CN103904313B - The preparation method of a kind of tin oxide-nitrogen-doped graphene aerosol composite material and application thereof - Google Patents
The preparation method of a kind of tin oxide-nitrogen-doped graphene aerosol composite material and application thereof Download PDFInfo
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- CN103904313B CN103904313B CN201410150954.0A CN201410150954A CN103904313B CN 103904313 B CN103904313 B CN 103904313B CN 201410150954 A CN201410150954 A CN 201410150954A CN 103904313 B CN103904313 B CN 103904313B
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- H01—ELECTRIC ELEMENTS
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- 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
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
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- 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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- H—ELECTRICITY
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses preparation method and the application in lithium ion battery negative preparation thereof of a kind of tin oxide-nitrogen-doped graphene aerosol composite material, concentrated ammonia liquor, Xi Yuan and PVP is added in graphene oxide aqueous dispersions, mix, carry out hydro-thermal reaction, hydrothermal temperature is 100-300 DEG C, reaction time 1-24h, reaction terminates afterproduct and to dialyse in ultra-pure water at least one sky; Then by sample at-20 DEG C of freezing 4h, and then-53 DEG C, freeze drying at least 12h in the environment of-30Pa; Gained sample is vacuumize 10h at 70 DEG C, then in argon gas atmosphere 550 DEG C of heat treatment 3h, to obtain final product.Aerogel material prepared by the present invention is the self-supporting material with certain toughness, through simple cutting and compacting can be directly used in battery assembling electrode material, what eliminate conductive agent and adhesive adds the tedious steps preparing electrode with traditional coating method, thus also reduces the cost of lithium ion battery while improving battery pack packing technique.
Description
Technical field
The present invention relates to preparation method and the application thereof of a kind of tin oxide-nitrogen-doped graphene aerosol composite material, belong to material science and technical field of electrochemistry.
Background technology
Lithium ion battery, as a kind of energy storing device, has the features such as environmental protection, light, high power capacity, long-life.Since it realizes commercialization, through constantly perfect, its production technology is day by day ripe, is widely used in small portable device.And the development of the progress of science and technology especially hybrid electric vehicle, propose higher requirement constantly to the performance of lithium ion battery.At present, commercial lithium ion battery negative material is main mainly with carbon class material, and the theoretical capacity of material with carbon element only has 372mAhg
-1, and high rate performance is poor, also there is solvent and embeds the potential safety hazard brought altogether, can not meet the demand of people to battery performance and fail safe.Therefore, Novel anode material and preparation technology thereof and performance study not only have important theory significance but also have important application prospect.
Tin-based material has higher theoretical capacity and good security performance as lithium ion battery negative material, and higher natural reserves, thus gets more and more people's extensive concerning.But tin-based material does to there is larger bulk effect when cycle charge discharge, can cause the destruction of material structure, finally cause the rapid decay of capacity.Therefore, alleviate tin-based material circulate embedding lithium time produce change in volume, improve electrode stability become tin-based material research key point.In two steps, be first reduced into simple substance tin, then simple substance tin carries out lithiation again in the embedding lithium reaction of stannic oxide materials.First step reaction is irreversible under normal circumstances, but when the size of material is reduced to nanoscale, first step reaction can be converted into reversible reaction, and therefore stannic oxide nano material capacity is expected to up to 1494mAhg
-1, the bulk effect of nano material can reduce greatly simultaneously.But tin oxide conductive is poor, and nano material is easily reunited and is caused a large amount of tin oxide inactivation, therefore needs to be combined with the material of good conductivity the structural stability improving material monolithic, effectively could improve the chemical property of material.
Grapheme material has good conductivity, large specific area, high flexibility and significant chemical stability, is a kind of ideal carrier material being applicable to electrochemical system.In lithium-ion battery system, the theoretical capacity of Graphene itself is also up to 744mAhg
-1, be therefore also the very promising lithium ion battery negative material of one.But because Graphene is a kind of two-dimensional material, the large π key of sheet interlayer easily interacts, and cause sheet of material stacking mutually, this structure is unfavorable for the transmission of ion, the amount of activated capacity of material can be caused to can not get playing, the doubly problem such as forthright difference.Document shows, capacity its theoretical capacity far little usually of Graphene, and decay is very fast, and therefore the structure of Graphene also needs reasonably to design.
Summary of the invention
The object of the present invention is to provide a kind of method and the application in lithium ion battery negative preparation thereof of being prepared tin oxide-nitrogen-doped graphene aerosol composite material by a step hydro-thermal.The aerogel material of preparation is the self-supporting material with certain toughness, through simple cutting and compacting can be directly used in battery assembling electrode material, what eliminate conductive agent and adhesive adds the tedious steps preparing electrode with traditional coating method, thus also reduces the cost of lithium ion battery while improving battery pack packing technique.
