CN112927952A - Flexible lithium titanate cathode of lithium ion hybrid capacitor and preparation method thereof - Google Patents

Flexible lithium titanate cathode of lithium ion hybrid capacitor and preparation method thereof Download PDF

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CN112927952A
CN112927952A CN201911244220.8A CN201911244220A CN112927952A CN 112927952 A CN112927952 A CN 112927952A CN 201911244220 A CN201911244220 A CN 201911244220A CN 112927952 A CN112927952 A CN 112927952A
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stainless steel
nitrogen
lithium
steel net
electrode
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阎景旺
李先锋
周仕贤
张华民
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
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    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention provides a flexible lithium titanate cathode of a lithium ion hybrid capacitor and a preparation method thereof. Different from the traditional electrode preparation mode, the electrode preparation does not need additives such as a binder and the like, and meanwhile, the flexible lithium titanate with high rate performance is finally obtained by utilizing the flexibility of a stainless steel net and matching with a thin active material layer.

Description

Flexible lithium titanate cathode of lithium ion hybrid capacitor and preparation method thereof
Technical Field
The invention belongs to the technical field of flexible electrodes in lithium ion capacitors or lithium ion batteries, and particularly relates to a flexible lithium titanate cathode of a lithium ion hybrid capacitor and a preparation method thereof.
Background
In recent years, with the increasing popularization of portable devices and wearable electronic products, flexible energy storage devices are more and more favored by people. In the current energy storage device, the lithium ion capacitor is the first choice for the next generation of energy storage device with high energy and power density because of the characteristics of lithium and super electricity. However, due to electrochemical hysteresis, the negative electrode becomes the primary reason for limiting the power output of a lithium ion capacitor, and is often limited by the intrinsic semi-infinite diffusion process of bulk electrodes as compared to surface controlled charge storage of porous electrodes. Spinel structure lithium titanate has negligible volume expansion, high de-intercalated lithium platform potential and excellent cycle stability, which attract extensive attention, however, the conductivity of the spinel structure lithium titanate is poor, and the rate capability is often improved by adopting nano structure design or surface coating and other modes. In addition, in the traditional electrode preparation, a conductive agent, a binder and the like need to be added into the slurry, so that the conductivity of the electrode and the overall energy density of the device are reduced, and the preparation cost is also increased. Meanwhile, the active material layer on the traditional electrode is too thick, so that the situation of falling failure is easy to occur when the electrode is bent, and the requirement of the flexible electrode is difficult to meet. Based on the above problems, preparing an electrode with excellent electrochemical and mechanical properties by a simple method is still the goal pursued by the researchers.
Disclosure of Invention
To solve the above technical problems, an object of the present invention is to provide a flexible electrode for a lithium ion capacitor. Depositing lithium titanate on a stainless steel net by using an electrostatic spray deposition method, and introducing Cetyl Trimethyl Ammonium Bromide (CTAB) to carry out carbon coating modification on the lithium titanate. Different from the traditional electrode preparation mode, the electrode preparation does not need additives such as a binder and the like, and meanwhile, the flexible lithium titanate with high rate performance is finally obtained by utilizing the flexibility of a stainless steel net and matching with a thin active material layer.
The invention provides a preparation method of the flexible electrode, which specifically comprises the following steps:
(1) dissolving cetyl trimethyl ammonium bromide in an organic solvent, stirring to form a uniform solution, adding lithium acetate and tetrabutyl titanate into the uniform solution, and stirring again to prepare a precursor solution;
(2) and spraying and depositing the precursor on a stainless steel net by using an electrostatic spray deposition method, and calcining the obtained sample to prepare the flexible electrode.
Based on the technical scheme, preferably, in the step (1), the dosage of the hexadecyl trimethyl ammonium bromide is 6-10 mg/ml;
based on the above technical scheme, preferably, in the step (1), the molar ratio of lithium acetate to tetrabutyl titanate is (4-4.5):5, and the concentration of tetrabutyl titanate in the precursor solution is 0.1 mmol/ml.
Based on the above technical scheme, preferably, in the step (1), the solvent is any one or more of ethanol, 1, 2-propylene glycol, ethylene glycol and isopropanol.
Based on the technical scheme, preferably, in the step (2), the electrostatic spray deposition conditions are that the substrate temperature is 150-.
