CN109742400B - Preparation method of porous carbon material, self-supporting secondary battery cathode and secondary battery - Google Patents
Preparation method of porous carbon material, self-supporting secondary battery cathode and secondary battery Download PDFInfo
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Abstract
The invention belongs to the technical field of secondary batteries, and particularly relates to a preparation method of a porous carbon material, the porous carbon material, a self-supporting secondary battery cathode and a secondary battery. The preparation method of the porous carbon material provided by the invention comprises the following steps: mixing an organic monomer, foam metal and an optional catalyst to perform in-situ polymerization reaction to obtain polymer-coated foam metal, and calcining to obtain the porous carbon material. The method utilizes the characteristic that the foam metal can be evaporated at high temperature, synchronously realizes the synthesis of the material and the removal of the template, and achieves the effect of twice the result with half the effort. In addition, the method has high repeatability, strong controllability and simple process, can realize large-scale production, and has great industrial application prospect. The porous carbon material prepared by the preparation method has good uniformity, and meanwhile, the porous carbon material has good ion conductivity, can be used as a self-supporting secondary battery cathode, and is beneficial to improving the electrochemical performance of the secondary battery.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a preparation method of a porous carbon material, the porous carbon material, a self-supporting secondary battery cathode and a secondary battery.
Background
The constant consumption of non-renewable resources such as fossil fuels and the like and the environmental problems caused thereby compel people to develop novel, renewable and environment-friendly energy storage devices. As one of the representatives of many energy storage devices, secondary batteries are popular due to their advantages such as high energy density, good cycle performance, and long cycle life, and are now widely used in daily life. However, the continuous development of the electronic market and the electric vehicle market puts higher demands on the performance of the secondary battery. The anode material, which is an important component of the secondary battery, is also the focus of research at the present stage.
Although the capacity of the metal lithium is high, the melting point of the lithium is low, the lithium is sensitive to air and is easy to oxidize, lithium dendrite is easy to grow on a lithium negative electrode, dead lithium is formed or short circuit is caused in the battery, the safety problem is obvious, and in addition, the lithium resource storage capacity is very limited, and the cost is high. These problems limit the application of lithium negative electrodes.
The negative electrode material of the secondary battery, which has been commercialized, is mainly graphite, and although it has a high compacted density and a relatively low price, it has unstable capacity performance due to its particle size, many surface defects, poor compatibility with an electrolyte, and many side reactions. In addition, in the process of preparing graphite into a negative electrode plate, an additional adhesive and a conductive agent are required, which in turn reduces the energy density of the secondary battery.
In view of this, the present invention is particularly proposed to solve at least one of the above-mentioned problems.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a porous carbon material, which comprises the steps of mixing an organic monomer, a foam metal and an optional catalyst, carrying out in-situ polymerization reaction to obtain a polymer-coated foam metal, and calcining to obtain the porous carbon material. The method has the advantages of high repeatability, strong controllability, simple process, realization of large-scale production and great industrial application prospect.
A second object of the present invention is to provide a porous carbon material having good uniformity and ion conductivity, which is useful for improving the cycle stability of a secondary battery when used as a negative electrode of the secondary battery.
A third object of the present invention is to provide a self-supporting secondary battery negative electrode, which is the above porous carbon material, and which does not require a metal current collector, and does not require addition of an additional binder and a conductive agent, and is advantageous for further improvement of the energy density of the secondary battery.
A fourth object of the present invention is to provide a secondary battery comprising the above self-supporting secondary battery negative electrode.
A fifth object of the present invention is to provide an electronic device, an electric tool, an electric vehicle, or an electric power storage system including the secondary battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
according to an aspect of the present invention, there is provided a method for preparing a porous carbon material, comprising the steps of:
mixing an organic monomer, foam metal and an optional catalyst to perform in-situ polymerization reaction to obtain polymer-coated foam metal, and calcining to obtain the porous carbon material.
