CN109979758A - High-performance supercapacitor electrode material and preparation method thereof - Google Patents

High-performance supercapacitor electrode material and preparation method thereof Download PDF

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Publication number
CN109979758A
CN109979758A CN201910155297.1A CN201910155297A CN109979758A CN 109979758 A CN109979758 A CN 109979758A CN 201910155297 A CN201910155297 A CN 201910155297A CN 109979758 A CN109979758 A CN 109979758A
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mof
preparation
capacitor
electrode material
nitrae
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房贞兰
徐宜秀
鞠强
赵丽娜
刘美丽
田云
徐文龙
黄维
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Nanjing Tech University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/46Metal oxides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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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)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention discloses a high-performance super capacitor electrode material and a preparation method thereof, wherein the high-performance super capacitor electrode material is Ni-MOF, Co-MOF and Ni-Co-MOF, and the three electrode materials are Ni (NO)3)2·6H2O or/and Co (NO)3)2·6H2O and 1, 4, 5, 8-naphthalene tetracarboxylic dianhydride are taken as raw materials and prepared by a low-temperature hydrothermal method. The invention has the advantages that: (1) ni and Co are used as raw materials, the storage capacity of the Ni and Co earth is rich, and the price is low; (2) the low-temperature hydrothermal method is adopted, the process is simple, the condition requirement is relatively loose, the cost is lower, and the repeatability is good; (3) prepared Ni-The MOF capacitance is high, and the novel electrode material has great potential for being applied to high-efficiency energy storage device materials; (4) the prepared Co-MOF has good capacitance cycling stability, the prepared Ni-Co-MOF has high capacitance and good capacitance cycling stability, and the two new electrode materials have great potential for being applied to sustainable and efficient energy storage device materials.

