CN106450306A - Preparation method and application of negative electrode material of tin phosphide sodium ion battery - Google Patents
Preparation method and application of negative electrode material of tin phosphide sodium ion battery Download PDFInfo
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- CN106450306A CN106450306A CN201611114811.XA CN201611114811A CN106450306A CN 106450306 A CN106450306 A CN 106450306A CN 201611114811 A CN201611114811 A CN 201611114811A CN 106450306 A CN106450306 A CN 106450306A
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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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- 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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- 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 relates to a preparation method and application of a negative electrode material of a tin phosphide sodium ion battery. The preparation method of the negative electrode material of the tin phosphide sodium ion battery comprises the following steps of performing ball milling pretreatment on poisonless commercial red phosphorus; preparing dispersing liquid of Sn salt; uniformly mixing the red phosphorus subjected to ball milling pretreatment and the dispersing liquid of the Sn salt; putting into a reaction kettle, and fully reacting, so as to obtain a turbid suspension; naturally cooling the turbid suspension, filtering to obtain a precipitate, washing, and drying, so as to obtain the negative electrode material of the tin phosphide sodium ion battery. The prepared negative electrode material of the tin phosphide sodium ion battery has the advantages that the problems of large irreversible capacity loss and poor conduction and circulation properties are solved when the pure phosphorus material is used for actually preparing a negative electrode of the sodium ion battery; high-poison white phosphorus or organic phosphorus is not used as a phosphorus source, so that the green and simple effects are realized, and the safety is high.
Description
Technical field
The present invention relates to battery material preparation field, more particularly to a kind of system of phosphorization tin anode material of lithium-ion battery
Preparation Method and application.
Background technology
Green novel energy source and power-saving technology are the basic assurances solving the energy and the difficult problem of environmental protection, with solar energy, wind energy, length
Course continuation mileage electric automobile and the development of intelligent grid, propose higher and higher requirement to new energy-storage system.For meeting day
Energy-conservation and ecological requirements that benefit increases, research and development height ratio capacity, high security, long-life, the electrical source of power of low cost and energy storage material
Material, has become as forward position research direction important in the world at present.Due to Na element in nature rich reserves, account for the earth's crust
The 2.64% of reserves and widely distributed, development cost is cheap.Compared with lithium rechargeable battery, sodium-ion battery (SIB) has
Low cost, safe the features such as it is considered to be there being very much the secondary cell system of development potentiality.At present, some are electric in the world
Sodium-ion battery technology is classified as an important basic and perspective study field by pool technology relatively advanced country, and
The energy-storage battery technological development direction paid close attention to as future.Try to explore that specific capacity is high, have extended cycle life, security performance
New anode material of lithium-ion battery system good, that temperature applicable range is wide, has become as research and development high-performance sodium ion in the world
The common problem of secondary battery electrode material.
Anode material of lithium-ion battery main research includes tin-based material, oxide, alloy material, sulfuration in recent years
Thing and phosphide etc..Wherein phosphorus (P) has very high theoretical capacity (2596mAh/g) as negative material, thus is subject to extensively
Concern, become one of focus of Recent study.But such material haves the shortcomings that poorly conductive, table during embedding removing sodium
Reveal huge Volumetric expansion, greatly constrain its practical application.Therefore, it is badly in need of carrying out necessary changing to such material
Property, lift its cycle performance, high rate performance etc. with comprehensive.In order to overcome these shortcomings, can be good using, stability high with electric conductivity
Good material with carbon element or metal are combined, and design special micro structure, the stability of holding structure, improve the utilization of active substance
Rate, improves the high rate performance of battery, and comprehensively takes into account various method of modifying, to obtain excellent combination electrode material.Existing literary composition
Offer multiplex hypertoxic, inflammable white phosphorus or organophosphors as phosphorus source, have that pollution is big, poor stability the shortcomings of, and specific capacity, multiplying power
Performance and cycle performance have much room for improvement.
Content of the invention
Based on this, it is an object of the invention to, a kind of phosphorization tin (hereinafter abbreviated as Sn is provided4P3) sodium-ion battery negative pole
The preparation method of material, the anode material of lithium-ion battery first charge-discharge efficiency being obtained by the present invention is high, specific capacity is high, again
Rate performance and good cycle, and technique green is easy, with low cost.
