CN114823153B - Flexible sodium ion capacitor electrode material - Google Patents
Flexible sodium ion capacitor electrode material Download PDFInfo
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- CN114823153B CN114823153B CN202210433953.1A CN202210433953A CN114823153B CN 114823153 B CN114823153 B CN 114823153B CN 202210433953 A CN202210433953 A CN 202210433953A CN 114823153 B CN114823153 B CN 114823153B
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- sodium ion
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- 239000003990 capacitor Substances 0.000 title claims abstract description 47
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 42
- 239000007772 electrode material Substances 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 128
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 70
- 238000010438 heat treatment Methods 0.000 claims abstract description 54
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 48
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 150000001621 bismuth Chemical class 0.000 claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 19
- 239000002041 carbon nanotube Substances 0.000 claims description 44
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 44
- 239000006185 dispersion Substances 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 26
- 238000000967 suction filtration Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 239000007773 negative electrode material Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 claims description 3
- 230000035939 shock Effects 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 12
- 238000005275 alloying Methods 0.000 abstract description 8
- 230000008859 change Effects 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 238000010298 pulverizing process Methods 0.000 abstract description 3
- 238000003828 vacuum filtration Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 28
- 239000002245 particle Substances 0.000 description 17
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 15
- 238000004146 energy storage Methods 0.000 description 14
- 239000010405 anode material Substances 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- -1 bismuth salt Chemical class 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001622 bismuth compounds Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The application provides a flexible sodium ion capacitor electrode material, which is a carbon-based two-dimensional film electrode material loaded with bismuth nano particles, wherein a carbon-based two-dimensional film loaded with metal bismuth salt is subjected to instantaneous heating. According to the method, the nano-scale metal bismuth is successfully loaded on the carbon-based two-dimensional film by combining vacuum filtration with instantaneous heating, the volume change of bismuth in the alloying process can be effectively relieved by the nano-scale size distribution, the problem of severe volume change of the metal bismuth in the alloying process is solved, the structural pulverization of the flexible electrode is effectively avoided, and the excellent cycling stability of the flexible sodium ion capacitor is ensured. Meanwhile, the carbon-based material is used as an instantaneous heating substrate, has excellent structural stability, and the heating time in the second level can also avoid damage to the carbon-based substrate.
Description
Technical Field
The application belongs to the field of secondary battery electrode materials. In particular to a flexible sodium ion capacitor electrode material.
Background
Currently, highly integrated wearable electronic devices are widely used in people's life, and portable, lightweight and flexible electronic devices are changing people's lifestyles. Meanwhile, the flexible wearable electronic product needs energy storage equipment with high volume ratio performance to drive so as to achieve the purposes of long endurance and meeting complex working conditions (such as mechanical deformation). Compared with other existing energy storage systems, the lithium ion battery is the energy storage device with the optimal performance in the application of the current mobile device, and has the highest energy density per unit mass/volume, long service life and wide working temperature range. Research into flexible lithium ion batteries has attracted considerable attention in both academia and industry. However, while lithium-based flexible energy storage devices have desirable volumetric performance, lower crust reserves result in increased cost of lithium resources. The price of lithium cathode materials (such as high nickel materials, lithium iron phosphate, etc.) used in lithium-based energy storage devices has risen year by year, and the development of lithium-based energy storage devices has been limited by the high cost.
In contrast, sodium has a natural abundance and is alkali metal as lithium, both of which have similar physicochemical properties. The low cost and high safety of the sodium-based energy storage device make the sodium-based energy storage device hopefully replace lithium to be used as a mainstream electrochemical energy storage system in the future to realize large-scale application, so that the development of the flexible sodium-based energy storage device with high volume ratio performance has extremely high market value and long-term strategic significance.
