CN105244504A - Graphene lithium ion battery - Google Patents
Graphene lithium ion battery Download PDFInfo
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- CN105244504A CN105244504A CN201510585648.4A CN201510585648A CN105244504A CN 105244504 A CN105244504 A CN 105244504A CN 201510585648 A CN201510585648 A CN 201510585648A CN 105244504 A CN105244504 A CN 105244504A
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- lithium ion
- graphene
- ion battery
- negative
- pole piece
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a graphene lithium ion battery. The preparation method comprises the steps of separately dispersing prepared a nano-particle positive electrode material, a binder, and a mixed conductive agent containing graphene into a prepared solvent, stirring and mixing uniformly to obtain a positive electrode sizing agent; separately dispersing prepared a nano-particle negative electrode material, the conductive agent and the binder into a prepared solvent, stirring and mixing uniformly to obtain a negative electrode sizing agent; coating the positive electrode sizing agent on the two side surfaces of a positive current collector, drying and cutting into a positive electrode pole piece; coating the negative electrode sizing agent on the two side surfaces of a negative current collector, drying and cutting into a negative electrode pole piece; and preparing the electric core of the graphene lithium ion battery from the positive electrode pole piece, a membrane, and the negative electrode pole piece in a laminating or winding manner.
Description
Technical field
The invention belongs to rechargeable battery technical field, be specifically related to a kind of lithium ion battery.
Background technology
Lithium ion battery is a kind of secondary rechargeable battery, main dependence lithium ion mobile working between a positive electrode and a negative electrode, and in charge and discharge process, lithium ion comes and goes and embeds and deintercalation between positive and negative two electrodes.Lithium battery interior adopts helically coiling or stack structure structure, is made up of positive pole, barrier film, negative pole, organic electrolyte, battery case.Organic polyelectrolyte solution is filled with in battery.Form whole polymer lithium electricity charge and discharge cycles system.In lithium ion battery, positive electrode occupies larger proportion, and the mass ratio of positive and negative pole material is 3:1 ~ 4:1.Anode material for lithium-ion batteries occupies core status in lithium battery, the performance of anode material for lithium-ion batteries directly affect lithium ion battery property indices, the cost of the positive electrode of lithium battery also directly determines battery cost height.The positive electrode of current commercial lithium example battery is mostly LiFePO4, LiMn2O4, cobalt acid lithium, adds a small amount of LiMn2O4 in nickle cobalt lithium manganate and nickle cobalt lithium manganate (ternary material).Those material energy densities are high, cheap, excellent in safety, are specially adapted to the development of electrokinetic cell.But the resistivity of these positive electrodes is large, electrode material utilization is low.And the positive electrode of business lithium battery is attached in collector plate, in order to increase conductivity between positive electrode and collector plate and adhesive force, the conductive agent increased between positive electrode and collector plate and binding agent, reduce the energy storage density of lithium battery, produce larger resistance and thermal resistance, in battery use procedure, lithium ion battery is generated heat, cause that service life of lithium battery is short, multiplying power is low, Nei Regao, utilance are low.
Graphene is the two dimensional crystal only having one deck atomic thickness being stripped out from graphite material, being made up of carbon atom.Graphene, as new material, has the specific surface of superelevation and superpower conductivity.High-ratio surface characteristic causes Graphene to have large DBP value, and imbibition and liquid-keeping property are that general conductive agent is incomparable.Under Graphene normal temperature, electron mobility is more than 15000cm2/Vs, and than CNT (carbon nano-tube) or silicon wafer height, electronics movement velocity wherein reaches 1/300 of the light velocity, considerably beyond the movement velocity of electronics in general conductor.And the resistivity of Graphene is only about 1 Ω m, than copper or silver lower, for resistivity is in the world minimum, conductivity best material.Graphene can be strengthened greatly the conductive capability of lithium ion battery as the conductive agent of commercial Li-ion batteries, but the cost of grapheme material is high, causes the cost of lithium ion battery too high, is unfavorable for applying.
Disclose as Chinese patent discloses No. 101572327 the lithium ion battery that a kind of Graphene is negative material, it comprises: metal shell, battery lead plate, electrolyte and barrier film.Anode electrode plate active material used is conventional anode material for lithium-ion batteries, comprises cobalt acid lithium, lithium phosphate, LiMn2O4, lithium nickelate, cobalt nickel lithium manganate ternary material etc.Electrolyte is lithium ion battery lithium hexafluorophosphate electrolyte solution, and negative pole adopts grapheme material.But the lithium ion battery of this disclosure of the invention also could not improve the problem that current anode material for lithium-ion batteries resistivity is large, stock utilization is low, and negative material all adopts Graphene to cause the manufacturing cost of battery to raise.
