CN111875792A - Preparation method of carboxymethyl cellulose polypyrrole conductive composite material - Google Patents
Preparation method of carboxymethyl cellulose polypyrrole conductive composite material Download PDFInfo
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- CN111875792A CN111875792A CN202010404954.4A CN202010404954A CN111875792A CN 111875792 A CN111875792 A CN 111875792A CN 202010404954 A CN202010404954 A CN 202010404954A CN 111875792 A CN111875792 A CN 111875792A
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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Abstract
The invention is suitable for the technical field of polymer composite materials, and provides a preparation method of a carboxymethyl cellulose polypyrrole conductive composite material, which comprises the steps of sequentially and respectively dissolving a carboxymethyl cellulose solution, a pyrrole solution and an ammonium persulfate solution in an aqueous medium, uniformly mixing the carboxymethyl cellulose solution and the pyrrole solution according to a certain proportion, then dropwise adding an oxidant ammonium sulfate solution, carrying out polymerization reaction for 2-3.5 hours at the temperature of 3 ℃, adding methanol into a reaction medium, and stopping the polymerization of pyrrole. Through a circulating centrifugal washing mode, washing carboxymethyl cellulose polypyrrole colloid from the reaction product, and finally concentrating, drying and crushing to obtain the carboxymethyl cellulose polypyrrole composite, wherein the conductivity of the composite prepared by the invention can reach more than 10S/cm, and the composite can be used for preparing flexible conductive materials, is suitable for lithium ion battery cathode adhesives, and has a good application prospect.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and particularly relates to a preparation method of a carboxymethyl cellulose polypyrrole conductive composite material.
Background
Among many conductive polymers, polypyrrole (PPy) has the advantages of good air stability, high conductivity, large variation range, easy synthesis and the like, and has attracted extensive attention. The conductive polymer material has the advantages of small internal resistance, good high power, high energy, large specific capacity and the like. The conductive polymers currently applied to the electrode material of the super capacitor include polypyrrole (PPy), Polyaniline (PANI), Polyacene (PAS), Polythiophene (PTH), polyparaphenylene (PPP), and the like.
Polypyrrole (PPy) is an earlier-discovered conductive polymer, and is widely used in electrode materials due to its simple synthesis method and high conductivity. However, when pure PPy is used as a capacitor material, the problems are poor mechanical properties, difficult processing, and the working voltage and the energy storage density are to be improved. The composite material not only has the advantages of each component, but also can effectively make up the defects of a single component, thereby being paid much attention to by people. The conductive polymer/inorganic composite material developed in recent years is an important electrode material and has a wide research prospect.
The natural cellulose is polysaccharide which is most widely distributed and contained in nature, and has abundant sources. Current cellulose modification technologies focus primarily on both etherification and esterification. Carboxymethylation is one of the etherification techniques. Carboxymethyl cellulose (CMC) is obtained after carboxymethylation of cellulose, and an aqueous solution of the carboxymethyl cellulose has the effects of thickening, film forming, adhesion, water retention, colloid protection, emulsification, suspension and the like, is widely applied to industries such as petroleum, food, medicine, textile, paper making and the like, and is one of the most important cellulose ethers. The sodium carboxymethyl cellulose can also be used in the lithium ion battery cathode slurry to play roles in thickening, dispersing and bonding. However, sodium carboxymethyl cellulose itself is an insulating material, and can affect the cycle performance and discharge capacity of the battery.
Disclosure of Invention
The invention provides a preparation method of a carboxymethyl cellulose polypyrrole conductive composite material, aiming at enhancing the conductivity and mechanical properties of a conductive polymer, and the carboxymethyl cellulose polypyrrole conductive composite material is used for a lithium ion battery cathode, so that the conductivity of the lithium ion battery cathode can be improved, and the cycle performance and electrochemical capacity of the battery can be improved.
The invention is realized in such a way that the preparation method of the carboxymethyl cellulose polypyrrole conductive composite material comprises the following steps:
s1, respectively dissolving carboxymethyl cellulose, pyrrole and ammonium persulfate in an aqueous medium to obtain a carboxymethyl cellulose solution, a pyrrole solution and an ammonium persulfate solution;
s2, uniformly mixing the carboxymethyl cellulose solution and the pyrrole solution, then dropwise adding an oxidant ammonium sulfate solution, and carrying out polymerization reaction for 2-3.5 hours at 3 ℃ to obtain a reaction medium;
s3, adding methanol into the reaction medium to terminate the polymerization of pyrrole to obtain a reaction product;
s4, washing the carboxymethyl cellulose polypyrrole colloid from the reaction product in a circulating centrifugal washing mode;
and S5, finally, sequentially concentrating, drying and crushing the carboxymethyl cellulose polypyrrole colloid to obtain the carboxymethyl cellulose polypyrrole compound.
Preferably, the carboxyl group content of the carboxymethyl cellulose solution is 1.0 to 2.5 mmol/g.
