CN106410199B - A kind of lithium ion battery graphene/ferro-tin alloy composite negative pole material preparation method - Google Patents

A kind of lithium ion battery graphene/ferro-tin alloy composite negative pole material preparation method Download PDF

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CN106410199B
CN106410199B CN201610831531.4A CN201610831531A CN106410199B CN 106410199 B CN106410199 B CN 106410199B CN 201610831531 A CN201610831531 A CN 201610831531A CN 106410199 B CN106410199 B CN 106410199B
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ferro
solution
graphene
tin alloy
negative pole
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CN106410199A (en
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沈小平
徐克强
季振源
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Jiangsu University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387Tin or alloys based on tin
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention belongs to field of composite material preparation, are related to a kind of preparation method of lithium ion battery graphene/ferro-tin alloy composite negative pole material.It has main steps that using natural flake graphite as raw material, after obtaining graphite oxide, by graphite oxide ultrasonic disperse in water and mixed alkoxide solution, adds SnCl4·5H2O and K3[Fe(CN)6] solution, 80-150 DEG C of 24 h of hydro-thermal reaction;After cooling, precipitating is collected, washs and is dried to obtain graphene oxide/Sn3[Fe(CN)6]4Presoma, then calcining presoma obtains graphene/ferro-tin alloy nanocomposite (FeSn under an inert atmosphere2@Sn/rGO).FeSn in graphene of the invention/ferro-tin alloy composite negative pole material2@Sn nanoparticle is closely attached to the surface of graphene, is uniformly dispersed, and is 200 mA g in current density when being used as lithium ion battery negative material‑1When first discharge specific capacity up to 1598 mAh g‑1, capacity is up to 970 mA h g after circulation 60 times‑1.Operation of the present invention is simple for process, and the reaction time is short, is easy to industrializing implementation.

Description

A kind of lithium ion battery graphene/ferro-tin alloy composite negative pole material preparation Method
Technical field
The invention belongs to field of composite material preparation, in particular to a kind of lithium ion battery is multiple with graphene/ferro-tin alloy Close the preparation method of negative electrode material.
Technical background
With being growing for demand for energy, people start to be dedicated to grinding for high efficiency high-energy density energy storage device Study carefully.For lithium ion battery due to energy density height, low-maintenance cost, self-discharge current is small, has become most popular chargeable electricity Pond is widely used in various electronic equipments and electric car.Traditional lithium ion battery negative material is graphite, hard carbon, soft The carbon materials such as carbon.As a kind of emerging carbon family member, graphene possesses many extremely excellent performances, such as high current-carrying Transport factor, great specific surface area, excellent heating conduction, good translucency, high chemical and thermal stability etc., make stone Black alkene is once it is found that cause the research boom of new round carbon material.In alternative negative electrode material, the theoretical of metallic tin holds Amount is up to 990 mAh g-1, and it is friendly with electrolyte, thus be concerned by people.But it not can avoid metal material yet simultaneously Common fault in lithium ion battery charge and discharge process: during lithium ion inserts embedding deintercalation, the volume change of electrode material is larger, and one As reach three times of raw material, so that the serious dusting of electrode material be caused even to crush, greatly reduce the stability of structure, Cycle performance is reduced, the performance of electrode material is seriously affected.A large number of studies show that the composite material exhibits of nanostructure go out more Excellent chemical property.The graphene for possessing excellent properties is combined with tin-based material and prepares graphene-based ferro-tin alloy and answers Negative electrode material is closed, is the effective way for preparing high performance lithium ionic cell cathode material.On the one hand, the ferro-tin alloy loaded in situ Nanoparticle can expand the lamella distance of graphene in the solid state, prevent it to be piled into graphite-structure, to keep graphene Superior function.On the other hand, between graphene and ferro-tin alloy nanoparticle there are synergistic effect, the furthermore tin of nanostructure Based alloy and as inert metal be added iron can effectively buffer electrode material it is huge during the insertion of lithium ion and abjection Structure collapses caused by large volume expands and the capacity as caused by structure collapses are decayed rapidly, so that composite material exhibits go out to compare The more superior chemical property of one pack system, or even generate some new characteristics.Before the present invention utilizes metal organic framework for the first time Body method is driven, has prepared graphene-based ferro-tin alloy composite material, the composite material is as lithium ion battery negative material, table Reveal higher specific capacity (970 mAh g-1) and excellent cyclical stability.