In the flexible sodium-based energy storage equipment, the flexible sodium ion capacitor integrates the advantages of the super capacitor and the secondary battery, and mainly adopts two positive and negative materials with different basic working principles. The non-Faraday charging and discharging process occurs on the capacitor carbon electrode, and the surface and near-surface constrained oxidation-reduction reaction occurs on the negative electrode. The preparation of the flexible electrode material is the core of the flexible sodium ion capacitor. The flexible electrode material with high volume ratio performance can provide higher energy density for the flexible sodium ion capacitor, and meanwhile, good circulation stability is maintained.
Compared with Li + ，Na + The larger ionic radius can lead to slow electrochemical reaction kinetics, low reversible capacity, poor rate capability and poor cycling stability of the sodium-based energy storage device in the charge and discharge process. The metal bismuth has larger interlayer spacing and higher theoretical capacity for storing sodium, so that a large amount of Na can be stored under low potential + And thus becomes a research hotspot of sodium-based energy storage devices. However, as an alloy type negative electrode material, the drastic volume change of metallic bismuth during alloying is a major limitation that hinders further application thereof.
In addition, in order to maintain a stable energy output of the flexible sodium ion capacitor under repeated mechanical deformation conditions, the flexible electrode material is required to have excellent mechanical properties. Therefore, electrode materials suitable for flexible sodium-based energy storage devices, which have both high volume ratio performance and excellent mechanical properties, are the key directions of research by researchers at present.
Disclosure of Invention
The application aims to provide a flexible sodium ion capacitor electrode material, which aims to develop a flexible electrode material with excellent mechanical stability, high volume ratio performance and rapid electrochemical reaction kinetics for a flexible sodium ion capacitor and solve the problem that metal bismuth is easy to pulverize due to severe volume change in an alloying process when the metal bismuth is used as a negative electrode material.
The purpose of the application is realized in the following way:
the embodiment of the application discloses a flexible sodium ion capacitor electrode material, which is prepared by loading bismuth nano particles with nano-scale particle size on a carbon-based two-dimensional film and preparing according to the following process:
1) Adding a carbon-based material into a surfactant solution and dispersing to obtain a carbon-phase dispersion liquid;
2) The metal bismuth salt and/or Bi are mixed according to a certain mass ratio 2 O 3 Adding into the carbon phase dispersion liquid and dispersing to obtain metal bismuth salt and/or Bi 2 O 3 A carbon phase dispersion;
3) The metal bismuth salt and/or Bi 2 O 3 Carrying out suction filtration and drying on the carbon phase dispersion liquid to obtain the supported metal bismuth salt and/or Bi 2 O 3 Is a carbon-based two-dimensional film;
4) For the obtained supported metal bismuth salt and/or Bi 2 O 3 The carbon-based two-dimensional film is subjected to instantaneous heating treatment, so that the carbon-based two-dimensional film electrode material loaded with bismuth nano particles and serving as a flexible sodium ion capacitor cathode material is obtained.
In a preferred embodiment, the instantaneous heating conditions of step 2) are: heating to 800-1500deg.C at a heating rate of 200-1200deg.C/s, and maintaining the temperature for 10-30-s. A more preferred embodiment is to maintain the heating time at 15.+ -.3 s.
In a preferred embodiment, the transient heating means includes, but is not limited to, microwave irradiation, joule heating, thermal shock with carbon, and the like.
In embodiments of the application, the instantaneous heating operation at the second level not only results in metallic bismuth salts and/or Bi 2 O 3 The bismuth nano particles with small and uniform particle size are reduced, the agglomeration problem does not exist, meanwhile, the damage of a carbon-based two-dimensional film structure is avoided, and the instant heating time has an important influence on the performance of the electrode material.
In one embodiment, in step 1) of the present example, the mass ratio of the carbon-based material to the surfactant in the solution is 1:2-3, and the dispersion process is carried out by magnetically stirring 2-4 h and then continuing to carry out ultrasonic treatment for 1-2 h. Further, the surfactant includes, but is not limited to, any one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, cetyltrimethylammonium bromide, triton, and the like.
In one embodiment, the carbon-based materials of the present application include, but are not limited to, carbon nanotubes, graphene, carbon nanofibers, and the like having sp 2 Carbon material of carbon hybrid structure.
