CN110120504A - A kind of phosphorus/tin/carbon compound cathode materials preparation method of richness phosphorus - Google Patents

A kind of phosphorus/tin/carbon compound cathode materials preparation method of richness phosphorus Download PDF

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CN110120504A
CN110120504A CN201910331410.7A CN201910331410A CN110120504A CN 110120504 A CN110120504 A CN 110120504A CN 201910331410 A CN201910331410 A CN 201910331410A CN 110120504 A CN110120504 A CN 110120504A
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phosphorus
preparation
tin
carbon
carbon nanotube
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杨化滨
李少淇
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Nankai University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/054Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387Tin or alloys based on tin
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention relates to a kind of phosphorus/tin/carbon compound cathode materials preparation methods of rich phosphorus, belong to sodium ion secondary battery negative electrode material and its technology of preparing.The composite material is made using red phosphorus, glass putty, graphite, pyrroles, Iron(III) chloride hexahydrate, methyl orange as raw material by two step high-energy ball milling methods.It first passes through high-energy ball milling and phosphorus/tin material is made, then it is obtained into final phosphorus/tin/carbon negative pole material with graphite and carbon nanotube ball-milling.The negative electrode material is by introducing suitable metallic tin into red phosphorus, the electric conductivity of red phosphorus is increased while ensure that material higher theoretical capacity, electric conductivity is further increased by composite graphite and carbon nanotube, and graphite and the unique structure of carbon nanotube being capable of volume expansions in buffer electrode cyclic process, their synergistic effect is so that the cyclical stability of negative electrode material greatly improves, the preparation method is safe and simple, used low raw-material cost, is suitable for commercial applications.

Description

A kind of phosphorus/tin/carbon compound cathode materials preparation method of richness phosphorus
Technical field
The present invention relates to sodium ion secondary battery negative electrode material and its technology of preparing, especially a kind of phosphorus/tin/carbon of rich phosphorus The preparation method of composite negative pole material.
Background technique
Lithium ion battery is as one of widest energy-accumulating medium of current era purposes, energy density with higher, nothing The advantages that memory effect, small environmental pollution, these advantages make it be widely used in mobile device (mobile phone, notebook electricity Brain), power vehicle and energy storage field.But the lithium metal content in the earth's crust is only 0.006%, global lithium resource produces Amount is difficult to maintain the following growing lithium demand, and is among these more than that 60% lithium is deposited in the form of mineral or brine It is special area, this also increases the exploitation difficulty of lithium to a certain extent.As the substitute of lithium ion battery, sodium ion Battery cost is lower, and sodium content is more abundant in the earth's crust, can obtain from seawater, it is particularly possible to be applied to extensive energy storage In system.The energy density of sodium-ion battery is lower than lithium ion battery, and finding suitable negative electrode material can satisfy raising battery The needs of capacity, while energy storage cost can also be substantially reduced.
Currently, the research of sodium-ion battery cathode focuses mostly in amorphous carbon material, metal and alloy materials, metal oxidation Object material, phosphorous-based materials and organic material etc..Wherein phosphate material theoretical specific capacity with higher (2596 mAh g-1), at Originally the advantages such as low and environmental-friendly can satisfy demand of the development to high specific energy batteries in the future.According to the phosphorus base studied at present Material can be roughly divided into: phosphorus carbon material, phosphatization tin material, phosphorus/transition metal material and ternary-alloy material of phosphorus etc..Phosphorus base The two big main problems that material faces at present are that poorly conductive and volume expansion are big, therefore enhance electric conductivity, buffer electrode volume Expansion can effectively improve the electrochemical stability of phosphorus base negative electrode material.
Chinese patent CN106450306A discloses the preparation method of phosphorization tin anode material of lithium-ion battery a kind of and answers With.This method carries out solvent thermal reaction using the red phosphorus and pink salt of pre- ball milling and phosphatization tin particles is made.Negative electrode material head is put in week Electric specific capacity is up to 800 mAh g-1, but its cyclical stability is poor, and the residual capacity after 20 weeks is 378 mAh g-1, and And preparation method is needed using autoclave, reaction temperature is high, and the reaction time is long, using organic solvent, post-processing it is complicated and It is easy to cause pollution.
Chinese patent CN108493425A discloses a kind of Sn4P3 nano particle sodium ion electricity of mesoporous carbon nanotube cladding The preparation method of pond negative electrode material.The preparation method is to first pass through multistep reaction to prepare mesoporous carbon-coated SnO2, then again With sodium hypophosphite is baking mixed that the negative electrode material is made.It is recycled 300 weeks with good electric conductivity and stable cycle performance Keep the reversible specific capacity of 299.9 mAh g-1.But the negative electrode material may cause its specific capacity low due to carbon content height, and Preparation method is complicated, is related to multistep heating water bath, solvent heat and high-temperature roasting reaction, includes formaldehyde in used raw material, Safety is poor.
