CN108199039A - A kind of graphene battery of large capacity quick charge - Google Patents

A kind of graphene battery of large capacity quick charge Download PDF

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CN108199039A
CN108199039A CN201711459360.8A CN201711459360A CN108199039A CN 108199039 A CN108199039 A CN 108199039A CN 201711459360 A CN201711459360 A CN 201711459360A CN 108199039 A CN108199039 A CN 108199039A
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parts
weight
battery
positive
graphene
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不公告发明人
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Changsha Shandao New Mstar Technology Ltd
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Changsha Shandao New Mstar Technology 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 present invention provides a kind of graphene batteries of large capacity quick charge, and the present invention relates to battery technology fields.The graphene battery of large capacity quick charge prepared by the present invention, it is made of positive plate, negative plate, diaphragm, electrolyte and battery case, efficiently solve the phenomenon that existing graphene battery storage volume is small and charging rate is slow, simultaneously, enhance the corrosion resistance of battery, service life is extended, stability is preferable, and to human body and environmentally friendly.Empirical tests, compared with conventional commercial graphene battery, under identical charge condition, the charging time is obviously shortened 34.94%, and battery efficiency can reach 87.73%.

Description

A kind of graphene battery of large capacity quick charge
Technical field
The present invention relates to battery technology field, more particularly, it relates to a kind of graphene battery of large capacity quick charge.
Background technology
Graphene is the carbon atom that a kind of planar monolayer is closely packaged into a bi-dimensional cellular lattice, and is every other The basic building module of the graphite material of dimension has in most thin, maximum specific surface area, most many histories such as hard, most tension most The peculiar properties such as epistasis matter and high-performance sensors function, similar catalyst function.The appearance of graphene is expected in construction material The numerous areas such as material, electronic device functional material cause material revolution.Since it claims with many many scholars of special nature Graphene is " material for changing 21 century ", and predicts " epoch that 21 century will be carbon (C) ".Compared to current material, graphite Alkene possesses numerous " most strong in history " performances.Most thin material：Only there are one the thickness of carbon atom, thickness is about single-layer graphene 0.335nm is equivalent to 20 a ten thousandths of a hair, there is nearly 1,500,000 layers or so of graphene in the graphite of 1 millimeters thick.
Graphene battery is that the characteristic of rapid, high volume shuttle is opened between graphene surface and electrode using lithium ion A kind of new energy battery sent out.At present, with the fast development of the technology of graphene battery, it is widely used in automobile, moves Dynamic equipment, aerospace, new energy field of batteries.However, due to the electronic fortune such as electric bicycle, electric motor car or electric vehicle The energy source of defeated tool, can only rely on the rechargeable battery of onboard, must but be limited to rechargeable battery provided it is limited Endurance and extremely long charging time have met with the bottleneck that is difficult to break through so as to cause popularizations of electric transportation tool, meanwhile, show Some graphene battery capacity are smaller, so as to increase charging times, reduce the service life of battery.
Invention content
The purpose of the present invention is to provide a kind of graphene battery of large capacity quick charge, to solve current graphene electricity Caused by when pond is applied to automobile industry, charging time of appearance is longer, capacity is too small the technical issues of charging times increase.
To achieve the above object, the present invention provides a kind of graphene batteries of large capacity quick charge.
The graphene battery of the large capacity quick charge of the present invention, by positive plate, negative plate, diaphragm, electrolyte and battery Shell forms, and the positive plate, negative plate are coated on aluminium foil by positive and negative electrode material form respectively, and the negative material is by three It aoxidizes two iron, micron silica flour, modified graphene oxide, spinel lithium manganate, fatty alcohol polyoxyethylene ether, cathode conductive agent, bear Pole binding agent composition；The negative electrode binder is made of terpene resin, carboxymethyl cellulose, polyacrylic acid and ethanol in proper amount； The cathode conductive agent is made of carbon black and carbon nanotube；The positive electrode is by spinel lithium titanate, fluorination stone Black alkene, polyvinylpyrrolidone, positive conductive agent, positive electrode binder composition；The positive electrode binder is gathered by gelatin, shell Sugar, sodium alginate and appropriate distilled water composition；The positive conductive agent be by polyaniline, carbon nano-fiber, expanded graphite and N-Methyl pyrrolidone forms.
