CN110459768A - A kind of octahedral structure iron phosphide/carbon composite and the preparation method and application thereof - Google Patents

A kind of octahedral structure iron phosphide/carbon composite and the preparation method and application thereof Download PDF

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Publication number
CN110459768A
CN110459768A CN201910749728.7A CN201910749728A CN110459768A CN 110459768 A CN110459768 A CN 110459768A CN 201910749728 A CN201910749728 A CN 201910749728A CN 110459768 A CN110459768 A CN 110459768A
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iron phosphide
carbon composite
octahedral structure
preparation
mixed solution
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童汇
黄英德
毛高强
喻万景
丁治英
郑俊超
张宝
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Central South University
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Central South University
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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
    • 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
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A kind of octahedral structure iron phosphide/carbon composite and the preparation method and application thereof, the composite material include carbon-coated iron phosphide in situ, and the iron phosphide particle size is 400 ~ 700nm, and particle is uniform, have octahedral structure；After the composite material is assembled into lithium ion battery, its lithium ion battery has many advantages, such as that good rate capability, good cycling stability, conductivity are high, the invention also includes the preparation methods of the octahedral structure iron phosphide/carbon composite, the operating method is simple, at low cost, controllability is strong, is suitable for industrialized production.

Description

A kind of octahedral structure iron phosphide/carbon composite and the preparation method and application thereof
Technical field
The present invention relates to a kind of lithium ion battery negative materials and the preparation method and application thereof, and in particular to a kind of lithium ion Cell negative electrode material octahedron iron phosphide/carbon composite and the preparation method and application thereof.
Background technique
With the increasingly shortage of the energy and getting worse for problem of environmental pollution, lithium ion battery is due to its energy density It is high, have extended cycle life, self discharge it is small, advantages of environment protection is more and more widely used in portable electronic device, mixing The fields such as power electric automobile and smart grid.However, with to height ratio capacity and high energy density cells technical need not Disconnected to increase, commercial graphitic anode material is due to its relatively low specific capacity (~ 350mAh.g at present-1) required without being able to satisfy. Therefore, high-energy density, high circulation stability are developed, the excellent novel advanced negative electrode material of high rate performance is traditional to substitute Negative electrode material is the most important thing.
At present in the research of phosphorio compound, for iron phosphide because its is cheap, storage capacity is abundant and has 926 mAh.g-1High theoretical specific capacity and have broad application prospects.However iron phosphide negative electrode material is violent in charge and discharge process Volume change (~ 202%), reunite it is low with conductivity, will lead to iron phosphide material electrodes polarization, crush, collector contact make electricity Pole active material quickly dissolves, and so as to cause the rapid decay of specific capacity, cycle performance is reduced.
CN103094565A discloses a kind of LiFePO4/iron phosphide/carbon composite nano-fiber, including following quality percentage Than the component of content: 50 ~ 99% LiFePO4,0.5 ~ 30% iron phosphide and 1 ~ 20% carbon, the LiFePO4/iron phosphide/carbon are multiple The average diameter of nanofiber is closed between 50 ~ 500nm, there are the spherical particles of iron phosphide in the fiber.What the invention provided LiFePO4/iron phosphide/carbon composite nano-fiber has good fiber morphology and electric conductivity, but the material electrochemical performance The means of modulation are exactly to change the viscosity of spinning solution, and most effective way is to change the concentration of polymer, polymer concentration Height, then fiber is thick；Polymer concentration is low, then fiber finer.The invention is inconvenient for operation and synthetic method is complicated.
CN105148958 A discloses a kind of method based on iron sulfide preparation high activity sulfur doping iron phosphide, feature It is to include the following steps: that vulcanized sodium and ferrous sulfate are dissolved in respectively in a certain amount of deionized water, then vulcanized sodium is added dropwise Enter into ferrous ions soln, what is obtained is precipitated as ferrous sulfide, and centrifugation washs, is spare after drying；By a certain amount of iron sulfide Powder and sodium hypophosphite mixing, after said mixture is then warming up to 250 ~ 550 DEG C under inert gas protection, heat treatment 1 ~ 2h.Furnace is down to room temperature after completion of the reaction, it is standby with the nitrogen inerting catalyst 1 hour, obtained containing 1% oxygen With；If iron sulfide to be substituted for the iron sulfide of support type, the sulfur doping iron phosphide of available support type.Although the synthesis side Method is simple, and still, the sulfur doping iron phosphide material property of synthesis is bad.
