CN107634206B - Flexible negative electrode material of lithium ion battery and preparation method thereof - Google Patents

Flexible negative electrode material of lithium ion battery and preparation method thereof Download PDF

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CN107634206B
CN107634206B CN201710833929.6A CN201710833929A CN107634206B CN 107634206 B CN107634206 B CN 107634206B CN 201710833929 A CN201710833929 A CN 201710833929A CN 107634206 B CN107634206 B CN 107634206B
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carbon cloth
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deionized water
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lithium ion
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CN107634206A (en
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张俊豪
于婷婷
袁爱华
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Jiangsu University of Science and Technology
Marine Equipment and Technology Institute Jiangsu University of Science and Technology
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Jiangsu University of Science and Technology
Marine Equipment and Technology Institute Jiangsu University of Science and Technology
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Abstract

The invention relates to a preparation method of a flexible negative electrode material of a lithium ion battery, which comprises the following steps: (1) carbon cloth surface treatment: ultrasonically cleaning the carbon cloth in deionized water, acetone and ethanol respectively; secondly, activating the clean carbon cloth by nitric acid; (2) zn2GeO4Preparation of the/carbon cloth composite material: under continuous strong stirring, Zn (NO) is added3)2·6H2O、GeO2、NH4F、CO(NH2)2And HNO3Dissolving in deionized water, and adjusting the pH value to 8 by using NaOH solution; then, putting the carbon cloth into the uniform solution, and transferring the carbon cloth into a polytetrafluoroethylene-lined stainless steel reaction kettle for heating; cooling to room temperature, washing the product with deionized water, and drying; finally, in N2Heat treatment under atmosphere to obtain Zn2GeO4A/carbon cloth composite material. The invention has the advantages that: by using GeO2As a raw material, the Zn is low in price, is beneficial to large-scale preparation and practical application, and is prepared by the preparation method2GeO4The carbon cloth composite material has excellent electrochemical performance.

Description

Flexible negative electrode material of lithium ion battery and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a flexible negative electrode material of a lithium ion battery and a preparation method thereof.
Background
With the increasing demand for energy, the decreasing of fossil fuel reserves and the increasing of environmental pollution, the development of new clean and efficient energy sources becomes a focus of attention. As an energy storage device, a lithium ion battery is widely applied to small-sized portable equipment due to the characteristics of environmental protection, portability, high capacity, long service life and the like, and is expected to replace traditional fossil energy in various fields and be applied to large-sized power batteries and energy storage batteries, so that the energy and environment problems which bother the world at present are solved. The electrode material of the lithium ion battery is the key to influence the performance of the lithium ion battery, and the current commercial lithium ion battery can not meet the requirements of people on the performance of the battery. Therefore, research and development of novel lithium ion battery anode materials have a great development space.
Compared with the traditional electrode, the flexible electrode has a plurality of outstanding characteristics, and the outstanding characteristics enable the flexible electrode to meet the requirements of novel flexible chemical energy storage devices. (1) The energy density is high: many flexible electrodes adopt flexible and high-conductivity carbon materials such as carbon nanotube paper, graphene films and the like as current collectors, and the current collectors fully exert the functions of the current collectors and are lighter than traditional metal current collectors; (2) flexibility: the flexible electrode can be bent and has the characteristic of flexibility, so that the flexible electrode can meet the requirements of certain special devices on flexible energy storage equipment; (3) the corrosion-resistant flexible electrode usually adopts a carbon material as a current collector, so that the corrosion of the electrolyte to the traditional current collector in the charging and discharging processes of the battery can be avoided.
In order to meet the requirements of modern society and increasingly outstanding energy problems, it is necessary to develop a flexible negative electrode material of a lithium ion battery, which has low cost, environmental protection and excellent electrochemical performance.
Disclosure of Invention
The invention aims to provide a preparation method of a flexible negative electrode material of a lithium ion battery, so as to prepare the flexible negative electrode material of the lithium ion battery, which has low cost, environmental protection and excellent electrochemical performance.