Further, the negative material is made of the raw material of following parts by weight：1-2 parts of di-iron trioxides, 5-10 parts Micron silica flour, 1-5 part graphene oxides, 3-5 parts of spinel lithium manganates, 7-11 parts of fatty alcohol polyoxyethylene ether, 1.5-3.5 parts bear Pole conductive agent, 4-6 part negative electrode binder.
Further, the positive electrode is made of the raw material of following parts by weight：2.5-4 parts of spinel lithium titanates, 1-5 Part fluorinated graphene, 6-12 parts of polyvinylpyrrolidones, 1-3 parts of positive conductive agent, 4-6 parts of positive electrode binders.
Further, the electrolyte be by diethyl carbonate, propene carbonate and dimethyl carbonate by weight 1:3:The mixing of 1 ratio is placed in polyethylene bottle, then the difluorine oxalic acid boracic acid lithium of a concentration of 1mol/L of 0.5 times of mixture weight Sealing preserves, and stands for 24 hours, then again by sodium chloride and lithium metasilicate by weight 1:It adds in into polyethylene bottle, shakes after 2 mixing Even, addition is 1 times of mixture weight, continues to stand for 24 hours to get electrolyte.
Further, the negative electrode binder is made of the raw material of following parts by weight：10-15 parts of terpene resins, 5-10 Part carboxymethyl cellulose, 5-7 parts of polyacrylic acid, ethanol in proper amount.
Further, the cathode conductive agent is made of the raw material of following parts by weight：1.1-2.2 parts of carbon blacks, 2.4-4.8 Part carbon nanotube.
Further, the positive electrode binder is made of the raw material of following parts by weight：2-8 parts of gelatin, 3-6 parts of shells gather Sugar, 2.5-4.5 parts of sodium alginates, appropriate distilled water.
Further, the positive conductive agent is made of the raw material of following parts by weight：1.2-3.8 parts of polyanilines, 2.2- 3.4 parts of carbon nano-fibers, 1-3 parts of expanded graphites, 6-7 parts of N-Methyl pyrrolidones.
Further, the terpene resin in the negative electrode binder, carboxymethyl cellulose weight ratio are 12-14:6-9.
Preferably, the terpene resin in negative electrode binder, carboxymethyl cellulose weight ratio are 13:7.5.
Further, the gelatin in the positive electrode binder, chitosan, sodium alginate weight ratio are：3-7:4-5:3-4.
Preferably, the gelatin in positive electrode binder, chitosan, sodium alginate weight ratio are：1:0.9:0.7.
Further, the graphene battery preparation method of the large capacity quick charge, includes the following steps：
1. prepared by positive conductive agent：The expanded graphite of the parts by weight is taken to be ground into grain size by airslide disintegrating mill be 0.8um, then same carbon nano-fiber, polyaniline and N-Methyl pyrrolidone be placed in homogenizer together, control rotating speed 2000r/min stirs 3min, then mixture is ground to the positive conductive agent that is uniformly dispersed to obtain；
2. prepared by positive electrode binder：By the gelatin of the parts by weight and distilled water according to weight ratio 1:6 ratios mix, side Side heating is stirred until the complete solvent of gelatin, it is 55 DEG C then to control solution temperature, adds chitosan and sodium alginate, is continued Stirring in solution without precipitating up to positive electrode binder；
3. prepared by positive electrode：In parts by weight, by spinel lithium titanate, fluorinated graphene, positive conductive agent, just very viscous Knot agent mixing is placed in magnetic stirring apparatus, then polyvinylpyrrolidone is configured to 50% solution, then add while stirring Enter 50% polyvinylpyrrolidonesolution solution, control addition speed, add and finish in 30min, then material is placed in agate and is ground It is ground in alms bowl, until ground 200 mesh sieves, obtains positive electrode；
4. prepared by cathode conductive agent：In parts by weight, carbon black, carbon nanotube are respectively put into and are put into 100 DEG C of vacuum drying oven Vacuum bakeout 48h, then mixing be ground, be ground to grain size for 0.8um to get cathode conductive agent；
5. prepared by negative electrode binder：In parts by weight, terpene resin, carboxymethyl cellulose, polyacrylic acid are placed in ball milling In tank, the ethyl alcohol of 7 times of mixed weight is added in, adds the agate ball milling pearl that 5 particle diameters are 2cm, it is enterprising in planetary ball mill Row 8h continues wet ball grinding, and rotating speed 250r/min, then under the protection of nitrogen, taking-up is placed on heated at constant temperature at 120 DEG C Then 2h descends heated at constant temperature 40min at 200 DEG C, up to negative electrode binder after natural cooling；
6. prepared by negative material：In parts by weight, by di-iron trioxide, micron silica flour, graphene oxide, spinelle mangaic acid Lithium, cathode conductive agent, negative electrode binder mixing, are ultrasonically treated 15min, add fatty alcohol polyoxyethylene ether, stirring 3h takes out very Sky, 200 mesh sieving, obtains negative material；
7. prepared by battery：Positive electrode and negative material are respectively coated on aluminium foil, after coating, in vacuum drying chamber The dry 2h at 40 DEG C, then to make positive plate and negative plate after 4MPa lower sheetings, place into 100 DEG C of vacuum bakeouts of vacuum drying oven 40min, it is then according to a conventional method that the sealing assembling of positive plate, negative plate and battery case is integral, inject the electrolyte into encapsulation Treated between positive plate and negative plate to get the graphene battery of large capacity quick charge.
