CN103715430A - Three-dimensional graphene reticular structure loaded carbon-coated tin nanometer material as well as preparation method and application thereof - Google Patents
Three-dimensional graphene reticular structure loaded carbon-coated tin nanometer material as well as preparation method and application thereof Download PDFInfo
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- 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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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The invention discloses a three-dimensional graphene reticular structure loaded carbon-coated tin nanometer material as well as a preparation method and an application thereof. The three-dimensional graphene reticular structure loaded carbon-coated tin nanometer material is formed by uniformly loading carbon-coated tin nanometer particles on a three-dimensional graphene network. The preparation method comprises the following preparation processes: fully dissolving and mixing NaCl serving as a dispersing agent and a template with a metallic tin source and a carbon source, carrying out freeze drying, and porphyrizing, thus obtaining a mixture; putting the mixture in a tubular furnace, and calcining under the effect of hydrogen catalysis, thus obtaining a calcined product; and washing the calcined product, thus obtaining the three-dimensional graphene reticular structure loaded carbon-coated tin nanometer material. The preparation method has the advantages that the preparation process is safe and harmless, the operation is simple, the yield is high, and when being used as an anode material for a lithium ion battery, the prepared three-dimensional graphene reticular structure loaded carbon-coated tin nanometer material has relatively high reversible capacity and cyclic stability.
Description
Technical field
The present invention relates to a kind of three-dimensional grapheme network structure load carbon covered stannum rice material and preparation and application, belong to electrode material of secondary lithium ion battery field.
Background technology
Lithium ion battery has the advantages such as energy density is large, working range is wide, discharge voltage is high, non-environmental-pollution, memory-less effect as a kind of secondary cell, compare with Ni-MH battery with NI-G, and it has extended cycle life, security performance is good.Thereby, lithium ion battery has been widely used in the portable sets such as mobile phone, video camera, camera, notebook computer at present, more in hybrid vehicle of new generation (HEV) and pure electric automobile (EV), serve as one of important energy source, also will be applied in military fields such as satellite and space flight future.
In lithium ion battery, the carbon negative pole material of extensive use is graphite at present, its theoretical capacity is 372 mA h/g, capacity is lower, be difficult to meet the demand of high power and energy density electric motor car, so, exploitation has a high discharge voltage, and the new type lithium ion battery in high power capacity and longer life-span is most important task.Tin base cathode material because possess high theoretical specific capacity (992mAh/g) (
j. Am. Chem. Soc,
2003,
1255652-5653), good conductivity, safety and environmental protection, the advantage such as cheap and be subject to focus, but its fatal weakness be exactly tin-based material in charge and discharge process due to the embedding of lithium ion with deviate from, can cause the violent expansion (being about 340%) of volume own, thereby be easy to cause active material that efflorescence occurs in cyclic process, so cause its cycle performance and high rate performance poor.
In order to improve this shortcoming of tin base cathode material, main solution has three at present: the one, active material is made to nanometer, and optimize its particle dispersion, make its not efflorescence as far as possible in expansion process, not broken; The 2nd, take to protect structure, be mainly compound with material with carbon element, prepare carbon clad structure, the volumetric expansion of restriction active material; The 3rd, aspect material, carry out alloy protecting, be mainly tin copper, tin iron, tin nickel, tin-cobalt alloy etc., similar alloy is alleviated volumetric expansion adding of non-active material owing to having when volumetric expansion.Second point wherein, because also having certain storage lithium performance, material with carbon element is subject to hot research, wherein, carbon nanosheet is as a kind of carbon nanomaterial of two-dimensional structure, due to compared with other zero dimensions, one dimension, three-dimensional structure has more active reaction sites, between lamella, be assembled into three-dimensional grapheme structure and more can be formed with the stereochemical structure that is beneficial to lithium ion and electric transmission, its as lithium ion battery negative material have clear superiority (
adv. Mater., 2012, 24:4097).