In one embodiment, in step 2) of the inventive example, the metal bismuth salt and/or Bi 2 O 3 The mass ratio of the carbon-based material to the carbon-based material is 2-3:1, a step of; the dispersing process is to grind the metal bismuth salt and/or Bi 2 O 3 Adding into the carbon phase dispersion liquid, magnetically stirring for 4-6 h, and then carrying out ultrasonic treatment for 30-60 min.
In one embodiment, the metallic bismuth salts of the present application include, but are not limited to, bi (NO 3 ) 3 ·5H 2 O、BiCl 3 Bismuth citrate, which may also be other inorganic trivalent bismuth compounds.
The purpose of the ultrasound in the above step 1) and step 2) is to obtain a carbon phase dispersion liquid and a metal bismuth salt/carbon phase dispersion liquid, respectively, which are excellent in the discreteness.
In one embodiment of the application, in the suction filtration operation, a carbon phase dispersion liquid obtained from 50-100 mg carbon-based materials can obtain a two-dimensional film with the thickness of 40-80 mu m, and the film thickness can be customized according to requirements.
In one embodiment of the application, deionized water is added during the suction filtration process to remove residual surfactant.
A more preferred embodiment is to prepare a bismuth nanoparticle-loaded carbon-based two-dimensional thin film electrode material according to the following procedure:
(1) Preparing a sodium dodecyl sulfate solution: dissolving sodium dodecyl sulfate in 500 mL deionized water, and maintaining the concentration at 1.4-1.8 mg mL −1 Stirring with magnetic stirrer for 20-40 min;
(2) Preparing a carbon phase dispersion liquid: adding a carbon-based material (including but not limited to carbon nano tubes, graphene, carbon nano fibers and the like) into the sodium dodecyl sulfate solution in the step (1) according to the mass ratio of sodium dodecyl sulfate=1:2, stirring 2-4 h by using a magnetic stirrer, and then carrying out ultrasonic treatment on the mixed solution for 1-2 h to obtain a carbon phase dispersion;
(3) Preparing a metal bismuth salt/carbon phase dispersion liquid: with metallic bismuth salts (including but not limited to Bi (NO) 3 ) 3 ·5H 2 O、BiCl 3 Bismuth citrate, etc.): carbon-based material = 3:1, adding the ground bismuth salt into the carbon phase dispersion liquid obtained in the step (2), stirring 4-6 h by using a magnetic stirrer, and then carrying out ultrasonic treatment on the mixed solution for 30-60 min to obtain a metal bismuth salt/carbon phase dispersion liquid;
(4) Vacuum filtering to prepare the bismuth salt-loaded carbon-based two-dimensional film material: placing the dispersion liquid obtained in the step (3) in a vacuum suction filtration device for suction filtration, adding deionized water 500-800 mL during the suction filtration, and drying 6-8 h in a vacuum oven after the two-dimensional film suction filtration is completed;
(5) And (3) carrying out instantaneous heating treatment on the two-dimensional film obtained in the step (4) for 10-30 and s to finally obtain the bismuth nanoparticle-loaded two-dimensional film anode material. The instantaneous heating condition is that the heating rate is 200-1200 ℃/s and the heating temperature is 800-1500 ℃.