Chinese patent CN101556998A disclose metal phosphide as ion secondary battery cathode material lithium and its Preparation method.The metal phosphide is made using the method that high-energy ball milling method and high temperature solid phase synthesis combine, metal phosphorizing Object crystallinity is high, wherein based on high-temperature roasting, however prolonged high-temperature roasting increases energy consumption, high-energy ball milling method mainly rises To powder size is reduced, increase the effect of two kinds of powder contact areas.In addition, the above-mentioned material of this method preparation is if appropriate for sodium Ion battery cathode material is on the knees of the gods.
Chinese patent CN106602020A discloses a kind of lithium ion battery metal phosphide negative electrode material and its preparation Method.Sn4P3/C composite material prepared by the method is made using high-energy ball milling method, and the content of wherein graphite is higher, follows Specific discharge capacity after ring 50 weeks is 750 mAh g-1, does not give full play to the advantage of the high theoretical capacity of red phosphorus.
Chinese patent CN107352521A discloses a kind of linear phosphatization tin compound and preparation method thereof.The compound is adopted It is made with the method that glass putty, phosphorus powder and aluminium powder elder generation ball milling are calcined again, the addition of aluminium powder helps to obtain linear phosphatization tin compound. The threadiness phosphorization tin is not used as negative electrode material to use, and preparation method, based on high temperature solid state reaction, having in roasting process can The higher white phosphorus of risk can be generated.In addition, this method preparation above-mentioned material if appropriate for anode material of lithium-ion battery not There is announcement.
Chinese patent CN109309199A discloses a kind of negative electrode of lithium ion battery red phosphorus/carbon nano tube compound material preparation Method.Red phosphorus and carbon nano tube dispersion liquid are uniformly mixed using low temperature liquid polymerization process and are freeze-dried obtained, work by the composite material Pass through 120 cyclic specific capacity 969 mAh g-1 of residue for negative electrode of lithium ion battery, effectively improves the electrochemistry of red phosphorus Can, but its preparation cost is higher, preparation method is also unfavorable for large-scale application.In addition, the above-mentioned material of this method preparation is No suitable anode material of lithium-ion battery is also unknown.
Chinese patent CN108550789A discloses a kind of sodium-ion battery red phosphorus cathode and preparation method thereof.The composite wood Material is made using red phosphorus, graphene and barium carbonate high-energy ball milling, and specific discharge capacity of the circulation after 50 weeks is 600 mAh g-1, stone Black alkene can effectively increase the electric conductivity of red phosphorus, and the addition of barium carbonate can promote battery high current charge-discharge application.But it is Improve the electric conductivity of red phosphorus, the composite material graphene additive amount is high, reduces red phosphorus content indirectly, leads to red phosphorus Gao Li It is not given full play of by the advantage of capacity.
Summary of the invention
The object of the present invention is to provide a kind of phosphorus/tin/carbon compound cathode materials preparation methods of rich phosphorus.Preparing phosphorus Increase phosphorus content on the basis of change tin, obtain rich phosphate material, the defect of above-mentioned influence phosphorous-based materials cyclical stability can be overcome, While guaranteeing higher phosphorus content, solves the problems, such as the negative electrode material that red phosphorus poorly conductive and volume expansion are big, prepare First effect with higher, higher specific capacity and stable cycle performance.
A kind of phosphorus/tin/carbon compound cathode materials preparation method of rich phosphorus provided by the invention passes through following steps:
1) red phosphorus and metallic tin powder are placed in ball milling in the ball grinder of stainless steel and P/Sn material is made;The wherein mass ratio of phosphorus and tin The molar ratio that phosphorus and tin are equivalent to for 0.4 ~ 9:1(is 6 ~ 138:4, compares Sn4P3, the above ratio is rich phosphate material);
2) it weighs 0.33 ~ 1.65g methyl orange to be dissolved under strong stirring in 100 ~ 600ml distilled water, obtains solution A, weigh 2.70 ~ 13.5g Iron(III) chloride hexahydrate is dissolved in 100 ~ 400ml distilled water, obtains solution B;
3) solution B of step 2 is added in solution A under the action of strong stirring, is added 0.68 thereto after 3 ~ 5min ~ 3.40g pyrrole monomer, 20 ~ 30h of strong stirring are filtered cleaning to product until filtrate presents colorless and transparent, are placed in true 8 ~ 10h is dried in empty drying box at 80 ~ 120 DEG C;
4) step 3) product is placed in vacuum tube furnace, and under an argon atmosphere, high temperature cabonization obtains carbon nanotube.
