CN112133573A - Preparation method of manganese dioxide asymmetric capacitor positive electrode composite material - Google Patents
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000003990 capacitor Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 33
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011572 manganese Substances 0.000 claims abstract description 9
- 239000002077 nanosphere Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 26
- 230000008021 deposition Effects 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 6
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 abstract description 10
- 239000007772 electrode material Substances 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 229910052748 manganese Inorganic materials 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 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
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a preparation method of a manganese dioxide asymmetric capacitor anode composite material, wherein the anode composite material is Ti/SnO2‑Sb2O5/CoS‑MnO2Preparing porous CoS nanospheres and MnO by a composite electrodeposition method and a hydrothermal method2Carrying out composite electrodeposition; the method is simple to operate, and the crystal structure and the porosity can be effectively controlled; the prepared CoS nanosphere has rich pore structure and better ductility, and can be used in combination with MnO2A porous channel easy for electrolyte ion transmission is generated in the codeposition process; in addition, due to the mutual synergistic effect of Co and Mn bimetal, the compound has higher capacitance and more stable crystal structure, and the utilization rate of the positive active substance is improved; by using the Ti/SnO2‑Sb2O5/CoS‑MnO2The asymmetric capacitor prepared from the composite electrode material has higher energy density and longer cycle life.
Description
Technical Field
The invention belongs to the technical field of manganese dioxide asymmetric capacitors, and particularly relates to a preparation method of a manganese dioxide asymmetric capacitor positive electrode composite material.
Background
The asymmetric capacitor is a hybrid capacitor in which a Faraday capacitive electrode material such as metal oxide and hydroxide is used as a positive electrode, and an electric double layer capacitive electrode material such as activated carbon is used as a negative electrode. Compared with other common super capacitors, the super capacitor has the characteristics of a double electric layer capacitor and a Faraday capacitor, so that the super capacitor has a higher working voltage window, can achieve higher energy density at the same time of higher power density, and has wide application prospect. MnO2The material has attracted much attention as the positive electrode material of the capacitor, not only because of the high theoretical capacity, but also because of the abundant resources, the low price and the environmental protection. However, a single MnO2The requirement of high performance capacitors cannot be met, and the actual capacity is far smaller than the theoretical capacity. On the one hand, because of MnO2The conductivity of (2) is poor, and the resistivity is higher; on the other hand, because the utilization rate of the lithium iron phosphate as the anode material is low, the dissolution of the anode material occurs in the charge-discharge cycle process due to the instability of the structure, so that the irreversible redox reaction is caused, the capacity attenuation is caused, and the cycle stability is poor.
Many methods have been used to prepare MnO of different shapes2And different forms of compounding, to improve energy density and cycle stability in various ways. Common preparation methods include sol-gel method, hydrothermal synthesis method, liquid-phase coprecipitation method, solid-phase method and electrodeposition method. Among them, as one of electrodeposition methods, the composite electrodeposition method can provide better connectivity between an active material and a substrate and easily control the crystal structure and porosity of a product, and thus has been widely used in recent years. The electrodeposition method containing the particles is traced to the preparation of the graphite copper composite coating on the self-lubricating surface of the automobile engine, and the research shows that the nano particles are suspended in the electrolyte and are co-deposited with metal to prepare the nano composite coating. However, in the prior artThe report of preparing the manganese dioxide asymmetric capacitor anode composite material which can meet the requirement of a high-performance capacitor and has stable structure and rich pore channels by adopting a composite electrodeposition method is not provided.
