CN103474658B - Flexible lithium ion secondary battery negative pole of a kind of lithium niobate composite carbon nanometer tube and preparation method thereof and application - Google Patents
Flexible lithium ion secondary battery negative pole of a kind of lithium niobate composite carbon nanometer tube and preparation method thereof and application Download PDFInfo
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- CN103474658B CN103474658B CN201310364699.5A CN201310364699A CN103474658B CN 103474658 B CN103474658 B CN 103474658B CN 201310364699 A CN201310364699 A CN 201310364699A CN 103474658 B CN103474658 B CN 103474658B
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- 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 flexible lithium ion secondary battery negative pole of a kind of lithium niobate composite carbon nanometer tube provided by the invention, described electrode is the pyrene of the load lithium niobate of polymer overmold or the carbon nano tube flexible electrode of pyrene derivatives modification.Additionally provide preparation method and the application of this electrode.Preparation technology is simple in this pole, with low cost, this electrode adopts the method for liquid phase growth in situ by lithium niobate material load coated with conductive polymer on the carbon nano tube network of high conductivity and thereon, utilize carbon nano-tube and conducting polymer compound system to have good flexible feature and prepare the flexible electrode film with certain mechanical strength, the flexibility of electrode can be realized well and improve the chemical property of lithium niobate material, this electrode have apparently higher than the charge/discharge capacity of lithium titanate anode and good cycle performance and close to 100% coulombic efficiency, mechanical property is good, excellent electrochemical performance, safe and reliable.
Description
Technical field
The invention belongs to battery material scientific domain, particularly the flexible lithium ion secondary battery negative pole of a kind of lithium niobate composite carbon nanometer tube, also relates to the preparation method of this electrode, also relates to the lithium rechargeable battery comprising this electrode.
Background technology
Carbonate electrolyte liquid is electrolyte the most frequently used in current lithium rechargeable battery system, this kind of electrolyte at discharge voltage lower than 1.0V(vs Li
+/ Li
0) time can decompose, form SEI film, thus affect fail safe and the cyclical stability of battery.In use all there are the problems referred to above in the carbon based negative electrodes material of current commercialization and silica-based, the tin base cathode material developed because oxidation-reduction potential is too low.
Li
4ti
5o
12as a kind of emerging negative material, oxidation-reduction potential is at 1.5V(vs Li
+/ Li
0) left and right, effectively can avoid the problems referred to above.But Li
4ti
5o
12theoretical specific capacity only have 175mAh/g, well below carbon back, silica-based or tin base cathode material.Therefore, in the urgent need to a kind of oxidation-reduction potential at 1.0V(vs Li
+/ Li
0), fail safe is good, cyclical stability is good, specific capacity is high Novel anode material.
The flexibility design of lithium rechargeable battery has also been subject to the extensive concern of academia.This battery adopts the interlayer sandwich structure of simple self-supporting negative pole-electrolyte and membrane layer-self-supporting positive pole to design, owing to eliminating collector, box hat and a large amount of organic electrolyte poured into, the specific energy density of battery and fail safe are greatly improved and application becomes more extensive.
Lithium niobate material is a kind of famous photoelectric material, and from existing report, this material also has the potentiality as ion secondary battery cathode material lithium, and the electrochemical window of application can be controlled in 1.0V(vs Li
+/ Li
0) more than, thus avoid electrolyte decomposition in use.
Summary of the invention
Goal of the invention: the first object of the present invention is to provide the flexible lithium ion secondary battery negative pole of lithium niobate composite carbon nanometer tube that a kind of fail safe is good, cyclical stability is good, specific capacity is high.
The second object of the present invention is to provide the preparation method of above-mentioned negative pole.
The third object of the present invention is to provide a kind of lithium rechargeable battery comprising this electrode.
Technical scheme: the flexible lithium ion secondary battery negative pole of a kind of lithium niobate composite carbon nanometer tube provided by the invention, described electrode is the pyrene of the load lithium niobate of polymer overmold or the carbon nano tube flexible electrode of pyrene derivatives modification.
