CN105006551A - Stannic phosphide/graphene composite cathode material for sodium-ion battery and preparation method thereof - Google Patents
Stannic phosphide/graphene composite cathode material for sodium-ion battery and preparation method thereof Download PDFInfo
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- CN105006551A CN105006551A CN201510299379.5A CN201510299379A CN105006551A CN 105006551 A CN105006551 A CN 105006551A CN 201510299379 A CN201510299379 A CN 201510299379A CN 105006551 A CN105006551 A CN 105006551A
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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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- 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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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 stannic phosphide/graphene composite cathode material for a sodium-ion battery and a preparation method thereof. The composite cathode material is a three-dimensional structure material formed by wrapping the surfaces of nano stannic phosphide particles with flake graphite. The preparation method comprises the steps of adding metal tin powder, phosphorus powder and grinding balls into a ball milling jar of a high-energy ball milling machine, performing chemical reaction while ball milling under the protection of inert gas or nitrogen atmosphere to obtain the nano stannic phosphide particles, then adding graphene dispersion liquid into the ball milling jar, further performing ball milling to enable the surfaces of the nano stannic phosphide particles to be evenly wrapped by the graphene, and arranging a ball milling product in an inert gas or nitrogen protection environment to perform heat processing so as to obtain the stannic phosphide/graphene composite cathode material. A testing result shows that the composite cathode material has very high charging-discharging specific capacity and stable circulating performance after the composite material serving as the cathode material for the sodium-ion battery is prepared into a half battery. The preparation method of the composite material is simple, reliable and good in process repeatability and in operability, is environmentally friendly and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of phosphorization tin for sodium-ion battery/Graphene anode material and preparation method thereof, belong to sodium-ion battery field.
Background technology
Lithium ion battery is current prevailing electrochemical energy storage system, along with popularizing rapidly of the mobile devices such as PC, video camera, mobile phone, and its application prospect good in electric motor car, hybrid vehicle, the demand of lithium battery constantly increases.But the price of lithium raises, the reserves bottleneck becoming batch production, large scale business such as limited.Sodium-ion battery receives extensive concern because sodium resource reserves are abundant, cost is low, the research and development of sodium-ion battery can relax the battery development limitation problem because lithium resource shortage causes to a certain extent, are considered to alternative lithium ion battery is equipped with power supply ideal chose as electric powered motor power supply of future generation and extensive energy-accumulating power station.Because the ionic radius (0.102nm) of sodium ion is than the ionic radius (0.76nm) large 55% of lithium ion, make sodium ion embed in battery material with deviate from more difficult than lithium ion, positive and negative electrode material is the core component of battery, its performance directly determines the chemical property of battery, thus, exploitation excellent performance, cheap anode material of lithium-ion battery will become the emphasis of research, also be significant challenge of current sodium-ion battery development.
Result of study shows, tin (847mAh g
-1) and phosphorus (2596mAh g
-1) all there is very high storage sodium capacity, its compound phosphorization tin can generate Na with sodium generation electrochemical reaction
15sn
4and Na
3p, therefore phosphorization tin has high volume and capacity ratio (6650mAh cm as sodium cell negative pole material
-3), but the electrons/ions conductivity low due to itself and there is serious volumetric expansion make its cyclical stability extremely low in deintercalation sodium process, cause its application limited, therefore how to improve the cyclical stability of phosphorization tin, become the key that phosphorization tin is studied as anode material of lithium-ion battery.At present, phosphorization tin causes its capacity rapid decay in deintercalation sodium process method due to volumetric expansion is not also effectively slowed down.And up to the present, also not prepared by Graphene and phosphorization tin effective compound the technology of composite material, more there is no related compound material as the relevant report of sode cell negative material.
Summary of the invention
For the defect that existing sodium-ion battery material exists, the object of the invention is to be that providing a kind of has the three-dimensional structure that flake graphite alkene evenly wraps up nanometer phosphorization tin particle, can be used for preparing the phosphorization tin/Graphene anode material of the sodium-ion battery with high charge-discharge specific capacity, good high rate performance and long circulation life.
Another object of the present invention is that to be to provide a kind of technique simple, reproducible, environmental friendliness, can the method preparing phosphorization tin/Graphene anode material of suitability for industrialized production.