Based on the above technical solution, preferably, the stainless steel net used is 316L stainless steel.
Based on the technical scheme, the stainless steel mesh is preferably 400-700 meshes, and the aperture is 26 μm.
Based on the technical scheme, the calcination condition is preferably 600-800 ℃ for 6 h.
Advantageous effects
(1) Compared with the traditional physical spraying method, the electrostatic spraying deposition method has higher efficiency, the morphology of the deposition product is more uniform, the structure increases the specific surface area of the material, is beneficial to contacting with electrolyte, and improves the reversible intercalation or deintercalation of lithium ions in material lattices, thereby having good electrochemical performance. Meanwhile, no binder and the like are needed in the whole preparation process, so that the preparation method is more economical.
(2) The hexadecyl trimethyl ammonium bromide forms a nitrogen-doped carbon layer outside the lithium titanate particles after high-temperature calcination, and the nitrogen-doped carbon layer is uniformly wrapped on the outer layer of the lithium titanate particles, so that the internal resistance of the lithium titanate electrode is reduced, and the rate capability of the electrode is greatly improved. As a surfactant, cetyl trimethyl ammonium bromide also effectively inhibits the agglomeration phenomenon of lithium titanate particles in the product generation process.
(3) Compared with the traditional aluminum foil, copper foil and the like, the stainless steel mesh substrate used in the invention has a three-dimensional structure, and the structure further improves the contact area of active substances and electrolyte and improves the ion conduction efficiency. Meanwhile, the flexibility of the stainless steel mesh is relied on, and the active substance is sprayed and deposited on the stainless steel mesh, so that the whole electrode has good mechanical property.
Drawings
FIG. 1 is a schematic diagram of a composite electrode prepared in example 1.
Fig. 2 is an SEM image of the composite electrode prepared in example 1.
Fig. 3 is a graph of the rate capability of the composite electrode prepared in example 1.
Fig. 4 is a graph of rate capability of the pure lithium titanate electrode prepared in comparative example 1.
Fig. 5 is an SEM image of a composite electrode prepared using a conventional physical spraying method in comparative example 8.
Detailed Description
Example 1
1. The flexible nitrogen-doped carbon-coated lithium titanate electrode is prepared by the following steps:
(1) 500mg of cetyltrimethylammonium bromide is dissolved in 50ml of ethanol to prepare a uniform solution;
(2) adding 4mmol of lithium acetate and 5mmol of tetrabutyl titanate into the uniform solution, and stirring to prepare a precursor solution;
(3) respectively ultrasonically cleaning a stainless steel net (600 meshes) with the thickness of 15cm multiplied by 10cm for 3 times by using hydrochloric acid, acetone and deionized water for pretreatment, then placing the stainless steel net on an instrument heating table, setting the temperature to be 300 ℃, putting the precursor solution prepared in the step (2) into an injector, setting the liquid flow rate to be 5ml/h, setting the distance between a nozzle and a stainless steel net substrate to be 5cm, setting the electrostatic voltage to be 7kV, and carrying out spraying deposition for 1 hour;
(4) and (4) transferring the sample obtained in the step (3) into a tubular furnace, sintering the sample at the temperature rise rate of 5 ℃ per minute and 700 ℃ for 6 hours in a muffle furnace under argon atmosphere, naturally cooling the sample to room temperature to obtain the flexible nitrogen-doped carbon-coated lithium titanate composite electrode, and using the electrode as a lithium ion capacitor cathode.
2. The lithium ion battery was assembled and tested as follows:
and cutting the electrode prepared in the step into a wafer with the diameter of 14mm to be used as a working electrode, and using a metal lithium sheet as a counter electrode to form the 2016 type button cell. Wherein the active material mass of the working electrode is 1.0mg, the Celgard2325 porous membrane is a diaphragm, and 1mol L of the active material is-1LiPF of6+ EC (ethylene carbonate) + DEC (diethyl carbonate) as an electrolyte, and a battery (Ar) was assembled in a glove box filled with argon gas>99.99％，H2O<1ppm，O2<1 ppm). And standing the assembled battery for 10 hours, and then carrying out performance test under the following test conditions: and respectively performing charge and discharge tests for 5 circles at different multiplying factors of 0.5C/1C/3C/5C/10C/20C/30C/50C, wherein the test voltage interval is 1-3V.
