CN110304614A - A kind of transition metal phosphide Fe2P negative electrode material - Google Patents
A kind of transition metal phosphide Fe2P negative electrode material Download PDFInfo
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- CN110304614A CN110304614A CN201910625551.XA CN201910625551A CN110304614A CN 110304614 A CN110304614 A CN 110304614A CN 201910625551 A CN201910625551 A CN 201910625551A CN 110304614 A CN110304614 A CN 110304614A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
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- 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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Abstract
A kind of transition metal phosphide Fe2P negative electrode material, is prepared from the following steps: (1) being uniformly mixed water with n,N-Dimethylformamide；(2) source of iron and organic ligand is added, stirring obtains mixed solution；(3) it sealing, heating reaction is cooling, filters, washs, and it is dry, obtain yellow powder；(4) in an inert atmosphere, it roasts, it is cooling, obtain black powder；(5) sodium hypophosphite and black powder are respectively placed in tube furnace upstream and downstream, in an inert atmosphere, roasted, it is cooling,.Gained negative electrode material 400~600nm of partial size of the invention, is assembled into battery, in 0.1 ~ 3V, 100 mAg‑1Under, initial charge specific capacity is up to 1241 mAhg‑1, 672 mAhg of first discharge specific capacity‑1, capacity retention ratio >=95% after circulation 100 is enclosed, preparation process is simple, and reaction temperature is low, and the period is short, at low cost.
Description
Technical field
The present invention relates to a kind of negative electrode materials, and in particular to a kind of lithium ion battery is negative with transition metal phosphide Fe2P
Pole material.
Background technique
With the consumption of the non-renewable fossil energy such as petroleum, natural gas, the arrival of energy crisis causes more and more
Concern.In this context, the novel high-energy electrochmical power source of green non-pollution has become the hot spot that countries in the world are competitively developed.Lithium
Ion battery is a kind of novel electrochmical power source, use respectively two reversibly the compounds of insertion and abjection lithium ion as
Positive and negative electrode and constitute.When due to iron phosphide as lithium ion battery negative material, theoretical specific capacity (926 with higher
mAh·g-1), and it is environmentally friendly and be concerned.However, since volume becomes iron phosphide negative electrode material in charge and discharge process
Change larger, and its electric conductivity is poor, and constrains its development.
CN102442652A, which is disclosed, a kind of prepares transition metal phosphide Fe2The new method of P, before being used as using ferric phosphate
Body is driven, potassium borohydride is as reducing agent, and 1:1.5-1:2 is ground in mortar in molar ratio with reducing agent by the phosphate of iron, mixes
It closes uniformly, reacts 30min in the case where 500-600 DEG C of argon gas is protected；Products therefrom is finely ground, is washed respectively with distilled water and dehydrated alcohol
Three times, then 60 DEG C of vacuum drying 12h, obtain product F e2P.Although primary raw material source needed for the preparation of this method material is rich
Richness, cheap, cost is relatively low.But resulting materials performance is bad.
CN104084224A discloses a kind of method for preparing iron phosphide and carbon composite construction using carbon-thermal reduction, specially
The preparation method of easy iron phosphide and carbon composite construction prepares iron phosphide and other metal phosphides and carbon suitable for magnanimity
Composite construction.This method uses Iron(III) chloride hexahydrate, ammonium dihydrogen phosphate and melamine for raw material, by dipping method with six
The mixed solution impregnated melamine of iron chloride hexahydrate and ammonium dihydrogen phosphate, then by high temperature pyrolysis method, in indifferent gas
High temperature pyrolysis melamine reducing metal phosphate is at metal phosphide under body, to obtain the composite construction of iron phosphide and carbon.
But raw material melamine needed for the preparation of this method material is toxic, and the reaction carries out at high temperature, can release high poison
Cyanide gas, synthetic reaction process are not easily controlled and pollute environment.
CN107749467A discloses a kind of shuttle shape structure carbon coating iron phosphide electrode material and preparation method thereof, the electricity
Carbon coating phosphatization iron particle is flocked together with shuttle shape structure in the material of pole, and carbon coating iron phosphide grain diameter is 10-
80nm, wherein the mass fraction of iron phosphide is 50-90%, and the shuttle shape structure carbon coating iron phosphide electrode material passes through polymerization, heat
Facture preparation.But composite material is assembled into battery and carries out electro-chemical test, it is 100 mAg in test electric current-1, electricity
Pressing range is under 0.02~3V, and reversible discharge capacity is 680 mAhg for the first time-1, capacity tends to be steady after 15 circulations
Fixed, after 100 circulations, capacity attenuation is 600 mAhg-1, illustrate that the material reversible capacity is lower.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide one kind in charge and discharge
Volume expansion is small in electric process, good conductivity, and charge-discharge performance is stablized, good cycle, and its preparation process is simple, instead
Answer temperature low, the period is short, transition metal phosphide Fe2P negative electrode material at low cost.