As a further preferable technical solution, in the polymer-coated metal foam, the volume ratio of the polymer to the metal foam is (5-10): 1, preferably (8-10): 1.
as a further preferred embodiment, the polymer comprises: any one or the combination of at least two of phenolic resin, polyaniline, polypyrrole, polythiophene or polydopamine;
preferably, the metal foam comprises zinc foam;
preferably, the catalyst comprises a mineral acid comprising concentrated hydrochloric acid and/or dilute sulfuric acid.
As a further preferable technical scheme, the mixing temperature is 10-50 ℃, and preferably 20-40 ℃;
preferably, the mixing time is 30-120min, preferably 60-100 min;
preferably, the calcination includes the steps of primary carbonization and secondary carbonization;
preferably, the temperature of the primary carbonization is 400-700 ℃, preferably 400-600 ℃;
preferably, the time for the primary carbonization is 3 to 7 hours, preferably 4 to 6 hours;
preferably, the temperature of the secondary carbonization is 900-1500 ℃, preferably 900-1000 ℃;
preferably, the time of the secondary carbonization is 2 to 5 hours, preferably 3 to 5 hours.
As a further preferable technical solution, the method for preparing the porous carbon material includes the steps of:
mixing phenol, low-carbon aldehyde, concentrated hydrochloric acid and foamed zinc at 80-100 ℃ to perform in-situ polymerization reaction to obtain foamed zinc coated by phenolic resin, performing primary carbonization on the foamed zinc coated by the phenolic resin at 600 ℃ and performing secondary carbonization at 1000 ℃ and 900 ℃ to obtain the porous carbon material.
As a further preferable technical solution, the low carbon aldehyde includes any one of formaldehyde, acetaldehyde or propionaldehyde or a combination of at least two of them;
preferably, the lower aldehyde is formaldehyde and/or acetaldehyde.
According to another aspect of the invention, the porous carbon material is prepared by the preparation method of the porous carbon material;
the pore diameter of the porous carbon material is 100-400 mu m, the porous carbon material has a three-dimensional framework structure, and the thickness of the framework is 50-150 mu m.
According to another aspect of the present invention, there is also provided a self-supporting secondary battery negative electrode, which is the porous carbon material prepared by the method for preparing the porous carbon material or the porous carbon material.
According to another aspect of the present invention, there is also provided a secondary battery including a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolytic solution;
wherein the negative electrode is the negative electrode of the self-supporting secondary battery.
According to another aspect of the present invention, there is also provided an electronic device, an electric tool, an electric vehicle, or an electric power storage system including the secondary battery.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the porous carbon material, the foamed metal is used as a template, the polymer generated in situ by the organic monomer is used as a carbon source, and the obtained polymer-coated foamed metal is calcined to obtain the porous carbon material. Wherein, in the calcining process, a melt structure is generated firstly, and then the template is evaporated, so that the obtained porous carbon material is more uniform.
2. The invention utilizes the characteristic that the foam metal can be evaporated at high temperature to synchronously realize the synthesis of the porous carbon material and the removal of the template, thereby achieving the effect of twice the result with half the effort. In addition, the method has high repeatability, strong controllability and simple process, can realize large-scale production, and has great industrial application prospect.
3. The porous carbon material prepared by the preparation method of the porous carbon material provided by the invention has good uniformity, and meanwhile, the porous carbon material has good ion conductivity, can be used as a negative electrode of a secondary battery, and is beneficial to improving the cycle stability of the secondary battery.
4. The porous carbon material provided by the invention is low in cost, environment-friendly and self-supporting, does not need a metal current collector, does not need to add extra binder and conductive agent, is directly used as the negative electrode of the secondary battery, is favorable for further improving the energy density of the secondary battery, and has wide application prospect in the field of the secondary battery. An electronic device, an electric tool, an electric vehicle, or an electric power storage system, which also includes the secondary battery, has at least the same advantages as the secondary battery.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is an SEM picture of a porous carbon material prepared by the preparation method provided by the present invention in example 1 of the present invention;
fig. 2 is a cycle performance diagram of a lithium ion battery assembled by using a porous carbon material prepared by the preparation method provided by the invention as a self-supporting negative electrode in example 1 of the invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but those skilled in the art will understand that the following embodiments and examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Those who do not specify the conditions are performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
It should be noted that:
in the present invention, all the embodiments and preferred methods mentioned herein can be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
The "ranges" disclosed herein may have one or more lower limits and one or more upper limits, respectively, in the form of lower limits and upper limits.
