CN108493426A - A kind of preparation method of carbon coating nickel phosphide composite material nanometer particle and its application in preparing sodium-ion battery - Google Patents
A kind of preparation method of carbon coating nickel phosphide composite material nanometer particle and its application in preparing sodium-ion battery Download PDFInfo
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- CN108493426A CN108493426A CN201810333563.0A CN201810333563A CN108493426A CN 108493426 A CN108493426 A CN 108493426A CN 201810333563 A CN201810333563 A CN 201810333563A CN 108493426 A CN108493426 A CN 108493426A
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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
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- 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
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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
- H01M4/58—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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y02E60/10—Energy storage using batteries
Abstract
A kind of preparation method of carbon coating nickel phosphide composite material nanometer particle and its application in preparing sodium-ion battery, are related to a kind of preparation and application of carbon coating nickel phosphide composite material nanometer particle.Purpose is to solve Ni2The low problem of the cycle life of the sodium-ion battery that P is prepared as anode material of lithium-ion battery.Preparation method：It is raw material by glycerine and Nickelous nitrate hexahydrate, isopropanol is solvent, hydro-thermal reaction obtains glyceric acid nickel, then it is carbon source to utilize glucose, glyceric acid nickel and glucose obtain carbon coating glyceric acid nickel composite material powder through hydro-thermal reaction, and carbon coating glyceric acid nickel composite material powder is using thermal decomposition and phosphatization.There is sodium-ion battery prepared by nano particle of the present invention high rate charge-discharge characteristic and cyclical stability, carbon coating can prevent negative material structural damage and the expansion of volume, have the invertibity of stable charge and discharge.The present invention is suitable for preparing carbon coating nickel phosphide composite material nanometer particle and sodium-ion battery.
Description
Technical field
The invention belongs to electrode material preparing technical fields, and in particular to a kind of carbon coating nickel phosphide composite material nanometer
The preparation method and application of grain.
Background technology
For portable electronic device, electric vehicle and electric network etc., high performance rechargeable battery right and wrong are developed
It is often important.For battery cathode, the theoretical storage sodium capacity of graphite cell cathode is 31mAh/g, far can not be met
Demand.This promotes researchers to having more height ratio capacity, compared with the searching of long circulation life electrode material.
Metal phosphide (Ni2P) have many advantages, such as higher theoretical specific capacity and rich reserves, it is considered to be it is most potential and
It can be in the following electrode material for being applied to high-energy density or power type sodium-ion battery.However Ni2There is also essence to lack by P
Fall into, be still unable to get at present can using practical application, using metal phosphide as the sodium-ion battery of cathode, main cause is：
Ni2During the repeatedly embedded and abjection of Na volume expansion, Ni after expansion can occur for P2P dusting and reunion, make Ni2P and afflux
Body loses electrical contact；Ni2P as electric conductivity existing for anode material of lithium-ion battery it is poor and reaction invertibity reduce it is too fast
Problem；Ni2P is low as the cycle life of sodium-ion battery prepared by cathode, passes through under conditions of current density is 50mA/g
After 100 discharge and recharge reactions, Ni2The cycle life of sodium-ion battery prepared by P cathode is only 124.6mAh/g.
Invention content
The present invention is in order to solve existing Ni2The cycle longevity for the sodium-ion battery that P is prepared as anode material of lithium-ion battery
Low problem is ordered, propose a kind of preparation method of carbon coating nickel phosphide composite material nanometer particle and its is preparing sodium-ion battery
In application.
The preparation method of carbon coating nickel phosphide composite material nanometer particle of the present invention carries out according to the following steps：
One, Nickelous nitrate hexahydrate and glycerine are dispersed in isopropanol, are then transferred into water heating kettle and carry out hydro-thermal reaction,
Powdered reaction product is obtained after hydro-thermal reaction, with ethyl alcohol washing powder shape reaction product 3~5 times, after collecting washing
Powdered reaction product is simultaneously dried in vacuo, and glyceric acid nickel by powder is obtained；The glyceric acid nickel by powder is in light green color；
The quality of the Nickelous nitrate hexahydrate and the volume ratio of isopropanol are (0.1g~0.4g)：52.5ml；
The volume ratio of the glycerine and isopropanol is (6.5mL~8.5mL):52.5mL；
The vacuum drying temperature is 60~80 DEG C, and the time is 10~13h；
The hydrothermal temperature is 160~200 DEG C, and the hydro-thermal reaction time is 8~13h；
Two, glyceric acid nickel by powder and glucose are dissolved in deionized water, are then transferred into water heating kettle, 160~
10~12h is reacted at 180 DEG C, obtains carbon coating glyceric acid nickel composite material powder；
The quality of the glyceric acid nickel by powder and glucose is (0.07g~0.1g):0.45g；
The quality of the glyceric acid nickel by powder and the volume ratio of deionized water are (0.07g~0.1g):30mL；
Three, carbon coating glyceric acid nickel composite material powder is dried in vacuo, the powdered reaction product after drying is carried out
Calcining, obtains carbon-coating nickel composite material nanometer particle；The carbon-coating nickel composite material nanometer particle nickel particle is black powder
End；
The vacuum drying temperature is 60~80 DEG C, and the time is 10~13h；
The calcine technology is：Calcining carries out in tube furnace, and calcination atmosphere is nitrogen atmosphere, and calcination temperature is 300~
500 DEG C, calcination time is 2~4h；
Four, the carbon-coating nickel composite material nanometer particle for obtaining step 3 carries out phosphorating treatment, obtains carbon coating phosphatization
Nickel composite material nano particle；
The parkerized technique is：Carbon-coating nickel composite material nanometer particle and sodium hypophosphite are respectively placed in quartz
Boat both ends, and quartz boat is placed in N2In the tube furnace of atmosphere, by one end for being placed with sodium hypophosphite of quartz boat towards tubular type
The N of stove2Then upstream end is calcined, calcination temperature is 300~500 DEG C, and calcination time is 2~4h；The carbon-coating nickel is multiple
The molar ratio (9.5~10.5) of condensation material nano particle and sodium hypophosphite：50.
