CN103579632A - Graphene composite negative current collector, preparation method thereof and lithium ion battery - Google Patents

Graphene composite negative current collector, preparation method thereof and lithium ion battery Download PDF

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Publication number
CN103579632A
CN103579632A CN201210257717.5A CN201210257717A CN103579632A CN 103579632 A CN103579632 A CN 103579632A CN 201210257717 A CN201210257717 A CN 201210257717A CN 103579632 A CN103579632 A CN 103579632A
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graphene
negative pole
composite negative
graphene composite
collector
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周明杰
吴凤
王要兵
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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

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Abstract

The invention discloses a graphene composite negative current collector, a preparation method thereof and a lithium ion battery. The graphene composite negative current collector comprises a graphene thin-film layer and a metal oxide layer combining with the surface of the graphene thin-film layer, and the metal oxide in the metal oxide layer is at least one of Cr2O3, MnO2, V2O5 and TiO2. The graphene composite negative current collector is high in mechanical strength and light in weight, and also is capable of effectively preventing lithium ions from being embedded in the graphene thin-film layer, avoiding generation of irreversible capacity and further improving the capacity. The preparation method is simple in technology, easily controllable in conditions and low in equipment requirements.

Description

Graphene composite negative pole collector and preparation method thereof, lithium ion battery
Technical field
The invention belongs to electrochemical power source technical field, specifically relate to a kind of Graphene composite negative pole collector and preparation method thereof, lithium ion battery.
Background technology
Collector is a kind of structure or part that collects electric current, and major function is that the electric current that cell active materials is produced collects, and electron channel is provided, and accelerates electric charge and shifts, and improves and discharges and recharges a coulomb efficiency.As collector, need to meet the features such as conductivity is high, good mechanical property, quality is light, internal resistance is little.
As collector, need quality light, because the influencing factor of the energy density of battery mainly contains the capacity of electrode material, the voltage of system and electrode material account for the proportion of the total weight of electrode active material layer, collector, sheathing material composition.Therefore, increase the performance that the energy-storage property of electrode material and the weight of each composition material of reduction device can effectively improve device.Wherein, the quality of reduction collector is a method that effectively improves energy density.In addition, while using as collector, need it can not embedding lithium, once because embedding lithium in collector, it be irreversible, the capacity that greatly reduces whole battery with and cycle performance; Because collection liquid surface carries electrode active material and contacts electrolyte, need it in electrolyte, to there is stability.If it is more perishable and dissolve at electrolyte, can cause the contact resistance between itself and electrode active material to enlarge markedly, affect the power density of battery, electrolyte is contaminated, affects the life-span of battery.
At present, in most document or in industry, anodal aluminium foil, the negative pole of adopting of general collector adopts Copper Foil.Because the density of metal collector is larger, quality is heavier, and the weight of general collector accounts for 20～25% of whole battery, and the proportion that electrode material accounts for whole battery greatly reduces, and finally causes the energy density of battery lower.Meanwhile, metal material is easily corroded, and then has affected the useful life of battery.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, provide a kind of quality light, not embedding lithium, and the Graphene composite negative pole collector that is difficult for being corroded.
Another object of the present invention is to provide a kind of technique simple, efficiency is high, the preparation method of the Graphene composite negative pole collector being easy to operate and control.
A further object of the present invention is to provide energy density high, the lithium ion battery of long service life.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A composite negative pole collector, the metal oxide layer that it comprises graphene film layer and is combined in described graphene film layer surface, the metal oxide in described metal oxide layer is Cr 2o 3, MnO 2, V 2o 5or TiO 2in at least one.
And a kind of preparation method of Graphene composite negative pole collector, comprises the steps:
Graphene suspension is adopted to miillpore filter vacuum filtration, by separated miillpore filter after filtration cakes torrefaction, obtain graphene film;
Using described graphene film as work electrode, be placed in and contain the alkaline electrolyte that concentration is the slaine of 0.25～0.5mol/L, in current density, be 0.5～3mA/cm 2constant current effect under electro-deposition 5～10min; Wherein, described slaine is for containing the slaine of Cr ion, slaine or the VO of the slaine of Mn ion, Ti ion 3at least one in the slaine of ion;
By the graphene film washing after electro-deposition, dry after, be placed in the environment of the gas that is full of inertia and at the temperature of 400～800 ℃ reductase 12～8 hour, cooling, obtain described Graphene composite negative pole collector.
The present invention also provides a kind of lithium ion battery, and this lithium ion battery comprises positive pole, battery diaphragm and the negative pole stacking gradually, and the collector of described negative pole is above-mentioned Graphene composite negative pole collector.
Above-mentioned Graphene composite negative pole collector is usingd graphene film layer as matrix, effectively strengthened the mechanical strength of this Graphene composite negative pole collector, reduced its weight, also make this Graphene composite negative pole collector there is excellent heat conductivility and electric conductivity simultaneously, and chemically stable, not perishable, long service life.At the metal oxide layer of this graphene film layer surface conjunction, can effectively protect lithium ion not embed in graphene film layer, avoid causing the generation of irreversible capacity, and then raising capacity.
