CN108899498B - Preparation method of environment-friendly flexible lithium ion battery positive electrode framework material - Google Patents
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Abstract
The invention provides a preparation method of an environment-friendly flexible lithium ion battery anode framework material, which comprises the following steps: providing a polyurethane sponge; providing aniline monomer, sulfuric acid solution and ammonium persulfate; adding an aniline monomer into a sulfuric acid solution, and then adding ammonium persulfate into a mixed solution of sulfuric acid and the aniline monomer to obtain a first mixed solution; adding polyurethane sponge into the first mixed solution to obtain a second mixed solution; reacting the second mixed solution for 8-12h at the temperature of 8-15 ℃, and drying to obtain modified polyurethane sponge; carbonizing the modified polyurethane sponge to obtain carbonized modified polyurethane sponge; aging the carbonized modified polyurethane sponge; preparing a graphene oxide solution; adding the aged carbonized modified polyurethane sponge into the graphene oxide solution, stirring and drying to obtain a modified polyurethane sponge/graphene oxide composite material; carrying out heat treatment on the modified polyurethane sponge/graphene oxide composite material to obtain a primary modified polyurethane sponge/graphene oxide composite material; and carrying out second aging on the primary modified polyurethane sponge/graphene oxide composite material.
Description
Technical Field
The invention relates to the technical field of environment-friendly materials, in particular to a preparation method of an environment-friendly flexible lithium ion battery positive electrode framework material.
Background
The development of human activities and society is not free from energy sources, coal, petroleum and natural gas account for a large part of energy source supply structures, the problem of environmental pollution is more and more serious along with the continuous increase of the use amount of fossil energy sources, the formation of fossil fuels requires long time, and the storage capacity on the earth is limited. With the increasing demand of energy, the problem of energy shortage is becoming more serious, and the development of new energy sources is pursuing. The new energy comprises solar energy, geothermal energy, wind energy and the like, the development difficulty of the new energy is high, and the requirements on storage and use equipment are high. The lithium ion battery is used as an energy storage device, and has the advantages of small volume, large capacity, convenience in carrying, environmental friendliness and the like, and becomes an important energy storage device. After the lithium ion battery is commercialized, electronic products such as MP4, mobile phones and notebook computers generally adopt the lithium ion battery as a power supply, and have a wide application prospect in the field of electric automobiles. The development and application of the lithium ion battery can greatly relieve a series of problems caused by energy shortage.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a preparation method of an environment-friendly flexible lithium ion battery anode framework material, so that the defects of the prior art are overcome.
In order to achieve the purpose, the invention provides a preparation method of an environment-friendly flexible lithium ion battery anode framework material, which is characterized by comprising the following steps of: the preparation method comprises the following steps:
providing a polyurethane sponge;
providing aniline monomer, sulfuric acid solution and ammonium persulfate;
adding an aniline monomer into a sulfuric acid solution, and then adding ammonium persulfate into a mixed solution of sulfuric acid and the aniline monomer to obtain a first mixed solution;
adding polyurethane sponge into the first mixed solution to obtain a second mixed solution;
reacting the second mixed solution for 8-12h at the temperature of 8-15 ℃, and drying to obtain modified polyurethane sponge;
carbonizing the modified polyurethane sponge to obtain carbonized modified polyurethane sponge;
aging the carbonized modified polyurethane sponge;
preparing a graphene oxide solution;
adding the aged carbonized modified polyurethane sponge into the graphene oxide solution, stirring and drying to obtain a modified polyurethane sponge/graphene oxide composite material;
carrying out heat treatment on the modified polyurethane sponge/graphene oxide composite material to obtain a primary modified polyurethane sponge/graphene oxide composite material;
and performing second aging on the primary modified polyurethane sponge/graphene oxide composite material to obtain the environment-friendly flexible lithium ion battery positive electrode framework material.
Preferably, in the above technical scheme, wherein the concentration of the sulfuric acid solution is 0.3-0.5mol/L, in the second mixed solution, the concentration of the aniline monomer is 0.15-0.2mol/L, the concentration of the ammonium persulfate is 0.15-0.2mol/L, and the content of the polyurethane sponge is 80-120 g/L.
