CN110797581B - Porous carbon material composite gel polymer electrolyte based on ultrahigh specific surface area and preparation method and application thereof - Google Patents

Porous carbon material composite gel polymer electrolyte based on ultrahigh specific surface area and preparation method and application thereof Download PDF

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CN110797581B
CN110797581B CN201911105935.5A CN201911105935A CN110797581B CN 110797581 B CN110797581 B CN 110797581B CN 201911105935 A CN201911105935 A CN 201911105935A CN 110797581 B CN110797581 B CN 110797581B
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郑文芝
孙瑞瑞
薛召
李林林
杨伟
邹汉波
陈胜洲
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Guangzhou University
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Abstract

The invention discloses a porous carbon material composite gel polymer electrolyte based on an ultrahigh specific surface area, and a preparation method and application thereof. The method comprises the following steps: firstly, carrying out hydrothermal reaction on sodium citrate, cobalt nitrate and potassium ferricyanide to prepare solid powder, roasting the solid powder at high temperature, carrying out acid soaking to prepare a porous structure carbon material, compounding the porous structure carbon material with polyvinylidene fluoride-hexafluoropropylene copolymer to prepare a polymer film, and finally activating the polymer film in electrolyte to obtain the porous carbon material composite gel polymer electrolyte. According to the invention, the porous carbon material is prepared by utilizing the metal frame structure, then is further etched to prepare the porous carbon material with ultrahigh specific surface area, and then is compounded with the gel electrolyte, so that the liquid absorption rate of the gel electrolyte can be greatly improved, and the ionic conductivity of the electrolyte membrane can be effectively improved.

Description

Porous carbon material composite gel polymer electrolyte based on ultrahigh specific surface area and preparation method and application thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a porous carbon material composite gel polymer electrolyte based on ultrahigh specific surface area, and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, no memory effect, low price, greenness, no pollution and the like, so the lithium ion battery is widely applied to 3C electronic products such as mobile phones, notebook computers, digital cameras and the like as a mobile power source, is applied to automobiles, ships and the like as a power source, and is applied to wind power generation, solar power generation, signal tower standby power sources and the like as an energy storage battery. At present, the lithium ion battery successfully occupies the 3C product market, but the performance of the lithium ion battery in the field of electric automobiles is far from satisfactory. The recent accidents of automobile fire have caused considerable concerns about lithium ion batteries. Battery safety problems are caused by different causes such as overcharge, abuse, internal or external short circuits of the battery, which are associated with the use of volatile, flammable and toxic liquid organic carbonate-based electrolytes.
Solid polymer electrolytes have several significant advantages over traditional organic carbonate-based electrolytes, mainly in non-volatility, low flammability, no electrolyte leakage, ease of processing, and high mechanical strength. In addition, the solid polymer electrolyte may use metallic lithium as a negative electrode, thereby exhibiting a higher energy density.
However, the conductivity of the all-solid polymer electrolyte is low at room temperature, the contact condition between the electrode and the electrolyte is very poor, the solubility of the electrolyte salt in the polymer matrix is low, and when the battery is charged, the low solubility of the electrolyte salt can cause severe polarization, so that the crystallization of the electrolyte salt occurs near the electrode. The gel polymer electrolyte realizes ion conduction by utilizing liquid electrolyte molecules fixed in the microstructure, so that the gel polymer electrolyte has higher conductivity. The composite inorganic nano material can further improve the performances of the gel polymer electrolyte such as mechanical strength, conductivity and the like, and the existing composite inorganic nano material such as silicon dioxide, aluminum oxide and the like has low porosity, so that the liquid electrolyte adsorbed in the gel electrolyte has less quality, and high conductivity cannot be realized.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a preparation method of a porous carbon material composite gel polymer electrolyte based on ultrahigh specific surface area.
The invention also aims to provide the composite gel polymer electrolyte based on the porous carbon material with the ultrahigh specific surface area, which is prepared by the method.
The invention further aims to provide application of the composite gel polymer electrolyte based on the porous carbon material with the ultrahigh specific surface area.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a porous carbon material composite gel polymer electrolyte based on an ultrahigh specific surface area comprises the following steps:
(1) dissolving sodium citrate and cobalt nitrate in an ethanol water solution, adding a potassium ferricyanide water solution, uniformly stirring, carrying out hydrothermal reaction at 100-120 ℃ for 10-24 hours, centrifuging, washing, and drying to obtain solid powder;
(2) roasting the solid powder at a constant temperature of 500-700 ℃ for 3-6 hours to obtain a porous cobalt oxide iron carbon composite electrode material;
(3) soaking the porous structure cobalt oxide iron carbon composite electrode material in an acid solution, washing, filtering and drying to obtain a porous structure carbon material;
(4) dissolving a porous structure carbon material and a polyvinylidene fluoride-hexafluoropropylene copolymer in an organic solvent, uniformly mixing to obtain a jelly, volatilizing to remove the solvent to obtain a polymer film, and activating the polymer film in an electrolyte to obtain the porous carbon material composite gel polymer electrolyte.