The preparation method of above-mentioned Graphene composite negative pole collector only need first prepare graphene film, then adopts electrodeposition process at this graphene film surface electrical precipitation layer of metal oxide, and its technique is simple, condition is easily controlled, low for equipment requirements, production efficiency, production cost is low, is suitable for suitability for industrialized production.In addition, adopt electrodeposition process, make metal oxide Direct precipitation on graphene film surface, make the metal oxide layer even thickness generating, and be combined with graphene film firmly, the mechanical strength that has strengthened Graphene composite negative pole collector, prevents coming off of metal oxide layer, has extended the useful life of Graphene composite negative pole collector.
Above-mentioned lithium ion battery is owing to containing above-mentioned Graphene composite negative pole collector, and therefore, the heat conductivility of this Graphene composite negative pole collector, chemically stable and uncorruptible performance make this lithium ion battery safety, long service life; This Graphene composite negative pole collector is with graphene film substituted metal collector, and its performance lightweight and not embedding lithium has effectively guaranteed the capacity of lithium ion battery, has improved the energy density of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is a kind of structural representation of embodiment of the present invention Graphene composite negative pole collector;
Fig. 2 is embodiment of the present invention Graphene composite negative pole collector preparation method's process chart.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Example of the present invention provides a kind of quality light, not embedding lithium, and the Graphene composite negative pole collector that is difficult for being corroded, and its structure is as shown in Figure 1.In Fig. 1, this Graphene composite negative pole collector comprises graphene film layer 1 and is combined in the two-sided metal oxide layer of graphene film layer 12.Wherein, the metal oxide in metal oxide layer is Cr 2o 3, MnO 2, V 2o 5or TiO 2in at least one.
Specifically, the thickness of above-mentioned metal oxide layer 2 is 1～3 μ m, is preferably 2 μ m.The metal oxide layer 2 of this preferred thickness can also effectively reduce the weight of Graphene composite negative pole collector in better protection lithium ion does not embed graphene film layer, avoids this Graphene composite negative pole collector conductance to have a negative impact.
The thickness of above-mentioned graphene film layer 1 is preferably 3～10 μ m, more preferably 5 μ m.In a preferred embodiment, above-mentioned metal oxide layer 2 adopts hereinafter mode and this graphene film layer 1 combination of described electro-deposition.Adopt electrodeposition process by metal oxide layer 2 Direct precipitations on graphene film 1 surface, make metal oxide layer 2 even thickness, and firm with graphene film 1 combination, strengthened the mechanical strength of Graphene composite negative pole collector, prevent coming off of metal oxide layer 2, extended the useful life of Graphene composite negative pole collector.
From the above mentioned, Graphene composite negative pole collector in above-described embodiment is usingd graphene film layer 1 as matrix, effectively strengthened the mechanical strength of this Graphene composite negative pole collector, reduced its weight, also make this Graphene composite negative pole collector there is excellent heat conductivility and electric conductivity simultaneously, and chemically stable, not perishable, long service life.At the metal oxide layer 2 of this graphene film layer 1 surface conjunction, can effectively protect lithium ion not embed in this Graphene thin layer, avoid causing the generation of irreversible capacity, and then improve battery capacity.
Example of the present invention also provides a kind of technique simple, and efficiency is high, the preparation method of the Graphene composite negative pole collector being easy to operate and control.Preparation method's technological process of this Graphene composite negative pole collector refers to Fig. 2, refers to Fig. 1 simultaneously, comprises the steps:
The preparation of step S01. graphene film: graphene suspension is adopted to miillpore filter vacuum filtration, by separated miillpore filter after filtration cakes torrefaction, obtain graphene film 1;
Step S02. adopts electrodeposition process to prepare metal oxide layer 2: step S01 being prepared to graphene film 1 as work electrode, be placed in and contain the alkaline electrolyte that concentration is the slaine of 0.25～0.5mol/L, is 0.5～3mA/cm in current density 2constant current effect under electro-deposition 5～10min; Wherein, the slaine in electrolyte is for containing the slaine of Cr ion, slaine or the VO of the slaine of Mn ion, Ti ion 3at least one in the slaine of ion;
Step S03. high temperature reduction is prepared Graphene composite negative pole collector: after 1 washing of the graphene film after step S02 electro-deposition, being dried, be placed in environment reductase 12～8 hour at the temperature of 400～800 ℃ of the gas that is full of inertia, cooling, obtain described Graphene composite negative pole collector.
Particularly, in above-mentioned steps S01, the concentration of graphene suspension has no particular limits, and the concentration of this graphene suspension can be high or low, and can adjust flexibly according to actual conditions.As when its concentration is low, in order to obtain as the graphene film of 3～10 μ m thickness, can the large graphene suspension of dose volume number; When its concentration is high, in order to prepare the graphene film of 3～10 μ m thickness, can the little graphene suspension of dose volume number.Wherein, this graphene suspension preferably obtains as follows:
Step S011: graphite oxide is added in solvent, and ultrasonic 0.5～1 hour, being mixed with concentration is the graphene oxide suspension of 0.25～1mg/ml;
Step S012: after the pH for preparing graphene oxide suspension in step S011 is adjusted to 10～11, add hydrazine hydrate, react at the temperature of 80～100 ℃ 12～24 hours, obtain graphene suspension; Wherein, the mass ratio of hydrazine hydrate and graphene oxide is 1:10～7:10.
