CN103311502A - Metal foil/graphene composite electrode plate and preparation method thereof - Google Patents
Metal foil/graphene composite electrode plate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a metal foil/graphene composite electrode plate and a preparation method thereof. The method comprises the following steps of firstly manufacturing the natural flake graphite into intercalation oxidized graphite by adopting an oxidation method; dispersing the intercalation oxidized graphite into a solvent to be ultrasonically processed into oxidized graphene solution; uniformly coating the oxidized graphene solution onto the surface of a metal foil to be dried in air; and finally carrying out heat treatment on the metal foil to obtain the metal foil/graphene composite electrode plate. The natural flake graphite is adopted as a raw material, so that the price is low, the method for preparing the composite electrode plate is simple, industrialized mass production can be realized, and compared with the traditional electrode plate with the adhesive, the metal foil/graphene composite electrode plate prepared by adopting the method is low in equivalent series resistance, and the power density of the battery can be efficiently improved.
Description
Technical field
The present invention relates to a kind of metal forming/graphene combination electrode sheet and preparation method thereof, belong to the electrode material preparation field.
Background technology
Along with improving constantly of living standard, the development of material progress, people are day by day urgent for the demand of novel green high efficient energy sources, but the but day by day exhaustion of traditional fossil energy, a large amount of consumption of fossil energy have also produced destructive influences to environment.In recent years, lithium ion battery because its have that the cell operating voltage is high, specific energy is large, have extended cycle life, memory-less effect, self discharge are little, can fast charging and discharging, operating temperature range is wide and security performance is good etc., and advantage has obtained develop rapidly.As the negative material of lithium ion battery, must have excellent embedding lithium performance; For anodal, relatively ripe mainly is to adopt metal forming (such as aluminium foil) as collector at present, then positive active material is made slurry and is coated on the metal forming, and drying is made positive pole after processing.The positive active material that is coated on the metal forming is more, and capacity of lithium ion battery is larger, and energy is higher.Tend to use binding agent in the process that applies, when the content of binding agent reduced, adhesive property descended, and the performance of battery can be had a greatly reduced quality.
At present, material with carbon element is coated in as positive active material and has obtained fast development on the metal forming.Be coated with carbon metal forming (as being coated with the carbon aluminium foil) very large advantage is arranged in lithium ion battery applications.Be coated with the carbon metal forming and can suppress battery polarization; reduce thermal effect; improve high rate performance, the reduction internal resistance of cell, improve consistency, increase the adhesion of cycle life, raising active material and the collector of battery, reduce the manufacturing cost of pole piece and protect collector by electrolyte corrosion etc.But coated particle shape material with carbon element will be used binding agent in being coated with the carbon process, and active material easily comes off in cyclic process, the performance of lithium ion battery is produced have a strong impact on.So the desirable carbon metal forming that is coated with is to use the two-dimentional Graphene with huge specific area as active material, and directly is coated in metal foil surface without binding agent.
Graphene has unique two-dimentional rock-steady structure, is conductivity best material in the world, and electronics movement velocity has therein reached one of three percentages of the light velocity, considerably beyond the movement velocity of electronics in general conductor; Graphene has larger specific area simultaneously, and theoretical specific area reaches 2630m
2/ g, considerably beyond the specific area of general material, and Graphene also has the superior performances such as high mechanical stability.Because Graphene has these outstanding performances, people are studying its purposes in nanoelectronics, nano composite material, lithium ion battery, ultracapacitor, hydrogen storage and biomaterial.
The carbon lithium ion cell positive material that is coated with that Graphene is coated in metal foil surface formation is might business-like positive electrode.As being in 201110302809.6 the Chinese patent literature at application number, the Zhou Mingjie of Haiyangwang Lighting Technology Co., Ltd. etc. proposed a kind of method by electro-deposition on metal collector electrode slice surface directly graphene coated/tin simple substance electrode material prepare the method for electrode slice, effectively improve the power density of battery.
Summary of the invention
The object of the present invention is to provide a kind of process simple, easy to operate, Graphene directly is coated in the method that collector foil surface prepares composite electrode pole piece, this electrode plates has excellent electric property.