Preferably, in the above technical solution, the carbonizing the modified polyurethane sponge includes the following steps:
putting the modified polyurethane sponge into a vacuum tube type heat treatment furnace;
carrying out carbonization heat treatment on the modified polyurethane sponge under the condition that the air pressure is lower than 0.001 Pa;
and carrying out cryogenic cooling treatment on the modified polyurethane sponge after the carbonization heat treatment.
Preferably, in the above technical solution, the carbonization heat treatment of the modified polyurethane sponge includes the following steps:
raising the temperature of the vacuum tube type heat treatment furnace to 400 ℃ at a first temperature raising rate;
then, the temperature of the vacuum tube type heat treatment furnace is increased to 700 ℃ at a second temperature increasing rate;
then, the temperature of the vacuum tube type heat treatment furnace is increased to 900-1000 ℃ at a third temperature-increasing rate;
then preserving heat for 4-6h to obtain the modified polyurethane sponge after carbonization heat treatment;
wherein the first temperature rise rate is less than the second temperature rise rate, and the second temperature rise rate is less than the third temperature rise rate.
Preferably, in the above technical solution, the cryogenic cooling treatment of the modified polyurethane sponge after the carbonization heat treatment includes the following steps:
cooling the modified polyurethane sponge after carbonization heat treatment to below 100 ℃ along with a furnace, and then putting the modified polyurethane sponge cooled along with the furnace into liquid nitrogen for cooling for 10-30 s.
Preferably, in the above technical scheme, the first temperature rise rate is 8-12 ℃/min, the second temperature rise rate is 10-15 ℃/min, and the third temperature rise rate is 12-17 ℃/min.
Preferably, in the above technical scheme, aging the carbonized modified polyurethane sponge comprises the following steps: and (3) placing the carbonized modified polyurethane sponge in an oven, wherein the temperature of the oven is 70-80 ℃, and the aging time is 10-20 h.
Preferably, in the above technical scheme, the heat treatment of the modified polyurethane sponge/graphene oxide composite material comprises the following steps:
putting the modified polyurethane sponge/graphene oxide composite material into a vacuum tube type heat treatment furnace;
carrying out heat treatment on the modified polyurethane sponge under the condition that the hydrogen flow is 100-200 sccm;
wherein the heat treatment conditions are as follows: the heat treatment temperature is 500-600 ℃, and the heat treatment time is 1-2 h.
Preferably, in the above technical scheme, the second aging of the primary modified polyurethane sponge/graphene oxide composite material comprises the following steps: and (3) placing the primary modified polyurethane sponge/graphene oxide composite material in an oven, wherein the temperature of the oven is 50-60 ℃, and the aging time is 10-20 h.
Compared with the prior art, the invention has the advantages that: in order to expand the application range of the lithium ion battery, the development of the flexible lithium ion battery anode framework material is a great research hotspot and difficulty at present. The prior art has already proposed the positive electrode framework material of flexible lithium ion battery based on resin sponge of melamine formaldehyde, this prior art has already solved the technical problem how to produce the positive electrode framework material of flexible lithium ion battery preliminarily, but this process still has many defects at present, for example: the melamine formaldehyde resin sponge has low internal pore size, shape and distribution uniformity, so when the sponge is used as a flexible positive electrode framework material, the internal resistivity of the positive electrode material is microscopic and uneven, the electrochemical performance of the positive electrode material is poor, and the defect that the melamine formaldehyde resin sponge flexible positive electrode material is difficult to overcome is actually caused. In view of this problem, there is no good solution in the prior art, because there is no other sponge and its matching process that can replace melamine formaldehyde resin sponge. This application is then fine has solved the difficult problem among the prior art, and this application has used the polyurethane sponge to replace melamine formaldehyde resin sponge, and the even degree of the inside pore size of polyurethane sponge, shape and distribution all is superior to melamine formaldehyde resin sponge far away. Meanwhile, the application also provides a matched production process suitable for producing the polyurethane sponge. Solves the technical problem that the prior art is lack of polyurethane sponge flexible anode materials.
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FIG. 1 is a flow diagram of a method according to an embodiment of the invention.