Description

High performance electrode material for super capacitor and preparation method thereof
Technical field
The present invention relates to a kind of electrode materials and preparation method thereof, and in particular to a kind of high performance electrode of super capacitor Material and preparation method thereof belongs to technical field of chemistry.
Background technique
With the exhaustion of fossil energy, the step of energy crisis increasingly closes on.To the urgent of the reliable and powerful energy Demand is greatly promoted the exploitation for sustainable and high-efficiency energy-storage device new material.
Supercapacitor (i.e. electrochemical capacitor) is most potential a kind of device for energy storage system, this master To be originated from that they are with good performance, such as energy density is higher, charge/discharge fast speed, service life cycle are longer. However, the energy density of supercapacitor is generally lower than the energy density of battery, therefore the energy density of supercapacitor is urgently Further development.
Classified according to energy storage mechanism, supercapacitor can be divided into the charge at from electrode/electrolyte interface point From double-layer capacitor (EDLC), or the Reversible redox reaction by being related to electrode material surface region stores electricity The pseudocapacitors of lotus.Compared with EDLC, pseudocapacitors usually have higher gravimetric capacitance and volumetric capacitance.Although transition metal The capacitative materials of the routine such as oxide and conducting polymer have been used for pseudocapacitors, but they still have higher cost, capacitor The disadvantages of cyclical stability is poor.
Metal-organic framework material (MOF) has been widely regarded as the strong candidate of supercapacitor, because it Be a kind of crystallization spongy material with significant surface area and adjustable aperture, and show further inorganic and organic knot The advantages of designability and accessibility that structure is constructed.However, the low conductivity of MOF and weak mechanical/chemical stability lead to electricity Rong Bugao and cycle performance are bad, limit their electrochemical applications.In order to solve these problems, many researchers utilize tool The organic molecule for having plane pi-conjugated constructs the novel MOF with unique texture, as the good of display high electrochemical performance Electrode material.Although however big pi-conjugated organic molecule can effectively improve conductivity, the lower oxidation of its density Reduction activation site unavoidably reduces gravimetric capacitance and volumetric capacitance.Small molecule can leave foot for redox active metal Enough spaces, but the disadvantage is that poorly conductive.Different from organic ligand, the metal ion of supercapacitor is normally limited to redox Active metal, usually first row transition metal (Fe, Co, Ni, Mn etc.), because they not only can effectively provide electrochemistry Activity, and element abundant is stored as the earth, it is low in cost.
Therefore, the conductivity and electrification of suitable pi-conjugated organic molecule and redox active coordination metal material are selected It learns stability and receives the extensive concern of people to prepare high performance supercapacitor elements material.
Summary of the invention
The purpose of the present invention is to provide capacitor is high or/and the electrode material for super capacitor of capacitor good cycling stability and Preparation method.
In order to achieve the above objectives, the present invention adopts the following technical scheme that:
The preparation method of high performance electrode material for super capacitor, which comprises the following steps:
Step1: at room temperature, by Ni (NO3)2·6H2O or/and Co (NO3)2·6H2O and Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic dianhydrides Mixing, obtains mixture;
Step2: said mixture is dissolved in N, the in the mixed solvent of N '-dimethylformamide, second alcohol and water stirs to get Uniformly mixed solution;
Step3: above-mentioned uniformly mixed solution is heated for 24 hours at 120 DEG C;
Step4: the solution after above-mentioned heat treatment is cooled to room temperature;
Step5: mother liquor is filtered, and obtained solid ethanol washing is multiple, and finally heated drying obtains powder.
Preparation method above-mentioned, which is characterized in that in Step1:
(1) Ni (NO is selected3)2·6H2When O, Ni (NO3)2·6H2The mass ratio of O and Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic dianhydrides is 2:1;
(2) Co (NO is selected3)2·6H2When O, Co (NO3)2·6H2The mass ratio of O and Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic dianhydrides is 2:1;
(3) Ni (NO is selected3)2·6H2O and Co (NO3)2·6H2When O, Ni (NO3)2·6H2O、Co(NO3)2·6H2O and 1, The mass ratio of 4,5,8- naphthalenetetracarbacidic acidic dianhydrides is 1:1:1.