In order to realize technical purpose of the present invention, the invention provides a kind of phosphorization tin for sodium-ion battery/Graphene anode material, this composite material is wrapped in nanometer phosphorization tin particle surface by flake graphite alkene and forms.
The solution of the present invention adopts the flake graphite alkene with high conductivity, high mechanical properties, bigger serface and high porosity to be wrapped in nanometer phosphorization tin particle surface, the monolithic conductive of electrode material can be improved on the one hand, telescopic Graphene effectively can alleviate again the volumetric expansion of nanometer phosphorization tin on the other hand, improve its structural stability in charge and discharge process, thus improve cycle performance of battery.
In preferred phosphorization tin/Graphene anode material, the quality of nanometer phosphorization tin accounts for 50 ~ 90% of nanometer phosphorization tin and Graphene gross mass.
In preferred phosphorization tin/Graphene anode material, the particle diameter of nanometer phosphorization tin particle is 200 ~ 800nm.
In preferred phosphorization tin/Graphene anode material, flake graphite alkene is wrapped in nanometer phosphorization tin particle surface by high-energy ball milling method; Described phosphorization tin particle reacts generation by metallic tin and phosphorus under ball milling condition.Can obtain particle diameter under ball milling condition is Nano grade, and the phosphorization tin particle that purity is high, then flake graphite alkene can be made evenly to be wrapped in nanometer phosphorization tin particle surface by high-energy ball milling method.
Present invention also offers a kind of method preparing described phosphorization tin/Graphene anode material, the method first joins in the ball grinder of high energy ball mill by metallic tin powder, phosphorus powder and abrading-ball, under inert gas or nitrogen protection, carry out ball milling and chemical reaction occurs simultaneously, obtain nanometer phosphorization tin particle; In ball grinder, add graphene dispersing solution again carry out ball milling further, make graphene uniform be wrapped in nanometer phosphorization tin particle surface, ball milling product is placed in inert gas or nitrogen protection environment, is warmed up to 650 ~ 750 DEG C and heat-treats, to obtain final product.
The method preparing phosphorization tin/Graphene anode material of the present invention also comprises following preferred version:
In preferred scheme, metallic tin powder is 3 ~ 3.5:4 with the ratio of the amount of substance of phosphorus powder.
In preferred scheme, the mass ratio of metallic tin powder and abrading-ball is 1:30 ~ 50.
In preferred scheme, the ball grinder rotating speed of high energy ball mill is 1000 ~ 1500r/min.
In preferred scheme, the time of metallic tin powder and phosphorus powder ball milling in high energy ball mill is 6 ~ 12h, and after adding graphene dispersing solution, the time of carrying out ball milling is further 1 ~ 3h.
In preferred scheme, graphene dispersing solution is obtained by ultrasonic disperse in aqueous by Graphene.
More preferably in scheme, the ultrasonic disperse time is 3 ~ 5h.
More preferably in scheme, the mass ratio of Graphene and metallic tin powder is 0.13 ~ 1.2:1.
In preferred scheme, heat treatment process is warmed up to 650 ~ 750 DEG C with the heating rate of 1 ~ 10 DEG C/min, insulation 2 ~ 3h.
The specific capacity assay method of phosphorization tin prepared by the present invention/Graphene negative material:
Take the phosphorization tin/Graphene negative material of a certain amount of above-mentioned synthesis, add 10wt% conductive black as conductive agent, 10wt% sodium alginate is as binding agent, add a small amount of water and be thoroughly mixed to form uniform pastel through grinding, be coated on Copper Foil matrix as test electrode, make button cell using sodium metal as to electrode, its electrolyte is 1M NaClO
4/ EC:DEC (1:1)+5wt% FEC, test charging and discharging currents density is 500mA/g.
Beneficial effect of the present invention: the present invention prepares nanometer phosphorization tin with metallic tin powder and phosphorus powder by high-energy ball milling method, high-energy ball milling method is adopted flake graphite alkene to be evenly wrapped in nanometer phosphorization tin surface more further, obtain a kind of phosphorization tin/Graphene negative material, it can be used for preparing the sodium-ion battery with high charge-discharge specific capacity, good high rate performance and long circulation life.Hinge structure, it has following advantage:
1, the present invention adopts the Graphene parcel nanometer phosphorization tin particle with high conductivity, high mechanical properties, bigger serface and porosity, Graphene can improve the monolithic conductive of electrode material on the one hand, telescopic Graphene effectively can alleviate again the volumetric expansion of nanometer phosphorization tin on the other hand, improve its structural stability in charge and discharge process, thus improve cycle performance of battery.