Fig. 1 is a diagram of a flexible nitrogen-doped carbon-coated lithium titanate composite electrode, the electrode has good flexibility, and no active substance falling-off phenomenon occurs after bending for 30 times, and a scanning electron microscope (sem) image (fig. 2) shows that the morphology of a deposition layer is rough, and the structure can increase the contact area between the active substance and an electrolyte. The result of the button cell rate performance test is shown in figure 3, and about 94mA h g is still obtained at 50 DEG C-1The specific capacity of the electrode is kept at 84% after 1000 cycles under 3C multiplying power, which shows that the electrode has better structural stability and good multiplying power performance.
Example 2
1. The flexible nitrogen-doped carbon-coated lithium titanate electrode is prepared by the following steps:
(1) 500mg of cetyltrimethylammonium bromide is dissolved in 50ml of ethanol to prepare a uniform solution;
(2) adding 4.5mmol of lithium acetate and 5mmol of tetrabutyl titanate into the uniform solution, and stirring to prepare a precursor solution;
(3) respectively ultrasonically cleaning a stainless steel net (600 meshes) with the thickness of 15cm multiplied by 10cm for 3 times by using hydrochloric acid, acetone and deionized water for pretreatment, then placing the stainless steel net on an instrument heating table, setting the temperature to be 300 ℃, putting the precursor solution prepared in the step (2) into an injector, setting the liquid flow rate to be 5ml/h, setting the distance between a nozzle and a stainless steel net substrate to be 5cm, setting the electrostatic voltage to be 7kV, and carrying out spraying deposition for 1 hour;
(4) and (4) transferring the sample obtained in the step (3) into a tubular furnace, sintering for 6 hours at 700 ℃ and at 5 ℃ per minute in a muffle furnace under argon atmosphere, naturally cooling to room temperature to obtain the composite electrode, and using the electrode as a lithium ion capacitor cathode.
The performance test is carried out according to the assembling mode and the test condition of the button cell battery in the example 1, and the specific capacity is about 91mA h g at 50 DEG C-1After the cell was cycled 1000 cycles at 3C rate, the capacity remained 89% of the initial value.
Example 3
(1) 500mg of cetyltrimethylammonium bromide is dissolved in 50ml of ethanol to prepare a uniform solution;
(2) adding 4mmol of lithium acetate and 5mmol of tetrabutyl titanate into the uniform solution, and stirring to prepare a precursor solution;
(3) respectively ultrasonically cleaning a stainless steel net (600 meshes) with the thickness of 15cm multiplied by 10cm for 3 times by using hydrochloric acid, acetone and deionized water for pretreatment, then placing the stainless steel net on an instrument heating table, setting the temperature to be 150 ℃, putting the precursor solution prepared in the step (2) into an injector, setting the liquid flow rate to be 5ml/h, setting the distance between a nozzle and a stainless steel net substrate to be 5cm, setting the electrostatic voltage to be 7kV, and carrying out spraying deposition for 1 hour;
(4) and (4) transferring the sample obtained in the step (3) into a tubular furnace, and sintering for 6 hours at 700 ℃ and at 5 ℃ per minute in a muffle furnace under argon atmosphere.
The performance test is carried out according to the assembling mode and the test condition of the button cell battery in the example 1, and the specific capacity is about 82mA h g at 50 DEG C-1After the battery was cycled 1000 cycles at 3C rate, the capacity remained 86% of the initial value.
Example 4
(1) 500mg of cetyltrimethylammonium bromide was dissolved in 50ml of ethylene glycol to prepare a homogeneous solution;
(2) adding 4mmol of lithium acetate and 5mmol of tetrabutyl titanate into the uniform solution, and stirring to prepare a precursor solution;
(3) respectively ultrasonically cleaning a stainless steel net (600 meshes) with the thickness of 15cm multiplied by 10cm for 3 times by using hydrochloric acid, acetone and deionized water for pretreatment, then placing the stainless steel net on an instrument heating table, setting the temperature to be 300 ℃, putting the precursor solution prepared in the step (2) into an injector, setting the liquid flow rate to be 1ml/h, setting the distance between a nozzle and a stainless steel net substrate to be 5cm, setting the electrostatic voltage to be 7kV, and carrying out spraying deposition for 5 hours;
(4) and (4) transferring the sample obtained in the step (3) into a tubular furnace, and sintering for 6 hours at 700 ℃ and at 5 ℃ per minute in a muffle furnace under argon atmosphere.