Preparation method above-mentioned, which is characterized in that in Step2, the N of in the mixed solvent, N '-dimethylformamide, second The volume ratio of alcohol and water is 1:1:1.
Preparation method above-mentioned, which is characterized in that in Step4, solution is with 5 DEG C of h-1、10℃·h-1Or 15 DEG C of h-1 Rate it is cooling.
The invention has the beneficial effects that:
(1) using Ni and Co as raw material, Ni and Co earth storage capacity is abundant, cheap;
(2) hydrothermal reaction at low temperature is used, simple process, condition requirement is more relaxed, and cost is relatively low, reproducible;
(3) with Ni (NO3)2·6H2O and Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic dianhydrides are the super electricity of Ni base two dimension MOF made from raw material Container electrode material capacitor is high, and this new electrode material has the great potential applied to high-efficiency energy-storage device materials;
(4) with Co (NO3)2·6H2O and Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic dianhydrides are the super electricity of Co base two dimension MOF made from raw material Container electrode material capacitor good cycling stability, this new electrode material, which has, is applied to sustainable and high-efficiency energy-storage device material The great potential of material;
(5) with Ni (NO3)2·6H2O、Co(NO3)2·6H2O and Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic dianhydrides are Ni- made from raw material Co adulterate two dimension MOF electrode material for super capacitor capacitor height and capacitor good cycling stability (Ni-Co dopant material shows association Same effect balances capacitor and capacitor cyclical stability), this new electrode material, which has, is applied to sustainable and high-efficiency energy-storage The great potential of device materials.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of Ni-MOF, Co-MOF and Ni-Co-MOF;
Fig. 2 is the infrared absorption spectra of Ni-MOF, Co-MOF and Ni-Co-MOF;
Fig. 3 is the thermal multigraph of Ni-MOF, Co-MOF and Ni-Co-MOF;
Fig. 4 is the uv absorption spectra of Ni-MOF, Co-MOF and Ni-Co-MOF;
It is 5mV s that Fig. 5, which is Ni-MOF, Co-MOF and Ni-Co-MOF in sweep speed,-1CV curve graph;
Fig. 6 is Ni-MOF, Co-MOF and Ni-Co-MOF in identical current density (1Ag-1) under charging and discharging curve figure;
Fig. 7 is Ni-MOF, Co-MOF and Ni-Co-MOF in identical current density (10Ag-1) under circulation 5000 circle after Capacitor cyclical stability performance map;
Fig. 8 is Ni-MOF, Co-MOF and Ni-Co-MOF in identical current density (10Ag-1) under capacitor and capacitor follow Ring stability two-dimensional plot.
Specific embodiment
Specific introduce is made to the present invention below in conjunction with the drawings and specific embodiments.
Embodiment 1:Ni base two dimension MOF electrode material for super capacitor
Step1: at room temperature, 200mg Ni (NO is weighed3)2·6H2O and 100mg1,4,5,8- naphthalenetetracarbacidic acidic dianhydrides, by two Person's mixing, obtains mixture.
Step2: said mixture is added to equipped with by 5ml N, N '-dimethylformamide, 5ml ethyl alcohol and 5ml water group At mixed solvent 20ml autoclave in, stir 0.5h, obtain uniformly mixed solution.
Step3: above-mentioned uniformly mixed solution is heated for 24 hours at 120 DEG C.
Step4: by the solution after above-mentioned heat treatment with 15 DEG C of h-1Rate of temperature fall it is cooling, until being cooled to room temperature.
Step5: mother liquor is filtered, and obtained solid ethanol washing is multiple, and finally heated drying obtains powder, The powder is Ni base two dimension MOF electrode material for super capacitor, is denoted as Ni-MOF.
Embodiment 2:Co base two dimension MOF electrode material for super capacitor
Step1: at room temperature, 200mg Co (NO is weighed3)2·6H2O and 100mg1,4,5,8- naphthalenetetracarbacidic acidic dianhydrides, by two Person's mixing, obtains mixture.
Step2: said mixture is added to equipped with by 5ml N, N '-dimethylformamide, 5ml ethyl alcohol and 5ml water group At mixed solvent 20ml autoclave in, stir 0.5h, obtain uniformly mixed solution.
Step3: above-mentioned uniformly mixed solution is heated for 24 hours at 120 DEG C.
Step4: by the solution after above-mentioned heat treatment with 15 DEG C of h-1Rate of temperature fall it is cooling, until being cooled to room temperature.
Step5: mother liquor is filtered, and obtained solid ethanol washing is multiple, and finally heated drying obtains powder, The powder is Co base two dimension MOF electrode material for super capacitor, is denoted as Co-MOF.
Embodiment 3:Ni-Co adulterates two dimension MOF electrode material for super capacitor
Step1: at room temperature, 100mg Co (NO is weighed3)2·6H2O、100mgNi(NO3)2·6H2O and 100mg1,4,5, 8- naphthalenetetracarbacidic acidic dianhydride, three is mixed, mixture is obtained.
Step2: said mixture is added to equipped with by 5ml N, N '-dimethylformamide, 5ml ethyl alcohol and 5ml water group At mixed solvent 20ml autoclave in, stir 0.5h, obtain uniformly mixed solution.
