CN114068796A - Preparation method of composite thermoelectric material based on regenerated nano-cellulose - Google Patents
Preparation method of composite thermoelectric material based on regenerated nano-cellulose Download PDFInfo
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- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/856—Thermoelectric active materials comprising organic compositions
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
- C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/004—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives inorganic compounds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
Abstract
The invention discloses a preparation method of a composite thermoelectric material based on regenerated nano-cellulose, which comprises the following steps: a. soaking paper with water, washing off impurities, diluting, and dispersing to obtain paper pulp; b. adding TEMPO, NaBr and NaClO into the paper pulp, and adjusting the pH value by using sodium hydroxide; c. repeatedly centrifuging and washing the solution obtained in the step b, thereby preparing and obtaining a nano cellulose aqueous solution; d. dispersing the SWCNT into an ethanol solvent to obtain a SWCNT suspension; e. mixing the nano-cellulose aqueous solution and the SWCNT suspension, and performing vacuum filtration to prepare a hydrogel film; f. freeze-drying the hydrogel film to obtain a porous regenerated nanocellulose/SWCNT composite aerogel film; g. and (3) carrying out cold pressing treatment on the porous regenerated nano-cellulose/SWCNT composite aerogel film to obtain the regenerated nano-cellulose/SWCNT composite aerogel film with a microporous structure.
Description
Technical Field
The invention relates to the technical field of thermoelectric materials, in particular to a preparation method of a composite thermoelectric material based on regenerated nano-cellulose.
Background
In recent years, with the development of miniaturization of wearable electronic devices, flexible organic thermoelectric materials are receiving more and more attention from researchers. Thermoelectric material can be with the direct electric energy that converts of the temperature difference between body surface and the environment to realize wearable electronic equipment's self-power supply, avoided traditional battery to charge repeatedly and frequently dismantled the trouble.
At present, although a single organic thermoelectric material has low thermal conductivity, the PF value is low, the thermoelectric performance of the material needs to be further improved, and the application occasions of wearable devices involve vibration and bending deformation with different frequencies, so that the material needs to have certain toughness and mechanical strength on the premise of keeping flexibility, and the current organic thermoelectric material is difficult to meet the self-power supply requirement of wearable electronic devices. In recent years, it has been found that the performance advantages of different components can be integrated by compounding different materials, and that a synergistic effect achieved by structural regulation can exhibit properties not possessed by a single material.
As is well known, as early as 4000 years ago, people begin to record information by using paper, and the information age is entered, the paper has the advantages of light weight, flexibility, repeated folding and abundant raw materials, and attracts the interest of researchers again, so that the paper is regarded as an organic functional material matrix material with great development potential, besides, most of the paper is made of natural cellulose, the cellulose is the most common renewable resource with an amphiphilic structure in the nature, the raw materials are abundant and easy to obtain, the annual output is about 7.5 × 1010 tons, and on the other hand, due to the wide application of the paper in the human society, a large amount of waste paper is generated every day, and the waste paper is ready for further recycling, so the research of compounding the paper with the existing single organic thermoelectric material is continuously increased by using the paper as a matrix. However, the conventional cellulose paper has some disadvantages, such as rough surface and low transparency due to large fiber diameter (20-40 m), and the mechanical properties are slightly insufficient, which limits the application of the conventional cellulose paper in the field of flexible organic thermoelectric materials, and therefore, it is still a challenging task to provide a cellulose @ organic composite thermoelectric material with high electrical conductivity, high Seebeck coefficient, low thermal conductivity and excellent mechanical properties.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a composite thermoelectric material based on regenerated nano-cellulose, which has higher electrical conductivity, high Seebeck coefficient, lower thermal conductivity and more excellent mechanical properties.