Detailed Description
The following detailed description of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
FIG. 1 is a flow diagram of a method according to an embodiment of the invention. As shown, the method of the present invention generally comprises:
step 101: providing a polyurethane sponge;
step 102: providing aniline monomer, sulfuric acid solution and ammonium persulfate;
step 103: adding an aniline monomer into a sulfuric acid solution, and then adding ammonium persulfate into a mixed solution of sulfuric acid and the aniline monomer to obtain a first mixed solution;
step 104: adding polyurethane sponge into the first mixed solution to obtain a second mixed solution;
step 105: reacting the second mixed solution for 8-12h at the temperature of 8-15 ℃, and drying to obtain modified polyurethane sponge;
step 106: carbonizing the modified polyurethane sponge to obtain carbonized modified polyurethane sponge;
step 107: aging the carbonized modified polyurethane sponge;
step 108: preparing a graphene oxide solution (wherein the concentration of the graphene oxide solution can be obtained according to limited experiments, and the document recommended value used in the application is 0.5mg/mL, but it should be noted that the concentration of the graphene oxide solution can be higher or lower than this value);
step 109: adding the aged carbonized modified polyurethane sponge into the graphene oxide solution, stirring and drying to obtain a modified polyurethane sponge/graphene oxide composite material;
step 110: carrying out heat treatment on the modified polyurethane sponge/graphene oxide composite material to obtain a primary modified polyurethane sponge/graphene oxide composite material;
step 111: and performing second aging on the primary modified polyurethane sponge/graphene oxide composite material to obtain the environment-friendly flexible lithium ion battery positive electrode framework material.
Example 1
The preparation method comprises the following steps: providing a polyurethane sponge; providing aniline monomer, sulfuric acid solution and ammonium persulfate; adding an aniline monomer into a sulfuric acid solution, and then adding ammonium persulfate into a mixed solution of sulfuric acid and the aniline monomer to obtain a first mixed solution; adding polyurethane sponge into the first mixed solution to obtain a second mixed solution; reacting the second mixed solution for 8 hours at the temperature of 8 ℃, and drying to obtain modified polyurethane sponge; carbonizing the modified polyurethane sponge to obtain carbonized modified polyurethane sponge; aging the carbonized modified polyurethane sponge; preparing a graphene oxide solution; adding the aged carbonized modified polyurethane sponge into the graphene oxide solution, stirring and drying to obtain a modified polyurethane sponge/graphene oxide composite material; carrying out heat treatment on the modified polyurethane sponge/graphene oxide composite material to obtain a primary modified polyurethane sponge/graphene oxide composite material; and performing second aging on the primary modified polyurethane sponge/graphene oxide composite material to obtain the environment-friendly flexible lithium ion battery positive electrode framework material. Wherein the concentration of the sulfuric acid solution is 0.3mol/L, the concentration of the aniline monomer in the second mixed solution is 0.15mol/L, the concentration of the ammonium persulfate in the second mixed solution is 0.15mol/L, and the content of the polyurethane sponge in the second mixed solution is 80 g/L. The carbonization of the modified polyurethane sponge comprises the following steps: putting the modified polyurethane sponge into a vacuum tube type heat treatment furnace; carrying out carbonization heat treatment on the modified polyurethane sponge under the condition that the air pressure is lower than 0.001 Pa; and carrying out cryogenic cooling treatment on the modified polyurethane sponge after the carbonization heat treatment. Wherein, the carbonization heat treatment of the modified polyurethane sponge comprises the following steps: raising the temperature of the vacuum tube type heat treatment furnace to 400 ℃ at a first temperature raising rate; then, the temperature of the vacuum tube type heat treatment furnace is increased to 700 ℃ at a second temperature increasing rate; then, the temperature of the vacuum tube type heat treatment furnace is increased to 900 ℃ at a third temperature increasing rate; then preserving heat for 4-6h to obtain the modified polyurethane sponge after carbonization heat treatment; wherein the first temperature rise rate is less than the second temperature rise rate, and the second temperature rise rate is less than the third temperature rise rate. Wherein, the deep cooling treatment of the modified polyurethane sponge after the carbonization heat treatment comprises the following steps: cooling the modified polyurethane sponge after carbonization heat treatment to below 100 ℃ along with a furnace, and then putting the modified polyurethane sponge cooled along with the furnace into liquid nitrogen for cooling for 10 s. Wherein the first heating rate is 8 ℃/min, the second heating rate is 10 ℃/min, and the third heating rate is 12 ℃/min. The aging of the carbonized modified polyurethane sponge comprises the following steps: and (3) placing the carbonized modified polyurethane sponge in an oven, wherein the temperature of the oven is 70 ℃, and the aging time is 10 h. The heat treatment of the modified polyurethane sponge/graphene oxide composite material comprises the following steps: putting the modified polyurethane sponge/graphene oxide composite material into a vacuum tube type heat treatment furnace; carrying out heat treatment on the modified polyurethane sponge under the condition that the hydrogen flow is 100 sccm; wherein the heat treatment conditions are as follows: the heat treatment temperature is 500 ℃, and the heat treatment time is 1 h. The second aging of the primary modified polyurethane sponge/graphene oxide composite material comprises the following steps: and (3) placing the primary modified polyurethane sponge/graphene oxide composite material in an oven, wherein the oven temperature is 50 ℃, and the aging time is 10 h.