2, the present invention prepares phosphorization tin/Graphene negative material by high-energy ball milling method is simple and easy, the nanometer phosphorization tin purity prepared by ball-milling method is high, uniform particles and particle diameter is being distributed in nanoscale, flake graphite is evenly wrapped in nanometer phosphorization tin surface simultaneously, further increases the chemical property of composite material.
3, operation is simple and reliable for high-energy ball milling method of the present invention, good process repeatability, environmental friendliness, is applicable to suitability for industrialized production.
4, phosphorization tin/graphene composite material of preparing of the present invention, during as anode material of lithium-ion battery, has very high charging and discharging capacity and good cycle performance and high rate performance.
Accompanying drawing explanation
The X ray diffracting spectrum (XRD) that [Fig. 1] is phosphorization tin in embodiment 1/Graphene anode material;
The scanning electron microscope (SEM) photograph (SEM) of phosphorization tin/Graphene anode material that [Fig. 2] obtains for embodiment 1;
The constant current charge-discharge performance map of the sodium-ion battery of the phosphorization tin that [Fig. 3] obtains for embodiment 1/Graphene anode material assembling;
The high rate performance figure of the sodium-ion battery of the phosphorization tin that [Fig. 4] obtains for embodiment 1/Graphene anode material assembling.
Embodiment
Following examples are intended to be described in further details content of the present invention, instead of the restriction to the claims in the present invention protection range.
Embodiment 1
Take raw material, phosphorus powder 0.125g, glass putty 0.6g, mixing abrading-ball 30g; Raw material are put into ball mill tank together with mixing abrading-ball, seals after passing into nitrogen, then carry out ball milling under room temperature, keep ball mill tank rotating speed to be 1500r/min in mechanical milling process, ball milling 6h; Take 0.275g Graphene; add 60ml deionized water; ultrasonic disperse 3h; obtain graphene dispersing solution, join in ball grinder, continue ball milling 2h; after suction filtration drying; be put in the drying box of 60 DEG C and dry, then in tube furnace, be warmed up to 750 DEG C with the heating rate of 5 DEG C/min under nitrogen protection and be incubated 3h, phosphorization tin/Graphene anode material that nanometer phosphorization tin content is 72.5wt% can be obtained.
The sode cell composite negative pole material adopting the present embodiment to prepare and sodium sheet are assembled into button cell, and its material list seeks peace chemical property as shown in the figure:
Can find out in Fig. 1 that position and the relative intensity of each diffraction maximum in phosphorization tin/Graphene negative material all match with JCPDS (JCPDS) card (71-2221), show that product is nanometer phosphorization tin, without other assorted peaks, show that material purity is very high, in mechanical milling process and heat treatment process, other reactions do not occur;
Can find out in Fig. 2 that Graphene successfully wraps nanometer phosphorization tin particle, the particle diameter of nanometer phosphorization tin particle is 400 ~ 600nm.
Fig. 3 shows the electrode adopting phosphorization tin/Graphene negative material to make, and at room temperature when 500mA/g constant-current discharge, first discharge specific capacity is 1010mAh/g, and circulation 80 circle specific capacity still can remain on 460mAh/g, shows good cycle performance;
Fig. 4 shows the high rate performance figure of electrode respective battery under different discharge-rate adopting phosphorization tin/Graphene anode material to make, can find that this composite material has excellent high rate performance, under large multiplying power 1000mA/g, capacity still can remain on 370mAh/g, and after current density slowly gets back to 500mA/g by big current, capacity is returned to 450mAh/g again.
Embodiment 2
Take raw material, phosphorus powder 0.125g, glass putty 0.6g, mixing abrading-ball 30g; Raw material are put into ball mill tank together with mixing abrading-ball, seals after passing into argon gas, then carry out ball milling under room temperature, keep ball mill tank rotating speed to be 1200r/min in mechanical milling process, ball milling 12h; Take 0.6g Graphene; add 100ml deionized water; ultrasonic disperse 3h; obtain graphene dispersing solution, join in ball grinder, continue ball milling 2h; after suction filtration drying; be put in the drying box of 60 DEG C and dry, then under argon shield, in tube furnace, be warmed up to 750 DEG C with the heating rate of 5 DEG C/min and be incubated 3h, phosphorization tin/Graphene anode material that nanometer phosphorization tin content is 54.7wt% can be obtained.