In order to solve the technical problems, the invention provides a preparation method of a composite thermoelectric material based on regenerated nano-cellulose, which comprises the following steps:
1) preparing a nano-cellulose aqueous solution:
a. soaking paper with water, washing off impurities, diluting with deionized water, and performing dispersion treatment to obtain paper pulp;
b. adding TEMPO, NaBr and NaClO into the paper pulp, and adjusting the pH value with sodium hydroxide to make the pH value alkaline;
c. repeatedly centrifuging and washing the solution obtained in the step b to enable the pH value of the solution to be neutral, thereby preparing and obtaining a nano cellulose aqueous solution;
2) preparation of SWCNT suspension:
d. dispersing the SWCNT into an ethanol solvent to obtain a SWCNT suspension;
3) preparing a regenerated nano-cellulose/SWCNT composite aerogel film:
e. mixing the nano-cellulose aqueous solution and the SWCNT suspension, and performing vacuum filtration to prepare a hydrogel film;
f. e, freeze-drying the hydrogel film obtained in the step e to obtain a porous regenerated nano-cellulose/SWCNT composite aerogel film;
g. and (3) carrying out cold pressing treatment on the porous regenerated nano-cellulose/SWCNT composite aerogel film to obtain the regenerated nano-cellulose/SWCNT composite aerogel film with a microporous structure.
The further technical scheme is as follows: in the step a, the concentration of the paper pulp is 0.1-10 wt%.
The further technical scheme is as follows: in the step a, the paper comprises toilet paper, rice paper, A4 paper and waste books and newspapers.
The further technical scheme is as follows: in the step a, the diluted solution is subjected to dispersion treatment by adopting a mechanical stirring, ball milling or ultrasonic dispersion method.
The further technical scheme is as follows: in the step b, the weight of TEMPO is 1-2 wt%, and the weight of NaBr is 10-15 wt%.
The further technical scheme is as follows: in the step b, the pH value is 10 after being adjusted by sodium hydroxide, and the concentration of the sodium hydroxide is 0.1-0.8 mol/L.
The further technical scheme is as follows: in the step c, the nano-cellulose obtained by repeated centrifugal washing is mixed with deionized water to prepare a nano-cellulose aqueous solution, and the concentration of the nano-cellulose aqueous solution is 0.1-5 wt%.
The further technical scheme is as follows: in the step d, the concentration of the SWCNT suspension is 0.01-1 wt%, and the SWCNT is dispersed in the ethanol solvent through mechanical stirring and ultrasonic treatment.
The further technical scheme is as follows: in the step f, during freeze drying, the freezing temperature is-50 to-80 ℃, and the freeze drying time is 4 to 24 hours.
The further technical scheme is as follows: in the step g, during cold pressing treatment, the pressure is 1-100 MPa, and the cold pressing time is 1-20 min.
Compared with the prior art, the preparation method takes paper with the main component of natural cellulose as a raw material, takes a TEMPO/NaBr/NaClO system as a cellulose dissociating agent to prepare the nano-cellulose, the nano-cellulose has the advantages of high length-diameter ratio, high mechanical property, abundant raw materials, low cost and the like, then the nano-cellulose is mixed with SWCNT to prepare the regenerated nano-cellulose/SWCNT composite aerogel film with the macroporous structure through suction filtration film forming and freeze drying technologies, the material is promoted to be densified through a room temperature cold pressing technology, the macroporous structure is eliminated, the multi-layer microporous structure is reserved, the thermal conductivity is reduced, the high electrical conductivity and the high Seebeck coefficient of the SWCNT are reserved, the regenerated nano-cellulose/SWCNT composite aerogel film with high thermoelectric property is obtained, and the regenerated nano-cellulose/SWCNT composite thermoelectric material based on the regenerated nano-cellulose prepared by the preparation method is known to be regulated and controlled through the microporous structure, the material has the advantages of high electrical conductivity, high Seebeck coefficient, low thermal conductivity, excellent mechanical property, simple preparation process and low cost.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood by those skilled in the art, the present invention is further described with reference to the following embodiments.
The invention provides a preparation method of a composite thermoelectric material based on regenerated nano-cellulose, which comprises the following steps:
1) preparing a nano-cellulose aqueous solution:
a. soaking paper with water, washing off impurities, diluting with deionized water, and dispersing to obtain paper pulp.
In the step, the paper comprises toilet paper, rice paper, A4 paper, waste books and newspapers and the like, and the main components of the paper are natural vitamins; preferably, the paper can be cut into pieces and then soaked in water to shorten the soaking time, and the concentration of the paper pulp is 0.1-10 wt%, preferably 1 wt%. Specifically, in the present invention, the diluted solution may be subjected to dispersion treatment by a method such as mechanical stirring, ball milling, or ultrasonic dispersion.
b. TEMPO, NaBr and NaClO are added to the pulp and the pH is adjusted to alkaline with sodium hydroxide.