And for example Chinese patent discloses No. 103545531 and discloses a kind of lithium ion battery.This lithium ion battery comprises spaced positive plate and negative plate.In this positive plate and negative plate, at least one comprises a collector.This collector is a graphene film.Described lithium ion battery has higher energy density and longer useful life.But problem that the lithium ion battery that this invention provides does not improve that the resistivity that conventional lithium ion battery positive electrode exists is large, stock utilization is low etc., and cost is too high, is unfavorable for applying.
For another example Chinese patent discloses the ultra-high magnifications LiFePO4 cylindrical battery that No. 203351704 discloses a kind of graphene-containing coating.The ultra-high magnifications LiFePO4 cylindrical battery of this Graphene coating, be made up of battery core, cylinder box hat, block etc., wherein battery core is formed together with membrane winding by anode pole piece, cathode pole piece, anode pole piece is made up of plus plate current-collecting body aluminium foil, Graphene coating, LiFePO4 coating, cathode pole piece is made up of negative current collector Copper Foil, Graphene coating, negative material coating, is filled with electrolyte between cylinder box hat and battery core.Anode pole piece is welded with positive pole ear, cathode pole piece is welded with negative lug.But, the ultra-high magnifications LiFePO4 cylindrical battery of the graphene-containing coating that this utility model provides is using Graphene coating as conductive agent, the mode of Graphene coating can increase the thickness of the both positive and negative polarity pole piece of battery, increase positive/negative plate and made the difficulty of battery by lamination or winding method, and cost too high being unfavorable for applies.
Disclose No. 204333111 for another Chinese patent and disclose a kind of copper-base graphite alkene polymer lithium battery cathode structure.This copper-base graphite alkene polymer lithium battery cathode structure comprises: negative pole graphite dielectric substrate, graphene film layer, Copper Foil.Growing graphene thin layer on the negative copper foil of affluxion body of polymer lithium electricity, graphene film skin attachment graphite dielectric substrate.But, this copper-base graphite alkene polymer lithium battery cathode structure problem of could not improving that the resistivity that traditional anode material of lithium battery exists is large, stock utilization is low etc.
Also disclose a kind of high-density graphite alkene lithium battery as Chinese patent discloses No. 204361191, it includes barrier film, plus plate current-collecting body conductive layer, graphene layer I, graphene layer II, negative current collector conductive layer; Barrier film is connected with plus plate current-collecting body conductive layer, and plus plate current-collecting body conductive layer is arranged on the centre position of the barrier film after symmetrical fold; Barrier film is connected with negative current collector conductive layer; Negative current collector conductive layer covers on the inner surface of the barrier film after symmetrical fold; Plus plate current-collecting body conductive layer is arranged at intervals with graphene layer I, negative current collector conductive layer is arranged at intervals with graphene layer II.But, the thickness that graphene layer can increase collector conductive layer is increased in the high-density graphite alkene lithium battery that this utility model provides, increase positive/negative plate makes battery difficulty by lamination or winding method, and use the method for graphene layer, cost too apply by high being unfavorable for.
Therefore, provide one can strengthen lithium ion cell positive conductivity, the preparation method improving the low cost lithium ion battery of positive material utilization ratio is the important directions of research.
Summary of the invention
The object of this invention is to provide a kind of graphene lithium ion battery and preparation method thereof, it can by adding Graphene in lithium ion battery conductive agent, optimize battery anode slurry and cathode size, improve the conductive capability of lithium ion cell positive and negative pole, reduction cell positive material is combined with positive collector plate, negative material is combined with negative collector plate the resistance produced, improve electrode utilance, to solve compared with low cost the problem that conventional lithium ion battery positive electrode resistance rate is large, electrode material utilization is low.
The positive pole of graphene lithium ion battery prepared in accordance with the present invention and positive collector plate, negative pole and negative collector plate are combined closely, conductive agent in positive pole coating layer and negative pole coating layer contains Graphene, the interpolation of Graphene reduces the resistance of lithium ion cell positive and negative pole, the advantage of the conductivity that Graphene is good, improve the conductivity of anode and negative pole, improve simultaneously anode material for lithium-ion batteries and negative material in repeated work process in the large problem of heat.