In the present invention, unless otherwise specified, the individual reactions or operation steps may or may not be performed in sequence. Preferably, the methods herein are performed sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
In a first aspect, in at least one embodiment, there is provided a method of preparing a porous carbon material, comprising the steps of:
mixing an organic monomer, foam metal and an optional catalyst to perform in-situ polymerization reaction to obtain polymer-coated foam metal, and calcining to obtain the porous carbon material.
The invention provides a preparation method of a porous carbon material aiming at the defects in the prior art, and the method takes foam metal as a template and a polymer generated in situ by an organic monomer as a carbon source, and the obtained polymer-coated foam metal is calcined to obtain the porous carbon material. In the calcining process, a melt structure is firstly generated, and then the template is evaporated to generate holes, so that the prepared porous carbon material is more uniform and can be used as a negative electrode of a self-supporting secondary battery, and the improvement of the cycle stability and the energy density of the secondary battery is facilitated.
Meanwhile, the invention utilizes the characteristic that the foam metal can be evaporated at high temperature to synchronously realize the synthesis of the material and the removal of the template, overcomes the defects that the conventional method can not control the structure and has long preparation flow, and achieves the effect of getting twice the result with half the effort. In addition, the method has high repeatability, strong controllability and simple process, can realize large-scale production, and has great industrial application prospect.
It should be noted that the present invention has no special requirement for the selection of the organic monomer, as long as the polymer can be generated in situ after the metal foam is immersed in the organic monomer solution, for example: the organic monomer may be a monomer such as pyrrole or aniline, pyrrole being polymerized to form polypyrrole, aniline being polymerized to form polyaniline; two monomers, such as phenol and formaldehyde, may also be polymerized to form phenolic resins, and the like.
The foam metal refers to a metal having a three-dimensional structure. The three-dimensional structure of the foam metal can ensure that the porous carbon material generated subsequently can realize self-support. The foam metal needs to form a metal melt environment in a certain temperature range, can evaporate and remove the template pores in another temperature range, and simultaneously realizes uniform synthesis of the porous carbon material and removal of the template, thereby achieving the effect of achieving twice the result with half the effort.
The meaning of the above "self-supporting" is: the porous carbon material prepared by the method can be directly used as the negative electrode of a secondary battery without a metal current collector or adding extra binder and conductive agent.
The meaning of "optionally catalyst" is: the addition or non-addition of the catalyst is selected according to different actual reactions. Some of the more extensive in situ polymerization reactions can be completed without the addition of catalyst, in which case the catalyst may not be added. While some in situ polymerization reactions must be carried out under the catalytic action of a catalyst, the addition of a catalyst is required.
After the organic monomer, the foam metal and the optional catalyst are mixed, the foam metal is completely immersed into the organic monomer solution, the organic monomer is subjected to a polymerization reaction in situ, the generated polymer is coated in the pores and on the surface of the foam metal to realize complete coating, and the foam metal coated with the polymer is calcined to obtain the porous carbon material.
In a preferred embodiment, in the polymer-coated metal foam, the volume ratio of polymer to metal foam is (5-10): 1, preferably (8-10): 1.
it should be noted that, the volume ratio of the polymer to the foam metal is important for realizing the present invention, and the suitable volume ratio can completely cover the foam metal, which is helpful for preparing the porous carbon material with better performance. Typically, but not by way of limitation, the volume ratio of polymer to metal foam may be 5: 1,6: 1,7: 1,7.5: 1,8: 1,9: 1 or 10: 1.
in a preferred embodiment, the polymer comprises: any one or the combination of at least two of phenolic resin, polyaniline, polypyrrole, polythiophene or polydopamine;
preferably, the metal foam comprises zinc foam;
preferably, the catalyst comprises a mineral acid comprising concentrated hydrochloric acid and/or dilute sulfuric acid.
