CN104577079A - Method for preparing tin-carbon composite negative electrode material - Google Patents

Method for preparing tin-carbon composite negative electrode material Download PDF

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Publication number
CN104577079A
CN104577079A CN201410800805.4A CN201410800805A CN104577079A CN 104577079 A CN104577079 A CN 104577079A CN 201410800805 A CN201410800805 A CN 201410800805A CN 104577079 A CN104577079 A CN 104577079A
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tin
preparation
mixture
carbon composite
graphite
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CN201410800805.4A
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Inventor
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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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
    • H01M4/362—Composites
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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 & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a method for preparing a tin-carbon composite negative electrode material. The tin-carbon composite negative electrode material is prepared by adopting a method for combining mechanochemistry and high-temperature hot carbon reduction. The method for preparing the negative electrode material comprises the following steps: 1, uniformly mixing graphite and a tin salt; 2, adding a solid alkaline substance into the mixture in the step 1 so as to carry out a mechanochemical reaction; 3, adding a certain amount of organic carbon source into the mixture in the step 2 for mixing; 4, sintering the mixture in the step 3 in a muffle furnace; and 5, washing, filtering and drying the tin-carbon mixture in the step 4, thereby obtaining the tin-carbon composite material. According to the negative electrode material prepared by the method disclosed by the invention, the capacity and cycle performance of the battery can be obviously improved.