For realizing above-mentioned technical purpose, the present invention by the following technical solutions:
A preparation method for tin oxide-nitrogen-doped graphene aerosol composite material, comprises the following steps:
(1) Hummers method is utilized to prepare the graphene oxide aqueous dispersions that concentration is 0.5-5mg/ml;
(2) add the concentrated ammonia liquor that mass concentration is 25-28% in the graphene oxide aqueous dispersions prepared to step (1), stir, the addition of concentrated ammonia liquor is: every 300mg graphene oxide adds 1-3ml concentrated ammonia liquor;
(3) add Xi Yuan, stirring and dissolving in the solution obtained to step (2), the amount that every 300mg graphene oxide adds Xi Yuan is: 0 < tin source addition≤1g;
(4) add polyvinylpyrrolidone (PVP), stirring and dissolving in the solution obtained to step (3), the consumption of PVP is: every 400mg Xi Yuan adds 20-100mgPVP (Mw=55000), ultrasonic disperse 2h;
(5) transfer in hydrothermal reaction kettle by the mixed liquor of step (4), carry out hydro-thermal reaction, hydrothermal temperature is 100-300 DEG C, reaction time 1-24h;
(6) step (5) gained sample to be dialysed in ultra-pure water at least one sky;
(7) by step (6) gained sample first at-20 DEG C of freezing 4h, and then at-53 DEG C, freeze drying at least 12h in the environment of-30Pa;
(8) by step (7) gained sample vacuumize 10h at 70 DEG C, then in argon gas atmosphere 550 DEG C of heat treatment 3h, to obtain final product;
Wherein, in step (3), the Xi Yuan added is one or more in butter of tin, stannous chloride or stannous sulfate, mixes with arbitrary proportion.
The tin oxide that the present invention prepares-nitrogen-doped graphene aerosol composite material, the particle diameter of its stannic oxide materials is 5nm ± 2nm, and the capacity after 100 times that circulates remains on 1100mAhg
-1, coulombic efficiency is more than 97% (except first lap).
The application in lithium ion battery negative preparation of the tin oxide that the present invention prepares-nitrogen-doped graphene aerosol composite material, required electrode film is cut out and be pressed into the material direct physical by drying and moulding, namely can be used as electrode for lithium-ion battery system.
Graphene aerosol not only can keep the original chemical property of Graphene, and its three-dimensional porous structure also can effectively prevent graphene nanometer sheet from mutually adsorbing, and provides the electronics special delivery path of multidimensional and shortens mass transfer distance.Therefore, tin oxide nanoparticles is combined with Graphene aerosol, not only be conducive to preventing graphene nanometer sheet mutually stacking, the problem of tin oxide conductive difference can also be improved, prevent the reunion of nano particle simultaneously, the bulk effect of buffer oxide tin in cyclic process, is conducive to the chemical property improving material.Because the embedding lithium of Graphene does not have obvious plateau potential, and Graphene is two-dimensional sheet material, unfavorable to ion diffuse in electrochemical system, and in Graphene, the element such as doping and modification boron, nitrogen effectively can improve the chemical property of material.Wherein N doping can produce a large amount of pyridine nitrogen and make material generation defect, and electronics redistributes, and chemical property is improved.Electron deficient structure is conducive to lithium ion and passes wherein, effectively can solve the diffusion problem of ion in graphene sheet layer.
Tin oxide of the present invention-nitrogen-doped graphene aerosol composite material and preparation method thereof, the one step hydro thermal method of employing, simple to operate, mild condition, the composition of material and pattern are all easy to control, environmentally safe.Synchronously can realize the doping of the hydrolysis of Xi Yuan, the reduction of graphene oxide, aerocolloidal formation and nitrogen, and composition is controlled; The composite structure prepared is stablized, and capacitance is high, directly can be used for lithium-ion battery system as electrode, eliminate the tedious steps that traditional coating method prepares electrode, reduce production cost, can be expected to realize suitability for industrialized production through simple cutting.
Accompanying drawing explanation
Fig. 1 is the photo of tin oxide-nitrogen-doped graphene aerogel material prepared by the embodiment of the present invention 1;
Fig. 2 is the charge-discharge performance figure of tin oxide-nitrogen-doped graphene aerogel material prepared by the embodiment of the present invention 1.
Embodiment
Below in conjunction with embodiment, content of the present invention is described.