Disclosure of Invention
The invention aims to provide Ti/SnO with stable structure and rich pore channels2-Sb2O5/CoS-MnO2According to the anode composite electrodeposition method of the composite electrode material, the energy density and the cycle life of the asymmetric capacitor prepared by using the electrode material are improved.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a manganese dioxide asymmetric capacitor positive electrode composite material comprises the following steps:
A、Ti/SnO2-Sb2O5preparation of the substrate:
a1, deoiling the Ti substrate with 10-20% alkali liquor, washing with water, washing with acid solution with the volume ratio of 1:2, etching the solution at 80 ℃ for 0.5-1h, and washing with deionized water;
a2, SnCl2·2H2O and SbCl3The molar ratio of the components is 9: 1 is dissolved in n-butyl alcohol, and three drops of concentrated hydrochloric acid are added to prepare coating liquid according to the content of SnO2-Sb2O5 of 10-20mg/cm 2;
a3, coating the coating liquid prepared in the step A2 on the Ti substrate treated in the step A, drying at the temperature of 100 ℃ and 150 ℃, thermally oxidizing at the temperature of 400 ℃ and 600 ℃ for 10-15min in an oxygen atmosphere, repeatedly operating until the coating liquid is completely coated, and sintering at the temperature of 400 ℃ and 600 ℃ for 0.5-1 h;
B. synthesis of porous CoS nanospheres:
b1, dissolving 1-2g of copolymer PEO-PPO-PEO in 50-70mL of distilled water;
b2, adding 25% ammonia water into 1M-2M cobalt salt solution to make NH4+And Co2+Is maintained at a molar ratio of 10: 1;
b3, adding 5-10mL of the mixed solution obtained in the step B2 into the copolymer solution obtained in the step B1, stirring at room temperature for 0.5-1h, adding 10-20 mL of 0.2-0.8M ascorbic acid, and stirring for 10-20 min;
b4, adding a proper amount of thiourea to ensure that the molar ratio of the thiourea to the cobalt is 2:1, transferring the mixture into a stainless steel autoclave, heating the mixture to 150 ℃ and 200 ℃, and keeping the temperature for 24 hours;
b5, collecting the generated black precipitate through centrifugation, and washing the black precipitate with ethanol and distilled water to remove the copolymer to obtain porous CoS nano particles;
C、Ti/SnO2-Sb2O5/CoS-MnO2preparing a positive electrode material:
c1, placing CoS nano-particles prepared in the step B5 at the concentration of 5-10mM in a manganese salt solution of 0.1-0.4M, adding strong acid to adjust the pH value to 3-5, and performing ultrasonic dispersion for 10-20 min;
c2 as Ti/SnO2-Sb2O5Is a working electrode, a platinum electrode is a counter electrode, and Ti/SnO is prepared by constant current deposition under the condition of magnetic stirring2-Sb2O5/CoS-MnO2And (4) a positive electrode.
Further, step A, the Ti matrix is 1cm × 2 cm.
Further, in the step A, the alkali liquor is NaOH, KOH or NaCO3One or more of (a).
Further, in the step A, the acid is HCl or H2SO4、HNO3One or more of (a).
Further, in step B2, the cobalt salt is CoCl2、Co(NO3)2、CoSO4One or more of (a).
Further, step C1, the manganese salt is Mn (NO)3)2、MnSO4、MnCl2One or more of (a).
Further, step C1, the strong acid is HNO3、HCl、H2SO4One or more of (a).
Further, in step C2, the constant current deposition current density is 5-20mA/cm 2, the deposition time is 0.5-3h, and the deposition temperature is room temperature.
Further, the constant current deposition has a current density of 15mA/cm 2 and a deposition time of 1 h.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, an anode composite electrodeposition method is utilized, firstly, the porous CoS nanospheres are prepared by a hydrothermal synthesis method, rich pore structures and good ductility of CoS play a role in guiding the deposition morphology of MnO2, and compared with pure manganese electrodeposition, the composite electrode with a porous channel, which is easy for electrolyte diffusion and transmission, can be prepared;
in addition, due to the mutual synergistic effect of Co and Mn bimetal, the composite has higher capacitance, the crystal structure is more stable, and the utilization rate of the positive active substance is improved;
the method is simple to operate, and when the prepared Ti/SnO2-Sb2O5/CoS-MnO2 composite electrode material is applied to the anode of the asymmetric capacitor, the energy density and the cycling stability of the capacitor are improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain, but not limit, the invention, and are incorporated in and constitute a part of this specification:
FIG. 1 is a graph of Ti/SnO prepared in example 32-Sb2O5/CoS-MnO2Scanning electron micrographs of the composite electrode material;
FIG. 2 shows that the current density of example 3 is 3Ag-1，CoS-MnO2Cycle performance diagram of/C asymmetric capacitor.
Detailed Description
The invention is further illustrated by the following examples:
example 1
Deoiling a Ti matrix of 1cm multiplied by 2cm by using 10% NaOH solution, washing by using water, washing by using sulfuric acid solution with the volume ratio of 1:2, etching for 0.5h at the temperature of 80 ℃ of the solution, and washing by using deionized water for later use. SnCl2·2H2O and SbCl3According to the following steps of 9: 1 molar ratio in n-butanol and three drops of concentrated hydrochloric acid were added to prevent hydrolysis. SnO by pressing2-Sb2O5The content is 10mg/cm2Preparing a coating solution, coating the coating solution on the treated Ti substrate by brush,drying at 120 deg.C, thermally oxidizing at 500 deg.C for 15min in oxygen atmosphere, repeating the operation until the coating liquid is completely coated, and sintering at 500 deg.C for 1 h.