The technical solution adopted by the present invention to solve the technical problems is as follows: a kind of transition metal phosphide Fe2P cathode
Material is prepared from the following steps:
(1) water is uniformly mixed with n,N-Dimethylformamide, obtains uniform solution；
(2) source of iron and organic ligand are added into uniform solution obtained by step (1), stirring and dissolving is uniform, obtains mixed solution；
(3) mixed solution obtained by step (2) is placed in autoclave, is sealed, heating is reacted, and cooling, filtering is washed
It washs, it is dry, obtain yellow powder；
(4) in an inert atmosphere by yellow powder obtained by step (3), it roasts, it is cooling, obtain black powder；
(5) black powder obtained by step (4) is placed in porcelain boat and is put in quartz ampoule upstream, sodium hypophosphite is placed in porcelain boat and is put in stone
English pipe downstream roasts in an inert atmosphere, cooling, obtains iron phosphide negative electrode material.
Preferably, in step (1), water is mixed with n,N-Dimethylformamide with volume ratio 1:3~7.
Preferably, in step (2), the molar ratio of ferro element and organic ligand is 0.5~4.0:1 in the source of iron.It is described
Ratio is too high or too low, is all not easy to form metallorganic framework material in step (3).
Preferably, in step (2), the molar concentration of iron ion is 0.01~0.20mol/L in the mixed solution.If iron
Ion concentration is excessively high, then gained metallorganic framework material is easy to reunite, if iron concentration is too low, being difficult to form metal has
Machine object framework material.The metal organic framework be by organic bridge ligand and inorganic metal ion be bonded have
Sequence network structure, generally when n,N-Dimethylformamide is as solvent, the organic matter framework material of Fe shows as shuttle shape or six
The face bodily form.
Preferably, in step (2), the source of iron is ferric sulfate, ferric nitrate or ferric trichloride and their hydrate etc.
One or more of.
Preferably, in step (2), the organic ligand is fumaric acid, terephthalic acid (TPA), trimesic acid or 3,5-
One or more of diaminobenzoic acid etc..The effect of the organic ligand is connection metal ion, forms organic matter and gold
Belong to the connected framework material of ion.
Preferably, in step (3), the temperature of the heating is 100~160 DEG C, the time of heating is 10~for 24 hours.
Preferably, in step (3), the mode of the washing is to be taken up in order of priority cross washing filtering with ethyl alcohol and deionized water
Object >=2 time.
Preferably, in step (3), the temperature of the drying is 60~100 DEG C, the dry time is 12~for 24 hours.
Preferably, in step (4), the temperature of the roasting is 400~600 DEG C, and the time of roasting is 2~6h.The temperature
It spends lower organic matter and is decomposed to form carbon, metal ion and oxygen atom therein are combined into oxide；If maturing temperature is too low, take out
When, it after contacting with the air can spontaneous combustion immediately.
Preferably, in step (4), the inert atmosphere is argon gas or nitrogen.Used in the present invention is high-purity argon gas
Or high pure nitrogen, purity >=99.99%(" % " are percentage by volume).
Preferably, in step (5), black powder is placed in porcelain boat and is put in quartz ampoule upstream, and sodium hypophosphite is placed in porcelain boat and puts
In quartz ampoule downstream, mass ratio is 1:10~20.
Preferably, in step (5), the temperature of the roasting is 250~350 DEG C, and the time of roasting is 2~4h.The temperature
PH can be decomposited by spending lower sodium hypophosphite3, PH3It can react with black powder ferroso-ferric oxide, generate iron phosphide.
Preferably, in step (5), the inert atmosphere is argon gas or nitrogen.Used in the present invention is high-purity argon gas
Or high pure nitrogen, purity >=99.99%(" % " are percentage by volume).
It is described to be cooled to cooled to room temperature in step (3)-step (5).
