CN105552342A - Flexible negative electrode with MnO2 attached onto carbon fiber of lithium ion battery and preparation method of flexible negative electrode - Google Patents
Flexible negative electrode with MnO2 attached onto carbon fiber of lithium ion battery and preparation method of flexible negative electrode Download PDFInfo
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- CN105552342A CN105552342A CN201610091503.3A CN201610091503A CN105552342A CN 105552342 A CN105552342 A CN 105552342A CN 201610091503 A CN201610091503 A CN 201610091503A CN 105552342 A CN105552342 A CN 105552342A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention relates to a flexible negative electrode with MnO2 attached onto carbon fibers of a lithium ion battery and a preparation method of the flexible negative electrode. A metal oxide in the prior art is wrapped inside the carbon nanofibers, and thus, the contact of the metal oxide serving as an active substance with an electrode and the de-intercalation process of the metal oxide with lithium ions are not promoted; and further, the metal oxide is Fe2O3, Fe3O4, Co3O4 and the like, and such metal oxide has a defect of relatively high de-intercalation lithium potential. The preparation method is characterized by comprising the following steps of firstly, preparing a flexible carbon nanofiber net, which comprises electrostatic spinning, pre-oxidation of a polymer nanofiber net and high-temperature calcination; secondly, preparing a flexible composite fiber thin film with an MnO2 nanowire attached onto the surfaces of the carbon nanofibers, placing the flexible carbon nanofiber net in a KMnO4 solution, and completing high-temperature reaction under process conditions of a reaction temperature of 150-200 DEG C and reaction time of 30-60 minutes; and finally, cutting the flexible carbon nanofiber net into the flexible negative electrode with MnO2 attached onto the carbon fibers of the lithium ion battery.
Description
Technical field
The present invention relates to a kind of carbon fiber attachment MnO
2the flexible negative pole of lithium ion battery and preparation method thereof, belong to lithium ion cell electrode technical field.
Background technology
Lithium ion battery has that energy density is high, output voltage is high, the outstanding advantages such as good cycling stability and environmental friendliness, becomes the leading chemical power source of portable type electronic product.Along with development that is flexible and wearable mobile electronic device, flexible or folding and lightening requirement is proposed to lithium ion battery, the lithium ion battery with this feature is called flexible lithium ion battery, the main technical requirements of flexible lithium ion battery to have flexible electrode, comprises flexible negative pole.
Flexible electrode has self supporting structure, can cutting, is directly used as lithium ion cell electrode.Its manufacture method overcomes the defect of inflexibility method for making its electrode, and meanwhile, energy density and the security performance of flexible electrode itself are increased dramatically.
The flexible negative pole manufacture method of existing one adopts electrostatic spinning technique, in conjunction with follow-up high-temperature calcination technique, produce metal oxide and carbon nano-fiber laminated film, this laminated film can directly as the flexible negative pole of lithium ion battery, not only there is excellent chemical property, and achieve flexibility, lightening.
But in described prior art, described metal oxide is wrapped in carbon nano-fiber inside, will be unfavorable for that described metal oxide is as active material and the contact of electrolyte and the deintercalation process of lithium ion like this; Further, described metal oxide is Fe
2o
3, Fe
3o
4, Co
3o
4deng, this quasi-metal oxides has the higher shortcoming of removal lithium embedded current potential.
Summary of the invention
The object of the invention is to develop and a kind of there is the flexible negative pole of the low metal oxide supported lithium ion battery on carbon nano-fiber surface of removal lithium embedded current potential.
The carbon fiber attachment MnO of the present invention
2the flexible negative pole of lithium ion battery be a kind of metal oxide and carbon nano-fiber laminated film, it is characterized in that, described metal oxide is MnO
2, described MnO
2form be nano wire, described nano wire is attached to described carbon nano-fiber surface, and form nano wire and carbon nano-fiber composite fibre, the diameter of described composite fibre is 300 ~ 400nm.