The carbon-coating nickel composite material nanometer particle prepared using the above method as the negative material of sodium-ion battery,
Prepare the application in sodium lithium ion battery；
Negative material of the carbon-coating nickel composite material nanometer particle as sodium-ion battery, is preparing sodium lithium-ion electric
Application in pond carries out according to the following steps：
One, carbon coating nickel phosphide composite material nanometer particle, acetylene black and polytetrafluoroethyl-ne dilute emulsion are uniformly mixed, are obtained
Slurry；The mass ratio of the carbon coating nickel phosphide composite material nanometer particle, acetylene black and polytetrafluoroethyl-ne dilute emulsion be (40~
70):(30~50):20；
Two, slurry is equably brushed to one of the nickel foam weighed in a diameter of 10~14mm with hairbrush
On surface, it is then 75~85 DEG C of 9~13h of vacuum drying in temperature, obtains cathode pole piece blank；
Three, cathode pole piece blank is placed on tablet press machine and carries out tabletting, obtain cathode pole piece；
Pressure when the progress tabletting is 15~20MPa, and the residence time is 8~10s；
Four, in argon gas atmosphere glove box, by from top to bottom the sequence of cathode pole piece, diaphragm and sodium positive plate is stacked simultaneously
It is placed in battery case, electrolyte is then added dropwise into battery case, battery case buckle closure and sealing are finally placed under room temperature
7.5~8.5h is stood, sodium lithium ion battery is obtained；Wherein, button cell is placed under room temperature the purpose for standing 7.5~8.5h is
Sodium lithium ion battery is set to be activated；
The diaphragm is mesoporous polypropylene screen；The battery case is CR2025 button cell shells；
The preparation method of the electrolyte is：By the NaClO of a concentration of 1M4Solution is dissolved in propene carbonate and carbonic acid two
In the mixed solution of ethyl ester, the fluorinated ethylene carbonate that mass fraction is 5~8% is then added, that is, is completed；The propylene carbonate
The volume ratio of ester and diethyl carbonate is 1：(1~3)；NaClO4The volume ratio of solution and diethyl carbonate is 1：(1~3)；
Reaction principle of the present invention is：
The present invention is first raw material by glycerine and Nickelous nitrate hexahydrate, and isopropanol is solvent, carries out hydro-thermal reaction, obtains sweet
Then oleic acid nickel utilizes glucose to obtain carbon coating glyceric acid nickel by hydro-thermal reaction for carbon source, glyceric acid nickel and glucose and answers
Condensation material powder, carbon coating glyceric acid nickel composite material powder is using having thermally decomposed to yield carbon-coating nickel composite material nanometer
Grain, carbon-coating nickel composite material nanometer particle finally obtain carbon coating nickel phosphide composite material nanometer particle by phosphatization.