Technical principle of the invention is: using water and n,N-Dimethylformamide as the suitable solvent of polarity, making source of iron
The metallorganic framework material generated with organic ligand can be grown to serve as hexahedral material in water-heat process；Pass through again
Roasting makes organic components therein be converted into carbon, so that carbon is effectively compound with metal oxide, finally by sodium hypophosphite
It decomposites the hydrogen phosphide come and phosphatization is carried out to the product after roasting, obtain transition metal phosphide Fe2P material.Due to saving
Metallorganic frame makes the stabilization for being conducive to keep structure, so that electrode material is highly stable in charge and discharge process,
The tap density and compacted density that material can also be improved simultaneously, improve the volume energy density of material.
Beneficial effects of the present invention:
(1) transition metal phosphide Fe2P ingredient of the present invention is FexP belongs to mesoporous material, is conducive to electrolyte and cathode material
Effective contact of material, can shorten transmission path of the lithium ion in negative electrode material, and can keep stablizing in charge and discharge process and tie
Structure is conducive to lithium ion in the shuttle of charge and discharge process, reduces volume expansion of the material in charge and discharge process, the metal of reservation
Organic framework can increase the electric conductivity of material；
(2) transition metal phosphide Fe2P negative electrode material of the present invention is assembled into battery, in 0.1~3.0V voltage range,
0.1C(1C=1000mA-g-1) under multiplying power, the gram volume that discharges for the first time is up to 1241 mAhg-1, initial charge capacity is up to 673
mAh·g-1, in charge and discharge process, there is preferable cycle performance due to stable structure；
(3) preparation process of transition metal phosphide Fe2P of the present invention is simple, and reaction temperature is low, and the period is short, at low cost.
Detailed description of the invention
Fig. 1 is the XRD diagram of 1 gained transition metal phosphide Fe2P negative electrode material of the embodiment of the present invention；
Fig. 2 is that the SEM of 1 gained transition metal phosphide Fe2P negative electrode material of the embodiment of the present invention schemes；
Fig. 3 be 1 gained transition metal phosphide Fe2P negative electrode material of the embodiment of the present invention for the first time with the 2nd charging and discharging curve
Figure；
Fig. 4 is the charging cycle curve graph of 1 gained transition metal phosphide Fe2P negative electrode material of the embodiment of the present invention；
Fig. 5 is that the SEM of 2 gained transition metal phosphide Fe2P negative electrode material of the embodiment of the present invention schemes；
Fig. 6 is the first charge-discharge curve graph of 2 gained transition metal phosphide Fe2P negative electrode material of the embodiment of the present invention；
Fig. 7 is the first charge-discharge curve graph of 3 gained transition metal phosphide Fe2P negative electrode material of the embodiment of the present invention.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and embodiments.
Embodiment 1
(1) by 10mL deionized water and 70mLN, dinethylformamide is uniformly mixed, and obtains 80mL uniform solution；
(2) 10mmol Iron(III) chloride hexahydrate and 10mmol terephthalic acid (TPA) are added into 80mL uniform solution obtained by step (1),
Stirring and dissolving is uniform, obtains mixed solution；
(3) mixed solution obtained by step (2) is placed in polytetrafluoroethylene (PTFE) autoclave, seals, is put into high temperature drying case,
At 120 DEG C, heating carries out reaction 12h, cooled to room temperature, and filtering is taken up in order of priority friendship with dehydrated alcohol and deionized water
Fork washing filtrate 4 times, in an oven, at 60 DEG C, drying for 24 hours, obtains yellow powder；
(4) by yellow powder obtained by step (3) in high-purity argon gas atmosphere, at 450 DEG C, roasting 5h, cooled to room temperature,
Obtain black ferroferric oxide powder；High-purity argon gas purity >=99.99%(" % " is percentage by volume)；
(5) black powder obtained by step (4) and sodium hypophosphite are put into porcelain boat according to the ratio of mass ratio 1:10, black powder
End is placed in porcelain boat and is put in quartz ampoule upstream, and sodium hypophosphite is placed in porcelain boat and is put in quartz ampoule downstream, in high-purity argon gas atmosphere,
At 350 DEG C, 2h is roasted, cooled to room temperature obtains brown phosphatization iron powder；High-purity argon gas purity >=99.99%(" % " is volume
Percentage).
As shown in Figure 1, the ingredient of transition metal phosphide Fe2P negative electrode material obtained by the present embodiment is FexP, free from admixture
It generates.