Preferably, the molar ratio of the sodium citrate to the cobalt nitrate to the potassium ferricyanide in the aqueous solution of potassium ferricyanide in the step (1) is (5-10): (3-10): 1.
preferably, the concentrations of the sodium citrate and the cobalt nitrate in the ethanol water solution in the step (1) are both 0.1-0.5 mol/L; preferably 0.15 to 0.25 mol/L.
Preferably, the volume ratio of ethanol to water in the ethanol aqueous solution in the step (1) is 1: (1-5).
Preferably, the concentration of the potassium ferricyanide aqueous solution in the step (1) is 0.1-0.4 mol/L, and preferably 0.1-0.2 mol/L.
Preferably, the hydrothermal reaction time in the step (1) is 10-12 h.
Preferably, the drying temperature in the step (1) is 80-120 ℃, and the drying is carried out until the weight is constant.
Preferably, the washing liquid used in the centrifugal washing in the step (1) is water, and the washing is performed for 1-5 times.
Preferably, the firing of step (2) is performed in a muffle furnace.
Preferably, the roasting temperature in the step (2) is 600-700 ℃, and the roasting time is 5-6 h.
Preferably, the porous cobalt oxide iron carbon composite electrode material in the step (3) is completely soaked in an acid solution.
Preferably, the acid solution in the step (3) is a hydrochloric acid aqueous solution with a concentration of 1-4 mol/L, and preferably a hydrochloric acid aqueous solution with a concentration of 1-2 mol/L.
Preferably, the soaking time in the step (3) is 12-36 hours.
Preferably, the washing liquid used in the washing in the step (3) is water, the drying temperature is 80-120 ℃, and the drying time is 6-24 hours.
Preferably, the mass ratio of the porous structure carbon material in the step (4) to the polyvinylidene fluoride-hexafluoropropylene copolymer is (1-10): 100, preferably (5-8): 100.
preferably, the mass ratio of the porous structure carbon material to the organic solvent in the step (4) is 1: (5-20).
Preferably, the organic solvent in step (4) is N-methylformamide.
Preferably, the method for removing the solvent by volatilization in the step (4) comprises the following steps: the gum was spread evenly on a plate and the solvent was evaporated at room temperature.
Preferably, the polymer film of step (4) is completely soaked in the electrolyte.
Preferably, the electrolyte in the step (4) is a carbonate solution containing 1-1.2 mol/L lithium hexafluorophosphate. The volume ratio of the solvent of the electrolyte is 1: 1: 1 of a mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate.
Preferably, the activation time in the step (4) is 2-10 h.
The porous carbon material composite gel polymer electrolyte based on the ultrahigh specific surface area is prepared by the method.
The application of the porous carbon material composite gel polymer electrolyte based on the ultrahigh specific surface area in the field of batteries is provided.
Preferably in the field of lithium ion batteries.
Compared with the prior art, the invention has the following advantages and beneficial effects:
according to the invention, the porous carbon material is prepared by utilizing the metal frame structure, then is further etched to prepare the porous carbon material with ultrahigh specific surface area, and then is compounded with the gel electrolyte, so that the liquid absorption rate of the gel electrolyte can be greatly improved, and the ionic conductivity of the electrolyte membrane can be effectively improved.
Drawings
FIG. 1 is a transmission electron microscope photograph of a porous structure carbon material obtained in example 1, wherein the right drawing is a partially enlarged view of the left drawing.
FIG. 2 is a graph showing the adsorption and desorption curves of the porous carbon materials prepared in examples 1 to 2.
FIG. 3 is a pore size distribution graph of the porous carbon materials prepared in examples 1 to 2.
FIG. 4 is a scanning electron micrograph of the gel electrolyte membrane prepared in comparative example 1.
FIG. 5 is a scanning electron micrograph of the gel electrolyte membrane obtained in example 1.
FIG. 6 is a scanning electron micrograph of a gel electrolyte membrane obtained in example 2.
FIG. 7 is a AC impedance spectrum of the gel electrolyte membrane obtained in comparative example 1 and examples 1 to 2.
FIG. 8 is a constant current charge/discharge curve at a current density of 10mA/g of the gel electrolyte membranes prepared in comparative example 1 and examples 1 to 2.
