CN104617300A - Method for preparing lithium ion battery anode/cathode material from reduced graphene oxide - Google Patents

Method for preparing lithium ion battery anode/cathode material from reduced graphene oxide Download PDF

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CN104617300A
CN104617300A CN201510065085.6A CN201510065085A CN104617300A CN 104617300 A CN104617300 A CN 104617300A CN 201510065085 A CN201510065085 A CN 201510065085A CN 104617300 A CN104617300 A CN 104617300A
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graphene oxide
lithium ion
graphene
ion battery
preparation
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李喜飞
李德军
熊东彬
鄯慧
董立天
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Tianjin Normal University
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Tianjin Normal University
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    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/23—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C01B32/192—Preparation by exfoliation starting from graphitic oxides
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 method for preparing a lithium ion battery anode/cathode material from reduced graphene oxide. The method comprises the following steps: performing ultrasonic dispersion on graphite oxide in an organic solvent, thereby obtaining a graphene oxide dispersion liquid; reducing by using an appropriate reducing agent or directly using a solvent, oxidizing graphene through oil bath backflow, a hydrothermal method or other reduction methods, thereby obtaining a reduced graphene oxide material containing part of oxygen-containing groups. When the prepared reduced graphene oxide material is used in a lithium ion battery anode material, a relatively high specific discharge capacity can be achieved, that is, is up to 280mAh/g, and good circulation stability and excellent rate performance are achieved. The prepared reduced graphene oxide material can be also used in a lithium ion battery cathode material, the specific discharge capacity can be kept being 900mAh/g and more than 900mAh/g after 100 rounds of charge/discharge circulation, and the circulation stability is relatively good. The method can be a significant study point of high-performance low-cost electrode materials of lithium ion batteries.

Description

A kind of method adopting redox graphene to prepare lithium ion battery plus-negative plate material
Technical field
The invention belongs to energy storage and transformation technology field, relate generally to a kind of method adopting redox graphene to prepare lithium ion battery plus-negative plate material.
Background technology
Lithium ion battery is a kind of mechanism of new electrochemical power sources that development in recent years is got up, it is the focus that countries in the world fall over each other to research and develop, it has the features such as volume is little, quality is light, specific energy is high, memory-less effect, long circulation life, has been widely used in the field such as mobile device, electric automobile energy.In each several part assembly of lithium ion battery, electrode material is core and the critical material of lithium ion battery.The quality of electrode material directly determines specific energy, the multinomial key performance such as cycle life and anti-load-bearing capacity of lithium ion battery.Therefore, develop high performance lithium ion battery and electrode material thereof, to the lifting of performance of lithium ion battery, especially the development significance of power-type lithium ion battery is great.In positive electrode, the more positive electrode of research mainly contains Li-Co-O system, Li-Ni-O system, Li-Mn-O system, ternary material and LiFePO at present 4deng material, although the development all obtained to a certain degree and practical application, but still have that actual specific capacity low (~ 160 mAh/g), cyclical stability are poor, the shortcoming such as resource-constrained, expensive and poor high rate performance.And current commercial lithium ion battery adopts cobalt acid lithium/graphite system mostly, due to this system material itself lower theoretical capacity restriction (graphite: 372 mAh/g), the requirement of ultra-thin mobile electronic product high-energy-density, high power density cannot be met, therefore, research and development Novel high-specific capacity flexible, high power density, low cost, environmentally friendly electrode material seem particularly necessary.