In addition, the embodiment of the application also designs a positive electrode material matched with the negative electrode material of the flexible sodium ion capacitor, which is prepared by compounding activated carbon and carbon-based materials according to a proper proportion and then vacuum filtering, wherein the electrode can be directly used as the positive electrode of the flexible sodium ion capacitor. The preparation process comprises the following steps:
(1) Preparing a sodium dodecyl sulfate solution: dissolving sodium dodecyl sulfate in 500 mL deionized water, and maintaining the concentration at 1.4-1.8 mg mL −1 Stirring with magnetic stirrer for 20-40 min;
(2) Preparing a carbon phase dispersion liquid: adding a carbon-based material into the sodium dodecyl sulfate solution in the step (1) in a mass ratio of the carbon-based material to the sodium dodecyl sulfate=1:2, stirring 2-4 h by using a magnetic stirrer, and then carrying out ultrasonic treatment on the mixed solution for 1-2 h to obtain a carbon-phase dispersion liquid;
(3) Preparing an activated carbon/carbon phase dispersion: adding activated carbon into the carbon phase dispersion liquid obtained in the step (2) according to the mass ratio of activated carbon to carbon-based material=2:1, stirring 4-6 h by using a magnetic stirrer, and then carrying out ultrasonic treatment on the mixed solution for 30-60 min to obtain an activated carbon/carbon phase dispersion liquid;
(4) Vacuum suction filtration is carried out to prepare the active carbon/carbon-based two-dimensional film anode material: and (3) placing the dispersion liquid obtained in the step (3) in a vacuum suction filtration device for suction filtration, adding deionized water 500-800 mL during the process, and drying 6-8 h in a vacuum oven after the two-dimensional film suction filtration is completed, so as to obtain the active carbon/carbon-based two-dimensional film anode material.
A further embodiment is a flexible sodium ion capacitor assembly process using the above positive/negative flexible electrode materials as follows:
1) Respectively connecting a nano bismuth/carbon-based negative electrode and an active carbon/carbon-based positive electrode which are matched in capacity with each other through conductive copper paste by a nickel tab and an aluminum tab;
2) Immersing the P (VDF-HFP) film in the electrolyte for 3-6 h, wherein the P (VDF-HFP) film immersed in the electrolyte is used as a quasi-solid electrolyte;
3) And a vacuum plastic package bag is used for assembling the flexible sodium ion capacitor.
The embodiment of the application has the beneficial technical effects of various aspects:
firstly, the carbon-based material with high conductivity and mechanical property is used as a flexible substrate, no conductive agent or binder is added, namely the carbon-based material can be used as the positive electrode/negative electrode of the flexible sodium ion capacitor without further treatment, and the carbon-based material has excellent conductivity and mechanical property, so that the process flow is further simplified, and the active site in the electrode is dredged. The carbon-based material (such as carbon nano tube, graphene, carbon nano fiber and the like) with excellent mechanical properties can ensure that the flexible electrode realizes complex mechanical deformation, so that the flexible sodium ion capacitor obtains excellent comprehensive sodium storage performance.
In the preparation process of the anode material, nano-scale metal bismuth is successfully loaded on a carbon-based two-dimensional film by combining vacuum suction filtration with instantaneous heating, the instantaneous heating in-situ reduction process has excellent heating efficiency, the high temperature generated by instantaneous heating ensures excellent conversion efficiency of bismuth salt and excellent nano-scale size distribution, bismuth nano-particles with the average particle size of 18 nm are uniformly coated on a carbon-based substrate, the nano-scale size distribution can effectively relieve the volume change of bismuth in the alloying process, the structural pulverization of a flexible electrode is effectively avoided, and excellent cycling stability of a flexible sodium ion capacitor is ensured. Solves the problem of severe volume change of the metal bismuth in the alloying process. Meanwhile, the carbon-based material is used as an instantaneous heating substrate, has excellent structural stability, and the heating time in the second level can also avoid damage to the carbon-based substrate.
Finally, the nano bismuth/carbon nano tube cathode prepared by the application is 5A g −1 At a high current density of 356 mAh g still −1 Is a specific discharge capacity of (a). The positive electrode of the active carbon/carbon nano tube is 1.6A g −1 Has a current density of 25 mAh g −1 Is a specific discharge capacity of (a).
The nano bismuth/carbon-based negative electrode and the active carbon/carbon-based positive electrode prepared by the application have excellent electrochemical performance and excellent mechanical performance, so that the assembled flexible sodium ion capacitor can meet complex use conditions, and a new development idea is developed for flexible energy storage devices. The constant current charge-discharge curve of the flexible sodium ion capacitor still has no abnormal distortion at different bending angles, and the constant current charge-discharge curve is 0.22 mA cm −2 After 1200 cycles of current density cycling, the capacity retention was approximately 91%. For simple and convenient compounding of the anode, the active carbon and the carbon-based material have excellent compatibility.