5) the P/Sn material of step 1) preparation and step 4) obtain carbon nanotube in the case where argon gas does protection gas, in planetary ball It is mixed in grinding machine, obtains final phosphorus base negative electrode material, i.e. P/Sn/C anode material.
Carbon nanotube described in step 5) can come from business carbon nanotube, carbon nano-fiber, carbon nanocoils, and directly It is replaced with part or all of graphite material, graphite is commercial graphite or natural graphite;Carbon material account for composite material quality 20 ~ 30%。
The ball milling condition of step 1) and step 5) is that the diameter of stainless steel ball-milling pearl is 5 ~ 10mm, and ratio of grinding media to material is 10:1 ~ 50: 1, with revolving speed 300 ~ 500rpm positive and negative rotation alternate run, 10 ~ 30min of every operating is spaced 0 ~ 10min, and Ball-milling Time is 5 ~ 40h.
Step 4) high temperature cabonization is 600 ~ 800 DEG C of 2 ~ 4h of roasting, and heating rate is 5 ~ 10 DEG C/min to get to carbon nanometer Pipe.
The P/Sn/C composite material and conductive agent and binder that the present invention prepares step 5) are with 8 ~ 6:1 of mass ratio ~ 2:1 ~ 2 It is placed in small beaker, slurry obtained is uniformly coated on copper foil, juxtaposition exists in a vacuum drying oven by magnetic agitation homogenate Dry 10 ~ 15h, is cut into the disk of diameter 13mm and obtains negative electrode tab in the pressure lower sheeting of 20MPa at 80 ~ 120 DEG C.
The present invention is with negative electrode tab obtained above, and using metallic sodium piece as to electrode, diaphragm is fibreglass diaphragm, electrolysis Liquid is EC/DMC (1:1 Vol%) solution for being added to the 1.0M NaClO4 of 5 Vol% FEC, is assembled into glove box C2032 button cell.
Phosphorus/tin/carbon composite of richness phosphorus provided by the invention is to pass through high-energy ball milling method by red phosphorus, glass putty and carbon source A kind of composite material of compound obtained phosphorus content higher (mass ratio of phosphorus and tin is 0.4 ~ 9:1).By adjusting composite material The mass-energy density of middle red phosphorus and glass putty accesses the composite material of different phosphorus contents, and the selection of carbon source includes graphitic carbon, carbon nanometer The mixture of pipe and the two.The negative electrode material be by phosphorous-based materials introduce metallic tin, improve its electric conductivity, in order into The electric conductivity that one step improves material continues to introduce carbon material, and graphite and the special construction of carbon nanotube can also play buffering The effect of electrode material volume expansion in charge and discharge process, so that the cyclical stability of integral composite is improved, meanwhile, The addition of graphite can play the role of lubrication in mechanical milling process, keep ball milling more abundant, reduce material loss.
Outstanding feature of the invention is to ensure that the higher theoretical appearance of material by introducing suitable metallic tin into red phosphorus The electric conductivity that red phosphorus is increased while amount further increases electric conductivity by composite graphite and carbon nanotube, and graphite and The unique structure of carbon nanotube can volume expansion in buffer electrode cyclic process, their synergistic effect is so that negative electrode material Cyclical stability greatly improve, the preparation method is safe and simple, used low raw-material cost, suitable for commercialization answer With.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) spectrogram of composite material prepared by embodiment 1.
Fig. 2 is scanning electron microscope (SEM) figure of composite material prepared by embodiment 1.
Fig. 3 is the electrochemistry cycle performance and coulombic efficiency figure of composite material prepared by embodiment 1.
Fig. 4 is X-ray diffraction (XRD) spectrogram of composite material prepared by embodiment 2.
Fig. 5 is the electrochemistry cycle performance and coulombic efficiency figure of composite material prepared by embodiment 6.
Fig. 6 is the high rate performance figure of composite material prepared by embodiment 6.
Specific embodiment
Embodiment 1:
Step 1: by red phosphorus and metallic tin powder with mass ratio 0.4:1(molar ratio 6:4), amount to the ball milling that 1g material is placed in stainless steel In tank, the diameter of stainless steel ball-milling pearl is each half of 5mm and 10mm mass, and ratio of grinding media to material 50:1 does the gas of protection gas in argon gas Under atmosphere, with revolving speed 400rpm positive and negative rotation alternate run, every operating 30min is spaced 5min, and Ball-milling Time 20h obtains P/Sn material Expect spare;
Step 2: it weighs 0.33g methyl orange and is dissolved under strong stirring in 100ml distilled water, obtain solution A, weigh 2.70g Iron(III) chloride hexahydrate is dissolved in 100ml distilled water, obtains solution B;
Step 3: the solution B in step 2 is added in solution A under the action of strong stirring, is added thereto after 3min Enter 0.68g pyrrole monomer, strong stirring 25h is filtered cleaning to product until filtrate presents colorless and transparent, is placed in vacuum 10h is dried in drying box at 80 DEG C;
Step 4: product in step 3 is placed in vacuum tube furnace, and under an argon atmosphere, 700 DEG C of roasting 2h, heating rate is 10 DEG C/min, it is spare to obtain carbon nanotube.