Step3: above-mentioned uniformly mixed solution is heated for 24 hours at 120 DEG C.
Step4: by the solution after above-mentioned heat treatment with 15 DEG C of h-1Rate of temperature fall it is cooling, until being cooled to room temperature.
Step5: mother liquor is filtered, and obtained solid ethanol washing is multiple, and finally heated drying obtains powder, The powder is Ni-Co doping two dimension MOF electrode material for super capacitor, is denoted as Ni-Co-MOF.
In order to compare the performance of Ni-MOF, Co-MOF and Ni-Co-MOF, we using this three products as sample carried out with Under some dependence tests.
1, crystal structure
The X-ray diffractogram of Ni-MOF, Co-MOF and Ni-Co-MOF are as shown in Figure 1.
As seen from Figure 1: the X-ray diffraction spectrogram of Ni-MOF, Co-MOF and the Ni-Co-MOF measured at room temperature is very It coincide.
This explanation: synthesized Ni-MOF, Co-MOF and Ni-Co-MOF has good purity, without impurity.
2, infrared absorption spectrum
The infrared absorption spectra of Ni-MOF, Co-MOF and Ni-Co-MOF are as shown in Figure 2.
As seen from Figure 2: the peak FTIR of Ni-MOF, Co-MOF and Ni-Co-MOF are almost the same.
This further demonstrates that Ni-MOF, Co-MOF and Ni-Co-MOF are isostructural, i.e., structures having the same.
3, thermogravimetric changes
The thermal multigraph of Ni-MOF, Co-MOF and Ni-Co-MOF are as shown in Figure 3.
As seen from Figure 3: the weightlessness of Ni-MOF, Co-MOF and Ni-Co-MOF mainly by organic component 341~ Caused by being decomposed within the scope of 370 DEG C.
This explanation: Ni-MOF, Co-MOF and Ni-Co-MOF have good thermal stability, and three has in wider temperature Spend the value applied in range.
4, ultra-violet absorption spectrum
The uv absorption spectra of Ni-MOF, Co-MOF and Ni-Co-MOF are as shown in Figure 4.
As seen from Figure 4: the absorption peak of Ni-MOF, Co-MOF and Ni-Co-MOF are almost the same.
This further demonstrates that Ni-MOF, Co-MOF and Ni-Co-MOF are isostructural, i.e., structures having the same.
5, chemical property
Ni-MOF, Co-MOF and Ni-Co-MOF are 5mV s in sweep speed-1CV curve graph it is as shown in Figure 5.
As shown in Figure 5: Ni-MOF, Co-MOF and Ni-Co-MOF produce a pair of of redox peaks, this is because they Faraday's reaction has occurred in inside, and the capacitor for showing that measurement generates is mainly based upon redox mechanism.
Ni-MOF, Co-MOF and Ni-Co-MOF are in identical current density (1A g-1) under charging and discharging curve figure such as Fig. 6 It is shown.
As shown in Figure 6: the capacitor of the capacitor ﹥ Co-MOF of the capacitor > Ni-Co-MOF of Ni-MOF.
As it can be seen that Ni-MOF has the higher advantage of capacitor, there is the great potential applied to high-efficiency energy-storage device materials.
Ni-MOF, Co-MOF and Ni-Co-MOF are in identical current density (10A g-1) under circulation 5000 circle after capacitor Cyclical stability performance map is as shown in Figure 7.
As shown in Figure 7: after the circle of circulation 5000, the capacitor of capacity retention (97.5%) the ﹥ Ni-Co-MOF of Co-MOF is protected The capacity retention (36.6%) of holdup (80.6%) ﹥ Ni-MOF, i.e. the capacitor cyclical stability ﹥ Ni-Co-MOF's of Co-MOF The capacitor cyclical stability of capacitor cyclical stability ﹥ Ni-MOF.
As it can be seen that Co-MOF has the advantages that capacitor cyclical stability is preferable, has and be applied to sustainable and high-efficiency energy-storage dress The great potential of material is set,
Ni-MOF, Co-MOF and Ni-Co-MOF are in identical current density (10A g-1) under capacitor and capacitor circulation it is steady Qualitative two-dimensional plot is as shown in Figure 8.
As shown in Figure 8: the capacitor cyclical stability of Co-MOF is best, but capacitor is minimum;Ni-MOF capacitor highest, but capacitor Cyclical stability is worst;The capacitor of Ni-Co-MOF is higher and capacitor cyclical stability is preferable.
As it can be seen that Ni-Co-MOF has optimal chemical property, has and be applied to sustainable and high-efficiency energy-storage device materials Great potential.
By Ni-MOF, Co-MOF and Ni-Co-MOF measurement result we can also be seen that:
(1) capacitor of MOF material and capacitor cyclical stability are related with its metal oxidation reduction activated centre;
(2) doping counterpart still maintains parent crystal topological structure, but doping shows synergistic effect with balancing capacitance With capacitor cyclical stability.
In conclusion being had using Ni-MOF, Co-MOF and Ni-Co-MOF that preparation method of the invention is prepared excellent Different capacitor and fairly good capacitor cyclical stability have and are applied to the huge latent of high-performance super capacitor electrode material Power.
It should be noted that the above embodiments do not limit the invention in any form, it is all to use equivalent replacement or equivalent change The mode changed technical solution obtained, falls within the scope of protection of the present invention.