Graphene, by the tightly packed carbon atom monoatomic layer nano material formed of bi-dimensional cellular shape lattice, is considered to the basic composition unit of other each dimension material with carbon elements, has the performances such as good heat conduction, conduction, high strength and excellent electrochemical stability.Graphene has special stuctures and properties because of it, becomes international scientific study hotspot, and the Two-dimensional Carbon material of this monolayer carbon atomic thickness has high theoretical specific surface area (2630m 2/ g) and cellular void structure, in addition, the electron mobility of material itself reaches 15000cm 2/ (vs), conductive coefficient reaches 5300W/(mK), the character that good chemical stability etc. are excellent makes Graphene have good using value and wide application prospect in fields such as conductive film, storage lithium device, nano-sensor and composite materials.Wherein the application of Graphene in lithium ion battery also obtains extensive concern, the theoretical specific surface area high due to it and cellular void structure, thus has higher storage lithium ability.Graphene and being widely studied based on the lithium ion battery negative material such as composite material of Graphene.But the agglomeration existed in the cyclic process of Graphene negative material causes electrode structure to destroy, and makes its stable circulation be deteriorated; Although specific capacity is higher, complicated process of preparation, cost are higher, limit its practical application for the negative material (Sn base, Si base etc.) of Graphene compound.
The present invention has applied for the patent that name is called " a kind of preparation method of anode material for lithium-ion batteries functionalization graphene " in 2014, what mainly solved at that time is the functional modification to Graphene and the problem as lithium ion battery novel anode material thereof, but along with deepening continuously of research, find that more extensive and easy method prepares functionalization graphene, and it can have been applied to the problem of positive pole and negative material simultaneously.Therefore, on original basis, the present invention is completed further.
Summary of the invention
Technical problem to be solved by this invention overcomes the defect of current lithium ion battery plus-negative plate material and the development and utilization to Graphene premium properties, and the present invention is mainly lithium ion battery and provides a kind of and have excellent electrochemical performance and the with low cost Graphene electrodes material that can be used as lithium ion cell positive and negative pole.
The present invention utilizes the oxy radical of partial reduction surface of graphene oxide, as the active site generation redox reaction be combined with lithium ion, thus produces removal lithium embedded effect, can be used as positive electrode; The defective bit that the structural behaviour utilizing Graphene special and its Surface oxygen-containing groups provide, can significantly improve its storage lithium ability, can be used as negative material.Redox graphene prepared by the present invention all shows excellent chemical property as the positive and negative pole material of lithium ion battery.Of the present invention one large innovative point is that the graphene oxide of reduction simultaneously as lithium ion battery plus-negative plate material, and can all show excellent chemical property.
Preparating mechanism of the present invention is:
Oxidation-reduction method is utilized to prepare redox graphene, utilize strong oxidizer to be oxidized by native graphite as the concentrated sulfuric acid, potassium permanganate, make the oxygen-containing functional group that its Surface Creation is a large amount of, as carbonyl, epoxy radicals, hydroxyl and carboxyl, making its graphite layers apart from expanding simultaneously, obtaining graphite oxide product.Due to the existence of a large amount of oxy radical, graphite oxide conductivity is poor, thus causes poor chemical property.The present invention is intended to prepared graphite oxide partial reduction, remove most oxy radical thus improve its electric conductivity, retain a part of oxy radical and lithium ion generation redox reaction, as the avtive spot of deintercalate lithium ions, also provide defective bit simultaneously thus improve lithium storage content.
The present invention realizes by following technical scheme:
A preparation method for partial reduction graphene oxide, comprises the following steps:
A () prepares graphene oxide suspension: be dispersed in by a certain amount of graphite oxide in a certain amount of deionized water/organic solvent respectively, utilize the ultrasonic 10 ~ 120min of Ultrasonic cell smash, forming concentration is the graphene oxide suspension of 0.01 ~ 100mg/mL, then by above-mentioned suspension centrifugal 2 ~ 600min under the speed of 10000 revs/min, to remove possible impurity.
B () prepares the graphene oxide of partial reduction: can be divided into 2 kinds of methods: the hot method of (1) hydrothermal/solvent; (2) oil bath circumfluence method.
(1) by graphene oxide suspension prepared in step (a) and a certain amount of reducing agent Homogeneous phase mixing, be placed in polytetrafluoroethylene reactor, react 0.5 ~ 500h at 40 ~ 400 DEG C of temperature, namely obtain the graphite oxide ene product of partial reduction.
