CN108807941A - The preparation method and application of iron phosphide nanometer sheet and biomass carbon composite material - Google Patents
The preparation method and application of iron phosphide nanometer sheet and biomass carbon composite material Download PDFInfo
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Abstract
The invention discloses a kind of iron phosphide nanometer sheets and the compound preparation method of biomass carbon.It is by using electrochemical method that iron phosphide nanometer sheet and biomass carbon film is compound, iron phosphide/biomass carbon Integrated electrode without binder is obtained, method is simple, easy to operate, and material preparation is of low cost；Iron phosphide and biomass carbon Material cladding are obtained into composite material for anode material of lithium-ion battery for the first time, the storage sodium of composite electrode is had excellent performance, stable structure.
Description
Technical field
The present invention relates to a kind of iron phosphide nanometer sheets and biomass carbon composite material and preparation method；The present invention is gone back simultaneously
It is related to application of the composite material as sodium ion battery electrode material, belongs to composite material and electrode material field.
Background technology
With the development and utilization of lithium ion battery, storage level of the elemental lithium in the earth's crust reduces year by year, develops a kind of energy
Become a kind of inexorable trend instead of the novel sodium-ion battery of lithium ion battery.Abundance of the sodium element in the earth's crust is higher, price
Cheap, the energy storage mechnism of sodium-ion battery is similar with lithium ion battery, is suitble to national smart grid energy storage technology extensive in this way
Application.And electrode material is the core of sodium-ion battery technology development, wherein biomass carbon material has cheap and easy to get, source
Abundant, high electric conductivity, can be directly as self-supporting electrode material after centainly handling.
Biomass carbon material is the natural topography formation porous material that hard carbon material can inherit biomass presoma.Mesh
Before, porous material is concerned as the negative material of battery, wherein the graphene layer and nano-pore that stack at random can be real
The storage of existing sodium ion.The good cycle performance and electric conductivity that biomass carbon material has, by vast research institution
It is utilized extensively with manufacturer.But the relatively low specific capacity of biomass carbon material (being less than 300mAh/g) affects biomass carbon material
Application as electrode material.The theoretical specific capacity of phosphatization iron electrode material higher (being more than 500mAh/g) be comparatively ideal sodium from
The negative material of sub- battery, but its serious volume change can lead to quickly declining for specific capacity during embedding sodium/removing sodium
Subtract.Therefore, compound using iron phosphide nanometer sheet and carbon material, the advantage for playing two kinds of materials had both improved the specific capacity of electrode material
The stability of material is realized again.In recent years, the method for synthesis iron phosphide nanometer sheet/carbon composite mostly first prepares iron oxide and receives
Rice piece/carbon complex, then carry out further phosphatization and obtain final product, several frequently seen method for bonderizing may be summarized to be solid phase phosphorus
Change method, wet chemical parco-lubrizing.Not only process is cumbersome for these methods, but also danger coefficient is higher.The present invention uses electrodeposition process
Iron phosphide nanometer sheet/biomass carbon composite material is obtained, which significantly improves the cycle life of sodium-ion battery, mesh
Before yet there are no relevant report.
Invention content
The purpose of the present invention is to provide a kind of electrodeposition process simple to operation to prepare iron phosphide nanometer sheet and biomass
Carbon composite, composite material significantly improve the cycle life of sodium-ion battery.