The present invention is achieved by the following technical solutions：
A kind of Sn4P3The preparation method of anode material of lithium-ion battery, comprises the following steps：
S1：Red phosphorus is taken to carry out ball milling pretreatment；
S2：Take Sn salt to be dissolved in solvent, prepare the dispersion liquid of Sn salt；
S3：By the red phosphorus mixing after the dispersion liquid of S2 gained Sn salt and S1 ball milling pretreatment, get a uniform mixture；
S4：S3 gained homogeneous mixture solotion is transferred in reactor, after reaction, obtains suspension；
S5：Filter S4 gained suspension and be precipitated thing, described precipitate is scrubbed, dry, obtains Sn4P3Sodium ion electricity
Pond negative material.
Further, in described S1, using wet method or dry ball milling, ball-milling medium is ethanol, NMP, DMF, argon, nitrogen or
Person's vacuum environment, the rotating speed of ball milling is 100～300rpm, and the time is 0.5～5h；Ball milling pearl is zirconia ball, described zirconium oxide
A diameter of 5～15mm of ball；Described ball milling pearl is 50 with the ball material mass ratio of red phosphorus:1～100:1；After described ball milling pretreatment
Red phosphorus particle diameter be less than 5 μm.Ball material mass ratio within this range, rotating speed and carry out ball milling in the time, can obtain larger dynamic
Can, obtain the less red phosphorus of particle diameter through ball-milling technology, the less red phosphorus of particle diameter is easy to react with Sn salt, obtain purer thing
Phase, and be more easy to obtain the homogeneous nano-particle of pattern.
Further, in described S2, described Sn salt is stannous chloride, stannous oxalate or stannous sulfate.
Further, in described S2, described solvent is ethanolamine, ethylene glycol or ethylenediamine.Such organic solvent is with respect to going
Ionized water etc., as reaction environment, is not likely to produce phosphate impurities.
Further, in described S2, the concentration of described dispersion liquid is 0.04～0.1mol/L.Available in this concentration range
The homogeneous nano-particle of pattern, is easy to increase specific surface area, the chemical property of reinforcing material.
Further, red phosphorus the rubbing according to Sn and P in described S3, after the dispersion liquid of S2 gained Sn salt and S1 ball milling pretreatment
That ratio is 4:3～4:9 selections, after both mixing, first carry out ultrasonic agitation using ultrasonic washing unit, and power is 100～200W,
Persistent period is 1～3h, retransfers into Ultrasonic cell smash, power is 400～500W, the persistent period is 10～30min.
Further, in described S4, described reactor temperature is 160～220 DEG C, and the response time is 20～40h.In this temperature
In degree and reaction time range, in final product, impurity is less, and thing compares pure, and more uncomplicated laundering.
Further, in described S5, described precipitate sequentially passes through dilute hydrochloric acid, deionized water, dehydrated alcohol are washed.Wash
The effect washed is the simple substance Sn impurity removing not sufficiently reactive Sn salt and producing.
Further, in described S5, described drying is vacuum dried 8～16h at being 50～90 DEG C.
Present invention also offers the Sn that a kind of preparation in accordance with the present invention is obtained4P3Anode material of lithium-ion battery.
Present invention also offers a kind of preparation method of sodium-ion battery negative plate, comprise the following steps：By system of the present invention
The Sn obtaining4P3Anode material of lithium-ion battery is coated on Copper Foil after mixing homogeneously with binding agent, conductive agent, drying, roll-in,
Obtain sodium-ion battery negative plate.
Further, described Sn4P3Anode material of lithium-ion battery is (70～80) with the weight ratio of binding agent, conductive agent:
(20～10):10；Described binding agent is polyvinylidene fluoride or sodium carboxymethyl cellulose；Described conductive agent is conductive carbon Super-
P or conductive black.
Further, the thickness of described coating is 100～180 μm；The thickness of described roll-in is 75～150 μm.Thick at these
In the range of degree, the loading capacity of single pole piece is moderate, is easy to being impregnated with of electrolyte, and difficult for drop-off.
Further, it is vacuum dried 5～24h at described drying is 50～100 DEG C.It is dried at such a temperature, not only can
Enough preferably dry complete, and impact will not be produced on the material of coating.
Present invention also offers the sodium-ion battery negative plate that a kind of preparation in accordance with the present invention is obtained.