The invention has the advantages that：
1st, the graphene battery of large capacity quick charge prepared by the present invention solves existing graphene battery storage and holds The phenomenon that small and charging rate is slow is measured, meanwhile, the corrosion resistance of battery is enhanced, extends service life, stability is preferable, and And to human body and environmentally friendly.Empirical tests, compared with conventional commercial graphene battery, under identical charge condition, during charging Between be obviously shortened 34.94%, battery efficiency can reach 87.73%.
2nd, negative material of the invention is with di-iron trioxide/graphene oxide composite material, then is subject to a micron silica flour, point Spar LiMn2O4, fatty alcohol polyoxyethylene ether, cathode conductive agent, negative electrode binder composition, wherein graphene have individual layer two dimension Honeycomb crystal lattice structure, can be multiple in its surface perfect adaptation formation di-iron trioxide/graphene oxide by ferric oxide particle Condensation material, one side di-iron trioxide, which is fixed on graphene sheet layer, can prevent from reuniting and accumulating, and improve available graphene Surface area makes compound have higher chemical property；On the other hand, graphene sheet layer support di-iron trioxide, lures it into Nanoparticle nucleation grows up and is dispersed in graphene film layer surface, effectively controls the shape of di-iron trioxide on the surface thereof State so that the graphene oxide battery of preparation is therefore with very high capacitance, and di-iron trioxide/graphene oxide is compound Two-dimentional superhigh specific surface area and excellent transmission Electronic Performance possessed by material can significantly improve di-iron trioxide leading in itself Electric energy power and the transmission diffusivity for improving lithium ion, are also added into a micron silica flour in addition, in reaction system so that silicon particle with The ferric oxide particle being embedded in lattice is wrapped on graphene film, and two-dimentional graphene film is as leading between particle Electric network reduces the contact resistance of entire cathode, improves the utilization rate of silicon and di-iron trioxide, while can also be shown after wrapping up The volume expansion of the buffering silicon of work, is more advantageous to the deintercalation of lithium ion, further improves the charge-discharge performance warp of lithium ion battery Verification, for the negative material of graphene battery of the present invention in the case where current density is 100mAh/g, charge and discharge capacity is up to 1279 respectively And 1687mAh/g, after 100 cycle periods, capacity is still up to 1018mAh.