In order to solve the technical problems, the technical scheme of the invention is as follows: the flexible negative electrode material of the lithium ion battery and the preparation method thereof have the innovation points that: the flexible negative electrode material of the lithium ion battery is Zn2GeO4Carbon cloth composite material and preparation thereofThe method comprises the following steps:
(1) carbon cloth surface treatment: ultrasonically cleaning a carbon cloth with the diameter of 13mm in deionized water, acetone and ethanol for 2 hours respectively; then, activating the clean carbon cloth for 2-6 hours by using nitric acid;
（2）Zn2GeO4preparation of the/carbon cloth composite material:
a. under the condition of continuously strong stirring, using zinc salt and germanium-containing compound as solute, dissolving it in deionized water, adding a certain quantity of urea, ammonium fluoride and HNO3Stirring the solution for 1 hour, and adjusting the pH value to 8 by using a NaOH solution;
b. putting the carbon cloth treated in the step (1) into the uniform solution, transferring the carbon cloth into a polytetrafluoroethylene-lined stainless steel reaction kettle, heating to 200 ℃, and keeping for 12-24 hours;
c. cooling to room temperature, washing the product with deionized water for 3 times, and drying in a vacuum drying oven at 60 ℃;
d. the product obtained by the above treatment is subjected to heat treatment at 450 ℃ for 2 hours in a nitrogen atmosphere to obtain Zn2GeO4A/carbon cloth composite material.
Further, in the step (1), the clean carbon cloth is activated by nitric acid for 4-6 hours.
Further, the zinc salt in the step (2) is Zn (NO)3)2·6H2O, the germanium-containing compound is GeO2(ii) a Wherein Zn (NO)3)2·6H2O、GeO2、NH4F、CO(NH2)2And HNO3The molar mass ratio of (1) to (5) to (4) is 2:1:2:5: 4. The deionized water is used in an amount of GeO per millimole2And 15-45 mL of deionized water is required. Because in this range, GeO2The conversion rate is more than 75 percent, and Zn is2GeO4The generation rate of the/carbon cloth composite material is more than 65%.
More preferably, the clean carbon cloth is activated with 6mmol of nitric acid for 6 hours in the step (2). Zn (NO)3)2·6H2O、GeO2、NH4F、CO(NH2)2And HNO3The molar mass ratio of (1) to (5) to (4) is 2:1:2:5: 4. The deionized water is used in an amount of GeO per millimole2And adding 30-35 mL of deionized water. Because in this range, GeO2Conversion rate is more than 90%, and Zn is obtained2GeO4The generation rate of the/carbon cloth composite material is more than 85 percent.
Further, the sealing and heating time in the step (2) is 18-24 h.
The invention has the advantages that: the invention discloses a preparation method of a flexible negative electrode material of a lithium ion battery, which adopts GeO2As a raw material, the Zn is low in price, is beneficial to large-scale preparation and practical application, and is prepared by the preparation method2GeO4The carbon cloth composite material has excellent electrochemical properties such as high specific capacity, long cycle life, large rate performance and the like.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is example 1 Zn2GeO4XRD spectrum of the/carbon cloth composite material.
FIG. 2 is example 1 Zn2GeO4Raman spectrum of the/carbon cloth composite material.
Fig. 3 is a FESEM photograph of a commercial carbon cloth composite of example 1.
FIG. 4 shows Zn of example 12GeO4FESEM photograph of/carbon cloth composite.
FIG. 5 shows Zn of example 12GeO4High-power FESEM photograph of/carbon cloth composite material
FIG. 6 is Zn prepared in example 12GeO4HRTEM photograph of nanorods.
FIG. 7 is a single Zn prepared in example 12GeO4HRTEM photograph of nanorods.
FIG. 8 is Zn prepared in example 12GeO4HRTEM photograph of nanorods.
FIG. 9 is Zn prepared in example 12GeO4EDX spectrum of the nanorods.