CN106345501, which is disclosed, a kind of prepares iron phosphide based on the carbon nano-tube modified composite material of magnetic ionic liquids Method and products thereof and application, the preparation method include the following steps: (1) by magnetic ionic liquids and carbon nanotube with quality It is uniformly mixed than 0.1 ~ 0.2:0.1 ~ 0.4, methanol is then added and continues grinding 15 ~ 45 minutes, dries to obtain composite material；(2) with Mass ratio 0.1 ~ 0.2:0.1 ~ 0.3 uniformly mixes composite material prepared by step (1) with sodium hypophosphite, in ar gas environment pipe 250 ~ 400 DEG C of heating obtain iron phosphide in 8 ~ 16 hours in formula furnace.Cathode is loaded to using the iron phosphide of preparation as liberation of hydrogen catalyst And be applied in electrolysis wate research, find it with good catalytic activity.But the material can not be applied to lithium-ion electric The use of pond negative electrode material.
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 are protected；Products therefrom is finely ground, is distinguished with distilled water and dehydrated alcohol Three times, then 60 DEG C of vacuum drying 12h, obtain product F e for washing2P.Although primary raw material needed for the preparation of this method material comes Source is abundant, and cheap, cost is relatively low.But resulting materials performance is bad.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, it is swollen to provide a kind of volume It is swollen it is small, chemical property is good, the excellent octahedral structure iron phosphide/carbon composite of cycle performance.
The further technical problems to be solved of the present invention are to provide a kind of octahedral structure phosphorus easy to operate, at low cost Change iron/carbon composite preparation method.
The technical solution adopted by the present invention to solve the technical problems is a kind of octahedral structure iron phosphide/Carbon anode material Expect composite material, including carbon-coated iron phosphide in situ, the iron phosphide particle size is 400 ~ 700nm.
The present invention further solves its technical problem the technical scheme adopted is that a kind of octahedral structure iron phosphide/carbon The preparation method of composite material, comprising the following steps:
(1) by FeCl3.6H2O powder is added in DMF solution, heats, and stirring obtains mixed solution；
(2) organic ligand powder is added into mixed solution obtained by step (1), heats, stirs, ultrasonic treatment obtains mixed solution；
(3) mixed solution obtained by step (2) being placed in autoclave, is sealed, solvent thermal reaction occurs for heating, and it is cooling, Centrifugation is washed, dry, obtains yellow powder；
(4) it by yellow powder obtained by step (3) in argon gas or nitrogen atmosphere, roasts, it is cooling, obtain black powder；
(5) porcelain boat for filling black powder obtained by step (4) is placed in quartz ampoule downstream, the porcelain boat for filling red phosphorus is placed in quartz ampoule Upstream roasts in argon gas or nitrogen atmosphere, cooling, obtains iron phosphide/carbon composite.
Preferably, in step (1), FeCl in the mixed solution3.6H2The molar concentration of O is 20mmol/L ~ 40mmol/ L, if FeCl in the mixed solution3. 6H2The molar concentration of O is excessively high or too low, is not easy and organic ligand in step (2) Form metallorganic framework material.
Preferably, in step (1), the heating temperature is 25 ~ 50 DEG C, and temperature is too low to be will be unable to guarantee FeCl3.6H2O powder The dissolution at end, temperature is excessively high, will lead to the solvent evaporation of the mixed solution.
Preferably, in step (1), the speed of the stirring is more preferable 400 ~ 700 turns/min of 80 ~ 800 turns/min(), The time of the stirring is 0.5 ~ 2h.
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 are connection metal ions, form organic matter and gold Belong to the connected framework material of ion.
Preferably, in step (2), the organic ligand and FeCl3.6H2The molar ratio of O is 0.25 ~ 2:1.If iron ion is dense Height is spent, then gained metallorganic framework material is easy to reunite, if iron concentration is too low, is difficult to form metallorganic bone Frame material.
Preferably, in step (2), the temperature of the heating is 25 ~ 50 DEG C；The speed of the stirring be 80~800 turns/ Min, the time of stirring are 0.5 ~ 2 h.