As preferably, described polymer is azole polymer.
Present invention also offers the preparation method of the flexible lithium ion secondary battery negative pole of above-mentioned lithium niobate composite carbon nanometer tube, comprise the following steps:
(1) preparation of the carbon nano-tube of pyrene or pyrene derivatives modification: carbon nano-tube is placed in pyrene solution or pyrene derivatives solution, stirs and make reaction, obtains the carbon nano-tube of pyrene or pyrene derivatives modification;
(2) preparation of the pyrene of load lithium niobate or the carbon nano-tube of pyrene derivatives modification: are added niobium source and lithium source mixed aqueous solution in the carbon nano-tube solution that pyrene or pyrene derivatives are modified, stirring makes reaction, heat treatment under blanket of nitrogen after reaction, obtains the pyrene of load lithium niobate or the carbon nano-tube of pyrene derivatives modification;
(3) preparation of electrode precursor slurry: the carbon nano-tube that the pyrene of load lithium niobate or pyrene derivatives are modified is added in pyrrole monomer solution, stir the carbon nano tube surface polymerization that pyrrole monomer is modified at pyrene or the pyrene derivatives of load lithium niobate, obtain electrode precursor slurry;
(4) preparation of flexible lithium ion secondary battery negative pole: electrode precursor slurry is adopted coating, the mode of spin coating or suction filtration is compounded on substrate, drying makes substrate separation, heat treatment, to obtain final product.
In step (1), in step (1), pyrene solution or pyrene derivatives solution are the aqueous solution or ethanolic solution, and its molar concentration is 0.02-1mol/L, and the mass ratio of described pyrene or pyrene derivatives and carbon nano-tube is 1:(0.5-10); Reaction time is 6-48h.
In step (2), described niobium source is niobium oxalate, and lithium source is lithium acetate, and the mol ratio in described niobium source, lithium source is 1:1; Carbon nano-tube and lithium acetate mass ratio are (2-10): 1, and reaction temperature is 50-70 DEG C, preferably 60 DEG C, and the reaction time is 8-24h, preferred 12h; Heat treatment temperature is 500-900 DEG C, preferably 700 DEG C, and heat treatment time is 4-6h, preferred 5h.
In step (3), stirring whipping temp is 0-40 DEG C, and mixing time is 6-15h; The mass ratio of described pyrrole monomer and carbon nano-tube is (0.5-5): 1.
In step (4), baking temperature is 80-110 DEG C, and drying time is 4-12h; Heat treatment temperature is 120-180 DEG C, preferably 155 DEG C, and heat treatment time is 1-3h, preferred 2h; Substrate is Kynoar substrate or silicon chip.
Present invention also offers the flexible lithium ion secondary battery negative pole of above-mentioned lithium niobate composite carbon nanometer tube and prepare the application in lithium rechargeable battery.
Beneficial effect: flexible lithium ion secondary battery negative pole preparation technology is simple for lithium niobate composite carbon nanometer tube provided by the invention, with low cost, this electrode adopts the method for liquid phase growth in situ by lithium niobate material load coated with conductive polymer on the carbon nano tube network of high conductivity and thereon, utilize carbon nano-tube and conducting polymer compound system to have good flexible feature and prepare the flexible electrode film with certain mechanical strength, the flexibility of electrode can be realized well and improve the chemical property of lithium niobate material, this electrode have apparently higher than the charge/discharge capacity of lithium titanate anode and good cycle performance and close to 100% coulombic efficiency, mechanical property is good, excellent electrochemical performance, safe and reliable.
Due to Li
4ti
5o
12similar, lithium niobate also also exists the not good shortcoming of conductivity, the present invention is by the carbon nano-tube compound by lithium niobate and high conductivity, and the conductivity of electrode integral can be significantly improved, thus is conducive to electrode and has in use given play to excellent chemical property.
The present invention utilizes carbon nano-tube and the distinctive mechanical property of conducting polymer to prepare flexible electrode, obtained flexible self-supporting electrode good mechanical performance.