To realize the above-mentioned technical purpose, the present invention proposes a kind of system of iron phosphide nanometer sheet and biomass carbon composite material
Preparation Method includes the following steps：
(1) biomass carbon film preparation：Between yulan leaf is placed in graphite flake, then under 700~800 DEG C of environment temperatures
Make annealing treatment within 1~2 hour, be then placed in aqueous slkali and handle 1~2 hour, then is placed in 9~10h of processing, shape in acid solution
At carbon film；
(2) preparation of electrolyte：The iron sulfate heptahydrate of different mol ratio is mixed with sodium hypophosphite and is dissolved in sweet ammonia
Acid is 2~3 with the pH value range in the mixed liquor of oxalic acid, adjusting solution, preferably uses sulphur acid for adjusting pH, obtains basic electrolysis
Liquid；
(3) preparation of composite material：The biomass carbon film that step (1) is obtained is used as working electrode, platinized platinum to electricity
Pole, Ag/AgCl is as reference electrode, and using the solution that step (2) obtains as electro-deposition electrolyte, hermetic electrolyte is passed through nitrogen in pond
Gas is preferably passed into nitrogen 10~15 minutes, and the composite material being electrodeposited into, obtained composite material is rushed with deionized water
It washes several times, preferably 4~5 times；
(4) reinforcing of composite material crystal structure：The composite material that step (3) obtains is placed in tube furnace, nitrogen is passed through
Gas shielded gas, heating rate are 1~2 DEG C/min, are warming up to 250~300 DEG C and naturally cool to room after keeping the temperature 1~2 hour
Temperature.
Preferably, in step (1), the aqueous slkali is 2~3mol/L KOH aqueous solutions, and the carbon film and KOH of formation are water-soluble
The mixing quality ratio of KOH in liquid is 1：2~4.
In step (1), the acid solution is in 0.5~1mol/L HCl/water solution.
In step (2), in step (2), the molar ratio of iron sulfate heptahydrate and sodium hypophosphite is 1：2~2：1；Glycine
Molar ratio with oxalic acid is (2.2~8.8):0.1；The mixed solution of iron sulfate heptahydrate and sodium hypophosphite and glycine and grass
The volume ratio of the mixed liquor of acid is 1:1.
Preferably, electrodeposition condition in step (3)：Electro-deposition current potential：- 1.0V~-1.5V；Electrodeposition time is 20min
~1h.
Step (4) nitrogen protection gas is passed through with the air inflow of 0.1~0.2L/min.
Present invention further proposes the above method prepare iron phosphide nanometer sheet/biomass carbon composite material as sodium from
The application of sub- battery electrode material.
Specifically, in use, by the composite material directly as sodium-ion battery negative plate, use glass fibre membrane for
Diaphragm, electrolyte are 1mol/L NaClO4, solvent is the mixture of isometric ethylene carbonate and diethyl carbonate, solvent
Contain the fluorinated ethylene carbonate that percent by volume is 5% as additive, is assembled into the glove box full of argon gas
CR2032 button sodium-ion batteries.
The present invention first makes annealing treatment wide yulan leaf under high temperature and nitrogen protection, obtains biomass carbon membrane material.
Biomass carbon material is as working electrode, and using platinized platinum as to electrode, silver/silver chlorate is as reference electrode, in seven hydrated sulfuric acids
Potentiostatic electrodeposition is carried out in the acidic mixed electrolyte of iron, sodium hypophosphite, glycine and oxalic acid, obtains iron phosphide nanometer
Piece/biomass carbon composite material.
The advantage of the invention is that：Iron phosphide nanometer sheet/biomass carbon composite material prepared by the present invention can be directly as
The negative material of sodium-ion battery can significantly improve the cycle of sodium-ion battery without in addition addition binder and activated carbon
Service life after being recycled 50 times under the current density of 100mA/g, achieves the charging capacity and 507.8mAh/g of 503.8mAh/g
Discharge capacity and capacity retention ratio are and simple for process, favorable reproducibility, easy to implement 99% or more.
Description of the drawings
Fig. 1 be the embodiment of the present invention 1 prepare iron phosphide nanometer sheet/biomass carbon composite material X-ray diffraction as a result,
Two iron (Fe of phosphatization is corresponded to respectively2P), iron phosphide (FeP), two iron phosphide (FeP2), four iron phosphide (FeP4) peak.