Step 5: by the P/Sn material of step 1 preparation and graphite and carbon nanotube obtained in step 4 with mass ratio 8: 1.5:0.5 amounts to 1g and is placed in the ball grinder of stainless steel, and the diameter of stainless steel ball-milling pearl is 5mm, ratio of grinding media to material 50:1, in argon Gas is done under the atmosphere of protection gas, replaces continuous operation 5h with revolving speed 500rpm positive and negative rotation to get phosphorus/tin/carbon composite (P/ is arrived Sn/G/CNTs).Wherein the selection of carbon source includes commercial graphite and carbon nanotube obtained in step 4, and graphite accounts for graphite and carbon The 75% of nanotube gross mass.
Step 6: the P/Sn/G/CNTs composite material of preparation is placed in mass ratio 6:2:2 with conductive agent and binder small In beaker, magnetic agitation homogenate.Slurry obtained is uniformly coated on copper foil, juxtaposition is in a vacuum drying oven at 120 DEG C Lower dry 15h is cut into the disk of diameter 13mm and obtains negative electrode tab in the pressure lower sheeting of 20MPa.Using metallic sodium piece as pair Electrode, diaphragm are fibreglass diaphragm, and electrolyte is the EC/DMC (1:1 for being added to the 1.0M NaClO4 of 5 Vol% FEC Vol%) solution is assembled into C2032 button cell in glove box.
Electrochemical property test (CT2001A, blue electricity) is carried out to the button cell installed.
Fig. 1 is X-ray diffraction (XRD) spectrogram of the P/Sn/G/CNTs composite material of above-mentioned preparation.It can from the figure Out, observe the diffraction maximum of graphite near 26.5o, other peak positions are corresponding with the peak of phosphorization tin in figure, phosphorus content compared with Phosphorization tin has been primarily formed when low.
Fig. 2 is scanning electron microscope (SEM) figure of the P/Sn/G/CNTs composite material of above-mentioned preparation.It can be with from the figure Find out the tubular structure of carbon nanotube and the lamellar structure of graphite.
Fig. 3 is the electrochemistry cycle performance and coulombic efficiency figure of the P/Sn/G/CNTs composite material of above-mentioned preparation.From the figure In as can be seen that first discharge specific capacity be 998.1 mAh g-1, charge specific capacity be 758.7 mAh g-1, for the first time coulomb imitate Rate is 76.0%, and for circulation after 100 weeks, discharge capacity is maintained at 705.2 mAh g-1.Should the result shows that, prepared P/Sn/G/ CNTs composite material coulombic efficiency for the first time with higher, higher specific capacity and preferable cyclical stability.
Embodiment 2:
Step 1: by red phosphorus and metallic tin powder with mass ratio 2.3:1(molar ratio 36:4), amount to the ball milling that 1g material is placed in stainless steel In tank, the diameter of stainless steel ball-milling pearl is each half of 5mm and 10mm mass, and ratio of grinding media to material 10:1 does the gas of protection gas in argon gas Under atmosphere, with revolving speed 400rpm positive and negative rotation alternate run, every operating 30min is spaced 10min, and Ball-milling Time 30h obtains P/Sn Materials for later use;
Step 2: it weighs 1.65g methyl orange and is dissolved under strong stirring in 600ml distilled water, obtain solution A, weigh 13.50g Iron(III) chloride hexahydrate is dissolved in 400ml distilled water, obtains solution B;
Step 3: the solution B in step 2 is added in solution A under the action of strong stirring, is added thereto after 5min Enter 3.40g pyrrole monomer, strong stirring is filtered cleaning for 24 hours, to product until filtrate presents colorless and transparent, is placed in vacuum 10h is dried in drying box at 80 DEG C;
Step 4: product in step 3 is placed in vacuum tube furnace, and under an argon atmosphere, 700 DEG C of roasting 2h, heating rate is 10 DEG C/min, it is spare to obtain carbon nanotube.
Step 5: by the P/Sn material of step 1 preparation and graphite and carbon nanotube obtained in step 4 with mass ratio 8: 1:1 amounts to 1g and is placed in the ball grinder of stainless steel, and the diameter of stainless steel ball-milling pearl is each half of 5mm and 10mm, and ratio of grinding media to material is 50:1 replaces continuous operation 40h under the atmosphere that argon gas does protection gas with revolving speed 500rpm positive and negative rotation to get phosphorus/tin/carbon is arrived Composite material (P/Sn/G/CNTs).Wherein the selection of carbon source includes commercial graphite and carbon nanotube obtained in step 4, graphite Account for the 50% of graphite and carbon nanotube gross mass.