Particularly, in this step S011, solvent is preferably deionized water, can certainly select the organic solvents such as ethanol, isopropyl alcohol, propyl alcohol.Graphite oxide can be commercial or preparation voluntarily, if while preparing voluntarily, its preferably but not only by the method for being prepared as follows, obtain:
Step 1): by graphite powder, potassium permanganate and the concentrated sulfuric acid according to 1 (g): 2～4 (g): the addition of 15～31 (ml) is mixed at the temperature lower than 10 ℃, obtains mixed solution;
Step 2): at room temperature (20 ℃～25 ℃) water-bath mixed solution, stir after 20～48h again, under condition of ice bath, in mixed solution, add deionized water, then add the deionized water solution that contains hydrogen peroxide to remove the complete potassium permanganate of unreacted, finally carry out Separation of Solid and Liquid, washing, obtain graphite oxide.
In one embodiment, this graphite oxide preparation method step:
0.5g500 order graphite powder is added in 0 ℃, the concentrated sulfuric acid of 11.5mL, add again 1.5g potassium permanganate, the temperature of mixture remains on below 10 ℃, stir 2h, then in room-temperature water bath, stir after 24h, under condition of ice bath, slowly add 46mL deionized water, after 15min, then add 140mL deionized water (wherein contain 2.5mL concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration, again with the hydrochloric acid that 250ml concentration is 10% wash, suction filtration, until filtrate is neutral, suction filtration, dry, obtain graphite oxide.
In the preparation method of above-mentioned graphite oxide, graphite powder can make natural graphite powder, expanded graphite powder etc.In addition, consider the size of Graphene in order to improve speed prepared by graphite oxide, the particle diameter of graphite powder is preferably 500 orders left and right and is advisable simultaneously.Certainly, this graphite oxide also can be bought acquisition in market.
In this step S012, under the condition that is 10～11 at 80～100 ℃ of temperature and pH, hydrazine hydrate and graphene oxide generation reduction reaction, remove the contained chemical groups such as part carboxy CO OH, hydroxyl OH, carbonyl C=O and epoxy radicals of graphene oxide, obtains Graphene.Wherein, the temperature of this reduction reaction is preferably 100 ℃; PH regulates and preferably adopts ammoniacal liquor.Certainly, except adopting ammoniacal liquor, also can adopt NaOH, potassium hydroxide etc. to regulate the pH of this reduction reaction.
In above-mentioned steps S01, vacuum degree during miillpore filter vacuum filtration is according to conventional condition.The filter cake obtaining after filtration is before being dried, preferably to its washing, to remove the impurity remaining in Graphene filter cake.The dry employing conventional drying of filter cake, as dry or low temperature drying, the temperature while adopting low temperature drying can be but be not only 40 ℃, to accelerate the dry of filter cake, shortens the time prepared by graphene film.After filtration cakes torrefaction, separation is also removed miillpore filter, obtains graphene film 1.
In above-mentioned steps S02, there is electrochemical reaction in the slaine in electrolyte under the effect of electric current, produces metal oxide.Wherein the slaine of Cr ion is preferably Cr (NO 3) 3.9H 2o, Cr (CH 3cOOH) 3in one or both; The slaine of Mn ion is preferably Mn (CH 3cOOH) 2; MnSO 4h 2in O one or both; The slaine of Ti ion is preferably TiCl 4, TiI 4or TiBr 4in one or more; The slaine of V ion is preferably NH 4vO 3, NaVO 3or KVO 3in one or more.As in electrochemical reaction, Cr (NO 3) 3.9H 2o generates Cr through electrochemical reaction 2o 3, Mn (CH 3cOOH) 2generate MnO 2, TiCl 4generate TiO 2, NH 4vO 3generate V 2o 5.And the oxide generating is deposited on graphene film 1 surface, form metal oxide layer 2.
In addition, at the pH of this alkaline electrolyte, be preferably 10～11, the electrochemical reaction forward that this pH scope is more conducive in electrodeposition process carries out.Therefore in a preferred embodiment, in order to adjust the pH of electrolyte, to adding concentration in above-mentioned electrolyte, be, the KOH of 0.1M.
Therefore, in one embodiment, the method that electrodeposition process in this step S02 is prepared metal oxide layer 2 is as follows: using the graphene film of preparing in above-mentioned steps S01 1 as work electrode, calomel electrode is made reference electrode, platinum electrode is made auxiliary electrode, under room temperature (20 ℃～25 ℃), this work electrode, reference electrode, auxiliary electrode are placed in to electrolyte, and according to the requirement of electro-deposition, each electrode is electrically connected to power supply, then power-on, under the effect of constant current, after electro-deposition 8min, obtain metal oxide/graphene film collector.Wherein, electrolyte contains metal salt solution and the 0.1M KOH solution that concentration is 0.3mol/L, and the current density that constant current is provided by galvanostat is 1.25mA/cm 2constant current.This embodiment, by the adjustment to technological parameter, makes the formed metal oxide layer even thickness of electro-deposition, and electrodepositing speed is high, and metal oxide layer 2 is firm with graphene film 1 combination.