(2) by graphene oxide suspension prepared in step (a) and a certain amount of reducing agent Homogeneous phase mixing, be placed in there-necked flask, when magnetic agitation, 15 ~ 200 DEG C of oil bath backflow 0.5 ~ 500h, namely obtain the graphite oxide ene product of partial reduction.
The purifying of (c) redox graphene: partial reduction graphite oxide ene product prepared in step (b) two kinds of methods is spent ionized water/absolute ethyl alcohol filtering and washing, after the freezing 0.5 ~ 200h of the product obtained, be placed in the dry 0.5 ~ 200h of freeze drier.
Further: the graphite oxide used in step (a), be prepared by the Hummers method of modification, step is as follows: (1) takes 0.1 ~ 5g graphite powder and 0.05 ~ 5gNaNO respectively 3homogeneous phase mixing; Under ice-water bath condition, add the dense H of 3 ~ 100mL 2sO 4stir, and slowly add 0.5 ~ 20g KMnO 4stir 1 ~ 5 hour, stirred at ambient temperature, after 1 ~ 5 day, adds the H that 10 ~ 500mL concentration is 1% ~ 10% 2sO 4stir 0.5 ~ 5 hour; Adding 0.5 ~ 20mL hydrogen peroxide is stirred to till solution do not occur bubble;
(2) clean: with the HNO of 5% ~ 10% 3clean 2 ~ 4 times, then use the HNO of 1% ~ 5% 3clean 2 ~ 3 times; Add deionized water eccentric cleaning to pH=7, namely the forced air drying at normal temperature 25 DEG C of gained solution obtains graphite oxide.
Further: organic solvent selected in step (a) includes but are not limited to ethanol, ethylene glycol, glycerol, DMF and NMP, most wherein preferably is ethylene glycol.
Further: the concentration of the graphene oxide suspension formed in step (a) is 0.01 ~ 100mg/mL, is more preferably 0.5 ~ 5 mg/mL, be preferably 1 ~ 3 mg/mL the most.
Further: in step (b), reducing agent can be selected but be not limited only to hydrazine hydrate, sodium borohydride, potassium borohydride, hydroquinones, hydroiodic acid, ethylenediamine, natrium citricum, vitamin C, the consumption of reducing agent is 0.1 ~ 100:1 with graphite oxide consumption mass ratio ratio, is preferably 0.5 ~ 5:1.
Further: in step (b) in method (1), can to select not add reducing agent, utilize the reproducibility of water/organic solvent itself to carry out partial reduction to graphene oxide.
Further: in step (b) in method (2), can to select not add reducing agent, utilize organic solvent (alcohols, as: ethanol, ethylene glycol and glycerol) itself to carry out partial reduction to graphene oxide.
SEM(surface sweeping Electronic Speculum is carried out to the redox graphene prepared by the present invention), FTIR(infrared spectrum), XPS(X X-ray photoelectron spectroscopy X), Raman(Raman spectrum) etc. phenetic analysis, result is as follows:
SEM characterizes explanation: the feature structure by the known prepared redox graphene pattern of SEM being many folds flaky texture, composite reduction graphene oxide.
Infrared spectrum FTIR characterizes explanation: the redox graphene remained on surface after partial reduction has the more oxygen-containing functional group be not reduced.
XPS(X X-ray photoelectron spectroscopy X) characterize explanation: prepared redox graphene material surface remains the oxygen-containing functional group of part, is mainly the groups such as hydroxyl, carbonyl, epoxy radicals and carboxyl.
Raman(Raman spectrum) characterize explanation: the redox graphene being rich in oxygen-containing functional group has more defective bit, and its degree of order comparatively graphite is low.
Emphasis of the present invention solves:
(1) the Hummers legal system improved is for high-quality graphite oxide.
(2) liquid phase method of multiple environmental protection and low cost can be adopted to carry out controlled reduction to graphite oxide, reserve part oxy radical, by controlling the reducing degree of graphene oxide thus regulating and controlling the quantity of its Surface oxygen-containing groups and optimize its conductivity, thus improve its chemical property.
