CN106450257A - Doped stannic oxide and graphene composite material and preparing method thereof - Google Patents

Doped stannic oxide and graphene composite material and preparing method thereof Download PDF

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Publication number
CN106450257A
CN106450257A CN201611007785.0A CN201611007785A CN106450257A CN 106450257 A CN106450257 A CN 106450257A CN 201611007785 A CN201611007785 A CN 201611007785A CN 106450257 A CN106450257 A CN 106450257A
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Prior art keywords
graphene
doped
oxide
salt
stannic oxide
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Inventor
施利毅
袁帅
王帅
巴超群
闵国全
王竹仪
赵尹
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Shanghai Industrial Institute For Research And Technology
University of Shanghai for Science and Technology
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Shanghai Industrial Institute For Research And Technology
University of Shanghai for Science and Technology
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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
    • H01M4/48—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
    • 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
    • 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

Abstract

The invention discloses a doped stannic oxide and graphene composite material and a preparing method thereof. Graphene is used as a skeleton of the compound, and doped stannic oxide grows on graphene in a in-situ mode to form the composite material of a spongy three-dimensional structure, wherein the mass ratio of doped stannic oxide to graphene is (3-7):1, the particle size of doped stannic oxide is 3-20 nm, and doped elements include at least one of W, F and Sb, and the ratio of the atom total weight of the doped elements to the atomic weight of Sn is 1:(0.01-100). The preparing process is simpler than the previous compounding method, reaction conditions are controllable, the problems that the previous composite material is large in interface resistance and internal resistance, load particles aggregate, the structure is instable are solved by the prepared material, and the doped stannic oxide and graphene composite material has excellent electrochemical performance such as high specific capacity, good cycle performance and excellent rate capability.