Fig. 2 is that biomass carbon film (such as figure a) prepared by the embodiment of the present invention 1 and iron phosphide nanometer sheet/biomass carbon are compound
The scanning electron microscope (SEM) photograph of material (such as figure b).
Fig. 3 is the embodiment of the present invention 2 (such as figure a), the phosphatization that embodiment 3 (such as figure b) and embodiment 4 are prepared (such as figure c)
The scanning electron microscope (SEM) photograph of iron/biomass carbon composite material.
Fig. 4 is that the embodiment of the present invention 1 (figure a), embodiment 2 (figure b), embodiment 3 (figure c), embodiment 4 (figure d) are made respectively
Sodium-ion battery cycle under 100mA/g current density of the standby iron phosphide/biomass carbon composite material as negative material
Performance curve.
Specific implementation mode
The following examples can be to the preparation of composite material of the present invention and its preparation of electrode material and chemical property
It is described in further detail.
Embodiment 1
(1) mixed solution of wide yulan leaf acetone and water is washed 2-3 times.It is 2 hours dry in 60 DEG C of baking oven.
It between blade is placed in graphite flake, then carries out making annealing treatment for 2 hours under 800 DEG C of environment temperatures, it is water-soluble to be placed in 3mol KOH
It is handled 2 hours in liquid, then is placed in 1mol/L HCl/water solution and handles 10 hours.
(2) using the biomass carbon film obtained in step (1) as working electrode, platinized platinum is used as to electrode, and silver/silver chlorate is made
It is placed in hermetic electrolyte pond for reference electrode.In the iron sulfate heptahydrate containing 0.72mol/L, the ortho phosphorous acid of 0.36mol/L
Sodium, the glycine of 0.11mol/L are passed through nitrogen 15 minutes in the hermetic electrolyte pond of the oxalic acid mixed electrolytic solution of 0.005mol/L
Afterwards, apply constant potential -1.5V to working electrode to deposit 30 minutes.After electro-deposition, 2-3 is washed with deionized in working electrode
Time.Obtain unformed iron phosphide nanometer sheet/biomass carbon composite material.
(3) unformed iron phosphide nanometer sheet/biomass carbon composite material is placed in tube furnace, with the air inlet of 0.2L/min
Amount is passed through nitrogen protection gas, and heating rate is 2 DEG C/min, cooled to room temperature after being warming up to 300 DEG C and keeping the temperature 1 hour,
The iron phosphide crystallized/biomass carbon composite material.
The iron phosphide obtained in embodiment/biomass carbon composite material is subjected to X-ray diffraction, Fig. 1 shows to use this method
It is two iron (Fe of phosphatization to prepare iron phosphide in iron phosphide/biomass carbon composite material2P), iron phosphide (FeP), two iron phosphide (FeP2)
And four iron phosphide (FeP4) mixture.Diffraction maximum in figure corresponds respectively to Fe2In P (JCPS no.51-0943)
(200) (111) (201) (300) crystal face, (011) crystal face in FeP (JCPS no.39-0809), FeP2(JCPS no.06-
0561) crystal face of (101) (110) (121) (122) in, FeP4In (JCPS no.34-0995) (052) (- 222) (-
241) (240) (152) (- 261) crystal face, illustrate that we are prepared is a kind of iron phosphide of mixed phase.
The iron phosphide obtained in embodiment/biomass carbon composite material is scanned electron microscope analysis, as seen from Figure 2
Biomass carbon film is porous structure, and iron phosphide is that nanometer sheet is equably grown in biomass in iron phosphide/biomass carbon composite material
On carbon film.