In addition, the instant heating method shortens the time and the economic cost, and the method is simple, convenient and efficient and is easy to realize large-scale commercial application.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of the negative electrode material prepared in example 1.
Fig. 2 (a) (b) (c) is a Scanning Electron Microscope (SEM) image of the anode materials prepared in examples 1, 2 and 3, respectively.
In fig. 3, (a) (b) (c) are statistical graphs of particle size distribution of the anode materials prepared in examples 1, 2 and 3, respectively.
Fig. 4 is a Scanning Electron Microscope (SEM) image of the positive electrode material prepared in example 1.
Fig. 5 is a graph of the rate performance data of the positive electrode material prepared in example 1.
Fig. 6 is a graph of the rate performance data of the anode materials prepared in examples 1, 2 and 3.
Fig. 7 is a graph of cycle performance data of the anode material prepared in example 1.
Fig. 8 is a graph showing constant current charge and discharge curves of the flexible sodium ion capacitor prepared in example 1.
Fig. 9 is a graph of cycle performance data for the flexible sodium-ion capacitor prepared in example 1.
Detailed Description
According to the application, the carbon nano tube loaded with the metal bismuth salt is prepared through vacuum suction filtration, and then the bismuth salt is reduced into bismuth nano particles in situ through instant heating treatment, so that the flexible sodium ion capacitor anode material can be obtained. And preparing the active carbon/carbon nano tube two-dimensional film by vacuum suction filtration to obtain the flexible sodium ion capacitor cathode material. And then the prepared positive/negative electrode material is further utilized to assemble and obtain the flexible sodium ion capacitor.
For a better understanding of the present application, reference will now be made in detail to the present application, examples of which are illustrated in the accompanying drawings, but are not intended to limit the application. The experimental raw materials used in the following examples are all commercially available and can also be prepared by conventional methods known to those skilled in the art; the laboratory apparatus used is commercially available.
Example 1
1. Preparation of nano bismuth/carbon nano tube two-dimensional film negative electrode
Step one: sodium dodecyl sulfate was dissolved in 500 mL deionized water to maintain the solution at a concentration of 1.4 mg mL −1 Stirring with a magnetic stirrer for 30 min.
Step two: adding carbon nanotubes into the sodium dodecyl sulfate solution in the first step in a mass ratio of carbon nanotubes to sodium dodecyl sulfate=1:2, stirring 2 h by using a magnetic stirrer, and then carrying out ultrasonic treatment on the mixed solution for 1 h to obtain a carbon nanotube dispersion; the parameters of the carbon nanotubes used in this step are single-walled carbon nanotubes having a length of 10-30 μm.
Step three: with Bi (NO) 3 ) 3 ·5H 2 O: carbon nanotube=3:1 mass ratio Bi (NO 3 ) 3 ·5H 2 O, adding the mixture into the carbon nano tube dispersion liquid obtained in the step two, stirring the mixture for 4 h by using a magnetic stirrer, and then carrying out ultrasonic treatment on the mixed solution for 40 min to obtain Bi (NO) 3 ) 3 ·5H 2 O/carbon nanotube dispersion.
Step four: and (3) placing the dispersion liquid obtained in the step (III) into a vacuum filtration device for filtration, adding deionized water 600 mL during the filtration, and drying 6 h in a vacuum oven after the two-dimensional film filtration is completed.
Step five: and (3) performing instantaneous heating treatment (heating rate 600 ℃/s and temperature 1100 ℃) on the two-dimensional film obtained in the step four for 15 s to obtain the bismuth nanoparticle-loaded two-dimensional film anode material.
2. Preparation of active carbon/carbon nano tube two-dimensional film positive electrode
Step one: sodium dodecyl sulfate was dissolved in a defined amount of deionized water to maintain the concentration of the solution at 1.4 mg mL −1 Stirring with a magnetic stirrer for 30 min.