The performance test is carried out according to the assembling mode and the test condition of the button cell battery in the example 1, and the specific capacity is about 87mA h g at 50 DEG C-1After the battery was cycled 1000 cycles at 3C rate, the capacity remained 86% of the initial value.
Example 5
(1) 500mg of cetyltrimethylammonium bromide was dissolved in 50ml of ethylene glycol to prepare a homogeneous solution;
(2) adding 4mmol of lithium acetate and 5mmol of tetrabutyl titanate into the uniform solution, and stirring to prepare a precursor solution;
(3) respectively ultrasonically cleaning a stainless steel net (600 meshes) with the thickness of 15cm multiplied by 10cm for 3 times by using hydrochloric acid, acetone and deionized water for pretreatment, then placing the stainless steel net on an instrument heating table, setting the temperature to be 300 ℃, putting the precursor solution prepared in the step (2) into an injector, setting the liquid flow rate to be 5ml/h, setting the distance between a nozzle and a stainless steel net substrate to be 5cm, setting the electrostatic voltage to be 7kV, and carrying out spraying deposition for 1 hour;
(4) and (4) transferring the sample obtained in the step (3) into a tubular furnace, and sintering for 6 hours at 700 ℃ and at 5 ℃ per minute in a muffle furnace under argon atmosphere.
The performance test is carried out according to the assembling mode and the test condition of the button cell battery in the embodiment 1, and the specific capacity is about 80mA h g at 50 DEG C-1After the cell was cycled 1000 cycles at 3C rate, the capacity remained 89% of the initial value.
Example 6
(1) 500mg of cetyltrimethylammonium bromide is dissolved in 50ml of ethanol to prepare a uniform solution;
(2) adding 4mmol of lithium acetate and 5mmol of tetrabutyl titanate into the uniform solution, and stirring to prepare a precursor solution;
(3) respectively ultrasonically cleaning a stainless steel net (400 meshes) with the thickness of 15cm multiplied by 10cm for 3 times by using hydrochloric acid, acetone and deionized water for pretreatment, then placing the stainless steel net on an instrument heating table, setting the temperature to be 300 ℃, putting the precursor solution prepared in the step (2) into an injector, setting the liquid flow rate to be 5ml/h, setting the distance between a nozzle and a stainless steel net substrate to be 5cm, setting the electrostatic voltage to be 7kV, and carrying out spraying deposition for 1 hour;
(4) and (4) transferring the sample obtained in the step (3) into a tubular furnace, and sintering for 6 hours at 700 ℃ and at 5 ℃ per minute in a muffle furnace under argon atmosphere.
The performance test is carried out according to the assembling mode and the test condition of the button cell battery in the example 1, and the specific capacity is about 83mA h g at 50 DEG C-1After the cell was cycled 1000 cycles at 3C rate, the capacity remained 88% of the initial value.
Comparative example 1
1. The pure lithium titanate electrode was prepared as follows:
(1) adding 4mmol of lithium acetate and 5mmol of tetrabutyl titanate into 50ml of ethanol, and stirring to prepare a precursor solution;
(2) respectively ultrasonically cleaning a stainless steel net (600 meshes) with the thickness of 15cm multiplied by 10cm for 3 times by using hydrochloric acid, acetone and deionized water for pretreatment, then placing the stainless steel net on an instrument heating table, setting the temperature to be 300 ℃, putting the precursor solution prepared in the step (2) into an injector, setting the liquid flow rate to be 5ml/h, setting the distance between a nozzle and a stainless steel net substrate to be 5cm, setting the electrostatic voltage to be 7kV, and carrying out spraying deposition for 1 hour;
(3) and (3) transferring the sample obtained in the step (2) into a tubular furnace, sintering for 6 hours at 700 ℃ and at 5 ℃ per minute in a muffle furnace under argon atmosphere, naturally cooling to room temperature to obtain the composite electrode, and using the electrode as a lithium ion capacitor cathode.
The performance test was performed according to the assembling method and the test conditions of the button cell battery in example 1, and the test results are shown in fig. 4.
Comparative example 2
A comparative experiment was conducted by changing the mesh of the stainless steel net 600 to 200 mesh under the conditions of example 1.