3rd, when preparing positive electrode, the binding agent being prepared by chitosan, gelatin and sodium alginate, seaweed have been selected Sour sodium is a kind of polysaccharide extracted in brown algae, contains the oxygen-containing functional groups such as carboxyl, hydroxyl, ether in chemical constitution, with anode In active material：Chemical interaction occurs for spinel lithium titanate, moreover it is possible to which the expansion of buffers active substance improves positive electrode Globality and stability, reduce polarization and impedance so that positive electrode shows good chemical property, while in system The gelatin of middle addition is not only more environmentally-friendly as dispersant, but also gelatin has high dispersion, high viscosity characteristic, the dispersion steady It is qualitative, the whole internal resistance of the interface impedance and battery of electrode and electrolyte can be reduced, improve positive electrode arrives electric conductivity, It can effectively solve the problem that positive electrode is easily swollen in the battery, and various substances made to reunite, reduce positive conductive Technical problem.When preparing positive electrode binder in the present invention, by gelatin, chitosan and sodium alginate by weight 1:0.9:0.7 It is mixed, that is to say, that gelatin, chitosan and sodium alginate quality are respectively 38.5%, 34.6% and 26.9%, through excessive It is secondary experiment it is found that gelatin, chitosan and sodium alginate composition binder system in, when gelatin, chitosan and sodium alginate When the one or two of three add in excessive, since gelatin, chitosan and sodium alginate are all with hydrophily, then electricity can be absorbed It solves liquid and expands so that anode destroys, contact variation between the various active materials in anode seriously leads to the strong of anode Polarization and low circulation performance.When the one or two of gelatin, chitosan and sodium alginate three add in very few, effect is bonded The bad regional area of fruit is easily scattered in the case where electrolyte penetrates into, and the structural stability of anode electrode is made to be deteriorated, therefore, Only when gelatin, chitosan and sodium alginate three are by weight 1:0.9:0.7 when being mixed, could be in positive electrode it is each The maximum effect of kind active material performance, whole anode system stability highest, chemical property are best.
4th, when preparing negative material, selected what is be prepared by terpene resin, carboxymethyl cellulose and polyacrylic acid Binding agent is added when three kinds of terpene resin, carboxymethyl cellulose and polyacrylic acid substances form compound water-based binder into negative When in the material of pole, since terpene resin is a kind of excellent tackifier, have that bonding force is strong, anti-aging property is good, heat-resisting, resistance to The excellent performances such as light, acid and alkali-resistance, nontoxic, with carboxymethyl cellulose, polyacrylic acid, the dispersion that can significantly improve negative material is steady It is qualitative, the electric conductivity of negative electrode is improved, improves the performance of battery, good cycling stability, in the present invention, by terpene resin, carboxylic In the negative electrode binder system of methylcellulose and polyacrylic acid composition, when terpene resin, carboxymethyl cellulose weight ratio are more than 13:When 7.5, that is to say, that terpene resin quality is excessive, then causes adhesive property too strong so that the various active materials of negative material Disperse it is uneven so that cathode cycle performance is unstable, so as to influence the overall stability of battery and chemical property.Work as terpene Olefine resin, carboxymethyl cellulose weight ratio are less than 13:When 7.5, that is to say, that terpene resin quality is too small, then cathode bond effect Bad, then the electrolyte in battery can infiltrate negative material, and capacitance forfeiture rate then greatly improves, and capacitance is reduced, and can be shown Writing reduces the chemical property of battery, shortens the cycle life of battery.Therefore, only when terpene resin, carboxymethyl cellulose weight Than being 13:When 7.5, adhesive property is optimal, and preferably, the polarization impedance of negative electrode is minimum, and will not cause electrolyte for dispersibility Negative material is infiltrated, the chemical property of battery is optimal, and cycle performance is also best.Empirical tests, by of the present invention heavy Measure than mixing negative electrode binder cathode, with the electric current of 175mA/g 2.5-4.2V recycle 500 times, specific discharge capacity from 135.9mAh/g drops to 134.2mAh/g.
Other than objects, features and advantages described above, the present invention also has other objects, features and advantages. The present invention is further detailed explanation below.
Specific embodiment
The embodiment of the present invention is described in detail below, but the present invention can be limited and be covered according to claim Multitude of different ways implement.