Step two: adding carbon nanotubes into the sodium dodecyl sulfate solution in the first step in a mass ratio of carbon nanotubes to sodium dodecyl sulfate=1:2, stirring 2 by using a magnetic stirrer h, and then carrying out ultrasonic treatment on the mixed solution for 1 h to obtain a carbon nanotube dispersion.
Step three: adding active carbon into the carbon nano tube dispersion liquid obtained in the step two according to the mass ratio of active carbon to carbon nano tube=2:1, stirring 4 h by using a magnetic stirrer, and then carrying out ultrasonic treatment on the mixed solution for 40 min to obtain the active carbon/carbon nano tube dispersion liquid.
Step four: and (3) placing the dispersion liquid obtained in the step (III) into a vacuum suction filtration device for suction filtration, adding deionized water 600 mL during the process, and drying 6 h in a vacuum oven after the two-dimensional film suction filtration is completed, so as to obtain the active carbon/carbon nano tube two-dimensional film anode material.
3. Assembly of flexible sodium-ion capacitor:
step one: respectively connecting a nickel tab and an aluminum tab with a nano bismuth/carbon nano tube negative electrode and an active carbon/carbon nano tube positive electrode which are matched in capacity through conductive copper paste;
step two: immersing the P (VDF-HFP) film into the electrolyte for 5 hours, wherein the P (VDF-HFP) film immersed with the electrolyte is used as a quasi-solid electrolyte;
step three: and a vacuum plastic package bag is used for assembling the flexible sodium ion capacitor.
Example 2
Example 2 differs from example 1 only in that the instantaneous heat treatment time was 20 s.
Example 3
Example 3 differs from example 1 only in that the instantaneous heat treatment time was 25 s.
The electrode materials and the capacitor prepared in examples 1, 2 and 3 were tested for performance. The method for testing the electrochemical performance of the electrode material comprises the following steps: (1) Electrochemical performance testing of the examples was performed using a button CR2025 battery system (using a New Wipe battery test system, voltage range was selected to be 0.1-3.5V, current density was 0.1-5 Ag) −1 ) The method comprises the steps of carrying out a first treatment on the surface of the (2) And (3) assembling the flexible sodium ion capacitor in a glove box by using a vacuum plastic package bag, wherein the test conditions are the same as those in the step (1).
1. X-ray diffraction analysis
The negative electrode material prepared in example 1 was subjected to X-ray diffraction analysis, and the results are shown in fig. 1. Fig. 1 is an X-ray diffraction chart of a nano bismuth/carbon nanotube anode after instantaneous heating treatment, and the result shows that after instantaneous heating, characteristic diffraction peaks of in-situ reduced bismuth nanoparticles can be in one-to-one correspondence with standard PDF cards JCPDS No 44-1246, which indicates that pure-phase bismuth nanoparticles are formed on a carbon-based two-dimensional film.
2. Scanning electron microscope analysis
SEM examination of the anode materials prepared in examples 1-3 was conducted, and the results are shown in FIG. 2. Fig. 2 is a scanning electron microscope image of a nano bismuth/carbon nanotube negative electrode with different instantaneous heating times (15 s, 20 s and 25 s), and it can be seen from the image that the different instantaneous heating times correspond to the very different particle size distributions of bismuth nanoparticles, and the bismuth nanoparticles have excellent morphology distribution after instantaneous heating 15 s (fig. 2 (a)), and as can be seen from the particle size distribution statistical chart of fig. 3 (a), the average particle size after instantaneous heating 15 s is 18 nm, the bismuth nanoparticles are tightly wrapped on the surface of the carbon nanotube, and the particle size distribution is very uniform. As can be seen from fig. 2 (b), the particle size of the bismuth nanoparticles after the instant heating of 20 s has significantly exceeded the diameter of the carbon nanotubes, the uniformity of the bismuth nanoparticles has been reduced compared to 15 s, and the particle size distribution statistical chart of fig. 3 (b) shows that the average particle size after the instant heating of 20 s is 53 nm. As can be seen from fig. 2 (c), bismuth nano-particles after instantaneous heating 25 s cannot be coated on the surface of a single carbon nanotube, and the particle size distribution statistical chart of fig. 3 (c) shows that the average particle size after instantaneous heating 25 s is 240 nm. The method comprises the steps of carrying out a first treatment on the surface of the
SEM examination was performed on the positive electrode material prepared in example 1, and the results are shown in fig. 4. Fig. 4 is a scanning electron microscope picture of an active carbon/carbon nanotube anode, and it can be seen from the picture that after the active carbon is compounded with the carbon nanotube, micron-sized active carbon particles are tightly coated by the carbon nanotube, so that efficient electron transmission of the anode can be ensured.