Summary of the invention
The present invention already allows for the problem in the prior art, using by the metal organic framework (Sn of iron content, tin3 [Fe(CN)6]4) be supported on the graphene film of sheet in situ, then thermally decompose on precursor preparation graphene in an inert atmosphere Load the compound of ferro-tin alloy nanoparticle.Not only method is novel simply, composite effect is good for the method, but also controllable product Pattern and micro-structure.
It is an object of that present invention to provide a kind of lithium ion battery graphene/ferro-tin alloy nano composition systems Preparation Method includes the following steps:
(1) it using natural flake graphite as raw material, is oxidized to obtain graphite oxide with Hummers method;
(2) it the preparation of solution a: by graphite oxide ultrasonic disperse made from step (1) in alcohol-water mixture, is aoxidized Graphene dispersing solution;
(3) preparation of solution b: tetravalence pink salt is dissolved in dilute hydrochloric acid solution, and a certain amount of block copolymer table is added Face activating agent;
(4) preparation of solution c: the potassium ferricyanide is dissolved in dilute hydrochloric acid solution;
(5) solution b is added in solution a, is stirred at room temperature, form mixed solution, it is molten that solution c is added to mixing In liquid, continue to stir, final resulting mixed solution is added in the reaction kettle of polytetrafluoroethyllining lining, then by reaction kettle It is placed in baking oven and carries out hydro-thermal reaction, by gained precipitation and centrifugal separation, deionized water washing is dry, obtains Sn3[Fe(CN)6]4/ RGO precursor;
(6) by step (5) resulting presoma, temperature programming after calcining, obtains stone to calcination temperature in an inert atmosphere Ferro-tin alloy composite negative pole material, i.e. graphene/ferro-tin alloy composite negative pole material are loaded on black alkene.
In step (2), the alcohol-water mixture is the mixed liquor or deionized water and ethyl alcohol of deionized water and ethylene glycol Mixed liquor, the concentration of graphite oxide is 1-5 mg/mL in the graphene oxide dispersion.
Tetravalence pink salt used is SnCl in step (3)4·5H2O, concentration are 10-30 mg/mL, the block copolymer Surfactant is polyethers F127.
Potassium ferricyanide solution concentration described in step (4) is 10-50 mg/mL.
Graphite oxide in mixed solution described in step (5): tetravalence pink salt: the mass ratio of the potassium ferricyanide is 17:80: 100-68:80:100, hydrothermal temperature are 80-150 DEG C, and the reaction time is 10-24 h.
Inert gas is nitrogen or argon gas in step (6), and heating rate is 2-5 DEG C/min, calcination temperature 600-800 DEG C, calcination time is 1-3 h.
Ferro-tin alloy nanoparticle is closely attached to the surface of redox graphene, and iron in products therefrom of the present invention Tin alloy nanoparticle is cube block structure, and side length is 50-150 nm.
Beneficial effects of the present invention:
This method operating procedure is simple and easy, and the reaction time is short, and Environmental Safety, at low cost, is easy to industrializing implementation, energy Potential application is in lithium ion battery negative material.
Detailed description of the invention
Fig. 1 is that redox graphene/ferro-tin alloy nanocomposite X-ray prepared by the embodiment of the present invention 1 is spread out Penetrate (XRD) map, wherein abscissa be the angle of diffraction (2 θ), unit be degree (°), ordinate is diffracted intensity, unit cps.
Fig. 2 is redox graphene/ferro-tin alloy nanocomposite transmission electron microscope prepared by the embodiment of the present invention 1 (TEM) photo.