As shown in Fig. 2, transition metal phosphide Fe2P negative electrode material obtained by the present embodiment is FexP。
The assembling of battery: weighing transition metal phosphide Fe2P negative electrode material obtained by 0.40g the present embodiment, is added
0.05g acetylene black makees conductive agent and 0.05g N-Methyl pyrrolidone makees binder, be applied on copper foil after mixing be made it is negative
Pole piece, with metal lithium sheet to be positive in vacuum glove box, using lithium electric separator as diaphragm, 1mol/L LiPF6/ EC:DMC(volume
Than 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
From the figure 3, it may be seen that being 3~0.01V, electric current 100mAg in charging/discharging voltage-1Under, institute's assembled battery is filled for the first time
Electric specific capacity is 673.7 mAhg-1, recharging specific capacity is 641mAhg-1, discharge capacity is 1241mAh for the first time
g-1, secondary discharge capacitance is 672 mAhg-1, material is able to maintain the stabilization of structure, volume expansion in charge and discharge process
Small, good conductivity makes discharge and recharge reaction high reversible.
It as shown in Figure 4, is 3~0.01V, current density 100mAg in charging/discharging voltage-1Under, it is filled after 200 circle of circulation
Electric specific capacity is 631mAhg-1, capacity retention ratio 98%, charge-discharge performance is stable, good cycle.
Embodiment 2
(1) by 20mL deionized water and 60mLN, dinethylformamide is uniformly mixed, and obtains 80mL uniform solution；
(2) 8mmol Fe(NO3)39H2O and 2mmol terephthalic acid (TPA), stirring are added into 80mL uniform solution obtained by step (1)
It is uniformly dissolved, obtains mixed solution；
(3) mixed solution obtained by step (2) is placed in polytetrafluoroethylene (PTFE) autoclave, seals, is put into high temperature drying case,
At 120 DEG C, heating carries out reaction 10h, cooled to room temperature, and filtering is taken up in order of priority friendship with dehydrated alcohol and deionized water
Fork washing filtering 4 times, in an oven, at 100 DEG C, dry 12h obtains yellow powder；
(4) by yellow powder obtained by step (3) in high-purity argon gas atmosphere, at 450 DEG C, roasting 4h, cooled to room temperature,
Obtain black ferroferric oxide powder;High-purity argon gas purity >=99.99%(" % " is percentage by volume)；
(5) black powder obtained by step (4) and sodium hypophosphite are put into porcelain boat according to the ratio of mass ratio 1:15, black powder
End is placed in porcelain boat and is put in quartz ampoule upstream, and sodium hypophosphite is placed in porcelain boat and is put in quartz ampoule downstream, in high-purity argon gas atmosphere,
At 350 DEG C, 3h is roasted, cooled to room temperature obtains brown phosphatization iron powder；High-purity argon gas purity >=99.99%(" % " is volume
Percentage).
Through detecting, the ingredient of transition metal phosphide Fe2P negative electrode material obtained by the present embodiment is FexP。
As shown in figure 5, transition metal phosphide Fe2P negative electrode material pattern obtained by the present embodiment is uniform.
The assembling of battery: weighing transition metal phosphide Fe2P negative electrode material obtained by 0.40g the present embodiment, is added
0.05g acetylene black makees conductive agent and 0.05g N-Methyl pyrrolidone makees binder, be applied on copper foil after mixing be made it is negative
Pole piece, with metal lithium sheet to be positive in vacuum glove box, using lithium electric separator as diaphragm, 1mol/L LiPF6/ EC:DMC(volume
Than 1:1) it is electrolyte, it is assembled into the button cell of CR2025.
As shown in fig. 6, being 3~0.01V in charging/discharging voltage, current density is 100 mAg-1Under, institute's assembled battery
Initial charge specific capacity is up to 611mAhg-1, first discharge specific capacity is up to 1068mAhg-1, material is in charge and discharge process
In be able to maintain the stabilization of structure, volume expansion is small, good conductivity, makes discharge and recharge reaction high reversible.
It is 3~0.01V, current density 100mAg in charging/discharging voltage through detecting-1Under, charge ratio after 200 circle of circulation
Capacity is 602.4mAhg-1, capacity retention ratio 95%, charge-discharge performance is stable, good cycle.