Description

Doped stannum oxide graphene composite material and preparation method thereof
Technical field
The present invention relates to a kind of lithium ion battery negative material and its synthetic method, the preparation in situ of particularly a kind of one-step method Doped stannum oxide graphene composite material and preparation method thereof.
Background technology
Increasingly reduce with fossil fuel reserves and gradually aggravate with environmental pollution, the new forms of energy of development clean and effective become The research emphasis of whole world people.Lithium ion battery, as a kind of novel energy storage apparatus, has energy height, running voltage height, follows Ring life-span length, advantages of environment protection, are widely used in the fields such as mixed power electric car, electric automobile, intelligent grid.
Electrode material is the key of impact battery energy density and service life, the lithium ion battery of current commercialization negative Pole material mostly is graphite, because its specific capacity is relatively low, can not meet the demand to battery performance for the people.Therefore study and open Send out novel cathode material for lithium ion battery extremely urgent.
Compared with conventional graphite, metal-oxide（As stannum oxide, silicon oxide etc.）Possesses higher reversible theoretical capacity.But When research in the last few years shows simple metal-oxide as negative pole, the embedded and abjection of lithium ion can cause material volume Serious change（Exceed the 300% of own vol）.Although making the metal oxide materials of different nanostructureds（Receive as extra small Meter Jing, nanometer rods, nano wire, nanotube etc.）Volumetric expansion can be solved the problems, such as, but simple metals oxide cathode is due in height Under electric current density, cycle performance difference restricts it and can not be commercialized.
Carbon-based（Graphene）Metal oxide composite is considered as one of negative material that most probable substitutes graphite, by The stacking of Graphene can be prevented in metal-oxide, Graphene provides enough to the change in volume of metal-oxide simultaneously Elastic space.But because the electric conductivity official post this negative material high rate performance of metal-oxide is not good enough and simply multiple Conjunction leads to metal-oxide and carbon-based material（Graphene）Between adhesion not enough, charge and discharge process is susceptible to particle Reunion, fragmentation, the problems such as come off.Therefore, prepare that a kind of specific capacity is high, internal resistance is low, constitutionally stable composite is to closing weight Will.
Content of the invention
An object of the present invention is for problems of the prior art, provides a kind of doped stannum oxide Graphene Complex.
The second object of the present invention is to provide the preparation method of this complex.
For achieving the above object, technical scheme provided by the present invention is as follows：
A kind of doped stannum oxide graphene complex is it is characterised in that this complex is using Graphene as skeleton, doping oxidation Stannum growth in situ on Graphene, forms the composite with spongy three dimensional structure, wherein Graphene and doped stannum oxide Mass ratio be：1：（3~7）；The particle size of described doped stannum oxide be 3 ~ 20 nm, doped chemical be W, F, Sb in extremely Few one kind, wherein the atom total amount of doped chemical and the atomic molar ratio of Sn are：1：（0.01~100）.
In above-mentioned doped stannum oxide, the atom total amount of doped chemical and the ratio of the atomic weight of Sn are 1：0.5~100.
A kind of method preparing above-mentioned doped stannum oxide graphene complex is it is characterised in that the concrete steps of the method For：
A. configuration quality concentration is the graphene oxide dispersion of 1～10 g/L, adds stannous oxalate, and dispersed；Described Graphene oxide with the mass ratio of stannous oxalate be：1：1~10 ；
B. add the salt of doped chemical in step A gained dispersion liquid；
C. step b gained dispersion liquid is reacted 6～72 hours at 100～200 DEG C, product is scrubbed, vacuum drying, obtains Doped stannum oxide graphene complex.
In above-mentioned step A, the solvent of dispersion liquid is water, methanol, ethanol or isopropanol.
In above-mentioned steps C, baking temperature is 100 ~ 200 DEG C, and drying time is 2 ~ 24h.
The salt of the doped chemical in above-mentioned step B is villiaumite, tungsten salt, tungstenic presoma or the antimonic salt of doped chemical.
The villiaumite of above-mentioned doped chemical is：Ammonium fluoride；Described tungsten salt is：Tungsten hexachloride；Described tungstenic presoma For：Tungsten powder and hydrogen peroxide；Described antimonic salt is Butter of antimony..
The square resistance of the composite of the present invention is 1 ~ 50 Ω/, and Ω/ is the unit of square resistance, and that is, ohm is every Square, specific capacity is more than 1000 mAh/g.
The present invention is successfully prepared capacity height, electric conductivity, constitutionally stable doped stannum oxide stone using situ synthesis techniques Black alkene composite.It is substrate that this material adopts Graphene, and stannum oxide growth in situ on Graphene is steady by formation of chemical bond Fixed composite construction, is simultaneously introduced heteroatom to doped sno_2, effectively increases the electric conductivity of composite, is formed three-dimensional Conductive structure, accelerates the transfer rate of electronics and lithium ion.The doped stannum oxide Graphene composite wood prepared by the method Material electrochemical performance, possesses specific capacity height, good cycling stability, the excellent feature of high rate performance.And preparation process letter Single, condition is controlled, with low cost, has Commercial Prospect.
This preparation technology flow process is simple, mild condition.This complex is used as to efficiently solve biography during lithium cell cathode material The problems such as system volumetric expansion in cyclic process for the metal oxide materials, reunion, internal resistance are high, makes battery possess higher specific volume Amount.The spongiosiss of this composite can form three-dimensional conductive system, improves electric transmission and lithium ion mobility speed, from And the high rate performance of battery is greatly improved.