According to an aspect of the present invention, a kind of graphene lithium ion battery is provided, the battery core of this graphene lithium ion battery comprises anode pole piece, cathode pole piece and the barrier film be arranged between described anode pole piece and described cathode pole piece, wherein, anode pole piece comprises plus plate current-collecting body and is arranged at the positive pole coating layer of described plus plate current-collecting body two sides respectively, positive pole coating layer is coated on described anode collection surface by nano particle positive electrode mixture and makes, positive electrode mixture is by positive electrode, binding agent, hybrid conductive agent and solvent are prepared from, wherein, Graphene is comprised in hybrid conductive agent.
Selectively, cathode pole piece comprises plus plate current-collecting body and is arranged at the negative pole coating layer of described negative current collector two sides respectively, negative pole coating layer is coated on negative pole currect collecting surface by negative material mixture and makes, and negative material mixture is prepared from by nano particle negative material, binding agent, hybrid conductive agent and solvent.Wherein, Graphene is comprised in hybrid conductive agent.
Preferably, in positive electrode mixture, Graphene content is 5 ~ 15 ‰, and in negative material mixture, Graphene content is 5 ~ 10 ‰.
Selectively, the positive electrode of this graphene lithium ion battery can be at least one in following material: LiFePO4, LiMn2O4, cobalt acid lithium or nickle cobalt lithium manganate.
Selectively, the negative material of this graphene lithium ion battery can be at least one in following material: native graphite, Delanium, carbonaceous mesophase spherules, tin-based oxide, silicon-base alloy, titanyl compound.
Selectively, the solvent of this graphene lithium ion battery is water.
Selectively, the binding agent of this graphene lithium ion battery can be at least one in following material: the copolymer of the copolymer of Kynoar, polytetrafluoroethylene, sodium carboxymethylcellulose, styrene and butadiene, acrylonitrile multiple copolymer, acrylonitrile and butadiene.
Selectively, the plus plate current-collecting body of this graphene lithium ion battery battery core is aluminium foil.
Selectively, the negative current collector of this graphene lithium ion battery battery core is Copper Foil.
Selectable, the positive pole of this graphene lithium ion battery battery core also can select other substitution material.
Selectable, the negative pole of this graphene lithium ion battery battery core also can select other substitution material.
According to a further aspect in the invention, a kind of preparation method of graphene lithium ion battery is provided, comprise: (1), preparation nano particle positive electrode, binding agent, hybrid conductive agent and solvent, ready nano particle positive electrode, binding agent, hybrid conductive agent are distributed to stirring solvent respectively and mix, makes anode sizing agent; (2), prepare nano particle negative material, conductive agent, binding agent and solvent, ready nano particle negative material, conductive agent, binding agent are distributed in solvent and are uniformly mixed, makes cathode size; (3), by anode sizing agent be coated on plus plate current-collecting body both side surface, shear after dry and make anode pole piece; (4), by cathode size be coated on negative current collector both side surface, shear after dry and make cathode pole piece; (5), anode pole piece, barrier film and cathode pole piece are made the battery core of graphene lithium ion battery by lamination or winding method.
Preferably, in step (1), anode sizing agent stirs is carry out in super shearing dispersing apparatus.
Wherein, the stirring of anode sizing agent is to make positive electrode mix with conductive agent, binding agent.
Selectively, the anode sizing agent in step (1) stirs and also can carry out in other equipment, as carried out in double-planet dispersing apparatus, as long as reach the effect stirred.
Preferably, in step (3), anode sizing agent is uniformly coated on the both side surface of described plus plate current-collecting body in vertical double spread mode, and in step (4), cathode size is uniformly coated on the both side surface of described negative current collector in vertical double spread mode.
Preferably, in step (3), (4), the drying of plus plate current-collecting body, negative current collector carries out in coating machine, and the time can be set as 3 ~ 5 minutes.
Selectable, in step (3), (4), plus plate current-collecting body, negative current collector also can be dry by other method, as natural drying.
Beneficial effect of the present invention is as follows: add the vigor that Graphene improves doff lithium when positive pole and negative pole work in (1) conductive agent, improve the utilance of positive electrode and negative material; (2) Graphene is added in hybrid conductive agent, reduce the positive pole internal resistance of lithium ion battery, negative pole internal resistance, improve the conductivity of anode and negative pole, improve simultaneously anode material for lithium-ion batteries and negative material in repeated work process in the large problem of heat, can realize within 6 minutes, being full of electricity fast and thering is no special requirement to quick charge temperature; (3) from the conventional conductive agent that existing lithium ion battery adopts or different as the mode of conductive agent using graphene film, the special preparation technique of anode pole piece of the present invention and cathode pole piece, provide significant conservation the manufacturing cost of battery.