Fig. 3 is that redox graphene/ferro-tin alloy nanocomposite prepared by the embodiment of the present invention 1 is used as lithium ion Cell negative electrode material is 200 mA g in current density-1Under cycle performance figure.
Specific embodiment:
Technical solution of the present invention is described in detail in the following with reference to the drawings and specific embodiments, but protection of the invention Range is not limited to these embodiments.
Embodiment 1:
By 80 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml ethylene glycol mixtures, 2 h of ultrasound are aoxidized Graphene dispersing solution.8 mlSnCl are added4·5H2The HCl solution of O and F127 (contains SnCl4·5H2O 140 mg, F127 150 Mg, HCl concentration are 0.01 mol/L), and 8 mlK are added after 30 min of stirring at normal temperature3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration are 0.01 mol/L), mixed liquor is added in 50 ml polytetrafluoroethylene (PTFE) by 30 min of stirring at normal temperature In the reaction kettle of lining, 120 DEG C of 24 h of hydro-thermal reaction, product is centrifuged in baking oven, washs to obtain with deionized water/dehydrated alcohol Obtain cube bulk Sn loaded on graphene3[Fe(CN)6]4Product is dried in vacuo by nanoparticle precursor at 45 DEG C. Presoma is placed in porcelain boat in N2It is calcined at 700 DEG C in the tube furnace of protection, heating rate is 5 DEG C/min, calcination time For 1 h, final product redox graphene/ferro-tin alloy nanocomposite (FeSn is obtained2@Sn/rGO).
Fig. 1 is the XRD diagram of product prepared by the embodiment of the present invention 1, other than the diffraction maximum of redox graphene, other Peak corresponds to FeSn2And Sn, illustrate redox graphene/ferro-tin alloy nanocomposite (FeSn2@Sn/rGO) successfully made It is standby to come out.
Fig. 2 is the TEM figure of product prepared by the embodiment of the present invention 1, it can be seen that ferro-tin alloy nano cubic block is uniform It is attached to the surface of redox graphene piece, wherein ferro-tin alloy nanoparticle side length is 50-150 nm.
Fig. 3 is redox graphene/ferro-tin alloy nanocomposite of the preparation of the embodiment of the present invention 1 as lithium ion Cell negative electrode material is 200 mA g in current density-1When cycle performance figure.
Embodiment 2:
By 80 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml ethylene glycol mixtures.8 ml are added SnCl4·5H2The HCl solution of O and F127 (contains SnCl4·5H2O 150 mg of 140 mg, F127, HCl concentration are 0.01 mol/ L), 30 min of stirring at normal temperature.Then 8 ml K are added3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration For 0.01 mol/L), 30 min of stirring at normal temperature, the reaction kettle of 50 ml polytetrafluoroethyllining linings of addition 100 DEG C of hydro-thermals in baking oven React 24 h.After natural cooling, sample is centrifugated, is washed respectively with deionized water and dehydrated alcohol, by product in 45 DEG C Lower vacuum drying.Obtained product is placed in porcelain boat, in N2700 DEG C of 1 h of calcining, heating rate in the tube furnace of protection For 5 DEG C/min, final product is obtained.
Embodiment 3:
By 70 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml alcohol mixeding liquids.8 ml SnCl are added4· 5H2The HCl solution of O and F127 (contains SnCl4·5H2O 150 mg of 140 mg, F127, HCl concentration are 0.01 mol/L), room temperature Stir 30 min.Then 8 ml K are added3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01 Mol/L), 30 min of stirring at normal temperature, the reaction kettle of 50 ml polytetrafluoroethyllining linings of addition 120 DEG C of hydro-thermal reactions 24 in baking oven h.After natural cooling, sample is centrifugated, is washed respectively with deionized water and dehydrated alcohol, vacuum is done at 45 DEG C by product It is dry.Obtained product is placed in porcelain boat, in N2700 DEG C of 1 h of calcining in the tube furnace of protection, heating rate be 5 DEG C/ Min obtains final product.