Embodiment 1
A kind of graphene battery of large capacity quick charge, by positive plate, negative plate, diaphragm, electrolyte and battery case Composition, the positive plate, negative plate are coated on aluminium foil by positive and negative electrode material form respectively, negative described in the negative material Pole material is made of the raw material of following parts by weight：1 part of di-iron trioxide, 5 parts of micron silica flours, 1 part of graphene oxide, 3 parts of points Spar LiMn2O4,7 parts of fatty alcohol polyoxyethylene ether, 1.5 parts of cathode conductive agents, 4 parts of negative electrode binders；The positive electrode by The raw material composition of following parts by weight：2.5 parts of spinel lithium titanates, 1 part of fluorinated graphene, 6 parts of polyvinylpyrrolidones, 1 part Positive conductive agent, 4 parts of positive electrode binders；The negative electrode binder is made of the raw material of following parts by weight：10 parts of terpenes trees Fat, 5 parts of carboxymethyl celluloses, 5 parts of polyacrylic acid, ethanol in proper amount；The cathode conductive agent by following parts by weight raw material Composition：1.1 parts of carbon blacks, 2.4 parts of carbon nanotubes；The positive electrode binder is made of the raw material of following parts by weight：2 parts bright Glue, 3 parts of chitosans, 2.5 parts of sodium alginates, appropriate distilled water；The positive conductive agent by following parts by weight raw material group Into：1.2 parts of polyanilines, 2.2 parts of carbon nano-fibers, 1 part of expanded graphite, 6 parts of N-Methyl pyrrolidones；The electrolyte be by Diethyl carbonate, propene carbonate and dimethyl carbonate are by weight 1:3:The mixing of 1 ratio is placed in polyethylene bottle, then The difluorine oxalic acid boracic acid lithium sealing of a concentration of 1mol/L of 0.5 times of mixture weight preserves, and stands for 24 hours, then again by sodium chloride With lithium metasilicate by weight 1:It adds in into polyethylene bottle, shakes up after 2 mixing, addition is 1 times of mixture weight, is continued quiet It puts for 24 hours to get electrolyte；
Embodiment 2
A kind of graphene battery of large capacity quick charge, by positive plate, negative plate, diaphragm, electrolyte and battery case Composition, the positive plate, negative plate are coated on aluminium foil by positive and negative electrode material form respectively, and the negative material is by following heavy Measure the raw material composition of number：2 parts of di-iron trioxides, 10 parts of micron silica flours, 5 parts of graphene oxides, 5 parts of spinel lithium manganates, 11 Part fatty alcohol polyoxyethylene ether, 3.5 parts of cathode conductive agents, 6 parts of negative electrode binders；The positive electrode is by following parts by weight Raw material composition：4 parts of spinel lithium titanates, 5 parts of fluorinated graphenes, 12 parts of polyvinylpyrrolidones, 3 parts of positive conductive agent, 6 parts Positive electrode binder；The negative electrode binder is made of the raw material of following parts by weight：15 parts of terpene resins, 10 parts of carboxymethyl fibres Dimension element, 7 parts of polyacrylic acid, ethanol in proper amount；The cathode conductive agent is made of the raw material of following parts by weight：2.2 parts of carbon blacks, 4.8 parts of carbon nanotubes；The positive electrode binder is made of the raw material of following parts by weight：8 parts of gelatin, 6 parts of chitosans, 4.5 Part sodium alginate, appropriate distilled water；The positive conductive agent is made of the raw material of following parts by weight：3.8 parts of polyanilines, 3.4 parts of carbon nano-fibers, 3 parts of expanded graphites, 7 parts of N-Methyl pyrrolidones；The electrolyte is by diethyl carbonate, carbon Acid propylene ester and dimethyl carbonate are by weight 1:3:The mixing of 1 ratio is placed in polyethylene bottle, then 0.5 times of mixture weight The difluorine oxalic acid boracic acid lithium sealing of a concentration of 1mol/L preserve, stand for 24 hours, then again by sodium chloride and lithium metasilicate by weight 1:It adds in into polyethylene bottle, shakes up after 2 mixing, addition is 1 times of mixture weight, continues to stand for 24 hours to get electrolysis Liquid.
Embodiment 3
A kind of graphene battery of large capacity quick charge, by positive plate, negative plate, diaphragm, electrolyte and battery case Composition, the positive plate, negative plate are coated on aluminium foil by positive and negative electrode material form respectively, and the negative material is by following heavy Measure the raw material composition of number：1.5 parts of di-iron trioxides, 7 parts of micron silica flours, 3 parts of graphene oxides, 4 parts of spinel lithium manganates, 9 Part fatty alcohol polyoxyethylene ether, 2.5 parts of cathode conductive agents, 5 parts of negative electrode binders；The positive electrode is by following parts by weight Raw material composition：3.2 parts of spinel lithium titanates, 3 parts of fluorinated graphenes, 9 parts of polyvinylpyrrolidones, 2 parts of positive conductive agent, 5 Part positive electrode binder；The negative electrode binder is made of the raw material of following parts by weight：13.5 parts of terpene resins, 7.5 parts of carboxylics Methylcellulose, 6 parts of polyacrylic acid, ethanol in proper amount；The cathode conductive agent is made of the raw material of following parts by weight：1.7 Part carbon black, 3.6 parts of carbon nanotubes；The positive electrode binder is made of the raw material of following parts by weight：5 parts of gelatin, 4.5 parts of shells Glycan, 3.5 parts of sodium alginates, appropriate distilled water；The positive conductive agent is made of the raw material of following parts by weight：2.5 part Polyaniline, 2.8 parts of carbon nano-fibers, 2 parts of expanded graphites, 6.5 parts of N-Methyl pyrrolidones；The electrolyte is by diethyl Carbonic ester, propene carbonate and dimethyl carbonate are by weight 1:3:The mixing of 1 ratio is placed in polyethylene bottle, then mixture The difluorine oxalic acid boracic acid lithium sealing of a concentration of 1mol/L of 0.5 times of weight preserves, and stands for 24 hours, then again by sodium chloride and silicic acid Lithium is by weight 1:It adding in into polyethylene bottle, shakes up after 2 mixing, addition is 1 times of mixture weight, is continued to stand for 24 hours, Up to electrolyte.
