CN103904357B - A kind of stretchable wire lithium ion battery and preparation method thereof - Google Patents
A kind of stretchable wire lithium ion battery and preparation method thereof Download PDFInfo
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- CN103904357B CN103904357B CN201410082805.5A CN201410082805A CN103904357B CN 103904357 B CN103904357 B CN 103904357B CN 201410082805 A CN201410082805 A CN 201410082805A CN 103904357 B CN103904357 B CN 103904357B
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- ion battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000835 fiber Substances 0.000 claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 32
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims abstract description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 13
- MWQJGSUQGMJVCS-UHFFFAOYSA-N N=[S+]C(F)(F)F.[Li] Chemical compound N=[S+]C(F)(F)F.[Li] MWQJGSUQGMJVCS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims abstract description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 13
- 239000002238 carbon nanotube film Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 239000007970 homogeneous dispersion Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011245 gel electrolyte Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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
-
- 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 belongs to energy storage device technical field, be specially a kind of stretchable wire lithium ion battery and preparation method thereof.The present invention prepares carbon nano-tube/LiMn2O4 composite fibre first respectively as positive pole, then prepares carbon nano-tube/lithium titanate composite fibre as negative pole; Then both positive and negative polarity fiber is wrapped on an elastic caoutchouc respectively, then is coated with one deck oxirane/succinonitrile/bis trifluoromethyl sulfimide lithium gel-like electrolyte, finally encapsulate, thus obtain a kind of wire lithium ion battery.This wire lithium ion battery has brand-new structure compared to other microdevices, does not need metal collector and binding agent, alleviates the weight and volume of battery, thus improves specific capacity and the energy density of battery.Meanwhile, this battery has good flexibility and tensility, be easy to establishment and integrated, thus have a good application prospect.
Description
Technical field
The invention belongs to miniature energy storage device technical field, be specifically related to a kind of stretchable wire lithium ion battery and material and preparation method thereof.
Background technology
Modern electronic equipment in the urgent need to stretchable electronic equipment, as [1-5] such as display, transducer, solar cells.These light weights, can stretch, characteristic that is collapsible, that can dress makes them in a lot of field such as electronic skin, intelligent robot, show good application prospect [6-8].Therefore, an energy storage system matched is worked out as ultracapacitor and lithium ion battery for its power supply is very necessary.Stretchable ultracapacitor is by some research work report [9-12].As everyone knows, ultracapacitor has high power density, but energy density is lower, therefore greatly limit it in very many-sided application.On the contrary, lithium ion battery energy density is higher, but stretchable lithium ion battery does not also realize.
Lithium ion battery due to its high energy density and fail safe, in ubiquity consumer portable electronic equipment.But lithium ion battery manufactures usually in a rigid plate, and this is unfavorable for many application, particularly on portable and high integrated equipment, because these equipment needs less, gentlier, more flexibly.Therefore people are in the urgent need to developing a kind of lithium ion battery of miniature flexible, to meet the demand of these equipment.People attempt preparing a kind of wire lithium ion battery [13,14] being negative pole with lithium metal line.Compared with conventional planar shape battery, the battery of line style can be made into textile or other structures easily to represent its unique wide application prospect [15-17], but, lithium electrode in battery significantly limit its application, and this wire battery is non-stretchable, in addition, also may destroy when bending.Therefore, people can replace lithium metal as negative pole in the urgent need to working out one, and flexible, can stretch, wearable lithium ion battery.
Summary of the invention
The object of the present invention is to provide a kind ofly to stretch, bent, can weave, the flexible wire lithium ion battery of high power capacity and preparation method thereof.