(3) graphene oxide of controlled partial reduction is applied to anode material for lithium-ion batteries and negative material, finds the key factor affecting its battery performance.
The present invention further discloses the application utilizing the redox graphene prepared by above-mentioned preparation method as lithium ion battery plus-negative plate material aspect.The result display of test:
(1) graphene oxide of partial reduction is applied to anode material for lithium-ion batteries, utilizes oxy radical as the avtive spot of removal lithium embedded, show very excellent chemical property.
(2) graphene oxide of partial reduction is applied to lithium ion battery negative material, the storage lithium advantage of the defective bit utilizing oxy radical to provide and redox graphene structure, show very excellent chemical property, its reversible capacity and cyclical stability excellence are in current commercial graphite and pure Graphene negative material.
(3) when functionalization graphene is as lithium ion battery plus-negative plate material, the oxy radical on its surface is more, the defective bit provided and embedding lithium avtive spot more, its lithium storage content is larger, but the too much oxygen content conductivity that causes it poor thus reduce its chemical property, by regulating and controlling reducing degree comprehensive regulation its oxy radical quantity and conductivity of graphene oxide, thus optimize its chemical property.
The present invention respectively using prepared redox graphene as positive pole, negative electrode active material, and natural carbon black, binding agent PVDF(Kynoar) in certain proportion (8:1:1) be prepared into lithium ion cell positive and negative material.
The step of preparation is:
(1) electrode active material, natural carbon black, binding agent PVDF(Kynoar is taken respectively according to the ratio of 8:1:1) carry out mixing and fully grinding (time 3h);
(2) above-mentioned pasty mixture is spread evenly across on aluminium foil and Copper Foil respectively, wherein coats on aluminium foil to obtain anode pole piece, coat on Copper Foil to obtain cathode pole piece.Vacuumize 12h at 100 DEG C;
(3) have the aluminium foil of electrode material and Copper Foil to be cut into the electrode slice of required size above-mentioned load respectively, in glove box, be assembled into buckle type electrochemical simulation half-cell, wherein comparison electrode is metal lithium sheet.
As follows to the electrochemical property test of electrode material:
Anode pole piece is assembled in glove box CR2032 type button simulation half-cell, carries out constant current charge-discharge test, to test its reversible specific capacity and cycle performance.Test condition is: voltage range: 1.5 ~ 4.5V; Current density: 50 mA/g; The circulation number of turns: 100 circles.
Cathode pole piece is assembled in glove box CR2032 type button simulation half-cell, carries out constant current charge-discharge test, to test its reversible specific capacity and cycle performance.Test condition is: voltage range: 0.01 ~ 3V; Current density: 100 mA/g; The circulation number of turns: 100 circles.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages and innovates:
(1) adopt native graphite to be raw material, with low cost, adopt improvement Hummers method to prepare redox graphene (RGO) Stability Analysis of Structures of partial reduction in conjunction with simple hydro thermal method and solvent-thermal method, quality is higher.
(2) green reducing agents such as water, ethylene glycol, natrium citricum can be selected, environmental protection and economy, the prepared reducing degree of redox graphene (RGO) and the quantity of the oxy radical on surface adjustable controlled.
(3) RGO prepared by contains abundant oxygen-containing functional group (carbonyl, hydroxyl, carboxyl etc.), when being applied to anode material for lithium-ion batteries, there is higher specific discharge capacity, excellent high rate performance and good cyclical stability (after 100 circles that circulate under 50mA/g current density, reversible specific capacity keeps 250 more than mAh/g), be better than current business cobalt acid lithium material (actual capacity 140 mAh/g); (4) when the RGO prepared by is applied to lithium ion battery negative material, due to a large amount of existence of its defective bit and the architectural feature of its three-dimensional, show the reversible specific capacity being better than commercial graphite material and Graphene negative pole, and its cyclical stability is greatly improved, (after 100 circles that circulate under 100mA/g current density, reversible specific capacity reaches 900 mAh/g.
