CN103682273A - Preparation method of tin-carbon composite material of lithium ion battery - Google Patents
Preparation method of tin-carbon composite material of lithium ion battery Download PDFInfo
- Publication number
- CN103682273A CN103682273A CN201310675626.8A CN201310675626A CN103682273A CN 103682273 A CN103682273 A CN 103682273A CN 201310675626 A CN201310675626 A CN 201310675626A CN 103682273 A CN103682273 A CN 103682273A
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- Prior art keywords
- tin
- carbon composite
- preparation
- lithium ion
- ion battery
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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
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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
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a tin-carbon composite material of a lithium ion battery. The preparation method comprises the following steps of (1) dissolving benzenediol and formaldehyde in ethyl alcohol, adding a catalyst to have synthesis reaction so as to obtain porous macromolecular phenolic resin, and naturally cooling, drying and pulverizing the porous macromolecular phenolic resin product into powder; (2) adding hydrochloric acid and SnCl3 into deionized water, and stirring the mixture until the SnCl3 is completely dissolved to obtain a tin salt solution; (3) adding the porous macromolecular phenolic resin powder into the tin salt solution according to the mass ratio of 1:2 to 1:4, immersing the porous macromolecular phenolic resin powder for 4h to 8h, stirring and dropwise adding 20% to 25% ammonia aqueous solution to obtain a mixed suspension solution, washing the mixed suspension solution by using gradually, and drying; and (4) igniting the dried mixture to obtain the tin-carbon composite material at the burning temperature of 600 to 700 DEG C. The tin-carbon composite material prepared by adopting the preparation method is simple in process, high in material specific capacity, good in circulating stability and long in service life.
Description
Technical field
The present invention relates to battery preparation field, relate in particular to a kind of preparation method of tin carbon composite of lithium ion battery.
Background technology
Lithium ion battery is because its energy density is high, and good cycle has been widely used since its commercialization, has replaced gradually traditional chemical power sources such as lead-acid battery.Particularly, along with day by day the highlighting of energy and environment problem, New Energy Industry has obtained increasing attention.At present, it is negative material that the lithium ion battery of production and application mainly adopts graphitized carbon, but the lithium storage content of graphite type material is not high.Tin carbon composite is owing to having very high theoretical gram volume (theoretical specific capacity is 990mAh/g), and low embedding lithium current potential, has higher stability and get most of the attention compared with other metal_based materials.But tin carbon composite is the same with other metal_based materials, in the process of removal lithium embedded, exist serious bulk effect, the powder of detached that causes material in charge and discharge process, cause the decay of capacity, not only reduced efficiency and the cycle performance of battery, and have serious potential safety hazard.
Therefore in the urgent need to providing, a kind of specific capacity is high, the lithium ion battery tin carbon composite of good cycling stability, long service life.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of tin carbon composite of lithium ion battery, has to prepare that specific capacity is high, a lithium ion battery of the tin carbon composite of good cycling stability, long service life.
To achieve these goals, the invention provides a kind of preparation method of tin carbon composite of lithium ion battery, comprise the steps: that (1) is to be dissolved in ethanol at 1: 2.5 by benzenediol and formaldehyde in molar ratio, add catalyst, synthetic reaction obtains porous polymer phenolic resins, the naturally cooling and dry rear grind into powder of product; (2) get the deionized water of 10-15 mass parts, add hydrochloric acid that 1-2 mass parts mass fraction is 37% and the SnCl of 5-7 mass parts
3, obtain tin-salt solution after being stirred to whole dissolvings; (3) by porous polymer phenolic resins powder in mass ratio 1: 2-1: 4 join in described tin-salt solution, soak after 4-8 hour, stir and dropwise add the ammonia aqueous solution of 20-25wt% to make mixing suspension, add ammonia aqueous solution amount by the pink salt in whole precipitation solutions, calculate and excessive, gained mixing suspension is filtered, and wash, be dried with distilled water; (4) light dried mixture, temperature during burning is 600-700 ℃, can generate tin carbon composite.
Step (4) further comprises afterwards: (5) add the tin carbon composite of generation in distilled water, utilizes the Ultrasonic Cleaning that frequency is 40-80Hz at least after secondary, to use centrifuge separated, and the product after separation is dried at 40-50 ℃ of temperature.
Wherein, the concentration of described benzenediol is 1-1.3mol/L, and the concentration of described formaldehyde is 1-2mol/L.
Wherein, dry described in step (1) is vacuumize 6-18 hour at 80-120 ℃ of temperature, and vacuum degree is 0.05-0.08MPa.
Wherein, dry described in step (3) is vacuumize 10-12 hour at 80-120 ℃ of temperature, and vacuum degree is 0.05-0.1MPa.
The tin carbon composite that adopts preparation method of the present invention to prepare, technique is simple, material specific capacity is high, good cycling stability, long service life.