The invention has the beneficial effects as follows：Preparation process is simple, on Graphene, size can for doped stannum oxide growth in situ Control.Little as resistance during negative material, specific capacity is high, life-span length, and high rate performance is excellent.
The present invention adopts one-step method fabricated in situ doped stannum oxide graphene composite material.This process is raw materials used to be easy to get, Preparation process is simple, reaction condition are gentle, synthesis is with low cost.The preparation process simultaneously also overcoming conventional composite is numerous Trivial, material structure is unstable, and particle agglomeration is serious, and Graphene stacks, and contact resistance is big, the problems such as internal resistance is high.By this legal system Standby doped stannum oxide graphene composite material has excellent chemical property：Life-span length, specific capacity are high, high rate performance is excellent Different.The process of the method is simple simultaneously, condition controlled it is adaptable to ion cathode material lithium and its industrialization.
Figure of description
The Scanning Electron microscope figure of Fig. 1 witch culture stannum oxide Graphene；
The curve of double curvature of Fig. 2 fluorine-doped tin oxide Graphene, as can be seen from the figure has 420 under the electric current density of 5A/g The capacity of mAh/g, after circulation, under the electric current density of 0.1 A/g, capacity can return to 1100 mAh/g；
Fig. 3 witch culture stannum oxide Graphene cyclic curve under 100 mAh/g electric current densities, as can be seen from the figure circulates 100 The specific capacity of 1150mAh/g is still kept after circle.
Specific embodiment
Raw material sources in following examples are as follows：
Stannous oxalate（Traditional Chinese medicines, AR）, ammonium fluoride（Traditional Chinese medicines, AR）, tungsten powder（Aladdin 99.98%）, hydrogen peroxide（Traditional Chinese medicines, AR）, six Tungsten chloride（Fertile triumphant 99.5%）, Butter of antimony.（Traditional Chinese medicines, AR）, methanol（Traditional Chinese medicines, AR）, ethanol（Traditional Chinese medicines, AR）, isopropanol（Traditional Chinese medicines, AR）, water（Used is deionized water）.
Graphene oxide（GO）Graphene oxide is prepared using the Hummers method changed（Sasha Stankovich, Richard D. Piner, SonBinh T. Nguyen, Rodney S. Ruoff. Synthesis and exfoliation of isocyanate-treated graphene oxide nanoplatelets. Carbon 2006, 44, 3342–3347.）
With reference to embodiment, the present invention is described in detail.
Embodiment one：Weigh 0.1 g graphene oxide, be dispersed in the water of 40 mL, add 0.5 g stannous oxalate, Stirring 1h, by the tungsten powder of 4.3mg and 90 μ L hydrogen peroxide（The presoma of tungsten needs to use hydrogen peroxide）It is added thereto after mixing, surpass Sound disperses 2h, is transferred in water heating kettle, adds 30 mL water, 170 DEG C of reaction 24h.Products in water and washing with alcohol is taken out after cooling For several times, 140 DEG C of vacuum drying 12h obtain witch culture stannum oxide graphene complex.By above-mentioned cathode composite materials specific capacity It is about 1100 mAh/g.
Embodiment two：Weigh 0.06g graphene oxide, be dispersed in the ethanol of 40 mL, add 0.4g stannous oxalate With 0.19 g ammonium fluoride, stir 0.5h, ultrasonic disperse 1h, be transferred in water heating kettle, add 30 mL water, 100 DEG C of reaction 48h.Cold But products in water and washing with alcohol are taken out for several times afterwards, 120 DEG C of vacuum drying 18h obtain fluorine-doped tin oxide graphene complex. Above-mentioned cathode composite materials specific capacity is about 1000 mAh/g.
Embodiment three：Weigh 0.12 g graphene oxide, be dispersed in the water of 40 mL, add 1g stannous oxalate, stir Mix 1.5h, add 31.5mg Butter of antimony., ultrasonic disperse 2h, be transferred in water heating kettle, add 30 mL water, 160 DEG C of reaction 48h. After cooling, for several times, 150 DEG C of vacuum drying 10h obtain antimony-doped tin oxide Graphene and are combined for taking-up products in water and washing with alcohol Thing.Above-mentioned cathode composite materials specific capacity is about 1100 mAh/g.
Example IV：Weigh 0.2g graphene oxide, be dispersed in the water of 40 mL, add 1 g stannous oxalate, stir Mix 0.5h, add 20.4 mg tungsten hexachlorides, ultrasonic disperse 1h, be transferred in water heating kettle, add 30 mL water, 180 DEG C of reactions 36h.After cooling, for several times, 160 DEG C of vacuum drying 8h obtain witch culture stannum oxide Graphene again for taking-up products in water and washing with alcohol Compound.Referring to Fig. 1, above-mentioned cathode composite materials specific capacity is about 1100 mAh/g.
Embodiment five：Weigh 0.9 g graphene oxide, be dispersed in the water of 40 mL, add 7 g stannous oxalates, stir Mix 2h, add 2.1 g ammonium fluorides, ultrasonic disperse 2h, be transferred in water heating kettle, add 30 mL water, 170 DEG C of reaction 48h.Cooling For several times, 120 DEG C of vacuum drying 16h obtain fluorine-doped tin oxide graphene complex for taking-up products in water and washing with alcohol afterwards.Will Above-mentioned cathode composite materials specific capacity is about 1200 mAh/g, still has the specific volume of 400 mAh/g under the electric current density of 5A/g Amount.Referring to Fig. 2.
Embodiment six：Weigh 0.5 g graphene oxide, be dispersed in the water of 40 mL, add 5g stannous oxalate, stir Mix 1.5h, add 0.15 g tungsten hexachloride, ultrasonic disperse 1h, be transferred in water heating kettle, add 30 mL water, 180 DEG C of reaction 24h. After cooling, for several times, 120 DEG C of vacuum drying 24h obtain witch culture stannum oxide Graphene and are combined for taking-up products in water and washing with alcohol Thing.Above-mentioned cathode composite materials specific capacity is about 1150 mAh/g, referring to Fig. 3.

