CN104538605A - Tin-carbon composite cathode material and preparation method thereof - Google Patents

Tin-carbon composite cathode material and preparation method thereof Download PDF

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CN104538605A
CN104538605A CN201410735658.7A CN201410735658A CN104538605A CN 104538605 A CN104538605 A CN 104538605A CN 201410735658 A CN201410735658 A CN 201410735658A CN 104538605 A CN104538605 A CN 104538605A
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preparation
tin
graphite
acid
suspension
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邱根萍
杨建锋
黄雨生
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JIANGXI ZHENGTUO NEW ENERGY TECHNOLOGY POLYTRON Co Ltd
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
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  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a tin-carbon composite cathode material and a preparation method thereof. The preparation method of the cathode material includes: A. blending graphite with a complexing agent to obtain a suspension liquid system; B. under stirring condition, adding a tin-containing compound and a dispersant into the suspension liquid system; C. adjusting the pH value of the suspension solution in step B by an alkali solution; D. under a stirring condition, adding a reducing agent-containing solution into the suspension liquid of step C to carry out reaction, and then performing filtering, washing and drying to obtain a cathode material precursor; and E. mixing and grinding the cathode material precursor and an organic polymer, and then conducting sintering in a muffle furnace, thus obtaining the tin-carbon composite material. The cathode material prepared by the method can significantly improve the capacity and cycle performance of batteries.

Description

A kind of tin carbon compound cathode materials and preparation method thereof
Technical field
The invention belongs to technical field of composite materials, relate to a kind of preparation of tin carbon composite; The invention still further relates to the application of this tin carbon composite at battery industry.
Background technology
Along with energy crisis and environmental problem highlight day by day, research and develop novel fungible energy source and energy-saving and emission-reduction have important development strategic importance.Such as, the electric motor car (EVs), hybrid vehicle (HEVs) etc. of development and use zero discharge.Lithium ion battery is widely used as important energy storage device, and starts to obtain certain application in the energy storage such as electric motor car (EVs), hybrid vehicle (HEVs).
Lithium ion battery negative material is the important component part of battery, and negative material occupies very important status in battery development.In current business-like lithium ion battery, generally use graphite as negative material.Although graphite is widely used in commercial Li-ion battery, its lower embedding lithium capacity and lower intercalation potential determine graphite and can not meet the Large Copacity such as automobile, high-power applications demand.For electrokinetic cell, require that electrode material should have the features such as high power capacity, high efficiency, high security.The theoretical specific capacity (994 mAh/g) of tin base cathode material for the twice of carbon based negative electrodes material (372 mAh/g) many, intercalation potential is moderate simultaneously, tin base cathode material is become be worth studying and has the lithium ion battery negative material of development potentiality.But the Volumetric expansion that tin-based material is huge causes, and its cycle performance is lower and irreversible capacity is larger.
For the method usually adopting composite material that solves the problem, tin-based material and carbon are carried out compound, and the tin carbon composite of gained possesses the high cycle performance of carbon and the high power capacity feature of tin.(Electrochimica Acta 121,2014,109 – 115) the using plasma chemical vapour deposition techniques such as Vanchiappan Aravindan obtain SnO 2the composite Nano wire material of@C, its gram volume and cycle characteristics are obviously better than stannic oxide nano wire, but this method apparatus expensive, complicated operation, is unfavorable for large-scale production.CN 102427127 A discloses a kind of method adopting ball milling mixing glass putty and carbon dust to prepare tin carbon composite, and composite material fine structure homogeneity prepared by the method is poor.Comparatively the method in forward position adopts to add pink salt in the solution, and introduce carbon by adding micropowder, expanded graphite, porous polymer phenolic resins or other macromolecular materials, then in-situ reducing or dry after high temperature sintering obtain tin carbon composite, as CN 103682273 A, CN 102832374 A.
Summary of the invention
In order to obtain, specific capacity is high, the tin carbon composite of good cycling stability be used as negative material, the invention provides a kind of tin carbon compound cathode materials, present invention also offers the preparation method of this tin carbon compound cathode materials.First by acid solution, hydrophiling is carried out, then by Sn to graphite 2+be dispersed in the suspension-turbid liquid containing graphite, by regulating pH, tin is converted into hydronium(ion) stannous oxide, and be deposited in graphite surface, through after a period of time, drip strong reductant (potassium borohydride, inferior sodium phosphate etc.) to suspension-turbid liquid again to reduce to hydronium(ion) stannous oxide, obtained negative material presoma.By negative material presoma and organic carbon source mechanical mixture, at high temperature, carbonizing reduction is further carried out to tin and becomes metallic tin, obtained tin carbon compound cathode materials.