Example 2
The preparation method comprises the following steps: providing a polyurethane sponge; providing aniline monomer, sulfuric acid solution and ammonium persulfate; adding an aniline monomer into a sulfuric acid solution, and then adding ammonium persulfate into a mixed solution of sulfuric acid and the aniline monomer to obtain a first mixed solution; adding polyurethane sponge into the first mixed solution to obtain a second mixed solution; reacting the second mixed solution for 12 hours at the temperature of 15 ℃, and drying to obtain modified polyurethane sponge; carbonizing the modified polyurethane sponge to obtain carbonized modified polyurethane sponge; aging the carbonized modified polyurethane sponge; preparing a graphene oxide solution; adding the aged carbonized modified polyurethane sponge into the graphene oxide solution, stirring and drying to obtain a modified polyurethane sponge/graphene oxide composite material; carrying out heat treatment on the modified polyurethane sponge/graphene oxide composite material to obtain a primary modified polyurethane sponge/graphene oxide composite material; and performing second aging on the primary modified polyurethane sponge/graphene oxide composite material to obtain the environment-friendly flexible lithium ion battery positive electrode framework material. Wherein the concentration of the sulfuric acid solution is 0.5mol/L, the concentration of the aniline monomer in the second mixed solution is 0.2mol/L, the concentration of the ammonium persulfate in the second mixed solution is 0.2mol/L, and the content of the polyurethane sponge in the second mixed solution is 120 g/L. The carbonization of the modified polyurethane sponge comprises the following steps: putting the modified polyurethane sponge into a vacuum tube type heat treatment furnace; carrying out carbonization heat treatment on the modified polyurethane sponge under the condition that the air pressure is lower than 0.001 Pa; and carrying out cryogenic cooling treatment on the modified polyurethane sponge after the carbonization heat treatment. Wherein, the carbonization heat treatment of the modified polyurethane sponge comprises the following steps: raising the temperature of the vacuum tube type heat treatment furnace to 400 ℃ at a first temperature raising rate; then, the temperature of the vacuum tube type heat treatment furnace is increased to 700 ℃ at a second temperature increasing rate; then, the temperature of the vacuum tube type heat treatment furnace is increased to 1000 ℃ at a third temperature increasing rate; then preserving heat for 6h to obtain the modified polyurethane sponge after carbonization heat treatment; wherein the first temperature rise rate is less than the second temperature rise rate, and the second temperature rise rate is less than the third temperature rise rate. Wherein, the deep cooling treatment of the modified polyurethane sponge after the carbonization heat treatment comprises the following steps: cooling the modified polyurethane sponge after carbonization heat treatment to below 100 ℃ along with a furnace, and then putting the modified polyurethane sponge cooled along with the furnace into liquid nitrogen for cooling for 30 s. Wherein the first heating rate is 12 ℃/min, the second heating rate is 15 ℃/min, and the third heating rate is 17 ℃/min. The aging of the carbonized modified polyurethane sponge comprises the following steps: and (3) placing the carbonized modified polyurethane sponge in an oven, wherein the temperature of the oven is 80 ℃, and the aging time is 20 h. The heat treatment of the modified polyurethane sponge/graphene oxide composite material comprises the following steps: putting the modified polyurethane sponge/graphene oxide composite material into a vacuum tube type heat treatment furnace; carrying out heat treatment on the modified polyurethane sponge under the condition that the hydrogen flow is 200 sccm; wherein the heat treatment conditions are as follows: the heat treatment temperature is 600 ℃, and the heat treatment time is 2 h. The second aging of the primary modified polyurethane sponge/graphene oxide composite material comprises the following steps: and (3) placing the primary modified polyurethane sponge/graphene oxide composite material in an oven, wherein the oven temperature is 60 ℃, and the aging time is 20 h.
