CN108520945A - Nano-tube array/carbon cloth composite material, flexible electrode, lithium ion battery and preparation method thereof - Google Patents
Nano-tube array/carbon cloth composite material, flexible electrode, lithium ion battery and preparation method thereof Download PDFInfo
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- CN108520945A CN108520945A CN201810204353.1A CN201810204353A CN108520945A CN 108520945 A CN108520945 A CN 108520945A CN 201810204353 A CN201810204353 A CN 201810204353A CN 108520945 A CN108520945 A CN 108520945A
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention belongs to the technical fields of battery material, disclose nano-tube array/carbon cloth composite material, flexible electrode, lithium ion battery and preparation method thereof.Nano-tube array/carbon cloth composite material obtains flexible FeOOH nano-tube arrays/carbon cloth compound using ferric trichloride etching nickel, cobalt binary presoma, then carbon coating is carried out, then the flexible electrode of FeS@C, FeP@C nanos pipe array/carbon cloth is obtained by solid phase vulcanizing, gas phase phosphatization respectively.The structural stability of the material of the present invention is good, has good cyclical stability and higher reversible specific capacity.
Description
Technical field
The invention belongs to electrode material fields, and in particular to nano-tube array/carbon cloth composite material, flexible electrode, lithium from
Sub- battery and preparation method thereof.
Background technology
With the extensive use of lithium ion battery, various hand-held and portable electronic devices pour in daily life.Therefore, respectively
Requirement of the kind electronic equipment to battery is also higher and higher.With becoming increasingly conspicuous for global energy problem, various countries are clear for a new generation
The exploitation of the clean energy seems very urgent.Lithium ion battery is the current internationally recognized desirable chemical energy, is had small, electric
The advantages that capacity is big, voltage is high is widely used in the electronic products such as mobile phone, laptop computer, the electric vehicle being growing
The development space of bigger will be brought to lithium ion battery in field.
In recent years, the research of flexible/foldable opto-electronic device attracts attention, but the thinking and base how to build flexibility
It is combined and at the same time obtains high battery performance, the excellent lithium-ion electric for bending stability in the lithium ion battery of nano material
Pond is still a huge difficult problem for perplexing most of scientific research personnel.In conjunction with both at home and abroad in energy storage field latest Progress,
Design construction has gone out a kind of novel flexible high-performance lithium ion electricity of the nano-wire array based on multilevel hierarchy/carbon cloth composite construction
Pond.
Iron-based material is since with higher energy density, raw material resources are abundant, and cheap, safety is good.By
The extensive concern of people.
Traditional iron-based nano-tube array material for preparing mostly uses greatly A2O3Template or growth ZnO arrays as template,
Preparation process be difficult to control, the consistency of the iron-based nanotube pattern of growth is poor, and and substrate combination it is poor.
Invention content
The object of the present invention is to provide nano-tube array/carbon cloth composite material and preparation method thereof；It provides with this nanometer
Flexible electrode prepared by the compound flexible electrode of pipe array/carbon cloth, lithium ion battery and preparation method thereof.
For achieving the above object, technical scheme is as follows,
A kind of preparation method of nano-tube array/carbon cloth composite and flexible electrode, includes the following steps:
(1) in a kettle, nickel metal salt, cobalt metal salt and urea is soluble in water, carbon cloth is added, stirs evenly, water
It after thermal response, is cooled to room temperature, forerunner's volume array will be obtained after product washing drying；
(2) forerunner's volume array is put into iron salt solutions keep the temperature, wash successively, dry after obtain flexibility
FeOOH nano-tube arrays/carbon cloth compound；
(3) the flexibility FeOOH nano-tube arrays/carbon cloth compound is immersed in glucose solution, is then air-dried, it is high
Temperature annealing obtains Fe3O4@C nanos pipe array/carbon cloth compound；
(4) selectively, by the Fe3O4@C nanos pipe array/carbon cloth compound is positioned over and is contained with sulphur or ortho phosphorous acid
In the ceramic vessel of sodium, high-temperature heat treatment obtains FeS@C nanos pipes array/carbon cloth compound or FeP@C nanos pipes array/carbon
Cloth compound；
(5) with the Fe3O4@C nanos pipe array/carbon cloth compound, FeS@C nanos pipes array/carbon cloth compound or
FeP@C nanos pipes array/carbon cloth compound prepares nano-tube array/carbon cloth composite and flexible electrode.