It should be noted that the polymer generated in situ by the organic monomer is an important guarantee for realizing the present invention as the carbon source, and if an inorganic carbon source such as glucose is adopted, since the concentration of the inorganic carbon source does not meet the requirement of the reaction, the coating of the foam metal cannot be realized, and further the preparation of the porous carbon material with the self-supporting function cannot be realized. Typically, but not limited to, the polymer may be any one of or a combination of at least two of phenolic resin, polyaniline, polypyrrole, polythiophene, or polydopamine;
the phenolic resin is prepared by the polycondensation of phenols and aldehydes, the monomers of polyaniline, polypyrrole, polythiophene and polydopamine are respectively aniline, pyrrole, thiophene and dopamine, the addition polymerization of aniline is polyaniline, the addition polymerization of pyrrole is polypyrrole, the addition polymerization of thiophene is polythiophene, and the addition polymerization of dopamine is polydopamine.
The foam metal is used as a template, a melt structure can be formed at a certain calcining temperature, and the uniformity of the porous carbon material is ensured. In addition, the foam metal has a three-dimensional structure, and the property provides a basis for the self-supporting function of the prepared porous carbon material. Typically, but not by way of limitation, the metal foam may be, for example, zinc foam.
In a preferred embodiment, the temperature of mixing is 10 to 50 ℃, preferably 20 to 40 ℃;
preferably, the mixing time is 30-120min, preferably 60-100 min;
preferably, the calcination includes a step of primary carbonization and secondary carbonization;
preferably, the temperature of the primary carbonization is 400-700 ℃, preferably 400-600 ℃;
preferably, the time for the primary carbonization is 3 to 7 hours, preferably 4 to 6 hours;
preferably, the temperature of the secondary carbonization is 900-1500 ℃, preferably 900-1000 ℃;
preferably, the time for the second carbonization is 2 to 5 hours, preferably 3 to 5 hours.
The invention has no special requirements on the mixing temperature and time, and can be carried out only by ensuring the smooth in-situ polymerization reaction (if the mixing time is too short, the temperature is too low, the in-situ polymerization reaction is not completely carried out, the product is too little, and if the mixing time is too long, the temperature is too high, the degree of the in-situ polymerization reaction is too large, and the reaction product is difficult to process). Typically, but not by way of limitation, the mixing time may be 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, or 120 min; the temperature of mixing may be 10 ℃, 20 ℃, 30 ℃, 40 ℃, 45 ℃ or 50 ℃.
It should be understood that the temperature and time of the primary carbonization are selected to provide a melt environment for the metal foam while initially completing the carbonization process of the polymer. If the temperature is too high and the time is too long, the foam metal begins to generate evaporation loss, and the melt environment cannot be ensured; if the temperature is too low, the time is too short, the carbonization process is incomplete, a large amount of gas is generated in the subsequent secondary carbonization process, the complete structure of the porous carbon material is damaged, and if the temperature of the primary carbonization is lower than the melting point temperature of the foam metal, a melt environment cannot be formed. Typically, but not first limiting, the temperature of the primary carbonization may be 400 ℃, 500 ℃, 600 ℃ or 700 ℃; the time for the primary carbonization can be 3h, 4h, 5h, 6h or 7 h.
The secondary carbonization process ensures the graphitization of the porous carbon material, so that the product has good conductivity; and secondly, completing the evaporation of the foam metal and removing the template. If the temperature is too high and the time is too long, the rapid loss of the foam metal can be caused, and the continuous structure of the porous carbon material can be damaged; if the temperature is too low, the time is too short, the graphitization degree of the porous carbon material is low, and the conductivity is poor. Typically, but not first limited, the temperature of the secondary carbonization may be 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃ or 1500 ℃; the time of the secondary carbonization can be 2h, 3h, 4h or 5 h.
The temperature increase rate for calcination in the present invention is not particularly limited. Typically, but not by way of limitation, the rate of temperature rise may be 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, 5 deg.C/min, 6 deg.C/min, or 7 deg.C/min. In addition, the calcination is performed under a protective atmosphere, and the protective gas may be argon, nitrogen, or the like.