Example 3
The preparation method comprises the following steps: providing a polyurethane sponge; providing aniline monomer, sulfuric acid solution and ammonium persulfate; adding an aniline monomer into a sulfuric acid solution, and then adding ammonium persulfate into a mixed solution of sulfuric acid and the aniline monomer to obtain a first mixed solution; adding polyurethane sponge into the first mixed solution to obtain a second mixed solution; reacting the second mixed solution for 9 hours at the temperature of 10 ℃, and drying to obtain modified polyurethane sponge; carbonizing the modified polyurethane sponge to obtain carbonized modified polyurethane sponge; aging the carbonized modified polyurethane sponge; preparing a graphene oxide solution; adding the aged carbonized modified polyurethane sponge into the graphene oxide solution, stirring and drying to obtain a modified polyurethane sponge/graphene oxide composite material; carrying out heat treatment on the modified polyurethane sponge/graphene oxide composite material to obtain a primary modified polyurethane sponge/graphene oxide composite material; and performing second aging on the primary modified polyurethane sponge/graphene oxide composite material to obtain the environment-friendly flexible lithium ion battery positive electrode framework material. Wherein the concentration of the sulfuric acid solution is 0.4mol/L, the concentration of the aniline monomer in the second mixed solution is 0.16mol/L, the concentration of the ammonium persulfate in the second mixed solution is 0.16mol/L, and the content of the polyurethane sponge in the second mixed solution is 90 g/L. The carbonization of the modified polyurethane sponge comprises the following steps: putting the modified polyurethane sponge into a vacuum tube type heat treatment furnace; carrying out carbonization heat treatment on the modified polyurethane sponge under the condition that the air pressure is lower than 0.001 Pa; and carrying out cryogenic cooling treatment on the modified polyurethane sponge after the carbonization heat treatment. Wherein, the carbonization heat treatment of the modified polyurethane sponge comprises the following steps: raising the temperature of the vacuum tube type heat treatment furnace to 400 ℃ at a first temperature raising rate; then, the temperature of the vacuum tube type heat treatment furnace is increased to 700 ℃ at a second temperature increasing rate; then, the temperature of the vacuum tube type heat treatment furnace is increased to 930 ℃ at a third temperature increasing rate; then preserving the heat for 5 hours to obtain the modified polyurethane sponge after carbonization heat treatment; wherein the first temperature rise rate is less than the second temperature rise rate, and the second temperature rise rate is less than the third temperature rise rate. Wherein, the deep cooling treatment of the modified polyurethane sponge after the carbonization heat treatment comprises the following steps: and (3) cooling the modified polyurethane sponge subjected to carbonization heat treatment to below 100 ℃ along with a furnace, and then putting the modified polyurethane sponge cooled along with the furnace into liquid nitrogen for cooling for 15 s. Wherein the first heating rate is 9 ℃/min, the second heating rate is 11 ℃/min, and the third heating rate is 13 ℃/min. The aging of the carbonized modified polyurethane sponge comprises the following steps: and (3) placing the carbonized modified polyurethane sponge in an oven, wherein the temperature of the oven is 75 ℃, and the aging time is 12 h. The heat treatment of the modified polyurethane sponge/graphene oxide composite material comprises the following steps: putting the modified polyurethane sponge/graphene oxide composite material into a vacuum tube type heat treatment furnace; carrying out heat treatment on the modified polyurethane sponge under the condition that the hydrogen flow is 130 sccm; wherein the heat treatment conditions are as follows: the heat treatment temperature is 530 ℃, and the heat treatment time is 1.5 h. The second aging of the primary modified polyurethane sponge/graphene oxide composite material comprises the following steps: and (3) placing the primary modified polyurethane sponge/graphene oxide composite material in an oven, wherein the oven temperature is 55 ℃, and the aging time is 13 h.