Embodiment
Below by reference example, the present invention is further elaborated, but these elaborations do not limit in any form the present invention.Unless otherwise stated, the implication that all Science and Technology terms used herein have belonging to the present invention and the those skilled in the art of correlative technology field understand usually.
The invention provides a kind of graphene lithium ion battery, the battery core of this graphene lithium ion battery comprises anode pole piece, cathode pole piece and the barrier film be arranged between described anode pole piece and described cathode pole piece, wherein, anode pole piece comprises plus plate current-collecting body and is arranged at the positive pole coating layer of described plus plate current-collecting body two sides respectively, positive pole coating layer is coated on described anode collection surface by nano particle positive electrode mixture and makes, positive electrode mixture is by positive electrode, binding agent, hybrid conductive agent and solvent are prepared from, wherein, Graphene is comprised in hybrid conductive agent.Cathode pole piece comprises plus plate current-collecting body and is arranged at the negative pole coating layer of described negative current collector two sides respectively, negative pole coating layer is coated on negative pole currect collecting surface by negative material mixture and makes, and negative material mixture is prepared from by nano particle negative material, binding agent, hybrid conductive agent and solvent.Wherein, Graphene is comprised in hybrid conductive agent.
Wherein, in positive electrode mixture, Graphene content is 10 ‰, and in negative material mixture, Graphene content is 8 ‰.The positive electrode of this graphene lithium ion battery is LiFePO4.The negative material of this graphene lithium ion battery is graphite.
Below in conjunction with specific embodiment the present invention made and elaborating further, but embodiment should not be construed as limiting the scope of the invention.
Embodiment 1
According to a kind of non-limiting embodiment of the present invention, provide a kind of preparation method of lithium iron phosphate dynamic battery, the method comprises the following steps.
Prepare lithium iron phosphate dynamic battery anode sizing agent: prepare lithium iron phosphate nano particle, binding agent, solvent and hybrid conductive agent, lithium iron phosphate nano particle, binding agent and solvent will be got out be distributed to hybrid conductive agent respectively and mix in super shearing dispersing apparatus, after stirring, make the anode sizing agent of ultralow temperature lithium iron phosphate dynamic battery.Hybrid conductive agent is by conductive black, ks-6, CNts and Graphene mixed preparing.
Prepare ultralow temperature lithium iron phosphate dynamic battery cathode size: prepare the coated Delanium of ultra-fine high-carbon, conductive agent, binding agent and solvent, ready supper-tiny artificial graphite, conductive agent, binding agent and solvent are distributed to surpass and shear the cathode size being mixed and made into lithium iron phosphate dynamic battery in dispersing apparatus.Conductive agent mixes obtained by conductive black, ks-6 and CNts.
Prepare the battery core of aluminium foil as lithium iron phosphate dynamic battery.
By automatic coating machine by ready anode sizing agent and cathode size respectively uniform vertical double spread in the both side surface of plus plate current-collecting body and negative current collector.
Shear after microwave drying and make lithium iron phosphate dynamic battery positive/negative plate, gained positive/negative plate is made the battery core of battery by lamination or winding method.
Electrolyte is injected, by lithium battery seal i.e. obtained lithium iron phosphate dynamic battery toward in lithium ion battery.
Embodiment 2
Optionally, all the other technology contents are identical with embodiment 1, and difference is: prepare in cathode size process, also can add Graphene in conductive agent.
Embodiment 3
Optionally, all the other technology contents are identical with embodiment 1, and difference is: the positive electrode of this graphene lithium ion battery can be LiMn2O4.
Embodiment 4
Optionally, all the other technology contents are identical with embodiment 1, and difference is: the positive electrode of this graphene lithium ion battery can be the mixture (that is, ternary battery) of cobalt acid lithium, LiMn2O4, lithium nickelate.
Although describe the preferred embodiment of the present invention in detail at this, but should be understood that the present invention is not limited to the concrete structure described in detail and illustrate here, other modification and variant can be realized when not departing from the spirit and scope of the invention by those skilled in the art.
Claims (10)
1. a graphene lithium ion battery, the battery core of described graphene lithium ion battery comprises: anode pole piece, cathode pole piece and the barrier film be arranged between described anode pole piece and described cathode pole piece, it is characterized in that: described anode pole piece comprises plus plate current-collecting body and is arranged at the positive pole coating layer of described plus plate current-collecting body two sides respectively, described positive pole coating layer is coated on described anode collection surface by positive electrode mixture and makes, described positive electrode mixture is by nano particle positive electrode, binding agent, hybrid conductive agent and solvent are prepared from, wherein, Graphene is comprised in described hybrid conductive agent.