Step 6: the P/Sn/G/CNTs composite material of above-mentioned preparation is set with conductive agent and binder with mass ratio 6:2:2 In small beaker, magnetic agitation homogenate.Slurry obtained is uniformly coated on copper foil, juxtaposition exists in a vacuum drying oven Dry 15h, is cut into the disk of diameter 13mm and obtains negative electrode tab in the pressure lower sheeting of 20MPa at 120 DEG C.With metallic sodium piece work For to electrode, diaphragm is fibreglass diaphragm, electrolyte be added to the 1.0M NaClO4 of 5 Vol% FEC EC/DMC (1: 1 Vol%) solution, C2032 button cell is assembled into glove box.
Electrochemical property test (CT2001A, blue electricity) is carried out to the button cell installed.
Fig. 4 is X-ray diffraction (XRD) spectrogram of the P/Sn/G/CNTs composite material of above-mentioned preparation.It can from the figure Out, without apparent peak, in 20o ~ 35o there are wider peak, which is mainly amorphous state.
The P/Sn/G/CNTs composite material of above-mentioned preparation forms oral examination battery testing chemical property as negative electrode material, First discharge specific capacity is 1567.4 mAh g-1, and charge specific capacity is 1148.9 mAh g-1, and coulombic efficiency is for the first time 73.3%, for circulation after 100 weeks, discharge capacity is maintained at 896.1 mAh g-1.
Embodiment 3:
Step 1: by red phosphorus and metallic tin powder with mass ratio 9:1(molar ratio 138:4), amount to the ball milling that 1g material is placed in stainless steel In tank, the diameter of stainless steel ball-milling pearl is 10mm, ratio of grinding media to material 30:1, is done under the atmosphere for protecting gas in argon gas, just with revolving speed 300 Invert alternate run, every operating 20min, be spaced 5min, Ball-milling Time be 5h to get arrive P/Sn material;
Step 2: it weighs 0.66g methyl orange and is dissolved under strong stirring in 200ml distilled water, obtain solution A, weigh 5.40g Iron(III) chloride hexahydrate is dissolved in 200ml distilled water, obtains solution B;
Step 3: the solution B in step 2 is added in solution A under the action of strong stirring, is added thereto after 3min Enter 1.36g pyrrole monomer, strong stirring 20h is filtered cleaning to product until filtrate presents colorless and transparent, is placed in vacuum 8h is dried in drying box at 120 DEG C;
Step 4: product in step 3 is placed in vacuum tube furnace, and under an argon atmosphere, 800 DEG C of roasting 3h, heating rate is 5 DEG C/min to get arrive carbon nanotube.
Step 5: by the P/Sn material of step 1 preparation and graphite with mass ratio 8:2, being placed in the ball grinder of stainless steel, The diameter of stainless steel ball-milling pearl is 5mm, ratio of grinding media to material 50:1, is done under the atmosphere for protecting gas in argon gas, positive and negative with revolving speed 300rpm It delivers and replaces continuous operation 20h to get P/Sn/G composite material is arrived.Wherein carbon source is selected as graphite, and graphite accounts for graphite and carbon is received The 100% of mitron gross mass.
Step 6: the P/Sn/G composite material of above-mentioned preparation is placed in mass ratio 6:2:2 with conductive agent and binder small In beaker, magnetic agitation homogenate.Slurry obtained is uniformly coated on copper foil, juxtaposition is in a vacuum drying oven at 120 DEG C Lower dry 15h is cut into the disk of diameter 13mm and obtains negative electrode tab in the pressure lower sheeting of 20MPa.Using metallic sodium piece as pair Electrode, diaphragm are fibreglass diaphragm, and electrolyte is the EC/DMC (1:1 for being added to the 1.0M NaClO4 of 5 Vol% FEC Vol%) solution is assembled into C2032 button cell in glove box.
Electrochemical property test (CT2001A, blue electricity) is carried out to the button cell installed.
The P/Sn/G composite material of above-mentioned preparation forms oral examination battery testing chemical property as negative electrode material, puts for the first time Electric specific capacity is 1804.5 mAh g-1, and charge specific capacity is 1380.1 mAh g-1, and coulombic efficiency is 76.5% for the first time, circulation After 50 weeks, discharge capacity is maintained at 926.5 mAh g-1.
