CN103247824A - Button-type lithium-ion battery based on novel carbon-based material and preparation method of button-type lithium-ion battery - Google Patents
Button-type lithium-ion battery based on novel carbon-based material and preparation method of button-type lithium-ion battery Download PDFInfo
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- CN103247824A CN103247824A CN2012100385005A CN201210038500A CN103247824A CN 103247824 A CN103247824 A CN 103247824A CN 2012100385005 A CN2012100385005 A CN 2012100385005A CN 201210038500 A CN201210038500 A CN 201210038500A CN 103247824 A CN103247824 A CN 103247824A
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- ion battery
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a preparation method of a lithium-ion battery adopting a novel carbon-based material as a lithium-ion battery negative electrode. The preparation method comprises the follow steps of: preparing a carbon nano tube, graphene and a carbon nano tube/graphene composite material, manufacturing a positive plate and a negative plate, assembling a button-type lithium-ion battery and pressing and sealing the battery. The button-type lithium-ion battery prepared by the method can greatly improve the battery capacity and the rate capability; and moreover, the influence on the active substance structure of the negative electrode is small in the charging and discharging process, and the stability and the cycle performance of the battery can be greatly improved.
Description
[technical field]
The present invention relates to technical field of lithium ion, specifically a kind of with the preparation method of lithium ion battery of novel carbon-based material as negative pole.
[background technology]
Under the overall situation of low-carbon economy, energy-saving and emission-reduction, lithium ion battery is as a kind of novel green cleaning energy-storage battery, and its advantage shows: the operating voltage height, in light weight, volume is little, specific energy is big, have extended cycle life, self-discharge rate is low, operating temperature range is wide, cryogenic property is good, non-environmental-pollution, memory-less effect etc.The buckle type lithium-ion battery is more cylindrical and the rectangular lithium ion battery cost is low, seals easily, and equipment requires simple.It can satisfy modern society's power consumption equipment miniaturization and light-weighted requirement, but commercialization is as the small-sized electronic product power supply, in products such as computer main board, instrument and meter, digital camera.
Carbon nano-tube has unique hollow structure and nano-scale, and its specific area is big, conductivity and chemical stability are good, is considered to the desirable negative material of lithium ion battery.Graphene is as another kind of novel nano material with carbon element, because its special two-dimensional structure and excellent crystallography quality, make it have high mobility, chemistry and mechanical stability, the electricity of the excellence that it possesses, calorifics and mechanical property are expected in the acquisition extensive use of fields such as high-performance nanometer electronic device, energy storage.Carbon nano-tube/graphene composite material can take full advantage of a peacekeeping two dimensional crystal structure of carbon nano-tube and Graphene uniqueness, effectively solve the negative pole volumetric expansion/contraction problem in the lithium ion battery repeated charge process, reach the capacity of lifting lithium ion battery and the effect of cycle life.
[summary of the invention]
Purpose of the present invention is for providing a kind of novel carbon-based material as lithium ion battery negative pole active materials.
Another object of the present invention is for providing a kind of preparation method who contains the buckle type lithium-ion battery of above-mentioned negative electrode active material.
Purpose of the present invention realizes by following measure: design a kind ofly with the preparation method of novel carbon-based material as lithium ion battery negative, comprise that specifically assembling and the compacting of anodal and negative pole film-making, buckle type lithium-ion battery sealed.Positive and negative electrode active material, conductive agent and adhesive are carried out after processed makes slurry, adopt and scrape the skill in using a kitchen knife in cookery and slurry evenly is coated on the positive and negative electrode collection liquid surface makes positive and negative electrode.After positive and negative electrode carried out vacuum drying treatment, adopt tablet press machine that it is suppressed, with card punch positive and negative electrode is cut into circular piece again.Adopt stacked method to be assembled in the button cell positive and negative electrode shell according to following stacking order, inject 1M LiPF simultaneously
6EC/DMC (mass ratio 1: 1) electrolyte: | anode cover | positive pole | electrolyte | barrier film | electrolyte | negative pole | pad | spring leaf | negative electrode casing |.Adopt small-sized hydraulic button cell packaging machine that prepared buckle type lithium-ion battery is sealed at last.
Described positive pole, mainly by the plus plate current-collecting body aluminum or aluminum alloy, and the positive active material, conductive agent and the binding agent that are attached on the plus plate current-collecting body are formed, wherein positive active material adopts LiFePO4 or LiMn2O4 or cobalt nickel LiMn2O4, and accounting for percentage by weight and be 80%-90%, conductive agent, to account for percentage by weight be that to account for percentage by weight be 5%-10% for 5%-10%, binding agent.