The assembling and performance test of sodium-ion battery：By iron phosphide nanometer sheet/biomass carbon material directly as sodium ion
Battery electrode piece.For sodium piece as electrode anode piece, glass-microfibre separator is diaphragm, 1mol/L NaClO4, solvent is isometric
Ethylene carbonate and diethyl carbonate, containing percent by volume be 5% fluorinated ethylene carbonate additive, full of argon
CR2032 button sodium-ion batteries are assembled into the glove box of gas.After battery standing 24 hours, in the current density of 100mA/g
Lower progress charge-discharge performance test, charge and discharge voltage is between 0.01~3.0V.From fig. 4, it can be seen that using our legal system
Standby iron phosphide nanometer sheet/biomass carbon composite material is applied to sodium-ion battery as electrode material, after 90 circle of cycle, fills
Specific discharge capacity is respectively 458.2mAh/g and 466.4mAh/g, and capacity retention ratio has good cyclicity 97% or more
Energy.Meanwhile after being recycled 50 times under the current density of 100mA/g, achieving the charging capacity and 507.8mAh/ of 503.8mAh/g
Effect of the discharge capacity and capacity retention ratio of g 99% or more.
Embodiment 2
(1) mixed solution of wide yulan leaf acetone and water is washed 2-3 times.It is 2 hours dry in 60 DEG C of baking oven.
Blade is placed in tube furnace, nitrogen protection gas is passed through with the air inflow of 0.2L/min, heating rate is 2 DEG C/min, heating
To 800 DEG C and keep the temperature 2 hours after cooled to room temperature, obtain biomass carbon film.It is small to be placed in processing 2 in 3mol KOH aqueous solutions
When, then be placed in 1mol/L HCl/water solution and handle 10 hours.
(2) using the biomass carbon film obtained in step (1) as working electrode, platinized platinum is used as to electrode, and silver/silver chlorate is made
It is placed in hermetic electrolyte pond for reference electrode.In the iron sulfate heptahydrate containing 0.36mol/L, the ortho phosphorous acid of 0.72mol/L
Sodium, the glycine of 0.22mol/L are passed through nitrogen 15 minutes in the hermetic electrolyte pond of the oxalic acid mixed electrolytic solution of 0.005mol/L
Afterwards, apply constant potential -1.5V to working electrode to deposit 30 minutes.After electro-deposition, 2-3 is washed with deionized in working electrode
Time.Obtain unformed iron phosphide nanometer sheet/biomass carbon composite material.
(3) unformed iron phosphide nanometer sheet/biomass carbon composite material is placed in tube furnace, with the air inlet of 0.2L/min
Amount is passed through nitrogen protection gas, and heating rate is 2 DEG C/min, cooled to room temperature after being warming up to 300 DEG C and keeping the temperature 1 hour,
The iron phosphide crystallized/biomass carbon composite material.
The assembling of sodium-ion battery and performance test conditions are same as Example 1 in the present embodiment.
Embodiment 3
(1) mixed solution of wide yulan leaf acetone and water is washed 2-3 times.It is 2 hours dry in 60 DEG C of baking oven.
Blade is placed in tube furnace, nitrogen protection gas is passed through with the air inflow of 0.2L/min, heating rate is 2 DEG C/min, heating
To 800 DEG C and keep the temperature 2 hours after cooled to room temperature, obtain biomass carbon film.It is small to be placed in processing 2 in 3mol KOH aqueous solutions
When, then be placed in 1mol/L HCl/water solution and handle 10 hours.
(2) using the biomass carbon film obtained in step (1) as working electrode, platinized platinum is used as to electrode, and silver/silver chlorate is made
It is placed in hermetic electrolyte pond for reference electrode.In the iron sulfate heptahydrate containing 0.36mol/L, the ortho phosphorous acid of 1.08mol/L
Sodium, the glycine of 0.44mol/L, after being passed through nitrogen 15 minutes in the hermetic electrolyte pond of the oxalic acid mixed electrolytic solution of 0.01mol/L,
Apply constant potential -1.5V to working electrode to deposit 30 minutes.After electro-deposition, working electrode is washed with deionized 2-3 times.
Obtain unformed iron phosphide nanometer sheet/biomass carbon composite material.