The carbon fiber attachment MnO of the present invention
2the flexible negative pole preparation method of lithium ion battery it is characterized in that:
One, the preparation of flexible carbon nano-fiber net
Polyacrylonitrile or polyvinyl alcohol are dissolved in solvent and obtains electrostatic spinning liquid; With described electrostatic spinning liquid for raw material, spinning voltage be 15 ~ 20kV, spinning distance completes electrostatic spinning under being the process conditions of 14 ~ 20cm, obtains polymeric nanofiber web; By the polymeric nanofiber web obtained calcining heat be 245 ~ 255 DEG C, calcination time is complete pre-oxidation under process conditions in 1 ~ 2 hour, obtains pre-oxidation nanometer fiber net; Again calcining heat be 600 ~ 800 DEG C, calcination time is 2 ~ 4 hours, complete high-temperature calcination under protective atmosphere process conditions, obtains flexible carbon nano-fiber net;
Two, carbon nano-fiber surface attachment MnO
2the preparation of the flexible compound fiber membrane of nano wire
Described flexible carbon nano-fiber net is placed in KMnO
4in solution, flexible carbon nano-fiber net and KMnO
4mass ratio be 1:1 ~ 1:2, obtain reactant liquor; By the reactant liquor obtained reaction temperature be 150 ~ 200 DEG C, the reaction time is complete pyroreaction under process conditions in 30 ~ 60 minutes, obtains carbon nano-fiber surface attachment MnO
2the flexible compound fiber membrane of nano wire;
Three, carbon fiber attachment MnO
2the preparation of the flexible negative pole of lithium ion battery
Described carbon nano-fiber surface attachment MnO
2namely the flexible compound fiber membrane of nano wire becomes carbon fiber attachment MnO through size cutting
2the flexible negative pole of lithium ion battery.
Its technique effect of the present invention is as described below.
At the product carbon fiber attachment MnO of the present invention
2the flexible negative pole of lithium ion battery in, MnO
2nano wire is wound around and is attached to carbon nano-fiber surface, form metal oxide nano-wire and the carbon nano-fiber composite fibre with secondary nucleocapsid structure, metal oxide obtains the flexible negative pole of its due lithium ion battery and dominates electric conductor status, the metal oxide with this leading position keeps contacting fully as active material and electrolyte, is conducive to embedding and the deintercalation of lithium ion; In addition, in composite fibre, carbon nano-fiber, on the one hand as conductive substrates, strengthens MnO
2the conductivity of nano wire, improves the mobility of electronics and lithium ion, as buffer medium, can also alleviate MnO on the other hand
2the self aggregation of nano wire itself and the volumetric expansion that causes because of lithium ion deintercalation and occur efflorescence, Fragmentation Phenomena, improve the cycle performance of the flexible negative pole of lithium ion battery; Further, MnO
2the feature such as have that theoretical specific capacity is high, density is high, removal lithium embedded current potential is low and voltage delay is little, this makes the performances such as the multiplying power of the flexible negative pole of lithium ion battery be improved comprehensively.
Accompanying drawing explanation
Fig. 1 is the carbon fiber attachment MnO of the present invention
2the scanning electron microscope diagram sheet of carbon nano-fiber prepared of the flexible negative pole preparation method of lithium ion battery.
Fig. 2 is the carbon fiber attachment MnO of the present invention
2the MnO for preparing of the flexible negative pole preparation method of lithium ion battery
2the scanning electron microscope diagram sheet of nano wire and carbon nano-fiber composite fibre, this figure is simultaneously as Figure of abstract.
Fig. 3 is the carbon fiber attachment MnO of the present invention
2the MnO for preparing of the flexible negative pole preparation method of lithium ion battery
2the X-ray diffraction curve chart of nano wire and carbon nano-fiber composite fibre.
Fig. 4 is the carbon fiber attachment MnO of the present invention
2the MnO for preparing of the flexible negative pole preparation method of lithium ion battery
2the x-ray photoelectron spectrum curve figure of nano wire and carbon nano-fiber composite fibre.
Fig. 5 is the carbon fiber attachment MnO of the present invention
2the charging and discharging curve figure of the flexible negative pole of lithium ion battery under 50mA/g current density, in figure, solid line be charging and discharging curve for the first time, and dotted line is the 50 charging and discharging curve.
Fig. 6 is the carbon fiber attachment MnO of the present invention
2the flexible negative pole of lithium ion battery 150 cycle performance figure under 50mA/g current density.
Embodiment
The carbon fiber attachment MnO of the present invention
2the flexible negative pole of lithium ion battery be a kind of metal oxide and carbon nano-fiber laminated film.Described metal oxide is MnO
2, described MnO
2form be nano wire, described nano wire is attached to described carbon nano-fiber surface, and form nano wire and carbon nano-fiber composite fibre, described carbon nano-fiber diameter is 180 ~ 250nm, and the diameter of described composite fibre is 300 ~ 400nm.