Stretchable wire lithium ion battery provided by the invention, comprise positive pole, negative pole and electrolyte, wherein, positive pole is the composite fibre be made up of carbon nano-tube and LiMn2O4, negative pole is the composite fibre be made up of carbon nano-tube and lithium titanate, positive polar fibers and negative pole fiber are wrapped on an elastic caoutchouc at a certain angle respectively equably, and positive and negative two electrodes do not contact with each other; Electrolyte is the gel compound of 0.2 ~ 0.6g oxirane, 0.2 ~ 0.6g succinonitrile and 0.2 ~ 0.5g bis trifluoromethyl sulfimide lithium, cover equably be wound with both positive and negative polarity fiber elastic caoutchouc on.Fiber is wrapped on an elastic caoutchouc at a certain angle, and winding angle (angle of the length direction of fiber and rubber) is generally advisable with 45 ° ~ 80 °.
In the present invention, the percentage by weight of described LiMn2O4 in positive pole composite fibre is 10% ~ 95%, and the percentage by weight of lithium titanate in negative pole composite fibre is 10% ~ 95%.
The preparation method of stretchable wire lithium ion battery provided by the invention, concrete steps are:
First, respectively the homogeneous dispersion of LiMn2O4 and lithium titanate is dripped over the carbon nanotube film, then add respectively and be twisted into carbon nano-tube/LiMn2O4 composite fibre and carbon nano-tube/lithium titanate composite fibre;
Then, be wrapped in equably respectively by two fibers on an elastic caoutchouc, two fibers can not contact;
Then, the elastic caoutchouc being tied with both positive and negative polarity fiber is smeared one deck oxirane/succinonitrile/bis trifluoromethyl sulfimide lithium gel-like electrolyte, as shown in Figure 1;
Finally encapsulate.
In the present invention, described LiMn2O4 is prepared by hydro thermal method.Described lithium titanate is prepared by solid state process.
In the present invention, carbon nano pipe array is prepared in tube furnace by chemical vapour deposition technique.Carbon nano pipe array height is at 100-300 μm.Carbon nano tube oriented arranging, top and bottom is all very clean, does not have the deposition of agraphitic carbon.Carbon nano-tube is many wall constructions, and caliber is 5-20nm.Carbon nano-tube fibre weight density is 0.2-0.7g/cm
3, the surface density of carbon nano-tube film is 1-2 μ g/cm
2.
In the present invention, carbon nano-tube film and carbon nano-tube fibre are all obtained by dry spinning by carbon nano pipe array.First be fixed on can spin carbon nano pipe array on sample stage, sample stage can rotate to realize fiber twisting; Then use blade from array edges pull-out continuous print carbon nano-tube film, and the roller be fixed on after carbon nano-tube film twisting is formed fiber for collecting. then open the motor of Quality control platform, sample is rotated with 2000r/min, open the motor controlling roller simultaneously, thus pull straight carbon nano-tube fibre, do not twist if rate of extension is 15cm/min., then obtain continuous print aligned carbon nanotube film.
Gel electrolyte in the present invention is made up of oxirane, succinonitrile, bis trifluoromethyl sulfimide lithium, and succinonitrile is used to suppress the crystallization of oxirane and promote dissociating of bis trifluoromethyl sulfimide lithium, thus realizes higher ionic mobility.Electrolyte has high conductivity ~ 10
-3s/cm.
Carbon nano-tube in the present invention/LiMn2O4 composite fibre diameter is approximately 170 μm (as shown in Figure 2 a), and carbon nano-tube/lithium titanate composite fibre diameter is approximately 130 μm (as shown in Figure 2 b).In composite fibre, LiMn2O4 and lithium titanate particle are evenly dispersed in carbon nano-tube fibre respectively.The structure of LiMn2O4 and lithium titanate is spinel structure.
