CN105006551B - A kind of sodium-ion battery phosphorization tin/Graphene anode material and preparation method thereof - Google Patents

A kind of sodium-ion battery phosphorization tin/Graphene anode material and preparation method thereof Download PDF

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CN105006551B
CN105006551B CN201510299379.5A CN201510299379A CN105006551B CN 105006551 B CN105006551 B CN 105006551B CN 201510299379 A CN201510299379 A CN 201510299379A CN 105006551 B CN105006551 B CN 105006551B
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tin
graphene
phosphorization
anode material
ion battery
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CN105006551A (en
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张治安
赵星星
杨富华
李劼
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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
    • 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
    • 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
    • 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
    • H01M4/36—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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

The invention discloses a kind of sodium-ion battery phosphorization tin/Graphene anode material and preparation method thereof; the anode material is that the three-dimensional structure material that nanometer phosphorization tin particle surface is constituted is wrapped in by flake graphite alkene; preparation method is that first metallic tin powder, phosphorus powder and abrading-ball are added in the ball grinder of high energy ball mill; under inert gas or nitrogen atmosphere protection; ball milling is carried out while chemically reacting, a nanometer phosphatization tin particles are obtained；Ball milling is further carried out to addition graphene dispersing solution in ball grinder again, graphene uniform is wrapped in a nanometer phosphorization tin particle surface, ball milling product is placed in inert gas or nitrogen environmental protection and is heat-treated, and obtains final product phosphorization tin/Graphene negative material；The composite is prepared into be tested after half-cell as anode material of lithium-ion battery and shows that it has the cycle performance of charging and discharging capacity very high and stabilization；The preparation method of the composite is simple and reliable, and good process repeatability is workable, environment-friendly, is adapted to industrialized production.

Description

A kind of sodium-ion battery phosphorization tin/Graphene anode material and preparation method thereof
Technical field
The present invention relates to a kind of phosphorization tin/Graphene anode material for sodium-ion battery and preparation method thereof, Belong to sodium-ion battery field.
Background technology
Lithium ion battery is current prevailing electrochemical energy storage system, with PC, video camera, mobile phone etc. The rapidly popularization of mobile device, and its good application prospect in terms of electric motor car, hybrid vehicle, the demand of lithium battery Constantly increase.But the bottleneck as batch production, large scale business such as the price of lithium is raised, reserves are limited.Sodium ion electricity Because sodium resource reserves are abundant, low cost receives extensive concern, the research and development of sodium-ion battery are to a certain extent in pond Can relax because the battery that lithium resource shortage triggers develops limitation problem, it is considered to be substitute lithium ion battery electronic as the next generation The ideal chose of automobile power power supply and extensive energy-accumulating power station with stand-by power source.Due to the ionic radius (0.102nm) of sodium ion Ionic radius (0.76nm) than lithium ion is big by 55% so that sodium ion is embedded in battery material and deviates from than lithium ion more Plus it is difficult, positive and negative electrode material is the core component of battery, and its performance directly determines the chemical property of battery, thus, exploitation Excellent performance, cheap anode material of lithium-ion battery will turn into the emphasis of research, be also current sodium-ion battery development A significant challenge.
Result of study shows, tin (847mAh g-1) and phosphorus (2596mAh g-1) all there is storage sodium capacity very high, its change Compound phosphorization tin can occur electrochemical reaction generation Na with sodium15Sn4And Na3P, therefore phosphorization tin has as sodium cell negative pole material High volume and capacity ratio (6650mAh cm-3), but due to itself low electrons/ions electrical conductivity and in deintercalation sodium process Middle have serious volumetric expansion and cause that its cyclical stability is extremely low, causes its application limited, therefore how to improve phosphorization tin Cyclical stability, into the key that phosphorization tin is studied as anode material of lithium-ion battery.At present, phosphatization is not slowed down effectively also Tin causes the method for its capacity rapid decay during deintercalation sodium due to volumetric expansion.And up to the present, will not also Graphene and the effectively compound technology for preparing composite of phosphorization tin, more without related compound material as sode cell negative material Relevant report.
