CN115895158B - Thermoelectric conversion material, thermoelectric conversion device, and preparation methods and applications thereof - Google Patents
Thermoelectric conversion material, thermoelectric conversion device, and preparation methods and applications thereof Download PDFInfo
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- CN115895158B CN115895158B CN202211472055.3A CN202211472055A CN115895158B CN 115895158 B CN115895158 B CN 115895158B CN 202211472055 A CN202211472055 A CN 202211472055A CN 115895158 B CN115895158 B CN 115895158B
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 54
- 239000004744 fabric Substances 0.000 claims abstract description 53
- 229920000767 polyaniline Polymers 0.000 claims abstract description 46
- 150000002500 ions Chemical class 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000000017 hydrogel Substances 0.000 claims abstract description 19
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 17
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 17
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 13
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000002484 cyclic voltammetry Methods 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 7
- -1 hydrogen ions Chemical class 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 229940075397 calomel Drugs 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- SYAVYWAMVZKGTF-UHFFFAOYSA-N 2-hydroxy-2-methylpentan-3-one Chemical compound CCC(=O)C(C)(C)O SYAVYWAMVZKGTF-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- LPNSCOVIJFIXTJ-UHFFFAOYSA-N 2-methylidenebutanamide Chemical compound CCC(=C)C(N)=O LPNSCOVIJFIXTJ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VSWIZZORKUCUDZ-UHFFFAOYSA-N bis(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)methanone Chemical compound CC1(O)C=CC=CC1C(=O)C1C(O)(C)C=CC=C1 VSWIZZORKUCUDZ-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- LUEHNHVFDCZTGL-UHFFFAOYSA-N but-2-ynoic acid Chemical compound CC#CC(O)=O LUEHNHVFDCZTGL-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- YMCOIFVFCYKISC-UHFFFAOYSA-N ethoxy-[2-(2,4,6-trimethylbenzoyl)phenyl]phosphinic acid Chemical compound CCOP(O)(=O)c1ccccc1C(=O)c1c(C)cc(C)cc1C YMCOIFVFCYKISC-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
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- 229910001416 lithium ion Inorganic materials 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000005676 thermoelectric effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention belongs to the technical field of thermoelectric conversion, and particularly relates to a thermoelectric conversion material, a thermoelectric conversion device, a preparation method and application thereof. The thermoelectric conversion material comprises double-network hydrogel and conductive ions, wherein the conductive ions are dispersed in the double-network hydrogel; the first network structure of the double-network hydrogel is obtained by copolymerization and cross-linking of unsaturated carboxylic acid monomers and acrylamide monomers, and the second network structure is obtained by cross-linking of carboxymethyl cellulose. The thermoelectric conversion material provided by the invention is an ionic double-network hydrogel, has temperature sensitivity and high Seebeck coefficient, and has high thermoelectric conversion efficiency; the thermoelectric conversion device assembled with the polyaniline/carbon cloth electrode has excellent energy storage performance, the specific area capacitance can reach 750mF/cm 2 at the highest, the energy density output of 1 hour can reach 88J/m 2, and the thermoelectric conversion device has good application prospect in the fields of Internet of things, sensor functions, wearable electronics and the like.
Description
Technical Field
The invention belongs to the technical field of thermoelectric conversion, and particularly relates to a thermoelectric conversion material, a thermoelectric conversion device, a preparation method and application thereof.
Background
Currently, due to the exhaustion of non-renewable fossil fuels, the utilization of energy and the protection of the environment are extremely challenged, low-grade heat energy (less than 140 ℃) from human bodies and industrial production is extremely concerned, and the collection and use of these low-grade heat energy provide new directions for the conversion and storage development of energy. The thermoelectric effect is an effective method, and can provide power for flexible electronic equipment, and the traditional thermoelectric generator and super capacitor can realize energy conversion and storage, but with the development of various self-powered equipment, the energy device with single function is difficult to realize energy conversion and storage at the same time. Therefore, the construction of the energy equipment integrating energy conversion and storage has important significance.