In charge and discharge process, the redox reaction of generation is:
Positive pole:
Negative pole:
The chemical property of the stretched wire lithium ion battery in the present invention as shown in Figure 3.Battery carries out loop test between the voltage of 1.5V to 3.2V and under the current density of 0.1mA/cm.The averaged discharge platform of battery is 2.2V, and the specific discharge capacity of first lap is 91.3mAh/g, and specific capacity calculates according to whole negative electrode.Carbon nano-tube in the electrodes as skeleton, stably LiMn2O4 and lithium titanate active material winding in the fibre, in addition as collector transmission electronic.Therefore inactive binding agent and metal collector is no longer needed in battery.The length specific capacity of battery is 0.36mAh/m.Two composite fibres are according to angle
θbe wrapped on elastic caoutchouc, as shown in Figure 1a.Length (the L of whole battery
2) can according to the length (L of composite fibre
1) calculate.Computing formula is:
l 2 =
l 1 × cos θ.Therefore, and stretch compared with fiber, after winding, length specific capacity improves (1/cos
θ1) doubly.The coulombic efficiency of battery first lap is 92.1%.After 50 circle circulations, capability retention is 95%, and after 100 circle circulations, capability retention is 78%, shows that battery has a good cycle performance.The energy density of battery and power density are respectively 10.6mWh/cm according to the volume computing of two electrodes
3and 0.294W/cm
3, be respectively 30mWh/g and 0.83W/g according to the Weight computation of two electrodes.
The wire that can stretch lithium ion battery is when being repeatedly stretched to 100%, and the structural intergrity of two composite fibre electrodes does not significantly change, as illustrated in figures 2 c and 2d.The structural intergrity of fiber also can be proved by the change of resistance in test drawing process.In the process being stretched to 100%, the resistance variations of two composite fibre electrodes is less than 1%.In drawing process, we also test the chemical property of lithium ion battery.As seen from Figure 4, under the amount of tension condition that 0-100% is different, the charging and discharging curve of battery can keep well.Under 100% amount of tension condition, the specific capacity conservation rate of battery is more than 90%.In addition, stretch 100% each, stretch after 200 times, the specific capacity conservation rate of battery is more than 80%.Battery, under the condition of 100% amount of tension, carries out long-acting loop test, and after 50 circles, capability retention is more than 90%.
For checking the chemical property of the wire lithium ion battery that can stretch further, we light a business LED with it, as shown in Figure 5.Be stretched in the process of 100% at battery, the brightness of LED does not significantly change.The high tensile property of wire battery is mainly contributed by the complex structure of filament of spring-like and elastic substrates and gel electrolyte.
The present invention is by a kind of carbon nano-tube/LiMn2O4 composite fibre of novelty of preparation and carbon nano-tube/lithium titanate composite fibre respectively as both positive and negative polarity, and the double-spiral structure designing a kind of winding prepares the wire lithium ion battery that can stretch.Wire battery can reach the specific capacity of 91.3mAh/g, and stretches after 200 times in stretching 100%, and capability retention is still more than 84%.In addition, the wire that can stretch battery also has light weight and the advantage such as flexible, therefore, in a lot of field particularly electronic device such as wearable, portable mobile apparatus, shows very promising using value.
Wire lithium ion battery of the present invention has brand-new structure compared to other microdevices, does not need metal collector and binding agent, alleviates the weight and volume of battery, thus improves specific capacity and the energy density of battery.Meanwhile, this battery has good flexibility and tensility, be easy to establishment and integrated, thus have a good application prospect.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of stretch wire lithium ion battery preparation process and stretching and dispose procedure of the present invention.Wherein, a is preparation process schematic diagram, and b is the schematic diagram of stretching and dispose procedure.
Fig. 2 is the ESEM of composite fibre.Wherein, a and b is the ESEM of carbon nano-tube/LiMn2O4 composite fibre and carbon nano-tube/lithium titanate composite fibre respectively, C and d is carbon nano-tube/LiMn2O4 composite fibre and the carbon nano-tube/ESEM of lithium titanate composite fibre after stretching 100% respectively.
Fig. 3 is the chemical property of wire battery of can stretching.Wherein, a is the charge-discharge performance of battery under 0.01mA/cm current density.B is the long-acting cycle performance of battery.C0 and C refers to the specific capacity of first lap and next circulation respectively.