FIG. 10 isZn prepared in example 12GeO4STEM picture of nanorod and its element dispersion spectrogram (Zn, Ge, O).
FIG. 11 is Zn prepared in example 12GeO4XPS full spectrum of the/carbon cloth composite material.
FIG. 12 is the flexible and bendable Zn prepared in example 12GeO4Optical photograph of/carbon cloth composite material.
FIG. 13 is a flexible Zn prepared in example 12GeO4The/carbon cloth composite material is used as a cyclic voltammetry curve of the lithium ion battery cathode material.
FIG. 14 is the flexible Zn prepared in example 12GeO4The charge-discharge curves of circles 1, 2 and 200 of the carbon cloth composite material as the lithium ion battery cathode material under constant current.
FIG. 15 is the flexible Zn prepared in example 12GeO4The/carbon cloth composite material is used as a charge-discharge cycle curve of the lithium ion battery cathode material under different currents.
FIG. 16 is the flexible Zn prepared in example 12GeO4The/carbon cloth composite material is used as a charge-discharge cycle curve of the lithium ion battery cathode material under constant current.
FIG. 17 is a flexible Zn prepared in example 12GeO4The Nyquist spectra of the/carbon cloth composite material and the commercial carbon cloth respectively used as the lithium ion battery cathode material.
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the scope of the embodiments described herein.
Example 1
In the preparation method of the flexible negative electrode material of the lithium ion battery, the flexible negative electrode material of the lithium ion battery is Zn2GeO4The preparation method of the/carbon cloth composite material comprises the following steps:
(1) carbon cloth surface treatment: ultrasonically cleaning a carbon cloth with the diameter of 13mm in deionized water, acetone and ethanol for 2 hours respectively; then, activating the clean carbon cloth for 6 hours by using nitric acid;
(2) Zn2GeO4preparation of the/carbon cloth composite material:
a. 2 mmol of Zn (NO) under continuous vigorous stirring3)2·6H2O、1 mmol GeO2、2 mmol NH4F、5mmol CO(NH2)2And 4 mmol HNO3Dissolving in 30 mL of deionized water, and adjusting the pH value to 8 by using a NaOH solution;
b. putting the carbon cloth treated in the step (1) into the uniform solution, transferring the carbon cloth into a polytetrafluoroethylene-lined stainless steel reaction kettle, heating to 200 ℃, and keeping for 24 hours;
c. cooling to room temperature, washing the product with deionized water for 3 times, and drying in a vacuum drying oven at 60 ℃;
d. the product obtained by the above treatment is subjected to heat treatment for 2 hours at 450 ℃ in a nitrogen atmosphere to obtain Zn2GeO4A/carbon cloth composite material. And finally collected for characterization.
Performing phase analysis on the powder by using Shimadzu XRD-6000X-ray powder diffraction (XRD) instrument, and CuKα(λ=0.15406 nm), graphite monochromator, tube voltage and current 40 kV and 20 mA, respectively, scanning speed 6.0o·min-1。
Figure 1 is an XRD spectrum of the product prepared in example 1. As can be seen from FIG. 1, the XRD spectrum has 2 theta of 10-80oHas a diffraction peak of type 2, wherein the diffraction peak is at about 26oAnd 43oNearby diffraction peaks with low intensity and broadening can be marked as (002) and (101) diffraction peaks (JCPDS card number 41-1487) of carbon cloth, the rest peaks with higher intensity and sharp peak type can be marked as crystal Zn of rhombohedral phase2GeO4The diffraction peak of (1). When the XRD result is analyzed, Zn removal is not found2GeO4And diffraction peaks outside the carbon cloth, indicating that the product is high-purity Zn2GeO4A/carbon cloth composite material.
The Raman spectrum was processed by a Spex 1403 type Raman spectrometer, and the powder was further confirmed by using an argon ion laser having a wavelength of 514.5 nm. FIG. 2 is Raman light of the productSpectra. Two distinct Raman peaks, each at 1594 cm, were observed-1And 1343 cm-1Corresponding to the G-band and D-band characteristic raman peaks of the graphitized carbon nanostructure. Is located at 765 cm-1Corresponds to the crystallized Zn2GeO4The nano-rod shows that the purity is very high.