Accompanying drawing illustrates:
Fig. 1 a, b, c are respectively the SEM(ESEM of the redox graphene of graphene oxide, reduction of ethylene glycol graphene oxide and aqueous solvent hydrothermal reduction) figure, Fig. 1 d is the TEM(transmission electron microscope of the redox graphene of aqueous solvent hydrothermal reduction) figure; The flaky texture that graphene oxide is many folds can be observed, redox graphene sheet after partial reduction is thinning to diminish, and present the hole shape structure of many nanometers to micron level, TEM figure is shown as transparent tulle shape structure, has the typical shape characteristic of Graphene.
Fig. 2 is infrared spectrum (FTIR) figure of redox graphene and graphene oxide, be the test result of graphite oxide (GO) that embodiment 1 uses and prepared redox graphene sample, can find out that redox graphene surface oxygen functional group compares the rare a large amount of minimizing of graphite oxide, but obtain the reservation of part, can find out simultaneously and extend the hydro-thermal reaction time, reducing degree can be higher, and residual oxy radical is fewer.
The full spectrogram of XPS of the three kind samples of Fig. 3 prepared by embodiment 1, can find out the prolongation along with the hydro-thermal reaction time, and oxygen content reduces, and this is the same with the result of FTIR test.
Fig. 4 a is embodiment 4 graphene oxide used (GO) and three kinds of redox graphene (RGO) samples cycle performance curve chart as anode material for lithium-ion batteries.Wherein RGO-I is the sample of hydrothermal reduction 1h, RGO-II is the sample of hydrothermal reduction 6h, RGO-III is the sample of hydrothermal reduction 12h, and can find out that graphene oxide is lower as its specific discharge capacity of positive electrode, the graphene oxide that cycle performance compares partial reduction is poor; And show high specific capacity through the redox graphene of aqueous solvent thermal reduction, and stable circulation performance is excellent; And the oxygen-containing functional group that the surface of graphene oxide of its reduction contains is more, and its specific capacity is larger, the sample RGO-I specific capacity of 1h reduction reaches 280mAh/g, and cyclical stability is fine.
Charging and discharging curve figure when Fig. 4 b is sample RGO-I test high rate performance in embodiment 4, charging and discharging currents density is respectively 50mA/g, 100mA/g, 200mA/g, 400mA/g, when current density is 400 mA/g, its reversible discharge specific capacity still reaches 175 mAh/g, show very excellent high rate performance, can high current charge-discharge be realized.
3 samples that Fig. 5 tests for embodiment 5 are as the cycle performance curve chart of lithium ion battery negative material.Can find out that the sample RGO-II of 6h hydrothermal reduction shows performance the most excellent, its first circle specific discharge capacity reaches 2560 mAh/g, although initially several irising out has showed irreversible capacity, but after being through 100 circle charge and discharge cycles, its specific discharge capacity is still stabilized in 900 more than mAh/g, has excellent storage lithium performance and cyclical stability.
Embodiment
Following embodiment is convenient to understand the present invention better, but does not limit the present invention.Experimental technique in following embodiment, if no special instructions, is conventional method.The natural carbon black of test material used in following embodiment, binding agent PVDF all have commercially available, and other are reagent shop and purchase available if no special instructions.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
First example: (1) first step, improvement Hummers legal system is for graphite oxide: 1, take 1g graphite powder and 0.5gNaNO respectively 3homogeneous phase mixing; 2, under ice-water bath condition, the dense H of 5mL is added 2sO 4stir, and slowly add 1.5g KMnO 4stir 1 hour; 3, stirred at ambient temperature is after 5 days, adds the H that 50mL concentration is 5% 2sO 4stir 1 hour; 4, appropriate (about 3mL) hydrogen peroxide (H is added 2o 2) be stirred to till solution do not occur bubble; 5, clean, with the HNO of 10% in the large beaker of 4000mL 3clean 2 times, then use the HNO of 5% 3clean 2 times; 6, add deionized water eccentric cleaning to pH=7, namely the forced air drying at normal temperature 25 DEG C of gained solution obtains graphite oxide.