The preparation method of this electrode material is the method for solution-phase reaction due to what adopt, experiment workable, experiment flow relative ease.
Accompanying drawing explanation
Fig. 1 is the SEM photo of the flexible lithium ion secondary battery negative pole of lithium niobate composite carbon nanometer tube.
Fig. 2 is the TEM photo of the pyrene of load lithium niobate or the carbon mano-tube composite of pyrene derivatives modification.
Fig. 3 is the charging and discharging curve of the lithium battery adopting the flexible lithium ion secondary battery negative pole of the present invention.
Fig. 4 is the cycle performance of the lithium battery adopting the flexible lithium ion secondary battery negative pole of the present invention.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, concrete material proportion, process conditions and result thereof described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
Embodiment 1
The flexible lithium ion secondary battery negative pole of lithium niobate composite carbon nanometer tube, i.e. the carbon nano tube flexible electrode of the pyrene derivatives modification of the load lithium niobate that azole polymer is coated, its preparation method comprises the following steps:
1. adding pyrene derivatives in the reactor, is solvent with ethanol, is configured to the pyrene derivatives ethanolic solution of 0.5mol/L, ultrasonic rear standing; Add carbon nano-tube, the mass ratio of described pyrene derivatives and carbon nano-tube is 1:5, and powerful ultrasonic agitation reaction 12h, obtains the carbon nano-tube that pyrene derivatives is modified;
2. under the condition keeping powerful ultrasonic agitation, the mixed solution of niobium oxalate containing mol ratio 1:1 and lithium acetate is slowly added in the reactor of the carbon nano-tube of modifying containing pyrene derivatives, carbon nano-tube and lithium acetate mass ratio are 6:1, after 60 DEG C of water-bath 12h, insert and be full of in the tube furnace of blanket of nitrogen, heat treatment 5 hours at 700 DEG C, the carbon nano-tube that the pyrene derivatives obtaining load lithium niobate is modified;
3. the carbon nano-tube that the pyrene derivatives of load lithium niobate is modified is added in pyrrole monomer solution, the mass ratio of described pyrrole monomer and carbon nano-tube is 2.5:1,20 DEG C are stirred 9h, and the carbon nano tube surface polymerization that pyrrole monomer is modified at the pyrene derivatives of load lithium niobate, obtains electrode precursor slurry;
4. electrode precursor slurry is coated on Kynoar substrate, 100 DEG C of dry 8h, utilizes capillary difference in dry run to realize the flexible electrical pole piece of coating and being separated of Kynoar substrate;
5. the flexible electrical pole piece heat treatment 2h at 155 DEG C of temperature will obtained, to obtain final product.
Electrode of the present invention is directly applied to lithium rechargeable battery; And detect the obtained each performance parameter of flexible lithium sulphur battery electrode, the results are shown in Figure 1 to Fig. 4.
Fig. 1 is the SEM photo of the flexible lithium ion secondary battery negative pole of lithium niobate composite carbon nanometer tube, and as shown in Figure 1, gained sample is composited by carbon nano-tube and lithium niobate sheet in microstructure, the two close contact.This phenomenon proved further by the TEM photo of the carbon mano-tube composite that the pyrene of Fig. 2 load lithium niobate or pyrene derivatives are modified.
Fig. 3 is the charging and discharging curve of the lithium battery adopting the flexible lithium ion secondary battery negative pole of the present invention, and as shown in Figure 3, the charge/discharge capacity of battery maintains more than 200mAh/g all the time, apparently higher than current commercialization or the various Li that researching and developing
4ti
5o
12electrode material.In figure, 1st-a curve represents first time charging curve, and 1st-b curve represents first time discharge curve, 2st-a curve represents second time charging curve, 2st-b curve represents second time discharge curve, and 3st-a curve represents third time charging curve, and 3st-b curve represents third time discharge curve.