In a preferred embodiment, a method for preparing a porous carbon material comprises the steps of:
mixing phenol, low-carbon aldehyde, concentrated hydrochloric acid and foamed zinc at 80-100 ℃ to perform in-situ polymerization reaction to obtain foamed zinc coated by phenolic resin, performing primary carbonization on the foamed zinc coated by the phenolic resin at 600 ℃ of 400-plus, and performing secondary carbonization at 1000 ℃ of 900-plus to obtain the porous carbon material.
Firstly, the three-dimensional structure of the foam zinc ensures that the porous carbon material generated subsequently has a self-supporting function. In addition, in the range of 400-600 ℃, the foamed zinc as a template can provide a melt environment which ensures the uniformity of the porous carbon material generated subsequently. Within the range of 900-1000 ℃, the foam zinc can be removed by evaporation, so that the synthesis of the porous carbon material and the removal of the template can be simultaneously realized, and the effect of achieving twice the result with half the effort is achieved.
The relevant parameters of the foamed zinc adopted by the invention are as follows:
pore diameter: 100-1000 μm; porosity: 50% -98%; the through hole rate: more than or equal to 98 percent; bulk density: 0.1-0.8g/cm3。
The amount of concentrated hydrochloric acid is appropriate. The catalytic effect of concentrated hydrochloric acid determines the extent to which the in situ polymerisation reaction proceeds. If the concentrated hydrochloric acid is too little, the in-situ polymerization reaction is not completely carried out; if the concentrated hydrochloric acid is excessive, the excessive acid can corrode the foam zinc and damage the template.
In a preferred embodiment, the lower aldehyde comprises any one of formaldehyde, acetaldehyde or propionaldehyde or a combination of at least two thereof;
preferably, the lower aldehyde is formaldehyde and/or acetaldehyde.
As the activity of the organic matter is reduced along with the increase of the carbon chain, the invention selects the low-carbon aldehyde as a raw material for synthesizing the phenolic resin. Typically, but not limitatively, the low carbon aldehyde can be selected from formaldehyde, acetaldehyde, a mixed aldehyde of formaldehyde and acetaldehyde, and the like.
In a second aspect, in at least one embodiment, there is provided a porous carbon material, produced by the above method for producing a porous carbon material;
the pore diameter of the porous carbon material is 100-400 mu m, the porous carbon material has a three-dimensional framework structure, and the thickness of the framework is 50-150 mu m.
The porous carbon material prepared by the preparation method of the porous carbon material provided by the invention has good uniformity and ion conductivity, is applied to the field of secondary batteries, and is beneficial to improving the cycle stability of the secondary batteries.
It is understood that the pore size, structure and thickness of the skeleton of the porous carbon material are related to the foam metal as a template. Typically, but not limited to, the pore size of the porous carbon material is 100 μm, 200 μm, 300 μm or 400 μm; the thickness of the skeleton is 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm or 150 μm.
In a third aspect, in at least one embodiment, there is provided a self-supporting secondary battery negative electrode, which is a porous carbon material obtained by the above-described method for producing a porous carbon material or the above-described porous carbon material.
The porous carbon material can be directly used as a self-supporting lithium ion battery cathode after being flattened and cut into a proper size and shape, a metal current collector is not needed, and an additional binder and a conductive agent are not needed, so that the energy density of the secondary battery is further improved.
In a fourth aspect, there is provided in at least one embodiment a secondary battery including a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolytic solution;
wherein the negative electrode is the self-supporting secondary battery negative electrode.
It is to be understood that the present invention is not particularly limited to the remaining components of the secondary battery, other than the negative electrode, the core of which is to include the porous carbon material of the present invention, and the remaining components or parts may be referred to the prior art.
The porous carbon material provided by the invention can be applied to secondary batteries such as lithium ion batteries and sodium ion batteries as a self-supporting secondary battery cathode.
The present invention will be described in further detail below mainly with reference to a lithium ion battery as an example, but it is understood that the secondary battery includes, but is not limited to, a lithium ion battery.
In a fifth aspect, in at least one embodiment, there is provided an electronic device, an electric tool, an electric vehicle, or an electric power storage system including the secondary battery described above.