Embodiment 3
(1) by 30mL deionized water and 60mLN, dinethylformamide is uniformly mixed, and obtains 90mL uniform solution；
(2) 0.4mmol Fe(NO3)39H2O and 0.8mmol 3,5- diamino are added into 90mL uniform solution obtained by step (1)
Benzoic acid, stirring and dissolving is uniform, obtains mixed solution；
(3) mixed solution obtained by step (2) is placed in polytetrafluoroethylene (PTFE) autoclave, seals, is put into high temperature drying case,
At 100 DEG C, heating is reacted for 24 hours, cooled to room temperature, and filtering is taken up in order of priority friendship with dehydrated alcohol and deionized water
Fork washing filtering 4 times, in an oven, at 60 DEG C, drying for 24 hours, obtains yellow powder；
(4) by yellow powder obtained by step (3) in high pure nitrogen atmosphere, at 450 DEG C, roasting 6h, cooled to room temperature,
Obtain black ferroferric oxide powder；High-purity argon gas purity >=99.99%(" % " is percentage by volume)；
(5) black powder obtained by step (4) and sodium hypophosphite are put into porcelain boat according to the ratio of mass ratio 1:15, black powder
End is placed in porcelain boat and is put in quartz ampoule upstream, and sodium hypophosphite is placed in porcelain boat and is put in quartz ampoule downstream, in high-purity argon gas atmosphere,
At 350 DEG C, 3h is roasted, cooled to room temperature obtains brown phosphatization iron powder；High-purity argon gas purity >=99.99%(" % " is volume
Percentage).
Through detecting, the ingredient of transition metal phosphide Fe2P negative electrode material obtained by the present embodiment is FexP。
Through detecting, transition metal phosphide Fe2P negative electrode material pattern obtained by the present embodiment is uniform, second particle size
It is evenly distributed, partial size is 4~5 μm.
The assembling of battery: hexagonal di-iron trioxide/carbon negative pole material obtained by 0.40g the present embodiment is weighed, 0.05g is added
Acetylene black makees conductive agent and 0.05g N-Methyl pyrrolidone makees binder, is applied on copper foil negative electrode tab is made after mixing,
With metal lithium sheet to be positive in vacuum glove box, using lithium electric separator as diaphragm, 1mol/L LiPF6/ EC:DMC(volume ratio 1:
1) it is electrolyte, is assembled into the button cell of CR2025.
As shown in fig. 6, being 3~0.01V in charging/discharging voltage, current density is 100 mAg-1Under, institute's assembled battery
Initial charge specific capacity is up to 609.6 mAhg-1, first discharge specific capacity is up to 1046mAhg-1, material is in charge and discharge
The stabilization of structure is able to maintain in journey, volume expansion is small, good conductivity, makes discharge and recharge reaction high reversible.
It is 3~0.01V, current density 100mAg in charging/discharging voltage through detecting-1Under, charge ratio after 200 circle of circulation
Capacity is 687mAhg-1, capacity retention ratio 95%, charge-discharge performance is stable, good cycle.
Claims (10)
1. a kind of transition metal phosphide Fe2P negative electrode material, which is characterized in that be prepared from the following steps:
(1) water is uniformly mixed with n,N-Dimethylformamide, obtains uniform solution；
(2) source of iron and organic ligand are added into uniform solution obtained by step (1), stirring and dissolving is uniform, obtains mixed solution；
(3) mixed solution obtained by step (2) is placed in autoclave, is sealed, heating is reacted, and cooling, filtering is washed
It washs, it is dry, obtain yellow powder；
(4) in an inert atmosphere by yellow powder obtained by step (3), it roasts, it is cooling, obtain black powder；
(5) black powder obtained by step (4) is placed in porcelain boat and is put in quartz ampoule upstream, sodium hypophosphite is placed in porcelain boat and is put in stone
English pipe downstream roasts in an inert atmosphere, cooling, obtains iron phosphide negative electrode material.
2. transition metal phosphide Fe2P negative electrode material according to claim 1, it is characterised in that: step (1), water with
N,N-dimethylformamide is with the mixing of volume ratio 1:3~7.
3. transition metal phosphide Fe2P negative electrode material according to claim 1 or 2, it is characterised in that: step (2)
In, the molar ratio of ferro element and organic ligand is 0.5~4.0:1 in the source of iron.
4. transition metal phosphide Fe2P negative electrode material according to claim 1 or 2, it is characterised in that: step (2)
In, the molar concentration of iron ion is 0.01~0.20 mol/L in the mixed solution.
5. transition metal phosphide Fe2P negative electrode material according to claim 1 or 2, it is characterised in that: step (2)
In, the source of iron is one of ferric sulfate, ferric nitrate, ferric acetyl acetonade or ferric trichloride and their hydrate or several
Kind: the organic ligand be one of fumaric acid, terephthalic acid (TPA), trimesic acid or 3,5- diaminobenzoic acid or
It is several.