Claims (7)

1. it is characterised in that this complex is using Graphene as skeleton, adulterate a kind of doped stannum oxide graphene complex oxygen Change stannum growth in situ on Graphene, form the composite with spongy three dimensional structure, wherein Graphene and doping oxidation The mass ratio of stannum is：1：（3~7）；The particle size of described doped stannum oxide is 3 ~ 20 nm, and doped chemical is in W, F, Sb The atom total amount of at least one, wherein doped chemical and the atomic molar ratio of Sn are：1：（0.01~100）.
2. doped stannum oxide graphene complex according to claim 1 is it is characterised in that in described doped stannum oxide The atom total amount of doped chemical and the ratio of the atomic weight of Sn are 1：0.5~100.
3. a kind of method preparing doped stannum oxide graphene complex according to claim 1 and 2 is it is characterised in that be somebody's turn to do The concretely comprising the following steps of method：
Configuration quality concentration is the graphene oxide dispersion of 1～10 g/L, adds stannous oxalate, and dispersed；Described Graphene oxide with the mass ratio of stannous oxalate is：1：1~10 ；
The salt of doped chemical is added in step A gained dispersion liquid；
Step b gained dispersion liquid is reacted 6～72 hours at 100～200 DEG C, product is scrubbed, vacuum drying, is adulterated Stannum oxide graphene complex.
4. preparation method according to claim 3 it is characterised in that in described step A the solvent of dispersion liquid be water, first Alcohol, ethanol or isopropanol.
5. preparation method according to claim 3 it is characterised in that in described step C baking temperature be 100 ~ 200 DEG C, do The dry time is 2 ~ 24h.
6. preparation method according to claim 3 is it is characterised in that the salt of doped chemical in described step B is doping The villiaumite of element, tungsten salt, tungstenic presoma or antimonic salt.
7. preparation method according to claim 6 is it is characterised in that the villiaumite of described doped chemical is：Ammonium fluoride；Institute The tungsten salt stated is：Tungsten hexachloride；Described tungstenic presoma is：Tungsten powder and hydrogen peroxide；Described antimonic salt is Butter of antimony..
CN201611007785.0A 2016-11-16 2016-11-16 Doped stannic oxide and graphene composite material and preparing method thereof Pending CN106450257A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107180964A (en) * 2017-06-26 2017-09-19 厦门大学 A kind of microwave method prepares method and the application of blended metal oxide/graphene composite nano material
CN107528062A (en) * 2017-03-31 2017-12-29 上海大学 A kind of preparation method of lithium battery tin base cathode material
CN109524170A (en) * 2018-10-30 2019-03-26 天津市职业大学 A kind of preparation method of graphene and fluorin-doped tin oxide transparent conductive film

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103332678A (en) * 2013-05-24 2013-10-02 东莞上海大学纳米技术研究院 Preparation methods of graphene and graphene-oxide compound
EP2647430A1 (en) * 2012-04-05 2013-10-09 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Method for preparing a catalyst mediating H2 evolution, said catalyst and uses thereof
CN104852022A (en) * 2015-03-27 2015-08-19 上海大学 Cathode material for lithium ion battery and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2647430A1 (en) * 2012-04-05 2013-10-09 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Method for preparing a catalyst mediating H2 evolution, said catalyst and uses thereof
CN103332678A (en) * 2013-05-24 2013-10-02 东莞上海大学纳米技术研究院 Preparation methods of graphene and graphene-oxide compound
CN104852022A (en) * 2015-03-27 2015-08-19 上海大学 Cathode material for lithium ion battery and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107528062A (en) * 2017-03-31 2017-12-29 上海大学 A kind of preparation method of lithium battery tin base cathode material
CN107180964A (en) * 2017-06-26 2017-09-19 厦门大学 A kind of microwave method prepares method and the application of blended metal oxide/graphene composite nano material
CN109524170A (en) * 2018-10-30 2019-03-26 天津市职业大学 A kind of preparation method of graphene and fluorin-doped tin oxide transparent conductive film

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Application publication date: 20170222