Fig. 4 is for stretching wire performance of lithium ion battery.Wherein, a is current density when being 0.01mA/cm, the charge-discharge performance of the wire that can stretch lithium ion battery under 0%, 20%, 40%, 60%, 80% to 100% amount of tension; B is the capability retention under different stretch amount; C is the capability retention under different stretch number of times; D is the cyclical stability under stretching 100% condition.
Fig. 5 is the optical photograph of wire lithium ion battery of can stretching.Wherein, a, b and c are that the wire lithium ion battery that can stretch is bent into the optical photograph of different shape; D lights the optical photograph of LED for the wire lithium ion battery that can stretch under 0%, 20%, 40%, 60%, 80% to 100% amount of tension.
Fig. 6 is the structural diagrams of wire lithium ion battery of can stretching.
Embodiment
Electrode material carbon nano-tube is prepared according to prior art and chemical vapor infiltration.First Kaolinite Preparation of Catalyst, catalyst adopts version to be Si/SiO
2/ Al
2o
3the composite material of/Fe, wherein Al
2o
3be positioned at the centre of silicon chip and Fe, as resilient coating, Fe is as the active ingredient of catalyst, and they obtain respectively by the film preparation of electron beam evaporation deposition instrument at silicon chip (Si) upper deposition one deck nano thickness.Wherein, SiO2 layer thickness is 300-1000 μm, Al2O3 layer thickness be 10-30nm, Fe layer thickness is 0.5-1.5nm.To the silicon base catalyst of catalyst be coated with towards upper, with the silicon dioxide backing carrying that a slice is larger, put into the quartz ampoule of tube furnace, near the temperature sensing device of tube furnace.Adjustment breather line flow is: argon gas: 200-600sccm hydrogen: 10-100sccm; Ethylene gas: 50-200sccm.Connecting line.First open argon gas, close hydrogen and ethylene gas.At room temperature ventilate 5-10min, to guarantee to get rid of the oxygen among pipeline and steam.Open hydrogen and ethene, 10-20min rises to 500-900 DEG C from room temperature, stablizes 5-20min, turns off ethene and hydrogen when program starts to lower the temperature voluntarily.Open stove when temperature is down to 50-150 DEG C, take out long at suprabasil height-oriented spun carbon nano pipe array.
LiMn
2o
4particle is by water heat transfer.The lithium hydroxide of 0.2-1g is dissolved in the deionized water of 20-80mL, then adds 0.5-2g manganese dioxide.The glucose of 1-2g and the deionized water of 20-80mL is added after stirring 1-3h.At the temperature of 100-400 DEG C, finally react 10-50 hour in a kettle..Li
4ti
5o
12particle is synthesized by solid state process, TiO
2and Li
2cO
3after certain proportion mixing, at 500-1000 DEG C of N
210-50h is heated under atmosphere.Last ball-milling treatment can obtain the lithium titanate particle of Nano grade.
In order to prepare carbon nano-tube/LiMn2O4 composite fibre, first appropriate LiMn2O4 being joined DMF and forming dispersion liquid, then dripping over the carbon nanotube film, finally utilize spinning-drawing machine to twist and namely obtain composite fibre.The preparation method of carbon nano-tube/lithium titanate composite fibre is identical with said method.
Gel electrolyte is prepared under nitrogen atmosphere in glove box.After the mixing of 0.2 ~ 0.6g oxirane, 0.2 ~ 0.6g succinonitrile and 0.2 ~ 0.5g bis trifluoromethyl sulfimide lithium, add the mixed liquor of acetone and carrene, after stirring 2-10h, namely obtain the gel electrolyte of clear.