Embodiment 4
A kind of above-described embodiment 1- graphene battery preparation methods of large capacity quick charge described in embodiment 3 include with Lower step:
1. prepared by positive conductive agent：The expanded graphite of the parts by weight is taken to be ground into grain size by airslide disintegrating mill be 0.8um, then same carbon nano-fiber, polyaniline and N-Methyl pyrrolidone be placed in homogenizer together, control rotating speed 2000r/min stirs 3min, then mixture is ground to the positive conductive agent that is uniformly dispersed to obtain；
2. prepared by positive electrode binder：By the gelatin of the parts by weight and distilled water according to weight ratio 1:6 ratios mix, side Side heating is stirred until the complete solvent of gelatin, it is 55 DEG C then to control solution temperature, adds chitosan and sodium alginate, is continued Stirring in solution without precipitating up to positive electrode binder；
3. prepared by positive electrode：In parts by weight, by spinel lithium titanate, fluorinated graphene, positive conductive agent, just very viscous Knot agent mixing is placed in magnetic stirring apparatus, then polyvinylpyrrolidone is configured to 50% solution, then add while stirring Enter 50% polyvinylpyrrolidonesolution solution, control addition speed, add and finish in 30min, then material is placed in agate and is ground It is ground in alms bowl, until ground 200 mesh sieves, obtains positive electrode；
4. prepared by cathode conductive agent：In parts by weight, carbon black, carbon nanotube are respectively put into and are put into 100 DEG C of vacuum drying oven Vacuum bakeout 48h, then mixing be ground, be ground to grain size for 0.8um to get cathode conductive agent；
5. prepared by negative electrode binder：In parts by weight, terpene resin, carboxymethyl cellulose, polyacrylic acid are placed in ball milling In tank, the ethyl alcohol of 7 times of mixed weight is added in, adds the agate ball milling pearl that 5 particle diameters are 2cm, it is enterprising in planetary ball mill Row 8h continues wet ball grinding, and rotating speed 250r/min, then under the protection of nitrogen, taking-up is placed on heated at constant temperature at 120 DEG C Then 2h descends heated at constant temperature 40min at 200 DEG C, up to negative electrode binder after natural cooling；
6. prepared by negative material：In parts by weight, by di-iron trioxide, micron silica flour, graphene oxide, spinelle mangaic acid Lithium, cathode conductive agent, negative electrode binder mixing, are ultrasonically treated 15min, add fatty alcohol polyoxyethylene ether, stirring 3h takes out very Sky, 200 mesh sieving, obtains negative material；
7. prepared by battery：Positive electrode and negative material are respectively coated on aluminium foil, after coating, in vacuum drying chamber The dry 2h at 40 DEG C, then to make positive plate and negative plate after 4MPa lower sheetings, place into 100 DEG C of vacuum bakeouts of vacuum drying oven 40min, it is then according to a conventional method that the sealing assembling of positive plate, negative plate and battery case is integral, inject the electrolyte into encapsulation Treated between positive plate and negative plate to get the graphene battery of large capacity quick charge.
Graphene battery charging time comparison prepared by 1 commercially available graphene lithium battery of table and the embodiment of the present invention
By table 1 it will be apparent that, compared with commercially available graphene battery, 1-3 of the embodiment of the present invention prepare graphene battery Under identical charge condition, the charging time significantly shortens.