An electronic device is an electronic device that performs various functions (e.g., playing music) using a secondary battery as a power source for operation. The electric power tool is an electric power tool that moves a component (e.g., a drill) using a secondary battery as a driving power source. The electric vehicle is an electric vehicle that runs on a secondary battery as a drive power source, and may be an automobile (including a hybrid vehicle) equipped with other drive sources in addition to the secondary battery. The power storage system is a power storage system that uses a secondary battery as a power storage source. For example, in a home electric power storage system, electric power is stored in a secondary battery serving as an electric power storage source, and the electric power stored in the secondary battery is consumed as needed to enable use of various devices such as home electronic products.
The present invention will be further described with reference to specific examples, comparative examples and the accompanying drawings.
Example 1
The embodiment provides a preparation method of a porous carbon material, which comprises the following steps:
4g of phenol and 2.5mL of formaldehyde solution were put in a beaker, and 10mL of concentrated hydrochloric acid was added thereto and stirred uniformly. Soaking the foamed zinc in the mixed solution, reacting at the temperature of 20 ℃ for 30mins, and after the in-situ polymerization reaction is finished, carrying out low-temperature vacuum drying on the product to obtain the foamed zinc coated by the phenolic resin (the volume ratio of the phenolic resin to the foamed zinc is 10: 1). Heating the obtained phenolic resin coated zinc foam to 500 ℃ at the heating rate of 5 ℃/min under the argon environment, preserving the heat for 6h, and carrying out primary carbonization; then heating to 1000 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and carrying out secondary carbonization. After the temperature is reduced, a porous carbon material is obtained (as shown in FIG. 1, the porous carbon material has a three-dimensional skeleton structure, the thickness of the skeleton is 50-150 μm, and the pore diameter is 100-400 μm).
Example 2
The embodiment provides a preparation method of a porous carbon material, which comprises the following steps:
3g of phenol and 2mL of formaldehyde solution were put in a beaker, and 5mL of concentrated hydrochloric acid was added thereto and stirred uniformly. Soaking the foamed zinc in the mixed solution, reacting at 10 ℃ for 120mins, and after the in-situ polymerization reaction is finished, carrying out low-temperature vacuum drying on the product to obtain the foamed zinc coated by the phenolic resin (the volume ratio of the phenolic resin to the foamed zinc is 8: 1). Heating the obtained phenolic resin coated zinc foam to 600 ℃ at the heating rate of 3 ℃/min under the argon environment, preserving the heat for 3h, and carrying out primary carbonization; then heating to 1000 ℃ at the heating rate of 5 ℃/min, preserving heat for 3h, and carrying out secondary carbonization. And after the temperature is reduced, obtaining the porous carbon material.
Example 3
The embodiment provides a preparation method of a porous carbon material, which comprises the following steps:
4g of phenol and 2.5mL of formaldehyde solution were put in a beaker, and 7mL of concentrated hydrochloric acid was added thereto and stirred uniformly. Soaking the foamed zinc in the mixed solution, reacting at 40 ℃ for 100mins, and after the in-situ polymerization reaction is finished, carrying out low-temperature vacuum drying on the product to obtain the foamed zinc coated by the phenolic resin (the volume ratio of the phenolic resin to the foamed zinc is 10: 1). Heating the obtained phenolic resin coated zinc foam to 400 ℃ at the heating rate of 3 ℃/min under the argon environment, preserving the heat for 4h, and carrying out primary carbonization; then heating to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat for 5h, and carrying out secondary carbonization. And after the temperature is reduced, obtaining the porous carbon material.
Example 4
The embodiment provides a preparation method of a porous carbon material, which comprises the following steps:
and 4mL of pyrrole is placed in a beaker, foamed zinc is soaked in the pyrrole solution and reacts for 60mins at the temperature of 50 ℃, and after the in-situ polymerization reaction is finished, the product is subjected to low-temperature vacuum drying to obtain polypyrrole-coated foamed zinc (the volume ratio of polypyrrole to foamed zinc is 5: 1). Heating the obtained polypyrrole-coated foamed zinc to 700 ℃ at a heating rate of 5 ℃/min in a nitrogen environment, preserving heat for 7 hours, and carrying out primary carbonization; then heating to 1500 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and carrying out secondary carbonization. And after the temperature is reduced, obtaining the porous carbon material.