Description

A kind of preparation method of tin carbon compound cathode materials
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.Such as, CN102185135B and CN102427127A discloses a kind of method adopting dielectric barrier discharge plasma auxiliary high-energy ball milling to prepare tin carbon composite, but ball-grinding machine that the method adopts is more complicated, the first charge-discharge efficiency of tin carbon composite is lower.Also have patent (as CN101017893B) to utilize the mode of ball milling to carry out carrying out premixed to tin and graphite material, then prepare glass putty composite material by the mode precipitating tin.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.After graphite mixes in ball grinder with pink salt, by adding solid basic material and pink salt generation mechanico-chemical reaction (QUOTE ), obtained tin-oxide is nanoscale and easily sticks to graphite surface, then this mixture is mixed with organic carbon source (as pitch etc.) and put into atmosphere furnace and carry out hot carbon reduction reaction, tin-oxide is reduced into simple substance tin, then tin carbon composite presoma is carried out removing slaine impurity by the mode of filtration washing, obtained tin carbon composite.
Present invention employs following technical proposals: a kind of preparation method of tin carbon compound cathode materials, the steps include:
1, graphite is mixed with pink salt;
2, mixture solid basic material being added step 1 carries out mechanico-chemical reaction;
3, the mixture in step 2 is added a certain amount of organic carbon source to mix;
4, the mixture of step 3 is sintered in Muffle furnace;
5, the tin carbon mix of step 4 carried out wash, filter, dry obtained tin carbon composite.
Wherein, in step 1, the mass ratio of tin and graphite is 0.03 ~ 0.8: 1, is more preferably 0.1 ~ 0.4: 1; Described graphite is sheet or globular graphite; Described sn-containing compound be stannous chloride, stannic chloride, STANNOUS SULPHATE CRYSTALLINE, stannous sulfate etc. one or more;
Wherein, the molar ratio of the tin in step 2 and solid alkaloids is 0.6 ~ 1: 1, is more preferably 0.8 ~ 0.9: 1;
Wherein, in step 3, the mass ratio of organic carbon source and graphite is 0.01 ~ 0.2: 1, is preferably 0.02 ~ 0.06: 1; Described organic carbon source for for pitch, phenolic resins, epoxy resin, poly-propionamide resin, Kynoar, polyoxyethylene-poly-oxypropylene polyoxyethylene etc. one or more;
Wherein, in step 4, roasting condition is vacuum baking or inert atmosphere roasting, and sintering temperature is within the scope of 600-1100 DEG C;
Wherein, in step 5, 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, and washing process adopts deionized water to wash;
Wherein, in step 1-3, mixed process is all mix on ball mill, and the quality of abrading-ball and graphite material is 0.2 ~ 10: 1, and Ball-milling Time is 1 ~ 100 h.
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 500 times of scanning electron microscope (SEM) photographs of embodiment 6 tin carbon compound cathode materials in the present invention.
Fig. 2 is 2000 times of scanning electron microscope (SEM) photographs of embodiment 6 tin carbon compound cathode materials in the present invention.
Embodiment
Preparation method's process of the present invention is as follows:
Be to weigh the example in mass ratio of tin and graphite at 0.03 ~ 0.8: 1, tin is introduced by sn-containing compound, ball milling 1 ~ 100 h in ball grinder, the quality of abrading-ball and graphite material is 0.2 ~ 10: 1, then one or more are added in NaOH, potassium hydroxide, calcium hydroxide, sodium carbonate, potash, urea as solid basic material, the molar ratio of tin and solid alkaloids is 0.6 ~ 1: 1, ball milling 1 ~ 100 h; Then add organic carbon source and carry out ball milling mixing, the mass ratio of organic carbon source and graphite is 0.01 ~ 0.2: 1, is preferably 0.02 ~ 0.06: 1; Described organic carbon source for for pitch, phenolic resins, epoxy resin, poly-propionamide resin, Kynoar, polyoxyethylene-poly-oxypropylene polyoxyethylene etc. one or more; Sintered with 600-1100 DEG C in Muffle furnace by gained mixture, then adopt deionized water wash and filter, obtained tin carbon compound cathode materials 8 ~ 18 hours 80 ~ 120 DEG C of vacuumize times, vacuum degree is 0.05 ~ 0.09 MPa.
For the ease of understanding, illustrate the present invention further below in conjunction with preferred embodiment.
Embodiment 1
45 g graphite and 1g stannous chloride are put into ball grinder ball milling 30 minutes, rotating speed is 300 rpm, wherein the quality of ball is 500 g, 0.6g natrium carbonicum calcinatum ball-milling reaction 5h is added again after it mixes, adding 2.0g pitch again carries out coated again, after ball milling 1h, by this mixture roasting 5h at nitrogen atmosphere 800 DEG C, obtained tin carbon composite presoma.By the washing of tin carbon composite presoma and filtration, 85 DEG C of dried overnight obtain tin carbon compound cathode materials, are designated as sample 1.
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 sample 1 is 380 mAh g -1, efficiency is that after 93.17%, 30 weeks, specific capacity is 348 mAh g first -1.
Embodiment 2-5
The preparation method of negative material is identical with embodiment 1, unlike, prepare 4 increment product, change the mass ratio of graphite and tin, be respectively 45:5,45:10,45:25 and 45:40, the amount of sodium carbonate controls identical with embodiment 1 with the mol ratio of tin simultaneously, and the consumption of natrium carbonicum calcinatum corresponds to 3g, 6g, 15g and 24g respectively, and prepared sample is designated as sample 2, sample 3, sample 4 and sample 5 respectively.