The present invention is achieved by the following technical solutions:
The preparation method of a kind of metal forming/graphene combination electrode sheet may further comprise the steps:
The first step: adopt oxidizing process that natural flake graphite is made the intercalation graphite oxide;
Described natural flake graphite refer to size at 50 orders to 5000 purpose natural flake graphites.
Described oxidizing process can be improved Standenmair method or improved Hummer method.
Concrete, the concrete operation step of described improved Standenmair method can be for adding 10 gram natural flake graphites in the mixed solution of every 95ml red fuming nitric acid (RFNA) (mass fraction is 65%-68%) and the 178ml concentrated sulfuric acid (mass fraction is 98%), stir 30min, add again 110 gram sodium chlorate, 25 ℃ of reaction 12h obtain blackish green intercalation graphite oxide powder through suction filtration, washing, 90 ℃ of vacuumizes.
Concrete, the concrete operation step of described improved Hummer method can be in double-layer glass reaction kettle, adds the mixture of 4 gram natural flake graphites and 4 gram sodium nitrate in every 100ml, the 50 ℃ of concentrated sulfuric acids (mass fraction is 98%), stirring reaction 2 hours; After the temperature of reaction system is reduced to 0 ℃, add 15 gram potassium permanganate, the temperature of mixture remains on 35 ℃, stirs 12 hours again; Add the 180ml deionized water, it is 90 ℃ that the temperature of reaction system raises, stirring reaction 1 hour; Add again the 110ml deionized water, continue 90 ℃ of stirring reactions 1 hour; Then add the hydrogen peroxide that 14ml concentration is 30wt%, the mixture color becomes glassy yellow afterwards; The hydrochloric acid solution that the mixture solid that obtains after centrifugal is 1mol/L with 1 liter of concentration washs three times, again with the deionized water washing, and last freeze drying, 60 ℃ of vacuumizes obtained intercalation graphite oxide powder in 48 hours.
Described intercalation graphite oxide refers to after oxidation, and graphite layers is apart from increase, and introduces oxygen-containing functional group in graphite aspect and edge; Described oxygen-containing functional group is hydroxyl, epoxy radicals, carboxyl and carbonyl.
Second step: the intercalation graphite oxide is scattered in the solvent, and graphene oxide solution is made in ultrasonic processing;
Described solvent is deionized water, methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-hexyl alcohol, propylene glycol, dimethyl formamide (DMF), 1-METHYLPYRROLIDONE (NMP), dimethyl sulfoxide (DMSO) (DMSO) or thionyl chloride.
The time of described ultrasonic processing is 1～60 minute; The concentration of graphene oxide is 0.05～10mg/ml in the described graphene oxide solution.
The 3rd step: graphene oxide solution evenly is coated in metal foil surface, dries in the air;
Described graphene oxide solution, soaked 5 seconds to 30 minutes for metal forming is immersed in the graphene oxide solution at the painting method of metal foil surface; Or use spraying coating process with the spraying plating of graphene oxide solution in metal foil surface.
Described metal forming is selected from aluminium foil, nickel foil, Copper Foil, iron foil and nickel foam; Described aluminium foil more preferably high-purity electrochemical polish aluminium foil, cloth hole aluminium foil or thickness is the lithium battery aluminum foil special of 0.01～0.025mm.
The width of described metal forming is 1cm～150cm.
Can allow tinsel continuously by graphene oxide solution or spray at tinsel continuously in the preparation process of electrode slice, realize the serialization large-scale industrial production; Also can realize the coating of graphene oxide on the tinsel of certain width and length.
The 4th step: namely obtain described metal forming/graphene combination electrode sheet through heat treatment.
Described heat treatment is in tube furnace, carries out under high vacuum or the inert gas shielding; The vacuum degree of described high vacuum is 10
-5-10
-2Pa; Described inert gas is selected from nitrogen, argon gas and helium.
Described heat treated temperature is 250 ℃～800 ℃, and the time is 1 minute～10 hours.
Graphene oxide in the described heat treatment process on the metal forming is reduced, and the close combination of the Graphene that generates in the simultaneous reactions process and metal foil substrate forms described metal forming/graphene combination electrode sheet.
Preferably, the thickness of Graphene is 1nm～20nm on described metal forming/graphene combination electrode sheet, corresponding approximately 2～50 Graphene atomic layer level thickness.