And three-dimensional grapheme material with carbon element preparation method is mainly template pyrolysismethod, chemical vapour deposition technique etc. at present.Wherein, template pyrolysismethod is with low cost, and preparation technology is simple, and coefficient of safety is high, is applicable to volume production.After template pyrolysismethod refers to source metal, carbon source and template are fully mixed, pyrolysis charring in inert atmosphere, obtains embedding or the nano-metal particle material of area load in carbon base body through subsequent treatment.Li etc. (
adv. Mater. 2013, 25,2474 – 2480) and utilize template pyrolysismethod to prepare three-dimensional grapheme carbon plate structure, lamellar spacing is about 5 nanometers, and three-dimensional grapheme network diameter is in 10um left and right, and surface is without Metal Supported.
Utilize improved template pyrolysismethod herein, prepare lamella as thin as a wafer, be self-assembled into three-dimensional grapheme shape, and the novel tin carbon composite of area load sijna rice grain, the rare report of its structure, preparation technology is simple, and has excellent properties as lithium ion battery negative material.
Summary of the invention
The object of this invention is to provide a kind of three-dimensional grapheme network structure load carbon covered stannum rice material and preparation and application.This material consists of to three-dimensional grapheme network carbon covered stannum rice grain uniform load, its preparation method process is simple, can volume production, this material has good charge-discharge performance, high rate performance and stability as lithium ion battery negative material, has a extensive future.
Technical scheme of the present invention realizes by following steps, a kind of three-dimensional grapheme network structure load carbon covered stannum rice material, it is characterized in that, this material is that the carbon covered stannum rice grain uniform load of uniform particle diameter is on three-dimensional grapheme network, wherein carbon covered stannum rice grain particle diameter is at 5-100nm, carbon coating layer thickness is 1-5nm, three-dimensional grapheme thickness is 1-10nm, three-dimensional grapheme network radius is at 1-10 μ m, and in this material, the mass percent of tin and total carbon is: (0.4-0.8): (0.6-0.2).
The preparation method of the three-dimensional grapheme network structure load carbon covered stannum rice material of said structure, is characterized in that comprising the following steps:
(1). with one or more in sucrose, glucose, citric acid, starch, be mixed into carbon source, take stannous chloride as Xi Yuan, carbon and the tin mol ratio in tin source of take in carbon source are (50 ~ 10): 1, take tin in tin source and the mass ratio of NaCl is (0.01-0.1): 1, carbon source, Xi Yuan and NaCl are added in deionized water and dissolved, stir wiring solution-forming, ultrasonicly again mix that to be placed on refrigerator freezing, treat that solution freeze over is placed on freeze drier and carries out vacuumize in-50 ℃, obtain mixture;
(2). the mixture grind into powder that step (1) is made, be laid in Noah's ark, be placed in tube furnace flat-temperature zone and calcine: with N
2, He or Ar a kind of or mix as inert gas source, the flow of first take passes into inert gas 30-60 minute with deaeration as 200 ~ 400 ml/min; Again with H
2as carrier gas, carrier gas flux is fixed as to 50 ~ 200ml/min, with programming rate intensification tube furnace to 650 ~ 800 ℃ of 1 ~ 10 ℃/min, insulation 1-8h carries out carbonization, after reaction finishes, is cooled to room temperature, obtains calcined product;
(3). collect the calcined product that step (2) makes, porphyrize, till being washed to and thering is no NaCl in calcined product, is to dry at 60 ~ 120 ℃ in temperature, obtains three-dimensional grapheme network structure load carbon covered stannum rice material.
This three-dimensional grapheme network structure load carbon covered stannum rice material is applied to lithium ion battery negative.
The present invention has the following advantages: the present invention utilizes raw material cheap and easy to get to prepare three-dimensional grapheme network structure load carbon covered stannum rice material, and with low cost, course of reaction is simple, controllability is strong, and sijna rice grain is better dispersed.This material structure homogeneous simultaneously, pattern is good, excellent performance, for lithium ion battery negative, there is very high specific capacity and fabulous cycle performance, under the current density of 200mA/g, circulate 100 times and still can keep specific capacity more than 1000mAh/g, and under the high current density of 10A/g, still keep the specific capacity of 270mAh/g.