In above-mentioned steps S03, effects on surface electro-deposition has the mode that the graphene film of metal oxide layer 2 washs directly to adopt deionized water to rinse it, to remove the metal oxide layer 2 remaining electrolyte in surface.
Surface electrical to this after washing deposits the dry mode of the graphene film of metal oxide layer 2 preferably first after naturally drying, and then vacuum bakeout is 1～3 hour.This vacuum bakeout, to reach further dewatered object, avoids Graphene oxidized in bake process simultaneously.
In this step S03, the graphene film that surface electrical deposits metal oxide layer 2 under the high temperature of 400～800 ℃ with the gas generation reduction reaction of inertia.By reduction reaction, residual as chemical groups such as carboxy CO OH, hydroxyl OH, carbonyl C=O further to remove in Graphene.
This step S03 in this reduction reaction process, the temperature of heating is preferably warming up to 400 ℃～800 ℃ with the rate of heat addition of 10 ℃/min, and keeps 2～8 hours at these 400 ℃～800 ℃, is preferably and keeps 2～4 hours, carries out reduction reaction.Adopt the rate of heat addition of 10 ℃/min, guarantee the complete of graphene film, avoid causing too soon owing to heating up the fragmentation of graphene film, effective energy efficient again, enhances productivity simultaneously.
The gas of the inertia in this reduction reaction process be preferably nitrogen, argon gas in one or both mists.When the gas of inertia is the mist of nitrogen and argon gas, this nitrogen is 1:1～3 with the mixed volume ratio of argon gas.
From the above mentioned, the preparation method of above-described embodiment Graphene composite negative pole collector only need first prepare graphene film, then adopt electrodeposition process at this graphene film surface electrical precipitation layer of metal oxide, its technique is simple, condition is easily controlled, low for equipment requirements, production efficiency, production cost is low, is suitable for suitability for industrialized production.In addition, adopt electrodeposition process, make metal oxide Direct precipitation on graphene film surface, make the metal oxide layer even thickness generating, and be combined with graphene film firmly, the intensity that has strengthened Graphene composite negative pole collector, prevents coming off of metal oxide layer, has extended the useful life of Graphene composite negative pole collector.
In addition, example of the present invention further provides a kind of energy density high, the lithium ion battery of long service life.This lithium ion battery comprises positive pole, battery diaphragm and the negative pole stacking gradually.Wherein, the Graphene composite negative pole collector that the collector of negative pole is mentioned above or the prepared Graphene composite negative pole collector of Graphene composite negative pole collector preparation method by mentioned earlier, for length, at this, no longer this Graphene composite negative pole collector is repeated.Just because of the lithium ion battery in the present embodiment, contain Graphene composite negative pole collector mentioned above, the heat conductivility of this Graphene composite negative pole collector, chemically stable and uncorruptible performance make this lithium ion battery safety, long service life; This Graphene composite negative pole collector is with graphene film substituted metal collector, and its performance lightweight and not embedding lithium has effectively guaranteed the capacity of lithium ion battery, has improved the energy density of lithium ion battery.
Concrete, as one embodiment of the invention, the preparation method of lithium ion battery in above-described embodiment is as follows:
1, preparation battery cathode:
1.1 prepare Graphene composite negative pole collector according to the preparation method of Graphene composite negative pole collector above;
1.2 mix graphite, conductive agent, binding agent in mass ratio for the ratio of 90:5:5, make slurry; Wherein binding agent can but be not limited only to polyvinylidene fluoride (PVDF), conductive agent can but be not limited only to acetylene black;
It is two-sided upper that 1.3 slurries that step 1.2 is made are coated in the Graphene composite negative pole collector of step 1 preparation, drying, roll film, trimming is processed, and makes anode plate for lithium ionic cell; Wherein, the thickness that slurry applies is according to the conventional thickness in this area.
2, preparation is to electrode: to battery, directly select lithium metal as to electrode.
3, the assembling of lithium ion battery:
By the negative pole of step 1 preparation, step 2 preparation electrode and barrier film are stacked gradually and are assembled into battery core, in the glove box of argon gas atmosphere and moisture be less than under the condition of 1.0ppm and be assembled in order lithium ion battery.Wherein, take the LiPF that concentration is 1mol/L 6ethylene carbonate (EC) and the mixed liquor of dimethyl carbonate (DMC) (volume ratio of EC and DMC is 1:1) be electrolyte, barrier film is polypropylene film.
By concrete a plurality of embodiment, Graphene composite negative pole collector and preparation method thereof and lithium ion battery are described below, with and the aspect such as performance.
Embodiment 1
A kind of Graphene composite negative pole collector and preparation method thereof:
As shown in Figure 1, it comprises graphene film layer 1 and is combined in the two-sided metal oxide layer of graphene film layer 12 this Graphene composite negative pole current collector structure.Wherein, the thickness of metal oxide layer 2 is 1 μ m, and oxide is Cr 2o 3; The thickness of graphene film layer 1 is 3 μ m.