Present invention employs following technical proposals: a kind of preparation method of tin carbon compound cathode materials, the steps include:
A, by graphite and complexing agent blended, obtain suspension-turbid liquid system;
B, under agitation, add sn-containing compound and dispersant successively to suspension-turbid liquid system;
The pH value of suspension-turbid liquid in C, use aqueous slkali regulating step B;
D, under stirring, the solution containing reducing agent is added in the suspension-turbid liquid of step C and reacts, then through filtering, cleaning, drying obtain negative material presoma.
E, negative material presoma and organic polymer mixed grinding, then sinter in Muffle furnace, obtains tin carbon compound cathode materials.
Wherein, the complexing agent in steps A and the mass ratio of graphite are 0.3 ~ 5: 1, are more preferably 0.5 ~ 2: 1; Described graphite is sheet or globular graphite; Described acid solution is one or more in hydrochloric acid, sulfuric acid, nitric acid; Described complexing agent is one or more in tartaric acid, citric acid, malic acid, succinic acid, ethylenediamine tetra-acetic acid, lactic acid, hydracrylic acid and their salt;
Wherein, the tin in step B and the mass ratio of graphite are 0.1 ~ 0.6: 1, are more preferably 0.2 ~ 0.4: 1;
Wherein, in step B, the molar ratio of dispersant and tin is 0.01 ~ 4: 1, is preferably 0.02 ~ 1.5: 1; Described sn-containing compound be stannous chloride, stannic chloride, STANNOUS SULPHATE CRYSTALLINE, stannous sulfate etc. one or more; Described dispersant be sucrose, fructose, ethylene glycol, polyethylene glycol etc. one or more;
Wherein, the pH value range controlling suspension-turbid liquid in step C, between 3 ~ 11, is more preferably 7 ~ 10; Described alkali lye is one or more of ammoniacal liquor, urea, urea, NaOH etc.;
Wherein, in step D, reaction temperature controls, at 20 ~ 90 DEG C, to be more preferably 45 ~ 85 DEG C;
Wherein, the reducing agent described in step D be potassium borohydride, sodium borohydride, inferior sodium phosphate, hydrazine hydrate etc. one or more;
Wherein, in step D, drying condition is vacuumize, and baking temperature is 80 ~ 120 DEG C, and drying time is 8 ~ 18 hours, and vacuum degree is 0.05 ~ 0.09 MPa;
Wherein, in step e, organic polymer and negative material presoma mass ratio are 0.05 ~ 0.6: 1, are more preferably 0.1 ~ 0.3: 1; Described organic polymer be pitch, phenolic resins, epoxy resin, poly-propionamide resin, Kynoar, polyoxyethylene-poly-oxypropylene polyoxyethylene etc. one or more.
The invention provides tin carbon compound cathode materials prepared by a kind of said method.
Tin carbon composite specific capacity prepared by the present invention is high, good cycling stability, and technique is simple, is applicable to batch production.
Accompanying drawing explanation
Fig. 1 is 1000 times of scanning electron microscope (SEM) photographs of embodiment 4 tin carbon compound cathode materials in the present invention.
Fig. 2 is 3000 times of scanning electron microscope (SEM) photographs of embodiment 4 tin carbon compound cathode materials in the present invention.
Embodiment
Embodiment 1
Be that 63 % nitric acid deionized waters are diluted to 50 ml by 20 ml concentration, after adding 10 g graphite, stir 4 hours under 85 DEG C of conditions, solution filtration washing was extremely neutral, 85 DEG C of dryings 12 hours.At 45 DEG C, the tartaric acid solution of 1 mol/l of the graphite after acidifying and 50 ml is uniformly mixed, add 2.8 g stannous chlorides again, after sub-tin to be chlorinated dissolves completely, then 5 ml ethylene glycol and 200 ml deionized waters are added successively, after mixing, with the sodium hydroxide solution of 4 mol/l, this suspension-turbid liquid pH is adjusted to 3.5.Under agitation, drop in suspension-turbid liquid by the 0.5mol/l solution of potassium borohydride of 150ml, after potassium borohydride liquid dropwises, continue stirring 2 hours, solution filters and spends deionized water to neutral, and 85 DEG C of dried overnight obtain negative material presoma.2g phenolic resins and above-mentioned negative material presoma are carried out ground and mixed, and under 900 DEG C of nitrogen atmospheres, roasting obtains sample A in 6 hours.