The prior art patent CN111564316A discloses a gel electrode and a full gel state ion thermoelectric super capacitor, the maximum volume specific capacitance can reach 983.6mF/cm 3, the maximum Seebeck coefficient is only 3.6mV/K, and the thermoelectric conversion performance is poor. The existing thermoelectric devices have low thermoelectric conversion efficiency, and a new thermoelectric conversion material needs to be developed to convert low-grade heat in the environment into electric energy.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the thermoelectric conversion material provided by the invention has a relatively high Seebeck coefficient and high thermoelectric conversion efficiency.
The invention also provides a preparation method and application of the thermoelectric conversion material.
The invention further provides a thermoelectric conversion device with the thermoelectric conversion material and application thereof.
A first aspect of the present invention proposes a thermoelectric conversion material comprising a double-network hydrogel and conductive ions dispersed in the double-network hydrogel; the first network structure of the double-network hydrogel is obtained by copolymerization and cross-linking of unsaturated carboxylic acid monomers and acrylamide monomers, and the second network structure is obtained by cross-linking of carboxymethyl cellulose.
According to the first aspect of the invention, at least the following beneficial effects are achieved:
The thermoelectric conversion material provided by the invention is an ionic double-network hydrogel, the unsaturated carboxylic acid monomer and acrylamide are copolymerized to obtain a first network structure, and the carboxymethyl cellulose is crosslinked to obtain a second network structure, so that a hydrogen bond effect is formed between an amide group and a carboxyl group in the thermoelectric conversion material at a lower temperature due to the special structure of the thermoelectric conversion material, and a molecular chain is contracted, so that the gel is dehydrated and becomes turbid; when the temperature is higher, the hydrogen bond between the amido and carboxyl is opened, the gel absorbs water and becomes transparent, and the temperature sensitivity of the thermoelectric conversion material provides a mode for constructing a gradient ion channel and enhancing the toughness of a matrix, so that the thermoelectric conversion material has a high Seebeck coefficient.
Preferably, the mass ratio of the unsaturated carboxylic acid monomer to the acrylamide monomer is 0.8-1.5: 1, more preferably 0.8 to 1.2:1, including but not limited to 0.8:1,0.9:1,1:1,1:1.1,1:1.2, etc.
Preferably, the mass ratio of the unsaturated carboxylic acid monomer to the carboxymethyl cellulose is 10-60: 1, more preferably 12 to 55:1, more preferably 15 to 50:1, including but not limited to 15:1,20: 1,25: 1,30: 1,40: 1,45: 1,50: 1, etc.
Preferably, the unsaturated carboxylic monomer is a C 3～C8 alkenoic acid or a C 3～C8 alkenoic acid, more preferably a C 3～C5 alkenoic acid or a C 3～C5 alkenoic acid, including but not limited to at least one of acrylic acid, methacrylic acid, butenoic acid, propynoic acid, butynoic acid.
Preferably, the acrylamide monomer comprises at least one of acrylamide, methacrylamide and ethylacrylamide.
Preferably, the concentration of the conductive ions in the dual-network hydrogel is 0.1 to 2mol/L, more preferably 0.2 to 1.0mol/L, including but not limited to 0.2mol/L, 0.5mol/L, 0.8mol/L, 1.0mol/L, etc.
Preferably, the conductive ions include at least one of hydrogen ions and metal ions; the metal ions comprise at least one of potassium ions, sodium ions and lithium ions.
Preferably, the hydrogen ions are derived from inorganic acids including at least one of sulfuric acid, hydrochloric acid, and nitric acid; the metal ions are derived from water-soluble metal salts, and the water-soluble metal salts comprise at least one of lithium chloride, potassium chloride, sodium chloride, lithium nitrate, potassium nitrate and sodium nitrate.
Preferably, the thermoelectric conversion material further comprises acid ions, such as sulfate ions.
In a second aspect of the present invention, there is provided a method for producing the thermoelectric conversion material, comprising the steps of:
s1, mixing unsaturated carboxylic acid monomers, acrylamide monomers and carboxymethyl cellulose, and curing to obtain double-network hydrogel;
s2, soaking the double-network hydrogel in a conductive ion solution to obtain the thermoelectric conversion material.