Embodiment 1:
The concentrated ammonia liquor of 1.5ml being joined 150ml concentration is 2mgml
-1graphene oxide aqueous dispersions in, stir 30min to mixing; Then join in solution by the PVP (Mw=55000) of 0.8g butter of tin and 160mg, stirring and dissolving, ultrasonic disperse 1h mixes to solution; Then mixed liquor is all transferred in hydrothermal reaction kettle, keep 160 DEG C to react 12h; Reaction terminates afterproduct and to dialyse in ultra-pure water at least one sky; Then by sample at-20 DEG C of freezing 4h, and then-53 DEG C, freeze drying at least 12h in the environment of-30Pa; Gained sample is vacuumize 10h at 70 DEG C, then in argon gas atmosphere 550 DEG C of heat treatment 3h, namely obtain tin oxide-nitrogen-doped graphene aerogel material.After measured, wherein the average grain diameter of granules of stannic oxide is 5nm, and the capacity after 100 times that circulates remains on 1100mAhg
-1left and right, coulombic efficiency is more than 97%.
Embodiment 2:
The concentrated ammonia liquor of 3ml being joined 600ml concentration is 0.5mgml
-1graphene oxide aqueous dispersions in, stir 30min to mixing; Then join in solution by the PVP (Mw=55000) of 1.0g butter of tin and 250mg, stirring and dissolving, ultrasonic disperse 1h mixes to solution; Then mixed liquor is all transferred in hydrothermal reaction kettle, keep 100 DEG C to react 24h; Reaction terminates afterproduct and to dialyse in ultra-pure water at least one sky; Then by sample at-20 DEG C of freezing 4h, and then-53 DEG C, freeze drying at least 12h in the environment of-30Pa; Gained sample is vacuumize 10h at 70 DEG C, then in argon gas atmosphere 550 DEG C of heat treatment 3h, namely obtain tin oxide-nitrogen-doped graphene aerogel material.After measured, the average grain diameter of its stannic oxide materials is 4nm, and the capacity after 100 times that circulates remains on 920mAhg
-1left and right, coulombic efficiency is more than 97%.
Embodiment 3:
The concentrated ammonia liquor of 1.5ml being joined 100ml concentration is 3mgml
-1graphene oxide aqueous dispersions in, stir 30min to mixing; Then join in solution by the PVP (Mw=55000) of 0.6g stannous sulfate and 75mg, stirring and dissolving, ultrasonic disperse 1h mixes to solution; Then mixed liquor is all transferred in hydrothermal reaction kettle, keep 180 DEG C to react 8h; Reaction terminates afterproduct and to dialyse in ultra-pure water at least one sky; Then by sample at-20 DEG C of freezing 4h, and then-53 DEG C, freeze drying at least 12h in the environment of-30Pa; Gained sample is vacuumize 10h at 70 DEG C, then in argon gas atmosphere 550 DEG C of heat treatment 3h, namely obtain tin oxide-nitrogen-doped graphene aerogel material.After measured, the average grain diameter of its stannic oxide materials is 5nm, and the capacity after 100 times that circulates remains on 1040mAhg
-1left and right, coulombic efficiency is more than 97%.
Embodiment 4:
The concentrated ammonia liquor of 1ml being joined 60ml concentration is 5mgml
-1graphene oxide aqueous dispersions in, stir 30min to mixing; Then join in solution by the PVP (Mw=55000) of 0.5g stannous chloride and 25mg, stirring and dissolving, ultrasonic disperse 1h mixes to solution; Then mixed liquor is all transferred in hydrothermal reaction kettle, keep 300 DEG C to react 1h; Reaction terminates afterproduct and to dialyse in ultra-pure water at least one sky; Then by sample at-20 DEG C of freezing 4h, and then-53 DEG C, freeze drying at least 12h in the environment of-30Pa; Gained sample is vacuumize 10h at 70 DEG C, then in argon gas atmosphere 550 DEG C of heat treatment 3h, namely obtain tin oxide-nitrogen-doped graphene aerogel material.After measured, the average grain diameter of its stannic oxide materials is 7nm, and the capacity after 100 times that circulates remains on 1000mAhg
-1left and right, coulombic efficiency is more than 97%.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (4)
1. a preparation method for tin oxide-nitrogen-doped graphene aerosol composite material, is characterized in that, comprise the following steps:
(1) Hummers method is utilized to prepare the graphene oxide aqueous dispersions that concentration is 0.5-5mg/ml;
(2) add concentrated ammonia liquor in the graphene oxide aqueous dispersions prepared to step (1), stir, the amount of concentrated ammonia liquor is: every 300mg graphene oxide adds 1-3ml concentrated ammonia liquor;
(3) add Xi Yuan, stirring and dissolving in the solution obtained to step (2), the amount that every 300mg graphene oxide adds Xi Yuan is: 0 < tin source addition≤1g;
(4) add the PVP that weight average molecular weight is 55000, stirring and dissolving in the solution obtained to step (3), the consumption of PVP is: every 400mg Xi Yuan adds 20-100mgPVP, ultrasonic disperse 2h;
(5) transfer in hydrothermal reaction kettle by the mixed liquor of step (4), carry out hydro-thermal reaction, hydrothermal temperature is 100-300 DEG C, and the reaction time is 1-24h;
(6) step (5) gained sample to be dialysed in ultra-pure water at least one sky;
(7) by step (6) gained sample first at-20 DEG C of freezing 4h, and then at-53 DEG C, freeze drying at least 12h in the environment of-30Pa;
(8) by step (7) gained sample vacuumize 10h at 70 DEG C, then in argon gas atmosphere 550 DEG C of heat treatment 3h, namely obtain tin oxide-nitrogen-doped graphene aerosol composite material;
Wherein, in step (3), the Xi Yuan added is the one in butter of tin, stannous chloride or stannous sulfate.