Described negative pole, mainly by negative current collector copper or copper alloy, and the negative electrode active material and the binding agent that are attached on the negative current collector are formed, wherein negative electrode active material adopts carbon nano-tube or Graphene or carbon nano-tube/graphene composite material, and accounting for percentage by weight and be 85%-90%, binding agent, to account for percentage by weight be 10%-15%.Carbon nano-tube adopts chemical vapour deposition technique direct growth and getting on the alloy sheet substrate base of nickel and cobalt or copper or iron; Graphene is for revising the preparation of Hummers method and hydrazine hydrate reduction process; Carbon nano-tube/graphene composite material is then mixed with carbon nano-tube and Graphene by ball-milling method.
The present invention compares with prior art, can significantly improve capacity and the high rate performance of lithium ion battery, and the influence of anticathode active material structure is very little in charge and discharge process, promotes stability and the cycle performance of battery greatly.
[description of drawings]
Fig. 1 is structural representation of the present invention.
Fig. 2 is Graphene shape appearance figure in one embodiment of the invention, and Graphene is transparence, illustrates that it is attached on the substrate with thinner thickness, has shown the two-dimensional structure that it is unique.
Fig. 3 for an embodiment among the present invention at 50mA g
-1Discharge and recharge under the current density and the cycle performance curve, its first discharge capacity can reach 481.2mAh g
-1, reversible capacity is 112.5mAh g after 50 circulations
-1, efficiency for charge-discharge finally remains on more than 95%.
Fig. 4 is the carbon nano-tube shape appearance figure of another embodiment among the present invention, and carbon nano-tube is twined alternately and formed the network cavernous structure, and density distribution is even.
Fig. 5 for another embodiment among the present invention at 50mAg
-1Discharge and recharge under the current density and the cycle performance curve, its first discharge capacity can reach 330.8mAh g
-1, reversible capacity is 181.5mAh g after 50 circulations
-1, efficiency for charge-discharge finally remains on more than 97%.
Appointment Fig. 1 is Figure of abstract.
Be anode cover referring to accompanying drawing 1,1; 2 is anodal; 3 is barrier film; 4 is negative pole; 5 is pad; 6 is spring leaf; 7 is negative electrode casing.
[embodiment]
The invention will be further described below in conjunction with accompanying drawing.
Embodiment 1
Adopt to revise the Hummers method and prepare graphene oxide, after being about to graphite powder and volume ratio and being 2: 1 nitric acid and sulfuric acid solution and mixing, under 80 ℃ of oil baths, stir; Filter the resulting solid residue in back and add ice bath in the sulfuric acid with potassium permanganate; Continue to add hydrogen peroxide then and obtain graphene oxide suspension; Obtain Graphene after adding the hydrazine hydrate reduction graphene oxide, its structure as shown in Figure 2.Graphene and Kynoar are carried out processed, after about 2 hours, are 9: 1 mixing with mass ratio in baking under 120 ℃ of normal pressures namely, the N-methyl pyrrolidone are added in the mixture of Graphene and Kynoar again, stir 1 hour under the room temperature, make slurry; Adopt the scraping blade method on Copper Foil, evenly to apply slurry, 60 ℃ of following constant pressure and dries 5 hours, make negative pole.Be to mix at 8: 1: 1 LiFePO4 and acetylene black, Kynoar with mass ratio, again the N-methyl pyrrolidone added in the mixture of LiFePO4 and acetylene black, Kynoar that stirring is 1 hour under the room temperature, makes slurry; Adopt the scraping blade method on aluminium foil, evenly to apply slurry, 60 ℃ of following constant pressure and dries 5 hours, make positive pole.With card punch positive and negative electrode and barrier film are washed into the disk that diameter is 14mm, and behind 0.5MPa pressure lower sheeting, circular positive and negative electrode are put into vacuum drying chamber toasted 12 hours down at 120 ℃.
According to | anode cover | positive pole | electrolyte | barrier film | electrolyte | negative pole | pad | spring leaf | negative electrode casing | lamination order assembling buckle type lithium-ion battery, inject 1M LiPF simultaneously
6EC/DMC (mass ratio 1: 1) electrolyte.Adopt small-sized hydraulic button cell packaging machine that prepared buckle type lithium-ion battery is sealed at last, finish making.Fig. 3 is that prepared buckle type lithium-ion battery is at 50mAg
-1Discharge and recharge under the current density and the cycle performance curve.
Adopt low pressure chemical vapor deposition equipment carbon nano-tube film on iron-nickel alloy sheet, wherein acetylene and hydrogen flowing quantity are respectively 50sccm and 250sccm, growth temperature is 550 ℃, and growth time is 40 minutes, and the pattern of growth gained carbon nano-tube as shown in Figure 4.Method prepares Graphene as described in example 1 above.Be to mix the stainless steel abrading-ball putting into ball grinder and be equipped with 10mm diameter at 1: 1 with carbon nano-tube and Graphene with mass ratio, add an amount of absolute ethyl alcohol as wet grinding media after, ball milling is 2 hours under argon shield, rotating speed is 350r min
-1, obtain carbon nano-tube/graphene composite material at last.Carbon nano-tube/graphene composite material is made negative pole as described in example 1 above; According to method as described in example 1 above, LiMn2O4 is made positive pole, and finish the making of buckle type lithium-ion battery.Fig. 5 is that prepared buckle type lithium-ion battery is at 50mA g
-1Discharge and recharge under the current density and the cycle performance curve.