FIG. 9 is a graph showing discharge performance curves of the gel electrolyte membranes prepared in comparative example 1 and examples 1 to 2 at different current densities.
FIG. 10 is a graph showing the cycle performance at a current density of 100mA/g of the gel electrolyte membranes prepared in comparative example 1 and examples 1 to 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
(1) Mixing 100 ml of 0.5mol/L aqueous solution of sodium citrate ethanol and 100 ml of 0.3mol/L aqueous solution of cobalt nitrate ethanol, wherein the volume ratio of ethanol to water is 1: 1, dropwise adding 50 ml of 0.2mol/L potassium ferricyanide aqueous solution, uniformly stirring, putting the mixed solution into a reaction kettle, sealing, carrying out hydrothermal reaction at 100 ℃ for 12 hours, naturally cooling after the reaction is finished, carrying out centrifugal washing with deionized water for three times, and carrying out forced air drying at 100 ℃ to constant weight to obtain purple solid powder.
(2) And roasting the purple solid powder in a muffle furnace at the high temperature of 700 ℃ for 6 hours to obtain the black cobalt oxide iron carbon composite electrode material with the porous structure.
(3) Completely soaking the black porous structure cobalt oxide iron carbon composite electrode material in 2mol/L hydrochloric acid aqueous solution for 24 hours, then washing with deionized water, filtering, and drying at 100 ℃ for 12 hours to obtain the black porous structure carbon material.
(4) Mixing a black porous structure carbon material and a polyvinylidene fluoride-hexafluoropropylene copolymer according to a mass ratio of 8: 100 is dissolved in N-methylformamide (prepared according to the mass ratio of the porous structure carbon material to the N-methylformamide being 1: 10), a uniform jelly is obtained by stirring, the jelly is uniformly coated on a flat plate, a black polymer film is obtained after the solvent is volatilized, the black polymer film is completely soaked in an electrolyte, the electrolyte is a carbonate solution containing 1mol/L lithium hexafluorophosphate (the solvent is ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate (the volume ratio is 1: 1: 1)), and after 6 hours of activation, the porous carbon material composite gel polymer electrolyte is obtained.
Example 2
(1) Mixing 100 ml of 0.5mol/L aqueous solution of sodium citrate ethanol and 100 ml of 0.5mol/L aqueous solution of cobalt nitrate ethanol, wherein the volume ratio of ethanol to water is 1: 1, dropwise adding 50 ml of 0.1mol/L potassium ferricyanide aqueous solution, uniformly stirring, putting the mixed solution into a reaction kettle, sealing, carrying out hydrothermal reaction at 100 ℃ for 10 hours, naturally cooling after the reaction is finished, carrying out centrifugal washing with deionized water for three times, and carrying out forced air drying at 100 ℃ to constant weight to obtain purple solid powder.
(2) And roasting the purple solid powder in a muffle furnace at the high temperature of 600 ℃ for 5 hours to obtain the black cobalt oxide iron carbon composite electrode material with the porous structure.
(3) Completely soaking the black porous structure cobalt oxide iron carbon composite electrode material in 1mol/L hydrochloric acid aqueous solution for 24 hours, then washing with deionized water, filtering, and drying at 100 ℃ for 12 hours to obtain the black porous structure carbon material.
(4) Mixing a black porous structure carbon material and a polyvinylidene fluoride-hexafluoropropylene copolymer according to a mass ratio of 5: dissolving 100 in N-methylformamide (prepared according to the mass ratio of the porous carbon material to the N-methylformamide being 1: 10), stirring to obtain a uniform jelly, uniformly coating the jelly on a flat plate, volatilizing a solvent to obtain a black polymer film, completely soaking the black polymer film in an electrolyte, wherein the electrolyte is a carbonate solution containing 1mol/L lithium hexafluorophosphate (the solvent is ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate (the volume ratio is 1: 1: 1)), and activating for 6 hours to obtain the porous carbon material composite gel polymer electrolyte.
Comparative example 1
Dissolving a polyvinylidene fluoride-hexafluoropropylene copolymer in N-methylformamide (prepared according to the mass ratio of the polyvinylidene fluoride-hexafluoropropylene copolymer to the N-methylformamide of 10: 8), stirring to obtain a uniform jelly, uniformly coating the jelly on a flat plate, volatilizing a solvent to obtain a white polymer film, completely soaking the white polymer film in an electrolyte, wherein the electrolyte is carbonate containing 1mol/L lithium hexafluorophosphate (the solvent is ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate solvent (the volume ratio is 1: 1: 1)), and activating for 6 hours to obtain the gel polymer electrolyte.