With respect to prior art, the preparation method of the present invention passes through solvent structure Sn4P3, effectively improve charge and discharge
Volumetric expansion during electricity circulation and reuniting effect, enhance the cycle performance of material, by introducing metal Sn, enhance phosphorus
The electric conductivity of sill and stability, and highly toxic phosphorus source, technique environmental protection need not be added in preparation process.This
Bright prepared Sn4P3Anode material of lithium-ion battery first charge-discharge efficiency height, specific capacity height, high rate performance and good cycle,
Solve that the irreversible capacity loss that phosphorous-based materials exist in the actual application preparing sodium-ion battery negative pole is big and electric conductivity
Problem that can be poor with cycle performance.
In order to more fully understand and implement, describe the present invention below in conjunction with the accompanying drawings in detail.
Brief description
The Sn that Fig. 1 prepares for embodiment 14P3The XRD figure of anode material of lithium-ion battery；
Fig. 2 is to be the Sn that embodiment 1 prepares4P3The SEM figure of anode material of lithium-ion battery；
The Sn that Fig. 3 prepares for embodiment 14P3The cycle performance figure of anode material of lithium-ion battery；
The Sn that Fig. 4 prepares for embodiment 14P3The high rate performance figure of anode material of lithium-ion battery；
The cycle performance figure of the red phosphorus anode material of lithium-ion battery that Fig. 5 prepares for comparative example 1.
Specific embodiment
Embodiment 1
In the present embodiment, a kind of Sn4P3The preparation method of anode material of lithium-ion battery, comprises the following steps：
S1：Take nontoxic business red phosphorus 0.372g, put into ball milling in stainless steel jar mill, ball milling pearl is oxygen not of uniform size
Change zirconium ball, it is 100 with the ball material mass ratio of red phosphorus:1, and it is filled with argon in mechanical milling process as protective gas, ball milling
Rotating speed is 300rpm, and the time is 3h, obtains the tiny red phosphorus of particle diameter (5 μm of ＜)；
S2：Take 1.805g bis- hydrated stannous chloride powder, add in 80mL ethylenediamine solvent, and entered by magnetic stirring apparatuss
Row stirs, and obtains SnCl2Dispersion liquid, concentration is 0.1mol/L；
S3：S1 gained tiny red phosphorus 0.372g is taken to add S2 gained SnCl2In dispersion liquid, first entered using ultrasonic washing unit
Row ultrasonic agitation, power is 100W, and the persistent period is 1h；Retransfer into Ultrasonic cell smash, power is 400W, when continuing
Between for 20min so that tiny red phosphorus and SnCl2Sufficiently mixed, got a uniform mixture；
S4：S3 gained homogeneous mixture solotion is transferred to reactor, reacts 40h in confined conditions, temperature is 200 DEG C,
Obtain suspension.
S4：After reaction terminates, allow S5 gained suspension natural cooling, be filtrated to get precipitate, more successively through dilute hydrochloric acid, go
The concentration of ionized water and absolute ethanol washing, wherein dilute hydrochloric acid is 0.05mol/L, and gained sediment is vacuum dried at 80 DEG C
10h, obtains Sn4P3Anode material of lithium-ion battery.
The present embodiment additionally provides a kind of preparation method of sodium-ion battery negative plate.Specifically, by this enforcement of 0.8g
The Sn that example is obtained4P3The binding agent polyvinylidene fluoride of anode material of lithium-ion battery and 0.1g, the conductive agent Super-P of 0.1g
Uniformly mix, be used N-Methyl pyrrolidone as solvent, be tuned into slurry, be coated on Copper Foil (thickness of coating is 100 μm),
And 10h, roll-in (thickness of roll-in be 80 μm) are dried through 80 DEG C of vacuum, it is prepared into sodium-ion battery negative plate.By the present embodiment
Prepared sodium-ion battery negative plate, metallic sodium piece, electrolyte are assembled into sodium-ion battery, are used for carrying out constant current charge-discharge survey
Examination, the electrolyte being used is containing 1.0M NaClO4EC/DEC/FEC (1:1:0.05Vol%).