2nd example: (2) first step, improvement Hummers legal system is for graphite oxide: 1, take 5g graphite powder and 5gNaNO respectively 3homogeneous phase mixing; 2, under ice-water bath condition, the dense H of 100mL is added 2sO 4stir, and slowly add 20g KMnO 4stir 5 hours; 3, stirred at ambient temperature is after 2 days, adds the H that 500mL concentration is 2% 2sO 4stir 5 hours; 4, appropriate (about 20mL) hydrogen peroxide (H is added 2o 2) be stirred to till solution do not occur bubble; 5, clean, with the HNO of 5% in the large beaker of 4000mL 3clean 4 times, then use the HNO of 3% 3clean 3 times; 6, add deionized water eccentric cleaning to pH=7, namely the forced air drying at normal temperature 25 DEG C of gained solution obtains graphite oxide.
Second step, aqueous solvent hydrothermal reduction graphene oxide: the graphite oxide 1, prepared fully grinds the powder (graphite oxide) obtaining brown color; 2, taking a certain amount of graphite oxide powder is scattered in a certain amount of deionized water, and obtaining concentration through Ultrasonic cell smash ultrasonic stripping 30min is the graphene oxide dispersion of 3mg/mL; 3, by above-mentioned dispersion liquid centrifugal 30min under the rotating speed of 10000 revs/min in centrifuge, the centrifugal impurity got off is removed; 4, the graphene oxide dispersion measuring 40mL is respectively placed in the polytetrafluoroethylene reactor of 3 50mL capacity, and 3 reactors react 1h, 6h and 12h respectively at 180 DEG C of temperature; 5, after the freezing 12h of the product obtained, in vacuum freeze drier, namely dry 24h obtains redox graphene (RGO) product, respectively called after RGO-I, RGO-II and RGO-III.
Embodiment 2
The first step is with embodiment 1 first example: (1)
Second step, natrium citricum oil bath circumfluence method redox graphene: the graphite oxide 1, prepared fully grinds the powder (graphite oxide) obtaining brown color; 2, taking 200mg graphite oxide powder is scattered in the deionized water of 100mL, and obtaining concentration through Ultrasonic cell smash ultrasonic stripping 30min is the graphene oxide dispersion of 2mg/mL; 3, by above-mentioned dispersion liquid centrifugal 40min under the rotating speed of 10000 revs/min in centrifuge, the centrifugal impurity got off is removed; 4, taking 2g natrium citricum adds in above-mentioned graphene oxide dispersion, when vigorous stirring in oil bath pan back flow reaction 12h at 80 DEG C of temperature; 5, above-mentioned product deionized water is detached washing, after the freezing 12h of product, in vacuum freeze drier, namely dry 24h obtains redox graphene (RGO) product.
Embodiment 3
The first step is with embodiment 1 first example: (2)
Second step, sodium borohydride reduction graphene oxide: the graphite oxide 1, prepared fully grinds the powder (graphite oxide) obtaining brown color; 2, taking 50mg graphite oxide powder is scattered in the deionized water of 100mL, and obtaining concentration through Ultrasonic cell smash ultrasonic stripping 15min is the graphene oxide dispersion of 0.5mg/mL; 3, by above-mentioned dispersion liquid centrifugal 20min under the rotating speed of 10000 revs/min in centrifuge, the centrifugal impurity got off is removed; 4, taking 0.1g sodium borohydride adds in above-mentioned graphene oxide dispersion, when vigorous stirring in room temperature reaction 6h; 5, above-mentioned product deionized water is detached washing, after the freezing 12h of product, in vacuum freeze drier, namely dry 24h obtains redox graphene (RGO) product.