Preferably, the mixing mass ratio of the carboxymethyl cellulose solution to the pyrrole solution is 100: 5.
preferably, the molar concentration of the oxidant ammonium sulfate solution is 0.2mol/L, and the dropping amount is 10-60 mL.
Preferably, in step S5, the carboxymethyl cellulose polypyrrole composite particles obtained by pulverization have a particle size of 0.15 to 5 μm.
Compared with the prior art, the invention has the beneficial effects that: the carboxymethyl cellulose polypyrrole composite is obtained, the conductivity of the composite prepared by the method can reach more than 10S/cm, and the composite can be used for preparing flexible conductive materials, is suitable for lithium ion battery cathode adhesives, and has a good application prospect.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of a carboxymethyl cellulose polypyrrole conductive composite material according to a first embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Referring to fig. 1, the present embodiment provides a technical solution: a preparation method of a carboxymethyl cellulose polypyrrole conductive composite material comprises the following steps:
s1, respectively dissolving carboxymethyl cellulose, pyrrole and ammonium persulfate in an aqueous medium to obtain a carboxymethyl cellulose solution, a pyrrole solution and an ammonium persulfate solution.
S2, uniformly mixing the carboxymethyl cellulose solution and the pyrrole solution, then dropwise adding an oxidant ammonium sulfate solution, and carrying out polymerization reaction for 2 hours at 3 ℃ to obtain a reaction medium. The carboxymethyl cellulose solution had a carboxymethyl group content of 1.75 mmol/g. The mixing mass ratio of the carboxymethyl cellulose solution to the pyrrole solution is 100: 5. the molar concentration of the oxidant ammonium sulfate solution is 0.2mol/L, and the dropping amount is 20 mL.
S3, adding 20mL of methanol into the reaction medium to terminate the polymerization of pyrrole, obtaining the reaction product.
S4, washing the carboxymethyl cellulose polypyrrole colloid from the reaction product by a circulating centrifugal washing mode.
And S5, finally, sequentially concentrating, drying and crushing the carboxymethyl cellulose polypyrrole colloid to obtain the carboxymethyl cellulose polypyrrole compound. The carboxymethyl cellulose polypyrrole composite particles obtained by crushing have the particle size of 0.15-5 microns. And can be dispersed in water system, the conductivity of the compound can reach more than 10S/cm.
Example 2
The embodiment provides a technical scheme: a preparation method of a carboxymethyl cellulose polypyrrole conductive composite material comprises the following steps:
s1, respectively dissolving carboxymethyl cellulose, pyrrole and ammonium persulfate in an aqueous medium to obtain a carboxymethyl cellulose solution, a pyrrole solution and an ammonium persulfate solution.
S2, uniformly mixing the carboxymethyl cellulose solution and the pyrrole solution, then dropwise adding an oxidant ammonium sulfate solution, and carrying out polymerization reaction for 3 hours at the temperature of 3 ℃ to obtain a reaction medium. The carboxymethyl cellulose solution had a carboxymethyl group content of 1.75 mmol/g. The mixing mass ratio of the carboxymethyl cellulose solution to the pyrrole solution is 100: 5. the molar concentration of the oxidant ammonium sulfate solution is 0.2mol/L, and the dropping amount is 30 mL.
S3, adding 20mL of methanol into the reaction medium to terminate the polymerization of pyrrole, obtaining the reaction product.
S4, washing the carboxymethyl cellulose polypyrrole colloid from the reaction product by a circulating centrifugal washing mode.
And S5, finally, sequentially concentrating, drying and crushing the carboxymethyl cellulose polypyrrole colloid to obtain the carboxymethyl cellulose polypyrrole compound. The carboxymethyl cellulose polypyrrole composite particles obtained by crushing have the particle size of 0.15-5 microns and can be dispersed in a water system, and the conductivity of the composite can reach more than 10S/cm.
Example 3
The embodiment provides a technical scheme: a preparation method of a carboxymethyl cellulose polypyrrole conductive composite material comprises the following steps:
s1, respectively dissolving carboxymethyl cellulose, pyrrole and ammonium persulfate in an aqueous medium to obtain a carboxymethyl cellulose solution, a pyrrole solution and an ammonium persulfate solution.
S2, uniformly mixing the carboxymethyl cellulose solution and the pyrrole solution, then dropwise adding an oxidant ammonium sulfate solution, and carrying out polymerization reaction for 3.5 hours at the temperature of 3 ℃ to obtain a reaction medium. The carboxymethyl cellulose solution had a carboxymethyl group content of 1.75 mmol/g. The mixing mass ratio of the carboxymethyl cellulose solution to the pyrrole solution is 100: 5. the molar concentration of the oxidant ammonium sulfate solution is 0.2mol/L, and the dropping amount is 50 mL.
S3, adding 20mL of methanol into the reaction medium to terminate the polymerization of pyrrole, obtaining the reaction product.
S4, washing the carboxymethyl cellulose polypyrrole colloid from the reaction product by a circulating centrifugal washing mode.