Preferably, in step (3), the temperature of the heating is 100 ~ 160 DEG C, and the time of heating is 4 ~ 18h.If when heating Between it is too short or too long, will affect the formation of crystal.
Preferably, in step (3), the method for the washing is to be taken up in order of priority intersection centrifugation with ethyl alcohol and deionized water to wash It washs.
Preferably, in step (3), 8000 ~ 10000 turns/min of revolving speed of the centrifugation, 8 ~ 12 min of centrifugation time, from Heart number >=6 time.
Preferably, in step (3), the temperature of the drying is 60 ~ 100 DEG C, and the dry time is 12 ~ 24 h.
Preferably, in step (4), the temperature of the roasting is 500 ~ 700 DEG C, and the time of roasting is 2 ~ 6h.The roasting At a temperature of, organic matter is decomposed to form carbon coating on the surface of metallic atom, forms carbon-coated octahedral structure in situ.If warm Height or too low is spent, then is difficult to obtain the octahedral structure of rule.
Preferably, in step (4), purity >=99.99% of the argon gas or nitrogen.
Preferably, in step (5), the mass ratio of the black powder and red phosphorus is 1:5 ~ 10.
Preferably, in step (5), the temperature of the roasting is 750 ~ 900 DEG C, and the time of roasting is 1 ~ 3h.In the roasting At a temperature of burning, red phosphorus distillation is phosphorus steam, is reacted with black powder obtained by above-mentioned steps (4), obtains retaining octahedral structure Iron phosphide/carbon composite.
Preferably, in step (5), the type of cooling is natural cooling.
Technical principle of the invention is: using DMF as suitable polar solvent, the gold for generating source of iron and organic ligand Category organic matter framework material can be formed as the material of octahedral structure during solvent heat；Make therein to have by roasting again Machine object conversion is carbon, and in-stiu coating is on the surface of metallic atom, finally by the phosphorus steam under high temperature to the production after roasting Object carries out phosphatization, obtains iron phosphide/carbon material of octahedral structure.To be conducive to protect due to saving metallorganic skeleton The stabilization of structure is held, so that electrode material is highly stable in charge and discharge process, while carbon coating in situ can not only alleviate body Product expansion, also improves the electric conductivity of material, it is made to show excellent chemical property.
Compared with prior art, the present invention has the following beneficial effects:
(1) octahedral structure iron phosphide/carbon composite ingredient of the present invention is FeP, belongs to poromerics, there is electrolyte Imitate and material shortens the diffusion path of lithium ion and electronics, accelerates the transition of ion and electronics.In-situ carbon packet simultaneously The volume for the FeP nanoparticle cyclic process being limited in porous carbon skeleton has not only been effectively relieved in the octahedral structure covered Expansion, while the metallorganic skeleton retained can increase the electric conductivity of material；(2) by the iron phosphide/carbon composite Negative electrode of lithium ion battery is made, is assembled into battery, in 0.1 ~ 3.0V voltage range, 1C(1C=1000mA.g-1) under big multiplying power, Still there are 737.7 mAh.g after 450 circle of circulation-1Specific discharge capacity, capacity retention ratio >=95%.In charge and discharge process, due to steady Fixed structure and there is preferable cycle performance；(3) preparation method technical process of the present invention is simple, and the period is short, at low cost.
Detailed description of the invention
Fig. 1 is 1 gained octahedral structure iron phosphide of the embodiment of the present invention/carbon composite XRD diagram；
Fig. 2 is 1 gained octahedral structure iron phosphide of the embodiment of the present invention/carbon composite SEM figure；
Fig. 3 is the preceding charging and discharging curve figure three times of 1 gained octahedral structure iron phosphide of the embodiment of the present invention/carbon composite；
Fig. 4 is 1 gained octahedral structure iron phosphide of the embodiment of the present invention/carbon composite charging cycle curve graph；
Fig. 5 is 2 gained octahedral structure iron phosphide of the embodiment of the present invention/carbon composite SEM figure；
Fig. 6 is the preceding charging and discharging curve figure three times of 2 gained octahedral structure iron phosphide of the embodiment of the present invention/carbon composite；
Specific embodiment
Invention is further described in detail with reference to embodiments, but protection scope of the present invention is not limited to following implementation Example.Chemical reagent used in each embodiment as described below is bought by routine business approach unless otherwise instructed.