Example 4
The preparation method comprises the following steps: providing a polyurethane sponge; providing aniline monomer, sulfuric acid solution and ammonium persulfate; adding an aniline monomer into a sulfuric acid solution, and then adding ammonium persulfate into a mixed solution of sulfuric acid and the aniline monomer to obtain a first mixed solution; adding polyurethane sponge into the first mixed solution to obtain a second mixed solution; reacting the second mixed solution for 8-12h at the temperature of 8-15 ℃, and drying to obtain modified polyurethane sponge; carbonizing the modified polyurethane sponge to obtain carbonized modified polyurethane sponge; aging the carbonized modified polyurethane sponge; preparing a graphene oxide solution; adding the aged carbonized modified polyurethane sponge into the graphene oxide solution, stirring and drying to obtain a modified polyurethane sponge/graphene oxide composite material; carrying out heat treatment on the modified polyurethane sponge/graphene oxide composite material to obtain a primary modified polyurethane sponge/graphene oxide composite material; and performing second aging on the primary modified polyurethane sponge/graphene oxide composite material to obtain the environment-friendly flexible lithium ion battery positive electrode framework material. Wherein the concentration of the sulfuric acid solution is 0.3-0.5mol/L, in the second mixed solution, the concentration of the aniline monomer is 0.15-0.2mol/L, the concentration of the ammonium persulfate is 0.15-0.2mol/L, and the content of the polyurethane sponge is 80-120 g/L. The carbonization of the modified polyurethane sponge comprises the following steps: putting the modified polyurethane sponge into a vacuum tube type heat treatment furnace; carrying out carbonization heat treatment on the modified polyurethane sponge under the condition that the air pressure is lower than 0.001 Pa; and carrying out cryogenic cooling treatment on the modified polyurethane sponge after the carbonization heat treatment. Wherein, the carbonization heat treatment of the modified polyurethane sponge comprises the following steps: raising the temperature of the vacuum tube type heat treatment furnace to 400 ℃ at a first temperature raising rate; then, the temperature of the vacuum tube type heat treatment furnace is increased to 700 ℃ at a second temperature increasing rate; then, the temperature of the vacuum tube type heat treatment furnace is increased to 900-1000 ℃ at a third temperature-increasing rate; then preserving heat for 4-6h to obtain the modified polyurethane sponge after carbonization heat treatment; wherein the first temperature rise rate is less than the second temperature rise rate, and the second temperature rise rate is less than the third temperature rise rate. Wherein, the deep cooling treatment of the modified polyurethane sponge after the carbonization heat treatment comprises the following steps: cooling the modified polyurethane sponge after carbonization heat treatment to below 100 ℃ along with a furnace, and then putting the modified polyurethane sponge cooled along with the furnace into liquid nitrogen for cooling for 10-30 s. Wherein the first heating rate is 8-12 ℃/min, the second heating rate is 10-15 ℃/min, and the third heating rate is 12-17 ℃/min. The aging of the carbonized modified polyurethane sponge comprises the following steps: and (3) placing the carbonized modified polyurethane sponge in an oven, wherein the temperature of the oven is 70-80 ℃, and the aging time is 10-20 h. The heat treatment of the modified polyurethane sponge/graphene oxide composite material comprises the following steps: putting the modified polyurethane sponge/graphene oxide composite material into a vacuum tube type heat treatment furnace; carrying out heat treatment on the modified polyurethane sponge under the condition that the hydrogen flow is 100-200 sccm; wherein the heat treatment conditions are as follows: the heat treatment temperature is 500-600 ℃, and the heat treatment time is 1-2 h. The second aging of the primary modified polyurethane sponge/graphene oxide composite material comprises the following steps: and (3) placing the primary modified polyurethane sponge/graphene oxide composite material in an oven, wherein the temperature of the oven is 50-60 ℃, and the aging time is 10-20 h.
The skeleton materials obtained in examples 1 to 4 were cut into a strip sample having an area of 1 cm square and a thickness of 50 μm, and the conductivity of the material was measured by a four-probe method. Meanwhile, by using the method in the prior art, the electrode cathode material is prepared by utilizing the framework material, the battery is assembled, and the initial battery capacity and the battery capacity (unit is milliampere per gram) after 100 charge-discharge cycles are tested. See table 1 for results.