2. graphene lithium ion battery as claimed in claim 1, it is characterized in that, described cathode pole piece comprises negative current collector and is arranged at the negative pole coating layer of described negative current collector two sides respectively, described negative pole coating layer is coated on described negative pole currect collecting surface by negative material mixture and makes, described negative material mixture is prepared from by nano particle negative material, binding agent, hybrid conductive agent and solvent, wherein, Graphene is comprised in described hybrid conductive agent.
3. graphene lithium ion battery as claimed in claim 2, it is characterized in that, in described positive electrode mixture, Graphene content is 5 ~ 15 ‰, and in described negative material mixture, Graphene content is 5 ~ 10 ‰.
4. graphene lithium ion battery as claimed in claim 3, it is characterized in that, described nano particle positive electrode is at least one in following material: LiFePO4, LiMn2O4, cobalt acid lithium or nickle cobalt lithium manganate.
5. graphene lithium ion battery as claimed in claim 4, it is characterized in that, described nano particle negative material is at least one in following material: native graphite, Delanium, carbonaceous mesophase spherules, tin-based oxide, silicon-base alloy or titanyl compound.
6. graphene lithium ion battery as claimed in claim 5, it is characterized in that, described plus plate current-collecting body is aluminium foil.
7. graphene lithium ion battery as claimed in claim 6, it is characterized in that, described negative current collector is Copper Foil.
8. the preparation method of the graphene lithium ion battery according to any one of claim 1 ~ 7, is characterized in that, comprising:
(1), prepare nano particle positive electrode, binding agent, hybrid conductive agent and solvent, ready nano particle positive electrode, binding agent, hybrid conductive agent are distributed to stirring solvent respectively and mix, makes anode sizing agent;
(2), prepare nano particle negative material, conductive agent, binding agent and solvent, ready nano particle negative material, conductive agent, binding agent are distributed in solvent and are uniformly mixed, makes cathode size;
(3), by anode sizing agent be coated on plus plate current-collecting body both side surface, shear after dry and make anode pole piece;
(4), by cathode size be coated on negative current collector both side surface, shear after dry and make cathode pole piece; And
(5), anode pole piece, barrier film and cathode pole piece are made the battery core of graphene lithium ion battery by lamination or winding method.
9. the manufacture method of graphene lithium ion battery as claimed in claim 8, is characterized in that, stirring in anode sizing agent described in step (1) is carry out in super shearing dispersing apparatus.
10. the manufacture method of graphene lithium ion battery as claimed in claim 9, it is characterized in that, described in step (3), anode sizing agent is uniformly coated on the both side surface of described plus plate current-collecting body in vertical double spread mode, and described in step (4), cathode size is uniformly coated on the both side surface of described negative current collector in vertical double spread mode.
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| CN201510585648.4A CN105244504A (en) | 2015-09-15 | 2015-09-15 | Graphene lithium ion battery |
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| CN201510585648.4A CN105244504A (en) | 2015-09-15 | 2015-09-15 | Graphene lithium ion battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106169606A (en) * | 2016-09-23 | 2016-11-30 | 涵谷新能源科技（上海）有限公司 | A kind of power lithium-ion battery |
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| CN102544502A (en) * | 2010-12-09 | 2012-07-04 | 中国科学院宁波材料技术与工程研究所 | Anode and cathode conductive additive for secondary lithium battery, method for preparing conductive additive, and method for preparing secondary lithium battery |
| CN102956894A (en) * | 2012-10-31 | 2013-03-06 | 内蒙古三信实业有限公司 | Preparation method of lithium iron phosphate material anode sheet |
| CN104882611A (en) * | 2015-04-01 | 2015-09-02 | 广东烛光新能源科技有限公司 | Electrochemical anodic electrode, power storage device containing anodic electrode, and preparation method thereof |
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2015
- 2015-09-15 CN CN201510585648.4A patent/CN105244504A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102544502A (en) * | 2010-12-09 | 2012-07-04 | 中国科学院宁波材料技术与工程研究所 | Anode and cathode conductive additive for secondary lithium battery, method for preparing conductive additive, and method for preparing secondary lithium battery |
| CN102956894A (en) * | 2012-10-31 | 2013-03-06 | 内蒙古三信实业有限公司 | Preparation method of lithium iron phosphate material anode sheet |
| CN104882611A (en) * | 2015-04-01 | 2015-09-02 | 广东烛光新能源科技有限公司 | Electrochemical anodic electrode, power storage device containing anodic electrode, and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106169606A (en) * | 2016-09-23 | 2016-11-30 | 涵谷新能源科技（上海）有限公司 | A kind of power lithium-ion battery |
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