Embodiment 1
Octahedral structure iron phosphide/carbon composite embodiment of the present invention includes carbon-coated iron phosphide in situ, the iron phosphide Particle size is 400 ~ 700nm.
The present embodiment octahedral structure iron phosphide/carbon negative pole material composite material preparation method, comprising the following steps:
(1) FeCl of 1mmol is weighed3.6H2O powder is added in the DMF solution of 50ml, is heated to 30 DEG C, stirs 1 h, stirring Speed be 800 turns/min, obtain mixed solution；
(2) terephthalic acid powder of 1mmol is added into mixed solution obtained by step (1), is heated to 30 DEG C, stirs 1 h, stirs The speed mixed is 800 turns/min, is then ultrasonically treated, obtains mixed solution；
(3) mixed solution obtained by step (2) is placed in polytetrafluoroethylene (PTFE) autoclave, seals, is placed in high temperature drying case, 120 DEG C are heated to, 8h is reacted, natural cooling is taken up in order of priority intersection centrifuge washing 6 times with ethyl alcohol and deionized water, centrifugal rotational speed For 8000 turns/min, each centrifugation time is 8min, is then placed it in baking oven, 60 DEG C of dryings for 24 hours, obtain yellow powder；
(4) by yellow powder obtained by step (3) in high-purity argon gas atmosphere, at 700 DEG C, 2h is roasted, natural cooling obtains black Powder.
(5) black powder obtained by step (4) and red phosphorus are put into porcelain boat according to mass ratio 1:5, black powder will be filled Porcelain boat be placed in quartz ampoule downstream, the porcelain boat for filling red phosphorus is placed in quartz ampoule upstream.In high-purity argon gas atmosphere, at 800 DEG C, 2h is roasted, natural cooling obtains brown iron phosphide/carbon composite powder.
Through detecting, octahedral structure iron phosphide/carbon composite ingredient obtained by the present embodiment is FeP, free from admixture.
As shown in Fig. 2, octahedral structure iron phosphide/carbon composite phosphatization iron particle obtained by the present embodiment is uniform.
The assembling of battery: octahedral structure iron phosphide/carbon composite 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, after mixing, is applied on copper foil and negative electrode tab is made, 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.
From the figure 3, it may be seen that being 3 ~ 0.01V, current density 100mA.g in charging/discharging voltage-1Under, institute's assembled battery is for the first time Charge specific capacity is 1043.8mAh.g-1, recharging specific capacity is 956.9mAh.g-1, first discharge specific capacity is 1827.4mAh.g-1, secondary discharge specific capacity is 1037.6mAh.g-1, the present embodiment resulting materials can in charge and discharge process The stabilization of structure is kept, volume expansion is small, good conductivity, makes discharge and recharge reaction high reversible.
It as shown in Figure 4, is 3 ~ 0.01V, current density 1A.g in charging/discharging voltage-1Under, discharge specific volume after 450 circle of circulation Amount is 737.7mAh.g-1, specific capacity conservation rate is 95%, and charge-discharge performance is stablized, good cycle.
Embodiment 2
(1) FeCl of 1.5mmol is weighed3.6H2O powder is added in the DMF solution of 80ml, is heated to 40 DEG C, is stirred 1 h, is stirred The speed mixed is 500 turns/min, obtains mixed solution；
(2) the trimesic acid powder of 1mmol is added into mixed solution obtained by step (1), is heated to 40 DEG C, stirs 0.5h, The speed of stirring is 500 turns/min, is then ultrasonically treated, obtains mixed solution；
(3) mixed solution obtained by step (2) is placed in polytetrafluoroethylene (PTFE) autoclave, seals, is placed in high temperature drying case, 120 DEG C are heated to, 12h is reacted, then natural cooling is taken up in order of priority intersection centrifuge washing 6 times with ethyl alcohol and deionized water, centrifugation Revolving speed is 9000 turns/min, and each centrifugation time is 8min, is then placed it in baking oven, 80 DEG C of dry 20h obtain yellow powder End；
(4) by yellow powder obtained by step (3) in high-purity argon gas atmosphere, at 500 DEG C, 3h is roasted, natural cooling obtains black Powder.