Embodiment 4:
Step 1: by red phosphorus and metallic tin powder with mass ratio 1:1(molar ratio 15:4), amount to the ball grinder that 1g material is placed in stainless steel In, the diameter of stainless steel ball-milling pearl is each half of 5mm and 10mm, and ratio of grinding media to material 50:1 is done in argon gas under the atmosphere for protecting gas, with 400 positive and negative rotation alternate run of revolving speed, every operating 30min, be spaced 5min, Ball-milling Time be 30h to get arrive P/Sn material;
Step 2: it weighs 0.33g methyl orange and is dissolved under strong stirring in 100ml distilled water, obtain solution A, weigh 2.70g Iron(III) chloride hexahydrate is dissolved in 100ml distilled water, obtains solution B;
Step 3: the solution B in step 2 is added in solution A under the action of strong stirring, is added thereto after 5min Enter 0.68g pyrrole monomer, strong stirring 30h is filtered cleaning to product until filtrate presents colorless and transparent, is placed in vacuum 10h is dried in drying box at 120 DEG C;
Step 4: product in step 3 is placed in vacuum tube furnace, and under an argon atmosphere, 700 DEG C of roasting 2h, heating rate is 10 DEG C/min to get arrive carbon nanotube.
Step 5: by the P/Sn material of step 1 preparation and carbon nanotube with mass ratio 8:2, it is placed in the ball grinder of stainless steel In, the diameter of stainless steel ball-milling pearl is 10mm, ratio of grinding media to material 20:1, under the atmosphere that argon gas does protection gas, with revolving speed 400rpm Positive and negative rotation replaces continuous operation 30h to get P/Sn/CNTs composite material is arrived.Wherein carbon source is selected as carbon nanotube, and graphite accounts for The 0% of graphite and carbon nanotube gross mass.
Step 6: the P/Sn/CNTs composite material of above-mentioned preparation is placed in conductive agent and binder with mass ratio 6:2:2 In small beaker, magnetic agitation homogenate.Slurry obtained is uniformly coated on copper foil, juxtaposition is in a vacuum drying oven 120 Dry 15h, is cut into the disk of diameter 13mm and obtains negative electrode tab in the pressure lower sheeting of 20MPa at DEG C.Using metallic sodium piece as To electrode, diaphragm is fibreglass diaphragm, and electrolyte is the EC/DMC (1:1 for being added to the 1.0M NaClO4 of 5 Vol% FEC Vol%) solution is assembled into C2032 button cell in glove box.
Electrochemical property test (CT2001A, blue electricity) is carried out to the button cell installed.
The P/Sn/CNTs composite material of above-mentioned preparation forms oral examination battery testing chemical property as negative electrode material, first Secondary specific discharge capacity is 1506.2 mAh g-1, and charge specific capacity is 1156.1 mAh g-1, and coulombic efficiency is 76.8% for the first time, After recycling 100 weeks, discharge capacity is maintained at 601.4 mAh g-1.
Embodiment 5:
Step 1: by red phosphorus and metallic tin powder with mass ratio 2.3:1(molar ratio 36:4), amount to the ball milling that 1g material is placed in stainless steel In tank, the diameter of stainless steel ball-milling pearl is each half of 5mm and 10mm mass, and ratio of grinding media to material 10:1 does the gas of protection gas in argon gas Under atmosphere, with revolving speed 400rpm positive and negative rotation alternate run, every operating 30min is spaced 10min, and Ball-milling Time is for 24 hours, to obtain P/Sn Materials for later use;
Step 2: it weighs 0.33g methyl orange and is dissolved under strong stirring in 100ml distilled water, obtain solution A, weigh 2.70g Iron(III) chloride hexahydrate is dissolved in 100ml distilled water, obtains solution B;
Step 3: the solution B in step 2 is added in solution A under the action of strong stirring, is added thereto after 5min Enter 0.68g pyrrole monomer, strong stirring 20h is filtered cleaning to product until filtrate presents colorless and transparent, is placed in vacuum 9h is dried in drying box at 120 DEG C;
Step 4: product in step 3 is placed in vacuum tube furnace, and under an argon atmosphere, 600 DEG C of roasting 4h, heating rate is 10 DEG C/min, it is spare to obtain carbon nanotube.
Step 5: by the P/Sn material of step 1 preparation and graphite and carbon nanotube obtained in step 4 with mass ratio 8: 1.5:0.5 amounts to 1g and is placed in the ball grinder of stainless steel, and the diameter of stainless steel ball-milling pearl is each half of 5mm and 10mm, ratio of grinding media to material For 50:1, under the atmosphere that argon gas does protection gas, with revolving speed 400rpm positive and negative rotation alternating continuous operation 30h to get to phosphorus/tin/ Carbon composite (P/Sn/G/CNTs).Wherein the selection of carbon source includes commercial graphite and carbon nanotube obtained in step 4, stone Ink accounts for the 75% of graphite and carbon nanotube gross mass.