Phosphorization tin/Graphene the anode material adopting the present embodiment to prepare and sodium sheet are assembled into button cell, and at room temperature, during with 500mA/g constant-current discharge, circulation 80 circle specific capacity still can remain on 400mAh/g; Show good cycle performance.
Embodiment 3
Take raw material, phosphorus powder 0.125g, glass putty 0.6g, mixing abrading-ball 30g; Raw material are put into ball mill tank together with mixing abrading-ball, seals after passing into nitrogen, then carry out ball milling under room temperature, keep ball mill tank rotating speed to be 1200r/min in mechanical milling process, ball milling 12h; Take 0.475g Graphene; add 80ml deionized water; ultrasonic disperse 3h; obtain graphene dispersing solution, join in ball grinder, continue ball milling 2h; after suction filtration drying; be put in the drying box of 60 DEG C and dry, then in tube furnace, be warmed up to 650 DEG C with the heating rate of 10 DEG C/min under nitrogen protection and be incubated 3h, phosphorization tin/Graphene anode material that nanometer phosphorization tin content is 60wt% can be obtained.
Phosphorization tin/Graphene the anode material adopting the present embodiment to prepare and sodium sheet are assembled into button cell, and at room temperature, during with 500mA/g constant-current discharge, circulation 80 circle specific capacity still can remain on 420mAh/g; Show good cycle performance.
Embodiment 4
Take raw material, phosphorus powder 0.125g, glass putty 0.6g, mixing abrading-ball 30g; Raw material are put into ball mill tank together with mixing abrading-ball, seals after passing into nitrogen, then carry out ball milling under room temperature, keep ball mill tank rotating speed to be 1400r/min in mechanical milling process, ball milling 8h; Take 0.475g Graphene; add 80ml deionized water; ultrasonic disperse 3h; obtain graphene dispersing solution, join in ball grinder, continue ball milling 2h; after suction filtration drying; be put in the drying box of 60 DEG C and dry, then in tube furnace, be warmed up to 750 DEG C with the heating rate of 5 DEG C/min under nitrogen protection and be incubated 3h, phosphorization tin/Graphene anode material that nanometer phosphorization tin content is 60wt% can be obtained.
Phosphorization tin/Graphene the anode material adopting the present embodiment to prepare and sodium sheet are assembled into button cell, and at room temperature, during with 500mA/g constant-current discharge, circulation 80 circle specific capacity still can remain on 430mAh/g; Show good cycle performance.
Embodiment 5
Take raw material, phosphorus powder 0.125g, glass putty 0.6g, mixing abrading-ball 30g; Raw material are put into ball mill tank together with mixing abrading-ball, seals after passing into nitrogen, then carry out ball milling under room temperature, keep ball mill tank rotating speed to be 1200r/min in mechanical milling process, ball milling 12h; Take 0.175g Graphene; add 80ml deionized water; ultrasonic disperse 3h; obtain graphene dispersing solution, join in ball grinder, continue ball milling 2h; after suction filtration drying; be put in the drying box of 60 DEG C and dry, then in tube furnace, be warmed up to 700 DEG C with the heating rate of 10 DEG C/min under nitrogen protection and be incubated 3h, phosphorization tin/Graphene anode material that nanometer phosphorization tin content is 80.5wt% can be obtained.
Phosphorization tin/Graphene the anode material adopting the present embodiment to prepare and sodium sheet are assembled into button cell, and at room temperature, during with 500mA/g constant-current discharge, circulation 80 circle specific capacity still can remain on 450mAh/g; Show good cycle performance.
Claims (10)
1. sodium-ion battery phosphorization tin/Graphene anode material, is characterized in that, is wrapped in nanometer phosphorization tin particle surface forms by flake graphite alkene.
2. phosphorization tin according to claim 1/Graphene anode material, is characterized in that, the quality of described nanometer phosphorization tin accounts for 50 ~ 90% of nanometer phosphorization tin and Graphene gross mass.
3. phosphorization tin according to claim 1/Graphene anode material, is characterized in that, the particle diameter of described nanometer phosphorization tin particle is 200 ~ 800nm.