This Graphene composite negative pole collector preparation method concrete steps are as follows:
S11. prepare graphene oxide suspension: graphite oxide is added in deionized water, ultrasonic 0.5h, being configured to concentration is the homodisperse graphene oxide suspension of 0.25mg/ml, then adds ammoniacal liquor, regulates pH value, makes its pH value reach 10;
S12. prepare graphene suspension: in graphene oxide suspension, add hydrazine hydrate (85%) (wherein mass ratio RN2H4/GO=1:10) solution, at the temperature of 100 ℃, react 12h, obtain graphene suspension;
S13. prepare graphene film: the graphene suspension that adopts miillpore filter vacuum filtration to obtain, after filtration, filter cake is placed in to baking oven in 40 ℃ of oven dry, then graphene film is taken off from filter membrane;
S14. prepare Cr 2o 3/ graphene film collector: graphene film prepared by step S13 is as work electrode, and calomel electrode is made reference electrode, and platinum electrode is made auxiliary electrode, at room temperature with the Cr (NO of 0.25mol/L 3) 3.9H 2o and 0.1M KOH solution are in electrolyte, and (current density is 1.25mA/cm by galvanostat, to provide constant current 2), under the effect of constant current, after electro-deposition 5min, with deionized water rinsing, obtain Cr 2o 3/ graphene film collector;
S15. prepare Graphene composite negative pole collector: Cr prepared by step S14 2o 3after/graphene film collector dries naturally, vacuum bakeout 1～3 hour, then by the Cr of gained 2o 3/ graphene film collector is put into the centre of heating furnace pipe and passes to highly purified nitrogen, then stove is heated, the rate of heat addition with 10 ℃/min is warming up to 500 ℃ of reaction temperatures, keep 2h, after completion of the reaction, cool to room temperature in inert atmosphere, obtains Graphene composite negative pole collector.
Embodiment 2
A kind of Graphene composite negative pole collector and preparation method thereof:
Graphene composite negative pole current collector structure in this Graphene composite negative pole current collector structure embodiment 1.Wherein, the thickness of metal oxide layer is 1 μ m, and oxide is MnO 2; The thickness of graphene film layer is 5 μ m.
This Graphene composite negative pole collector preparation method concrete steps are as follows:
S21. prepare graphene oxide suspension: graphite oxide is added in ethanol, ultrasonic 1h, being configured to concentration is the homodisperse graphene oxide suspension of 1mg/ml, then adds ammoniacal liquor, regulates pH value, makes its pH value reach 11;
S22. prepare graphene suspension: in graphene oxide suspension, add hydrazine hydrate (85%) (mass ratio RN wherein 2h 4/ GO=7:10) solution reacts 24h at the temperature of 100 ℃, obtains graphene suspension;
S23. prepare graphene film: the graphene suspension that adopts miillpore filter vacuum filtration to obtain, after filtration, filter cake is placed in to baking oven in 40 ℃ of oven dry, then graphene film is taken off from filter membrane;
S24. prepare MnO 2/ graphene film collector: graphene film prepared by step S23 is as work electrode, and calomel electrode is made reference electrode, and platinum electrode is made auxiliary electrode, at room temperature with the Mn (CH of 0.5mol/L 3cOOH) 2solution and 0.1M KOH are in electrolyte, and (current density is 1.25mA/cm by galvanostat, to provide constant current 2), under the effect of constant current, after electro-deposition 10min, with deionized water rinsing, obtain MnO 2/ graphene film collector;
S25. prepare Graphene composite negative pole collector: MnO prepared by step S24 2after/graphene film collector dries naturally, vacuum bakeout 1-3 hour, then by the MnO of gained 2/ graphene film collector is put into the centre of heating furnace pipe and passes to highly purified argon gas, then stove is heated, the rate of heat addition with 10 ℃/min is warming up to 400 ℃ of reaction temperatures, keep 2h, after completion of the reaction, cool to room temperature in inert atmosphere, obtains Graphene composite negative pole collector.
Embodiment 3
A kind of Graphene composite negative pole collector and preparation method thereof:
Graphene composite negative pole current collector structure in this Graphene composite negative pole current collector structure embodiment 1.Wherein, the thickness of metal oxide layer is 2 μ m, and oxide is V 2o 5; The thickness of graphene film layer is 8 μ m.