Claims (6)
1. the preparation method of a buckle type lithium-ion battery, its structure adopts stacked structure, comprises positive pole, negative pole, electrolyte, barrier film, pad, spring leaf, anode cover and negative electrode casing.The positive and negative electrode material is coated in the positive and negative electrode collection liquid surface is made into positive and negative electrode, positive and negative electrode is superimposed together again, barrier film is put in the centre, injects electrolyte, seals in last and pad, spring leaf stacked pack into anode cover and the negative electrode casing.
2. positive pole as claimed in claim 1, it comprises plus plate current-collecting body and is attached to positive electrode on the plus plate current-collecting body that it is characterized in that: described plus plate current-collecting body is aluminum or aluminum alloy; Described positive electrode comprises LiFePO4 or LiMn2O4 or bores nickel LiMn2O4, conductive agent, binding agent, and wherein to account for percentage by weight be that to account for percentage by weight be that to account for percentage by weight be 5%-10% for 5%-10%, binding agent for 80%-90%, conductive agent for LiFePO4 or LiMn2O4 or cobalt nickel LiMn2O4.
3. negative pole as claimed in claim 1, it comprises negative current collector and is attached to negative material on the negative current collector that it is characterized in that: described negative current collector is copper or copper alloy; Described negative material comprises carbon nano-tube or Graphene or carbon nano-tube/graphene composite material, binding agent, and wherein to account for percentage by weight be that to account for percentage by weight be 10%-15% for 85%-90%, binding agent for carbon nano-tube or Graphene or carbon nano-tube/graphene composite material.
4. lithium ion battery negative material as claimed in claim 3 is characterized in that: the carbon nano-tube in the described negative material adopts chemical vapour deposition technique direct growth and getting on the alloy sheet substrate base of nickel and cobalt or copper or iron.
5. lithium ion battery negative material as claimed in claim 3 is characterized in that: the Graphene in the described negative material is for revising the preparation of Hummers method and hydrazine hydrate reduction process.
6. lithium ion battery negative material as claimed in claim 3 is characterized in that: described carbon nano-tube/graphene composite material is mixed by ball-milling method.
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| CN2012100385005A CN103247824A (en) | 2012-02-14 | 2012-02-14 | Button-type lithium-ion battery based on novel carbon-based material and preparation method of button-type lithium-ion battery |
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| CN2012100385005A CN103247824A (en) | 2012-02-14 | 2012-02-14 | Button-type lithium-ion battery based on novel carbon-based material and preparation method of button-type lithium-ion battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450154A (en) * | 2016-11-30 | 2017-02-22 | 哈尔滨工业大学 | Preparation method for in-situ growth of graphene on surface of aluminum current collector of lithium ion battery |
| CN107634225A (en) * | 2017-08-31 | 2018-01-26 | 福建新峰二维材料科技有限公司 | A kind of Dual-ion cell preparation method using hard carbon positive electrode |
| CN108110201A (en) * | 2017-12-27 | 2018-06-01 | 惠州亿纬锂能股份有限公司 | A kind of pole piece fixed mechanism and button cell |
| CN108232282A (en) * | 2017-12-25 | 2018-06-29 | 惠州Tcl金能电池有限公司 | Button cell and preparation method thereof |
-
2012
- 2012-02-14 CN CN2012100385005A patent/CN103247824A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450154A (en) * | 2016-11-30 | 2017-02-22 | 哈尔滨工业大学 | Preparation method for in-situ growth of graphene on surface of aluminum current collector of lithium ion battery |
| CN106450154B (en) * | 2016-11-30 | 2019-03-08 | 哈尔滨工业大学 | A kind of preparation method of lithium ion battery aluminium collection liquid surface growth in situ graphene |
| CN107634225A (en) * | 2017-08-31 | 2018-01-26 | 福建新峰二维材料科技有限公司 | A kind of Dual-ion cell preparation method using hard carbon positive electrode |
| CN108232282A (en) * | 2017-12-25 | 2018-06-29 | 惠州Tcl金能电池有限公司 | Button cell and preparation method thereof |
| CN108110201A (en) * | 2017-12-27 | 2018-06-01 | 惠州亿纬锂能股份有限公司 | A kind of pole piece fixed mechanism and button cell |
| CN108110201B (en) * | 2017-12-27 | 2021-08-24 | 惠州亿纬锂能股份有限公司 | Pole piece fixing mechanism and button cell |
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Application publication date: 20130814 |