Embodiment
Below in conjunction with embodiment, the preparation method of the tin carbon composite of lithium ion battery provided by the invention is elaborated.
Embodiment mono-
Prepare porous polymer phenolic resins powder
Benzenediol and formaldehyde are to be dissolved at 1: 2.5 in ethanol in molar ratio, and wherein the concentration of benzenediol is 1mol/L, and formaldehyde is 1mol/L.Add concentration in the acid of 2mol/L as catalyst, synthetic reaction obtains porous polymer phenolic resins.After product is naturally cooling, smash to pieces, at 80 ℃ of temperature, vacuumize is 6 hours, and vacuum degree is 0.05MPa, grind into powder.
Configure stanniferous chloride solution
The deionized water of getting 10 mass parts joins in beaker, adds the hydrochloric acid of 1 mass parts mass fraction 37%, the SnCl of 5 mass parts
3, stir it is all dissolved, obtain tin-salt solution.
Prepare stanniferous macromolecule resin
The porous polymer phenolic resins powder making is joined in ready tin-salt solution, and the mass ratio of porous polymer phenolic resins powder and tin-salt solution is 1: 2.Soak after 4 hours, dropwise add the ammonia aqueous solution of 20wt%, vigorous stirring in adding the process of ammonia aqueous solution, add the amount of ammonia aqueous solution by the pink salt in whole precipitation solutions, to calculate and excessive a little, obtain mixing suspension.Gained mixing suspension is filtered, and wash with distilled water, at 80 ℃ of temperature, vacuumize is 10 hours, and vacuum degree is 0.05MPa.
Prepare tin carbon composite
Dried mixture is lighted, and temperature during burning is 600 ℃, can generate multiduty tin carbon composite.
Clean tin carbon composite
The tin carbon composite of generation is added in distilled water, utilize the Ultrasonic Cleaning 2 times that frequency is 40Hz, then the product after cleaning is separated with centrifuge, the product after separation is dried at 40 ℃ of temperature.
Embodiment bis-
Prepare porous polymer phenolic resins powder
Benzenediol and formaldehyde are to be dissolved at 1: 2.5 in ethanol in molar ratio, and wherein the concentration of benzenediol is 1.3mol/L, and formaldehyde is 2mol/L.Add concentration in the acid of 4mol/L as catalyst, synthetic reaction obtains porous polymer phenolic resins.After product is naturally cooling, smash to pieces, at 120 ℃ of temperature, vacuumize is 18 hours, and vacuum degree is 0.08MPa, afterwards grind into powder.
Configure stanniferous chloride solution
The deionized water of getting 15 mass parts joins in beaker, adds hydrochloric acid that 2 mass parts mass fractions are 37% and the SnCl of 5 mass parts
3, stir it is all dissolved, obtain tin-salt solution.
Prepare stanniferous macromolecule resin
The porous polymer phenolic resins powder making is joined in ready tin-salt solution, and the mass ratio of porous polymer phenolic resins and pink salt is 1: 4.Soak after 4 hours, to the ammonia aqueous solution that dropwise adds 25wt% in solution, vigorous stirring in adding the process of ammonia aqueous solution, add the amount of ammonia aqueous solution by the pink salt in whole precipitation solutions, to calculate and excessive a little, make mixing suspension.Gained mixing suspension is filtered, and wash with distilled water, at 120 ℃ of temperature, vacuumize is 12 hours, and vacuum degree is 0.1MPa.
Prepare tin carbon composite
Dried mixture is lighted, and temperature during burning is 700 ℃, can generate multiduty tin carbon composite.
Clean tin carbon composite
The tin carbon composite of generation is added in distilled water, utilize the Ultrasonic Cleaning 4 times that frequency is 80Hz, then the product after cleaning is separated with centrifuge, the product after separation is dried at 50 ℃ of temperature.
Comparative example
Butter of tin is dissolved in ethanol, forms homogeneous phase solution; Homogeneous phase solution is lighted, and temperature during burning is 500 ℃, after solution completing combustion, forms tin carbon composite.Other same embodiment mono-.
Adopt respectively the tin carbon composite of embodiment mono-, two and comparative example to make the negative plate of same size, take lithium sheet as to electrode again, electrolyte is the EC(ethyl carbonate ester of 1.5mol/L LiPF6)+DMC(dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is celgard2400 film, in being full of the glove box of argon gas atmosphere, be assembled into CR2025 type button cell, and under the condition of constant current 0.2C, carry out cycle performance test.The tin carbon composite that embodiment mono-of the present invention prepares with two is compared with the tin carbon composite of comparative example, and first discharge specific capacity has promoted more than 20%, and cycle life has improved more than 50%.