The obtained electrode material was subjected to scanning electron microscope test, liquid absorption rate test, and charge/discharge performance test, and the test results are shown in fig. 1 to 10.
And (3) testing the liquid absorption rate: the weighed polymer film (W1) was immersed in the liquid electrolyte for 1 hour and then taken out, the liquid electrolyte on the surface was gently sucked off by filter paper, and the film was weighed (W2) and the liquid absorption rate of the polymer film was calculated as (W2-W1)/W1 × 100%, and the average value was obtained by performing three parallel measurements on each sample film.
The gel polymer electrolyte membrane is subjected to conductivity test at room temperature, the body resistance of the gel polymer electrolyte membrane is tested through alternating current impedance, the conductivity of the gel polymer electrolyte membrane is indirectly obtained according to the following formula
Figure GDA0002664053070000071
Wherein: is conductivity (mS/cm), d is thickness (cm) of electrolyte membrane, RbIs the bulk resistance (omega) and A is the area (cm) of the electrode2)。
And (3) testing the battery performance: lithium iron phosphate, polyvinylidene fluoride-hexafluoropropylene and acetylene black are dissolved in N-methyl pyrrolidone (the total solid content and the mass concentration are 60%) according to the mass ratio of 8: 1, the uniform slurry is formed by mechanical stirring, the uniform slurry is coated on an aluminum foil and is heated and dried to prepare a positive plate, lithium is used as a negative electrode, the gel electrolyte prepared in the embodiment or the electrolyte prepared in the comparative example is used as a diaphragm, the lithium is assembled into a 2032 type button cell in a glove box, and the test is carried out after the lithium, the polyvinylidene fluoride-hexafluoropropylene and the acetylene black are placed for 1 hour.
TABLE 1 pore Structure data of porous Structure carbon Material obtained in examples 1 to 2
Figure GDA0002664053070000072
TABLE 2 liquid absorption Rate of porous carbon Material composite gel Polymer electrolyte prepared in examples 1 to 2
Figure GDA0002664053070000073
As can be seen from the transmission electron microscope image in fig. 1, the particle size of the carbon material particles with the porous structure prepared in example 1 is about 200nm, and the carbon nanotubes are distributed on the surface of the material with the porous structure, so that more pore channel structures can be provided, and the material can realize a high specific surface area.
As can be seen from fig. 2 and fig. 3, the adsorption and desorption curves and the pore size distribution curve charts of the porous structure carbon material prepared in examples 1 to 2, the adsorption and desorption curves of the porous structure carbon material belong to type iv isotherms, and have an obvious H2 hysteresis loop, which indicates that the porous structure carbon material has a rich mesoporous structure. As can be seen from the pore structure data of the porous structure carbon materials prepared in examples 1 to 2 in Table 1, the specific surface areas of the porous structure carbon materials prepared in examples 1 to 2 were 1360.17 m and 1119.52m, respectively2In terms of/g, the average pore diameters were 5.96 and 4.69nm, respectively.
FIGS. 4 to 6 are scanning electron micrographs of the gel electrolyte membranes prepared in comparative example 1 and examples 1 to 2. The porous structure carbon material composite gel polymer electrolyte prepared in the embodiment has more 5-10 micron pores, and can contain more liquid electrolyte to improve the ionic conductivity of the electrolyte membrane.
As can be seen from table 2, the liquid absorption rates of the gel electrolyte membranes prepared in comparative example 1 and examples 1 to 2 were 172.17%, 282.76% and 254.56%, respectively, and the liquid absorption rate of example 1 was 100% higher than that of comparative example 1. According to the calculation of the AC impedance test data in FIG. 7, the ionic conductivities of the gel electrolyte membranes prepared in comparative example 1 and examples 1-2 were 1.42X 10- 3S/cm、5.63×10-3S/cm、5.07×10-3S/cm, the ion conductivity of the gel electrolyte membrane compounded with the porous carbon material is obviously improved.
FIG. 8 is a constant current charge/discharge curve at a current density of 10mA/g of a lithium ion battery assembled with the gel electrolyte membrane prepared in comparative example 1 and examples 1 to 2. All batteries can normally discharge at room temperature, the specific discharge capacity of the cathode material lithium iron phosphate is close, the specific discharge capacity of the embodiment 1 is the largest (146mAh/g), and the specific discharge capacity of the comparative example 1 is the smallest (139mAh/g), which shows that the performance difference of different electrolytes is smaller when the batteries are discharged at a small current.