Preferably, in step (1), the nickel metal salt is nickel chloride, and cobalt metal salt is cobalt chloride, nickel chloride, cobalt chloride
Soluble in water with urea, obtained a concentration of 0.1~0.4mol/L of nickel chloride, cobalt chloride concentration is 0.2~0.8mol/L, urine
A concentration of 1.0~3.0mol/L of element.
Preferably, in step (1), the reaction kettle compactedness is 60~90%, and the washing is to use deionized water and second
Alcoholic solution washs, and the drying temperature is 50~100 DEG C, and the hydro-thermal reaction time is 5~24 hours, the hydro-thermal reaction temperature
Degree is 80~150 DEG C, and the carbon cloth size is 3cm × 6cm.
Preferably, in step (2), the iron salt solutions be liquor ferri trichloridi, the liquor ferri trichloridi it is a concentration of
0.02~0.08mol/L；The temperature of the heat preservation is 20~80 DEG C, and the time of the heat preservation is 6~18 hours；The drying
Temperature is 30~60 DEG C, and the time of the drying is 6~18 hours.
Preferably, in step (3), a concentration of 0.2~0.8mol/L of the glucose solution, the soaking time be for
5~24 hours.
Preferably, in step (4), the dosage of the sulphur is 0.05~0.2g, the dosage of the sodium hypophosphite is 0.5~
2.0g。
Preferably, in step (4), the temperature of the high-temperature heat treatment is 200~600 DEG C, and the time of high-temperature heat treatment is 2
~8 hours, protective atmosphere was argon gas.
A kind of nano-tube array/carbon cloth composite material, the composite material is Fe3O4@C nanos pipe array/carbon cloth is compound
Object, FeS@C nanos pipes array/carbon cloth compound or FeP@C nanos pipes array/carbon cloth compound, the nano-tube array it is straight
Diameter is 100~200 nanometers, and length is 3~6 microns.
A kind of nano-tube array/carbon cloth composite and flexible electrode, the flexible electrode include that above-mentioned nano-tube array/carbon cloth is multiple
Condensation material.
A kind of lithium ion battery, the battery include above-mentioned nano-tube array/carbon cloth composite and flexible electrode.
The advantages of the present invention are as follows：
1) it is characteristic of the invention that providing a kind of method system with in-situ deposition and etching nickel, the subcarbonate of cobalt binary
For the compound flexible electrode of nano-tube array/carbon cloth of regular appearance, preparation method is simply controllable, can replace traditional anodic oxygen
Change method or template.
2) the compound flexible electrode of nano-tube array/carbon cloth of the invention reduces technique, alleviates whole matter without coating
Amount, and played with the huge network transmission electronic edge of three-dimensional structure carbon cloth with this, greatly improve the multiplying power of battery
Performance and has excellent cyclical stability.
3) the compound flexible electrode of nano-tube array/carbon cloth of the invention is widely used in terms of miniaturized electronic devices
Foreground.
4) the compound flexible electrode of nano-tube array/carbon cloth of the invention significantly increases electrode material and is connect with electrolyte
Tactile area provides more lithiums, sodium-ion battery diffusion admittance.
5) the compound flexible electrode of nano-tube array/carbon cloth of the invention reduces the techniques such as coating, without binder and leads
Electric agent can really reflect the electrochemical properties of electrode material itself, reduce cost.
Description of the drawings
Fig. 1 is nickel, the SEM of forerunner's volume array of the subcarbonate of cobalt binary schemes.
Fig. 2 is that the SEM of FeOOH nano-tube arrays/carbon cloth compound schemes.
Fig. 3 is Fe3O4The SEM of@C nanos pipe array/carbon cloth compound schemes.
Fig. 4 is Fe3O4The TEM of@C nanos pipe array/carbon cloth compound schemes.