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 sample 2 is 420 mAh g -1, efficiency is that after 91.19%, 30 weeks, specific capacity is 367 mAh g first -1; The first discharge specific capacity of sample 3 is 451 mAh g -1, efficiency is that after 88.21%, 30 weeks, specific capacity is 383 mAh g first -1; The first discharge specific capacity of sample 4 is 493 mAh g -1, efficiency is that after 86.11%, 30 weeks, specific capacity is 412 mAh g first -1; The first discharge specific capacity of sample 5 is 522 mAh g -1, efficiency is that after 80.63%, 30 weeks, specific capacity is 441 mAh g first -1.
Embodiment 6
45 g graphite and 10g stannous chloride are put into ball grinder ball milling 30 minutes, rotating speed is 300 rpm, wherein the quality of ball is 500 g, 6g natrium carbonicum calcinatum ball-milling reaction 15h is added again after it mixes, adding 2.0g pitch again carries out coated again, after ball milling 1h, by this mixture roasting 5h at nitrogen atmosphere 800 DEG C, obtained tin carbon composite presoma.By the washing of tin carbon composite presoma and filtration, 85 DEG C of dried overnight obtain tin carbon compound cathode materials, are designated as sample 6.
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 sample 6 is 462 mAh g -1, efficiency is that after 87.72%, 30 weeks, specific capacity is 387 mAh g first -1.
Embodiment 7-9
The preparation method of negative material is identical with embodiment 6, unlike, prepare 3 increment product, change the ball-milling reaction time of graphite, tin and natrium carbonicum calcinatum, be respectively 25h, 50h and 100h, and be designated as sample 7, sample 8 and sample 9 respectively.
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 sample 7 is 466 mAh g -1, efficiency is that after 87.90%, 30 weeks, specific capacity is 377 mAh g first -1; The first discharge specific capacity of sample 8 is 453 mAh g -1, efficiency is that after 88.21%, 30 weeks, specific capacity is 362 mAh g first -1; The first discharge specific capacity of sample 9 is 448 mAh g -1, efficiency is that after 87.61%, 30 weeks, specific capacity is 351 mAh g first -1.
Embodiment 10-11
The preparation method of negative material is identical with embodiment 6, unlike, prepare 2 increment product, change sintering temperature, be respectively 600 DEG C and 1100 DEG C, and be designated as sample 10 and sample 11 respectively.
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 sample 10 is 444 mAh g -1, efficiency is that after 86.47%, 30 weeks, specific capacity is 351 mAh g first -1; The first discharge specific capacity of sample 11 is 448 mAh g -1, efficiency is that after 83.61%, 30 weeks, specific capacity is 358 mAh g first -1.
Embodiment 12
45 g graphite and 9.5g stannous sulfate are put into ball grinder ball milling 30 minutes, rotating speed is 300 rpm, wherein the quality of ball is 500 g, 6g NaOH ball-milling reaction 15h is added again after it mixes, adding 2.0g Phenolic resin powder again carries out coated again, after ball milling 1h, by this mixture roasting 5h at nitrogen atmosphere 900 DEG C, obtained tin carbon composite presoma.By the washing of tin carbon composite presoma and filtration, 85 DEG C of dried overnight obtain tin carbon compound cathode materials, are designated as sample 12.
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 sample 12 is 469 mAh g -1, efficiency is that after 88.37%, 30 weeks, specific capacity is 373 mAh g first -1.
Embodiment 13
45 g graphite and 11.5g stannic chloride are put into ball grinder ball milling 30 minutes, rotating speed is 300 rpm, wherein the quality of ball is 500 g, 6g natrium carbonicum calcinatum ball-milling reaction 15h is added again after it mixes, adding 1.0g Phenolic resin powder again carries out coated again, after ball milling 1h, by this mixture roasting 5h at nitrogen atmosphere 900 DEG C, obtained tin carbon composite presoma.By the washing of tin carbon composite presoma and filtration, 85 DEG C of dried overnight obtain tin carbon compound cathode materials, are designated as sample 13.
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 sample 13 is 452 mAh g -1, efficiency is that after 89.12%, 30 weeks, specific capacity is 368 mAh g first -1.
Comparative example 1
45 g graphite, 2g pitch and 6.0g tin ash powder are put into ball grinder ball milling 15h, and rotating speed is 300 rpm, and wherein the quality of ball is 500 g, by this mixture roasting 5h at nitrogen atmosphere 800 DEG C, and obtained tin carbon composite presoma.By the washing of tin carbon composite presoma and filtration, 85 DEG C of dried overnight obtain tin carbon compound cathode materials, are designated as comparative sample 1.
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 428 mAh g -1, efficiency is that after 73.12%, 30 weeks, specific capacity is 349 mAh g first -1.
Comparative example 2
45 g graphite, 2g pitch and 4.6g tin powder are put into ball grinder ball milling 15h, and rotating speed is 300 rpm, and wherein the quality of ball is 500 g, by this mixture roasting 5h at nitrogen atmosphere 800 DEG C, and obtained tin carbon composite presoma.By the washing of tin carbon composite presoma and filtration, 85 DEG C of dried overnight obtain tin carbon compound cathode materials, are designated as comparative sample 2.
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 449 mAh g -1, efficiency is that after 76.95%, 30 weeks, specific capacity is 352 mAh g first -1.