This Graphene composite negative pole collector preparation method concrete steps are as follows:
S31. graphene oxide suspension: graphite oxide is added in isopropyl alcohol, ultrasonic 0.5h, being configured to concentration is the homodisperse graphene oxide suspension of 0.25mg/ml, then adds ammoniacal liquor, regulates pH value, makes its pH value reach 10;
S32. prepare graphene suspension: in graphene oxide suspension, add hydrazine hydrate (85%) (mass ratio RN wherein 2h 4/ GO=1:10) solution reacts 12h at the temperature of 100 ℃, obtains graphene suspension;
S33. prepare graphene film: the graphene suspension that adopts miillpore filter vacuum filtration to obtain, after filtration, filter cake is placed in to baking oven in 40 ℃ of oven dry, then graphene film is taken off from filter membrane;
S34. prepare V 2o 5/ graphene film collector: graphene film prepared by step S33 is as work electrode, and calomel electrode is made reference electrode, and platinum electrode is made auxiliary electrode, at room temperature with the NH of 0.25mol/L 4vO 3solution metal salt solution and 0.1M KOH are in electrolyte, and (current density is 1.25mA/cm by galvanostat, to provide constant current 2), under the effect of constant current, after electro-deposition 5min, with deionized water rinsing, obtain V 2o 5/ graphene film collector;
S35. prepare Graphene composite negative pole collector: V prepared by step S34 2o 5after/graphene film collector dries naturally, vacuum bakeout 1-3 hour, then by the V of gained 2o 5/ graphene film collector is put into the centre of heating furnace pipe and passes to the mist that highly purified volume ratio is 1:2 nitrogen and argon gas, then stove is heated, the rate of heat addition with 10 ℃/min is warming up to 500 ℃ of reaction temperatures, keep 4h, after completion of the reaction, cool to room temperature in inert atmosphere, obtains metal oxide/graphene film collector.
Embodiment 4
A kind of Graphene composite negative pole collector and preparation method thereof:
Graphene composite negative pole current collector structure in this Graphene composite negative pole current collector structure embodiment 1.Wherein, the thickness of metal oxide layer is 3 μ m, and oxide is TiO 2; The thickness of graphene film layer is 10 μ m.
This Graphene composite negative pole collector preparation method concrete steps are as follows:
S41. prepare graphene oxide suspension: graphite oxide is added in deionized water, ultrasonic 1h, being configured to concentration is the homodisperse graphene oxide suspension of 1mg/ml, then adds ammoniacal liquor, regulates pH value, makes its pH value reach 11;
S42. prepare graphene suspension: in graphene oxide suspension, add hydrazine hydrate (85%) (mass ratio RN wherein 2h 4/ GO=7:10) solution reacts 24h at the temperature of 100 ℃, obtains graphene suspension;
S43. prepare graphene film: the graphene suspension that adopts miillpore filter vacuum filtration to obtain, after filtration, filter cake is placed in to baking oven in 40 ℃ of oven dry, then graphene film is taken off from filter membrane;
S44. prepare TiO 2/ graphene film collector: graphene film prepared by step S43 is as work electrode, and calomel electrode is made reference electrode, and platinum electrode is made auxiliary electrode, at room temperature with the TiCl of 0.25mol/L 4solution and 0.1M KOH are in electrolyte, and (current density is 1.25mA/cm by galvanostat, to provide constant current 2), under the effect of constant current, after electro-deposition 5min, with deionized water rinsing, obtain TiO 2/ graphene film collector;
S45. prepare Graphene composite negative pole collector: TiO prepared by step S44 2after/graphene film collector dries naturally, vacuum bakeout 1-3 hour, again the collector of gained be put into the centre of heating furnace pipe and pass to highly purified argon gas, then stove is heated, the rate of heat addition with 10 ℃/min is warming up to 800 ℃ of reaction temperatures, keeps 2h, after completion of the reaction, cool to room temperature in inert atmosphere, obtains metal oxide/graphene film collector.
Embodiment 5
A kind of Graphene composite negative pole collector and preparation method thereof:
Graphene composite negative pole current collector structure in this Graphene composite negative pole current collector structure embodiment 1.Wherein, the thickness of metal oxide layer is 2 μ m, and oxide is that mol ratio is the TiO of 1: 1 2with Cr 2o 3mixture; The thickness of graphene film layer is 6 μ m.
This Graphene composite negative pole collector preparation method concrete steps are as follows:
S51. prepare graphene oxide suspension: with reference to the step S41 of above-described embodiment 4;
S52. prepare graphene suspension: with reference to the step S42 of above-described embodiment 4;
S53. prepare graphene film: with reference to the step S43 of above-described embodiment 4;
S54. prepare TiO 2-Cr 2o 3/ graphene film collector: graphene film prepared by step S53 is as work electrode, and calomel electrode is made reference electrode, and platinum electrode is made auxiliary electrode, at room temperature with the Cr (CH of 0.25mol/L 3cOOH) 3with TiBr 4mixture solution and 0.1M KOH be electrolyte (in electrolyte, Cr (CH 3cOOH) 3with TiBr 4mol ratio be 2:1), (current density is 1.25mA/cm by galvanostat, to provide constant current 2), under the effect of constant current, after electro-deposition 4min, with deionized water rinsing, obtain TiO 2-Cr 2o 3/ graphene film collector;
S55. prepare Graphene composite negative pole collector: TiO prepared by step S54 2-Cr 2o 3after/graphene film collector dries naturally, vacuum bakeout 1-3 hour, again the collector of gained be put into the centre of heating furnace pipe and pass to highly purified argon gas, then stove is heated, the rate of heat addition with 10 ℃/min is warming up to 800 ℃ of reaction temperatures, keeps 2h, after completion of the reaction, cool to room temperature in inert atmosphere, obtains metal oxide/graphene film collector.