Embodiment 4:
By 70 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml alcohol mixeding liquids.8 ml SnCl are added4· 5H2The HCl solution of O and F127 (contains SnCl4·5H2150 mg of O140 mg, F127, HCl concentration are 0.01 mol/L), room temperature Stir 30 min.Then 8 ml K are added3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01 Mol/L), 30 min of stirring at normal temperature, the reaction kettle of 50 ml polytetrafluoroethyllining linings of addition 150 DEG C of hydro-thermal reactions 24 in baking oven h.After natural cooling, sample is centrifugated, is washed respectively with deionized water and dehydrated alcohol, vacuum is done at 45 DEG C by product It is dry.Obtained product is placed in porcelain boat, in N2700 DEG C of 1 h of calcining in the tube furnace of protection, heating rate be 5 DEG C/ Min obtains final product.
Embodiment 5:
By 70 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml ethylene glycol mixtures.8 ml are added SnCl4·5H2The HCl solution of O and F127 (contains SnCl4·5H2O 150 mg of 140 mg, F127, HCl concentration are 0.01 mol/ L), 30 min of stirring at normal temperature.Then 8 ml K are added3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration For 0.01 mol/L), 30 min of stirring at normal temperature, the reaction kettle of 50 ml polytetrafluoroethyllining linings of addition 100 DEG C of hydro-thermals in baking oven React 24 h.After natural cooling, sample is centrifugated, is washed respectively with deionized water and dehydrated alcohol, by product in 45 DEG C Lower vacuum drying.Obtained product is placed in porcelain boat, in N2600 DEG C of 1 h of calcining, heating rate in the tube furnace of protection For 5 DEG C/min, final product is obtained.
Embodiment 6:
By 70 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml ethylene glycol mixtures.8 ml are added SnCl4·5H2The HCl solution of O and F127 (contains SnCl4·5H2O 150 mg of 140 mg, F127, HCl concentration are 0.01 mol/ L), 30 min of stirring at normal temperature.Then 8 ml K are added3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration For 0.01 mol/L), 30 min of stirring at normal temperature, the reaction kettle of 50 ml polytetrafluoroethyllining linings of addition 100 DEG C of hydro-thermals in baking oven React 24 h.After natural cooling, sample is centrifugated, is washed respectively with deionized water and dehydrated alcohol, by product in 45 DEG C Lower vacuum drying.Obtained product is placed in porcelain boat, in N2800 DEG C of 1 h of calcining, heating rate in the tube furnace of protection For 5 DEG C/min, final product is obtained.
Embodiment 7:
By 90 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml ethylene glycol mixtures.8 ml are added SnCl4·5H2The HCl solution of O and F127 (contains SnCl4·5H2O 150 mg of 140 mg, F127, HCl concentration are 0.01 mol/ L), 30 min of stirring at normal temperature.Then 8 ml K are added3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration For 0.01 mol/L), 30 min of stirring at normal temperature, the reaction kettle of 50 ml polytetrafluoroethyllining linings of addition 100 DEG C of hydro-thermals in baking oven React 24 h.After natural cooling, sample is centrifugated, is washed respectively with deionized water and dehydrated alcohol, by product in 45 DEG C Lower vacuum drying.Obtained product is placed in porcelain boat, in N2700 DEG C of 1 h of calcining, heating rate in the tube furnace of protection For 2 DEG C/min, final product is obtained.
Embodiment 8:
By 90 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml ethylene glycol mixtures.8 ml are added SnCl4·5H2The HCl solution of O and F127 (contains SnCl4·5H2O 150 mg of 140 mg, F127, HCl concentration are 0.01 mol/ L), 30 min of stirring at normal temperature.Then 8 ml K are added3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration For 0.01 mol/L), 30 min of stirring at normal temperature, the reaction kettle of 50 ml polytetrafluoroethyllining linings of addition 100 DEG C of hydro-thermals in baking oven React 24 h.After natural cooling, sample is centrifugated, is washed respectively with deionized water and dehydrated alcohol, by product in 45 DEG C Lower vacuum drying.Obtained product is placed in porcelain boat, in N2600 DEG C of 1 h of calcining, heating rate in the tube furnace of protection For 2 DEG C/min, final product is obtained.