Preferably, at least one of N, N' -methylenebisacrylamide and epichlorohydrin is also added in the step S1. The addition of N, N' -methylene bisacrylamide can promote the copolymerization and crosslinking of unsaturated carboxylic acid monomers and acrylamide to form a first network structure, and epichlorohydrin is a crosslinking agent of carboxymethyl cellulose to promote the formation of a second network structure.
Preferably, the mass of the N, N' -methylenebisacrylamide is 0.0001 to 0.002%, more preferably 0.0005 to 0.001% of the total mass of the unsaturated carboxylic acid-based monomer and the acrylamide-based monomer.
Preferably, the volume-mass ratio of the epichlorohydrin to the carboxymethyl cellulose is 50 μl:0.1 to 1g, more preferably 50. Mu.L: 0.1 to 0.5g, more preferably 50. Mu.L: 0.1-0.3 g.
Preferably, a photoinitiator is also added before curing in step S1, said photoinitiator comprising at least one of 2-hydroxy-2-methyl propenone, 2-hydroxy-2-methyl-phenylketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl-phenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone.
Preferably, the mass of the photoinitiator is 0.1 to 2%, more preferably 0.1 to 1% of the total mass of the unsaturated carboxylic acid-based monomer and the acrylamide-based monomer.
Preferably, water is also added in the step S1, and the volume mass ratio of the water to the unsaturated carboxylic acid monomer is 1-10 mL:1g, more preferably 3 to 8mL:1g, more preferably 5mL: about 1 g.
Preferably, the curing in step S1 is ultraviolet light curing, and the curing time is 1 to 10min, more preferably 2 to 6min.
Preferably, in step S2, the concentration of the conductive ion solution is 0.1 to 2M (based on the concentration of the conductive ions), more preferably 0.5 to 1.0M.
Preferably, in step S2, the soaking time is about 1 to 5 days, more preferably about 3 days.
In a third aspect of the present invention, there is provided a thermoelectric conversion device including the thermoelectric conversion material.
Preferably, the thermoelectric conversion device further includes polyaniline/carbon cloth electrodes, and the thermoelectric conversion material is disposed between the polyaniline/carbon cloth electrodes.
The thermoelectric conversion material adopted by the thermoelectric conversion device has high Seebeck coefficient and high thermoelectric conversion efficiency, and polyaniline in the polyaniline/carbon cloth electrode can not only enhance the conductivity of the electrode, but also generate oxidation-reduction reaction, and the electrochemical performance of the thermoelectric conversion device is enhanced in cooperation with the thermoelectric conversion material.
Polyaniline undergoes the following oxidation-reduction reactions during thermoelectric conversion:
preferably, the polyaniline/carbon cloth electrode comprises polyaniline and carbon cloth, and the polyaniline is coated on the surface of the carbon cloth.
Preferably, the polyaniline/carbon cloth electrode is prepared by an electrochemical method, and specifically prepared by a preparation method comprising the following steps:
Immersing carbon cloth into aniline electrolyte by adopting a cyclic voltammetry, controlling the voltage range of a three-electrode system to be-0.5-1.5V, and scanning for 20-60 circles at a scanning speed of 30-70 mV/s to obtain the polyaniline/carbon cloth electrode.
Preferably, the cyclic voltammetry sweep voltage is in the range of-0.2 to 1V, more preferably-0.2 to 0.8V.
Preferably, the sweep rate is 40 to 60mV/s, including but not limited to 40mV/s, 45mV/s, 50mV/s, 55mV/s, 60mV/s, etc.
Preferably, the number of scanning turns is 30-60 turns, more preferably 40-60 turns, including but not limited to 40 turns, 45 turns, 50 turns, 55 turns, 60 turns, etc.
Preferably, the aniline electrolyte comprises aniline, citric acid and sulfuric acid, and specifically, the aniline and the citric acid are dispersed in a sulfuric acid solution. The mass ratio of the aniline to the citric acid is 0.8-8: 1, more preferably 1 to 5:1, including but not limited to 1:1,2:1,3:1,4:1,5:1, etc. The concentration of the sulfuric acid solution is 0.1 to 1M, more preferably 0.4 to 0.6M, such as about 0.5M; the volume mass ratio of the sulfuric acid solution to the aniline is 30-50 mL:1g, more preferably 35 to 45mL:1g, such as 40mL:1g.