Embodiment 6
, its preparation method is as follows:
S61, preparation battery cathode:
S611, select the Graphene composite negative pole collector of embodiment 1 preparation as collector;
S612, the ratio that is 90:5:5 according to mass ratio, mix graphite, Kynoar binding agent and conductive agent acetylene black, obtains slurry;
S613, slurry is coated on Graphene composite negative pole collector, drying, roll film, trimming is processed, and makes lithium ion battery negative;
S62, prepare counter electrode of battery: directly select lithium metal as to electrode;
The assembling of S63, lithium ion battery:
Will to electrode, barrier film, negative pole in order stack of laminations dress up battery core, the LiPF that the concentration of take is 1mol/L 6ethylene carbonate (EC) and the mixed liquor of dimethyl carbonate (DMC) (volume ratio 1:1) be electrolyte, polypropylene film is barrier film, in the glove box of argon gas atmosphere, when being less than 1.0ppm, moisture is assembled in order lithium ion button shape cell.
Comparison example 1
, its preparation method is with reference to embodiment 6, and difference is to using Copper Foil directly as negative current collector in this comparison example.Other as electrolyte, barrier film, all identical with embodiment 6 to electrode.
Comparison example 2
, its preparation method is with reference to embodiment 6, and difference is to using in this comparison example that the graphene film of preparation in embodiment 1 is directly as negative current collector, and in this comparison example, negative pole currect collecting surface does not have electro-deposition Cr 2o 3metal oxide layer.Other as electrolyte, barrier film, all identical with embodiment 6 to electrode.
Battery charging/discharging performance testing:
The fastening lithium ionic cell of above-described embodiment 6, comparison example 1,2 preparations is carried out to charge-discharge performance test after standing 12 hours: the test of the lithium-inserting amount of graphite material is all 0.005～3.0V (vs.Li/Li at charge and discharge potential +) in scope, the condition that current density is 20mA/g completes.Result through charge-discharge performance test is as shown in table 1 below:
Table 1
Figure BDA00001925425200151
By test data in table 1, can be found out, in the test of charge and discharge capacity first, in embodiment 5 capacity of charge and discharge first of the lithium ion battery that contains burning of preparation higher than in comparison example 2 directly with the lithium ion battery of graphene film discharge capacity first.Using the lithium ion battery in embodiment 5 first charge and discharge capacity with in comparison example 1, directly with existing metal, as the lithium ion battery of collector, compare, in the embodiment of the present invention 5 lithium ion battery first charge and discharge capacity be obviously better than in comparison example 1 the directly lithium ion battery as collector with existing metal.Hence one can see that, on graphene film surface, adds metal oxide layer, can reduce the irreversible embedding lithium of collector, raising capacity.In addition, Graphene, as collector, effectively reduces the weight of collector, and therefore, lithium ion battery prepared by the embodiment of the present invention is lightweight.In associative list 1, data can further draw again, lithium ion battery energy density prepared by the embodiment of the present invention
The performance of the lightweight and not embedding lithium of this Graphene composite negative pole collector, has effectively guaranteed the capacity of lithium ion battery, has improved the energy density of lithium ion battery.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (10)

1. a Graphene composite negative pole collector, is characterized in that: comprise graphene film layer and the metal oxide layer that is combined in described graphene film layer surface, the metal oxide in described metal oxide layer is Cr 2o 3, MnO 2, V 2o 5or TiO 2in at least one.
2. Graphene composite negative pole collector according to claim 1, is characterized in that: the thickness of described metal oxide layer is 1～3 μ m.
3. Graphene composite negative pole collector according to claim 1, is characterized in that: the thickness of described graphene film layer is 3～10 μ m.
4. according to the arbitrary described Graphene composite negative pole collector of claim 1～3, it is characterized in that: described metal oxide layer adopts the mode of electro-deposition to be combined with described graphene film layer.
5. a preparation method for Graphene composite negative pole collector, comprises the steps:
Graphene suspension is adopted to miillpore filter vacuum filtration, by separated miillpore filter after filtration cakes torrefaction, obtain graphene film;
Using described graphene film as work electrode, be placed in and contain the alkaline electrolyte that concentration is the slaine of 0.25～0.5mol/L, in current density, be 0.5～3mA/cm 2constant current effect under electro-deposition 5～10min; Wherein, described slaine for containing the slaine of Cr ion, the slaine of Mn ion, the slaine of Ti ion, VO 3at least one in the slaine of ion;
By the graphene film washing after electro-deposition, dry after, be placed in the environment of the gas that is full of inertia and at the temperature of 400～800 ℃ reductase 12～8 hour, cooling, obtain described Graphene composite negative pole collector.
6. the preparation method of Graphene composite negative pole collector according to claim 5, is characterized in that: the slaine of described Cr ion is Cr (NO 3) 3.9H 2o or Cr (CH 3cOOH) 3in one or both; The slaine of described Mn ion is Mn (CH 3cOOH) 2or MnSO 4h 2in O one or both; The slaine of described Ti ion is TiCl 4, TiI 4or TiBr 4in one or more; The slaine of described V ion is NH 4vO 3, NaVO 3or KVO 3in one or more.