In this step, TEMPO, NaBr and NaClO may be added and then stirred at room temperature to mix thoroughly. The TEMPO, NaBr and NaClO are calculated based on the solid content of the pulp, the weight of TEMPO is 1-2 wt%, the weight of NaBr is 10-15 wt%, the pH value is 10 after being adjusted by sodium hydroxide, the concentration of the sodium hydroxide is 0.1-0.8 mol/L, preferably 0.5mol/L, and the weight of NaClO is about 10.
c. And (c) repeatedly centrifuging and washing the solution obtained in the step b to enable the pH value of the solution to be neutral, thereby preparing and obtaining the nano-cellulose aqueous solution.
In the step, nano-cellulose obtained by repeated centrifugal washing is mixed with deionized water to prepare nano-cellulose aqueous solution, and the concentration of the nano-cellulose aqueous solution is 0.1-5 wt%; preferably, after the solution obtained in step b is transparent and has no significant change in pH value, repeated centrifugal washing is carried out.
2) Preparation of SWCNT suspension:
d. SWCNTs were dispersed in ethanol solvent to give a SWCNT suspension.
In this step, the concentration of the SWCNT suspension is 0.01-1 wt%, and the SWCNTs are dispersed in the ethanol solvent by mechanical stirring and ultrasonic treatment, i.e., the SWCNT suspension is a suspension formed after the SWCNTs and ethanol are fully mixed after mechanical stirring and ultrasonic treatment.
3) Preparing a regenerated nano-cellulose/SWCNT composite aerogel film:
e. and mixing the nano-cellulose aqueous solution and the SWCNT suspension, and performing vacuum filtration to prepare the hydrogel film.
f. And e, freeze-drying the hydrogel film obtained in the step e to obtain a porous regenerated nano-cellulose/SWCNT composite aerogel film.
In the step, the freezing temperature is-50 to-80 ℃ and the freezing drying time is 4 to 24 hours during freezing drying, in the invention, the freezing temperature is preferably-70 ℃ and the drying time is preferably 12 hours.
g. And (3) carrying out cold pressing treatment on the porous regenerated nano-cellulose/SWCNT composite aerogel film to obtain the regenerated nano-cellulose/SWCNT composite aerogel film with a microporous structure.
In the step, during cold pressing treatment, the pressure is 1-100 MPa, and the cold pressing time is 1-20 min.
Understandably, the steps in the method for preparing the composite thermoelectric material based on the regenerated nano-cellulose can be sequentially adjusted, combined and deleted according to actual needs, for example, the SWCNT suspension can be prepared first and then the nano-cellulose aqueous solution can be prepared, the nano-cellulose aqueous solution can be prepared first and then the SWCNT suspension can be prepared, and the steps can be adjusted according to actual needs.
The method for preparing the composite thermoelectric material based on regenerated nano-cellulose according to the present invention will be described with reference to the following specific examples.
Example 1
(1) 2g of waste rice paper is cut into pieces, impurities are washed away, 200mL of water is used for soaking, the mixture is stirred for 4 hours at room temperature, and then a homogenizer is used for processing for 1 hour to prepare paper pulp with a certain concentration;
(2) adding 0.032g of TEMPO, 0.2g of sodium bromide and 20mL of sodium hypochlorite, stirring at room temperature, and dropwise adding a 0.5mol/L sodium hydroxide aqueous solution to adjust the pH value so as to maintain the pH value at about 10;
(3) after the solution in the step (2) is transparent and the pH value is not changed remarkably, centrifuging at 8000rpm to remove supernatant, diluting the centrifugal precipitate with water, repeating the process for three times, and separating to obtain a nano-cellulose aqueous solution;
(4) adding 0.5g of SWCNT powder into 100mL of ethanol to obtain a SWCNT suspension with a certain concentration;
(5) fully mixing 200mL of the nano-cellulose aqueous solution obtained in the step (3) and 50mL of the SWCNT suspension (carbon tube suspension) obtained in the step (4), and performing vacuum filtration to prepare a hydrogel film;
(6) freeze-drying the hydrogel film obtained in the step (5) at-70 ℃ for 12h to obtain a porous regenerated nano-cellulose/SWCNT composite aerogel film;
(7) and (4) cold-pressing the regenerated nano-cellulose/SWCNT composite aerogel film obtained in the step (6) for 5min at room temperature under the condition of 20MPa to obtain the regenerated nano-cellulose/SWCNT composite aerogel film with a microporous structure.