Embodiment 4
Electrode preparation and electrochemical property test
The first step, the graphene oxide of employing prepared by embodiment 1 and the method for different redox graphene sample preparation anode material for lithium-ion batteries:
Respectively by the graphene oxide prepared by embodiment 1, redox graphene RGO-I, RGO-II, RGO-III and natural carbon black, binding agent PVDF(Kynoar) in certain proportion (mass ratio 8:1:1) be prepared into anode material for lithium-ion batteries, detailed method is:
(1) take graphene oxide GO 0.032g respectively according to the ratio of 8:1:1, natural carbon black 0.004g, binding agent PVDF0.004g add a small amount of solvent NMP (1-Methyl-2-Pyrrolidone) and carry out mixing and fully grinding (time 2h), obtain pastel A; Pastel I, II and III is obtained with redox graphene RGO-I, RGO-II and RGO-III respectively according to the step preparing pastel A;
(2) respectively above-mentioned pasty mixture is coated on aluminium foil, vacuumize 12h at 100 DEG C;
(3) have the aluminium foil of electrode material to be cut into the electrode slice of required size above-mentioned load, obtain 4 kinds of anode pole pieces, vacuumize 12h at 80 DEG C, be assembled into CR2025 type button cell respectively in glove box, wherein comparison electrode is lithium sheet.
Carry out the test of constant current charge-discharge cycle performance to above-mentioned button cell, concrete charging/discharging voltage scope is 1.5 ~ 4.5V, and charging and discharging currents is 50mA/g, and its result is as shown in accompanying drawing 4a.
Carry out high rate performance test to the button cell that redox graphene RGO-I forms, concrete charging/discharging voltage scope is 1.5 ~ 4.5V, and charging and discharging currents is followed successively by 50mA/g, 100mA/g, 200mA/g, 400mA/g, under its different current density, charging and discharging curve as depicted in fig. 4b.
Embodiment 5
Electrode preparation and electrochemical property test
The first step, adopts the method for the different redox graphene sample preparation lithium ion battery negative materials prepared by embodiment 1:
Respectively by redox graphene RGO-I, RGO-II, the RGO-III prepared by embodiment 1 and natural carbon black, binding agent PVDF(Kynoar) in certain proportion (mass ratio 8:1:1) be prepared into lithium ion battery negative material, detailed method is:
(1) take redox graphene RGO-I 0.04g respectively according to the ratio of 8:1:1, natural carbon black 0.005g, binding agent PVDF0.005g add a small amount of solvent NMP (1-Methyl-2-Pyrrolidone) and carry out mixing and fully grinding (time 2h), obtain pastel I; Pastel II and III is obtained with redox graphene RGO-II and RGO-III respectively according to the step preparing pastel I.
(2) respectively above-mentioned pasty mixture is coated on Copper Foil, vacuumize 12h at 100 DEG C;
(3) have the Copper Foil of electrode material to be cut into the electrode slice of required size above-mentioned load, obtain 3 kinds of cathode pole pieces, vacuumize 12h at 80 DEG C, be assembled into CR2025 type button cell respectively in glove box, wherein comparison electrode is lithium sheet.
Carry out the test of constant current charge-discharge cycle performance respectively to above-mentioned button cell, concrete charging/discharging voltage scope is 0.01 ~ 3V, and charging and discharging currents is 100mA/g, and its cycle performance and specific discharge capacity are as shown in Figure 5.
Embodiment 6
Electrode preparation and electrochemical property test
The first step, adopts the method for redox graphene (RGO) the sample preparation anode material for lithium-ion batteries prepared by embodiment 2: prepare positive electrode method with embodiment 4 the same.
Second step, the assembling of battery and electrochemical property test, the same manner as in Example 4.Its cycle performance and high rate performance excellence.
By the enforcement of above embodiment, can reach a conclusion is:
(1) redox graphene prepared by the present invention can be used as the application of lithium ion battery plus-negative plate material.
(2) during the application of redox graphene as anode material for lithium-ion batteries, along with the oxygen-containing functional group on its surface increases, its specific capacity improves, and cyclical stability is better, and the key influence factor that its specific capacity known increases is that the oxygen-containing functional group on surface increases.