Embodiment 2
In the present embodiment, a kind of Sn4P3The preparation method of anode material of lithium-ion battery, comprises the following steps：
S1：Take nontoxic business red phosphorus 0.558g, put into ball milling in stainless steel jar mill, ball milling pearl is oxygen not of uniform size
Change zirconium ball, it is 100 with the ball material mass ratio of red phosphorus:1, and it is filled with argon in mechanical milling process as protective gas, ball milling
Rotating speed is 300rpm, and the time is 0.5h, obtains the tiny red phosphorus of particle diameter (5 μm of ＜)；
S2：Take 1.805g bis- hydrated stannous chloride powder, add in 80mL ethylenediamine solvent, and entered by magnetic stirring apparatuss
Row stirs, and obtains SnCl2Dispersion liquid, concentration is 0.1mol/L；
S3：S1 gained tiny red phosphorus 0.558g is taken to add S2 gained SnCl2In dispersion liquid, first entered using ultrasonic washing unit
Row ultrasonic agitation, power is 100W, and the persistent period is 3h；Retransfer into Ultrasonic cell smash, power is 400W, when continuing
Between for 30min so that tiny red phosphorus and SnCl2Sufficiently mixed, got a uniform mixture；
S4：S3 gained homogeneous mixture solotion is transferred to reactor, reacts 40h in confined conditions, temperature is 200 DEG C,
Obtain suspension.
S4：After reaction terminates, allow S5 gained suspension natural cooling, be filtrated to get precipitate, more successively through dilute hydrochloric acid, go
The concentration of ionized water and absolute ethanol washing, wherein dilute hydrochloric acid is 0.05mol/L, and gained sediment is vacuum dried at 80 DEG C
10h, obtains Sn4P3Anode material of lithium-ion battery.
The present embodiment additionally provides a kind of preparation method of sodium-ion battery negative plate.Specifically, by this enforcement of 0.8g
The Sn that example is obtained4P3The binding agent polyvinylidene fluoride of anode material of lithium-ion battery and 0.1g, the conductive agent Super-P of 0.1g
Uniformly mix, be used N-Methyl pyrrolidone as solvent, be tuned into slurry, be coated on Copper Foil (thickness of coating is 100 μm),
And 10h, roll-in (thickness of roll-in be 80 μm) are dried through 80 DEG C of vacuum, it is prepared into sodium-ion battery negative plate.By the present embodiment
Prepared sodium-ion battery negative plate, metallic sodium piece, electrolyte are assembled into sodium-ion battery, are used for carrying out constant current charge-discharge survey
Examination, the electrolyte being used is containing 1.0M NaClO4EC/DEC/FEC (1:1:0.05Vol%).
Embodiment 3
In the present embodiment, a kind of Sn4P3The preparation method of anode material of lithium-ion battery, comprises the following steps：
S1：Take nontoxic business red phosphorus 0.372g, put into ball milling in stainless steel jar mill, ball milling pearl is oxygen not of uniform size
Change zirconium ball, it is 50 with the ball material mass ratio of red phosphorus:1, and be filled with argon in mechanical milling process as protective gas, the turning of ball milling
Speed is 100rpm, and the time is 3h, obtains the tiny red phosphorus of particle diameter (5 μm of ＜)；
S2：Take 1.805g bis- hydrated stannous chloride powder, add in 200mL ethylenediamine solvent, and pass through magnetic stirring apparatuss
It is stirred uniformly, obtaining SnCl2Dispersion liquid, concentration is 0.04mol/L；
S3：S1 gained tiny red phosphorus 0.372g is taken to add S2 gained SnCl2In dispersion liquid, first entered using ultrasonic washing unit
Row ultrasonic agitation, power is 100W, and the persistent period is 1h；Retransfer into Ultrasonic cell smash, power is 400W, when continuing
Between for 20min so that tiny red phosphorus and SnCl2Sufficiently mixed, got a uniform mixture；
S4：S3 gained homogeneous mixture solotion is transferred to reactor, reacts 20h in confined conditions, temperature is 180 DEG C,
Obtain suspension.
S4：After reaction terminates, allow S5 gained suspension natural cooling, be filtrated to get precipitate, more successively through dilute hydrochloric acid, go
The concentration of ionized water and absolute ethanol washing, wherein dilute hydrochloric acid is 0.05mol/L, and gained sediment is vacuum dried at 80 DEG C
10h, obtains Sn4P3Anode material of lithium-ion battery.