Embodiment 9:
By 70 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml ethylene glycol mixtures.8 ml are added SnCl4·5H2The HCl solution of O and F127 (contains SnCl4·5H2O 150 mg of 140 mg, F127, HCl concentration are 0.01 mol/ L), 30 min of stirring at normal temperature.Then 8 ml K are added3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration For 0.01 mol/L), 30 min of stirring at normal temperature, the reaction kettle of 50 ml polytetrafluoroethyllining linings of addition 100 DEG C of hydro-thermals in baking oven React 24 h.After natural cooling, sample is centrifugated, is washed respectively with deionized water and dehydrated alcohol, by product in 45 DEG C Lower vacuum drying.Obtained product is placed in porcelain boat, in N2800 DEG C of 1 h of calcining, heating rate in the tube furnace of protection For 2 DEG C/min, final product is obtained.
Embodiment 10:
By 30 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml ethylene glycol mixtures.8 ml are added SnCl4·5H2The HCl solution of O and F127 (contains SnCl4·5H2O 150 mg of 140 mg, F127, HCl concentration are 0.01 mol/ L), 30 min of stirring at normal temperature.Then 8 ml K are added3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration For 0.01 mol/L), 30 min of stirring at normal temperature, the reaction kettle of 50 ml polytetrafluoroethyllining linings of addition 100 DEG C of hydro-thermals in baking oven React 24 h.After natural cooling, sample is centrifugated, is washed respectively with deionized water and dehydrated alcohol, by product in 45 DEG C Lower vacuum drying.Obtained product is placed in porcelain boat, in N2700 DEG C of 1 h of calcining, heating rate in the tube furnace of protection For 5 DEG C/min, final product is obtained.
Embodiment 11:
By 50 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml ethylene glycol mixtures.8 ml are added SnCl4·5H2The HCl solution of O and F127 (contains SnCl4·5H2O 150 mg of 140 mg, F127, HCl concentration are 0.01 mol/ L), 30 min of stirring at normal temperature.Then 8 ml K are added3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration For 0.01 mol/L), 30 min of stirring at normal temperature, the reaction kettle of 50 ml polytetrafluoroethyllining linings of addition 120 DEG C of hydro-thermals in baking oven React 24 h.After natural cooling, sample is centrifugated, is washed respectively with deionized water and dehydrated alcohol, by product in 45 DEG C Lower vacuum drying.Obtained product is placed in porcelain boat, in N2700 DEG C of 1 h of calcining, heating rate in the tube furnace of protection For 5 DEG C/min, final product is obtained.
Embodiment 12:
By 50 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml ethylene glycol mixtures.8 ml are added SnCl4·5H2The HCl solution of O and F127 (contains SnCl4·5H2O 150 mg of 140 mg, F127, HCl concentration are 0.01 mol/ L), 30 min of stirring at normal temperature.Then 8 ml K are added3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration For 0.01 mol/L), 30 min of stirring at normal temperature, the reaction kettle of 50 ml polytetrafluoroethyllining linings of addition 150 DEG C of hydro-thermals in baking oven React 24 h.After natural cooling, sample is centrifugated, is washed respectively with deionized water and dehydrated alcohol, by product in 45 DEG C Lower vacuum drying.Obtained product is placed in porcelain boat, in N2700 DEG C of 1 h of calcining, heating rate in the tube furnace of protection For 5 DEG C/min, final product is obtained.