Accompanying drawing explanation
Fig. 1 is the SEM photo of the three-dimensional grapheme network structure load carbon covered stannum rice material that obtains of the embodiment of the present invention 1.From this view it is apparent that three-dimensional grapheme network pattern.
Fig. 2 is the SEM photo of the three-dimensional grapheme network structure load carbon covered stannum rice material that obtains of the embodiment of the present invention 1.From this view it is apparent that three-dimensional grapheme sheet thickness.
Fig. 3 is the SEM photo of the three-dimensional grapheme network structure load carbon covered stannum rice material that obtains of the embodiment of the present invention 1.The carbon covered stannum rice grain of load from this view it is apparent that three-dimensional grapheme surface.
Fig. 4 is the TEM photo of the three-dimensional grapheme network structure load carbon covered stannum rice material that obtains of the embodiment of the present invention 1.From this view it is apparent that the high dispersion of carbon covered stannum rice grain.
Fig. 5 is the TEM photo of the three-dimensional grapheme network structure load carbon covered stannum rice material that obtains of the embodiment of the present invention 1.From this view it is apparent that carbon covered stannum rice grain particle diameter is evenly distributed.
Fig. 6 is the HRTEM photo of the three-dimensional grapheme network structure load carbon covered stannum rice material that obtains of the embodiment of the present invention 1.From this view it is apparent that the carbon coating layer on carbon covered stannum rice grain surface.
Fig. 7 is the XRD collection of illustrative plates of the three-dimensional grapheme network structure load carbon covered stannum rice material that obtains of the embodiment of the present invention 1.
Fig. 8 is the nitrogen constant temperature adsorption desorption collection of illustrative plates of the three-dimensional grapheme network structure load carbon covered stannum rice material that obtains of the embodiment of the present invention 1.
The charge-discharge performance figure of the lithium ion battery negative that the three-dimensional grapheme network structure load carbon covered stannum rice material that Fig. 9 obtains for the employing embodiment of the present invention 1 makes, in figure :-■-be discharge curve,-●-be charging curve,---be efficiency curve.
The charge-discharge magnification performance map of the lithium ion battery negative that the three-dimensional grapheme network structure load carbon covered stannum rice material that Figure 10 obtains for the employing embodiment of the present invention 1 makes, in figure :-■-be discharge curve ,-●-be charging curve.
Embodiment
Below in conjunction with specific embodiment, particular content of the present invention is described as follows:
Embodiment 1:
Take 2.5g citric acid, 0.384g stannous chloride and 14.7g NaCl, mixture is dissolved in the deionized water of 50ml, with the magnetic stirring apparatus of mixing speed 300r/min, stirring and dissolving wiring solution-forming, and then take the ultrasonic 15min of ultrasonic device that power is 400W, mix.The solution mixing is put into refrigerator overnight and freeze, be placed on-50 ℃ of vacuumizes in freeze drier, until dry, obtain mixture.Milled mixtures, the mixed-powder of getting 10g is placed in Noah's ark, and Noah's ark is put into tube furnace, passes into the Ar inert gas 30min deaeration of 200ml/min, then with the H of 200ml/min
2for carrier gas and with the programming rate of 10 ℃/min, be warming up to 750 ℃ of temperature, insulation 2h carries out carburizing reagent, after reaction finishes, under Ar atmosphere protection, is cooled to room temperature, obtains calcined product.Collect calcined product, porphyrize, till being washed to and thering is no NaCl in product, at 80 ℃, dry, obtain three-dimensional grapheme network structure load carbon covered stannum rice material, its three-dimensional grapheme thickness is < 3nm, and carbon covered stannum rice grain particle diameter is 5 ~ 30 nm, and carbon coating layer thickness is 1 nm.
With prepared material, PVDF, conductive carbon black mass ratio is that 8:1:1 meter is applied to copper sheet as negative pole, with the LiPF of 1M
6as electrolyte, using lithium sheet as positive pole, make half-cell, its 100 circles that circulate under the current density of 200mA/g still keep specific capacity more than 1000mAh/g, as shown in Figure 9, and there is excellent multiplying power cycle performance, under the current density of 10A/g, still there is the specific capacity of 270mAh/g, as shown in figure 10.