Step 6: the P/Sn/G/CNTs composite material of preparation is placed in mass ratio 6:2:2 with conductive agent and binder small In beaker, magnetic agitation homogenate.Slurry obtained is uniformly coated on copper foil, juxtaposition is in a vacuum drying oven at 120 DEG C Lower dry 15h is cut into the disk of diameter 13mm and obtains negative electrode tab in the pressure lower sheeting of 20MPa.Using metallic sodium piece as pair Electrode, diaphragm are fibreglass diaphragm, and electrolyte is the EC/DMC (1:1 for being added to the 1.0M NaClO4 of 5 Vol% FEC Vol%) solution is assembled into C2032 button cell in glove box.
Electrochemical property test (CT2001A, blue electricity) is carried out to the button cell installed.
The P/Sn/G/CNTs composite material of above-mentioned preparation forms oral examination battery testing chemical property as negative electrode material, First discharge specific capacity is 2032.7 mAh g-1, and charge specific capacity is 1573.8 mAh g-1, and coulombic efficiency is for the first time 77.4%, for circulation after 100 weeks, discharge capacity is maintained at 724.2 mAh g-1.
Embodiment 6:
Step 1: by red phosphorus and metallic tin powder with mass ratio 1:1(molar ratio 15:4), amount to the ball grinder that 2g material is placed in stainless steel In, the diameter of stainless steel ball-milling pearl is each half of 5mm and 10mm mass, and ratio of grinding media to material 50:1 does the atmosphere of protection gas in argon gas Under, with revolving speed 400rpm positive and negative rotation alternate run, every operating 30min is spaced 5min, and Ball-milling Time 30h obtains P/Sn material It is spare;
Step 2: it weighs 1.65g methyl orange and is dissolved under strong stirring in 600ml distilled water, obtain solution A, weigh 13.50g Iron(III) chloride hexahydrate is dissolved in 400ml distilled water, obtains solution B;
Step 3: the solution B in step 2 is added in solution A under the action of strong stirring, is added thereto after 3min Enter 3.40g pyrrole monomer, strong stirring is filtered cleaning for 24 hours, to product until filtrate presents colorless and transparent, is placed in vacuum 10h is dried in drying box at 120 DEG C;
Step 4: product in step 3 is placed in vacuum tube furnace, and under an argon atmosphere, 700 DEG C of roasting 4h, heating rate is 10 DEG C/min, it is spare to obtain carbon nanotube.
Step 5: by the P/Sn material of step 1 preparation and graphite and carbon nanotube obtained in step 4 with mass ratio 8: 1.5:0.5 amounts to 1g and is placed in the ball grinder of stainless steel, and the diameter of stainless steel ball-milling pearl is 5mm, ratio of grinding media to material 50:1, in argon Gas is done under the atmosphere of protection gas, replaces continuous operation 30h with revolving speed 500rpm positive and negative rotation to get phosphorus/tin/carbon composite is arrived (P/Sn/G/CNTs).The wherein selection of carbon source includes commercial graphite and carbon nanotube obtained in step 4, graphite account for graphite and The 75% of carbon nanotube gross mass.
Step 6: the P/Sn/G/CNTs composite material of preparation is placed in mass ratio 6:2:2 with conductive agent and binder small In beaker, magnetic agitation homogenate.Slurry obtained is uniformly coated on copper foil, juxtaposition is in a vacuum drying oven at 120 DEG C Lower dry 15h is cut into the disk of diameter 13mm and obtains negative electrode tab in the pressure lower sheeting of 20MPa.Using metallic sodium piece as pair Electrode, diaphragm are fibreglass diaphragm, and electrolyte is the EC/DMC (1:1 for being added to the 1.0M NaClO4 of 5 Vol% FEC Vol%) solution is assembled into C2032 button cell in glove box.
Electrochemical property test (CT2001A, blue electricity) is carried out to the button cell installed.
Fig. 5 is that the P/Sn/G/CNTs composite material of above-mentioned preparation forms oral examination battery testing electrochemistry as negative electrode material Performance map, as can be seen from the figure its first discharge specific capacity is 1437.8 mAh g-1, and charge specific capacity is 1147.9 mAh G-1, coulombic efficiency is 79.8% for the first time, and for circulation after 100 weeks, specific discharge capacity is 1048.0 mAh g-1, which has Higher specific capacity and stable cycle performance.
Fig. 6 be above-mentioned preparation P/Sn/G/CNTs composite material high rate performance figure, it can be seen from the figure that even if The circulation of the composite material still has stable cycle performance can under the current density of 4.0A g-1 under high current density Inverse specific capacity is 526.5 mAh g-1, and when current density returns to 0.1 A g-1, reversible capacity returns to 1179.1 mAh g-1, Show excellent high rate performance and cyclical stability.