Example 5
This example provides a method for preparing a porous carbon material, except that the amount of phenol was changed to 1g and the amount of formaldehyde was changed to 2mL, so that the volume ratio of phenolic resin to zinc foam in the phenolic resin-coated zinc foam was 4: 1, the remaining preparation steps were the same as in example 1.
Example 6
This example provides a method for preparing a porous carbon material, except that the amount of phenol was changed to 1.5g and the amount of formaldehyde was changed to 2mL, so that the volume ratio of phenolic resin to zinc foam in the phenolic resin-coated zinc foam was 5: 1, the remaining preparation steps were the same as in example 1.
Example 7
This example provides a method for preparing a porous carbon material, except that the amount of phenol was changed to 2g and the amount of formaldehyde was changed to 2.5mL, so that the volume ratio of phenolic resin to zinc foam in the phenolic resin-coated zinc foam was 7: 1, the remaining preparation steps were the same as in example 1.
Example 8
This example provides a method for preparing a porous carbon material, except that the amount of phenol was changed to 3g and the amount of formaldehyde was changed to 2mL, so that the volume ratio of phenolic resin to zinc foam in the phenolic resin-coated zinc foam was 8: 1, the remaining preparation steps were the same as in example 1.
Example 9
This example provides a method for preparing a porous carbon material, except that the amount of phenol was changed to 3g and the amount of formaldehyde was changed to 2.5mL, so that the volume ratio of phenolic resin to zinc foam in the phenolic resin-coated zinc foam was 9: 1, the remaining preparation steps were the same as in example 1.
Example 10
This example provides a method for preparing a porous carbon material, which is the same as that of example 1, except that the organic monomer is dopamine 2g, and the catalyst is dilute sulfuric acid to prepare polydopamine-coated zinc foam.
Example 11
This example provides a method for preparing a porous carbon material, which is the same as in example 1, except that 1.5g of aniline was used as the organic monomer to prepare polyaniline-coated zinc foam.
Example 12
This example provides a method for preparing a porous carbon material, which was the same as in example 1 except that the formaldehyde solution was replaced with an acetaldehyde solution.
Example 13
This example provides a method for producing a porous carbon material, which was the same as in example 1 except that the formaldehyde solution was replaced with a propionaldehyde solution.
Note: the porous carbon material prepared by the embodiments can realize a self-supporting function, and can be directly used as a lithium ion battery cathode.
Comparative example 1
This comparative example provides a preparation method of a porous carbon material, except that the zinc foam was directly immersed in a phenolic resin solution and stirred for 30mins, and the product was vacuum dried at low temperature to obtain a phenolic resin-coated zinc foam (the volume ratio of phenolic resin to zinc foam was 10: 1), and the remaining preparation steps were the same as in example 1.
The experimental results of this comparative example are: the porous carbon material prepared by the comparative example cannot completely coat the foam zinc with the phenolic resin, and further cannot realize the self-supporting function, and the prepared porous carbon material is smeared and then is used as the negative electrode of the lithium ion battery.
Comparative example 2
This comparative example provides a method for preparing a porous carbon material, which is the same as in example 1 except that the zinc foam was directly immersed in a glucose solution (the volume ratio of glucose to zinc foam was 10: 1).
The experimental results of this comparative example are: the porous carbon material prepared by the comparative example cannot realize complete coating of the zinc foam by glucose, further cannot realize a self-supporting function, and needs to be smeared to serve as a negative electrode of a lithium ion battery.
Comparative example 3
This comparative example provides a method of preparing a porous carbon material, which was the same as in example 1 except that zinc particles were used instead of the zinc foam.
The experimental results of this comparative example are: the porous carbon material prepared by the comparative example cannot form a three-dimensional skeleton structure, so that the self-supporting function cannot be realized, and the prepared porous carbon material is smeared and then used as a negative electrode of a lithium ion battery.