Embodiment 2:
Take 2.5g citric acid, 0.384g stannous chloride and 14.7gNaCl, mixture is dissolved in the deionized water of 50ml, with the magnetic stirring apparatus of mixing speed 300r/min, stirring and dissolving wiring solution-forming, and then take the ultrasonic 15min of ultrasonic device that power is 400W, mix.The solution mixing is put into refrigerator overnight and freeze, be placed on-50 ℃ of vacuumizes in freeze drier, until dry, obtain mixture.Milled mixtures, the mixed-powder of getting 6g is placed in Noah's ark, and Noah's ark is put into tube furnace, passes into the Ar inert gas 30min deaeration of 200ml/min, then with the H of 200ml/min
2for carrier gas and with the programming rate of 10 ℃/min, be warming up to 700 ℃ of temperature, insulation 6h carries out carburizing reagent, after reaction finishes, under Ar atmosphere protection, is cooled to room temperature, obtains calcined product.Collect calcined product, porphyrize till being washed to and thering is no NaCl in product, is dried at 80 ℃, obtains three-dimensional grapheme network structure load carbon covered stannum rice material.
Embodiment 3:
Take 2.5g citric acid, 0.768g stannous chloride and 14.7gNaCl, mixture is dissolved in the deionized water of 50ml, with the magnetic stirring apparatus of mixing speed 300r/min, stirring and dissolving wiring solution-forming, and then take the ultrasonic 15min of ultrasonic device that power is 400W, mix.The solution mixing is put into refrigerator overnight and freeze, be placed on-50 ℃ of vacuumizes in freeze drier, until dry, obtain mixture.Milled mixtures, the mixed-powder of getting 6g is placed in Noah's ark, and Noah's ark is put into tube furnace, passes into the Ar inert gas 30min deaeration of 200ml/min, then with the H of 200ml/min
2for carrier gas and with the programming rate of 10 ℃/min, be warming up to 800 ℃ of temperature, insulation 6h carries out carburizing reagent, after reaction finishes, under Ar atmosphere protection, is cooled to room temperature, obtains calcined product.Collect calcined product, porphyrize till being washed to and thering is no NaCl in product, is dried at 80 ℃, obtains three-dimensional grapheme network structure load carbon covered stannum rice material.
Embodiment 4:
Take 5g citric acid, 0.384g stannous chloride and 14.7gNaCl, mixture is dissolved in the deionized water of 50ml, with the magnetic stirring apparatus of mixing speed 300r/min, stirring and dissolving wiring solution-forming, and then take the ultrasonic 15min of ultrasonic device that power is 400W, mix.The solution mixing is put into refrigerator overnight and freeze, be placed on-50 ℃ of vacuumizes in freeze drier, until dry, obtain mixture.Milled mixtures, the mixed-powder of getting 6g is placed in Noah's ark, and Noah's ark is put into tube furnace, passes into the Ar inert gas 30min deaeration of 200ml/min, then with the H of 200ml/min
2for carrier gas and with the programming rate of 10 ℃/min, be warming up to 800 ℃ of temperature, insulation 8h carries out carburizing reagent, after reaction finishes, under Ar atmosphere protection, is cooled to room temperature, obtains calcined product.Collect calcined product, porphyrize till being washed to and thering is no NaCl in product, is dried at 80 ℃, obtains three-dimensional grapheme network structure load carbon covered stannum rice material.
Claims (3)
1. a three-dimensional grapheme network structure load carbon covered stannum rice material, it is characterized in that, this material is that the carbon covered stannum rice grain uniform load of uniform particle diameter is on three-dimensional grapheme network, wherein carbon covered stannum rice grain particle diameter is at 5-100nm, carbon coating layer thickness is 1-5nm, three-dimensional grapheme thickness is 1-10nm, and three-dimensional grapheme network radius is at 1-10um, and in this material, the mass percent of tin and total carbon is: (0.4-0.8): (0.6-0.2).