More than obtained tin carbon composite is positive pole, and lithium sheet is negative pole, and electrolyte is the LiPF of 1mol/l 6eC/DMC(1:1) solution, barrier film is polypropylene, polyethylene composite diaphragm.The ratio of active material: CMC:SBR=96:2:2 prepares pole piece.Test charge-discharge magnification is 0.2 C, and charging/discharging voltage is the first discharge specific capacity of 0.005-2.000 V, A sample is 510 mAh g -1, efficiency is that after 89.17%, 30 weeks, specific capacity is 430 mAh g first -1.
Embodiment 2
Be that 63 % nitric acid deionized waters are diluted to 50 ml by 20 ml concentration, after adding 10 g graphite, stir 4 hours under 85 DEG C of conditions, solution filtration washing was extremely neutral, 80 DEG C of dryings 18 hours.At 85 DEG C, the sodium citrate solution of 0.5 mol/l of the graphite after acidifying and 50 ml is uniformly mixed, add 2.8 g stannous chlorides again, after sub-tin to be chlorinated dissolves completely, then 5 ml ethylene glycol and 200 ml deionized waters are added successively, after mixing, with the sodium hydroxide solution of 4 mol/l, this suspension-turbid liquid pH is adjusted to 5.7.The 0.1 mol/l solution of potassium borohydride of 150ml is heated to 85 DEG C, under agitation, the 0.1 mol/l solution of potassium borohydride of 150ml is dropped in suspension-turbid liquid, after dropwising, continue stirring 2 hours, solution filters and spends deionized water to neutral, and 95 DEG C of dried overnight obtain negative material presoma.2g phenolic resins and above-mentioned negative material presoma are carried out ground and mixed, and under 900 DEG C of nitrogen atmospheres, roasting obtains sample B in 6 hours.
More than obtained tin carbon composite is positive pole, and lithium sheet is negative pole, and electrolyte is the LiPF of 1mol/l 6eC/DMC(1:1) solution, barrier film is polypropylene, polyethylene composite diaphragm.The ratio of active material: CMC:SBR=96:2:2 prepares pole piece.Test charge-discharge magnification is 0.2 C, and charging/discharging voltage is the first discharge specific capacity of 0.005-2.000 V, B sample is 537 mAh g -1, efficiency is that after 91.19%, 30 weeks, specific capacity is 481 mAh g first -1.
Embodiment 3
Be that 63 % nitric acid deionized waters are diluted to 50 ml by 20 ml concentration, after adding 10 g graphite, stir 4 hours under 85 DEG C of conditions, solution filtration washing was extremely neutral, 85 DEG C of dryings 12 hours.At 75 DEG C, the potassium sodium tartrate solution of 0.3 mol/l of the graphite after acidifying and 50 ml is uniformly mixed, add 2.8 g stannous chlorides again, after sub-tin to be chlorinated dissolves completely, then 5 ml polyethylene glycol and 200 ml deionized waters are added successively, after mixing, with the ammonia spirit of 2 mol/l, this suspension-turbid liquid pH is adjusted to 7.6.75 DEG C will be heated to, under agitation, the 0.2 mol/l ortho phosphorous acid sodium solution of 150ml be dropped in suspension-turbid liquid, after dropwising, continue stirring 2 hours, solution filters and spends deionized water to neutral, and 80 DEG C of dried overnight obtain negative material presoma.2g pitch and above-mentioned negative material presoma are carried out ground and mixed, and under 650 DEG C of nitrogen atmospheres, roasting obtains sample C in 6 hours.
More than obtained tin carbon composite is positive pole, and lithium sheet is negative pole, and electrolyte is the LiPF of 1mol/l 6eC/DMC(1:1) solution, barrier film is polypropylene, polyethylene composite diaphragm.The ratio of active material: CMC:SBR=96:2:2 prepares pole piece.Test charge-discharge magnification is 0.2 C, and charging/discharging voltage is 0.005-2.000 V, and the first discharge specific capacity of C sample is 528 mAh g -1, efficiency is that after 90.37%, 30 weeks, specific capacity is 468 mAh g first -1.