Preferably, the electrodes of the three-electrode system comprise carbon cloth, graphite sheets and calomel electrodes.
Preferably, the thermoelectric conversion device comprises a thermoelectric generator.
In a fourth aspect of the present invention, applications of the thermoelectric conversion material and the thermoelectric conversion device in the internet of things field, the sensing field, or the wearable field are provided.
Compared with the prior art, the invention has at least the following beneficial effects:
The thermoelectric conversion material provided by the invention is an ionic double-network hydrogel, has temperature sensitivity and high Seebeck coefficient, and has excellent thermoelectric performance; the thermoelectric conversion device with the polyaniline/carbon cloth-thermoelectric conversion material-polyaniline/carbon cloth sandwich structure, which is assembled with the polyaniline/carbon cloth electrode, has excellent energy storage performance, the specific area capacitance can reach 750mF/cm 2 at most, and the energy density is high.
The preparation method of the thermoelectric conversion material and the thermoelectric conversion device provided by the invention is simple and easy to implement, mild in condition, easy to obtain raw materials, good in repeatability and good in application prospect in the fields of Internet of things, sensor functions, wearable electronics and the like.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 shows the temperature sensitivity of the ion thermoelectric gel of example 1, (a) macroscopic schematic diagram of the temperature sensitivity, (b) transmittance-temperature curve;
FIG. 2 shows (a) cyclic voltammetry characteristic curve and (b) CV curve area-turn curve of the flexible electrode of polyaniline/carbon cloth prepared with different number of scanning turns according to the present invention;
FIG. 3 is a physical diagram of a flexible polyaniline/carbon cloth electrode according to example 1 of the present invention;
FIG. 4 is an SEM image of (a) a carbon cloth flexible electrode and (b) a polyaniline/carbon cloth flexible electrode of example 1 of the present invention;
FIG. 5 is (a) an open circuit voltage versus time curve and (b) a power density versus time curve for a thermoelectric generator of comparative example 1 of the present invention;
FIG. 6 is a schematic structural diagram of a thermoelectric generator according to embodiment 1 of the present invention;
FIG. 7 is a graph of (a) cyclic voltammetry characteristics curve and (b) specific area capacitance-current density curve of a thermoelectric generator of example 1 of the present invention;
fig. 8 is a graph of power density versus time for a thermoelectric generator of example 1 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
The starting materials used in the examples below, unless otherwise specified, are all commercially available from conventional sources; the adopted technology adopts the conventional technology in the field unless specified otherwise; the operating temperatures employed, unless otherwise specified, were room temperature (20.+ -. 5 ℃ C.).
Example 1
The thermoelectric conversion material is prepared in the embodiment, and the thermoelectric generator is further prepared by using the material, and the specific process is as follows:
(1) 10g of aniline and 10g of citric acid were dispersed in 400mL of 0.5M sulfuric acid to obtain an electrolyte.
(2) And (3) assembling a three-electrode system by using carbon cloth (2X 5 cm), graphite sheets (2X 5 cm) and calomel electrodes, and immersing the three-electrode system into the electrolyte obtained in the step (1).
(3) And setting a voltage window to be-0.2-0.8V by adopting a cyclic voltammetry, and scanning at a scanning speed of 50mV/s for 50 circles to obtain the polyaniline/carbon cloth flexible electrode.
(4) 5G of acrylic acid, 5g of acrylamide, 0.1g of carboxymethyl cellulose, 1mg of N, N' -methylenebisacrylamide and 50. Mu.L of epichlorohydrin were dissolved in 25mL of water with sufficient stirring.
(5) 0.1G of 2-hydroxy-2-methylpropionone was added to the solution obtained in step (4).
(6) Injecting into self-made mold, and irradiating with ultraviolet lamp for 5min to obtain gel.
(7) Immersing the gel obtained in the step (6) in 0.5M sulfuric acid solution for 3 days to obtain the ion thermoelectric gel.