Technique effect of the present invention and advantage are:
1. overall technology route innovation adopts naturally occurring crystalline flake graphite to be raw material, and is cheap, and the method for employing chemical oxidation can prepare the graphene oxide solution of different solvents, variable concentrations.
2. by the collector foil being immersed in the graphene oxide solution or adopting spraying coating process at the ultra-thin graphene oxide layer of collector foil surface coverage one deck, again when Overheating Treatment just can be reduced graphene oxide, with active material Graphene Direct precipitation on the collector foil.By adjusting the concentration of graphene oxide solution, the length of collector foil soak time in graphene oxide solution and spraying coating process etc., can realize that the ultra-thin Graphene of different-thickness applies, and graphene film can evenly be attached to collector foil surface securely, method is simple, is suitable for large-scale industrial production.
3. with respect to the electrode slice of traditional adding binding agent, preparation technology is simple for this metal forming/Graphene electrodes sheet, and equivalent series resistance is lower, adopts this metal forming/Graphene electrodes sheet can effectively improve the power density of battery.
Description of drawings
The SEM Electronic Speculum figure of high-purity electrochemical polish aluminium foil of Fig. 1 embodiment 1 preparation/graphene combination electrode sheet
The SEM Electronic Speculum figure (cloth hole aluminium foil average pore size is 70nm) of the cloth mesoporous metal aluminium foil of Fig. 2 embodiment 2 preparations/graphene combination electrode sheet
Lithium battery aluminum foil special (the SEM Electronic Speculum figure of thickness 0.01～0.025mm)/graphene combination electrode sheet of Fig. 3 embodiment 3 preparations
The SEM Electronic Speculum figure (cloth hole aluminium foil average pore size is 350nm) of the cloth mesoporous metal aluminium foil of Fig. 4 embodiment 4 preparations/graphene combination electrode sheet
The SEM Electronic Speculum figure of the Copper Foil of Fig. 5 embodiment 5 preparations/graphene combination electrode sheet
Embodiment
Below by specific instantiation technical scheme of the present invention is described.Should be understood that one or more method steps that the present invention mentions do not repel before and after described combination step also exists the additive method step or can also insert the additive method step between these step of clearly mentioning; Should also be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.And, except as otherwise noted, the numbering of various method steps is only for differentiating the convenient tool of various method steps, but not ordering or the enforceable scope of restriction the present invention for limiting various method steps, the change of its relativeness or adjustment, in the situation that without essence change technology contents, when also being considered as the enforceable category of the present invention.
The method of testing explanation:
1.FESEM test specification: adopt Hitachi S4700 to carry out sample test.Metal forming is immersed in the graphene oxide solution, after the taking-up, in air, dries, test behind the nitrogen blowing after the high-temperature heat treatment.
2. Graphene coating layer thickness measuring and calculating.Because metal foil surface rises and falls greatly, be difficult to use atomic force microscope (AFM) directly to test thickness, adopt monocrystal silicon substrate to carry out simultaneously identical experiment, and carry out AFM and determine coating layer thickness.That is, coating layer thickness is not directly to determine at metal foil surface test AFM, but carries out simultaneously the AFM of experiment test in monocrystal silicon substrate.
Embodiment 1: prepare high-purity electrochemical polish aluminium foil/graphene combination electrode sheet
(1) adopt the standby graphite oxide powder of improved Hummer legal system:
In double-layer glass reaction kettle, the mixtures of 4 gram 50 purpose natural flake graphites and 4 gram sodium nitrate are joined in 50 ℃, the 100ml concentrated sulfuric acid (mass fraction is 98%) stirring reaction 2 hours; After the temperature of reaction system is reduced to 0 ℃, add 15 gram potassium permanganate, the temperature of mixture remains on 35 ℃, stirs 12 hours again; Then add the 180ml deionized water, it is 90 ℃ that the temperature of reaction system raises, stirring reaction 1 hour; Add the 110ml deionized water again, continue 90 ℃ of reactions after 1 hour, adding 14ml concentration is the hydrogen peroxide of 30wt%, and the mixture color becomes glassy yellow afterwards; The mixture solid that obtains after centrifugal is the hydrochloric acid solution washing three times of 1mol/L with 1L concentration, again with the deionized water washing, and last freeze drying, 60 ℃ of vacuumizes obtained the graphite oxide powder in 48 hours again.