The carbon fiber attachment MnO of the present invention
2its embodiment of lithium ion battery flexible negative pole preparation method as described below:
One, the preparation of flexible carbon nano-fiber net
Polyacrylonitrile or polyvinyl alcohol are dissolved in after stirring in solvent and obtain electrostatic spinning liquid, described solvent is DMF or water.With described electrostatic spinning liquid for raw material, spinning voltage be 15 ~ 20kV, spinning distance completes electrostatic spinning under being the process conditions of 14 ~ 20cm, collect on screen at aluminium foil and obtain polymeric nanofiber web.By the polymeric nanofiber web obtained calcining heat be 245 ~ 255 DEG C, calcination time is complete pre-oxidation under process conditions in 1 ~ 2 hour, calciner is Muffle furnace, furnace temperature rises to calcining heat from room temperature with the heating rate of 1 ~ 1.5 DEG C/min, obtains pre-oxidation nanometer fiber net.Again calcining heat be 600 ~ 800 DEG C, calcination time is 2 ~ 4 hours, complete high-temperature calcination under protective atmosphere process conditions; calciner is tube furnace; furnace temperature rises to calcining heat from room temperature with the heating rate of 1 ~ 1.5 DEG C/min; form protective atmosphere by argon gas or nitrogen, obtain flexible carbon nano-fiber net.
Two, carbon nano-fiber surface attachment MnO
2the preparation of the flexible compound fiber membrane of nano wire
In a kettle. described flexible carbon nano-fiber net is placed in KMnO
4in solution, static 1 hour, flexible carbon nano-fiber net and KMnO
4mass ratio be 1:1 ~ 1:2, obtain reactant liquor.The reactor that reactant liquor is housed is placed in baking oven, reaction temperature be 150 ~ 200 DEG C, the reaction time is complete pyroreaction under process conditions in 30 ~ 60 minutes, the chemical reaction occurred is:
4MnO
4 -+3C+H
2O→4MnO
2+CO
3 2-+2HCO
3 -
After reaction terminates, reactor is cooled to room temperature with baking oven, obtains carbon nano-fiber surface attachment MnO
2the flexible compound fiber membrane of nano wire, with deionized water rinsing, dry process.
Three, carbon fiber attachment MnO
2the preparation of the flexible negative pole of lithium ion battery
Described carbon nano-fiber surface attachment MnO
2namely the flexible compound fiber membrane of nano wire becomes carbon fiber attachment MnO through size cutting
2the flexible negative pole of lithium ion battery.
Illustrate the present invention further below.
One, the preparation of flexible carbon nano-fiber net
Take 1g amount molecular weight be 100000 polyacrylonitrile join 9g amount DMF in, be heated to 50 DEG C of magnetic agitation 12 hours, obtain electrostatic spinning liquid.With described electrostatic spinning liquid for raw material, spinning voltage be 18kV, spinning distance for 18cm, spinning time be the process conditions of 2 hours under complete electrostatic spinning, collect on screen at aluminium foil and obtain polymeric nanofiber web.By the polymeric nanofiber web obtained calcining heat be 250 DEG C, calcination time is complete pre-oxidation under process conditions in 1 hour, calciner is Muffle furnace, furnace temperature rises to calcining heat from room temperature with the heating rate of 1 ~ 1.5 DEG C/min, obtains pre-oxidation nanometer fiber net.Again calcining heat be 600 DEG C, calcination time is 2 hours, complete high-temperature calcination under protective atmosphere process conditions; calciner is tube furnace; furnace temperature rises to calcining heat from room temperature with the heating rate of 1 DEG C/min; form protective atmosphere by nitrogen, obtain flexible carbon nano-fiber net, as shown in Figure 1; visible; the flexible carbon nano-fiber network fiber size uniform obtained, and smooth surface, fibre diameter is 180nm.
Two, carbon nano-fiber surface attachment MnO
2the preparation of the flexible compound fiber membrane of nano wire
The KMnO of 40mg amount will be taken in a kettle.