The present embodiment additionally provides a kind of preparation method of sodium-ion battery negative plate.Specifically, by this enforcement of 0.8g
The Sn that example is obtained4P3The binding agent polyvinylidene fluoride of anode material of lithium-ion battery and 0.1g, the conductive agent Super-P of 0.1g
Uniformly mix, be used N-Methyl pyrrolidone as solvent, be tuned into slurry, be coated on Copper Foil (thickness of coating is 100 μm),
And 10h, roll-in (thickness of roll-in be 80 μm) are dried through 80 DEG C of vacuum, it is prepared into sodium-ion battery negative plate.By the present embodiment
Prepared sodium-ion battery negative plate, metallic sodium piece, electrolyte are assembled into sodium-ion battery, are used for carrying out constant current charge-discharge survey
Examination, the electrolyte being used is containing 1.0M NaClO4EC/DEC/FEC (1:1:0.05Vol%).
Embodiment 4
In the present embodiment, a kind of Sn4P3The preparation method of anode material of lithium-ion battery, comprises the following steps：
S1：Take nontoxic business red phosphorus 0.372g, put into ball milling in stainless steel jar mill, ball milling pearl is oxygen not of uniform size
Change zirconium ball, it is 100 with the ball material mass ratio of red phosphorus:1, and it is filled with argon in mechanical milling process as protective gas, ball milling
Rotating speed is 300rpm, and the time is 3h, obtains the tiny red phosphorus of particle diameter (5 μm of ＜)；
S2：Take 1.64g stannous oxalate powder, add in 80mL ethanol amine solvent, and be stirred by magnetic stirring apparatuss
Uniformly, obtain SnC2O4Dispersion liquid, concentration is 0.1mol/L；
S3：S1 gained tiny red phosphorus 0.372g is taken to add S2 gained SnCl2In dispersion liquid, first entered using ultrasonic washing unit
Row ultrasonic agitation, power is 100W, and the persistent period is 3h；Retransfer into Ultrasonic cell smash, power is 400W, when continuing
Between for 30min so that tiny red phosphorus and SnCl2Sufficiently mixed, got a uniform mixture；
S4：S3 gained homogeneous mixture solotion is transferred to reactor, reacts 40h in confined conditions, temperature is 200 DEG C,
Obtain suspension.
S4：After reaction terminates, allow S5 gained suspension natural cooling, be filtrated to get precipitate, more successively through dilute hydrochloric acid, go
The concentration of ionized water and absolute ethanol washing, wherein dilute hydrochloric acid is 0.05mol/L, and gained sediment is vacuum dried at 80 DEG C
10h, obtains Sn4P3Anode material of lithium-ion battery.
The present embodiment additionally provides a kind of preparation method of sodium-ion battery negative plate.Specifically, by this enforcement of 0.8g
The Sn that example is obtained4P3The binding agent polyvinylidene fluoride of anode material of lithium-ion battery and 0.1g, the conductive agent Super-P of 0.1g
Uniformly mix, be used N-Methyl pyrrolidone as solvent, be tuned into slurry, be coated on Copper Foil (thickness of coating is 100 μm),
And 10h, roll-in (thickness of roll-in be 80 μm) are dried through 80 DEG C of vacuum, it is prepared into sodium-ion battery negative plate.By the present embodiment
Prepared sodium-ion battery negative plate, metallic sodium piece, electrolyte are assembled into sodium-ion battery, are used for carrying out constant current charge-discharge survey
Examination, the electrolyte being used is containing 1.0M NaClO4EC/DEC/FEC (1:1:0.05Vol%).
It should be noted that Sn of the present invention4P3In the preparation method of anode material of lithium-ion battery, aforementioned four
The parameter of embodiment, all from preferably parameter value, is only presently preferred embodiments of the present invention, not the present invention is done any
Pro forma restriction, those skilled in the art select preferably other specification also in the protection model of the present invention according to present invention
In enclosing.
Comparative example 1
In this comparative example, directly adopt business red phosphorus as anode material of lithium-ion battery.This comparative example is also
Provide a kind of preparation method of sodium-ion battery negative plate.Specifically, by the business red phosphorus sodium-ion battery negative pole material of 0.8g
Material is uniformly mixed with the binding agent polyvinylidene fluoride of 0.1g, the conductive agent Super-P of 0.1g, is made using N-Methyl pyrrolidone
For solvent, be tuned into slurry, be coated on Copper Foil (thickness of coating be 100 μm), and through vacuum 80 DEG C 10h, roll-in (roll-in are dried
Thickness be 80 μm) be prepared into sodium-ion battery negative plate.By the prepared sodium-ion battery negative plate of the present embodiment, metallic sodium
Piece, electrolyte are assembled into sodium-ion battery, are used for carrying out constant current charge-discharge test, the electrolyte being used is containing 1.0M
NaClO4EC/DEC/FEC (1:1:0.05Vol%).