(2) ethanolic solution of preparation 0.05mg/ml graphite oxide:
Get 5mg graphite oxide powder and place the 200ml beaker, add 100ml ethanol, ultrasonic 30 minutes, obtain the ethanolic solution of brown graphene oxide.
(3) the high-purity electrochemical polish aluminium foil of 1 * 1cm is immersed in the 0.05mg/ml graphene oxide ethanolic solution, soak time is 5 seconds, the high-purity electrochemical polish aluminium foil after soaking is immersed in the air dries.
High-purity electrochemical polish aluminium foil that (4) will be coated with graphene oxide places the quartz ampoule of tube furnace, the high-purity argon gas protection, and 250 ℃ of heat treatment 1 minute obtains high-purity electrochemical polish aluminium foil/graphene combination electrode sheet.
The high-purity electrochemical polish aluminium foil of the present embodiment/graphene combination electrode sheet SEM test scan figure as shown in Figure 1.Counter sample on the AFM test silicon wafer shows approximately 1nm of Graphene coating layer thickness.
Embodiment 2: preparation cloth mesoporous metal aluminium foil/graphene combination electrode sheet (cloth hole aluminium foil average pore size is 70nm)
(1) adopt the standby intercalation graphite oxide powder of improved Stamdenmair legal system:
10 grams, 5000 order natural flake graphites are joined in the mixed solution of 95ml red fuming nitric acid (RFNA) (mass fraction is 65%-68%) and the 178ml concentrated sulfuric acid (mass fraction is 98%), stir 30min, add again 110 gram sodium chlorate, 25 ℃ of reaction 12h obtain blackish green intercalation graphite oxide powder through suction filtration, washing, 90 ℃ of vacuumizes.
(2) preparation 10mg/ml graphite oxide aqueous solution:
Get 1000mg intercalation graphite oxide powder and place the 200ml beaker, add the 100ml deionized water, ultrasonic 30 minutes, obtain the brown graphene oxide solution of 10mg/ml.
(3) be that the cloth hole aluminium foil of 60～100nm is immersed in the 10mg/ml graphite oxide aqueous solution with 100 * 100cm aperture, soak time is 30 minutes, and the cloth hole aluminium foil after soaking is dried in air.
The cloth hole aluminium foil that (4) will be coated with graphene oxide places the quartz ampoule of tube furnace, the high pure nitrogen protection, and 800 ℃ of heat treatment 10 hours obtains cloth hole aluminium foil/graphene combination electrode sheet.
The present embodiment cloth hole aluminium foil/graphene combination electrode sheet SEM test scan figure as shown in Figure 2.Counter sample on the AFM test silicon wafer shows approximately 20nm of Graphene coating layer thickness.
Embodiment 3: preparation lithium battery aluminum foil special (thickness 0.01～0.025mm)/graphene combination electrode sheet
(1) adopts the standby intercalation graphite oxide powder of improved Hummer legal system;
In double-layer glass reaction kettle, be that the mixtures of 2500 purpose natural flake graphites and 4 gram sodium nitrate join in 50 ℃, the 100ml concentrated sulfuric acid (mass fraction is 98%) stirring reaction 2 hours with 4 gram order numbers; After the temperature of reaction system is reduced to 0 ℃, add 15 gram potassium permanganate, the temperature of mixture remains on 35 ℃, stirs 12 hours again; Add the 180ml deionized water, it is 90 ℃ that the temperature of reaction system raises, and stirring reaction 1 hour adds the 110ml deionized water again, continues 90 ℃ of reactions 1 hour, and adding 14ml concentration is the hydrogen peroxide of 30wt%, and the mixture color becomes glassy yellow afterwards.The hydrochloric acid solution that the mixture solid that obtains after centrifugal is 1mol/L with 1 liter of concentration washs three times, again with the deionized water washing, and last freeze drying, 60 ℃ of vacuumizes obtained intercalation graphite oxide powder in 48 hours again.
(2) preparation 1mg/ml graphene oxide DMF solution:
Get 100mg intercalation graphite oxide powder and place the 200ml beaker, add 100ml DMF, ultrasonic 40 minutes, obtain brown graphene oxide DMF solution.
