting Ni3P material is placed 1 hour in 0.5mol/L tartaric acid solution, then dries 12 hours at 120 DEG C, is warmed up to 350 DEG C with the heating rate of 1 DEG C/min under an argon atmosphere and calcines 3 hours, can obtain nickel foam self-supporting Ni3P/C material.
Nickel foam self-supporting Ni to embodiment 4 gained3The preparation of P/C composite negative pole and chemical property analysis: the nickel foam self-supporting Ni that will prepare3It is 1.2cm positive plate that P/C composite is cut into diameter, with metallic sodium sheet for electrode, being assembled into CR2025 button cell in anaerobism glove box.At 25 DEG C, between 0.01-3.0V, carry out 200 charge and discharge cycles, nickel foam self-supporting Ni with the multiplying power of 100mA/g with at 500mA/g3P/C composite capability retention is high, it is shown that excellent chemical property.
Embodiment 5
1. by 2*4cm nickel foam successively in 2.0mol/L sodium hydrate aqueous solution, dehydrated alcohol and deionized water for ultrasonic 0.7 hour.
2. weigh 6.83g nickel sulfate to dissolve in deionized water, be configured to the saline solution that concentration is 1.3mol/L.
3. the Tween80 of 4.0g is added in above-mentioned saline solution, stir 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 in autoclave, at 120 DEG C, be incubated 15 hours.
5. treat that autoclave naturally cools to room temperature, take out nickel foam, in deionized water and ethanol ultrasonic 1 hour respectively, at 120 DEG C dry 12 hours, nickel foam self-supporting Ni (OH) can be obtained2。
6. weighing 5.0g sodium hypophosphite is that phosphorus source adds above-mentioned nickel foam self-supporting Ni (OH)2In, it is warmed up to 500 DEG C with the heating rate of 5 DEG C/min under an argon atmosphere and sinters 2 hours, nickel foam self-supporting Ni can be obtained3P material.
7. by above-mentioned prepared nickel foam self-supporting Ni3P material is placed in 0.8mol/L citric acid solution 1 hour, dries 12 hours at 120 DEG C, is warmed up to 350 DEG C with the heating rate of 1 DEG C/min under an argon atmosphere and calcines 3 hours, can obtain nickel foam self-supporting Ni3P/C material.
Nickel foam self-supporting Ni to embodiment 5 gained3The preparation of P/C composite negative pole and chemical property analysis: the nickel foam self-supporting Ni that will prepare3It is 1.2cm positive plate that P/C composite is cut into diameter, with metallic sodium sheet for electrode, being assembled into CR2025 button cell in anaerobism glove box.At 25 DEG C, between 0.01-3.0V, carry out 200 charge and discharge cycles, nickel foam self-supporting Ni with the multiplying power of 100mA/g with at 500mA/g3P/C composite capability retention is high, it is shown that excellent chemical property.
Claims (10)
1. a sodium-ion battery negative pole nickel foam self-supporting lamellar Ni3The preparation method of P/C composite, it is characterised in that comprise the following steps:
1) by nickel foam successively in the sodium hydrate aqueous solution of 0.5-2mol/L, dehydrated alcohol and deionized water for ultrasonic 0.5-1 hour；
2) weigh nickel salt to dissolve in deionized water, be configured to the nickel salt solution that concentration is 0.5-2mol/L；
3) surfactant is added step 2) in gained nickel salt solution, stir 0.5-1 hour at 50-80 DEG C, obtain mixed solution；
4) step 3) gained mixed solution is placed in autoclave, and the nickel foam that step 1) is handled well is put in autoclave, at 100-200 DEG C, be incubated 5-24 hour；
5) question response still naturally cools to room temperature, takes out nickel foam, in deionized water and ethanol ultrasonic 0.5-1 hour respectively, at 80-120 DEG C dry 4 ~ 12 hours, namely obtains nickel foam self-supporting Ni (OH)2；
6) weighing sodium hypophosphite is that phosphorus source adds step 5) gained nickel foam self-supporting Ni (OH)2In, 300-600 DEG C sinters 3-10 hour under an argon atmosphere, namely obtains nickel foam self-supporting Ni3P material；
7) by nickel foam self-supporting Ni prepared by step 6)3P material is placed 1-3 hour in 0.1-2mol/L organic carbon source aqueous solution, then dries 4 ~ 12 hours at 80-120 DEG C, calcines 5-12 hour for 300-500 DEG C under an argon atmosphere, namely obtains nickel foam self-supporting Ni3P/C composite.
2. preparation method according to claim 1, it is characterised in that step 2) described in nickel salt be one or more in nickel nitrate, nickel sulfate and nickel acetate.
3. preparation method according to claim 1, it is characterised in that step 3) described in surfactant be one or more in hexamethylenetetramine, PEG, PVP, Span and Tween series, the consumption of surfactant is the 5～20% of nickel salt quality.
4. preparation method according to claim 1, it is characterised in that step 3) described surfactant addition is 2-10g.
5. preparation method according to claim 1, it is characterised in that step 6) described in sodium hypophosphite add quality be 0.5-5g.
6. preparation method according to claim 1, it is characterised in that step 6) it is be warmed up to 300-600 DEG C with the heating rate of 1-5 DEG C/min to calcine 3-10 hour.
7. preparation method according to claim 1, it is characterised in that step 7) described in organic carbon source be one or more in glucose, sucrose, tartaric acid, starch and citric acid.
8. preparation method according to claim 1, it is characterised in that step 7) described organic carbon source consumption is nickel salt quality 5～20%.
9. preparation method according to claim 1, it is characterised in that step 7) it is be warmed up to 300-500 DEG C with the heating rate of 1-5 DEG C/min to calcine 5-12 hour.
10. a kind of sodium-ion battery negative pole nickel foam self-supporting lamellar Ni that the preparation method described in any one of claim 1-9 prepares3P/C composite, it is characterised in that lamellar Ni in this composite3P/C homoepitaxial is in nickel foam, and carbon film is uniformly coated on Ni3P surface, Ni3The thickness of P sheet is 20-100 nanometer, and in composite, the content of carbon is 5 ~ 20wt.%.
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