It is known that the evaluation index of thermoelectric properties of a material is dimensionless thermoelectric figure of merit ZT ═ S2Sigma T/kappa, wherein S, sigma, T and kappa are Seebeck coefficient, electric conductivity, absolute temperature and thermal conductivity of the material respectively, so that the material is required to have the characteristics of large Seebeck coefficient, high electric conductivity and low thermal conductivity due to excellent thermoelectric performance, and organic polymers and composite materials thereof are often used with power factors of PF (power factor) and S (power factor) due to low thermal conductivity2Sigma is used to measure the thermoelectric performance of the material.
The mixture ratio obtained according to the embodiment hasThe thermoelectric properties of the regenerated nanocellulose/SWCNT composite aerogel film with the microporous structure are as follows: the conductivity was 763.8S cm-1Seebeck coefficient of 54.3 μ VK-1And a thermal conductivity of less than 0.5Wm-1K-1。
Example 2
The method is the same as example 1, except that the waste rice paper in the step (1) of the step 1 is changed into A4 paper, and the conductivity of the regenerated nano-cellulose/SWCNT composite aerogel membrane with the microporous structure finally obtained in the example is 532.3S cm-1Seebeck coefficient of 50.7 μ VK-1。
Example 3
The procedure is the same as example 1 except that 50mL of SWCNT suspension (carbon tube suspension) in step (5) of step 1 is changed to 20mL, and the conductivity of the regenerated nano-cellulose/SWCNT composite aerogel film finally obtained in this example is 128.8S cm-1Seebeck coefficient of 51.4 μ VK-1。
Example 4
The method is the same as example 1, except that 20MPa in the step (7) of the step 1 is changed into 30MPa, and the conductivity of the regenerated nano-cellulose/SWCNT composite aerogel film finally obtained in the example is 792.7S cm-1Seebeck coefficient of 51.2 μ VK-1。
Example 5
The method is the same as example 1, except that the cold pressing time of 5min in the step (7) is changed into 10min in the implementation 1, and the conductivity of the regenerated nano-cellulose/SWCNT composite aerogel film finally obtained in the example is 807.2Scm-1Seebeck coefficient of 51.8 mu VK-1。
To sum up, the preparation method of the invention uses paper with a main component of natural cellulose as a raw material, uses SWCNT as a thermoelectric functional component, endows the material with a microporous structure by combining a freeze drying technology and a room temperature cold pressing technology, reduces the thermal conductivity, and simultaneously retains the high conductivity and the high Seebeck coefficient from a carbon tube component to obtain the regenerated nano-cellulose/SWCNT composite material with high thermoelectric property, namely, the paper is used as the raw material, a TEMPO/NaBr/NaClO system is used as a cellulose dissociating agent to prepare the nano-cellulose, the nano-cellulose has the advantages of high length-diameter ratio, rich raw materials with high mechanical property, low cost and the like, and then the nano-cellulose is mixed with the SWCNT to prepare the regenerated nano-cellulose/SWCNT composite aerogel film with the macroporous structure by suction filtration film forming and freeze drying technologies, and the material is promoted to be densified by the room temperature cold pressing technology, the method has the advantages that a macroporous structure is eliminated, a multi-layer microporous structure is reserved, the microporous structure can reduce the thermal conductivity of the material through phonon scattering effect, and compared with the macroporous structure, the pore diameter of the microporous structures is smaller, the mechanical property and the electrical conductivity of the composite material can not be obviously reduced, the high electrical conductivity and the high Seebeck coefficient of the SWCNT can be reserved, and the regenerated nano-cellulose/SWCNT composite aerogel film with high thermoelectric property is obtained.
The foregoing is considered as illustrative of the preferred embodiments of the invention and is not to be construed as limiting the invention in any way. Various equivalent changes and modifications can be made by those skilled in the art based on the above embodiments, and all equivalent changes and modifications within the scope of the claims should fall within the protection scope of the present invention.