First, 1.35g of copolymer PEO-PPO-PEO was dissolved in 60mL of distilled water. In 1M CoCl2·2H2Adding a proper amount of 25% ammonia water into O to ensure that NH is generated4+And Co2+Is maintained at a molar ratio of 10: 1. 6mL of the mixed solution was added to the copolymer solution, and after stirring at room temperature for 0.5h, 15mL of 0.6M ascorbic acid was added and stirred for 15 min. Adding a proper amount of thiourea to ensure that the molar ratio of the thiourea to the cobalt is 2:1, transferring the mixture into a stainless steel autoclave, heating the mixture to 160 ℃, and keeping the temperature for 24 hours. Finally, the resulting black precipitate was collected by centrifugation, washed several times with ethanol and distilled water, and the copolymer was removed to give porous CoS nanoparticles.
6mM CoS nanoparticles prepared as described above were loaded in 0.2M Mn (NO)3)2Adding HNO into the solution3Adjusting the pH value to 4, and ultrasonically dispersing for 15 min. With Ti/SnO2-Sb2O5Is a working electrode, a platinum electrode is a counter electrode, and constant current deposition is adopted under the condition of magnetic stirring, wherein the current density is 5mA/cm2The deposition time is 2h, and the deposition temperature is room temperature. The Ti/SnO is prepared by controlling the conditions and electrodepositing2-Sb2O5/CoS-MnO2And (4) a positive electrode.
Example 2
Deoiling a Ti matrix of 1cm multiplied by 2cm by using 10% NaOH solution, washing by using water, washing by using sulfuric acid solution with the volume ratio of 1:2, etching for 0.5h at the temperature of 80 ℃ of the solution, and washing by using deionized water for later use. SnCl2·2H2O and SbCl3According to the following steps of 9: 1 molar ratio in n-butanol and three drops of concentrated hydrochloric acid were added to prevent hydrolysis. SnO by pressing2-Sb2O5The content is 10mg/cm2Preparing coating liquid, coating the coating liquid on a treated Ti substrate, drying at 120 ℃, then thermally oxidizing for 15min at 500 ℃ in an oxygen atmosphere, repeating the operation until the coating liquid is completely coated, and finally sintering for 1h at 500 ℃.
First, 1.35g of copolymer PEO-PPO-PEO was dissolved in 60mL of distilled water. At 1M CoCl2·2H2Adding a proper amount of 25% ammonia water into O to ensure that NH is generated4+And Co2+Is maintained at a molar ratio of 10: 1. 6mL of the mixed solution was added to the copolymer solution, and after stirring at room temperature for 0.5h, 15mL of 0.6M ascorbic acid was added and stirred for 15 min. Adding a proper amount of thiourea to ensure that the molar ratio of the thiourea to the cobalt is 2:1, transferring the mixture into a stainless steel autoclave, heating the mixture to 160 ℃, and keeping the temperature for 24 hours. Finally, the resulting black precipitate was collected by centrifugation, washed several times with ethanol and distilled water, and the copolymer was removed to give porous CoS nanoparticles.
6mM CoS nanoparticles prepared as described above were loaded in 0.2M Mn (NO)3)2Adding HNO into the solution3Adjusting the pH value to 4, and ultrasonically dispersing for 15 min. With Ti/SnO2-Sb2O5Is a working electrode, a platinum electrode is a counter electrode, and constant current deposition is adopted under the condition of magnetic stirring, wherein the current density is 10mA/cm2The deposition time is 1.5h, and the deposition temperature is room temperature. The Ti/SnO is prepared by controlling the conditions and electrodepositing2-Sb2O5/CoS-MnO2And (4) a positive electrode.
Example 3
Deoiling a Ti matrix of 1cm multiplied by 2cm by using 10% NaOH solution, washing by using water, washing by using sulfuric acid solution with the volume ratio of 1:2, etching for 0.5h at the temperature of 80 ℃ of the solution, and washing by using deionized water for later use. SnCl2·2H2O and SbCl3According to the following steps of 9: 1 molar ratio in n-butanol and three drops of concentrated hydrochloric acid were added to prevent hydrolysis. SnO by pressing2-Sb2O5The content is 10mg/cm2Preparing coating liquid, coating the coating liquid on a treated Ti substrate, drying at 120 ℃, then thermally oxidizing for 15min at 500 ℃ in an oxygen atmosphere, repeating the operation until the coating liquid is completely coated, and finally sintering for 1h at 500 ℃.