And S5, finally, sequentially concentrating, drying and crushing the carboxymethyl cellulose polypyrrole colloid to obtain the carboxymethyl cellulose polypyrrole compound. The carboxymethyl cellulose polypyrrole composite particles obtained by crushing have the particle size of 0.15-5 microns. And can be dispersed in water system, the conductivity of the compound can reach more than 10S/cm.
Example 4
The embodiment provides a technical scheme: a preparation method of a carboxymethyl cellulose polypyrrole conductive composite material comprises the following steps:
s1, respectively dissolving carboxymethyl cellulose, pyrrole and ammonium persulfate in an aqueous medium to obtain a carboxymethyl cellulose solution, a pyrrole solution and an ammonium persulfate solution.
S2, uniformly mixing the carboxymethyl cellulose solution and the pyrrole solution, then dropwise adding an oxidant ammonium sulfate solution, and carrying out polymerization reaction for 2.5 hours at the temperature of 3 ℃ to obtain a reaction medium. The carboxymethyl cellulose solution had a carboxymethyl group content of 2.5 mmol/g. The mixing mass ratio of the carboxymethyl cellulose solution to the pyrrole solution is 100: 5. the molar concentration of the oxidant ammonium sulfate solution is 0.2mol/L, and the dropping amount is 60 mL.
S3, adding 20mL of methanol into the reaction medium to terminate the polymerization of pyrrole, obtaining the reaction product.
S4, washing the carboxymethyl cellulose polypyrrole colloid from the reaction product by a circulating centrifugal washing mode.
And S5, finally, sequentially concentrating, drying and crushing the carboxymethyl cellulose polypyrrole colloid to obtain the carboxymethyl cellulose polypyrrole compound. The carboxymethyl cellulose polypyrrole composite particles obtained by crushing have the particle size of 0.15-5 microns. And can be dispersed in water system, the conductivity of the compound can reach more than 10S/cm.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (5)
1. A preparation method of a carboxymethyl cellulose polypyrrole conductive composite material is characterized by comprising the following steps: the method comprises the following steps:
s1, respectively dissolving carboxymethyl cellulose, pyrrole and ammonium persulfate in an aqueous medium to obtain a carboxymethyl cellulose solution, a pyrrole solution and an ammonium persulfate solution;
s2, uniformly mixing the carboxymethyl cellulose solution and the pyrrole solution, then dropwise adding an oxidant ammonium sulfate solution, and carrying out polymerization reaction for 2-3.5 hours at 3 ℃ to obtain a reaction medium;
s3, adding methanol into the reaction medium to terminate the polymerization of pyrrole to obtain a reaction product;
s4, washing the carboxymethyl cellulose polypyrrole colloid from the reaction product in a circulating centrifugal washing mode;
and S5, finally, sequentially concentrating, drying and crushing the carboxymethyl cellulose polypyrrole colloid to obtain the carboxymethyl cellulose polypyrrole compound.
2. The preparation method of the carboxymethyl cellulose polypyrrole conductive composite material according to claim 1, characterized in that: the carboxymethyl cellulose solution has a carboxymethyl group content of 1.0-2.5 mmol/g.
3. The preparation method of the carboxymethyl cellulose polypyrrole conductive composite material according to claim 1, characterized in that: the mixing mass ratio of the carboxymethyl cellulose solution to the pyrrole solution is 100: 5.
4. the preparation method of the carboxymethyl cellulose polypyrrole conductive composite material according to claim 1, characterized in that: the molar concentration of the oxidant ammonium sulfate solution is 0.2mol/L, and the dropping amount is 10-60 mL.
5. The preparation method of the carboxymethyl cellulose polypyrrole conductive composite material according to claim 1, characterized in that: in step S5, the carboxymethyl cellulose polypyrrole composite particles obtained by crushing have a particle size of 0.15 to 5 microns.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113667257A (en) * | 2021-05-14 | 2021-11-19 | 赛轮集团股份有限公司 | Modified nano-cellulose/polypyrrole composite material and preparation method thereof, antistatic rubber composition and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448144A (en) * | 2013-09-15 | 2015-03-25 | 赵宝瀛 | Preparation method for carboxymethyl cellulose grafted copolymer |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448144A (en) * | 2013-09-15 | 2015-03-25 | 赵宝瀛 | Preparation method for carboxymethyl cellulose grafted copolymer |
Non-Patent Citations (1)
| Title |
|---|
| CLAUDIA SASSO: ""Carboxymethylcellulose: A conductivity enhancer and film-forming agent for processable polypyrrole from aqueous medium"", 《SYNTHETIC METALS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113667257A (en) * | 2021-05-14 | 2021-11-19 | 赛轮集团股份有限公司 | Modified nano-cellulose/polypyrrole composite material and preparation method thereof, antistatic rubber composition and preparation method thereof |
| CN113667257B (en) * | 2021-05-14 | 2023-09-29 | 赛轮集团股份有限公司 | Modified nanocellulose/polypyrrole composite material and preparation method thereof, antistatic rubber composition and preparation method thereof |
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Application publication date: 20201103 |