(3) unformed iron phosphide nanometer sheet/biomass carbon composite material is placed in tube furnace, with the air inlet of 0.2L/min
Amount is passed through nitrogen protection gas, and heating rate is 2 DEG C/min, cooled to room temperature after being warming up to 300 DEG C and keeping the temperature 1 hour,
The iron phosphide crystallized/biomass carbon composite material.
The assembling of sodium-ion battery and performance test conditions are same as Example 1 in the present embodiment.
Embodiment 4
(1) mixed solution of wide yulan leaf acetone and water is washed 2-3 times.It is 2 hours dry in 60 DEG C of baking oven.
Blade is placed in tube furnace, nitrogen protection gas is passed through with the air inflow of 0.2L/min, heating rate is 2 DEG C/min, heating
To 800 DEG C and keep the temperature 2 hours after cooled to room temperature, obtain biomass carbon film.It is small to be placed in processing 2 in 3mol KOH aqueous solutions
When, then be placed in 1mol/L HCl/water solution and handle 10 hours.
(2) using the biomass carbon film obtained in step (1) as working electrode, platinized platinum is used as to electrode, and silver/silver chlorate is made
It is placed in hermetic electrolyte pond for reference electrode.In the iron sulfate heptahydrate containing 0.36mol/L, the ortho phosphorous acid of 1.08mol/L
Sodium after being passed through nitrogen 15 minutes in the hermetic electrolyte pond of the sodium sulphate mixed electrolytic solution of 0.88mol/L, applies working electrode permanent
Current potential -1.5V is deposited 30 minutes.After electro-deposition, working electrode is washed with deionized 2-3 times.Obtain unformed phosphatization
Iron/biomass carbon composite material.
(3) unformed iron phosphide/biomass carbon composite material is placed in tube furnace, is passed through with the air inflow of 0.2L/min
Nitrogen protection gas, heating rate are 2 DEG C/min, and cooled to room temperature after being warming up to 300 DEG C and keeping the temperature 1 hour is tied
The iron phosphide of crystallization/biomass carbon composite material.
Fig. 3 is phosphatization prepared by the embodiment of the present invention 2 (such as figure a), embodiment 3 (such as figure b) and embodiment 4 (such as figure c)
The scanning electron microscope (SEM) photograph of iron/biomass carbon composite material.As can be seen from the results, scheme the deposit in a on carbon film surface to show
For irregular fold, the deposit for scheming carbon film surface in b is in nanometer flakelet shape, schemes the deposit on carbon film surface in c in small
The microballoon of particle composition.The specific surface area for the iron phosphide deposit that these three methods obtain is obviously without iron phosphide in embodiment 1
Nanometer sheet is big.Therefore iron phosphide nanometer sheet is more advantageous to Na in embodiment 1+Storage.
Fig. 4 is that the embodiment of the present invention 1 (figure a), embodiment 2 (figure b), embodiment 3 (figure c), embodiment 4 (figure d) are made respectively
Sodium-ion battery cycle under 100mA/g current density of the standby iron phosphide/biomass carbon composite material as negative material
Performance curve.In conjunction with scanning electron microscope (SEM) photograph it is found that the variation of the component ratio with electrolyte solution, the phosphorus that electrochemical deposition obtains
The nanostructure for changing iron is also different, gradually increases with the surface area of iron phosphide nanometer sheet, the storage sodium position of iron phosphide nanostructure
Point gradually increases, and the cyclical stability of active material also gradually increases, therefore the iron phosphide nanometer sheet synthesized in 1 method of embodiment
Specific capacity and cyclical stability be best.
In conclusion iron phosphide nanometer sheet/biomass carbon composite material prepared by the present invention can be directly as sodium ion electricity
The negative material in pond can significantly improve the cycle life of sodium-ion battery without in addition addition binder and activated carbon,
After being recycled 50 times under the current density of 100mA/g, the electric discharge of the charging capacity and 507.8mAh/g that achieve 503.8mAh/g is held
Amount and capacity retention ratio is 99% or more, and it is simple for process, favorable reproducibility, easy to implement.