2 commercially available large capacity graphene battery of table is compared with graphene battery charge-discharge performance prepared by the embodiment of the present invention (voltage of electric current, 2.5V in 0.5mA/mg carries out charge-discharge test)
As shown in Table 2, the graphene battery that prepared by the embodiment of the present invention is than commercially available large capacity graphene battery charge and discharge Efficiency significantly improves.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, that is made any repaiies Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims (4)

1. a kind of graphene battery of large capacity quick charge, by positive plate, negative plate, diaphragm, electrolyte and battery case group Into the positive plate, negative plate are coated on aluminium foil by positive and negative electrode material form respectively, it is characterised in that：
The negative material is made of the raw material of following parts by weight：1-2 parts of di-iron trioxides, 5-10 parts of micron silica flours, 1-5 Part graphene oxide, 3-5 parts of spinel lithium manganates, 7-11 parts of fatty alcohol polyoxyethylene ether, 1.5-3.5 parts of cathode conductive agents, 4-6 Part negative electrode binder；
The negative electrode binder is made of the raw material of following parts by weight：10-15 parts of terpene resins, 5-10 parts of carboxymethyl celluloses Element, 5-7 parts of polyacrylic acid, ethanol in proper amount；
The cathode conductive agent is made of the raw material of following parts by weight：1.1-2.2 parts of carbon blacks, 2.4-4.8 parts of carbon nanotubes；
The positive electrode is made of the raw material of following parts by weight：2.5-4 parts of spinel lithium titanates, 1-5 parts of fluorographites Alkene, 6-12 part polyvinylpyrrolidone, 1-3 parts of positive conductive agent, 4-6 parts of positive electrode binders；
The positive electrode binder is made of the raw material of following parts by weight：2-8 parts of gelatin, 3-6 parts of chitosans, 2.5-4.5 parts Sodium alginate, appropriate distilled water；
The positive conductive agent is made of the raw material of following parts by weight：1.2-3.8 parts of polyanilines, 2.2-3.4 parts of nano-sized carbons Fiber, 1-3 part expanded graphite, 6-7 parts of N-Methyl pyrrolidones；
Terpene resin, carboxymethyl cellulose weight ratio in the negative electrode binder are 12-14:6-9；
Gelatin, chitosan, sodium alginate weight ratio in the positive electrode binder are：3-7:4-5:3-4；
The electrolyte is by weight 1 by diethyl carbonate, propene carbonate and dimethyl carbonate:3:1 ratio is mixed Conjunction is placed in polyethylene bottle, and the then difluorine oxalic acid boracic acid lithium sealing of a concentration of 1mol/L of 0.5 times of mixture weight preserves, quiet It puts for 24 hours, then again by sodium chloride and lithium metasilicate by weight 1:It adds in into polyethylene bottle, shakes up, addition is mixed after 2 mixing 1 times of polymer weight, continue stand for 24 hours to get.
2. a kind of graphene battery of large capacity quick charge according to claim 1, it is characterised in that：The cathode Terpene resin, carboxymethyl cellulose weight ratio in binding agent are 13:7.5.
3. a kind of graphene battery of large capacity quick charge according to claim 1, it is characterised in that：The anode Gelatin, chitosan, sodium alginate weight ratio in binding agent are：1:0.9:0.7.