(8) And (3) assembling the polyaniline/carbon cloth flexible electrode and the ion thermoelectric gel obtained in the step (3) into the ion thermoelectric generator with a sandwich structure according to the sequence of the electrode-ion thermoelectric gel-electrode.
Example 2
The thermoelectric conversion material is prepared in the embodiment, and the thermoelectric generator is further prepared by using the material, and the specific process is as follows:
(1) 10g of aniline and 5g of citric acid were dispersed in 400mL of 0.5M sulfuric acid to obtain an electrolyte.
(2) And (3) assembling a three-electrode system by using carbon cloth (2X 5 cm), graphite sheets and calomel electrodes, and immersing the three-electrode system in the electrolyte obtained in the step (1).
(3) And setting a voltage window to be-0.2-0.8V by adopting a cyclic voltammetry, and scanning at a scanning speed of 50mV/s for 50 circles to obtain the polyaniline/carbon cloth flexible electrode.
(4) 5G of acrylic acid, 5g of acrylamide, 0.2g of carboxymethyl cellulose, 1mg of N, N' -methylenebisacrylamide and 50. Mu.L of epichlorohydrin were dissolved in 25mL of water with sufficient stirring.
(5) 0.1G of 2-hydroxy-2-methylpropionone was added to the solution obtained in step (4).
(6) Injecting into self-made mold, and irradiating with ultraviolet lamp for 5min to obtain gel.
(7) Immersing the gel obtained in the step (6) in 0.5M sulfuric acid solution for 3 days to obtain the ion thermoelectric gel.
(8) And (3) assembling the polyaniline/carbon cloth flexible electrode and the ion thermoelectric gel obtained in the step (3) into the ion thermoelectric generator with a sandwich structure according to the sequence of the electrode-ion thermoelectric gel-electrode.
Example 3
The thermoelectric conversion material is prepared in the embodiment, and the thermoelectric generator is further prepared by using the material, and the specific process is as follows:
(1) 10g of aniline and 2.5g of citric acid were dispersed in 400mL of 0.5M sulfuric acid to obtain an electrolyte.
(2) And (3) assembling a three-electrode system by using carbon cloth (2X 5 cm), graphite sheets and calomel electrodes, and immersing the three-electrode system into the electrolyte obtained in the step (1).
(3) And setting a voltage window to be-0.2-0.8V by adopting a cyclic voltammetry, and scanning at a scanning speed of 50mV/s for 50 circles to obtain the polyaniline/carbon cloth flexible electrode.
(4) 5G of acrylic acid, 5g of acrylamide, 0.3g of carboxymethyl cellulose, 1mg of N, N' -methylenebisacrylamide and 50. Mu.L of epichlorohydrin were dissolved in 25mL of water with sufficient stirring.
(5) 0.1G of 2-hydroxy-2-methylpropionone was added to the solution obtained in step (4).
(6) Injecting into self-made mold, and irradiating with ultraviolet lamp for 5min to obtain gel.
(7) Immersing the gel obtained in the step (6) in 0.5M sulfuric acid solution for 3 days to obtain the ion thermoelectric gel.
(8) And (3) assembling the polyaniline/carbon cloth flexible electrode and the ion thermoelectric gel obtained in the step (3) into the ion thermoelectric generator with a sandwich structure according to the sequence of the electrode-ion thermoelectric gel-electrode.
Comparative example 1
The comparative example prepared a thermoelectric generator, which was different from example 1 in that a carbon cloth electrode was used instead of polyaniline/carbon cloth flexible electrode, and the specific process was:
(1) The procedure for the preparation of the ion thermoelectric gel was similar to that of example 1;
(2) And assembling the carbon cloth electrode and the ion thermoelectric gel into the ion thermoelectric generator with a sandwich structure according to the sequence of the electrode-ion thermoelectric gel-electrode.
Test examples
The test example tested the performance of thermoelectric conversion materials, polyaniline/carbon cloth electrodes, and thermoelectric generators. Wherein:
1. Thermoelectric conversion material (ion thermoelectric gel)
Temperature-sensitive performance test: and measuring the light transmittance of the sample within the range of 10-40 ℃ by adopting an in-situ variable-temperature ultraviolet spectrometer, wherein the wavelength parameter of the ultraviolet-visible spectrophotometer is set to 560nm, and the measuring optical path parameter is 3cm.