Claims (10)
1. A preparation method of a composite thermoelectric material based on regenerated nano-cellulose is characterized by comprising the following steps:
1) preparing a nano-cellulose aqueous solution:
a. soaking paper with water, washing off impurities, diluting with deionized water, and performing dispersion treatment to obtain paper pulp;
b. adding TEMPO, NaBr and NaClO into the paper pulp, and adjusting the pH value with sodium hydroxide to make the pH value alkaline;
c. repeatedly centrifuging and washing the solution obtained in the step b to enable the pH value of the solution to be neutral, thereby preparing and obtaining a nano cellulose aqueous solution;
2) preparation of SWCNT suspension:
d. dispersing the SWCNT into an ethanol solvent to obtain a SWCNT suspension;
3) preparing a regenerated nano-cellulose/SWCNT composite aerogel film:
e. mixing the nano-cellulose aqueous solution and the SWCNT suspension, and performing vacuum filtration to prepare a hydrogel film;
f. e, freeze-drying the hydrogel film obtained in the step e to obtain a porous regenerated nano-cellulose/SWCNT composite aerogel film;
g. and (3) carrying out cold pressing treatment on the porous regenerated nano-cellulose/SWCNT composite aerogel film to obtain the regenerated nano-cellulose/SWCNT composite aerogel film with a microporous structure.
2. The method of preparing a composite thermoelectric material based on regenerated nanocellulose as claimed in claim 1, wherein in said step a, the concentration of pulp is 0.1 to 10 wt%.
3. The method for preparing a composite thermoelectric material based on regenerated nanocellulose as claimed in claim 1, wherein in said step a, said paper includes toilet paper, rice paper, a4 paper and waste books and newspapers.
4. The method for preparing a composite thermoelectric material based on regenerated nanocellulose as claimed in claim 1, wherein in said step a, the diluted solution is subjected to dispersion treatment by using mechanical stirring, ball milling or ultrasonic dispersion method.
5. The method for preparing a composite thermoelectric material based on regenerated nanocellulose as claimed in claim 1, wherein in said step b, the weight of TEMPO is 1-2 wt% and the weight of NaBr is 10-15 wt%.
6. The method for preparing a composite thermoelectric material based on regenerated nanocellulose as claimed in claim 1, wherein in said step b, pH is 10 after adjusting with sodium hydroxide, and concentration of said sodium hydroxide is 0.1-0.8 mol/L.
7. The method for preparing a composite thermoelectric material based on regenerated nanocellulose as claimed in claim 1, wherein in said step c, the nanocellulose obtained by repeated centrifugal washing is mixed with deionized water to prepare a nanocellulose aqueous solution, and the concentration of the nanocellulose aqueous solution is 0.1-5 wt%.
8. The method for preparing a regenerated nanocellulose-based composite thermoelectric material of claim 1, wherein in said step d, the SWCNT suspension concentration is 0.01% -1 wt%, and the SWCNTs are dispersed into the ethanol solvent by mechanical stirring and ultrasonic treatment.
9. The method for preparing a composite thermoelectric material based on regenerated nanocellulose as claimed in claim 1, wherein in the step f, the freezing temperature is-50 to-80 ℃ and the freezing drying time is 4 to 24 hours.
10. The preparation method of the composite thermoelectric material based on regenerated nano-cellulose in the claim 1, wherein in the step g, the pressure of the cold pressing treatment is 1-100 MPa, and the time of the cold pressing treatment is 1-20 min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115819848A (en) * | 2022-11-28 | 2023-03-21 | 浙江大学 | Multifunctional nano-cellulose composite solution and preparation method and application thereof |
| CN115852687A (en) * | 2022-12-27 | 2023-03-28 | 东北林业大学 | High-performance N-type ion thermoelectric material, thermoelectric battery, and preparation method and application thereof |
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2021
- 2021-11-15 CN CN202111348841.8A patent/CN114068796A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115819848A (en) * | 2022-11-28 | 2023-03-21 | 浙江大学 | Multifunctional nano-cellulose composite solution and preparation method and application thereof |
| CN115819848B (en) * | 2022-11-28 | 2024-04-30 | 浙江大学 | Multifunctional nano-cellulose composite solution and preparation method and application thereof |
| CN115852687A (en) * | 2022-12-27 | 2023-03-28 | 东北林业大学 | High-performance N-type ion thermoelectric material, thermoelectric battery, and preparation method and application thereof |
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