A kind of 4. graphene battery preparation method of large capacity quick charge according to claim 1, which is characterized in that packet Include following steps：
1. prepared by positive conductive agent：The expanded graphite of the parts by weight is taken to be ground into grain size as 0.8um by airslide disintegrating mill, Then same carbon nano-fiber, polyaniline and N-Methyl pyrrolidone are placed in homogenizer together, control rotating speed 2000r/ Min stirs 3min, then mixture is ground to the positive conductive agent that is uniformly dispersed to obtain；
2. prepared by positive electrode binder：By the gelatin of the parts by weight and distilled water according to weight ratio 1:6 ratios mix, side stirring Until the complete solvent of gelatin, it is 55 DEG C then to control solution temperature, adds chitosan and sodium alginate, continues to stir for side heating Into solution without precipitating up to positive electrode binder；
3. prepared by positive electrode：In parts by weight, by spinel lithium titanate, fluorinated graphene, positive conductive agent, positive electrode binder Mixing is placed in magnetic stirring apparatus, then polyvinylpyrrolidone is configured to 50% solution, then add in while stirring 50% polyvinylpyrrolidonesolution solution controls addition speed, adds and finishes, then material is placed in agate mortar in 30min Middle grinding until ground 200 mesh sieves, obtains positive electrode；
4. prepared by cathode conductive agent：In parts by weight, carbon black, carbon nanotube are respectively put into and are put into 100 DEG C of vacuum of vacuum drying oven Toast 48h, then mixing be ground, be ground to grain size for 0.8um to get cathode conductive agent；
5. prepared by negative electrode binder：In parts by weight, terpene resin, carboxymethyl cellulose, polyacrylic acid are placed in ball grinder, The ethyl alcohol of 7 times of mixed weight is added in, adds the agate ball milling pearl that 5 particle diameters are 2cm, 8h is carried out on planetary ball mill and is held Continuous wet ball grinding, rotating speed 250r/min, then under the protection of nitrogen, taking-up is placed on heated at constant temperature 2h at 120 DEG C, then The lower heated at constant temperature 40min at 200 DEG C, up to negative electrode binder after natural cooling；
6. prepared by negative material：In parts by weight, by di-iron trioxide, micron silica flour, graphene oxide, spinel lithium manganate, Cathode conductive agent, negative electrode binder mixing, be ultrasonically treated 15min, add fatty alcohol polyoxyethylene ether, stirring 3h vacuumize, 200 mesh are sieved, and obtain negative material；
7. prepared by battery：Positive electrode and negative material are respectively coated on aluminium foil, after coating, in 40 in vacuum drying chamber Dry 2h at DEG C, then to make positive plate and negative plate after 4MPa lower sheetings, 100 DEG C of vacuum bakeout 40min of vacuum drying oven are placed into, Then it is according to a conventional method that the sealing assembling of positive plate, negative plate and battery case is integral, after injecting the electrolyte into encapsulation process Positive plate and negative plate between to get large capacity quick charge graphene battery.
CN201711459360.8A 2017-12-28 2017-12-28 A kind of graphene battery of large capacity quick charge Withdrawn CN108199039A (en)

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CN109004211A (en) * 2018-07-23 2018-12-14 西安交通大学 A kind of zero strain liquid for power grid energy storage consolidates metal battery and production method
CN109301370A (en) * 2018-09-06 2019-02-01 苏州菲丽丝智能科技有限公司 A kind of graphene battery
CN109713270A (en) * 2018-12-26 2019-05-03 成都新柯力化工科技有限公司 A kind of power battery lithium titanate clad anode material and preparation method
CN109935832A (en) * 2018-11-21 2019-06-25 万向一二三股份公司 A kind of lithium ion battery silicon substrate negative electrode binder and the cathode piece preparation method using the binder
US20200063929A1 (en) * 2018-06-22 2020-02-27 National Tree Company Apparatus and method for harvesting energy for a light
US10718478B2 (en) * 2018-06-22 2020-07-21 National Chirstmas Products LLC Apparatus and method for harvesting energy for a light
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US20200063929A1 (en) * 2018-06-22 2020-02-27 National Tree Company Apparatus and method for harvesting energy for a light
US10718478B2 (en) * 2018-06-22 2020-07-21 National Chirstmas Products LLC Apparatus and method for harvesting energy for a light
US10851956B2 (en) * 2018-06-22 2020-12-01 National Christmas Products Llc Apparatus and method for harvesting energy for a light
CN109004211A (en) * 2018-07-23 2018-12-14 西安交通大学 A kind of zero strain liquid for power grid energy storage consolidates metal battery and production method
CN109004211B (en) * 2018-07-23 2020-06-19 西安交通大学 Zero-strain liquid-solid metal battery for power grid energy storage and manufacturing method
CN109301370A (en) * 2018-09-06 2019-02-01 苏州菲丽丝智能科技有限公司 A kind of graphene battery
CN109935832A (en) * 2018-11-21 2019-06-25 万向一二三股份公司 A kind of lithium ion battery silicon substrate negative electrode binder and the cathode piece preparation method using the binder
CN109713270A (en) * 2018-12-26 2019-05-03 成都新柯力化工科技有限公司 A kind of power battery lithium titanate clad anode material and preparation method
CN112803000A (en) * 2019-11-14 2021-05-14 孚能科技(赣州)股份有限公司 Composition for battery negative plate coating, battery negative plate coating slurry, and preparation method and application thereof
CN113921813A (en) * 2021-09-30 2022-01-11 武汉中原长江科技发展有限公司 Novel high-specific-energy seawater battery

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