7. the preparation method of Graphene composite negative pole collector according to claim 5, it is characterized in that: in the reduction step of described 400～800 ℃, after the graphene film washing after electro-deposition, being dried, be placed in the environment of the gas that is full of inertia, then with the rate of heat addition of 10 ℃/min be warming up to 400 ℃～800 ℃ and at the temperature of described 400～800 ℃ reductase 12～8 hour.
8. the preparation method of Graphene composite negative pole collector according to claim 5, is characterized in that: the gas of described inertia is one or both the mist in nitrogen or argon gas.
9. the preparation method of Graphene composite negative pole collector according to claim 5, is characterized in that: described graphene suspension is to prepare and obtain as follows:
Graphite oxide is added in solvent, and ultrasonic 0.5～1 hour, being mixed with concentration is the graphene oxide suspension of 0.25～1mg/ml;
After the pH of described graphene oxide suspension is adjusted to 10～11, add hydrazine hydrate, at the temperature of 80～100 ℃, react 12～24 hours, obtain graphene suspension; Wherein, the mass ratio of hydrazine hydrate and graphene oxide is 1:10～7:10.
10. a lithium ion battery, comprises the positive pole, battery diaphragm and the negative pole that stack gradually, it is characterized in that: the collector of described negative pole is the arbitrary described Graphene composite negative pole collector of claim 1～4.
CN201210257717.5A 2012-07-24 2012-07-24 Graphene composite negative current collector, preparation method thereof and lithium ion battery Pending CN103579632A (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104477892A (en) * 2014-12-12 2015-04-01 盐城市新能源化学储能与动力电源研究中心 Preparation method of flake graphene and flake graphene device prepared by same
CN105185605A (en) * 2015-08-27 2015-12-23 长春工业大学 Loaded graphene/metallic compound-contained electrode preparation method based on hollow cathode plasma reduction and nitridation
CN106601979A (en) * 2016-12-08 2017-04-26 德阳九鼎智远知识产权运营有限公司 Anode of secondary battery
CN106960973A (en) * 2015-10-21 2017-07-18 成都九十度工业产品设计有限公司 A kind of preparation method of the three-phase composite electrode of vanadium cell
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CN108847358A (en) * 2018-05-22 2018-11-20 上海工程技术大学 The preparation method and application of three-dimensional porous manganese dioxide/graphene composite material
CN109873160A (en) * 2017-12-05 2019-06-11 宁德时代新能源科技股份有限公司 Current collector, pole piece thereof and battery
CN110660993A (en) * 2018-06-29 2020-01-07 宁德时代新能源科技股份有限公司 Negative pole piece, preparation method thereof and electrochemical device
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WO2023056591A1 (en) * 2021-10-08 2023-04-13 宁德时代新能源科技股份有限公司 Composite positive electrode current collector, pole piece, and secondary battery
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080131779A1 (en) * 2006-11-27 2008-06-05 Denso Corporation Electric current collector, electrode and charge accumulating device
CN101894679A (en) * 2009-05-20 2010-11-24 中国科学院金属研究所 Method for preparing graphene-based flexible super capacitor and electrode material thereof
CN102509634A (en) * 2011-10-31 2012-06-20 中国科学院苏州纳米技术与纳米仿生研究所 Graphene-based flexible multilayer composite film and preparing method thereof
CN102576876A (en) * 2009-08-10 2012-07-11 巴特尔纪念研究院 Self assembled multi-layer nanocomposite of graphene and metal oxide materials

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080131779A1 (en) * 2006-11-27 2008-06-05 Denso Corporation Electric current collector, electrode and charge accumulating device
CN101894679A (en) * 2009-05-20 2010-11-24 中国科学院金属研究所 Method for preparing graphene-based flexible super capacitor and electrode material thereof
CN102576876A (en) * 2009-08-10 2012-07-11 巴特尔纪念研究院 Self assembled multi-layer nanocomposite of graphene and metal oxide materials
CN102509634A (en) * 2011-10-31 2012-06-20 中国科学院苏州纳米技术与纳米仿生研究所 Graphene-based flexible multilayer composite film and preparing method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN104477892B (en) * 2014-12-12 2016-08-24 盐城市新能源化学储能与动力电源研究中心 Flaky graphite alkene device prepared by the preparation method of a kind of flaky graphite alkene and use the method
CN105185605A (en) * 2015-08-27 2015-12-23 长春工业大学 Loaded graphene/metallic compound-contained electrode preparation method based on hollow cathode plasma reduction and nitridation
CN105185605B (en) * 2015-08-27 2017-11-10 长春工业大学 Load the electrode preparation method of graphene/metallic compound
CN106960973A (en) * 2015-10-21 2017-07-18 成都九十度工业产品设计有限公司 A kind of preparation method of the three-phase composite electrode of vanadium cell
CN106960973B (en) * 2015-10-21 2019-10-25 成都九十度工业产品设计有限公司 A kind of preparation method of the three-phase composite electrode of vanadium cell
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