The content of the invention
For the defect that existing sodium-ion battery material is present, it is to provide a kind of with sheet that the purpose of the present invention is Graphene uniform wraps up the three-dimensional structure of nanometer phosphatization tin particles, and can be used to prepare has high charge-discharge specific capacity, good multiplying power The phosphorization tin of the sodium-ion battery of performance and long circulation life/Graphene anode material.
It is to provide a kind of process is simple, reproducible that another object of the present invention is, environment-friendly, can industrial metaplasia The method for preparing phosphorization tin/Graphene anode material produced.
In order to realize technical purpose of the invention, the invention provides a kind of phosphorization tin/graphite for sodium-ion battery Alkene anode material, the composite is wrapped in a nanometer phosphorization tin particle surface by flake graphite alkene and constituted.
The solution of the present invention is using the sheet stone with high conductivity, high mechanical properties, bigger serface and high porosity Black alkene is wrapped in a nanometer phosphorization tin particle surface, on the one hand can improve the monolithic conductive of electrode material, on the other hand can stretch The Graphene of contracting can effectively alleviate the volumetric expansion of nanometer phosphorization tin again, improve its Stability Analysis of Structures in charge and discharge process Property, so as to improve cycle performance of battery.
The quality of nanometer phosphorization tin accounts for nanometer phosphorization tin and Graphene in preferred phosphorization tin/Graphene anode material The 50~90% of gross mass.
The particle diameter of nanometer phosphatization tin particles is 200~800nm in preferred phosphorization tin/Graphene anode material.
Flake graphite alkene is to be wrapped in nanometer by high-energy ball milling method in preferred phosphorization tin/Graphene anode material Phosphorization tin particle surface；Described phosphatization tin particles react generation by metallic tin and phosphorus under ball milling condition.Under ball milling condition Particle diameter can be obtained for Nano grade, and purity phosphatization tin particles high, then by high-energy ball milling method flake graphite alkene can be made uniform It is wrapped in a nanometer phosphorization tin particle surface.
Present invention also offers a kind of method for preparing described phosphorization tin/Graphene anode material, the method is First metallic tin powder, phosphorus powder and abrading-ball are added in the ball grinder of high energy ball mill, under inert gas or nitrogen protection, are carried out Ball milling chemically reacts simultaneously, obtains a nanometer phosphatization tin particles；Further enter to addition graphene dispersing solution in ball grinder again Row ball milling, makes graphene uniform be wrapped in a nanometer phosphorization tin particle surface, and ball milling product is placed in inert gas or nitrogen protection ring In border, it is warmed up to 650~750 DEG C and is heat-treated, obtains final product.
The method for preparing phosphorization tin/Graphene anode material of the invention also includes following preferred scheme：
The ratio between amount of material of metallic tin powder and phosphorus powder is 3~3.5 in preferred scheme:4.
Metallic tin powder and the mass ratio of abrading-ball are 1 in preferred scheme:30~50.
The ball grinder rotating speed of high energy ball mill is 1000~1500r/min in preferred scheme.
The time of metallic tin powder and the phosphorus powder ball milling in high energy ball mill is 6~12h in preferred scheme, adds Graphene After dispersion liquid, the time for further carrying out ball milling is 1~3h.
Graphene dispersing solution is obtained in aqueous by Graphene by ultrasonic disperse in preferred scheme.
More preferably the ultrasonic disperse time is 3~5h in scheme.
More preferably Graphene and the mass ratio of metallic tin powder are 0.13~1.2 in scheme:1.
Heat treatment process is to be warmed up to 650~750 DEG C, insulation 2 with the heating rate of 1~10 DEG C/min in preferred scheme ~3h.
The specific volume quantity measuring method of phosphorization tin/Graphene negative material prepared by the present invention：
Weigh the phosphorization tin/Graphene negative material of a certain amount of above-mentioned synthesis, add 10wt% conductive blacks as leading Electric agent, 10wt% sodium alginates as binding agent, plus it is a small amount of water is ground is thoroughly mixed to form uniform pastel, be coated in copper As test electrode on paper tinsel matrix, button cell is made as to electrode using metallic sodium, its electrolyte is 1M NaClO4/EC： DEC(1:1)+5wt% FEC, test charging and discharging currents density is 500mA/g.