Embodiment 13:
By 50 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml ethylene glycol mixtures.8 ml are added SnCl4·5H2The HCl solution of O and F127 (contains SnCl4·5H2O 150 mg of 140 mg, F127, HCl concentration are 0.01 mol/ L), 30 min of stirring at normal temperature.Then 8 ml K are added3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration For 0.01 mol/L), 30 min of stirring at normal temperature, the reaction kettle of 50 ml polytetrafluoroethyllining linings of addition 100 DEG C of hydro-thermals in baking oven React 24 h.After natural cooling, sample is centrifugated, is washed respectively with deionized water and dehydrated alcohol, by product in 45 DEG C Lower vacuum drying.Obtained product is placed in porcelain boat, in N2600 DEG C of 1 h of calcining, heating rate in the tube furnace of protection For 2 DEG C/min, final product is obtained.
Embodiment 14:
By 100 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml ethylene glycol mixtures.8 ml are added SnCl4·5H2The HCl solution of O and F127 (contains SnCl4·5H2O 150 mg of 140 mg, F127, HCl concentration are 0.01 mol/ L), 30 min of stirring at normal temperature.Then 8 ml K are added3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration For 0.01 mol/L), 30 min of stirring at normal temperature, the reaction kettle of 50 ml polytetrafluoroethyllining linings of addition 100 DEG C of hydro-thermals in baking oven React 24 h.After natural cooling, sample is centrifugated, is washed respectively with deionized water and dehydrated alcohol, by product in 45 DEG C Lower vacuum drying.Obtained product is placed in porcelain boat, in N2700 DEG C of 1 h of calcining, heating rate in the tube furnace of protection For 5 DEG C/min, final product is obtained.
Embodiment 15:
By 100 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml ethylene glycol mixtures.8 ml are added SnCl4·5H2The HCl solution of O and F127 (contains SnCl4·5H2O 150 mg of 140 mg, F127, HCl concentration are 0.01 mol/ L), 30 min of stirring at normal temperature.Then 8 ml K are added3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration For 0.01 mol/L), 30 min of stirring at normal temperature, the reaction kettle of 50 ml polytetrafluoroethyllining linings of addition 120 DEG C of hydro-thermals in baking oven React 24 h.After natural cooling, sample is centrifugated, is washed respectively with deionized water and dehydrated alcohol, by product in 45 DEG C Lower vacuum drying.Obtained product is placed in porcelain boat, in N2600 DEG C of 1 h of calcining, heating rate in the tube furnace of protection For 5 DEG C/min, final product is obtained.
Embodiment 16:
By 100 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml ethylene glycol mixtures.8 ml are added SnCl4·5H2The HCl solution of O and F127 (contains SnCl4·5H2O 150 mg of 140 mg, F127, HCl concentration are 0.01 mol/ L), 30 min of stirring at normal temperature.Then 8 ml K are added3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration For 0.01 mol/L), 30 min of stirring at normal temperature, the reaction kettle of 50 ml polytetrafluoroethyllining linings of addition 150 DEG C of hydro-thermals in baking oven React 24 h.After natural cooling, sample is centrifugated, is washed respectively with deionized water and dehydrated alcohol, by product in 45 DEG C Lower vacuum drying.Obtained product is placed in porcelain boat, in N2800 DEG C of 1 h of calcining, heating rate in the tube furnace of protection For 5 DEG C/min, final product is obtained.
Embodiment 17:
By 120 mg graphite oxide ultrasonic disperses in 10 ml water and 14 ml ethylene glycol mixtures.8 ml are added SnCl4·5H2The HCl solution of O and F127 (contains SnCl4·5H2O 150 mg of 140 mg, F127, HCl concentration are 0.01 mol/ L), 30 min of stirring at normal temperature.Then 8 ml K are added3[Fe(CN)6] solution (and contain K3[Fe(CN)6] 175.6 mg, HCl concentration For 0.01 mol/L), 30 min of stirring at normal temperature, the reaction kettle of 50 ml polytetrafluoroethyllining linings of addition 150 DEG C of hydro-thermals in baking oven React 24 h.After natural cooling, sample is centrifugated, is washed respectively with deionized water and dehydrated alcohol, by product in 45 DEG C Lower vacuum drying.Obtained product is placed in porcelain boat, in N2800 DEG C of 1 h of calcining, heating rate are in the tube furnace of protection 5 DEG C/min, obtain final product.