Fig. 5 is that the SEM of FeS@C nanos pipes array/carbon cloth compound schemes.
Fig. 6 is that the TEM of FeS@C nanos pipes array/carbon cloth compound schemes.
Fig. 7 is that the SEM of FeP@C nanos pipes array/carbon cloth compound schemes.
Fig. 8 is that figure is swept in the power spectrum face of the TEM of FeP@C nanos pipes array/carbon cloth compound.
Fig. 9 is the XRD diagram of FeOOH nano-tube arrays/carbon cloth compound.
Figure 10 is Fe3O4The XRD diagram of@C nanos pipe array/carbon cloth compound.
Figure 11 is the XRD diagram of FeS@C nanos pipes array/carbon cloth compound.
Figure 12 is the XRD diagram of FeP@C nanos pipes array/carbon cloth compound.
Figure 13 is Fe3O4The charge and discharge electrograph of@C nanos pipe array/carbon cloth compound.
Figure 14 is Fe3O4The cycle performance figure of@C nanos pipe array/carbon cloth compound.
Figure 15 is the charge and discharge electrograph of FeS C nanos pipe array/carbon cloth compound.
Figure 16 is the cycle performance figure of FeS@C nanos pipes array/carbon cloth compound.
Figure 17 is the charge and discharge electrograph of FeP C nanos pipe array/carbon cloth compound.
Figure 18 is the cycle performance figure of FeP@C nanos pipes array/carbon cloth compound.
(a) and (b) is flexible current-collecting body carbon cloth in Figure 19.
Specific implementation mode
With reference to specific embodiment, the present invention is further illustrated.
The instrument used in embodiment includes with reagent：
Glucose (Aladdin, analysis pure), ferric chloride (FeCl36H2O) (Aladdin, analysis are pure), CoCL2 6H2O (Aladdin,
Analyze pure), six water nickel chlorides (Aladdin, analysis pure), sulphur powder (Aladdin, analysis are pure), distilled water, ethyl alcohol, carbon cloth (Taiwan carbon
Can).
Air dry oven, hydrothermal reaction kettle, tube furnace, argon gas atmosphere glove box, battery sealing machine, blue electric battery testing
Instrument, scanning electron microscope (Carl Zeiss Supra 40), transmission electron microscope (JEM-2100F).
FeOOH nano-tube arrays/carbon cloth compound
By the nickel chloride of the 0.2mol/L of 80mL, the mixed solution of 0.4mol/L cobalt chlorides and 2.0mol/L urea, it is added
Carbon cloth (as shown in figure 19), stirs evenly, and is put into the reaction kettle that volume is 100mL, and 120 DEG C of hydro-thermal reactions are cooling after 6 hours
To room temperature, product is washed with deionized water and ethyl alcohol, forerunner's volume array is obtained after 80 DEG C of dryings；The forerunner's volume array that will be obtained
It is put into the liquor ferri trichloridi of 0.05mol/L 50 DEG C and keeps the temperature 12 hours, deionized water and ethyl alcohol washing, 60 DEG C of dryings 12 are small
When.It is as shown in Figure 2 to can be obtained FeOOH nano-tube arrays/carbon cloth compound flexible.As shown in Fig. 2, passing through ferric trichloride original
Position deposition and etching have obtained FeOOH nano-tube arrays/carbon cloth compound.Fig. 9 is FeOOH nano-tube arrays/carbon cloth compound
XRD diagram, it was demonstrated that by in-situ deposition and etching carbon method obtain FeOOH nano-tube arrays/carbon cloth compound.
Fe3O4@C nanos pipe array/carbon cloth compound and its flexible electrode
FeOOH nano-tube arrays obtained above/carbon cloth compound is immersed in 0.5mol/L glucose solutions 12 is small
When.Then natural air drying, 500 DEG C of high-temperature process 3 hours.It can be obtained Fe flexible3O4@C nanos pipe array/carbon cloth compound
As shown in Figure 3.Figure 10 is Fe3O4The XRD diagram of@C nanos pipe array/carbon cloth compound, it was demonstrated that added by in-situ deposition and etching
The method of glucose solution absorption packet carbon obtains Fe3O4@C nanos pipes array/carbon cloth compound.It can from the scanning electron microscope (SEM) photograph of Fig. 3
To find out Fe3O4@C nano pipes have regular pattern.Fig. 4 is Fe3O4The transmission electron microscope picture of@C, it was demonstrated that prepare Fe3O4@C are empty
The nanotube of the heart.