Claims (8)
1. a kind of preparation method of iron phosphide nanometer sheet and biomass carbon composite material, which is characterized in that include the following steps：
(1) biomass carbon film preparation：Between yulan leaf is placed in graphite flake, then carried out under 700~800 DEG C of environment temperatures
It makes annealing treatment within 1~2 hour, is then placed in aqueous slkali and handles 1~2 hour, then be placed in 9~10h of processing in acid solution, form carbon
Film；
(2) preparation of electrolyte：The iron sulfate heptahydrate of different mol ratio is mixed with sodium hypophosphite and be dissolved in glycine with
In the mixed liquor of oxalic acid, the pH value range for adjusting solution is 2~3, obtains basic electrolyte；
(3) preparation of composite material：As working electrode, platinized platinum is used as to electrode the biomass carbon film that step (1) is obtained,
Ag/AgCl is as reference electrode, and using the solution that step (2) obtains as electro-deposition electrolyte, in hermetic electrolyte pond, it is heavy to carry out electricity
The composite material accumulated, obtained composite material are rinsed several times with deionized water；
(4) reinforcing of composite material crystal structure：The composite material that step (3) obtains is placed in tube furnace, nitrogen guarantor is passed through
Gas is protected, heating rate is 1~2 DEG C/min, cooled to room temperature after being warming up to 250~300 DEG C and keeping the temperature 1~2 hour.
2. preparation method according to claim 1, it is characterised in that：In step (1), the aqueous slkali is 2~3mol/L
KOH aqueous solutions, the carbon film of formation are 1 with the mixing quality ratio of the KOH in KOH aqueous solutions：2~4.
3. preparation method according to claim 1, it is characterised in that：In step (1), the acid solution be 0.5~
In 1mol/L HCl/water solution.
4. preparation method according to claim 1, it is characterised in that：In step (2), iron sulfate heptahydrate and ortho phosphorous acid
The molar ratio of sodium is 1：2~2：1；The molar ratio of glycine and oxalic acid is (2.2~8.8):0.1；Iron sulfate heptahydrate and time Asia
The mixed solution of sodium phosphate is 1 with the volume ratio of glycine and the mixed liquor of oxalic acid:1.
5. preparation method according to claim 1, it is characterised in that：Electrodeposition condition in step (3)：Electro-deposition current potential：-
1.0V~-1.5V；Electrodeposition time is 20min~1h.
6. preparation method according to claim 1, it is characterised in that：Step (4) nitrogen protection gas is with 0.1~0.2L/
The air inflow of min is passed through.
7. iron phosphide nanometer sheet/biomass carbon composite material prepared by claim 1 the method is as sodium-ion battery electrode
The application of material.
8. application according to claim 7, by the composite material directly as sodium-ion battery negative plate, using glass fibers
Dimension film is diaphragm, and electrolyte is 1mol/L NaClO4, solvent is the mixing of isometric ethylene carbonate and diethyl carbonate
Object, solvent contain the fluorinated ethylene carbonate that percent by volume is 5% as additive, are assembled in the glove box full of argon gas
At CR2032 button sodium-ion batteries.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN109599542A (en) * | 2018-11-15 | 2019-04-09 | 江苏科技大学 | A kind of phosphatization cobalt biomass carbon composite material and preparation method and application |
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| CN110386594A (en) * | 2019-04-04 | 2019-10-29 | 江西师范大学 | A kind of preparation method of nanoporous iron phosphide cube |
| CN110386594B (en) * | 2019-04-04 | 2022-03-04 | 江西师范大学 | Preparation method of nano porous iron phosphide cube |
| CN111517297A (en) * | 2020-04-02 | 2020-08-11 | 太原理工大学 | Preparation method and application of heterostructure/graphene composite material |
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