Measure of merit contrasts
Material phase analysis are carried out using X ' Pert PRO X-ray diffractometer and obtains XRD figure, radiation source Cu target K alpha ray, λ=
0.15406nm, the pipe in test process is pressed as 40kV, and pipe flow is 40mA, and sweep speed is 5 °/min；Using Zeiss
Ultra55 field emission scanning electron microscope observation pattern obtains SEM figure；Surveyed using Shenzhen new Weir BTS-5V3A-S1 battery
Test system carries out constant current charge-discharge test and obtains constant current charge-discharge performance map.
Fig. 1 is the Sn that embodiment 1 is obtained4P3The XRD figure of anode material of lithium-ion battery, from figure 1 it appears that diffraction
Peak corresponds to standard card JCPDS No.74-0255, is Sn4P3Phase, degree of crystallinity is high, no dephasign.
Fig. 2 is the Sn that embodiment 1 is obtained4P3The SEM figure of anode material of lithium-ion battery, figure it is seen that embodiment 1
Prepared for granular Sn4P3Anode material of lithium-ion battery.
Fig. 3 is the Sn that embodiment 1 is obtained4P3The cycle performance figure of anode material of lithium-ion battery, from figure 3, it can be seen that
Carry out constant current charge-discharge test under the electric current density of 100mA/g, potential window is 0.01～2.5V, first discharge specific capacity is high
Reach 800mAh/g, be recycled to the 20th week, specific discharge capacity is still maintained at 378mAh/g.
The Sn that Fig. 4 prepares for embodiment 14P3The high rate performance figure of anode material of lithium-ion battery, permissible from Fig. 4
Find out, under high current 1000mA/g, specific discharge capacity still has～200mAh/g, shows this Sn4P3Anode material of lithium-ion battery
There is good high rate performance.
The cycle performance figure of the red phosphorus anode material of lithium-ion battery that Fig. 5 prepares for comparative example 1, from Fig. 5
As can be seen that carrying out constant current charge-discharge test under the electric current density of 100mA/g, discharge 1897mAh/g first, declines within the 2nd week
Reduce to 219mAh/g, cycle performance is poor.
With respect to prior art, the preparation method of the present invention passes through solvent structure Sn4P3, effectively improve charge and discharge
Volumetric expansion during electricity circulation and reuniting effect, enhance the cycle performance of material, by introducing metal Sn, enhance phosphorus
The electric conductivity of sill and stability, and highly toxic phosphorus source, technique environmental protection need not be added in preparation process.This
Bright prepared Sn4P3Anode material of lithium-ion battery first charge-discharge efficiency height, specific capacity height, high rate performance and good cycle,
Solve that the irreversible capacity loss that phosphorous-based materials exist in the actual application preparing sodium-ion battery negative pole is big and electric conductivity
Problem that can be poor with cycle performance.
Embodiment described above only have expressed the several embodiments of the present invention, and its description is more concrete and detailed, but simultaneously
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
Say, without departing from the inventive concept of the premise, some deformation can also be made and improve, these broadly fall into the protection of the present invention
Scope.
Claims (10)
1. a kind of preparation method of phosphorization tin anode material of lithium-ion battery it is characterised in that：Comprise the following steps：
S1：Red phosphorus is taken to carry out ball milling pretreatment；
S2：Take Sn salt to be dissolved in solvent, prepare the dispersion liquid of Sn salt；
S3：By the red phosphorus mixing after the dispersion liquid of S2 gained Sn salt and S1 ball milling pretreatment, get a uniform mixture；
S4：S3 gained homogeneous mixture solotion is transferred in reactor, after reaction, obtains suspension；
S5：Filter S4 gained suspension and be precipitated thing, described precipitate is scrubbed, dry, obtains phosphorization tin sodium-ion battery
Negative material.