The morphology, particle size and elemental composition of the product were characterized using a field emission scanning electron microscope (FESEM, JEOL JSM-6300F), a transmission electron microscope (ZEISSMerlin Compact, acceleration voltage 200 kV) and an EDXA spectrometer.
Fig. 3 is a FESEM of a commercial carbon cloth, as can be seen from fig. 3, the carbon cloth is a bundle of densely organized fibers, which is actually a two-dimensional ordered network structure of a hand-knitted fabric, with the carbon fibers having a smooth surface (inset) and a diameter of about 8.5 μm. To save cost, commercial GeO was used for the experiments2Preparing Zn by taking particles as raw materials and carbon cloth as a carrier2GeO4A/carbon cloth composite material.
FIG. 4 is Zn2GeO4According to the FESEM image of the/carbon cloth composite material at low power, the fiber staggered structure of the carbon fiber cloth still exists as can be seen from figure 4. Each carbon fiber is covered with countless Zn2GeO4Nanorods, having an overall diameter of about 10 μm. As can be seen from the high power FESEM image in FIG. 5, Zn2GeO4The nano rods are uniform in size, about 80nm in length and about 30nm in width, and are uniformly loaded on the surface of the carbon cloth. The two are in surface contact, thereby greatly improving the conduction of electrons and effectively preventing Zn2GeO4The nano rods are stacked mutually. The layered nano structure of the composite material provides a large active surface and a large active space, and provides a buffer site for repeated intercalation and deintercalation of lithium ions.
From TEM of the product of FIG. 6, it can be seen that Zn is loaded on the carbon cloth by the method of the present invention2GeO4The nano-rod has uniform appearance and good dispersion. As can be seen from the high power TEM of FIG. 7, Zn2GeO4The nanorods were about 30nm in diameter, consistent with SEM results. FIG. 8 is Zn2GeO4High power TEM image of nanorods, inset is their corresponding Selected Area Electron Diffraction (SAED) image, indicating Zn2GeO4The nano-rod is single crystal and has good crystallization state. Lattice fringes with a pitch of 0.71 and 0.30 nm respectively correspond to Zn2GeO4The (110) and (113) crystal planes of the rhombohedral phase, indicating Zn2GeO4The growth direction of the nano rod is along the crystal plane (110). FIG. 9 is Zn2GeO4The EDS energy spectrum of the nanorod shows that the sample contains four elements of C, Zn, Ge and O. FIG. 10 shows Zn2GeO4The STEM chart and the element dispersion spectrogram (Zn, Ge and O) of the nanorod show that the Zn, Ge and O elements are uniformly distributed. FIG. 11 is a photoelectron spectrum of a sample, which proves that the sample contains three elements of Zn, Ge and O.
FIG. 12 shows Zn2GeO4Optical picture of/carbon cloth composite material, as can be seen from the picture, Zn2GeO4The/carbon cloth composite material has excellent flexibility and can be used as a flexible electrode material. Zn is added2GeO4The carbon cloth composite material is directly used for a lithium ion battery cathode, a commercial metal lithium sheet is used as a counter electrode in the battery assembly process, a Celgard2400 microporous film is used as a diaphragm, and LiPF is used as electrolyte6The button cell was assembled by dissolving a mixture of ethylene carbonate, diethyl carbonate and dimethyl carbonate (1:1:1) at a concentration of 1 mol/L in a 2032 type battery case in a glove box filled with argon gas. The water content and oxygen content are both controlled below 1 ppm. And standing the mounted button cell at room temperature for 8 hours to be tested. The constant current charge-discharge test and the rate performance test are both tested on a Land CT 2001A (Wuhan) battery tester, the charge-discharge voltage interval of the lithium ion battery is 0.01-3.0V, and the temperature is 25 ℃.