2. tin oxide-nitrogen-doped graphene aerosol composite material of preparing of preparation method according to claim 1, it is characterized in that, wherein the particle diameter of stannic oxide nano material is 5nm ± 2nm, and the capacity after 100 times that circulates remains on 1100mAhg
-1, the coulombic efficiency except first lap is more than 97%.
3. the application in lithium ion battery in negative material prepared by tin oxide according to claim 2-nitrogen-doped graphene aerosol composite material.
4. the application in lithium ion battery in negative material prepared by tin oxide-nitrogen-doped graphene aerosol composite material as claimed in claim 3, it is characterized in that, required electrode film is cut out and be pressed into the tin oxide of drying and moulding-nitrogen-doped graphene aerosol composite material direct physical.
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| CN104659345B (en) * | 2015-02-06 | 2017-08-29 | 中国石油大学(华东) | A kind of composite and button cell prepared therefrom for lithium battery |
| CN105185956B (en) * | 2015-06-19 | 2018-01-12 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of spongy 3 SiC 2/graphite alkene and CNT composite negative pole material |
| CN112151780A (en) * | 2020-09-21 | 2020-12-29 | 江苏塔菲尔新能源科技股份有限公司 | Nano lithium iron phosphate/graphene oxide composite material and preparation method and application thereof |
| CN112903762A (en) * | 2021-02-09 | 2021-06-04 | 建木柔电(深圳)智能设备有限公司 | Carbon monoxide gas sensor based on graphene aerosol material |
| CN114392730B (en) * | 2022-01-11 | 2023-09-12 | 河南康宁特环保科技股份有限公司 | Preparation method of high-dispersion hierarchical pore Ti-based SCR catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185144A (en) * | 2011-04-02 | 2011-09-14 | 浙江大学 | Metal oxide/graphene composite material and preparation method thereof |
| CN102324522A (en) * | 2011-10-28 | 2012-01-18 | 中国科学院上海硅酸盐研究所 | Nitrogen-doped graphene/tin oxide nano composite material and preparation method thereof |
| CN102891319A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Preparation method of graphite composite material of lithium ion battery |
| CN103346301A (en) * | 2013-06-25 | 2013-10-09 | 上海交通大学 | Preparation method and application of three-dimensional-structure graphene-base metal oxide composite material |
-
2014
- 2014-04-15 CN CN201410150954.0A patent/CN103904313B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185144A (en) * | 2011-04-02 | 2011-09-14 | 浙江大学 | Metal oxide/graphene composite material and preparation method thereof |
| CN102324522A (en) * | 2011-10-28 | 2012-01-18 | 中国科学院上海硅酸盐研究所 | Nitrogen-doped graphene/tin oxide nano composite material and preparation method thereof |
| CN102891319A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Preparation method of graphite composite material of lithium ion battery |
| CN103346301A (en) * | 2013-06-25 | 2013-10-09 | 上海交通大学 | Preparation method and application of three-dimensional-structure graphene-base metal oxide composite material |
Non-Patent Citations (1)
| Title |
|---|
| "新型纳米结构锡基锂离子电池负极材料的制备及性能研究";谭春晖;《中国博士学位论文全文数据库 工程科技II辑》;20131015;摘要，第82页第1段－第113页最后1段 * |
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