The Fe that will be prepared3O4@C nanos pipe array/carbon cloth compound is used in argon gas atmosphere glove box, is made with lithium metal
To be tested at button cell electrode assembling.Test condition is：Charging and discharging currents density is 500mA/g, charge and discharge cut-off
Voltage is 0.01V~3.0V.It tests obtained voltage-capacity curve graph and sees Figure 13.Figure 13 is Fe manufactured in the present embodiment3O4@C
The voltage of the lithium ion battery of nano-tube array/carbon cloth compound-specific capacity performance curve.As shown in figure 13, the present embodiment system
Reversible capacity is 1085.4mAh/g to standby composite material for the first time, and the 120th cycle is recycled to from the 2nd time, and capacity is not substantially bright
Aobvious decaying, Fe flexible3O4The@C nanos pipe array/excellent cyclical stability of carbon cloth complex shows.
Fe manufactured in the present embodiment3O4@C nanos pipe array/carbon cloth compound is used for lithium ion battery, the collection of flexible electrode
Fluid using it is foldable have carbon cloth flexible, flexible electrode be just cover with iron-based nano material carbon cloth be cut into it is required
Size dresses up battery testing.The cycle performance curve for the button cell being assembled into is as shown in figure 14.Figure 14 is Fe3O4@C nano pipes
The cycle performance curve graph of array/carbon cloth cathode composite materials lithium ion battery.It can be seen that the cathode composite materials
Lithium ion battery shows higher specific capacity.
FeS@C nanos pipes array/carbon cloth compound and its flexible electrode
The Fe that will be obtained3O4@C nanos pipe array/carbon cloth compound and 0.1g sulphur powders are placed in porcelain Noah's ark, 500 DEG C of heat treatments 3
Hour, obtain the flexible electrode of FeS@C nanos pipes array/carbon cloth compound.FeS@C are can be seen that from the scanning electron microscope (SEM) photograph of Fig. 5
Nanotube has regular pattern.Figure 11 is the XRD diagram of FeS@C nanos pipes array/carbon cloth compound, it was demonstrated that by in-situ deposition and
Etching plus the method for solid phase vulcanizing obtain FeS C nanos pipe array/carbon cloth compound.Fig. 6 is the transmission electron microscope picture of FeS C,
Proof prepares the nanotube that FeS@C are hollow.
The FeS@C nanos pipes array/carbon cloth compound that will be obtained, in argon gas atmosphere glove box, using lithium metal as pair
Electrode assembling is tested at button cell.Test condition is：Charging and discharging currents density is 200mA/g, charge and discharge blanking voltage
For 1.0V~3.0V.It tests obtained voltage-capacity curve graph and sees Figure 15.Figure 15 is FeS@C nano pipes manufactured in the present embodiment
The voltage of array lithium ion battery-specific capacity performance curve.As shown in figure 15, composite material manufactured in the present embodiment is reversible for the first time
Capacity is 558.4mAh/g.
FeS@C nanos pipe array/carbon cloth compound manufactured in the present embodiment is used for lithium ion battery, the afflux of flexible electrode
Body has a carbon cloth flexible using foldable, flexible electrode be just cover with iron-based nano material carbon cloth be cut into it is required big
It is small, dress up battery testing.The cycle performance curve for the button cell being assembled into is as shown in figure 16.Figure 16 is that the FeS@C prepared receive
The cycle performance curve graph of the cathode material lithium ion battery of mitron array/carbon cloth compound.It can be seen that the present embodiment system
Standby composite material shows higher specific capacity and good cyclical stability.