(3) the lithium battery aluminum foil special with 5 * 5cm is immersed in the 1mg/ml graphene oxide DMF solution, and soak time is 20 minutes, and the aluminium foil after soaking is dried in air.
The aluminium foil that (4) will be coated with graphene oxide places the quartz ampoule of tube furnace, high-purity helium protection, and 650 ℃ of heat treatment 40 minutes obtains aluminium foil/graphene combination electrode sheet.
The present embodiment lithium battery aluminum foil special/graphene combination electrode sheet SEM test scan figure as shown in Figure 3.Counter sample on the AFM test silicon wafer shows approximately 7nm of Graphene coating layer thickness.
Embodiment 4: cloth mesoporous metal aluminium foil/graphene combination electrode sheet (cloth hole aluminium foil average pore size is 350nm)
(1) adopt the standby intercalation graphite oxide powder of improved Stamdenmair legal system:
10 grams, 325 order natural flake graphites are joined in the mixed solution of 95ml red fuming nitric acid (RFNA) (mass fraction is 65%-68%) and the 178ml concentrated sulfuric acid (mass fraction is 98%), stir 30min, add again 110 gram sodium chlorate, 25 ℃ of reaction 12h obtain blackish green intercalation graphite oxide powder through suction filtration, washing, 90 ℃ of vacuumizes.
(2) preparation 2mg/ml graphite oxide nmp solution:
Get 200mg intercalation graphite oxide powder and place the 200ml beaker, add 100ml NMP, ultrasonic 10 minutes, obtain brown graphene oxide nmp solution.
(3) utilize spray gun the graphene oxide nmp solution to be painted on the surface of cloth mesoporous metal aluminium foil, in air, dry.
The cloth mesoporous metal aluminium foil that (4) will be coated with graphene oxide places the quartz ampoule of tube furnace, and the pressure that is evacuated in the quartz ampoule is 0.2 * 10
-2Pa, 750 ℃ of heat treatment 5 minutes obtains cloth mesoporous metal aluminium foil/graphene combination electrode sheet.
The present embodiment cloth mesoporous metal aluminium foil/graphene combination electrode sheet SEM test scan figure as shown in Figure 4.Counter sample on the AFM test silicon wafer shows approximately 10nm of Graphene coating layer thickness.
Embodiment 5: preparation Copper Foil/graphene combination electrode sheet
(1) adopts the standby intercalation graphite oxide powder of improved Hummer legal system;
In double-layer glass reaction kettle, be that the mixtures of 1200 purpose natural flake graphites and 4 gram sodium nitrate join in 50 ℃, the 100ml concentrated sulfuric acid (mass fraction is 98%) stirring reaction 2 hours with 4 gram order numbers; After the temperature of reaction system is reduced to 0 ℃, add 15 gram potassium permanganate, the temperature of mixture remains on 35 ℃, stirs 12 hours again; Add the 180ml deionized water, it is 90 ℃ that the temperature of reaction system raises, and stirring reaction 1 hour adds the 110ml deionized water again, continues 90 ℃ of reactions 1 hour, and adding 14ml concentration is the hydrogen peroxide of 30wt%, and the mixture color becomes glassy yellow afterwards.The hydrochloric acid solution that the mixture solid that obtains after centrifugal is 1mol/L with 1 liter of concentration washs three times, again with the deionized water washing, and last freeze drying, 60 ℃ of vacuumizes obtained intercalation graphite oxide powder in 48 hours again.
(2) preparation 4mg/ml graphene oxide DMSO solution:
Get 400mg intercalation graphite oxide powder and place the 200ml beaker, add 100ml DMSO, ultrasonic 10 minutes, obtain brown graphene oxide DMSO solution.
(3) Copper Foil with 4 * 4cm is immersed in the 4mg/ml graphene oxide DMSO solution, and soak time is 20 minutes, and the Copper Foil after soaking is dried in air.
The Copper Foil that (4) will be coated with graphene oxide places the quartz ampoule of tube furnace, and the pressure that is evacuated in the quartz ampoule is 3 * 10
-5Pa, 550 ℃ of heat treatment 50 minutes obtains Copper Foil/graphene combination electrode sheet.