Embodiment 4
Be that 63 % nitric acid deionized waters are diluted to 50 ml by 20 ml concentration, after adding 10 g graphite, under 500 W ultrasound conditions ultrasonic 30 minutes, solution filtration washing to neutral, 85 DEG C of dryings 12 hours.At 85 DEG C, the potassium sodium tartrate solution of 0.7 mol/l of the graphite after acidifying and 50 ml is uniformly mixed, add 2.7 g stannous sulfates again, after stannous sulfate dissolves completely, then 0.5 g sucrose and 200 ml deionized waters are added successively, after mixing, with the ammonia spirit of 2 mol/l, this suspension-turbid liquid pH is adjusted to 8.8.85 DEG C will be heated to, under agitation, the 0.2 mol/l sodium borohydride solution of 150ml be dropped in suspension-turbid liquid, after dropwising, continue stirring 2 hours, solution filters and spends deionized water to neutral, and 80 DEG C of dried overnight obtain negative material presoma.2g polyoxyethylene-poly-oxypropylene polyoxyethylene (P123) and above-mentioned negative material presoma are carried out ground and mixed, and under 600 DEG C of nitrogen atmospheres, roasting obtains sample D in 6 hours.
More than obtained tin carbon composite is positive pole, and lithium sheet is negative pole, and electrolyte is the LiPF of 1mol/l 6eC/DMC(1:1) solution, barrier film is polypropylene, polyethylene composite diaphragm.The ratio of active material: CMC:SBR=96:2:2 prepares pole piece.Test charge-discharge magnification is 0.2 C, and charging/discharging voltage is the first discharge specific capacity of 0.005-2.000 V, D sample is 557 mAh g -1, efficiency is that after 90.73%, 30 weeks, specific capacity is 503 mAh g first -1.
Embodiment 5-7
The preparation method of negative material is identical with embodiment 4, unlike, prepare 3 increment product, sinter under 300 DEG C, 800 DEG C and 1100 DEG C of nitrogen atmospheres respectively, obtained sample is respectively E, F, G.
More than obtained tin carbon composite is positive pole, and lithium sheet is negative pole, and electrolyte is the LiPF of 1mol/l 6eC/DMC(1:1) solution, barrier film is polypropylene, polyethylene composite diaphragm.The ratio of active material: CMC:SBR=96:2:2 prepares pole piece.Test charge-discharge magnification is 0.2 C, and charging/discharging voltage is the first discharge specific capacity of 0.005-2.000 V, E sample is 504 mAh g -1, efficiency is that after 92.11%, 30 weeks, specific capacity is 449 mAh g first -1.The first discharge specific capacity of F sample is 532mAh g -1, efficiency is that after 91.44%, 30 weeks, specific capacity is 478mAh g first -1.The first discharge specific capacity of G sample is 538mAh g -1, efficiency is that after 90.45%, 30 weeks, specific capacity is 421 mAh g first -1.
Embodiment 8
Be that 63 % nitric acid deionized waters are diluted to 50 ml by 20 ml concentration, after adding 10 g graphite, under 500 W ultrasound conditions ultrasonic 30 minutes, solution filtration washing to neutral, 85 DEG C of dryings 12 hours.At 85 DEG C, the potassium sodium tartrate solution of 0.3 mol/l of the graphite after acidifying and 50 ml is uniformly mixed, add 4.3 g stannous sulfates again, after stannous sulfate dissolves completely, then 3 ml polyethylene glycol and 200 ml deionized waters are added successively, after mixing, with the ammonia spirit of 2 mol/l, this suspension-turbid liquid pH is adjusted to 8.6.85 DEG C will be heated to, under agitation, the 0.2 mol/l sodium borohydride solution of 150ml be dropped in suspension-turbid liquid, after dropwising, continue stirring 2 hours, solution filters and spends deionized water to neutral, and 80 DEG C of dried overnight obtain negative material presoma.2 ml polyethylene glycol and above-mentioned negative material presoma are carried out ground and mixed, and under 600 DEG C of nitrogen atmospheres, roasting obtains sample H in 6 hours.
More than obtained tin carbon composite is positive pole, and lithium sheet is negative pole, and electrolyte is the LiPF of 1mol/l 6eC/DMC(1:1) solution, barrier film is polypropylene, polyethylene composite diaphragm.The ratio of active material: CMC:SBR=96:2:2 prepares pole piece.Test charge-discharge magnification is 0.2 C, and charging/discharging voltage is the first discharge specific capacity of 0.005-2.000 V, H sample is 542 mAh g -1, efficiency is that after 90.25%, 30 weeks, specific capacity is 451 mAh g first -1.