The present invention has the beneficial effect that：
1, the raw material sources that preparation method of the present invention uses are abundant, and method is easy to operate, pollution-free, are suitable for industrial metaplasia
Production, it is of low cost；
2, carbon coating nickel phosphide composite material nanometer particle prepared by the present invention can be used as anode material of lithium-ion battery,
And possesses high rate charge-discharge characteristic and cyclical stability, commercialization sode cell negative material can be used as；
3, carbon coating nickel phosphide composite material nanometer particle prepared by the present invention is prepared as anode material of lithium-ion battery
Sodium-ion battery in, current density be 50mA/g under before two circle sodium-ion batteries specific discharge capacity be respectively
714.6mAh/g, 569.5mAh/g, and by 100 times cycle after sodium-ion battery put specific capacitance still keep 254mAh/g with
On, there is higher cycle life；
4, in carbon coating nickel phosphide composite material nanometer particle prepared by the present invention, the surface coated carbon of nickel phosphide is without fixed
Type carbon can improve the electric conductivity of nickel phosphide, widen ionic transport passages, prevent electrolyte and Ni2Directly contact causes to bear P
The destruction of pole material structure and the expansion of volume, and the surface coated carbon of nickel phosphide is relatively stable and external pressure is resisted in enough formation
Elastic layer, can occasionally prevent Na during lithium deintercalation because of Ni2Ni caused by the structure and volume change of P2P electrode dusting
And Ni2P reunites, so as to improve Ni2The storage sodium performance of P；In addition nickel phosphide can prevent electricity as electrode material by after carbon coating
Side reaction occurs for pole and electrolyte, the product of side reaction can be avoided to be deposited in electrode material surface, and then from avoiding hindering ion
Diffusion；
5, carbon coating nickel phosphide composite material nanometer particle prepared by the present invention is nanostructure, can not only pass through shortening
Diffusion length can increase the contact area of active material and electrolyte to improve electrolyte to promote the transport of ion
Wetability；
6, in carbon coating nickel phosphide composite material nanometer particle prepared by the present invention, nickel phosphide can be prevented phosphorus after carbon coating
Change nickel and side reaction occurs for electrolyte, so during the insertion lithium of Na and de- lithium, nickel phosphide is protected by carbon, chemical constitution
Substantially do not change, thus the electrode of carbon coating nickel phosphide composite material nanometer particle preparation there are stable charge and discharge can
It is too fast to solve the problems, such as that reaction invertibity reduces for inverse property.
Description of the drawings：
Fig. 1 is the XRD spectrum of nickel phosphide and carbon coating nickel phosphide composite material nanometer particle prepared by embodiment 1,1 in figure
Corresponding carbon coating nickel phosphide composite material nanometer particle, 2 correspond to nickel phosphide；
Fig. 2 is Ni prepared by comparative example 12The SEM of P schemes；
Fig. 3 is the SEM figures of carbon coating nickel phosphide composite material nanometer particle prepared by embodiment 1；
Fig. 4 is Ni prepared by comparative example 12The TEM of P schemes；
Fig. 5 is the TEM figures of carbon coating nickel phosphide composite material nanometer particle prepared by embodiment 1；
Fig. 6 is in embodiment 1, is that the sodium ion for preparing of battery cathode is electric using carbon coating nickel phosphide composite material nanometer particle
The preceding two circles charging and discharging curve figure in pond；Curve 1 is the charging and discharging curve of the 1st circle in figure, and curve 2 is the charging and discharging curve of the 2nd circle；
Fig. 7 is with Ni2Sodium-ion battery prepared by P cathode and carbon coating nickel phosphide composite material nanometer particle battery cathode
High rate performance curve graph under different current densities；Curve 1 is carbon coating nickel phosphide composite material nanometer particle battery cathode
Discharge-rate performance curve under the sodium-ion battery difference current density of preparation；Curve 2 is nickel phosphide composite material nanometer
Discharge-rate performance curve under sodium-ion battery difference current density prepared by grain battery cathode；
Fig. 8 is Ni2Sodium-ion battery prepared by P cathode and carbon coating nickel phosphide composite material nanometer particle battery cathode
Cycle performance figure；Curve 1 is corresponded to using carbon coating nickel phosphide composite material nanometer particle as the cyclicity of cell negative electrode material in figure
Can, curve 2 corresponds to the cycle performance that nickel phosphide composite material nanometer particle is cell negative electrode material.
Specific implementation mode
Technical solution of the present invention is not limited to act specific implementation mode set forth below, further includes between each specific implementation mode
Arbitrary reasonable combination.
Specific implementation mode one：The preparation method of present embodiment carbon coating nickel phosphide composite material nanometer particle is by following
Step carries out：
One, Nickelous nitrate hexahydrate and glycerine are dispersed in isopropanol, are then transferred into water heating kettle and carry out hydro-thermal reaction,
Powdered reaction product is obtained after hydro-thermal reaction, with ethyl alcohol washing powder shape reaction product 3~5 times, after collecting washing
Powdered reaction product is simultaneously dried in vacuo, and glyceric acid nickel by powder is obtained；
The quality of the Nickelous nitrate hexahydrate and the volume ratio of isopropanol are (0.1g~0.4g)：52.5ml；
The volume ratio of the glycerine and isopropanol is (6.5mL~8.5mL):52.5mL；
Two, glyceric acid nickel by powder and glucose are dissolved in deionized water, are then transferred into water heating kettle, 160~
10~12h is reacted at 180 DEG C, obtains carbon coating glyceric acid nickel composite material powder；
The quality of the glyceric acid nickel by powder and glucose is (0.07g~0.1g):0.45g；
The quality of the glyceric acid nickel by powder and the volume ratio of deionized water are (0.07g~0.1g):30mL；
Three, carbon coating glyceric acid nickel composite material powder is dried in vacuo, the powdered reaction product after drying is carried out
Calcining, obtains carbon-coating nickel composite material nanometer particle；
Four, the carbon-coating nickel composite material nanometer particle for obtaining step 3 carries out phosphorating treatment, obtains carbon coating phosphatization
Nickel composite material nano particle.