Beneficial effects of the present invention：The present invention prepares nanometer phosphorization tin with metallic tin powder and phosphorus powder by high-energy ball milling method, Flake graphite alkene is uniformly further wrapped in by a nanometer phosphatization tin surfaces using high-energy ball milling method, a kind of phosphorization tin/stone is obtained Black alkene negative material, it can be used to prepare the sodium ion with high charge-discharge specific capacity, good high rate performance and long circulation life Battery.Compared with the prior art, it has the advantage that：
1st, the present invention is received using the Graphene parcel with high conductivity, high mechanical properties, bigger serface and porosity Rice phosphatization tin particles, one side Graphene can improve the monolithic conductive of electrode material, on the other hand telescopic Graphene The volumetric expansion of nanometer phosphorization tin can effectively be alleviated again, its structural stability in charge and discharge process is improved, so as to improve Cycle performance of battery.
2nd, the present invention simply prepares phosphorization tin/Graphene negative material by high-energy ball milling method, is prepared by ball-milling method Nanometer phosphorization tin purity is high, and particle is uniform and particle diameter is being distributed in nanoscale, while flake graphite to be uniformly wrapped in a nanometer phosphorus Change tin surfaces, further increase the chemical property of composite.
3rd, operation is simple and reliable for high-energy ball milling method of the invention, and good process repeatability is environment-friendly, is adapted to industry metaplasia Produce.
4th, phosphorization tin/graphene composite material prepared by the present invention, during as anode material of lithium-ion battery, with very high Charging and discharging capacity and good cycle performance and high rate performance.
Brief description of the drawings
【Fig. 1】It is the X ray diffracting spectrum (XRD) of phosphorization tin/Graphene anode material in embodiment 1；
【Fig. 2】The scanning electron microscope (SEM) photograph (SEM) of phosphorization tin/Graphene anode material obtained in embodiment 1；
【Fig. 3】The constant current of the sodium-ion battery of phosphorization tin/Graphene anode material assembling obtained in embodiment 1 is filled Discharge performance figure；
【Fig. 4】The sodium-ion battery of phosphorization tin/Graphene anode material assembling is forthright again obtained in embodiment 1 Can figure.
Specific embodiment
Following examples are intended to be described in further details present invention, are protected rather than to the claims in the present invention The limitation of scope.
Embodiment 1
Weigh raw material, phosphorus powder 0.125g, glass putty 0.6g, mixing abrading-ball 30g；Raw material are put into together with abrading-ball is mixed In ball mill tank, sealed after being passed through nitrogen, then carry out ball milling at room temperature, holding ball mill tank rotating speed is in mechanical milling process 1500r/min, ball milling 6h；0.275g Graphenes are weighed, 60ml deionized waters are added, ultrasonic disperse 3h obtains graphene dispersion Liquid, is added in ball grinder, continues ball milling 2h, after suction filtration is dried, is put in drying in 60 DEG C of drying box, is then protected in nitrogen Under in tube furnace with the heating rate of 5 DEG C/min be warmed up to 750 DEG C and be incubated 3h, you can obtaining a nanometer phosphatization Theil indices is The phosphorization tin of 72.5wt%/Graphene anode material.
Button cell is assembled into using sode cell composite negative pole material manufactured in the present embodiment and sodium piece, its material characterization and Chemical property is as shown in the figure：
Be can be seen that in Fig. 1 each diffraction maximum in phosphorization tin/Graphene negative material position and relative intensity and JCPDS (JCPDS) card (71-2221) matches, and shows product for nanometer phosphorization tin, without other miscellaneous peaks, Show that material purity is very high, other reactions do not occur in mechanical milling process and heat treatment process；
It can be seen that Graphene successfully wraps a nanometer phosphatization tin particles in Fig. 2, the particle diameter of nanometer phosphatization tin particles is 400 ~600nm.