Fig. 4 is the cycle performance curve of the lithium battery adopting the flexible lithium ion secondary battery negative pole of the present invention, as shown in Figure 4 this application of electrode on battery except in initial charge and discharge process capacity have except certain decay, in charge and discharge process thereafter, show comparatively stable charge/discharge capacity and coulombic efficiency close to 100%.
In sum, the present invention has technique advantage simple, easy and simple to handle in the making of flexible negative pole, the composite battery electrode of the carbon nano-tube be prepared into and lithium niobate material have apparently higher than the charge/discharge capacity of lithium titanate anode and good cycle performance and close to 100% coulombic efficiency, have the potentiality becoming new type lithium ion secondary battery negative pole.
Embodiment 2
The flexible lithium ion secondary battery negative pole of lithium niobate composite carbon nanometer tube, i.e. the carbon nano tube flexible electrode of the pyrene derivatives modification of the load lithium niobate that azole polymer is coated, its preparation method comprises the following steps:
1. adding pyrene derivatives in the reactor, is solvent with water, is configured to the pyrene derivatives ethanolic solution of 0.02mol/L, ultrasonic rear standing; Add carbon nano-tube, the mass ratio of described pyrene derivatives and carbon nano-tube is 1:0.5, and powerful ultrasonic agitation reaction 48h, obtains the carbon nano-tube that pyrene derivatives is modified;
2. under the condition keeping powerful ultrasonic agitation, the mixed solution of niobium oxalate containing mol ratio 1:1 and lithium acetate is slowly added in the reactor of the carbon nano-tube of modifying containing pyrene derivatives, carbon nano-tube and lithium acetate mass ratio are 2:1, after 70 DEG C of water-bath 8h, insert and be full of in the tube furnace of blanket of nitrogen, heat treatment 6 hours at 500 DEG C, the carbon nano-tube that the pyrene derivatives obtaining load lithium niobate is modified;
3. the carbon nano-tube that the pyrene derivatives of load lithium niobate is modified is added in pyrrole monomer solution, the mass ratio of described pyrrole monomer and carbon nano-tube is 0.5:1,40 DEG C are stirred 6h, and the carbon nano tube surface polymerization that pyrrole monomer is modified at the pyrene derivatives of load lithium niobate, obtains electrode precursor slurry;
4. electrode precursor slurry is coated on Kynoar substrate, 80 DEG C of dry 12h, utilizes capillary difference in dry run to realize the flexible electrical pole piece of coating and being separated of Kynoar substrate;
5. the flexible electrical pole piece heat treatment 1h at 180 DEG C of temperature will obtained, to obtain final product.
Embodiment 3
The flexible lithium ion secondary battery negative pole of lithium niobate composite carbon nanometer tube, i.e. the carbon nano tube flexible electrode of the pyrene modification of the load lithium niobate that azole polymer is coated, its preparation method comprises the following steps:
1. adding pyrene in the reactor, is solvent with ethanol, is configured to the pyrene ethanolic solution of 1mol/L, ultrasonic rear standing; Add carbon nano-tube, the mass ratio of described pyrene and carbon nano-tube is 1:10, and powerful ultrasonic agitation reaction 6h, obtains the carbon nano-tube that pyrene is modified;
2. under the condition keeping powerful ultrasonic agitation, the mixed solution of niobium oxalate containing mol ratio 1:1 and lithium acetate is slowly added in the reactor of the carbon nano-tube of modifying containing pyrene, carbon nano-tube and lithium acetate mass ratio are 10:1, after 50 DEG C of water-bath 24h, insert and be full of in the tube furnace of blanket of nitrogen, heat treatment 4 hours at 900 DEG C, the carbon nano-tube that the pyrene obtaining load lithium niobate is modified;
3. the carbon nano-tube that the pyrene of load lithium niobate is modified is added in pyrrole monomer solution, the mass ratio of described pyrrole monomer and carbon nano-tube is 5:1,0 DEG C is stirred 15h, and the carbon nano tube surface polymerization that pyrrole monomer is modified at the pyrene of load lithium niobate, obtains electrode precursor slurry;
4. electrode precursor slurry is coated on smooth silicon chip, 110 DEG C of dry 4h, utilizes capillary difference in dry run to realize the separation of the peaceful whole silicon chip of flexible electrical pole piece of coating;
5. the flexible electrical pole piece heat treatment 3h at 120 DEG C of temperature will obtained, to obtain final product.