Present embodiment has following advantageous effect：
1, the raw material sources that present embodiment preparation method uses are abundant, and method is easy to operate, pollution-free, are suitable for industry
Metaplasia is produced, of low cost；
2, carbon coating nickel phosphide composite material nanometer particle prepared by present embodiment can be used as sodium-ion battery cathode
Material, and possess high rate charge-discharge characteristic and cyclical stability, commercialization sode cell negative material can be used as；
3, carbon coating nickel phosphide composite material nanometer particle prepared by present embodiment is as anode material of lithium-ion battery
In the sodium-ion battery of preparation, the specific discharge capacity of two circle sodium-ion batteries is respectively before being under 50mA/g in current density
714.6mAh/g, 569.5mAh/g, and by 100 times cycle after sodium-ion battery put specific capacitance still keep 254mAh/g with
On, there is higher cycle life；
4, in carbon coating nickel phosphide composite material nanometer particle prepared by present embodiment, the surface coated carbon of nickel phosphide is
Agraphitic carbon can improve the electric conductivity of nickel phosphide, widen ionic transport passages, prevent electrolyte and Ni2P directly lead by contact
The expansion of negative material structural damage and volume is caused, and the surface coated carbon of nickel phosphide is relatively stable and enough is formationed is resisted outside
The elastic layer of pressure can occasionally prevent Na during lithium deintercalation because of Ni2Ni caused by the structure and volume change of P2P electrode
Dusting and Ni2P reunites, so as to improve Ni2The storage sodium performance of P；In addition nickel phosphide can be hindered as electrode material by after carbon coating
Only side reaction occurs for electrode and electrolyte, the product of side reaction can be avoided to be deposited in electrode material surface, and then from avoiding hindering
The diffusion of ion；
5, carbon coating nickel phosphide composite material nanometer particle prepared by present embodiment is nanostructure, can not only be passed through
Shorten diffusion length to promote the transport of ion, and the contact area of active material and electrolyte can be increased to improve electricity
Solve liquid wetability；
6, in carbon coating nickel phosphide composite material nanometer particle prepared by present embodiment, nickel phosphide can be hindered after carbon coating
Only side reaction occurs for nickel phosphide and electrolyte, so during the insertion lithium of Na and de- lithium, nickel phosphide is protected by carbon, chemistry
Structure does not change substantially, so the electrode of carbon coating nickel phosphide composite material nanometer particle preparation has stable charge and discharge
Invertibity, solve the problems, such as reaction invertibity reduce it is too fast.
Specific implementation mode two：The present embodiment is different from the first embodiment in that：It is dried in vacuo described in step 1
Temperature be 60~80 DEG C, the time be 10~13h.Other steps and parameter are same as the specific embodiment one.
Specific implementation mode three：The present embodiment is different from the first and the second embodiment in that：Hydro-thermal described in step 1
Reaction temperature is 160~200 DEG C, and the hydro-thermal reaction time is 8~13h.Other steps and parameter and specific implementation mode one or two
It is identical.
Specific implementation mode four：Unlike one of present embodiment and specific implementation mode one to three：Described in step 3
Vacuum drying temperature is 60~80 DEG C, and the time is 10~13h.Other steps and one of parameter and specific implementation mode one to three
It is identical.
Specific implementation mode five：Unlike one of present embodiment and specific implementation mode one to four：Described in step 3
Calcine technology is：Calcining carries out in tube furnace, and calcination atmosphere is nitrogen atmosphere, and calcination temperature is 300~500 DEG C, when calcining
Between be 2~4h.Other steps and parameter are identical as one of specific implementation mode one to four.
Specific implementation mode six：Unlike one of present embodiment and specific implementation mode one to five：Described in step 4
Parkerized technique is：
Carbon-coating nickel composite material nanometer particle and sodium hypophosphite are respectively placed in quartz boat both ends, and quartz boat is placed in
N2In the tube furnace of atmosphere, by one end for being placed with sodium hypophosphite of quartz boat towards the N of tube furnace2Then upstream end is forged
It burns, calcination temperature is 300~500 DEG C, and calcination time is 2~4h；The carbon-coating nickel composite material nanometer particle and hypophosphorous acid
The molar ratio (9.5~10.5) of sodium：50.Other steps and parameter are identical as one of specific implementation mode one to five.
Specific implementation mode seven：Cathode of the present embodiment carbon-coating nickel composite material nanometer particle as sodium-ion battery
Material, the application in preparing sodium lithium ion battery.