In order to further study the electrochemical behavior of the material in the charging and discharging processes, the button cell was subjected to cyclic voltammetry curve test at a test voltage of 0.01-3V and at a scan rate of 0.01 mV/s, as shown in FIG. 13. A stronger discharge peak appears at 0.28V during the 1 st circle discharge, and Zn2GeO4With Li+The decomposition of the electrolyte and the generation of an irreversible SEI film. However, at turns 2 and 3, this peak was gradually shifted, appearing at 0.58V and 0.43V, respectively. Sweeping at the anodeDuring the drawing, a broad oxidation peak at 1.1V was observed, which was associated with delithiation of the metal alloy compound. Notably, the CV curves did not change significantly at cycles 2 and 3, revealing Zn2GeO4The/carbon cloth composite material has good stability and reversibility in the process of lithium ion intercalation and deintercalation.
FIG. 14 is Zn2GeO4The charging and discharging curve of the carbon cloth composite material as the cathode material has a voltage interval of 0.01-3V and a current density of 200 mA g-1The charging and discharging specific capacities of the first ring are 2576.1 and 1768.1 mA h g respectively-1Coulombic efficiency was 68.6%. Under the current density, the discharge specific capacity of the lithium ion battery can still be maintained at 1302.3 mA h g after charging and discharging for 200 circles-1The coulombic efficiency is as high as 99.9%. FIG. 15 shows Zn2GeO4The carbon cloth composite material has better multiplying power performance, the voltage window of charging and discharging is 0.01-3V, and the current density is respectively 100 mA g, 200 mA g, 500 mA, 800 mA g and 1000 mA g-1The specific discharge capacity of the material can reach 1615.9, 1496, 1265.8, 1222.2 and 1032.1 mA h g-1When the current is as high as 2A g-1The specific discharge capacity can still reach 847.5 mA h g-1。
FIG. 16 shows the electrode material at a constant current density of 200 mA g-1The performance after 200 cycles of charge and discharge can still reach 1302.3 mA h g-1The excellent charge and discharge performance of the electrode material is fully demonstrated. By comparison, Zn2GeO4The nano-rods are loaded on the carbon cloth grid structure, so that the conductivity of the material can be improved, and the structural integrity of the material can be improved. Second, Zn2GeO4The layered structure of the/carbon cloth composite material is the insertion and extraction of lithium ions, and Zn2GeO4The volume change of the nanorods provides sufficient buffer space.
In order to further study the lithium storage mechanism of the material as a negative electrode material, the resistance of charge transfer during the electrochemical reaction of the material is analyzed by an alternating current impedance method. FIG. 17 shows flexible Zn2GeO4Carbon cloth composite material and commercial carbon cloth as lithium ionAnd Nyquist spectrum of the anode material of the sub-battery. The impedance plot shows that each impedance curve can be divided into two parts, namely a semicircle (high frequency region) and a diagonal line (low frequency region). Generally, the semicircular impedance of the high frequency region is due to the interface resistance of the electrode and the electrolyte, and the resistance of the linear region is due to the diffusion impedance of lithium ions in the electrode. The results show Zn2GeO4The/carbon cloth composite electrode showed lower charge transfer resistance after 200 cycles than the fresh cell, indicating that the fresh cell had the highest charge transfer resistance. In contrast to the inset, Zn2GeO4The high frequency half circle of the/carbon cloth composite is much smaller than the half circle of the carbon cloth, indicating that the Zn2GeO 4/carbon cloth composite also has a lower charge transfer resistance than the carbon cloth electrode. The reduced charge transfer resistance is due to Zn2GeO4The/carbon cloth composite material can effectively provide Li+And the transmission channel improves the contact area of the electrolyte and the material. In addition, the results show that the diffusivity of lithium ions decreases with the increase in the number of charge-discharge cycles.
The above analysis proves that Zn prepared by the preparation method2GeO4The carbon cloth composite material has excellent electrochemical properties such as high specific capacity, long cycle life, large rate performance and the like.