In order to prepare the wire lithium ion battery that can stretch, be wrapped on an elastic caoutchouc with the even angle of 45 ° ~ 80 ° respectively by two both positive and negative polarity composite fibres, two fibers can not contact.The elastic caoutchouc being tied with both positive and negative polarity fiber is smeared one deck oxirane/succinonitrile/bis trifluoromethyl sulfimide lithium gel-like electrolyte.Finally encapsulate.
The structure of carbon nano tube composite fibre is characterized by scanning electron microscopy (SEM, HitachiFE-SEMS-4800operatedat1kV).The chemical property of battery is by Arbin multi-channel electrochemical tester (Arbin, MSTAT-5V/10mA/16Ch). tensile property completes on measurer for pulling force (HY-0350).
list of references
[1]KimDH,AhnJH,ChoiWM,etal.Science.
2008,320(5875):507-511.
[2]SekitaniT,NakajimaH,MaedaH,etal.Naturematerials.
2009,8(6):494-499.
[3]YamadaT,HayamizuY,YamamotoY,etal.Naturenanotechnology.
2011,6(5):296-301.
[4]LipomiDJ,VosgueritchianM,TeeBCK,etal.Naturenanotechnology,.
2011,6(12):788-792.
[5]LipomiDJ,TeeBCK,VosgueritchianM,AdvancedMaterials.
2011,23(15):1771-1775.
[6]KaltenbrunnerM,SekitaniT,ReederJ,Nature.
2013,499(7459):458-463.
[7]CaiL,SongL,LuanP,Scientificreports.
2013,3.
[8]SomeyaT,SekitaniT,IbaS,ProceedingsoftheNationalAcademyofSciencesoftheUnitedStatesofAmerica.
2004,101(27):9966-9970.
[9]LiX,GuT,WeiB,Nanoletters.
2012,12(12):6366-6371.
[10]HuL,PastaM,MantiaFL,Nanoletters.
2010,10(2):708-714.
[11]ZhaoC,WangC,YueZ,ACSappliedmaterials&interfaces.
2013,5(18):9008-9014.
[12]YuC,MasarapuC,RongJ,AdvancedMaterials.
2009,21(47):4793-4797.
[13]LinH,WengW,RenJ,AdvancedMaterials,
2013.
[14]RenJ,LiL,ChenC,etal.AdvancedMaterials.
2013,25(8):1155-1159.
[15]RenJ,BaiW,GuanG,etal.AdvancedMaterials.
2013,25(41):5965-5970.
[16]ChenT,QiuL,YangZ,etal.ChemicalSocietyReviews.
2013,42(12):5031-5041.
[17]LeeYH,KimJS,NohJ,etal.Nanoletters.
2013,13(11):5753-5761.。
Claims (6)
1. a stretchable wire lithium ion battery, it is characterized in that comprising positive pole, negative pole and electrolyte, wherein, positive pole is the composite fibre be made up of carbon nano-tube and LiMn2O4, negative pole is the composite fibre be made up of carbon nano-tube and lithium titanate, positive polar fibers and negative pole fiber are wrapped on an elastic caoutchouc with the angle of 45 ° ~ 80 ° respectively equably, and positive and negative two electrodes do not contact with each other; Electrolyte is the gel compound of 0.2 ~ 0.6g oxirane, 0.2 ~ 0.6g succinonitrile and 0.2 ~ 0.5g bis trifluoromethyl sulfimide lithium, cover equably be wound with both positive and negative polarity fiber elastic caoutchouc on.
2. stretchable wire lithium ion battery according to claim 1, it is characterized in that the percentage by weight of described LiMn2O4 in positive pole composite fibre is 10% ~ 95%, the percentage by weight of lithium titanate in negative pole composite fibre is 10% ~ 95%.
3. stretchable wire lithium ion battery according to claim 1 and 2, is characterized in that described carbon nano-tube is prepared in tube furnace by chemical vapour deposition technique; Carbon nano pipe array height is at 100-300 μm, and carbon nano-tube is many wall constructions, and caliber is 5-20nm, and carbon nano-tube fibre weight density is 0.2-0.7g/cm
3, the surface density of carbon nano-tube film is 1-2 μ g/cm
2.