Present embodiment has following advantageous effect：
1, carbon coating nickel phosphide composite material nanometer particle prepared by present embodiment is as anode material of lithium-ion battery
In the sodium-ion battery of preparation, the specific discharge capacity of two circle sodium-ion batteries is respectively before being under 50mA/g in current density
714.6mAh/g, 569.5mAh/g, and by 100 times cycle after sodium-ion battery put specific capacitance still keep 254mAh/g with
On, there is higher cycle life；
2, present embodiment carbon coating nickel phosphide composite material nanometer particle is nanostructure, can not only be expanded by shortening
Distance is dissipated to promote the transport of ion, and can increase the contact area of active material and electrolyte to improve electrolyte profit
It is moist；
3, in present embodiment carbon coating nickel phosphide composite material nanometer particle, nickel phosphide can be prevented phosphatization after carbon coating
Side reaction occurs for nickel and electrolyte, so during the insertion lithium of Na and de- lithium, nickel phosphide is protected by carbon, chemical constitution base
This does not change, so the electrode of carbon coating nickel phosphide composite material nanometer particle preparation has the reversible of stable charge and discharge
Property, it is too fast to solve the problems, such as that reaction invertibity reduces.
Specific implementation mode eight：Present embodiment is unlike specific implementation mode seven：Utilize carbon-coating nickel composite wood
The method that material nano particle prepares sodium lithium ion battery as the negative material of sodium-ion battery carries out according to the following steps：
One, carbon coating nickel phosphide composite material nanometer particle, acetylene black and polytetrafluoroethyl-ne dilute emulsion are uniformly mixed, are obtained
Slurry；
The mass ratio of the carbon coating nickel phosphide composite material nanometer particle, acetylene black and polytetrafluoroethyl-ne dilute emulsion is (40
~70):(30~50):20；
Two, slurry is equably brushed to one of the nickel foam weighed in a diameter of 10~14mm with hairbrush
On surface, it is then 75~85 DEG C of 9~13h of vacuum drying in temperature, obtains cathode pole piece blank；
Three, cathode pole piece blank is placed on tablet press machine and carries out tabletting, obtain cathode pole piece；
Four, in argon gas atmosphere glove box, by from top to bottom the sequence of cathode pole piece, diaphragm and sodium positive plate is stacked simultaneously
It is placed in battery case, electrolyte is then added dropwise into battery case, battery case buckle closure and sealing are finally placed under room temperature
7.5~8.5h is stood, sodium lithium ion battery is obtained.Other steps and parameter are identical as specific implementation mode seven.
Specific implementation mode nine：Present embodiment is unlike specific implementation mode eight：Tabletting is carried out described in step 3
When pressure be 15~20MPa, the residence time be 8~10s.Other steps and parameter are identical as specific implementation mode eight.
Specific implementation mode ten：Present embodiment is unlike specific implementation mode eight or nine：Diaphragm described in step 4
For mesoporous polypropylene screen；The battery case is CR2025 button cell shells.Other steps and parameter and specific implementation mode eight
Or nine is identical.
Beneficial effects of the present invention are verified using following embodiment：
Embodiment 1：
The preparation method of the present embodiment carbon coating nickel phosphide composite material nanometer particle carries out according to the following steps：
One, Nickelous nitrate hexahydrate and glycerine are dispersed in isopropanol, are then transferred into water heating kettle and carry out hydro-thermal reaction,
Powdered reaction product is obtained after hydro-thermal reaction, with ethyl alcohol washing powder shape reaction product 4 times, collects the powder after washing
Shape reaction product is simultaneously dried in vacuo, and glyceric acid nickel by powder is obtained；The glyceric acid nickel by powder is in light green color；
The quality of the Nickelous nitrate hexahydrate and the volume ratio of isopropanol are 0.1g：52.5ml；
The volume ratio of the glycerine and isopropanol is 7.5:52.5mL；
The vacuum drying temperature is 80 DEG C, time 12h；
The hydrothermal temperature is 180 DEG C, the hydro-thermal reaction time 12h；
Two, glyceric acid nickel by powder and glucose are dissolved in deionized water, are then transferred into water heating kettle, at 160 DEG C
Lower reaction 12h obtains carbon coating glyceric acid nickel composite material powder；
The quality of the glyceric acid nickel by powder and glucose is 0.09g:0.45g；
The quality of the glyceric acid nickel by powder and the volume ratio of deionized water are 0.09g:30mL；
Three, carbon coating glyceric acid nickel composite material powder is dried in vacuo, the powdered reaction product after drying is carried out
Calcining, obtains carbon-coating nickel composite material nanometer particle；The carbon-coating nickel composite material nanometer particle nickel particle is black powder
End；
The vacuum drying temperature is 80 DEG C, time 12h；
The calcine technology is：Calcining carries out in tube furnace, and calcination atmosphere is nitrogen atmosphere, and calcination temperature is 400 DEG C,
Calcination time is 3h；
Four, the carbon-coating nickel composite material nanometer particle for obtaining step 3 carries out phosphorating treatment, obtains carbon coating phosphatization
Nickel composite material nano particle；
The parkerized technique is：Carbon-coating nickel composite material nanometer particle and sodium hypophosphite are respectively placed in quartz
Boat both ends, and quartz boat is placed in N2In the tube furnace of atmosphere, by one end for being placed with sodium hypophosphite of quartz boat towards tubular type
The N of stove2Then upstream end is calcined, calcination temperature is 300 DEG C, calcination time 3h；The carbon-coating nickel composite material is received
Rice grain and the molar ratio of sodium hypophosphite 10：50.