FeP@C nanos pipes array/carbon cloth compound and its flexible electrode
The Fe that will be obtained3O4@C nanos pipe array/carbon cloth compound and 1.0g sodium hypophosphites are placed in porcelain Noah's ark, in argon gas
Under atmosphere, 350 DEG C of heat treatments obtain FeP@C nanos pipes array/carbon cloth compound in 5 hours.It can from the scanning electron microscope (SEM) photograph of Fig. 7
Going out FeP@C nano pipes has regular pattern.Fig. 8 is the picture that the transmission electron microscope power spectrum face of FeP@C is swept, it was demonstrated that obtained FeP@C
It is hollow nanotube.Figure 12 is the XRD diagram of FeP@C nanos pipes array/carbon cloth compound, it was demonstrated that passes through in-situ deposition and quarter
The method of erosion aerating phase phosphatization obtains FeP@C nanos pipes array/carbon cloth compound.
By obtained FeP@C nanos pipes array/carbon cloth compound as shown in fig. 7, in argon gas atmosphere glove box, with gold
Category lithium, which is used as, tests electrode assembling at button cell.Test condition is：Charging and discharging currents density is 500mA/g, charge and discharge
Electric blanking voltage is 0.01V~3.0V.It tests obtained voltage-specific capacity curve graph and sees Figure 17.Figure 17 is prepared for the present embodiment
FeP@C nanos pipes array/carbon cloth compound lithium ion battery voltage-specific capacity performance curve.As shown in figure 17, this reality
Applying composite material prepared by example, reversible capacity is 999.6 mAh/g for the first time, the 270th cycle is recycled to from the 2nd time, capacity is basic
Do not decay significantly.
FeP@C nanos pipe array/carbon cloth compound manufactured in the present embodiment is used for lithium ion battery, the afflux of flexible electrode
Body has a carbon cloth flexible using foldable, flexible electrode be just cover with iron-based nano material carbon cloth be cut into it is required big
It is small, dress up battery testing.The cycle performance curve for the button cell being assembled into is as shown in figure 18.Figure 18 is that the FeP@C prepared receive
The cycle performance curve graph of the cathode material lithium ion battery of mitron array/carbon cloth compound.It can be seen that the present embodiment system
Standby composite material shows higher specific capacity and good cyclical stability.
The implementation of the present invention is not limited to this, and the above according to the invention is known using the ordinary skill of this field
Knowledge and customary means, under the premise of not departing from above-mentioned basic fundamental thought of the invention, the present invention can also make other a variety of shapes
Modification, replacement or the change of formula, all fall within rights protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nano-tube array/carbon cloth composite and flexible electrode, which is characterized in that include the following steps:
(1) in a kettle, nickel metal salt, cobalt metal salt and urea is soluble in water, carbon cloth is added, stirs evenly, hydro-thermal is anti-
Ying Hou is cooled to room temperature, and will obtain forerunner's volume array after product washing drying；
(2) forerunner's volume array is put into iron salt solutions keep the temperature, wash successively, dry after obtain flexible FeOOH and receive
Mitron array/carbon cloth compound；
(3) the flexibility FeOOH nano-tube arrays/carbon cloth compound is immersed in glucose solution, is then air-dried, high temperature moves back
Fire obtains Fe3O4@C nanos pipe array/carbon cloth compound；
(4) selectively, by the Fe3O4@C nanos pipe array/carbon cloth compound, which is positioned over, is contained with sulphur or sodium hypophosphite
In ceramic vessel, high-temperature heat treatment, obtains FeS@C nanos pipes array/carbon cloth compound or FeP@C nanos pipes array/carbon cloth is multiple
Close object；
(5) with the Fe3O4@C nanos pipe array/carbon cloth compound, FeS@C nanos pipes array/carbon cloth compound or FeP@C receive
Mitron array/carbon cloth compound prepares nano-tube array/carbon cloth composite and flexible electrode.