4be dissolved in 25mL water and prepare KMnO
4solution, is placed in described KMnO by the described flexible carbon nano-fiber net that 30mg measures
4in solution, static 1 hour, make KMnO
4the flexible carbon nano-fiber net of solution impregnation, flexible carbon nano-fiber net and KMnO
4mass ratio be 1:1.3, obtain reactant liquor.The reactor that reactant liquor is housed is placed in baking oven, reaction temperature be 180 DEG C, the reaction time is complete pyroreaction under process conditions in 30 minutes, the chemical reaction occurred is:
4MnO
4 -+3C+H
2O→4MnO
2+CO
3 2-+2HCO
3 -
After reaction terminates, reactor is cooled to room temperature with baking oven, obtains carbon nano-fiber surface attachment MnO
2the flexible compound fiber membrane of nano wire, with deionized water rinsing, dry process.As shown in Figure 2, visible, smooth carbon nano-fiber surface is covered by dense nano wire, and the composite fibre diameter obtained is 310nm.As shown in Figure 3, visible, there is C and MnO
2diffraction maximum, prove that product flexible compound fiber membrane is really by C and MnO
2two kinds of materials are composited.As shown in Figure 4, visible, containing C, Mn, O element in product flexible compound fiber membrane, confirm carbon nano-fiber surface attachment MnO further
2the generation of the flexible compound fiber membrane of nano wire.
Three, carbon fiber attachment MnO
2the preparation of the flexible negative pole of lithium ion battery
By described carbon nano-fiber surface attachment MnO
2the flexible compound fiber membrane of nano wire is cut to the disk of diameter 12mm, namely becomes carbon fiber attachment MnO
2the flexible negative pole of lithium ion battery, using lithium sheet as to electrode, take concentration as the LiPF of 1mol/L
6eC/DEC mixed liquor be electrolyte, wherein volume ratio EC:DEC=1:1, with Celgard2400 polypropylene film for barrier film, complete in glove box button cell assembling.Test the chemical property of the button cell assembled.As shown in Figure 5, under room temperature in 0.01 ~ 3V voltage range, under the current density of 50mA/g, the specific discharge capacity of described button cell reaches 1180.6mAh/g, and charge specific capacity reaches 715.8mAh/g, far above current business-like lithium ion battery.As shown in Figure 6, under room temperature in 0.01 ~ 3V voltage range, under the current density of 50mA/g, the specific capacity after 150 times that circulates still remains 649.2mAh/g, illustrates that described button cell has good cyclical stability.
Compared with above-mentioned example, or take 1g amount molecular weight be 78000 polyvinyl alcohol join in 25mL high purity water, be heated to 90 DEG C of magnetic agitation 12 hours, obtain electrostatic spinning liquid.With described electrostatic spinning liquid for raw material, spinning voltage be 14kV, spinning distance for 18cm, spinning time be the process conditions of 2 hours under complete electrostatic spinning, collect on screen at aluminium foil and obtain polymeric nanofiber web.Ensuing pre-oxidation is identical with above-mentioned example with high-temperature calcination, obtains flexible carbon nano-fiber net, and fibre diameter is 250nm.Carbon nano-fiber surface attachment MnO
2the preparation of the flexible compound fiber membrane of nano wire is identical with above-mentioned example, and the diameter of composite fibre is 400nm.
Compared with above-mentioned example, the preparation method of flexible carbon nano-fiber net is identical.Carbon nano-fiber surface attachment MnO
2the preparation of the flexible compound fiber membrane of nano wire is different from above-mentioned example part and is, flexible carbon nano-fiber net and KMnO
4mass ratio be 1:2, namely KMnO
4the amount of taking be 60mg, now, the MnO of carbon nano-fiber surface attachment
2nano wire approaches to saturation, and increases the KMnO in electrostatic spinning liquid further
4content on the test result of chemical property without impact.
Claims (6)
1. a carbon fiber attachment MnO
2the flexible negative pole of lithium ion battery be a kind of metal oxide and carbon nano-fiber laminated film, it is characterized in that, described metal oxide is MnO
2, described MnO
2form be nano wire, described nano wire is attached to described carbon nano-fiber surface, and form nano wire and carbon nano-fiber composite fibre, the diameter of described composite fibre is 300 ~ 400nm.
2. carbon fiber attachment MnO according to claim 1
2the flexible negative pole of lithium ion battery, it is characterized in that, described carbon nano-fiber diameter is 180 ~ 250nm.