Negative material of the carbon-coating nickel composite material nanometer particle as sodium-ion battery, is preparing sodium lithium-ion electric
Application in pond carries out according to the following steps：
One, carbon coating nickel phosphide composite material nanometer particle, acetylene black and polytetrafluoroethyl-ne dilute emulsion are uniformly mixed, are obtained
Slurry；The mass ratio of the carbon coating nickel phosphide composite material nanometer particle, acetylene black and polytetrafluoroethyl-ne dilute emulsion is 50:
30:20；
Two, slurry is equably brushed on one of the nickel foam of a diameter of 12mm weighed surface with hairbrush
On, it is then 80 DEG C of vacuum drying 10h in temperature, obtains cathode pole piece blank；
Three, cathode pole piece blank is placed on tablet press machine and carries out tabletting, obtain cathode pole piece；
Pressure when the progress tabletting is 18MPa, residence time 10s；
Four, in argon gas atmosphere glove box, by from top to bottom the sequence of cathode pole piece, diaphragm and sodium positive plate is stacked simultaneously
It is placed in battery case, electrolyte is then added dropwise into battery case, battery case buckle closure and sealing are finally placed under room temperature
8h is stood, sodium lithium ion battery is obtained；Wherein, it is to make sodium lithium ion battery button cell to be placed under room temperature and stand the purpose of 8h
It is activated；
The diaphragm is mesoporous polypropylene screen；The battery case is CR2025 button cell shells；
The preparation method of the electrolyte is：By the NaClO of a concentration of 1M4Solution is dissolved in propene carbonate and carbonic acid two
In the mixed solution of ethyl ester, the fluorinated ethylene carbonate that mass fraction is 5~8% is then added, that is, is completed；The propylene carbonate
The volume ratio of ester and diethyl carbonate is 1：1；NaClO4The volume ratio of solution and diethyl carbonate is 1：1；
Embodiment 1 prepare nickel phosphide and carbon coating nickel phosphide composite material nanometer particle XRD spectrum as shown in Figure 1,
1 corresponds to carbon coating nickel phosphide composite material nanometer particle in figure, and 2 correspond to nickel phosphide；In Fig. 1 40.7 °, 44.5 °, 47.3 °,
54.2 °, 54.9 °, 66.2 °, 72.6 °, 74.6 ° of corresponding respectively and hexagonal phase Ni2(111) of P (JCPDS No.03-0953)
Crystal face, (201) crystal face, (210) crystal face, (300) crystal face, (211) crystal face, (310) crystal face, (311) crystal face and (400) crystal face,
Further relate to the Ni that the present embodiment successfully prepares hexagonal phase2P(JCPDS No.03-0953)；Fig. 3 is multiple for carbon coating nickel phosphide
The SEM of condensation material nano particle schemes；From the figure 3, it may be seen that carbon coating nickel phosphide composite material nanometer particle maintains Ni2The pattern of P,
And the carbon that can see adhesion is covered in spherical Ni2P ball surfaces；Fig. 5 is carbon coating nickel phosphide composite material nanometer particle
TEM schemes；As shown in Figure 5, carbon coating nickel phosphide composite material nanometer particle surface is smooth, it was confirmed that the present embodiment is successfully prepared
Carbon coating nickel phosphide composite material nanometer particle.