FIG. 9 is a graph showing discharge performance curves of lithium ion batteries assembled with the gel electrolyte membranes prepared in comparative example 1 and examples 1 to 2 at different current densities. With the increase of discharge current, the gel electrolyte of the composite porous carbon material shows better rate performance, and the specific capacity of the lithium ion battery anode material assembled by the porous carbon material composite gel electrolyte membrane prepared in the embodiment 1 under the current density of 200mA/g is 123mAh/g, which is far more than 58mAh/g of the comparative example 1.
Fig. 10 is a cycle performance curve of the lithium ion battery assembled by the gel electrolyte membranes prepared in comparative example 1 and examples 1-2 at a current density of 100mA/g, and the result shows that the lithium ion battery still maintains a high capacity retention rate after 1000 times of charging and discharging, which indicates that the gel electrolyte membrane prepared in the examples has good stability.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a porous carbon material composite gel polymer electrolyte is characterized by comprising the following steps:
(1) dissolving sodium citrate and cobalt nitrate in an ethanol water solution, adding a potassium ferricyanide water solution, uniformly stirring, carrying out hydrothermal reaction at 100-120 ℃ for 10-24 hours, centrifuging, washing, and drying to obtain solid powder;
(2) roasting the solid powder at a constant temperature of 500-700 ℃ for 3-6 hours to obtain a porous cobalt oxide iron carbon composite electrode material;
(3) soaking the porous structure cobalt oxide iron carbon composite electrode material in an acid solution, washing, filtering and drying to obtain a porous structure carbon material;
(4) dissolving a porous structure carbon material and a polyvinylidene fluoride-hexafluoropropylene copolymer in an organic solvent, uniformly mixing to obtain a jelly, volatilizing to remove the solvent to obtain a polymer film, and activating the polymer film in an electrolyte to obtain the porous carbon material composite gel polymer electrolyte.
2. The preparation method of the porous carbon material composite gel polymer electrolyte according to claim 1, wherein the molar ratio of the sodium citrate, the cobalt nitrate and the potassium ferricyanide in the aqueous solution of the potassium ferricyanide in the step (1) is (5-10): (3-10): 1;
the mass ratio of the porous structure carbon material to the polyvinylidene fluoride-hexafluoropropylene copolymer in the step (4) is (1-10): 100.
3. the preparation method of the porous carbon material composite gel polymer electrolyte according to claim 2, wherein the mass ratio of the porous structure carbon material in the step (4) to the polyvinylidene fluoride-hexafluoropropylene copolymer is (5-8): 100.
4. the preparation method of the porous carbon material composite gel polymer electrolyte according to claim 1 or 2, wherein the concentrations of the sodium citrate and the cobalt nitrate in the ethanol aqueous solution in the step (1) are both 0.1-0.5 mol/L; the concentration of the potassium ferricyanide aqueous solution is 0.1-0.4 mol/L.
5. The preparation method of the porous carbon material composite gel polymer electrolyte according to claim 4, wherein the soaking time in the step (3) is 12-36 hours; and (4) activating for 2-10 h.
6. The preparation method of the porous carbon material composite gel polymer electrolyte according to claim 4, wherein the volume ratio of ethanol to water in the ethanol aqueous solution in the step (1) is 1: (1-5); the acid solution in the step (3) is a hydrochloric acid aqueous solution with the concentration of 1-4 mol/L; the mass ratio of the porous structure carbon material to the organic solvent in the step (4) is 1: (5-20); and (4) the electrolyte is a carbonate solution containing 1-1.2 mol/L lithium hexafluorophosphate.
7. The preparation method of the porous carbon material composite gel polymer electrolyte according to claim 4, wherein the hydrothermal reaction time in the step (1) is 10-12 h; roasting in the step (2) at the temperature of 600-700 ℃ for 5-6 h; and (4) the solvent of the electrolyte in the step (4) is a solvent with the volume ratio of 1: 1: 1 of a mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate.
8. The preparation method of the porous carbon material composite gel polymer electrolyte according to claim 4, wherein the drying temperature in the step (1) is 80-120 ℃, and the drying is carried out to constant weight; washing liquid used for centrifugal washing is water, and washing is carried out for 1-5 times;
completely soaking the porous structure cobalt oxide iron carbon composite electrode material in an acid solution; the washing liquid used for washing is water, the drying temperature is 80-120 ℃, and the drying time is 6-24 hours;
the organic solvent in the step (4) is N-N methylformamide; the polymer film is completely immersed in the electrolyte.
9. A porous carbon material composite gel polymer electrolyte prepared by the method of any one of claims 1 to 8.
10. Use of a porous carbon material composite gel polymer electrolyte according to claim 9 in the field of batteries.
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