Fig. 1a is a schematic diagram showing the temperature sensitivity of the ion thermoelectric gel, and fig. 1b is a graph showing the transmittance-temperature curve of the ion thermoelectric gel, wherein the transmittance increases with increasing temperature, the transmittance is 50% at 25 ℃, and the critical dissolution temperature (UCST) temperature is 25 ℃. As shown in fig. 1a, at about 10 ℃ on the left side of the ionothermal gel (lower than UCST), amide groups in the hydrogel form a hydrogen bond network with carboxyl groups, the molecular weight shrinks, and the gel is water-withdrawing and becomes turbid; the right side of the ion thermoelectric gel is at about 40 ℃ (higher than UCST), no hydrogen bond is formed between amido and carboxyl, the ion thermoelectric gel absorbs water, is transparent, and can see the gray background of the substrate; the ion thermoelectric gel prepared by the invention has temperature sensitivity, and network structures with different crosslinking densities can be obtained by controlling the temperature, so that a mode is provided for constructing a gradient ion channel and enhancing the toughness of a matrix.
2. Polyaniline/carbon cloth flexible electrode
And (3) setting a voltage window of-0.2-0.8V by adopting a cyclic voltammetry at a scanning speed of 50mV/s, and respectively scanning for 40, 45, 50 and 60 circles to obtain a polyaniline/carbon cloth flexible electrode, and testing the polyaniline/carbon cloth flexible electrode with different circles of scanning.
FIG. 2a is a Cyclic Voltammogram (CV) curve under different scanning turns, wherein the scanning turns of the curve are 40-60, and the obtained polyaniline/carbon cloth electrode has better electrochemical performance, wherein the electrochemical performance of the polyaniline/carbon cloth electrode obtained by the scanning turns of the curve is relatively better; fig. 2b shows the area of the CV curve closure under different number of scanning turns, wherein 50 turns of scanning result in a larger CV curve closure area, and the obtained polyaniline/carbon cloth flexible electrode has relatively better performance, wherein the polyaniline not only can enhance the conductivity of the electrode, but also can undergo oxidation-reduction reaction in the thermoelectric conversion process, and cooperatively improves the thermoelectric conversion efficiency.
Fig. 3 is a digital photograph of the polyaniline/carbon cloth flexible electrode obtained in example 1 (scan 50 turns), fig. 4a is an SEM image of the carbon cloth flexible electrode, and fig. 4b is an SEM image of the polyaniline/carbon cloth flexible electrode after deposition of polyaniline, which can be successfully deposited on the surface of the carbon cloth by cyclic voltammetry polyaniline without surface modification of the carbon cloth, as shown in fig. 4 b.
3. Thermoelectric generator
The cyclic voltammetry characteristic curve testing method comprises the following steps: scanning was performed using electrochemical workstation testing at scan rates of 1mV/s, 5mV/s, 10mV/s, 30mV/s, respectively, over a voltage range of-0.2 to 0.8V.
The test method of open circuit voltage, power density and energy density comprises the following steps: the device is fixed on a temperature control table, is connected with an electrochemical workstation, is externally connected with a resistor box after the constant voltage is stable, and continuously measures the open-circuit voltage. Finally, the voltage is converted to power density and energy density by the following formula.
Pd＝U2/(R·S)
Ed＝U2/(R·S)·t
Wherein U is open circuit voltage, P d is power density, E d is energy density, R is resistance, S is contact area of gel and electrode, and t is continuous output time.
The specific area capacitance testing method comprises the following steps: the specific area capacitance (Ca, unit: mF cm -2) of the symmetrical supercapacitor device was calculated according to the following formula.
Where I/S represents the current density (mA cm -2), t is the discharge time (S), S is the surface area of the single electrode (cm 2), and DeltaV is the discharge voltage range.