Claims (6)

1. a kind of lithium ion battery graphene/ferro-tin alloy composite negative pole material preparation method, which is characterized in that including with Lower step:
(1) it using natural flake graphite as raw material, is oxidized to obtain graphite oxide with Hummers method;
(2) preparation of solution a: by graphite oxide ultrasonic disperse made from step (1) in alcohol-water mixture, graphite oxide is obtained Alkene dispersion liquid;
(3) preparation of solution b: tetravalence pink salt is dissolved in dilute hydrochloric acid solution, and it is living that a certain amount of block copolymer surface is added Property agent;
(4) preparation of solution c: the potassium ferricyanide is dissolved in dilute hydrochloric acid solution;
(5) solution b is added in solution a, is stirred at room temperature, formed mixed solution, solution c is added to mixed solution In, continue to stir, final resulting mixed solution is added in the reaction kettle of polytetrafluoroethyllining lining, is then set reaction kettle Hydro-thermal reaction is carried out in baking oven, by gained precipitation and centrifugal separation, deionized water washing is dry, obtains Sn3[Fe(CN)6]4/ RGO precursor;
(6) step (5) resulting presoma program in nitrogen or argon atmosphere is warming up to calcination temperature, after calcining, obtained Ferro-tin alloy composite negative pole material, i.e. graphene/ferro-tin alloy composite negative pole material are loaded on graphene.
2. a kind of lithium ion battery graphene/ferro-tin alloy composite negative pole material preparation method according to claim 1, It is characterized by: the alcohol-water mixture is the mixed liquor or deionized water and second of deionized water and ethylene glycol in step (2) The mixed liquor of alcohol, the concentration of graphite oxide is 1-5 mg/mL in the graphene oxide dispersion.
3. a kind of lithium ion battery graphene/ferro-tin alloy composite negative pole material preparation method according to claim 1, It is characterized by: tetravalence pink salt used is SnCl in step (3)4·5H2O, concentration are 10-30 mg/mL, the block copolymerization Object surfactant is polyethers F127.
4. a kind of lithium ion battery graphene/ferro-tin alloy composite negative pole material preparation method according to claim 1, It is characterized in that, potassium ferricyanide solution concentration described in step (4) is 10-50 mg/mL.
5. a kind of lithium ion battery graphene/ferro-tin alloy composite negative pole material preparation method according to claim 1, It is characterized in that, graphite oxide in mixed solution described in step (5): tetravalence pink salt: the mass ratio of the potassium ferricyanide is 17: 80:100-68:80:100, hydrothermal temperature are 80-150 DEG C, and the reaction time is 10-24 h.
6. a kind of lithium ion battery graphene/ferro-tin alloy composite negative pole material preparation method according to claim 1, It is characterized in that, heating rate is 2-5 DEG C/min in step (6), calcination temperature is 600-800 DEG C, calcination time 1-3 h。
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CN107195884B (en) * 2017-06-01 2019-11-29 河南理工大学 A kind of lithium metasilicate doped graphene lithium ion battery negative material and preparation method thereof
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102800849A (en) * 2012-07-23 2012-11-28 浙江大学 Transition metal tin compound/graphene composite material and preparation method and application thereof
CN103290246A (en) * 2013-05-27 2013-09-11 南京师范大学 Preparation method of three-dimensional nano porous tin-base alloy for lithium-ion battery negative electrode

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102800849A (en) * 2012-07-23 2012-11-28 浙江大学 Transition metal tin compound/graphene composite material and preparation method and application thereof
CN103290246A (en) * 2013-05-27 2013-09-11 南京师范大学 Preparation method of three-dimensional nano porous tin-base alloy for lithium-ion battery negative electrode

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Facile synthesis of graphene supported FeSn2";Ya Ye等;《RSC Advances》;20140331;第4卷;全文 *
"Preparation and electrochemical performances of nanoscale";C.Q. Zhang等;《Journal of Alloys and Compounds》;20070312;第457卷;全文 *

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