Claims (1)
1. a preparation method for the flexible lithium ion secondary battery negative pole of lithium niobate composite carbon nanometer tube, is characterized in that: comprise the following steps:
(1) preparation of the carbon nano-tube of pyrene or pyrene derivatives modification: carbon nano-tube is placed in pyrene solution or pyrene derivatives solution, stirs and make reaction, obtains the carbon nano-tube of pyrene or pyrene derivatives modification; Pyrene solution or pyrene derivatives solution are the aqueous solution or ethanolic solution, and its molar concentration is 0.02-1mol/L, and the mass ratio of described pyrene or pyrene derivatives and carbon nano-tube is 1:(0.5-10); Reaction time is 6-48h;
(2) preparation of the pyrene of load lithium niobate or the carbon nano-tube of pyrene derivatives modification: are added niobium source and lithium source mixed aqueous solution in the carbon nano-tube solution that pyrene or pyrene derivatives are modified, stirring makes reaction, heat treatment under blanket of nitrogen after reaction, obtains the pyrene of load lithium niobate or the carbon nano-tube of pyrene derivatives modification; Described niobium source is niobium oxalate, and lithium source is lithium acetate, and the mol ratio in described niobium source, lithium source is 1:1; Carbon nano-tube and lithium acetate mass ratio are (2-10): 1, and reaction temperature is 50-70 DEG C, and the reaction time is 8-24h; Heat treatment temperature is 500-900 DEG C, and heat treatment time is 4-6h;
(3) preparation of electrode precursor slurry: the carbon nano-tube that the pyrene of load lithium niobate or pyrene derivatives are modified is added in pyrrole monomer solution, stir the carbon nano tube surface polymerization that pyrrole monomer is modified at pyrene or the pyrene derivatives of load lithium niobate, obtain electrode precursor slurry; Whipping temp is 0-40 DEG C, and mixing time is 6-15h; The mass ratio of described pyrrole monomer and carbon nano-tube is (0.5-5): 1;
(4) preparation of flexible lithium ion secondary battery negative pole: electrode precursor slurry is adopted coating, the mode of spin coating or suction filtration is compounded on substrate, drying makes substrate separation, heat treatment, to obtain final product; Heat treatment temperature is 120-180 DEG C, and heat treatment time is 1-3h; Substrate is Kynoar substrate or silicon chip.
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| CN109802130A (en) * | 2018-12-24 | 2019-05-24 | 肇庆市华师大光电产业研究院 | A kind of lithium ion one-shot battery nanometer anode material and preparation method thereof |
| CN110098385B (en) * | 2019-01-16 | 2022-07-12 | 上海普澜特夫精细化工有限公司 | Silicon-hard carbon composite material and preparation method thereof |
| CN110380048A (en) * | 2019-07-05 | 2019-10-25 | 南京理工大学 | Nanostructure LiNbO3/ Graphene electrodes material and preparation method thereof |
| CN112713276B (en) * | 2020-12-30 | 2022-05-03 | 苏州绿科智能机器人研究院有限公司 | Energy storage battery for new energy vehicle |
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| CN101752560B (en) * | 2010-01-13 | 2011-10-19 | 北京大学 | Lithium titanate-carbon composite nano-material, preparation method thereof and application thereof |
| CN102332557B (en) * | 2011-01-28 | 2014-01-15 | 东莞新能源科技有限公司 | Safe cathode of lithium ion battery |
| CN102145885A (en) * | 2011-03-04 | 2011-08-10 | 南京师范大学 | Method for preparing surface phosphorylated water-soluble carbon nanotube and prepared carbon nanotube |
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