TABLE 1
The following describes comparative examples of the present invention, which are intended to highlight and demonstrate the advantages of the process of the present application, and for ease of reading, the technical solutions are described in simplified form, and steps and parameters not explicitly written can be considered as consistent with example 1.
Comparative example 1
Adding ammonium persulfate into a sulfuric acid solution, then adding polyurethane sponge, and then adding an aniline monomer.
Comparative example 2
And (3) reacting the second mixed solution for 30 hours at the temperature of 5 ℃, and drying to obtain the modified polyurethane sponge.
Comparative example 3
The carbonized modified polyurethane sponge is not aged, and the carbonized modified polyurethane sponge is directly added into the graphene oxide solution.
Comparative example 4
And (3) not carrying out secondary ageing on the primary modified polyurethane sponge/graphene oxide composite material.
Comparative example 5
The concentration of the sulfuric acid solution is 0.15mol/L, in the second mixed solution, the concentration of the aniline monomer is 0.15mol/L, the concentration of the ammonium persulfate is 0.15mol/L, and the content of the polyurethane sponge is 20 g/L.
Comparative example 6
The modified polyurethane sponge after carbonization heat treatment is not subjected to cryogenic cooling treatment.
Comparative example 7
The first temperature rise rate is 10 ℃/min, the second temperature rise rate is 10 ℃/min, and the third temperature rise rate is 10 ℃/min.
Comparative example 8
The first temperature rise rate is 10 ℃/min, the second temperature rise rate is 5 ℃/min, and the third temperature rise rate is 3 ℃/min.
Comparative example 9
The aging of the carbonized modified polyurethane sponge comprises the following steps: and (3) placing the carbonized modified polyurethane sponge in an oven, wherein the oven temperature is 100 ℃, and the aging time is 5 hours.
Comparative example 10
Putting the modified polyurethane sponge/graphene oxide composite material into a vacuum tube type heat treatment furnace; carrying out heat treatment on the modified polyurethane sponge under the condition that the hydrogen flow is 500 sccm; wherein the heat treatment conditions are as follows: the heat treatment temperature is 700 ℃, and the heat treatment time is 4 h.
Comparative example 11
Putting the modified polyurethane sponge/graphene oxide composite material into a vacuum tube type heat treatment furnace; carrying out heat treatment on the modified polyurethane sponge under the condition that the hydrogen flow is 300 sccm; wherein the heat treatment conditions are as follows: the heat treatment temperature is 150 ℃, and the heat treatment time is 5 h.
Comparative example 12
The second aging of the primary modified polyurethane sponge/graphene oxide composite material comprises the following steps: and (3) placing the primary modified polyurethane sponge/graphene oxide composite material in an oven, wherein the oven temperature is 80 ℃, and the aging time is 5 h.
The skeleton materials prepared in comparative examples 1 to 12 were cut into long test pieces having an area of 1 cm square and a thickness of 50 μm, and the conductivity of the materials was measured by a four-probe method. Meanwhile, by using the method in the prior art, the electrode cathode material is prepared by utilizing the framework material, the battery is assembled, and the initial battery capacity and the battery capacity (unit is milliampere per gram) after 100 charge-discharge cycles are tested. See table 2 for results.
TABLE 2
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (9)
1. A preparation method of an environment-friendly flexible lithium ion battery anode framework material is characterized by comprising the following steps: the preparation method comprises the following steps:
providing a polyurethane sponge;
providing aniline monomer, sulfuric acid solution and ammonium persulfate;
adding the aniline monomer into the sulfuric acid solution, and then adding the ammonium persulfate into a mixed solution of sulfuric acid and the aniline monomer to obtain a first mixed solution;
adding the polyurethane sponge into the first mixed solution to obtain a second mixed solution;
reacting the second mixed solution for 8-12h at the temperature of 8-15 ℃, and drying to obtain modified polyurethane sponge;
carbonizing the modified polyurethane sponge to obtain carbonized modified polyurethane sponge;
aging the carbonized modified polyurethane sponge;
preparing a graphene oxide solution;
adding the aged carbonized modified polyurethane sponge into the graphene oxide solution, stirring and drying to obtain a modified polyurethane sponge/graphene oxide composite material;
carrying out heat treatment on the modified polyurethane sponge/graphene oxide composite material to obtain a primary modified polyurethane sponge/graphene oxide composite material;
and carrying out second aging on the primary modified polyurethane sponge/graphene oxide composite material to obtain the environment-friendly flexible lithium ion battery positive electrode framework material.