Comparative example 1：
The preparation method of this comparative example nickel phosphide carries out according to the following steps：
One, Nickelous nitrate hexahydrate and glycerine are dispersed in isopropanol, are then transferred into water heating kettle and carry out hydro-thermal reaction,
Powdered reaction product is obtained after hydro-thermal reaction, with ethyl alcohol washing powder shape reaction product 4 times, collects the reaction after washing
Product is precipitated and is dried in vacuo, and obtains glyceric acid nickel by powder；
The quality of the Nickelous nitrate hexahydrate and the volume ratio of isopropanol are 0.1g：52.5ml；
The volume ratio of the glycerine and isopropanol is 7.5:52.5mL；
The vacuum drying temperature is 80 DEG C, time 12h；
The hydrothermal temperature is 180 DEG C, the hydro-thermal reaction time 12h；
Two, glyceric acid nickel by powder is dried in vacuo, the powdered reaction product after drying is calcined, simple substance is obtained
Nickel；
The vacuum drying temperature is 80 DEG C, time 12h；
The calcine technology is：Calcining carries out in tube furnace, and calcination atmosphere is nitrogen atmosphere, and calcination temperature is 400 DEG C,
Calcination time is 3h；
Three, the elemental nickel for obtaining step 2 carries out phosphorating treatment, obtains nickel phosphide；
The parkerized technique is：Elemental nickel and sodium hypophosphite are respectively placed in quartz boat both ends, and by quartz boat
It is placed in N2In the tube furnace of atmosphere, by one end for being placed with sodium hypophosphite of quartz boat towards the N of tube furnace2Upstream end, then into
Row calcining, calcination temperature are 300 DEG C, calcination time 3h；
Fig. 2 is Ni2The SEM of P schemes；As shown in Figure 2, Ni2P is in spherical, Ni2P is made of the subelement of nanostructure；Fig. 4 is
Ni2The TEM of P schemes；As shown in Figure 4, Ni2P is in spherical, Ni2P is made of the subelement of nanostructure；
Under conditions of charging/discharging voltage ranging from 0-3V, the sodium-ion battery prepared to embodiment 1 and comparative example are tested
The cycle of high rate performance and battery of preceding two the circles charging and discharging curve, battery of the sodium-ion battery of preparation under different current densities
Performance；
Fig. 6 is in embodiment 1, is that the sodium ion for preparing of battery cathode is electric using carbon coating nickel phosphide composite material nanometer particle
The preceding two circles charging and discharging curve figure in pond；Curve 1 is the charging and discharging curve of the 1st circle in figure, and curve 2 is the charging and discharging curve of the 2nd circle；
From fig. 6 it can be seen that the sodium for preparing as anode material of lithium-ion battery of carbon coating nickel phosphide composite material nanometer particle from
The first lap charging and discharging capacity of sub- battery is 714.6mAh/g, and the second circle specific discharge capacity is 569.5mAh/g；
Fig. 7 is with Ni2Sodium-ion battery prepared by P cathode and carbon coating nickel phosphide composite material nanometer particle battery cathode
High rate performance curve graph under different current densities；Curve 1 is carbon coating nickel phosphide composite material nanometer particle battery cathode
Discharge-rate performance curve under the sodium-ion battery difference current density of preparation；Curve 2 is nickel phosphide composite material nanometer
Discharge-rate performance curve under sodium-ion battery difference current density prepared by grain battery cathode；It can be seen from figure 7 that
Current density is respectively carbon coating phosphatization under conditions of 50mAh/g, 100mAh/g, 200mAh/g, 400mAh/g and 800mAh/g
The reversible specific capacity of sodium-ion battery prepared by nickel composite material nano particle battery cathode respectively reaches 714.6mAh/g,
217.6mAh/g, 160.5mAh/g, 122.5mAh/g and 108.4mAh/g, Ni2The reversible ratio of sodium-ion battery prepared by P cathode
Capacity respectively reaches 561mAh/g, 86.2mAh/g, 52.6mAh/g, 36.9mAh/g and 19.5mAh/g；Illustrate carbon coating phosphatization
The reversible specific capacity of sodium-ion battery prepared by nickel composite material nano particle battery cathode is far above Ni2P；
Fig. 8 is Ni2Sodium-ion battery prepared by P cathode and carbon coating nickel phosphide composite material nanometer particle battery cathode
Cycle performance figure；Curve 1 is corresponded to using carbon coating nickel phosphide composite material nanometer particle as the cyclicity of cell negative electrode material in figure
Can, curve 2 corresponds to the cycle performance that nickel phosphide composite material nanometer particle is cell negative electrode material；As can be seen from Figure 8, exist
Current density is after 100 discharge and recharge reactions, carbon coating nickel phosphide composite material nanometer particle is electric under conditions of 50mA/g
The cycle life of sodium-ion battery prepared by pond cathode is stablized in 254mAh/g, Ni2The cycle of sodium-ion battery prepared by P cathode
Service life stablizes following in 124.6mAh/g, carbon coating nickel phosphide composite material nanometer particle the battery cathode sodium-ion battery prepared
The ring service life is significantly larger than Ni2P cathode.