First, 1.35g of copolymer PEO-PPO-PEO was dissolved in 60mL of distilled water. In 1M CoCl2·2H2Adding a proper amount of 25% ammonia water into O to ensure that NH is generated4+And Co2+Is maintained at a molar ratio of 10: 1. 6mL of the mixed solution was added to the copolymer solution, and after stirring at room temperature for 0.5h, 15mL of 0.6M ascorbic acid was added and stirred for 15 min. Adding a proper amount of sulfurUrea, thiourea and cobalt molar ratio 2:1, was transferred to a stainless steel autoclave and heated to 160 ℃ for 24 h. Finally, the resulting black precipitate was collected by centrifugation, washed several times with ethanol and distilled water, and the copolymer was removed to give porous CoS nanoparticles.
6mM CoS nanoparticles prepared as described above were loaded in 0.2M Mn (NO)3)2Adding HNO into the solution3Adjusting the pH value to 4, and ultrasonically dispersing for 15 min. With Ti/SnO2-Sb2O5Is a working electrode, a platinum electrode is a counter electrode, and constant current deposition is adopted under the condition of magnetic stirring, wherein the current density is 15mA/cm2The deposition time is 1h, and the deposition temperature is room temperature. The Ti/SnO is prepared by controlling the conditions and electrodepositing2-Sb2O5/CoS-MnO2The scanning electron micrograph of the electrode is shown in figure 1. The prepared composite positive electrode and the active carbon negative electrode are assembled into an asymmetric capacitor in 1M potassium hydroxide, and the current density is 3A g-1The results of the cycle stability in time are shown in FIG. 2.
Example 4
Deoiling a Ti matrix of 1cm multiplied by 2cm by using 10% NaOH solution, washing by using water, washing by using sulfuric acid solution with the volume ratio of 1:2, etching for 0.5h at the temperature of 80 ℃ of the solution, and washing by using deionized water for later use. SnCl2·2H2O and SbCl3According to the following steps of 9: 1 molar ratio in n-butanol and three drops of concentrated hydrochloric acid were added to prevent hydrolysis. SnO by pressing2-Sb2O5The content is 10mg/cm2Preparing coating liquid, coating the coating liquid on a treated Ti substrate, drying at 120 ℃, then thermally oxidizing for 15min at 500 ℃ in an oxygen atmosphere, repeating the operation until the coating liquid is completely coated, and finally sintering for 1h at 500 ℃.
First, 1.351g of copolymer PEO-PPO-PEO was dissolved in 60mL of distilled water. In 1M CoCl2·2H2Adding a proper amount of 25% ammonia water into O to ensure that NH is generated4+And Co2+Is maintained at a molar ratio of 10: 1. 6mL of the mixed solution was added to the copolymer solution, and after stirring at room temperature for 0.5h, 15mL of 0.6M ascorbic acid was added and stirred for 15 min. Adding appropriate amount of thiourea to make the molar ratio of thiourea to cobalt be 2:1, transferring to stainless steelThe steel autoclave was heated to 160 ℃ and held for 24 h. Finally, the resulting black precipitate was collected by centrifugation, washed several times with ethanol and distilled water, and the copolymer was removed to give porous CoS nanoparticles.
6mM CoS nanoparticles prepared as described above were loaded in 0.2M Mn (NO)3)2Adding HNO into the solution3Adjusting the pH value to 4, and ultrasonically dispersing for 15 min. With Ti/SnO2-Sb2O5Is a working electrode, a platinum electrode is a counter electrode, and constant current deposition is adopted under the condition of magnetic stirring, wherein the current density is 20mA/cm2The deposition time is 0.5h, and the deposition temperature is room temperature. The Ti/SnO is prepared by controlling the conditions and electrodepositing2-Sb2O5/CoS-MnO2And (4) a positive electrode.
Test results are shown in Table 1, prepared Ti/SnO2-Sb2O5/CoS-MnO2The composite electrode has a rich pore structure, and is beneficial to permeation and diffusion of electrolyte. The energy density of the asymmetric capacitor assembled by the electrode prepared by the method can reach 48Wh kg at most-1At 3A g-1The capacity retention after 8000 cycles of cycling was still 90.4%.
TABLE 1
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the scope of the claims of the present invention.