(3) during the application of redox graphene as lithium ion battery negative material, the oxygen-containing functional group on its surface and defect potential energy improve lithium storage content, and the electric conductivity of material is also a crucial influencing factor.
(4) the present invention has prepared the lithium ion both positive and negative polarity grapheme material had compared with height ratio capacity and excellent cycle performance and high rate performance, this to promote high performance lithium ion battery development and solve energy shortage etc. and have great importance.
The above embodiment only have expressed several better embodiment of the present invention; it describes comparatively concrete and detailed; but therefore can not be interpreted as the restriction to scope of patent protection of the present invention, the protection range of patent of the present invention is because being as the criterion with depended on claim.

Claims (8)

1. adopt redox graphene to prepare a method for lithium ion battery plus-negative plate material, it is characterized in that being undertaken by following step:
(1) Hummers legal system is improved for graphite oxide:
1) 0.1 ~ 5g graphite powder and 0.05 ~ 5gNaNO is taken respectively 3homogeneous phase mixing;
2), under ice-water bath condition, the dense H of 3 ~ 100mL is added 2sO 4stir, and slowly add 0.5 ~ 20g KMnO 4stir 0.5 ~ 5 hour;
3) stirred at ambient temperature is after 1 ~ 5 day, and adding 10 ~ 500mL concentration is 1% ~ 10%(w/w) H 2sO 4stir 0.5 ~ 5 hour;
4) adding 0.5 ~ 20mL hydrogen peroxide is stirred to till solution do not occur bubble;
5) clean, with 5% ~ 10%(w/w in beaker) HNO 3clean 2 ~ 4 times, then use 1% ~ 5%(w/w) HNO 3clean 2 ~ 3 times;
6) add deionized water eccentric cleaning to pH=7, namely the forced air drying at normal temperature 25 DEG C of gained solution obtains graphite oxide;
(2) by graphite oxide ultrasonic disperse in water/organic solvent, obtain graphene oxide dispersion; Select suitable reducing agent reduction, by oil bath backflow, hydro thermal method or other reducing process redox graphene, obtain and carry part oxy radical redox graphene material;
(3) freeze drying is carried out to preceding product, obtain solid reduction graphite oxide ene product.
2. preparation method according to claim 1, is characterized in that: in step (2), and described organic solvent is ethanol, ethylene glycol, glycerol, DMF(dimethyl formamide), NMP(N-methyl pyrrolidone), acetic acid or n-butanol.
3. preparation method according to claim 1, is characterized in that: in step (2), and described reducing agent is hydrazine hydrate, sodium borohydride, potassium borohydride, hydroquinones, hydroiodic acid, ethylenediamine, natrium citricum, vitamin C, glucose, ammoniacal liquor or urea.
4. preparation method according to claim 1, is characterized in that: in step (2), and the concentration of middle formed graphene oxide suspension is 0.01 ~ 100mg/mL.
5. preparation method according to claim 1, is characterized in that: in step (2), and the consumption of reducing agent is 0.1 ~ 1000:1 with graphite oxide consumption mass ratio ratio.
6. preparation method according to claim 1, is characterized in that: as selected bath oiling in step (2), its reaction temperature is 15 ~ 200 DEG C.
7. preparation method according to claim 1, is characterized in that: as selected hydro thermal method in step (2), its reaction temperature is 40 ~ 400 DEG C.
8. the redox graphene adopting claim 1 method to prepare is for the preparation of the application of anode material for lithium-ion batteries and negative material aspect.
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CN110828194B (en) * 2019-11-06 2021-05-28 蚌埠学院 Method for preparing layered beta-nickel hydroxide/graphene material by utilizing induction effect of surface charge
CN110828194A (en) * 2019-11-06 2020-02-21 蚌埠学院 Method for preparing layered β -nickel hydroxide/graphene material by utilizing induction effect of surface charge
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US11961667B2 (en) 2021-05-27 2024-04-16 The Regents Of The University Of California Devices and methods for high voltage and solar applications
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