Fig. 3 shows the electrode being made of phosphorization tin/Graphene negative material, at room temperature in 500mA/g constant-current discharges When, first discharge specific capacity is 1010mAh/g, and circulation 80 is enclosed specific capacity and may remain in 460mAh/g, shows good following Ring performance；
Fig. 4 shows the electrode respective battery being made of phosphorization tin/Graphene anode material in different discharge-rates Under high rate performance figure, it can be found that the composite has excellent high rate performance, under big multiplying power 1000mA/g, capacity is still 370mAh/g is positively retained at, capacity is returned to 450mAh/g again after current density slowly returns to 500mA/g by high current.
Embodiment 2
Weigh raw material, phosphorus powder 0.125g, glass putty 0.6g, mixing abrading-ball 30g；Raw material are put into together with abrading-ball is mixed In ball mill tank, sealed after being passed through argon gas, then carry out ball milling at room temperature, holding ball mill tank rotating speed is in mechanical milling process 1200r/min, ball milling 12h；0.6g Graphenes are weighed, 100ml deionized waters are added, ultrasonic disperse 3h obtains graphene dispersion Liquid, is added in ball grinder, continues ball milling 2h, after suction filtration is dried, is put in drying in 60 DEG C of drying box, is then protected in argon gas Under in tube furnace with the heating rate of 5 DEG C/min be warmed up to 750 DEG C and be incubated 3h, you can obtaining a nanometer phosphatization Theil indices is The phosphorization tin of 54.7wt%/Graphene anode material.
Button cell is assembled into using phosphorization tin manufactured in the present embodiment/Graphene anode material and sodium piece, in room Under temperature, during with 500mA/g constant-current discharges, circulation 80 is enclosed specific capacity and may remain in 400mAh/g；Show good cyclicity Energy.
Embodiment 3
Weigh raw material, phosphorus powder 0.125g, glass putty 0.6g, mixing abrading-ball 30g；Raw material are put into together with abrading-ball is mixed In ball mill tank, sealed after being passed through nitrogen, then carry out ball milling at room temperature, holding ball mill tank rotating speed is in mechanical milling process 1200r/min, ball milling 12h；0.475g Graphenes are weighed, 80ml deionized waters are added, ultrasonic disperse 3h obtains graphene dispersion Liquid, is added in ball grinder, continues ball milling 2h, after suction filtration is dried, is put in drying in 60 DEG C of drying box, is then protected in nitrogen Under in tube furnace with the heating rate of 10 DEG C/min be warmed up to 650 DEG C and be incubated 3h, you can obtaining a nanometer phosphatization Theil indices is The phosphorization tin of 60wt%/Graphene anode material.
Button cell is assembled into using phosphorization tin manufactured in the present embodiment/Graphene anode material and sodium piece, in room Under temperature, during with 500mA/g constant-current discharges, circulation 80 is enclosed specific capacity and may remain in 420mAh/g；Show good cyclicity Energy.
Embodiment 4
Weigh raw material, phosphorus powder 0.125g, glass putty 0.6g, mixing abrading-ball 30g；Raw material are put into together with abrading-ball is mixed In ball mill tank, sealed after being passed through nitrogen, then carry out ball milling at room temperature, holding ball mill tank rotating speed is in mechanical milling process 1400r/min, ball milling 8h；0.475g Graphenes are weighed, 80ml deionized waters are added, ultrasonic disperse 3h obtains graphene dispersion Liquid, is added in ball grinder, continues ball milling 2h, after suction filtration is dried, is put in drying in 60 DEG C of drying box, is then protected in nitrogen Under in tube furnace with the heating rate of 5 DEG C/min be warmed up to 750 DEG C and be incubated 3h, you can obtaining a nanometer phosphatization Theil indices is The phosphorization tin of 60wt%/Graphene anode material.
Button cell is assembled into using phosphorization tin manufactured in the present embodiment/Graphene anode material and sodium piece, in room Under temperature, during with 500mA/g constant-current discharges, circulation 80 is enclosed specific capacity and may remain in 430mAh/g；Show good cyclicity Energy.