Example 2:
the difference from the example 1 is that the carbon cloth with the diameter of 13mm is respectively cleaned in deionized water, acetone and ethanol for 2 hours by ultrasonic cleaning; no activation with nitric acid was used. 2 mmol of Zn (NO) under continuous vigorous stirring3)2·6H2O、1 mmolGeO2、2 mmol NH4F、5 mmol CO(NH2)2And 4 mmol HNO3Dissolving in 30 mL of deionized water, and adjusting the pH value to 8 by using a NaOH solution; transferring the mixture into a polytetrafluoroethylene-lined stainless steel reaction kettle, heating to 200 ℃, and keeping for 12 hours; cooling to room temperature, washing the product with deionized water for 3 times, and drying in a vacuum drying oven at 60 ℃; the product obtained by the above treatment is in N2Heat treatment at 450 deg.C for 2 hr under atmosphere to obtain Zn2GeO4A/carbon cloth composite material. The yield of the product obtained was 75%, however Zn2GeO4The yield of the/carbon cloth composite material is about 70 percent, and the basic parameters are as follows: zn2GeO4The nanorods are about 300 nm long and about 100nm wide.
Example 3:
the difference from the example 2 is that the carbon cloth with the diameter of 13mm is respectively cleaned in deionized water, acetone and ethanol for 2 hours by ultrasonic cleaning; activation with 6mmol nitric acid was carried out for 2 h. 2 mmol of Zn (NO) under continuous vigorous stirring3)2·6H2O、1mmol GeO2、2 mmol NH4F、5 mmol CO(NH2)2And 4 mmol HNO3Dissolving in 30 mL of deionized water, and adjusting the pH value to 8 by using a NaOH solution; transferring the mixture into a polytetrafluoroethylene-lined stainless steel reaction kettle, heating to 200 ℃, and keeping for 12 hours; cooling to room temperature, washing the product with deionized water for 3 times, and drying in a vacuum drying oven at 60 ℃; the product obtained by the above treatment is subjected to heat treatment at 450 ℃ for 2 hours in a nitrogen atmosphere to obtain Zn2GeO4A/carbon cloth composite material. The yield of the product obtained is 80%, however Zn2GeO4The yield of the/carbon cloth composite material is about 75%, and the basic parameters are as follows: zn2GeO4The nanorods are about 220nm long and about 70 nm wide.
Example 4:
the difference from the example 3 is that the carbon cloth with the diameter of 13mm is respectively cleaned in deionized water, acetone and ethanol for 2 hours by ultrasonic cleaning; activation was carried out with 6mmol of nitric acid for 4 hours. 2 mmol of Zn (NO) under continuous vigorous stirring3)2·6H2O、1 mmol GeO2、2 mmol NH4F、5 mmol CO(NH2)2And 4 mmol HNO3Dissolving in 30 mL of deionized water, and adjusting the pH value to 8 by using a NaOH solution; transferring the mixture into a polytetrafluoroethylene-lined stainless steel reaction kettle, heating to 200 ℃, and keeping for 12 hours; cooling to room temperature, washing the product with deionized water for 3 times, and drying in a vacuum drying oven at 60 ℃; the product obtained by the above treatment is shown in N2Heat treatment at 450 deg.C for 2 hr under atmosphere to obtain Zn2GeO4A/carbon cloth composite material. The yield of the product obtained was 85%, however Zn2GeO4The yield of the/carbon cloth composite material is about 75%, and the basic parameters are as follows: zn2GeO4The nanorods are about 150 nm long and about 50 nm wide.