Comparative example 3
Comparative experiments were conducted by replacing the stainless steel mesh substrate with a foamed nickel substrate to prepare an electrode under the conditions of example 1.
Comparative example 4
A comparative experiment was carried out under the conditions of example 1, changing the substrate temperature from 300 ℃ to 100 ℃.
Comparative example 5
Comparative experiments were carried out under the conditions of example 1, changing the electrostatic voltage from 7kV to 3 kV.
Comparative example 6
Comparative experiments were carried out under the conditions of example 1, with the calcination temperature being changed from 700 ℃ to 300 ℃.
Table 1 compares the properties of example 1 with those of comparative examples 2-6, comparing the differences in properties for different preparation conditions.
TABLE 1
Figure BDA0002307063900000061
Figure BDA0002307063900000071
Note that: in comparative example 3, the sample of the foamed nickel substrate was significantly inflexible and fractured after 5 times of bending, compared to the stainless steel mesh substrate. The lithium titanate sample synthesized at the calcination temperature in the comparative example 6 has titanium dioxide impure phase and impure phase.
Comparative example 7
At the temperature of 150 ℃ and 250 ℃, lithium titanate is synthesized by hydrothermal reaction, and the prepared slurry is coated on a stainless steel net for comparison experiment. Experiment results show that the thickness of the coating layer is difficult to control, and the phenomenon that the active substance falls off occurs when the coating layer is bent, so that the performance is sharply reduced. In addition, the hydrothermal process is complicated and long-lasting, and does not meet the goal of efficiently preparing the flexible electrode.
Comparative example 8
The precursor solution was sprayed on a stainless steel mesh substrate using an air gun using the conventional physical spraying method under the conditions of example 1, and calcined to prepare a composite electrode. The experiment result shows that the active substances are seriously fallen off, and the scanning electron microscope picture (figure 5) shows that the lithium titanate particles are large, which is not beneficial to improving the multiplying power performance of the material. The specific capacity is only 47mAh/g when the test is carried out at 50C.

Claims (9)

1. A preparation method of a flexible electrode is characterized by comprising the following steps:
(1) dissolving cetyl trimethyl ammonium bromide in an organic solvent, stirring to obtain a solution A, adding lithium acetate and tetrabutyl titanate into the solution A, and stirring to obtain a precursor solution;
(2) and spraying and depositing the precursor solution on a stainless steel net by using an electrostatic spray deposition method, and calcining to obtain the flexible electrode.
2. The method according to claim 1, wherein the concentration of cetyltrimethylammonium bromide in the solution a is 6-10 mg/ml.
3. The process according to claim 1, wherein the molar ratio of lithium acetate to tetrabutyl titanate is 4-4.5: 5; in the precursor solution, the concentration of tetrabutyl titanate is 0.1 mmol/ml.
4. The method according to claim 1, wherein the solvent is at least one of ethanol, 1, 2-propanediol, ethylene glycol, and isopropanol.
5. The production method according to claim 1, wherein the conditions of the electrostatic spray deposition method are: the temperature of the stainless steel net is 150-.
6. The method according to claim 1, wherein the stainless steel net is made of 316L stainless steel; the stainless steel net is 400-700 meshes, and the aperture is 20-50 μm.
7. The method as claimed in claim 1, wherein the calcination is carried out under 600-800 ℃ for 6-8 h.
8. A flexible electrode manufactured by the manufacturing method of any one of claims 1 to 7, wherein the flexible electrode comprises a stainless steel mesh and a deposition layer; the deposition layer is carbon-coated lithium titanate, and the thickness of the deposition layer is 1-2.5 mu m; the particle size of the lithium titanate is 50-90 nm; the thickness of the carbon coating layer is 2-5nm, and the carbon coating layer is a nitrogen-doped carbon coating layer; and nitrogen is doped into carbon in three forms of pyridine nitrogen, graphite nitrogen and pyrrole nitrogen, and the doping amount in the nitrogen-doped carbon coating layer accounts for 1-6 wt% of the carbon content.
9. Use of the flexible electrode according to claim 8 as a negative electrode in a lithium ion capacitor or battery.
CN201911244220.8A 2019-12-06 2019-12-06 Flexible lithium titanate cathode of lithium ion hybrid capacitor and preparation method thereof Pending CN112927952A (en)

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