2. the preparation method of nano-tube array according to claim 1/carbon cloth composite and flexible electrode, which is characterized in that step
Suddenly in (1), the nickel metal salt is nickel chloride, and cobalt metal salt is cobalt chloride, and the nickel chloride, cobalt chloride and urea are dissolved in water
In, obtained a concentration of 0.1~0.4mol/L of nickel chloride, cobalt chloride concentration are 0.2~0.8mol/L, urea concentration be 1.0~
3.0mol/L。
3. the preparation method of nano-tube array according to claim 1/carbon cloth composite and flexible electrode, which is characterized in that step
Suddenly in (1), the reaction kettle compactedness is 60~90%, and the washing is washed with deionized water and ethanol solution, described dry
Dry temperature is 50~100 DEG C, and the hydro-thermal reaction time is 5~24 hours, and the hydrothermal temperature is 80~150 DEG C, institute
It is 3cm × 6cm to state carbon cloth size.
4. the preparation method of nano-tube array according to claim 1/carbon cloth composite and flexible electrode, which is characterized in that step
Suddenly in (2), the iron salt solutions are liquor ferri trichloridi, a concentration of 0.02~0.08mol/L of the liquor ferri trichloridi；Institute
The temperature for stating heat preservation is 20~80 DEG C, and the time of the heat preservation is 6~18 hours；The temperature of the drying is 30~60 DEG C, institute
It is 6~18 hours to state the dry time.
5. the preparation method of nano-tube array according to claim 1/carbon cloth composite and flexible electrode, which is characterized in that step
Suddenly in (3), a concentration of 0.2~0.8mol/L of the glucose solution, the soaking time is 5~24 hours.
6. the preparation method of nano-tube array according to claim 1/carbon cloth composite and flexible electrode, which is characterized in that step
Suddenly in (4), the dosage of the sulphur is 0.05~0.2g, and the dosage of the sodium hypophosphite is 0.5~2.0g.
7. the preparation method of nano-tube array according to claim 1/carbon cloth composite and flexible electrode, which is characterized in that step
Suddenly in (4), the temperature of the high-temperature heat treatment is 200~600 DEG C, and the time of high-temperature heat treatment is 2~8 hours, protective atmosphere
For argon gas.
8. a kind of nano-tube array/carbon cloth composite material, which is characterized in that the composite material is Fe3O4@C nano pipes array/
Carbon cloth compound, FeS@C nanos pipes array/carbon cloth compound or FeP@C nanos pipes array/carbon cloth compound, the nanotube
The diameter of array is 100~200 nanometers, and length is 3~6 microns.
9. a kind of nano-tube array/carbon cloth composite and flexible electrode, which is characterized in that the flexible electrode includes claim 8
The nano-tube array/carbon cloth composite material.
10. a kind of lithium ion battery, which is characterized in that the nano-tube array/carbon cloth of the battery pack containing claim 9 is multiple
Close flexible electrode.
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| CN110102236A (en) * | 2019-03-25 | 2019-08-09 | 南京工业大学 | Preparation method and application of monodisperse metal compound for rapid load growth on flexible carbon substrate by microwave technology |
| CN110357168A (en) * | 2019-05-14 | 2019-10-22 | 江西师范大学 | A kind of preparation method of lithium ion battery negative material |
| CN113346072A (en) * | 2021-04-30 | 2021-09-03 | 华中科技大学 | Integrated forming interface stabilization treatment method and flexible lithium ion battery |
| CN114613975A (en) * | 2022-04-21 | 2022-06-10 | 重庆科技学院 | Preparation method of carbon-coated cobaltous oxide nanowire array/carbon cloth composite lithium ion battery flexible negative electrode material |
| CN114709429A (en) * | 2022-03-02 | 2022-07-05 | 江苏科技大学 | Cotton carbon cloth/nitrogen-doped nano carbon/carbon nano tube flexible integrated electrode and preparation method and application thereof |
| CN115207278A (en) * | 2022-09-13 | 2022-10-18 | 深圳海润新能源科技有限公司 | Negative pole piece, preparation method thereof, battery and electric equipment |
| CN115512977A (en) * | 2022-10-14 | 2022-12-23 | 重庆文理学院 | FeP hollow nanorod for supercapacitor and preparation method thereof |
| CN115966679A (en) * | 2023-01-18 | 2023-04-14 | 华南理工大学 | Na 2 FeP 2 O 7 @ C nanotube array/carbon cloth compound, preparation method thereof and sodium-ion battery |
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