2. phosphorization tin anode material of lithium-ion battery according to claim 1 preparation method it is characterised in that：Described S1
In, using wet method or dry ball milling, ball-milling medium is ethanol, NMP, DMF, argon, nitrogen or vacuum environment, the rotating speed of ball milling
For 100～300rpm, the time is 0.5～5h；Ball milling pearl is zirconia ball, a diameter of 5～15mm of described zirconia ball；Described
Ball milling pearl is 50 with the ball material mass ratio of red phosphorus:1～100:1；The particle diameter of the red phosphorus after described ball milling pretreatment is less than 5 μm.
3. phosphorization tin anode material of lithium-ion battery according to claim 1 preparation method it is characterised in that：Described S2
In, described Sn salt is stannous chloride, stannous oxalate or stannous sulfate；Described solvent is ethanolamine, ethylene glycol or ethylenediamine；Described
The concentration of dispersion liquid is 0.04～0.1mol/L.
4. phosphorization tin anode material of lithium-ion battery according to claim 1 preparation method it is characterised in that：Described S3
In, the red phosphorus after the dispersion liquid of S2 gained Sn salt and S1 ball milling pretreatment is 4 according to the mol ratio of Sn and P:3～4:9 selections, two
After person's mixing, first ultrasonic agitation is carried out using ultrasonic washing unit, power is 100～200W, and the persistent period is 1～3h, then turns
Move into Ultrasonic cell smash, power is 400～500W, the persistent period is 10～30min.
5. phosphorization tin anode material of lithium-ion battery according to claim 1 preparation method it is characterised in that：Described S4
In, described reactor temperature is 160～220 DEG C, and the response time is 20～40h.
6. phosphorization tin anode material of lithium-ion battery according to claim 1 preparation method it is characterised in that：Described S5
In, described precipitate sequentially passes through dilute hydrochloric acid, deionized water, dehydrated alcohol are washed；Described drying is true at being 50～90 DEG C
Empty dry 8～16h.
7. a kind of phosphorization tin anode material of lithium-ion battery it is characterised in that：Described phosphorization tin anode material of lithium-ion battery by
The preparation method described in any claim in claim 1～6 is obtained.
8. a kind of preparation method of sodium-ion battery negative plate it is characterised in that：Comprise the following steps：By described in claim 6
Phosphorization tin anode material of lithium-ion battery mix homogeneously with binding agent, conductive agent after be coated on Copper Foil, drying, roll-in,
Obtain sodium-ion battery negative plate.
9. sodium-ion battery negative plate according to claim 7 preparation method it is characterised in that：Described phosphorization tin sodium from
Sub- cell negative electrode material is (70～80) with the weight ratio of binding agent, conductive agent:(20～10):10；Described binding agent is poly- inclined
Difluoroethylene or sodium carboxymethyl cellulose；Described conductive agent is conductive carbon Super-P or conductive black；The thickness of described coating is
100～180 μm；Described drying is vacuum dried 5～24h at being 50～100 DEG C；The thickness of described roll-in is 75～150 μm.
10. a kind of sodium-ion battery negative plate it is characterised in that：Described sodium-ion battery negative plate is described in claim 8 or 9
Preparation method be obtained.
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Cited By (10)
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| CN109698326A (en) * | 2017-10-23 | 2019-04-30 | 中国石油大学(华东) | A kind of organic phosphorization tin/oxidized graphite composite material for sodium-ion battery cathode |
| 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 |
| CN108493425A (en) * | 2018-04-12 | 2018-09-04 | 合肥工业大学 | A kind of preparation method of the Sn4P3 nano particle anode material of lithium-ion batteries of mesoporous carbon nanotube cladding |
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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 |
| CN109244409A (en) * | 2018-09-20 | 2019-01-18 | 济南大学 | A kind of porous Sn/Sn of carbon-coated nano4P3Composite material and preparation method |
| CN109244409B (en) * | 2018-09-20 | 2021-09-10 | 济南大学 | Carbon-coated nano porous Sn/Sn4P3Composite material and preparation method thereof |
| CN114105760A (en) * | 2021-10-09 | 2022-03-01 | 温州大学 | Nano flaky tin oxalate high-performance lithium-storing and sodium-storing material and battery |
| CN116130624A (en) * | 2022-12-30 | 2023-05-16 | 浙江维思通新材料有限公司 | Preparation process of composite sodium ion battery anode material |
| CN116130624B (en) * | 2022-12-30 | 2023-12-01 | 浙江维思通新材料有限公司 | Preparation process of composite sodium ion battery anode material |
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