Example 5:
the difference from the example 4 is that the carbon cloth with the diameter of 13mm is respectively cleaned in deionized water, acetone and ethanol for 2 hours by ultrasonic cleaning; activated with 6mmol nitric acid for 6 hours. 2 mmol of Zn (NO) under continuous vigorous stirring3)2·6H2O、1 mmol GeO2、2 mmol NH4F、5 mmol CO(NH2)2And 4 mmol HNO3Dissolving in 15 mL of deionized water, and adjusting the pH value to 8 by using a NaOH solution; transferring the mixture into a polytetrafluoroethylene-lined stainless steel reaction kettle, heating to 200 ℃, and keeping for 12 hours; cooling to room temperature, washing the product with deionized water for 3 times, and drying in a vacuum drying oven at 60 ℃; the product obtained by the above treatment is shown in N2Heat treatment at 450 deg.C for 2 hr under atmosphere to obtain Zn2GeO4A/carbon cloth composite material. The yield of the product obtained was 88%, but Zn2GeO4The yield of the/carbon cloth composite material is about 79 percent, and the basic parameters are as follows: zn2GeO4The nanorods are about 70 nm long and about 20nm wide.
Example 6:
the difference from the example 5 is that the carbon cloth with the diameter of 13mm is respectively cleaned in deionized water, acetone and ethanol for 2 hours by ultrasonic cleaning; activation was carried out with 6mmol nitric acid for 6 hours. 2 mmol of Zn (NO) under continuous vigorous stirring3)2·6H2O、1 mmol GeO2、2 mmol NH4F、5 mmol CO(NH2)2And 4 mmol HNO3Dissolving in 45mL of deionized water, and adjusting the pH value to 8 by using a NaOH solution; transferring the mixture into a polytetrafluoroethylene-lined stainless steel reaction kettle, heating to 200 ℃, and keeping for 12 hours; cooling to room temperature, washing the product with deionized water for 3 times, and drying in a vacuum drying oven at 60 ℃; the product obtained by the above treatment is shown in N2Heat treatment at 450 deg.C for 2 hr under atmosphere to obtain Zn2GeO4A/carbon cloth composite material. The yield of the product obtained was 92%, however Zn2GeO4Carbon clothThe yield of the composite material is about 84%, and the basic parameters are as follows: zn2GeO4The nanorods were about 110 nm long and about 45 nm wide.
Example 7:
the difference from the example 6 is that the carbon cloth with the diameter of 13mm is respectively cleaned in deionized water, acetone and ethanol for 2 hours by ultrasonic cleaning; activation was carried out with 6mmol nitric acid for 6 hours. 2 mmol of Zn (NO) under continuous vigorous stirring3)2·6H2O、1 mmol GeO2、2 mmol NH4F、5 mmol CO(NH2)2And 4 mmol HNO3Dissolving in 30 mL of deionized water, and adjusting the pH value to 8 by using a NaOH solution; transferring the mixture into a polytetrafluoroethylene-lined stainless steel reaction kettle, heating to 200 ℃, and keeping for 12 hours; cooling to room temperature, washing the product with deionized water for 3 times, and drying in a vacuum drying oven at 60 ℃; the product obtained by the above treatment is shown in N2Heat treatment at 450 deg.C for 2 hr under atmosphere to obtain Zn2GeO4A/carbon cloth composite material. The yield of the product obtained was 95%, however Zn2GeO4The yield of the/carbon cloth composite material is about 89%, and the basic parameters are as follows: zn2GeO4The nanorods are about 40 nm long and about 15nm wide.