Claims (10)
1. a kind of preparation method of carbon coating nickel phosphide composite material nanometer particle, it is characterised in that：This method is according to the following steps
It carries out：
One, Nickelous nitrate hexahydrate and glycerine are dispersed in isopropanol, are then transferred into water heating kettle and carry out hydro-thermal reaction, hydro-thermal
Powdered reaction product is obtained after reaction, with ethyl alcohol washing powder shape reaction product 3~5 times, collects the powder after washing
Shape reaction product is simultaneously dried in vacuo, and glyceric acid nickel by powder is obtained；
The quality of the Nickelous nitrate hexahydrate and the volume ratio of isopropanol are (0.1g~0.4g)：52.5ml；
The volume ratio of the glycerine and isopropanol is (6.5mL~8.5mL):52.5mL；
Two, glyceric acid nickel by powder and glucose are dissolved in deionized water, are then transferred into water heating kettle, at 160~180 DEG C
10~12h of lower reaction obtains carbon coating glyceric acid nickel composite material powder；
The quality of the glyceric acid nickel by powder and glucose is (0.07g~0.1g):0.45g；
The quality of the glyceric acid nickel by powder and the volume ratio of deionized water are (0.07g~0.1g):30mL；
Three, carbon coating glyceric acid nickel composite material powder is dried in vacuo, the powdered reaction product after drying is calcined,
Obtain carbon-coating nickel composite material nanometer particle；
Four, the carbon-coating nickel composite material nanometer particle for obtaining step 3 carries out phosphorating treatment, and it is multiple to obtain carbon coating nickel phosphide
Condensation material nano particle.
2. the preparation method of carbon coating nickel phosphide composite material nanometer particle according to claim 1, it is characterised in that：Step
A rapid vacuum drying temperature is 60~80 DEG C, and the time is 10~13h.
3. the preparation method of carbon coating nickel phosphide composite material nanometer particle according to claim 1 or 2, feature exist
In：Hydrothermal temperature described in step 1 is 160~200 DEG C, and the hydro-thermal reaction time is 8~13h.
4. the preparation method of carbon coating nickel phosphide composite material nanometer particle according to claim 3, it is characterised in that：Step
The rapid three vacuum drying temperature is 60~80 DEG C, and the time is 10~13h.
5. the preparation method of carbon coating nickel phosphide composite material nanometer particle according to claim 1,2 or 4, feature exist
In：Calcine technology described in step 3 is：Calcining carries out in tube furnace, and calcination atmosphere is nitrogen atmosphere, and calcination temperature is 300~
500 DEG C, calcination time is 2~4h.
6. the preparation method of carbon coating nickel phosphide composite material nanometer particle according to claim 5, it is characterised in that：Step
The rapid four parkerized technique is：
Carbon-coating nickel composite material nanometer particle and sodium hypophosphite are respectively placed in quartz boat both ends, and quartz boat is placed in N2Gas
In the tube furnace of atmosphere, by one end for being placed with sodium hypophosphite of quartz boat towards the N of tube furnace2Then upstream end is calcined,
Calcination temperature is 300~500 DEG C, and calcination time is 2~4h；The carbon-coating nickel composite material nanometer particle and sodium hypophosphite
Molar ratio (9.5~10.5)：50.
7. the cathode material of carbon-coating nickel composite material nanometer particle prepared by method as described in claim 1 as sodium-ion battery
Material, the application in preparing sodium lithium ion battery.
8. application according to claim 7, it is characterised in that：Using carbon-coating nickel composite material nanometer particle as sodium
The method that the negative material of ion battery prepares sodium lithium ion battery carries out according to the following steps：
One, carbon coating nickel phosphide composite material nanometer particle, acetylene black and polytetrafluoroethyl-ne dilute emulsion are uniformly mixed, obtain pulpous state
Object；
The mass ratio of the carbon coating nickel phosphide composite material nanometer particle, acetylene black and polytetrafluoroethyl-ne dilute emulsion be (40~
70):(30~50):20；
Two, slurry is equably brushed on one of the nickel foam of a diameter of 10~14mm weighed surface with hairbrush
On, it is then 75~85 DEG C of 9~11h of vacuum drying in temperature, obtains cathode pole piece blank；
Three, cathode pole piece blank is placed on tablet press machine and carries out tabletting, obtain cathode pole piece；
Four, it in argon gas atmosphere glove box, is placed in by from top to bottom the sequence of cathode pole piece, diaphragm and sodium positive plate is stacked
In battery case, electrolyte is then added dropwise into battery case, by battery case buckle closure and sealing, is finally placed under room temperature and stands
7.5~8.5h obtains sodium lithium ion battery.
9. application according to claim 8, it is characterised in that：Described in step 3 carry out tabletting when pressure be 15~
20MPa, residence time are 8~10s.
10. application according to claim 8, it is characterised in that：Diaphragm described in step 4 is mesoporous polypropylene screen；It is described
Battery case is CR2025 button cell shells.
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| CN110707321A (en) * | 2019-10-23 | 2020-01-17 | 合肥国轩高科动力能源有限公司 | Copper-coated hollow nickel phosphide material and preparation method and application thereof |
| CN111661829A (en) * | 2020-06-16 | 2020-09-15 | 浙江大学 | Carbon-coated tungsten-doped metal phosphide and preparation method thereof |
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| CN113611866A (en) * | 2021-08-02 | 2021-11-05 | 合肥工业大学 | Flexible self-supporting sodium-ion battery cathode material and preparation method thereof |
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