(5) black powder obtained by step (4) and red phosphorus are put into porcelain boat according to mass ratio 1:8, black powder will be filled Porcelain boat be placed in quartz ampoule downstream, the porcelain boat for filling red phosphorus is placed in quartz ampoule upstream.In high-purity argon gas atmosphere, at 750 DEG C, 3h is roasted, natural cooling obtains brown iron phosphide/carbon composite powder.
Through detecting, octahedral structure iron phosphide/carbon composite ingredient obtained by the present embodiment is FeP, free from admixture.
As shown in figure 5, octahedral structure iron phosphide/carbon composite structures pattern obtained by the present embodiment is uniform.Battery Assembling: weighing octahedral structure iron phosphide/carbon composite obtained by 0.40g the present embodiment, and 0.05g acetylene black is added and makees conductive agent Make binder with 0.05g N-Methyl pyrrolidone, after mixing, is applied on copper foil and negative electrode tab is made, in vacuum glove box It is anode with metal lithium sheet, using lithium electric separator as diaphragm, 1mol/L LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, assembling At the button cell of CR2025.
It will be appreciated from fig. 6 that being 3 ~ 0.01V, current density 100mA.g in charging/discharging voltage-1Under, institute's assembled battery is for the first time Charge specific capacity is 738.6 mAh.g-1, recharging specific capacity is 699.4mAh.g-1, first discharge specific capacity is 1395.4mAh.g-1, secondary discharge specific capacity is 747.8mAh.g-1, the present embodiment resulting materials can in charge and discharge process The stabilization of structure is kept, volume expansion is small, good conductivity, makes discharge and recharge reaction high reversible.
It is 3 ~ 0.01V, current density 1A.g in charging/discharging voltage through detecting-1Under, specific discharge capacity after 450 circle of circulation For 526.8mAh.g-1, specific capacity conservation rate is 95%, and charge-discharge performance is stablized, good cycle.
Embodiment 3
(1) FeCl of 2mmol is weighed3.6H2O powder is added in the DMF solution of 60ml, is heated to 50 DEG C, stirs 1 h, stirring Speed be 400 turns/min, obtain mixed solution；
(2) the amino terephthalic acid powder of 4mmol is added into mixed solution obtained by step (1), is heated to 50 DEG C, stirring 2h, the speed of stirring are 800 turns/min, and ultrasonic treatment obtains mixed solution；
(3) mixed solution obtained by step (2) is placed in polytetrafluoroethylene (PTFE) autoclave, seals, is placed in high temperature drying case, 150 DEG C are heated to, 16h is reacted, then natural cooling is taken up in order of priority intersection centrifuge washing 6 times with ethyl alcohol and deionized water, centrifugation Revolving speed is 10000 turns/min, and each centrifugation time is 8min, is then placed it in baking oven, 100 DEG C of dry 16h obtain yellow powder End；
(4) by yellow powder obtained by step (3) in high-purity argon gas atmosphere, at 600 DEG C, 3h is roasted, natural cooling obtains black Powder.
(5) black powder obtained by step (4) and red phosphorus are put into porcelain boat according to mass ratio 1:10, black powder will be filled Porcelain boat be placed in quartz ampoule downstream, the porcelain boat for filling red phosphorus is placed in quartz ampoule upstream.In high-purity argon gas atmosphere, at 900 DEG C, 2h is roasted, natural cooling obtains brown iron phosphide/carbon composite powder.
Through detecting, octahedral structure iron phosphide/carbon composite ingredient obtained by the present embodiment is FeP, free from admixture.
Through detecting, octahedral structure iron phosphide/carbon composite structures obtained by the present embodiment are stablized, and pattern is uniform, particle Size is between 400 ~ 700nm.
The assembling of battery: octahedral structure iron phosphide/carbon composite 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, after mixing, is applied on copper foil and negative electrode tab is made, 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.
It is 3 ~ 0.01V, current density 100mA.g in charging/discharging voltage through detecting-1Under, institute's assembled battery is filled for the first time Electric specific capacity is 637.3mAh.g-1, recharging specific capacity is 641mAh.g-1, discharge capacity is 1241mAh.g for the first time-1, Secondary discharge capacitance is 672mAh.g-1, the present embodiment resulting materials are able to maintain the stabilization of structure, body in charge and discharge process Product expands small, good conductivity, makes discharge and recharge reaction high reversible.