Embodiment 5
Weigh raw material, phosphorus powder 0.125g, glass putty 0.6g, mixing abrading-ball 30g；Raw material are put into together with abrading-ball is mixed In ball mill tank, sealed after being passed through nitrogen, then carry out ball milling at room temperature, holding ball mill tank rotating speed is in mechanical milling process 1200r/min, ball milling 12h；0.175g Graphenes are weighed, 80ml deionized waters are added, ultrasonic disperse 3h obtains graphene dispersion Liquid, is added in ball grinder, continues ball milling 2h, after suction filtration is dried, is put in drying in 60 DEG C of drying box, is then protected in nitrogen Under in tube furnace with the heating rate of 10 DEG C/min be warmed up to 700 DEG C and be incubated 3h, you can obtaining a nanometer phosphatization Theil indices is The phosphorization tin of 80.5wt%/Graphene anode material.
Button cell is assembled into using phosphorization tin manufactured in the present embodiment/Graphene anode material and sodium piece, in room Under temperature, during with 500mA/g constant-current discharges, circulation 80 is enclosed specific capacity and may remain in 450mAh/g；Show good cyclicity Energy.

Claims (8)

1. the method for preparing sodium-ion battery phosphorization tin/Graphene anode material, it is characterised in that first by metallic tin powder, Phosphorus powder and abrading-ball are added in the ball grinder of high energy ball mill, under inert gas or nitrogen protection, are carried out ball milling and are occurred simultaneously Chemical reaction, obtains a nanometer phosphatization tin particles；Ball milling is further carried out to addition graphene dispersing solution in ball grinder again, makes graphite Alkene is uniformly wrapped in a nanometer phosphorization tin particle surface, and ball milling product is placed in inert gas or nitrogen environmental protection, is warmed up to 650 ~750 DEG C are heat-treated, and obtain final product and phosphorization tin/Graphene that nanometer phosphorization tin particle surface is constituted is wrapped in by flake graphite alkene Anode material.
2. the method for preparing sodium-ion battery phosphorization tin/Graphene anode material according to claim 1, its feature It is that the quality of described nanometer phosphorization tin accounts for the 50~90% of nanometer phosphorization tin and Graphene gross mass.
3. the method for preparing sodium-ion battery phosphorization tin/Graphene anode material according to claim 1, its feature It is that the particle diameter of described nanometer phosphatization tin particles is 200~800nm.
4. the method for preparing sodium-ion battery phosphorization tin/Graphene anode material according to claim 1, its feature It is that the ratio between described metallic tin powder and the amount of material of phosphorus powder are 3~3.5:4；Described metallic tin powder and the quality of abrading-ball Than being 1:30~50.
5. the method for preparing sodium-ion battery phosphorization tin/Graphene anode material according to claim 1, its feature It is that the ball grinder rotating speed of described high energy ball mill is 1000~1500r/min.
6. the method for preparing sodium-ion battery phosphorization tin/Graphene anode material according to claim 1, its feature It is that the time of metallic tin powder and the phosphorus powder ball milling in high energy ball mill is 6~12h, after adding graphene dispersing solution, further The time for carrying out ball milling is 1~3h.
7. the method for preparing sodium-ion battery phosphorization tin/Graphene anode material according to claim 1, its feature It is that described graphene dispersing solution is obtained in aqueous by Graphene by ultrasonic disperse；The described ultrasonic disperse time It is 3~5h；Described Graphene is 0.13~1.2 with the mass ratio of metallic tin powder:1.
8. the method for preparing sodium-ion battery phosphorization tin/Graphene anode material according to claim 1, its feature It is that described heat treatment process is to be warmed up to 650~750 DEG C with the heating rate of 1~10 DEG C/min, is incubated 2~3h.
CN201510299379.5A 2015-06-03 2015-06-03 A kind of sodium-ion battery phosphorization tin/Graphene anode material and preparation method thereof Expired - Fee Related CN105006551B (en)

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