Embodiment 9-11
The preparation method of negative material is identical with embodiment 4, unlike, prepare 3 increment product, add the potassium sodium tartrate solution of the 0.7mol/l of 25 ml, 75ml and 150ml respectively, obtained sample is respectively I, J, K.
More than obtained tin carbon composite is positive pole, and lithium sheet is negative pole, and electrolyte is the LiPF of 1mol/l 6eC/DMC(1:1) solution, barrier film is polypropylene, polyethylene composite diaphragm.The ratio of active material: CMC:SBR=96:2:2 prepares pole piece.Test charge-discharge magnification is 0.2 C, and charging/discharging voltage is the first discharge specific capacity of 0.005-2.000 V, I sample is 486 mAh g -1, efficiency is that after 90.91%, 30 weeks, specific capacity is 434 mAh g first -1.The first discharge specific capacity of J sample is 533mAh g -1, efficiency is that after 90.89%, 30 weeks, specific capacity is 488mAh g first -1.The first discharge specific capacity of K sample is 512mAh g -1, efficiency is that after 90.05%, 30 weeks, specific capacity is 451 mAh g first -1.
Embodiment 12-13
The preparation method of negative material is identical with embodiment 3, unlike, prepare 2 increment product, add 1 ml and 15ml ethylene glycol respectively, obtained sample is respectively L, M.
More than obtained tin carbon composite is positive pole, and lithium sheet is negative pole, and electrolyte is the LiPF of 1mol/l 6eC/DMC(1:1) solution, barrier film is polypropylene, polyethylene composite diaphragm.The ratio of active material: CMC:SBR=96:2:2 prepares pole piece.Test charge-discharge magnification is 0.2 C, and charging/discharging voltage is the first discharge specific capacity of 0.005-2.000 V, L sample is 476 mAh g -1, efficiency is that after 88.92%, 30 weeks, specific capacity is 407 mAh g first -1.The first discharge specific capacity of M sample is 461mAh g -1, efficiency is that after 91.89%, 30 weeks, specific capacity is 413mAh g first -1.
Comparative example 1
At 85 DEG C, the potassium sodium tartrate solution of 0.7 mol/l of 10 g graphite and 50 ml is uniformly mixed, add 2.7 g stannous sulfates again, after stannous sulfate dissolves completely, then 0.5 g sucrose and 200 ml deionized waters are added successively, after mixing, with the ammonia spirit of 2 mol/l, this suspension-turbid liquid pH is adjusted to 8.8.85 DEG C will be heated to, under agitation, the 0.2 mol/l sodium borohydride solution of 150ml be dropped in suspension-turbid liquid, after dropwising, continue stirring 2 hours, solution filters and spends deionized water to neutral, and 80 DEG C of dried overnight obtain negative material presoma.2g polyoxyethylene-poly-oxypropylene polyoxyethylene (P123) and above-mentioned negative material presoma are carried out ground and mixed, and under 600 DEG C of nitrogen atmospheres, roasting obtains comparative sample 1 in 6 hours.
More than obtained tin carbon composite is positive pole, and lithium sheet is negative pole, and electrolyte is the LiPF of 1mol/l 6eC/DMC(1:1) solution, barrier film is polypropylene, polyethylene composite diaphragm.The ratio of active material: CMC:SBR=96:2:2 prepares pole piece.Test charge-discharge magnification is 0.2 C, and charging/discharging voltage is 0.005-2.000 V, and the first discharge specific capacity of comparative sample 1 is 468 mAh g -1, efficiency is that after 92.37%, 30 weeks, specific capacity is 387 mAh g first -1.
Comparative example 2
Be that 63 % nitric acid deionized waters are diluted to 50 ml by 20 ml concentration, after adding 10 g graphite, under 500 W ultrasound conditions ultrasonic 30 minutes, solution filtration washing to neutral, 85 DEG C of dryings 12 hours.At 85 DEG C, the potassium sodium tartrate solution of 0.7 mol/l of the graphite after acidifying and 50 ml is uniformly mixed, add 2.7 g stannous sulfates again, after stannous sulfate dissolves completely, then 0.5 g sucrose and 200 ml deionized waters are added successively, after mixing, with the ammonia spirit of 2 mol/l, this suspension-turbid liquid pH is adjusted to 8.8.85 DEG C will be heated to, under agitation, the 0.2 mol/l sodium borohydride solution of 150ml be dropped in suspension-turbid liquid, after dropwising, continue stirring 2 hours, solution filters and spends deionized water to neutral, and 80 DEG C of dried overnight obtain negative material presoma.Presoma roasting under 600 DEG C of nitrogen atmospheres is obtained comparative sample 2 in 6 hours.