Claims (5)

1. the preparation method of high performance electrode material for super capacitor, which comprises the following steps:
Step1: at room temperature, by Ni (NO3)2·6H2O or/and Co (NO3)2·6H2O and Isosorbide-5-Nitrae, the mixing of 5,8- naphthalenetetracarbacidic acidic dianhydrides, Obtain mixture;
Step2: said mixture is dissolved in N, the in the mixed solvent of N '-dimethylformamide, second alcohol and water stirs to get mixing Uniform solution;
Step3: above-mentioned uniformly mixed solution is heated for 24 hours at 120 DEG C;
Step4: the solution after above-mentioned heat treatment is cooled to room temperature;
Step5: mother liquor is filtered, and obtained solid ethanol washing is multiple, and finally heated drying obtains powder.
2. preparation method according to claim 1, which is characterized in that in Step1:
(1) Ni (NO is selected3)2·6H2When O, Ni (NO3)2·6H2O and Isosorbide-5-Nitrae, the mass ratio of 5,8- naphthalenetetracarbacidic acidic dianhydrides are 2:1;
(2) Co (NO is selected3)2·6H2When O, Co (NO3)2·6H2O and Isosorbide-5-Nitrae, the mass ratio of 5,8- naphthalenetetracarbacidic acidic dianhydrides are 2:1;
(3) Ni (NO is selected3)2·6H2O and Co (NO3)2·6H2When O, Ni (NO3)2·6H2O、Co(NO3)2·6H2O and Isosorbide-5-Nitrae, 5, The mass ratio of 8- naphthalenetetracarbacidic acidic dianhydride is 1:1:1.
3. preparation method according to claim 1, which is characterized in that in Step2, the N of in the mixed solvent, N '-diformazan Base formamide, second alcohol and water volume ratio be 1:1:1.
4. preparation method according to claim 1, which is characterized in that in Step4, solution is with 5 DEG C of h-1、10℃·h-1 Or 15 DEG C of h-1Rate it is cooling.
5. the high performance electrode of super capacitor material that the preparation method as described in Claims 1-4 any one is prepared Material.
CN201910155297.1A 2019-03-01 2019-03-01 High-performance supercapacitor electrode material and preparation method thereof Pending CN109979758A (en)

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Publication number Priority date Publication date Assignee Title
CN111921529A (en) * 2020-08-18 2020-11-13 三峡大学 Preparation method and application of nickel-cobalt metal organic framework/nickel-cobalt metal hydroxide heterogeneous material
CN115043391A (en) * 2022-05-27 2022-09-13 合肥学院 MOF-derived two-dimensional microporous carbon nanosheet material and preparation method thereof

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CN109267153A (en) * 2018-08-30 2019-01-25 济南大学 A kind of four acid anhydrides Ni-MOF crystalline material of naphthalene and its preparation method and application
CN109320728A (en) * 2018-08-30 2019-02-12 济南大学 A kind of Co-MOF crystal fibre material and its preparation method and application

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CN103151180A (en) * 2013-03-21 2013-06-12 兰州理工大学 Organic high-polymer super capacitor electrode material and preparation method thereof
CN103985562A (en) * 2014-06-11 2014-08-13 福州大学 Preparation method of super-capacitor electrode material
CN104992848A (en) * 2015-06-30 2015-10-21 中国地质大学(武汉) Binary metal organic framework material applied to super capacitor and preparation method for binary metal organic framework material
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Publication number Priority date Publication date Assignee Title
CN111921529A (en) * 2020-08-18 2020-11-13 三峡大学 Preparation method and application of nickel-cobalt metal organic framework/nickel-cobalt metal hydroxide heterogeneous material
CN111921529B (en) * 2020-08-18 2022-03-04 三峡大学 Preparation method and application of nickel-cobalt metal organic framework/nickel-cobalt metal hydroxide heterogeneous material
CN115043391A (en) * 2022-05-27 2022-09-13 合肥学院 MOF-derived two-dimensional microporous carbon nanosheet material and preparation method thereof

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Application publication date: 20190705