The above is only the preferred embodiments of the present invention; not the present invention is done to any pro forma restriction; should be understood that; for those skilled in the art; do not departing under the prerequisite of technical solution of the present invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (5)
1. a preparation method for the tin carbon composite of lithium ion battery, is characterized in that, comprises the steps:
(1) by benzenediol and formaldehyde, be to be dissolved at 1: 2.5 in ethanol in molar ratio, add catalyst, synthetic reaction obtains porous polymer phenolic resins, the naturally cooling and dry rear grind into powder of product;
(2) get the deionized water of 10-15 mass parts, add hydrochloric acid that 1-2 mass parts mass fraction is 37% and the SnCl of 5-7 mass parts
3, obtain tin-salt solution after being stirred to whole dissolvings;
(3) by porous polymer phenolic resins powder in mass ratio 1: 2-1: 4 join in described tin-salt solution, soak after 4-8 hour, stir and dropwise add the ammonia aqueous solution of 20-25wt% to make mixing suspension, add ammonia aqueous solution amount by the pink salt in whole precipitation solutions, calculate and excessive, gained mixing suspension is filtered, and wash, be dried with distilled water;
(4) light dried mixture, temperature during burning is 600-700 ℃, can generate tin carbon composite.
2. the preparation method of the tin carbon composite of lithium ion battery according to claim 1, is characterized in that, step (4) further comprises afterwards:
(5) the tin carbon composite of generation is added in distilled water, utilize the Ultrasonic Cleaning that frequency is 40-80Hz at least after secondary, to use centrifuge separated, the product after separation is dried at 40-50 ℃ of temperature.
3. the preparation method of the tin carbon composite of lithium ion battery according to claim 1, is characterized in that, the concentration of described benzenediol is 1-1.3mol/L, and the concentration of described formaldehyde is 1-2mol/L.
4. the preparation method of the tin carbon composite of lithium ion battery according to claim 1, is characterized in that, dry described in step (1) is vacuumize 6-18 hour at 80-120 ℃ of temperature, and vacuum degree is 0.05-0.08MPa.
5. the preparation method of the tin carbon composite of lithium ion battery according to claim 1, is characterized in that, dry described in step (3) is vacuumize 10-12 hour at 80-120 ℃ of temperature, and vacuum degree is 0.05-0.1MPa.
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| CN201310675626.8A CN103682273A (en) | 2013-12-11 | 2013-12-11 | Preparation method of tin-carbon composite material of lithium ion battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105406076A (en) * | 2014-09-11 | 2016-03-16 | 华为技术有限公司 | Composite negative electrode material and secondary battery thereof |
| 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 |
| CN107265433A (en) * | 2017-05-12 | 2017-10-20 | 中国科学院上海硅酸盐研究所 | Three-dimensional porous nitrating carbon material and its preparation method and application |
| CN111952549A (en) * | 2019-05-16 | 2020-11-17 | 宝山钢铁股份有限公司 | Carbon-coated lithium battery negative electrode material with yolk-eggshell structure and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102208605A (en) * | 2011-04-25 | 2011-10-05 | 长安大学 | Method for preparing tin-carbon nano composite electrode material |
| CN102255079A (en) * | 2011-05-17 | 2011-11-23 | 奇瑞汽车股份有限公司 | Stannum-carbon composite material used for lithium ion battery cathode, preparation method thereof and lithium ion battery |
| CN102891291A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Method for manufacturing tin-carbon composite material of ion battery |
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2013
- 2013-12-11 CN CN201310675626.8A patent/CN103682273A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208605A (en) * | 2011-04-25 | 2011-10-05 | 长安大学 | Method for preparing tin-carbon nano composite electrode material |
| CN102255079A (en) * | 2011-05-17 | 2011-11-23 | 奇瑞汽车股份有限公司 | Stannum-carbon composite material used for lithium ion battery cathode, preparation method thereof and lithium ion battery |
| CN102891291A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Method for manufacturing tin-carbon composite material of ion battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105406076A (en) * | 2014-09-11 | 2016-03-16 | 华为技术有限公司 | Composite negative electrode material and secondary battery thereof |
| CN105406076B (en) * | 2014-09-11 | 2019-01-08 | 华为技术有限公司 | A kind of composite negative pole material and its secondary cell |
| 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 |
| CN107265433A (en) * | 2017-05-12 | 2017-10-20 | 中国科学院上海硅酸盐研究所 | Three-dimensional porous nitrating carbon material and its preparation method and application |
| CN111952549A (en) * | 2019-05-16 | 2020-11-17 | 宝山钢铁股份有限公司 | Carbon-coated lithium battery negative electrode material with yolk-eggshell structure and preparation method thereof |
| CN111952549B (en) * | 2019-05-16 | 2021-08-17 | 宝山钢铁股份有限公司 | Carbon-coated lithium battery negative electrode material with yolk-eggshell structure and preparation method thereof |
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Application publication date: 20140326 |