Claims (7)

1. a preparation method for tin carbon compound cathode materials, comprising:
1, graphite is mixed with pink salt;
2, mixture solid basic material being added step 1 carries out mechanico-chemical reaction;
3, the mixture in step 2 is added a certain amount of organic carbon source to mix;
4, the mixture of step 3 is sintered in Muffle furnace;
5, the tin carbon mix of step 4 carried out filter, wash, dry obtained tin carbon composite.
2. preparation method according to claim 1, is characterized in that, described solid basic material is one or more in NaOH, potassium hydroxide, calcium hydroxide, sodium carbonate, potash, urea.
3. preparation method according to claim 1, is characterized in that, the molar ratio of tin and solid alkaloids is 0.6 ~ 1: 1.
4. preparation method according to claim 1, is characterized in that, the molar ratio of tin and solid alkaloids is 0.8 ~ 0.9: 1.
5. the preparation method according to Claims 2 or 3, is characterized in that, the mass ratio of tin and graphite is 0.03 ~ 0.8: 1.
6. the preparation method according to claim 1,2,3,4 or 5, is characterized in that, in step 5, 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 2, organic carbon source and negative material presoma mass ratio are 0.01 ~ 0.1: 1; Described organic polymer is one or more in pitch, phenolic resins, epoxy resin, poly-propionamide resin, Kynoar, polyoxyethylene-poly-oxypropylene polyoxyethylene.
7. the preparation method according to claim 2,3,4,5 or 6, is characterized in that, in step 1-3, mixed process is all mix on ball mill, and Ball-milling Time is 1 ~ 100 h.
CN201410800805.4A 2014-12-22 2014-12-22 Method for preparing tin-carbon composite negative electrode material Pending CN104577079A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104835947A (en) * 2015-05-29 2015-08-12 田东 Preparation method for graphite/ silicon composite negative electrode material
CN104993108A (en) * 2015-05-29 2015-10-21 田东 Preparation method of lithium titanate/tin composite cathode material
CN105047868A (en) * 2015-06-13 2015-11-11 田东 Preparation method of high-capacity lithium battery anode material
CN108807873A (en) * 2018-04-25 2018-11-13 福建翔丰华新能源材料有限公司 A method of preparing the tin carbon lithium ion negative material of copper Sb doped
CN115692612A (en) * 2022-11-03 2023-02-03 福州大学 Tin-carbon negative electrode material and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104835947A (en) * 2015-05-29 2015-08-12 田东 Preparation method for graphite/ silicon composite negative electrode material
CN104993108A (en) * 2015-05-29 2015-10-21 田东 Preparation method of lithium titanate/tin composite cathode material
CN105047868A (en) * 2015-06-13 2015-11-11 田东 Preparation method of high-capacity lithium battery anode material
CN108807873A (en) * 2018-04-25 2018-11-13 福建翔丰华新能源材料有限公司 A method of preparing the tin carbon lithium ion negative material of copper Sb doped
CN108807873B (en) * 2018-04-25 2021-06-25 深圳市翔丰华科技股份有限公司 Method for preparing copper-antimony doped tin-carbon lithium ion negative electrode material
CN115692612A (en) * 2022-11-03 2023-02-03 福州大学 Tin-carbon negative electrode material and preparation method thereof

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