Claims (9)
1. The preparation method of the manganese dioxide asymmetric capacitor positive electrode composite material is characterized by comprising the following steps:
A、Ti/SnO2-Sb2O5preparation of the substrate:
a1, deoiling the Ti substrate with 10-20% alkali liquor, washing with water, washing with acid solution with the volume ratio of 1:2, etching the solution at 80 ℃ for 0.5-1h, and washing with deionized water;
a2, SnCl2·2H2O and SbCl3The molar ratio of the components is 9: 1 is dissolved in n-butyl alcohol, and three drops of concentrated hydrochloric acid are added to prepare coating liquid according to the content of SnO2-Sb2O5 of 10-20mg/cm 2;
a3, coating the coating liquid prepared in the step A2 on the Ti substrate treated in the step A, drying at the temperature of 100 ℃ and 150 ℃, thermally oxidizing at the temperature of 400 ℃ and 600 ℃ for 10-15min in an oxygen atmosphere, repeatedly operating until the coating liquid is completely coated, and sintering at the temperature of 400 ℃ and 600 ℃ for 0.5-1 h;
B. synthesis of porous CoS nanospheres:
b1, dissolving 1-2g of copolymer PEO-PPO-PEO in 50-70mL of distilled water;
b2, adding 25% ammonia water into 1M-2M cobalt salt solution to make NH4+And Co2+Is maintained at a molar ratio of 10: 1;
b3, adding 5-10mL of the mixed solution obtained in the step B2 into the copolymer solution obtained in the step B1, stirring at room temperature for 0.5-1h, adding 10-20 mL of 0.2-0.8M ascorbic acid, and stirring for 10-20 min;
b4, adding a proper amount of thiourea to ensure that the molar ratio of the thiourea to the cobalt is 2:1, transferring the mixture into a stainless steel autoclave, heating the mixture to 150 ℃ and 200 ℃, and keeping the temperature for 24 hours;
b5, collecting the generated black precipitate through centrifugation, and washing the black precipitate with ethanol and distilled water to remove the copolymer to obtain porous CoS nano particles;
C、Ti/SnO2-Sb2O5/CoS-MnO2preparing a positive electrode material:
c1, placing CoS nano-particles prepared in the step B5 at the concentration of 5-10mM in a manganese salt solution of 0.1-0.4M, adding strong acid to adjust the pH value to 3-5, and performing ultrasonic dispersion for 10-20 min;
c2 as Ti/SnO2-Sb2O5Is a working electrode, a platinum electrode is a counter electrode, and Ti/SnO is prepared by constant current deposition under the condition of magnetic stirring2-Sb2O5/CoS-MnO2And (4) a positive electrode.
2. The method for preparing the manganese dioxide asymmetric capacitor positive electrode composite material as claimed in claim 1, wherein the method comprises the following steps: and step A, the Ti matrix is 1cm multiplied by 2 cm.
3. The method for preparing the manganese dioxide asymmetric capacitor positive electrode composite material as claimed in claim 1, wherein the method comprises the following steps: step A, the alkali liquor is NaOH, KOH and NaCO3One or more of (a).
4. The method for preparing the manganese dioxide asymmetric capacitor positive electrode composite material as claimed in claim 1, wherein the method comprises the following steps: in the step A, the acid is HCl or H2SO4、HNO3One or more of (a).
5. The method for preparing the manganese dioxide asymmetric capacitor positive electrode composite material as claimed in claim 1, wherein the method comprises the following steps: step B2, the cobalt salt is CoCl2、Co(NO3)2、CoSO4One or more of (a).
6. The method for preparing the manganese dioxide asymmetric capacitor positive electrode composite material as claimed in claim 1, wherein the method comprises the following steps: step C1, the manganese salt is Mn (NO)3)2、MnSO4、MnCl2One or more of (a).
7. The method for preparing the manganese dioxide asymmetric capacitor positive electrode composite material as claimed in claim 1, wherein the method comprises the following steps: step C1, the strong acid is HNO3、HCl、H2SO4One or more of (a).
8. The method for preparing the manganese dioxide asymmetric capacitor positive electrode composite material as claimed in claim 1, wherein the method comprises the following steps: and step C2, the constant current deposition current density is 5-20mA/cm < 2 >, the deposition time is 0.5-3h, and the deposition temperature is room temperature.
9. The method for preparing the manganese dioxide asymmetric capacitor positive electrode composite material as claimed in claim 8, wherein the method comprises the following steps: the current density of the constant current deposition is 15mA/cm < 2 >, and the deposition time is 1 h.
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