More than obtained tin carbon composite is positive pole, and lithium sheet is negative pole, and electrolyte is the LiPF of 1mol/l 6eC/DMC(1:1) solution, barrier film is polypropylene, polyethylene composite diaphragm.The ratio of active material: CMC:SBR=96:2:2 prepares pole piece.Test charge-discharge magnification is 0.2 C, and charging/discharging voltage is 0.005-2.000 V, and the first discharge specific capacity of comparative sample 2 is 546 mAh g -1, efficiency is that after 90.53%, 30 weeks, specific capacity is 463 mAh g first -1.

Claims (10)

1. a preparation method for tin carbon compound cathode materials, comprising:
A. by graphite and complexing agent blended, obtain suspension-turbid liquid system;
B. under agitation, sn-containing compound and dispersant is added successively to suspension-turbid liquid system;
C. by the pH value of suspension-turbid liquid in aqueous slkali adjustment step B;
D. under stirring, the solution containing reducing agent is added in the suspension-turbid liquid of step C and react, then obtain negative material presoma through filtration, cleaning, drying;
E. negative material presoma and organic polymer mixed grinding, then sinter in Muffle furnace, obtains tin carbon compound cathode materials.
2. preparation method according to claim 1, is characterized in that, the mass ratio of tin and graphite is for being 0.2 ~ 0.4: 1.
3. preparation method according to claim 2, is characterized in that, in step e, in a vacuum or inert atmosphere, sinters at 300-1100 DEG C.
4. preparation method according to claim 3, is characterized in that, before described steps A, also comprise and acidification is carried out to described graphite, the method of described acidification is: under agitation, is mixed by graphite and be heated to 70-100 DEG C with acid solution, process 2-5 hour; Or under ultrasound condition, graphite is mixed with acid solution and ultrasonicly processes 10-40 minute.
5. preparation method according to claim 4, is characterized in that, in described step D, described reducing agent is one or more in potassium borohydride, sodium borohydride, inferior sodium phosphate, hydrazine hydrate.
6. preparation method according to claim 5, is characterized in that, reduction reaction is 45-85 DEG C.
7. the preparation method according to Claims 2 or 3, is characterized in that, the complexing agent in steps A and the mass ratio of graphite are 0.5 ~ 2: 1.
8. preparation method according to claim 7, is characterized in that, described complexing agent is one or more in tartaric acid, citric acid, malic acid, succinic acid, ethylenediamine tetra-acetic acid, lactic acid, hydracrylic acid and their salt.
9. the preparation method according to claim 1,2,3,4 or 5, is characterized in that, in step D, drying condition is vacuumize, and baking temperature is 80 ~ 120 DEG C, and drying time is 8 ~ 18 hours, and vacuum degree is 0.05 ~ 0.09 MPa; In step e, organic polymer and negative material presoma mass ratio are 0.1 ~ 0.3: 1; Described organic polymer be pitch, phenolic resins, epoxy resin, poly-propionamide resin, Kynoar, polyoxyethylene-poly-oxypropylene polyoxyethylene etc. one or more.
10. a tin carbon compound cathode materials, is characterized in that, adopts method according to claim 1 to prepare, and wherein the mass ratio of tin and graphite is for being 0.2 ~ 0.4: 1.
CN201410735658.7A 2014-12-08 2014-12-08 Tin-carbon composite cathode material and preparation method thereof Pending CN104538605A (en)

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CN106229490A (en) * 2016-09-10 2016-12-14 天津大学 A kind of preparation method and application of the stannum carbon composite nano granule of hollow structure
CN107644988A (en) * 2017-09-19 2018-01-30 电子科技大学 Carbon-based lithium battery aeroge of cellulose in-situ and preparation method thereof
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Publication number Priority date Publication date Assignee Title
CN106229490A (en) * 2016-09-10 2016-12-14 天津大学 A kind of preparation method and application of the stannum carbon composite nano granule of hollow structure
CN107665972A (en) * 2017-07-05 2018-02-06 中国矿业大学 A kind of Sn@C-material preparation methods of high-performance kalium ion battery negative material
CN107665972B (en) * 2017-07-05 2020-04-17 中国矿业大学 Preparation method of Sn @ C material of high-performance potassium ion battery negative electrode material
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