2. The preparation method of the environment-friendly flexible lithium ion battery positive electrode framework material according to claim 1, characterized by comprising the following steps: wherein the concentration of the sulfuric acid solution is 0.3-0.5mol/L, the concentration of the aniline monomer in the second mixed solution is 0.15-0.2mol/L, the concentration of the ammonium persulfate in the second mixed solution is 0.15-0.2mol/L, and the content of the polyurethane sponge is 80-120 g/L.
3. The preparation method of the environment-friendly flexible lithium ion battery positive electrode framework material according to claim 1, characterized by comprising the following steps: the carbonization of the modified polyurethane sponge comprises the following steps:
putting the modified polyurethane sponge into a vacuum tube type heat treatment furnace;
carrying out carbonization heat treatment on the modified polyurethane sponge under the condition that the air pressure is lower than 0.001 Pa;
and carrying out cryogenic cooling treatment on the modified polyurethane sponge after the carbonization heat treatment.
4. The preparation method of the environment-friendly flexible lithium ion battery positive electrode framework material according to claim 3, characterized by comprising the following steps: wherein, the carbonization heat treatment of the modified polyurethane sponge comprises the following steps:
raising the temperature of the vacuum tube type heat treatment furnace to 400 ℃ at a first temperature raising rate;
then, the temperature of the vacuum tube type heat treatment furnace is increased to 700 ℃ at a second temperature increasing rate;
then, the temperature of the vacuum tube type heat treatment furnace is increased to 900-1000 ℃ at a third temperature-increasing rate;
then preserving heat for 4-6h to obtain the modified polyurethane sponge after carbonization heat treatment;
wherein the first temperature rise rate is less than the second temperature rise rate, and the second temperature rise rate is less than the third temperature rise rate.
5. The preparation method of the environment-friendly flexible lithium ion battery positive electrode framework material according to claim 4, characterized by comprising the following steps: wherein, the deep cooling treatment of the modified polyurethane sponge after the carbonization heat treatment comprises the following steps:
and cooling the modified polyurethane sponge after carbonization heat treatment to below 100 ℃ along with a furnace, and then putting the modified polyurethane sponge cooled along with the furnace into liquid nitrogen for cooling for 10-30 s.
6. The preparation method of the environment-friendly flexible lithium ion battery positive electrode framework material according to claim 4, characterized by comprising the following steps: wherein the first heating rate is 8-12 ℃/min, the second heating rate is 10-15 ℃/min, and the third heating rate is 12-17 ℃/min.
7. The preparation method of the environment-friendly flexible lithium ion battery positive electrode framework material according to claim 1, characterized by comprising the following steps: the aging of the carbonized modified polyurethane sponge comprises the following steps: and (3) placing the carbonized modified polyurethane sponge in an oven, wherein the oven temperature is 70-80 ℃, and the aging time is 10-20 h.
8. The preparation method of the environment-friendly flexible lithium ion battery positive electrode framework material according to claim 1, characterized by comprising the following steps: the heat treatment of the modified polyurethane sponge/graphene oxide composite material comprises the following steps:
putting the modified polyurethane sponge/graphene oxide composite material into a vacuum tube type heat treatment furnace;
carrying out heat treatment on the modified polyurethane sponge/graphene oxide composite material under the condition that the hydrogen flow is 100-200 sccm;
wherein the heat treatment conditions are as follows: the heat treatment temperature is 500-600 ℃, and the heat treatment time is 1-2 h.
9. The preparation method of the environment-friendly flexible lithium ion battery positive electrode framework material according to claim 1, characterized by comprising the following steps: the second aging of the primary modified polyurethane sponge/graphene oxide composite material comprises the following steps: and placing the primary modified polyurethane sponge/graphene oxide composite material in an oven, wherein the temperature of the oven is 50-60 ℃, and the aging time is 10-20 h.
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