Example 8:
the difference from the example 7 is that the carbon cloth with the diameter of 13mm is respectively cleaned in deionized water, acetone and ethanol for 2 hours by ultrasonic cleaning; activated with 6mmol nitric acid for 6 h. 2 mmol of Zn (NO) under continuous vigorous stirring3)2·6H2O、1mmol GeO2、2 mmol NH4F、5 mmol CO(NH2)2And 4 mmol HNO3Dissolving in 30 mL of deionized water, and adjusting the pH value to 8 by using a NaOH solution; transferring the mixture into a polytetrafluoroethylene-lined stainless steel reaction kettle, heating to 200 ℃, and keeping for 18 hours; cooling to room temperature, washing the product with deionized water for 3 times, and drying in a vacuum drying oven at 60 ℃; the product obtained by the above treatment is shown in N2Heat treatment at 450 deg.C for 2 hr under atmosphere to obtain Zn2GeO4A/carbon cloth composite material. The yield of the product obtained was 95%, however Zn2GeO4The yield of the/carbon cloth composite material is about90%, basic parameters: zn2GeO4The nanorods are about 60 nm long and about 25 nm wide.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (5)

1. A preparation method of a flexible negative electrode material of a lithium ion battery is characterized by comprising the following steps: the flexible negative electrode material of the lithium ion battery is Zn2GeO4The carbon cloth composite material takes carbon cloth fiber as a substrate, and Zn with the diameter of 30nm and the length of 80nm is loaded on the carbon fiber with the diameter of 8.5 mu m2GeO4The nanorod is loaded with a single fiber with the diameter of 10 mu m, and the preparation method comprises the following steps:
(1) carbon cloth surface treatment: ultrasonically cleaning a carbon cloth with the diameter of 13mm in deionized water, acetone and ethanol for 2 hours respectively; then, activating the clean carbon cloth for 2-6 hours by using nitric acid;
(2)Zn2GeO4preparation of the/carbon cloth composite material:
a. under the condition of continuously strong stirring, using zinc salt and germanium-containing compound as solute, dissolving it in deionized water, adding a certain quantity of urea, ammonium fluoride and HNO3Stirring the solution for 1 hour, and adjusting the pH value to 8 by using a NaOH solution; the zinc salt is Zn (NO)3)2·6H2O, the germanium-containing compound being GeO2(ii) a Wherein Zn (NO)3)2·6H2O、GeO2、NH4F、CO(NH2)2And HNO3In a molar ratio of 2:1:2:5: 4;
b. putting the carbon cloth treated in the step (1) into the uniform solution, transferring the carbon cloth into a polytetrafluoroethylene-lined stainless steel reaction kettle, heating to 200 ℃, and keeping for 12-24 hours;
c. cooling to room temperature, washing the product with deionized water for 3 times, and drying in a vacuum drying oven at 60 ℃;
d. the product obtained by the above treatment is subjected to heat treatment for 2 hours at 450 ℃ in a nitrogen atmosphere to obtain Zn2GeO4A/carbon cloth composite material.
2. The preparation method of the flexible negative electrode material of the lithium ion battery according to claim 1, characterized in that: and (2) activating the clean carbon cloth for 4-6 hours by using nitric acid in the step (1).
3. The preparation method of the flexible negative electrode material of the lithium ion battery according to claim 1, characterized in that: the dosage of the deionized water in the step (2) is every millimole of GeO2And 15-45 mL of deionized water is required.
4. The preparation method of the flexible negative electrode material of the lithium ion battery according to claim 3, characterized in that: the dosage of the deionized water in the step (2) is every millimole of GeO2And adding 30-35 mL of deionized water.
5. The preparation method of the flexible negative electrode material of the lithium ion battery according to claim 4, characterized in that: and (3) sealing and heating for 18-24 hours in the step (2).
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102544479A (en) * 2011-12-15 2012-07-04 华中科技大学 Preparation method of zinc cobaltate array/carbon cloth composite anode material of lithium ion battery
CN105200665A (en) * 2015-07-19 2015-12-30 东北师范大学 Preparation method of lithium ion battery zinc germanate/carbon complex fiber cathode material
CN106186049A (en) * 2016-07-14 2016-12-07 南京大学 A kind of hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102544479A (en) * 2011-12-15 2012-07-04 华中科技大学 Preparation method of zinc cobaltate array/carbon cloth composite anode material of lithium ion battery
CN105200665A (en) * 2015-07-19 2015-12-30 东北师范大学 Preparation method of lithium ion battery zinc germanate/carbon complex fiber cathode material
CN106186049A (en) * 2016-07-14 2016-12-07 南京大学 A kind of hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Controlled growth of hexagonal Zn2GeO4 nanorods on carbon fibers for photocatalytic oxidation of p-toluidine";Guohua Jiang,et al.;《RSC Advances》;20150306;第5卷;第25801-25805页 *

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