3. a carbon fiber attachment MnO
2the flexible negative pole preparation method of lithium ion battery, it is characterized in that:
One, the preparation of flexible carbon nano-fiber net: polyacrylonitrile or polyvinyl alcohol are dissolved in solvent and obtains electrostatic spinning liquid; With described electrostatic spinning liquid for raw material, spinning voltage be 15 ~ 20kV, spinning distance completes electrostatic spinning under being the process conditions of 14 ~ 20cm, obtains polymeric nanofiber web; By the polymeric nanofiber web obtained calcining heat be 245 ~ 255 DEG C, calcination time is complete pre-oxidation under process conditions in 1 ~ 2 hour, obtains pre-oxidation nanometer fiber net; Again calcining heat be 600 ~ 800 DEG C, calcination time is 2 ~ 4 hours, complete high-temperature calcination under protective atmosphere process conditions, obtains flexible carbon nano-fiber net;
Two, carbon nano-fiber surface attachment MnO
2the preparation of the flexible compound fiber membrane of nano wire: described flexible carbon nano-fiber net is placed in KMnO
4in solution, flexible carbon nano-fiber net and KMnO
4mass ratio be 1:1 ~ 1:2, obtain reactant liquor; By the reactant liquor obtained reaction temperature be 150 ~ 200 DEG C, the reaction time is complete pyroreaction under process conditions in 30 ~ 60 minutes, obtains carbon nano-fiber surface attachment MnO
2the flexible compound fiber membrane of nano wire;
Three, carbon fiber attachment MnO
2the preparation of the flexible negative pole of lithium ion battery: described carbon nano-fiber surface attachment MnO
2namely the flexible compound fiber membrane of nano wire becomes carbon fiber attachment MnO through size cutting
2the flexible negative pole of lithium ion battery.
4. carbon fiber attachment MnO according to claim 3
2the flexible negative pole preparation method of lithium ion battery, it is characterized in that, described solvent is DMF or water.
5. carbon fiber attachment MnO according to claim 3
2the flexible negative pole preparation method of lithium ion battery, it is characterized in that, pre-oxidation calciner is Muffle furnace, and furnace temperature rises to calcining heat from room temperature with the heating rate of 1 ~ 1.5 DEG C/min.
6. carbon fiber attachment MnO according to claim 3
2the flexible negative pole preparation method of lithium ion battery, it is characterized in that, the calciner of high-temperature calcination is tube furnace, and furnace temperature rises to calcining heat from room temperature with the heating rate of 1 ~ 1.5 DEG C/min; Protective atmosphere is formed by argon gas or nitrogen.
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Cited By (11)
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| CN105870448A (en) * | 2016-06-08 | 2016-08-17 | 常熟理工学院 | High-capacity metallic oxide and carbon nanofiber composite flexible electrode film |
| CN106299290A (en) * | 2016-09-12 | 2017-01-04 | 华南理工大学 | A kind of amorphous Mn oxide/graphite composite nano materials and preparation method thereof and the application in lithium ion battery |
| CN106925220A (en) * | 2017-04-22 | 2017-07-07 | 杨彦成 | A kind of preparation method of manganese dioxide/carbon composite nano tube |
| CN107564729A (en) * | 2017-08-02 | 2018-01-09 | 苏州柔能纳米科技有限公司 | The preparation method of flexible nano netty compound material |
| CN108172796A (en) * | 2017-12-27 | 2018-06-15 | 肇庆市华师大光电产业研究院 | A kind of preparation method of nanometer fibrous niobium pentaoxide/sulphur composite positive pole |
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| CN113054175A (en) * | 2021-03-15 | 2021-06-29 | 西北工业大学 | Flexible zinc ion battery anode material MnO2Preparation method of/C film |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105870448A (en) * | 2016-06-08 | 2016-08-17 | 常熟理工学院 | High-capacity metallic oxide and carbon nanofiber composite flexible electrode film |
| CN106299290A (en) * | 2016-09-12 | 2017-01-04 | 华南理工大学 | A kind of amorphous Mn oxide/graphite composite nano materials and preparation method thereof and the application in lithium ion battery |
| CN106925220A (en) * | 2017-04-22 | 2017-07-07 | 杨彦成 | A kind of preparation method of manganese dioxide/carbon composite nano tube |
| CN109208121B (en) * | 2017-07-07 | 2021-01-26 | 同济大学 | Super-flexible carbon material capable of being folded randomly and repeatedly and preparation method thereof |
| CN109208121A (en) * | 2017-07-07 | 2019-01-15 | 同济大学 | It can any folding super flexible carbon material and preparation method thereof |
| CN107564729A (en) * | 2017-08-02 | 2018-01-09 | 苏州柔能纳米科技有限公司 | The preparation method of flexible nano netty compound material |
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| CN113871212A (en) * | 2021-11-29 | 2021-12-31 | 桂林电子科技大学 | Manganese dioxide/carbon film composite material with core-shell structure and preparation method and application thereof |
| CN113871212B (en) * | 2021-11-29 | 2022-12-27 | 桂林电子科技大学 | Manganese dioxide/carbon film composite material with core-shell structure and preparation method and application thereof |
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