3. Multiplying power performance detection
FIG. 5 is a graph showing the rate performance data of the active carbon/carbon nanotube positive electrode, which shows that the active carbon/carbon nanotube positive electrode has excellent rate performance of 1.6 Ag −1 Has a current density of 25 mAh g −1 Is a specific discharge capacity of (a).
FIG. 6 is a plot of rate performance data for nano bismuth/carbon nanotube cathodes at 15 s for different instantaneous heating times (15 s, 20 s and 25 s)The flexible electrode was at 5A g under transient heating time −1 The specific discharge capacity can reach 356 mAh g under the high current density −1 The nano-scale bismuth particles can provide rich alloying active sites for the charge and discharge process, ensure rapid electrochemical reaction kinetics and present excellent rate capability. This corresponds to the characterization result of the scanning electron microscope in fig. 2. And at 5A g at an instantaneous heating time of 20 s, 25 s −1 At current density of 344 mAh g respectively −1 、307 mAh g −1 The rate performance is lower than that of the instantaneous heating 15 s, which also corresponds to the characterization result of the scanning electron microscope in fig. 2, because the more excellent particle size distribution after the instantaneous heating 15 s provides more abundant active sites for the alloying process, and the excellent nano-state distribution provides rapid electrochemical reaction kinetics, ensures excellent ion and electron conductivity, and further realizes excellent rate performance.
4. Cycle number test
FIG. 7 is a graph showing cycle performance data for a nano bismuth/carbon nanotube negative electrode at 5 Ag −1 After the flexible electrode circulates 1000 times under the current density, the performance is stable, and the capacity retention rate is close to 100%, which shows that the nano-scale bismuth particles prepared by the application can effectively relieve the volume change of the bismuth particles, avoid the pulverization of the electrode structure and ensure the excellent circulation stability of the nano-bismuth/carbon nano-tube negative electrode.
5. Charging and discharging of capacitor with different bending angles
Fig. 8 is a constant current charge-discharge graph of the flexible sodium ion capacitor assembled by the nano bismuth/carbon nanotube negative electrode and the active carbon/carbon nanotube positive electrode (example 1) at bending angles of 0 °, 90 ° and 180 °, respectively, and it can be seen from the graph that the flexible sodium ion capacitor can still stably work at different bending angles of 0-180 °, and the charge-discharge curve has no abnormal distortion, which indicates that the flexible sodium ion capacitor has excellent electrochemical stability and exhibits excellent practical application potential.
6. Capacitor cycle performance
FIG. 9 shows a nano bismuth/carbon nano tube negative electrode and activated carbonCycling performance of the Flexible sodium-ion capacitor assembled with carbon nanotube Positive electrode (example 1) at 0.22 mA cm −2 The capacity retention rate is close to 91% after 1200 cycles of stable cycling of the flexible sodium ion capacitor at the current density of (a).
Comparative example 1
Comparative example 1 differs from example 1 in that no instantaneous heat treatment was performed.
Comparative example 2
Comparative example 2 is different from example 1 in that the instantaneous heat treatment operation was changed to high temperature calcination (1100 ℃ C., 1.5 h).