2. by a preparation method for two-dimentional porous graphite carbon-coating nickel tin alloy material claimed in claim 1, it is characterized in that comprising the following steps:
(1). with one or more in sucrose, glucose, citric acid, starch, be mixed into carbon source, take stannous chloride as Xi Yuan, carbon and the tin mol ratio in tin source of take in carbon source are (50 ~ 10): 1, take tin in tin source and the mass ratio of NaCl is (0.01-0.1): 1, carbon source, Xi Yuan and NaCl are added in deionized water and dissolved, stir wiring solution-forming, more ultrasonic mixing; Be placed on refrigerator freezing, treat that solution freeze over is placed on freeze drier and carries out vacuumize in-50 ℃, obtain mixture;
(2). the mixture grind into powder that step (1) is made, be laid in Noah's ark, be placed in tube furnace flat-temperature zone and calcine: with N
2, He or Ar a kind of or mix as inert gas source, the flow of first take passes into inert gas 30-60 minute with deaeration as 200 ~ 400 ml/min; Again with H
2as carrier gas, carrier gas flux is fixed as to 50 ~ 200ml/min, with programming rate intensification tube furnace to 650 ~ 800 ℃ of 1 ~ 10 ℃/min, insulation 5-8h carries out carbonization, after reaction finishes, is cooled to room temperature, obtains calcined product;
(3). collect the calcined product that step (2) makes, porphyrize, till being washed to and thering is no NaCl in calcined product, is to dry at 60 ~ 120 ℃ in temperature, obtains three-dimensional grapheme network structure load carbon covered stannum rice material.
3. by an application for three-dimensional grapheme network structure load carbon covered stannum rice material claimed in claim 1, for lithium ion battery negative.
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| CN104103808A (en) * | 2014-07-31 | 2014-10-15 | 中国科学院上海硅酸盐研究所 | Flake-like tin-carbon composite material for lithium ion battery and preparation method for flake-like tin-carbon composite material |
| CN105067586A (en) * | 2015-08-12 | 2015-11-18 | 天津大学 | Nitrogen-doped three-dimensional graphene loaded carbon coated copper substrate material and preparation method |
| CN105161721A (en) * | 2015-08-04 | 2015-12-16 | 天津大学 | Three-dimensional composite material formed by filling carbon-encapsulated tin granules into graphene interlaminations and by filling graphene layers with carbon-encapsulated tin granules and preparation method for three-dimensional composite material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324497A (en) * | 2011-09-21 | 2012-01-18 | 上海大学 | A kind of graphene-supported carbon coats the preparation method of the lithium cell cathode material of tin antimony |
| CN102332572A (en) * | 2011-09-21 | 2012-01-25 | 广东达之邦新能源技术有限公司 | Anode material and manufacturing method thereof as well as lithium ion battery and negative plate thereof |
| WO2012020561A1 (en) * | 2010-08-10 | 2012-02-16 | 大学共同利用機関法人自然科学研究機構 | Carbon nanostructure, metal-supported carbon nanostructure, lithium ion secondary battery, process for production of carbon nanostructure, and process for production of metal-supported carbon nanostructure |
| CN103035877A (en) * | 2011-10-09 | 2013-04-10 | 海洋王照明科技股份有限公司 | Graphene/elemental tin combined electrode plate and preparation method of same |
-
2013
- 2013-12-23 CN CN201310715311.1A patent/CN103715430B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012020561A1 (en) * | 2010-08-10 | 2012-02-16 | 大学共同利用機関法人自然科学研究機構 | Carbon nanostructure, metal-supported carbon nanostructure, lithium ion secondary battery, process for production of carbon nanostructure, and process for production of metal-supported carbon nanostructure |
| CN102324497A (en) * | 2011-09-21 | 2012-01-18 | 上海大学 | A kind of graphene-supported carbon coats the preparation method of the lithium cell cathode material of tin antimony |
| CN102332572A (en) * | 2011-09-21 | 2012-01-25 | 广东达之邦新能源技术有限公司 | Anode material and manufacturing method thereof as well as lithium ion battery and negative plate thereof |
| CN103035877A (en) * | 2011-10-09 | 2013-04-10 | 海洋王照明科技股份有限公司 | Graphene/elemental tin combined electrode plate and preparation method of same |
Non-Patent Citations (5)
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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