The present embodiment Copper Foil/graphene combination electrode sheet SEM test scan figure as shown in Figure 5.Counter sample on the AFM test silicon wafer shows approximately 12nm of Graphene coating layer thickness.
According to above identical preparation method, can also prepare the compound electric pole piece of nickel foil, iron foil, nickel foam foil and Graphene, to meet the different needs.
Claims (14)
1. the preparation method of metal forming/graphene combination electrode sheet comprises the steps:
(1) adopt oxidizing process that natural flake graphite is made the intercalation graphite oxide;
(2) the intercalation graphite oxide is scattered in the solvent, graphene oxide solution is made in ultrasonic processing;
(3) graphene oxide solution evenly is coated in metal foil surface, dries in the air;
(4) namely obtain described metal forming/graphene combination electrode sheet through heat treatment.
2. the preparation method of a kind of metal forming as claimed in claim 1/graphene combination electrode sheet is characterized in that, the described natural flake graphite of step (1) refer to size at 50 orders to 5000 purpose natural flake graphites.
3. the preparation method of a kind of metal forming as claimed in claim 1/graphene combination electrode sheet is characterized in that, the described oxidizing process of step (1) is improved Standenmair method or improved Hummer method.
4. the preparation method of a kind of metal forming as claimed in claim 1/graphene combination electrode sheet is characterized in that, the described intercalation graphite oxide of step (1) refers to after oxidation, and graphite layers is apart from increase, and introduces oxygen-containing functional group in graphite aspect and edge; Described oxygen-containing functional group is hydroxyl, epoxy radicals, carboxyl and carbonyl.
5. the preparation method of a kind of metal forming as claimed in claim 1/graphene combination electrode sheet, it is characterized in that, described solvent is deionized water, methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-hexyl alcohol, propylene glycol, dimethyl formamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO) or thionyl chloride.
6. the preparation method of a kind of metal forming as claimed in claim 1/graphene combination electrode sheet is characterized in that, the concentration of the middle graphene oxide of the described graphene oxide solution of step (2) is 0.05～10mg/ml.
7. the preparation method of a kind of metal forming as claimed in claim 1/graphene combination electrode sheet, it is characterized in that, the described graphene oxide solution of step (3), soaked 5 seconds to 30 minutes for metal forming is immersed in the graphene oxide solution at the painting method of metal foil surface; Or use spraying coating process with the spraying plating of graphene oxide solution in metal foil surface.
8. the preparation method of a kind of metal forming as claimed in claim 1/graphene combination electrode sheet is characterized in that, the described metal forming of step (3) is selected from aluminium foil, nickel foil, Copper Foil, iron foil and nickel foam.
9. the preparation method of a kind of metal forming as claimed in claim 8/graphene combination electrode sheet is characterized in that, described aluminium foil is selected from the lithium battery aluminum foil special that high-purity electrochemical polish aluminium foil, cloth hole aluminium foil and thickness are 0.01～0.025mm.
10. such as the preparation method of power a kind of metal forming claimed in claim 1/graphene combination electrode sheet, it is characterized in that, the described heat treatment of step (4) is in tube furnace, carries out under high vacuum or the inert gas shielding.
11. the preparation method of a kind of metal forming as claimed in claim 10/graphene combination electrode sheet is characterized in that the vacuum degree of described high vacuum is 10
-5-10
-2Pa; Described inert gas is selected from nitrogen, argon gas and helium.
12. the preparation method of a kind of metal forming as claimed in claim 1/graphene combination electrode sheet is characterized in that, the described heat treated temperature of step (4) is 250 ℃～800 ℃, and the time is 1 minute～10 hours.
13. the preparation method of a kind of metal forming as claimed in claim 1/graphene combination electrode sheet is characterized in that the thickness of Graphene is 1nm～20nm on described metal forming/graphene combination electrode sheet.
14. by the metal forming of the preparation method of the arbitrary described a kind of metal forming of claim 1-13/graphene combination electrode sheet preparation/graphene combination electrode sheet.
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| CN104944414A (en) * | 2014-03-27 | 2015-09-30 | 纳米新能源生命科技（唐山）有限责任公司 | Graphene thin film, graphene super capacitor and preparation method of graphene thin film and graphene super capacitor |
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