4. phosphorization tin according to claim 1/Graphene anode material, is characterized in that, described flake graphite alkene is wrapped in nanometer phosphorization tin particle surface by high-energy ball milling method; Described phosphorization tin particle reacts generation by metallic tin and phosphorus under ball milling condition.
5. prepare the method for the phosphorization tin/Graphene anode material described in any one of Claims 1 to 4, it is characterized in that, first metallic tin powder, phosphorus powder and abrading-ball are joined in the ball grinder of high energy ball mill, under inert gas or nitrogen protection, carry out ball milling and chemical reaction occurs simultaneously, obtain nanometer phosphorization tin particle; In ball grinder, add graphene dispersing solution again carry out ball milling further, make graphene uniform be wrapped in nanometer phosphorization tin particle surface, ball milling product is placed in inert gas or nitrogen protection environment, is warmed up to 650 ~ 750 DEG C and heat-treats, to obtain final product.
6. method according to claim 5, is characterized in that, described metallic tin powder is 3 ~ 3.5:4 with the ratio of the amount of substance of phosphorus powder; Described metallic tin powder and the mass ratio of abrading-ball are 1:30 ~ 50.
7. method according to claim 5, is characterized in that, the ball grinder rotating speed of described high energy ball mill is 1000 ~ 1500r/min.
8. method according to claim 5, is characterized in that, the time of metallic tin powder and phosphorus powder ball milling in high energy ball mill is 6 ~ 12h, and after adding graphene dispersing solution, the time of carrying out ball milling is further 1 ~ 3h.
9. method according to claim 5, is characterized in that, described graphene dispersing solution is obtained by ultrasonic disperse in aqueous by Graphene; The described ultrasonic disperse time is 3 ~ 5h; Described Graphene and the mass ratio of metallic tin powder are 0.13 ~ 1.2:1.
10. method according to claim 5, is characterized in that, described heat treatment process is warmed up to 650 ~ 750 DEG C with the heating rate of 1 ~ 10 DEG C/min, insulation 2 ~ 3h.
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| CN106450306A (en) * | 2016-12-07 | 2017-02-22 | 华南师范大学 | Preparation method and application of negative electrode material of tin phosphide sodium ion battery |
| CN107352521A (en) * | 2017-08-24 | 2017-11-17 | 济南大学 | A kind of wire phosphatization tin compound and preparation method thereof |
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| CN109698326B (en) * | 2017-10-23 | 2021-04-02 | 中国石油大学(华东) | Organic tin phosphide/graphite oxide composite material for negative electrode of sodium-ion battery |
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| CN110034283A (en) * | 2018-09-17 | 2019-07-19 | 南方科技大学 | Phosphorization tin composite material and preparation method and application |
| CN109841820A (en) * | 2019-03-18 | 2019-06-04 | 华南理工大学 | A kind of lithium ion battery amorphous Sn 4 P 3/phosphorus/few layer graphene negative electrode material and the preparation method and application thereof |
| CN109980200A (en) * | 2019-03-21 | 2019-07-05 | 北京工业大学 | A kind of noncrystal phosphorus base negative electrode material of domain Dispersed precipitate and preparation method thereof |
| CN110993913A (en) * | 2019-12-06 | 2020-04-10 | 湘潭大学 | Tin phosphide/expanded graphite cathode composite material of sodium ion battery and preparation method thereof |
| CN111048765A (en) * | 2019-12-27 | 2020-04-21 | 中国地质大学（北京） | Battery composite electrode material and preparation method and application thereof |
| CN111048765B (en) * | 2019-12-27 | 2021-09-28 | 中国地质大学（北京） | Preparation method of battery composite electrode material |
| CN111933893A (en) * | 2020-07-27 | 2020-11-13 | 西北工业大学 | Flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode and preparation method thereof |
| CN111933893B (en) * | 2020-07-27 | 2023-04-07 | 西北工业大学 | Flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode and preparation method thereof |
| CN113540443A (en) * | 2021-05-17 | 2021-10-22 | 江汉大学 | Phosphorus/tin composite material, heterojunction phosphorus/tin/carbon composite material and application thereof |
| CN114068897A (en) * | 2021-11-05 | 2022-02-18 | 齐鲁工业大学 | Tin triphosphate electrode material for potassium ion battery, preparation method and application thereof |
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