4. stretchable wire lithium ion battery according to claim 1, it is characterized in that described LiMn2O4 is prepared by hydro thermal method, described lithium titanate is prepared by solid state process.
5. a preparation method for stretchable wire lithium ion battery as claimed in claim 1, is characterized in that concrete steps are:
First, respectively the homogeneous dispersion of LiMn2O4 and lithium titanate is dripped over the carbon nanotube film, then add respectively and be twisted into carbon nano-tube/LiMn2O4 composite fibre, carbon nano-tube/lithium titanate composite fibre;
Then, be wrapped in equably respectively by two composite fibres on an elastic caoutchouc, two fibers can not contact;
Then, the elastic caoutchouc being tied with both positive and negative polarity composite fibre is smeared one deck oxirane/succinonitrile/bis trifluoromethyl sulfimide lithium gel composite electrolyte;
Finally encapsulate.
6. can stretch the wire lithium ion battery application in field of electronic devices as claimed in claim 1.
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| CN104392845B (en) * | 2014-10-17 | 2017-03-29 | 复旦大学 | A kind of stretchable linear supercapacitor and preparation method of lithium ion battery |
| CN104617336B (en) * | 2015-02-12 | 2017-04-19 | 中国工程物理研究院化工材料研究所 | Linear flexible lithium ion battery and preparation method thereof |
| CN105047999B (en) * | 2015-07-31 | 2017-07-07 | 复旦大学 | Fibrous hydridization energy storage device with high-energy-density and high power density and preparation method thereof |
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| KR102140308B1 (en) * | 2016-12-09 | 2020-07-31 | 주식회사 엘지화학 | Flexible Secondary Battery |
| FR3064116B1 (en) * | 2017-03-15 | 2021-07-16 | Ecole Nat Superieure Des Mines | DEFORMABLE ACCUMULATOR |
| CN107591559B (en) * | 2017-09-29 | 2019-10-11 | 北京航空航天大学 | A kind of lithium ion battery and preparation method of fibrous structure |
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| CN109950639B (en) * | 2019-02-20 | 2021-03-19 | 中国科学院电工研究所 | Metal ion battery and preparation method thereof |
| CN110028789A (en) * | 2019-04-11 | 2019-07-19 | 东华大学 | A kind of preparation method of high-strength wearable strain sensing fiber |
| CN112186241B (en) * | 2020-09-16 | 2022-08-26 | 新疆大学 | Fibrous lithium ion battery with double-spiral structure and preparation method and device thereof |
| CN114628622A (en) * | 2022-03-15 | 2022-06-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | Aluminum ion battery and application thereof |
| CN114899506B (en) * | 2022-05-24 | 2024-02-23 | 哈尔滨工业大学 | Preparation method of telescopic fibrous quasi-solid water system lithium ion battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103155228A (en) * | 2010-08-14 | 2013-06-12 | 塞恩有限责任公司 | Electrode assembly having fiber-shaped structures, and battery including same |
Family Cites Families (2)
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|---|---|---|---|---|
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| US8993172B2 (en) * | 2011-12-10 | 2015-03-31 | Kalptree Energy, Inc. | Li-ion battery and battery active components on metal wire |
-
2014
- 2014-03-09 CN CN201410082805.5A patent/CN103904357B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103155228A (en) * | 2010-08-14 | 2013-06-12 | 塞恩有限责任公司 | Electrode assembly having fiber-shaped structures, and battery including same |
Non-Patent Citations (1)
| Title |
|---|
| Twisting Carbon Nanotube Fibers for Both Wire-Shaped Micro-Supercapacitor and Micro-Battery;Jing Ren等;《Advanced Materials》;20121122;第25卷(第8期);第1155-1159页 * |
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