Comparative example 1 the P (AA-AM)/CMC/H 2SO4 ion thermoelectric gel prepared by the present invention was assembled with a common electrode (carbon cloth electrode) to form a thermoelectric generator, and fig. 5a is an open circuit voltage of the thermoelectric generator of comparative example 1 at a temperature difference of 20K, up to 0.45V, and a seebeck coefficient of 22.5mW/K; FIG. 5b is a graph of power versus time for the thermoelectric generator of comparative example 1 in series with a 3kΩ resistor box at a temperature difference of 20K, and an energy density of 13J/m 2 in 1 hour, demonstrating that the thermoelectric hydrogel of the present invention has a high Seebeck coefficient and high thermoelectric conversion efficiency.
In the embodiment 1 of the invention, the P (AA-AM)/CMC/H 2SO4 ion thermoelectric gel and the polyaniline/carbon cloth electrode are assembled to obtain the thermoelectric generator with a sandwich structure of polyaniline/carbon cloth electrode-ion thermoelectric gel (P (AA-AM)/CMC/H 2SO4) -polyaniline/carbon cloth electrode, and the structure is shown in figure 6. As can be seen from fig. 7a and 7b, the thermoelectric generator of example 1 has good electrochemical performance, and the maximum specific area capacitance reaches 750mF/cm 2. Fig. 8 is a graph of power versus time for the thermoelectric generator of example 1 in series with a 3kΩ resistor box at a temperature difference of 20K, with an energy density output of 88J/m 2 for 1 hour, which is significantly higher than that of the thermoelectric generator of comparative example 1 (carbon cloth electrode-ion thermoelectric gel (P (AA-AM)/CMC/H 2SO4) -carbon cloth electrode), mainly because the oxidation-reduction reaction occurs due to the polyaniline after the ion thermoelectric gel and the polyaniline/carbon cloth are assembled into the thermoelectric generator, and the polyaniline can enhance the conductivity of the electrode, and the electrochemical performance of the thermoelectric generator is enhanced in cooperation with the ion thermoelectric gel, and the energy density is further improved.
The performance of the ionic thermoelectric gel and thermoelectric generator prepared in examples 2 to 3 is similar to that of example 1, and will not be described here again.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (3)
1. A thermoelectric conversion device, characterized in that the thermoelectric conversion device comprises a thermoelectric conversion material;
The thermoelectric conversion material comprises double-network hydrogel and conductive ions, wherein the conductive ions are dispersed in the double-network hydrogel; the first network structure of the double-network hydrogel is obtained by copolymerization and cross-linking of unsaturated carboxylic acid monomers and acrylamide monomers, and the second network structure is obtained by cross-linking of carboxymethyl cellulose;
the mass ratio of the unsaturated carboxylic acid monomer to the acrylamide monomer is 0.8-1.5: 1, a step of;
The mass ratio of the unsaturated carboxylic acid monomer to the carboxymethyl cellulose is 10-60: 1, a step of;
The conductive ions are hydrogen ions;
the thermoelectric conversion material is produced by a method comprising the steps of:
s1, mixing unsaturated carboxylic acid monomers, acrylamide monomers and carboxymethyl cellulose, and curing to obtain double-network hydrogel;
S2, soaking the double-network hydrogel in a conductive ion solution to obtain the thermoelectric conversion material;
In the step S1, the curing is ultraviolet curing, and the curing time is 1-5 min;
at least one of N, N' -methylene bisacrylamide and epichlorohydrin is also added in the step S1;
The thermoelectric conversion device further comprises a polyaniline/carbon cloth electrode; the thermoelectric conversion material is arranged between the polyaniline/carbon cloth electrodes.
2. The thermoelectric conversion device according to claim 1, wherein the polyaniline/carbon cloth electrode is produced by a production method comprising the steps of:
Immersing carbon cloth into aniline electrolyte by adopting a cyclic voltammetry, controlling the voltage range of a three-electrode system to be-0.5-1.5V, and scanning for 20-60 circles at a scanning speed of 30-70 mV/s to obtain the polyaniline/carbon cloth electrode.
3. Use of the thermoelectric conversion device according to any of claims 1-2 in the internet of things field, in the sensing field or in the wearable field.
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