The electrode materials prepared in comparative examples 1 and 2 were used as negative electrode rate performance (detection is referred to as "3, rate performance detection") and the results showed that: in comparative example 1, since the instantaneous heat treatment was not performed, the metal bismuth salt failed to provide a capacity of 0.2A g as an active material −1 Has a current density of only 35 mAh g −1 The capacity of which is mainly contributed by the carbon nanotubes; in comparative example 2, at 5A g −1 At a current density of only 205 mAh g −1 。
The bismuth nanoparticles of the negative electrode material prepared in comparative example 2 were subjected to scanning electron microscope analysis, and the result was: since high temperature calcination does not have an instantaneous temperature rise-rapid quenching mechanism, the heating process is extremely slow and is in a molten state for a long time so that the obtained bismuth does not have a uniform distribution morphology and even is partially separated from the carbon substrate.
The electrode materials prepared in comparative examples 1 and 2 were subjected to cycle number test, and the results were: in comparative example 1, the concentration of the catalyst was 0.8A g −1 Only 500 cycles, the capacity retention was 74%; comparative example 2 at 5A g −1 Only 600 cycles, the capacity retention was 85%.
The foregoing examples illustrate only the preferred embodiments of the application and are described in more detail, but are not to be construed as limiting the scope of the application. It should be noted that it would be apparent to one skilled in the art that the present application could be practiced without departing from the applicationSeveral variations and modifications are possible under the light of the clear idea, which are all within the scope of the application. In addition, other embodiments within the scope of the claimed application, including the rate of temperature rise, soak temperature, other inorganic trivalent bismuth compounds, other compounds having sp 2 All embodiments relating to the mass ratio of the carbon material of the carbon hybrid structure and the metal bismuth salt to the carbon-based material can reach a level substantially equivalent to the negative electrode material prepared in examples 1 to 3 described above, and thus are not exemplified.
Claims (6)
1. The flexible sodium ion capacitor electrode material is characterized by being prepared according to the following process:
1) Adding a carbon-based material into a surfactant solution and dispersing to obtain a carbon-phase dispersion liquid;
2) Bismuth salts and/or Bi of metals 2 O 3 Adding into the carbon phase dispersion liquid and dispersing to obtain metal bismuth salt and/or Bi 2 O 3 Carbon phase dispersion, bismuth metal salt and/or Bi 2 O 3 The mass ratio of the carbon-based material to the carbon-based material is 2-3:1;
3) The metal bismuth salt and/or Bi 2 O 3 Carrying out suction filtration and drying on the carbon phase dispersion liquid to obtain the supported metal bismuth salt and/or Bi 2 O 3 Is a carbon-based two-dimensional film;
4) For the obtained supported metal bismuth salt and/or Bi 2 O 3 Performing instantaneous heating treatment on the carbon-based two-dimensional film to obtain a carbon-based two-dimensional film electrode material which can be used as a flexible sodium ion capacitor negative electrode material and is loaded with bismuth nano particles;
the instantaneous heating conditions are: heating to 800-1500deg.C at a heating rate of 200-1200deg.C/s, and maintaining the temperature for 10-30-s.
2. The flexible sodium ion capacitor electrode material of claim 1, wherein the instantaneous heating is by microwave irradiation, joule heating, or carbon thermal shock.
3. The flexible sodium ion capacitor electrode material of claim 1, wherein the metallic bismuth salt is Bi (NO 3 ) 3 ·5H 2 O、BiCl 3 Or bismuth citrate.
4. The flexible sodium ion capacitor electrode material of claim 1, wherein the carbon-based material is a material having sp 2 Carbon material of carbon hybrid structure.
5. The flexible sodium ion capacitor electrode material of claim 4, wherein the carbon-based material is carbon nanotubes, graphene or carbon nanofibers.
6. The flexible sodium ion capacitor electrode material of any one of claims 1 to 5, wherein in step 2), the dispersing process is to grind the metal bismuth salt and/or Bi 2 O 3 Adding into the carbon phase dispersion liquid, magnetically stirring for 4-6 h, and then carrying out ultrasonic treatment for 30-60 min.
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