6. transition metal phosphide Fe2P negative electrode material according to claim 1 or 2, it is characterised in that: step (3)
In, the temperature of the heating is 100~160 DEG C, the time of heating is 10~for 24 hours.
7. transition metal phosphide Fe2P negative electrode material according to claim 1 or 2, it is characterised in that: step (3)
In, the method for the washing is to be taken up in order of priority cross washing filtrate >=3 time with ethyl alcohol and deionized water；The temperature of the drying
Be 60~100 DEG C, the dry time be 12~for 24 hours.
8. transition metal phosphide Fe2P negative electrode material according to claim 1 or 2, it is characterised in that: step (4)
In, the temperature of the roasting is 400~600 DEG C, 2~6h of time of roasting.
9. transition metal phosphide Fe2P negative electrode material according to claim 1 or 2, it is characterised in that: step (5)
In, the mass ratio of the black powder and sodium hypophosphite is 1:10~20.
10. transition metal phosphide Fe2P negative electrode material according to claim 1 or 2, it is characterised in that: step (5)
In, the temperature of the roasting is 250~350 DEG C, 2~4h of time of roasting.
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| CN201910625551.XA CN110304614A (en) | 2019-07-11 | 2019-07-11 | A kind of transition metal phosphide Fe2P negative electrode material |
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| CN111841540A (en) * | 2020-07-24 | 2020-10-30 | 扬州大学 | Spinel type CuFe rich in oxygen vacancy2O4Method for preparing photocatalyst |
| CN112054194A (en) * | 2020-08-07 | 2020-12-08 | 西安理工大学 | Phosphorus-modified lithium ion battery positive electrode material and preparation method and application thereof |
| CN113072044A (en) * | 2021-03-25 | 2021-07-06 | 安徽师范大学 | Core-shell structure FeP nano-chain, preparation method thereof and application thereof in battery |
| CN113529125A (en) * | 2021-06-16 | 2021-10-22 | 佛山市格瑞芬新能源有限公司 | Iron phosphide composite material and preparation method and application thereof |
| CN115377605A (en) * | 2022-08-22 | 2022-11-22 | 成都大学 | Hollow metal oxide-metal phosphide heterojunction material and preparation method and application thereof |
| CN115385317A (en) * | 2022-09-23 | 2022-11-25 | 宜都兴发化工有限公司 | Method for preparing mesoporous nano iron phosphate by pseudomorphic conversion method |
| CN115445643A (en) * | 2022-08-03 | 2022-12-09 | 中山大学 | Hollow spherical bimetallic phosphide catalyst and preparation method and application thereof |
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| CN111841540A (en) * | 2020-07-24 | 2020-10-30 | 扬州大学 | Spinel type CuFe rich in oxygen vacancy2O4Method for preparing photocatalyst |
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| CN112054194A (en) * | 2020-08-07 | 2020-12-08 | 西安理工大学 | Phosphorus-modified lithium ion battery positive electrode material and preparation method and application thereof |
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| CN113072044A (en) * | 2021-03-25 | 2021-07-06 | 安徽师范大学 | Core-shell structure FeP nano-chain, preparation method thereof and application thereof in battery |
| CN113072044B (en) * | 2021-03-25 | 2022-06-21 | 安徽师范大学 | Core-shell structure FeP nano-chain, preparation method thereof and application thereof in battery |
| CN113529125A (en) * | 2021-06-16 | 2021-10-22 | 佛山市格瑞芬新能源有限公司 | Iron phosphide composite material and preparation method and application thereof |
| CN115445643A (en) * | 2022-08-03 | 2022-12-09 | 中山大学 | Hollow spherical bimetallic phosphide catalyst and preparation method and application thereof |
| CN115445643B (en) * | 2022-08-03 | 2023-12-22 | 中山大学 | Hollow spherical bimetallic phosphide catalyst and preparation method and application thereof |
| CN115377605A (en) * | 2022-08-22 | 2022-11-22 | 成都大学 | Hollow metal oxide-metal phosphide heterojunction material and preparation method and application thereof |
| CN115385317A (en) * | 2022-09-23 | 2022-11-25 | 宜都兴发化工有限公司 | Method for preparing mesoporous nano iron phosphate by pseudomorphic conversion method |
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