The above is only a preferred embodiment of the present invention.It should be pointed out that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. a kind of phosphorus/tin/carbon compound cathode materials preparation method of richness phosphorus, it is characterised in that pass through following steps:
1) red phosphorus and metallic tin powder are placed in ball milling in the ball grinder of stainless steel and P/Sn material is made;
2) methyl orange is dissolved in appropriate distilled water under strong stirring, obtains solution A, weigh appropriate Iron(III) chloride hexahydrate It is dissolved in appropriate distilled water, obtains solution B;
3) solution B of step 2 is added in solution A under the action of strong stirring, pyrroles is added thereto after 3 ~ 5min Monomer, strong stirring, to product be filtered cleaning until filtrate present it is colorless and transparent, be placed in a vacuum drying oven drying;
4) step 3) product is placed in vacuum tube furnace, and under an argon atmosphere, high temperature cabonization obtains carbon nanotube;
5) the P/Sn material of step 1) preparation and step 4) obtain carbon nanotube in the case where argon gas does protection gas, in planetary ball mill Middle mixing obtains final phosphorus base negative electrode material, i.e. P/Sn/C composite negative pole material.
2. preparation method according to claim 1, it is characterised in that the mass ratio of phosphorus and tin in step 1) is 0.4 ~ 9: 1。
3. preparation method according to claim 1, it is characterised in that the ball milling condition of step 1) and step 5) is stainless steel The diameter of ball milling pearl is 5 ~ 10mm, and ratio of grinding media to material is 10:1 ~ 50:1, with revolving speed 300 ~ 500rpm positive and negative rotation alternate run, every operating 10 ~ 30min, is spaced 0 ~ 10min, and Ball-milling Time is 5 ~ 40h.
4. preparation method according to claim 1, it is characterised in that step 3) vacuum drying temperature is 80 ~ 120 DEG C, dry Time is 8 ~ 10h.
5. preparation method according to claim 1, it is characterised in that carbon nanotube described in step 5) can come from business Carbon nanotube, carbon nano-fiber, carbon nanocoils, and directly replaced with part or all of graphite material.
6. preparation method according to claim 1, it is characterised in that carbon material accounts for the 20 ~ 30% of composite material quality.
7. a kind of phosphorus/tin/carbon compound cathode materials preparation method of richness phosphorus, it is characterised in that pass through following steps:
1) red phosphorus and metallic tin powder are placed in ball milling in the ball grinder of stainless steel and P/Sn material is made;The wherein mass ratio of phosphorus and tin For 0.4 ~ 9:1 of phosphorus;
2) it weighs 0.33 ~ 1.65g methyl orange to be dissolved under strong stirring in 100 ~ 600ml distilled water, obtains solution A, weigh 2.70 ~ 13.5g Iron(III) chloride hexahydrate is dissolved in 100 ~ 400ml distilled water, obtains solution B;
3) solution B of step 2 is added in solution A under the action of strong stirring, is added 0.68 thereto after 3 ~ 5min ~ 3.40g pyrrole monomer, 20 ~ 30h of strong stirring are filtered cleaning to product until filtrate presents colorless and transparent, are placed in true 8 ~ 10h is dried in empty drying box at 80 ~ 120 DEG C;
4) step 3) product is placed in vacuum tube furnace, and under an argon atmosphere, high temperature cabonization obtains carbon nanotube;High temperature cabonization is 600 ~ 800 DEG C of 2 ~ 4h of roasting, heating rate are 5 ~ 10 DEG C/min;
5) the P/Sn material of step 1) preparation and step 4) obtain carbon nanotube in the case where argon gas does protection gas, in planetary ball mill Middle mixing obtains final phosphorus base negative electrode material, i.e. P/Sn/C composite negative pole material;
The ball milling condition of step 1) and step 5) is that the diameter of stainless steel ball-milling pearl is 5 ~ 10mm, and ratio of grinding media to material is 10:1 ~ 50:1, with Revolving speed 300 ~ 500rpm positive and negative rotation alternate run, 10 ~ 30min of every operating are spaced 5 ~ 10min, and Ball-milling Time is 5 ~ 30h;
Carbon nanotube described in step 5) can come from business carbon nanotube, carbon nano-fiber, carbon nanocoils, and directly use portion Divide or whole graphite materials are replaced.
8. phosphorus/the tin for the rich phosphorus that any preparation method of claim 1 ~ 7 obtains/carbon compound cathode materials preparation cathode Piece.
9. the sodium-ion battery of negative electrode tab composition according to any one of claims 8.
10. sodium-ion battery according to claim 8, it is characterised in that the sodium-ion battery is C2032 button cell.
CN201910331410.7A 2019-04-24 2019-04-24 A kind of phosphorus/tin/carbon compound cathode materials preparation method of richness phosphorus Pending CN110120504A (en)

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Application publication date: 20190813