It is 3~0.01V, current density 1A.g in charging/discharging voltage through detecting-1Under, specific discharge capacity after 450 circle of circulation For 427.7mAh.g-1, specific capacity conservation rate is 97%, and charge-discharge performance is stablized, good cycle.

Claims (10)

1. a kind of octahedral structure iron phosphide/carbon composite, which is characterized in that described including carbon-coated iron phosphide in situ Iron phosphide particle size is 400 ~ 700nm.
2. a kind of preparation method of octahedral structure iron phosphide/carbon composite, which comprises the following steps:
(1) by FeCl3.6H2O powder is added in DMF solution, heats, and stirring obtains mixed solution；
(2) organic ligand powder is added into mixed solution obtained by step (1), heats, stirs, ultrasonic treatment obtains mixed solution；
(3) mixed solution obtained by step (2) being placed in autoclave, is sealed, solvent thermal reaction occurs for heating, and it is cooling, Centrifugation is washed, dry, obtains yellow powder；
(4) it by yellow powder obtained by step (3) in argon gas or nitrogen atmosphere, roasts, it is cooling, obtain black powder；
(5) porcelain boat for filling black powder obtained by step (4) is placed in quartz ampoule downstream, the porcelain boat for filling red phosphorus is placed in quartz ampoule Upstream roasts in argon gas or nitrogen atmosphere, cooling, obtains iron phosphide/carbon composite.
3. octahedral structure iron phosphide/carbon composite preparation method according to claim 2, which is characterized in that step (1) in, FeCl in the mixed solution3.6H2The molar concentration of O is 20mmol/L ~ 40mmol/L, and the temperature of the heating is 25 ~ 50 DEG C, the speed of the stirring is 80 ~ 800 turns/min, more preferable 400 ~ 700 turns/min, time 0.5 of the stirring ~ 2h。
4. the iron phosphide of the octahedral structure according to Claims 2 or 3/carbon composite preparation method, which is characterized in that step Suddenly in (2), the organic ligand is fumaric acid, terephthalic acid (TPA), trimesic acid or 3, in 5- diaminobenzoic acid It is one or more of.
5. the iron phosphide of the octahedral structure according to one of claim 2 ~ 4/carbon composite preparation method, feature exist In, in step (2), the organic ligand and FeCl3.6H2The molar ratio of O is 0.25 ~ 2:1；The temperature of the heating is 25 ~ 50 ℃；The speed of the stirring is 80 ~ 800 turns/min, and the mixing time is 0.5 ~ 2 h.
6. the iron phosphide of the octahedral structure according to one of claim 2 ~ 5/carbon composite preparation method, feature exist In in step (3), the temperature of the heating is 100 ~ 160 DEG C, and the time of the heating is 4 ~ 18h.
7. the iron phosphide of the octahedral structure according to one of claim 2 ~ 6/carbon composite preparation method, feature exist In in step (3), the method for the washing is to be taken up in order of priority intersection centrifuge washing with ethyl alcohol and deionized water, the centrifugation 8000 ~ 10000 turns/min of revolving speed, 8 ~ 12 min of centrifugation time, are centrifuged number >=6 time, and the temperature of the drying is 60 ~ 100 DEG C, drying time is 12 ~ 24 h.
8. according to the iron phosphide of octahedral structure described in claim 2 ~ 7/carbon composite preparation method, which is characterized in that step Suddenly in (4), the temperature of the roasting is 500 ~ 700 DEG C, and the time of roasting is 2 ~ 6h, the purity of the argon gas or nitrogen >= 99.99%。
9. the iron phosphide of the octahedral structure according to one of claim 2 ~ 8/carbon composite preparation method, feature exist In in step (5), the mass ratio of the black powder and red phosphorus is 1:5 ~ 10, and the temperature of the roasting is 750 ~ 900 DEG C, roasting The time of burning is 1 ~ 3h.
10. a kind of octahedral structure iron phosphide as described in claim 1/application of the carbon composite in lithium ion battery.
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