Examples of the experiments
The porous carbon materials provided in examples 1 to 5 were used as the negative electrode directly, the porous carbon materials provided in comparative examples 1 to 3 were smeared and then used as the negative electrode, and LiFePO was used4After smearAs a button cell assembled on a positive electrode, a cycle test is performed in a voltage window range of 2.5-4.5V and at a current density of 1C, and the performance is shown in table 1 (wherein, fig. 2 is a cycle performance diagram of a lithium ion battery assembled by directly using a porous carbon material prepared by the preparation method provided in example 1 as a negative electrode, and after 200 cycles, the specific capacity is maintained at 342 mAh/g):
TABLE 1 Performance data of button cell assembled with porous carbon materials prepared in examples and comparative examples
From the relevant data in the table, the following conclusions can be drawn: the porous carbon material with the self-supporting function can be smoothly prepared by adopting the preparation method, and the porous carbon material is directly used as the negative electrode of the lithium ion battery, so that the excellent cycling stability and high energy density are shown.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (14)
1. A method for producing a porous carbon material, characterized by comprising the steps of:
mixing phenol, foamed zinc and concentrated hydrochloric acid to perform in-situ polymerization reaction to obtain foamed zinc coated by phenolic resin, and calcining to obtain a porous carbon material;
wherein the mixing of phenol, zinc foam and concentrated hydrochloric acid comprises: adding 10mL of concentrated hydrochloric acid into 4g of phenol and 2.5mL of formaldehyde solution to obtain a mixed solution, and soaking the foamed zinc in the mixed solution;
the volume ratio of the phenolic resin to the foamed zinc is 10: 1;
the calcination includes a step of primary carbonization and secondary carbonization;
the temperature of the primary carbonization is 400-700 ℃, and the time is 3-7 h;
the temperature of the secondary carbonization is 1000-1500 ℃, and the time is 2-5 h.
2. The method for producing a porous carbon material according to claim 1, wherein the temperature of mixing is 10 to 50 ℃.
3. The method for preparing a porous carbon material according to claim 2, wherein the temperature of the mixing is 20 to 40 ℃.
4. The method for preparing a porous carbon material according to claim 2, wherein the mixing time is 30-120 min.
5. The method for producing a porous carbon material according to claim 4, wherein the mixing time is 60 to 100 min.
6. The method for preparing a porous carbon material according to claim 2, wherein the temperature of the primary carbonization is 400-600 ℃.
7. The method for preparing a porous carbon material according to claim 2, wherein the time for the primary carbonization is 4 to 6 hours.
8. The method for producing a porous carbon material according to claim 2, characterized in that the temperature of the secondary carbonization is 1000 ℃.
9. The method for preparing a porous carbon material according to claim 2, wherein the time for the secondary carbonization is 3 to 5 hours.
10. The method for producing a porous carbon material according to claim 1, comprising the steps of:
mixing phenol, formaldehyde, concentrated hydrochloric acid and foamed zinc at 80-100 ℃ to perform in-situ polymerization reaction to obtain foamed zinc coated by phenolic resin, performing primary carbonization on the foamed zinc coated by the phenolic resin at 600 ℃ and 400 ℃, and performing secondary carbonization at 1000 ℃ to obtain the porous carbon material.
11. A porous carbon material characterized by being produced by the method for producing a porous carbon material according to any one of claims 1 to 10;
the pore diameter of the porous carbon material is 100-400 mu m, the porous carbon material has a three-dimensional framework structure, and the thickness of the framework is 50-150 mu m.
12. A self-supporting secondary battery negative electrode, characterized in that the self-supporting secondary battery negative electrode is a porous carbon material produced by the method for producing a porous carbon material according to any one of claims 1 to 10 or the porous carbon material according to claim 11.
13. A secondary battery is characterized by comprising a positive electrode, a negative electrode, a diaphragm between the positive electrode and the negative electrode and an electrolyte;
wherein the negative electrode is the negative electrode for a self-supporting secondary battery of claim 12.
14. An electronic device, an electric tool, an electric vehicle, or an electric power storage system comprising the secondary battery according to claim 13.
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