CN112768257A - Nickel-cobalt oxide flexible electrode and preparation method and application thereof - Google Patents
Nickel-cobalt oxide flexible electrode and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000004917 carbon fiber Substances 0.000 claims abstract description 73
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 72
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 72
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 61
- 239000008103 glucose Substances 0.000 claims abstract description 61
- 239000004744 fabric Substances 0.000 claims abstract description 59
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000005520 cutting process Methods 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 6
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 6
- 239000004753 textile Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 18
- 238000005452 bending Methods 0.000 description 16
- 229910044991 metal oxide Inorganic materials 0.000 description 10
- 150000004706 metal oxides Chemical class 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000004146 energy storage Methods 0.000 description 6
- 238000013112 stability test Methods 0.000 description 6
- 241000282414 Homo sapiens Species 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000010408 sweeping Methods 0.000 description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910015189 FeOx Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012933 kinetic analysis Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- 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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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
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Abstract
The invention discloses a nickel-cobalt oxide flexible electrode and a preparation method and application thereof, and belongs to the field of self-powered sensing systems. The preparation method of the nickel-cobalt oxide flexible electrode comprises the following steps: (1) cutting the carbon fiber cloth into rectangular strips with a certain size, and cleaning the surface of the carbon fiber cloth; (2) preparing hydrophilic carbon fiber cloth CF of a flexible substrate; (3) CF @ NiCo-precursPreparing an or flexible electrode; (4) nickel-cobalt oxide flexible electrode CF @ NiCoO2Preparation of @ N-C. And provides an application of the supercapacitor based on the nickel-cobalt oxide flexible electrode and the wearable glucose sensor. The invention is based on CF @ NiCoO2The process for preparing the supercapacitor and the glucose sensor by using the @ N-C is simple, excellent in performance and low in cost, and has high economic benefit.
Description
Technical Field
The invention relates to a nickel-cobalt oxide flexible electrode and a preparation method and application thereof, belonging to the field of self-powered sensing systems.
Background
With the increasing of human living standard year by year and the continuous development of information technology, the general attention of society caused by human health problems to know real-time physical state in time becomes the urgent need of people[1-3]. Different from the traditional medical treatment mode, the wearable technology has the characteristics of portability, remote monitoring and real-time monitoring, gradually changes the medical diagnosis mode, and provides a way for people to quickly master various health data in real time[4-5]。
Under the urgent needs of human beings nowadays, the future electronic equipment must be twistable and deformable, and the electronic equipment will be applied to the fields which cannot be related to the rigid electronic equipment at present[6-8]. The demand for flexible, lightweight, high safety energy storage devices has also increased substantially. The design and manufacture of electrochemical energy storage systems with high flexibility, high energy and power density dominate most rechargeable energy storage markets today. Conventional lithium ion-based batteries (LIBs) suffer from the disadvantage of being bulky, rigid, and therefore unsuitable for portable/wearable electronics. Furthermore, the heat generated by lithium ion batteries can affect human skin, limiting their use in wearable devices. In the field of electrochemical energy storage, supercapacitors are one of the promising energy storages due to their fast charge/dischargeThe electric capacity and long cycle life have attracted great interest in academic and industrial fields[7-9]. Furthermore, the advent of all-solid-state supercapacitors easily meets the demands for flexibility and various deformations (e.g., bending and twisting) as wearable electronics. Energy storage performance is also a key factor affecting the use of wearable electronics. Supercapacitors have a different mechanism than conventional capacitors and therefore have an energy density that far exceeds that of conventional capacitors. Conventional secondary batteries, such as lithium ion batteries, store energy based on intercalation and deintercalation of lithium ions, and have relatively low capacity at high current density, so that flexible supercapacitors with higher power density have become a focus of attention of researchers[10-14]。
The flexible super capacitor has the advantages of good mechanical flexibility, high power density, long cycle life, high charging and discharging speed, light weight, small volume, high safety, diversified electrode material and device structures and the like, and basically meets the requirements of small flexible electronic products. However, compared with a flexible lithium ion battery, the energy density of the flexible supercapacitor is too low, the voltage window is small, and the large-scale popularization and use of the flexible supercapacitor are limited, and the electrochemical performance of the flexible supercapacitor is mainly determined by a flexible electrode. Therefore, it is important to design and develop a flexible electrode having high performance.
Metal oxides, such as ruthenium oxide (RuOx), manganese oxide (MnOx), nickel oxide (NiOx), cobalt oxide (CoOx), iron oxide (FeOx) and titanium oxide (TiO)2) And the like exhibit higher energy density in supercapacitors than conventional carbon materials. Meanwhile, the metal oxide-based enzyme-free glucose sensor has lower cost and better stability than an electrochemical enzyme glucose sensor, can adapt to wider application environment, and is an enzyme-free glucose sensor electrode material with application prospect[10,15]. However, most metal oxides belong to semiconductors or insulators, and the low conductivity of the metal oxides limits the application of single metal oxides in the electrochemical field.
The ions in the bimetallic oxide have multiple valence states, can participate in the faradaic reaction, and have better conductivity than the single metal oxide. The synthesis method, the element composition and the proportion of the bimetal oxide are reasonably designed and constructed, and the advantages of two single metal oxides can be expected to be exerted simultaneously. And a flexible conductive substrate with a high specific surface area is further compounded with the bimetallic oxide, so that the material has flexibility while the integral conductivity and the active area of the electrode are improved, and the creation and controllable construction of the flexible metal oxide-based enzyme-free sensor electrode material with high power density, high energy density, high stability and high glucose detection capability can be expected.
(1)Kim J.,Campbell A.S.,de Avila B.E.F.,et al.Wearable biosensors for healthcare monitoring[J].Nature Biotechnology,2019,37(4):389-406.
(2)Sun P.,Qiu M.,Li M.,et al.Stretchable Ni@NiCoP textile for wearable energy storage clothes[J].Nano Energy,2019,55:506-515.
(3)N.Zhu,S.Han,S.Gan,J.Ulstrup,Q.Chi,Adv.Funct.Mater.2013,23,5297.
(4)Ma J.,Jiang Y.,Shen L.,et al.Wearable biomolecule smartsensors based on one-step fabricated berlin green printed arrays[J].Biosens Bioelectron,2019,144:111637.
(5)Sun T.,Shen L.,Jiang Y.,et al.Wearable Textile Supercapacitors for Self-Powered Enzyme-Free Smartsensors[J].ACS Appl Mater Interfaces,2020,12(19):21779-21787.
(6)Shen L.,Du L.,Tan S.,et al.Flexible electrochromic supercapacitor hybrid electrodes based on tungsten oxide films and silver nanowires[J].Chem Commun(Camb),2016,52(37):6296-6299.
(7)Liao Q.,Li N.,Jin S.,et al.All-Solid-State Symmetric Supercapacitor Based on Co3O4 Nanoparticles on Vertically Aligned Graphene[J].ACS Nano,2015,9(5):5310-5317.
(8)Cheng M.,Duan S.,Fan H.,et al.Core@shell CoO@Co3O4 nanocrystals assembling mesoporous microspheres for high performance asymmetric supercapacitors[J].Chemical Engineering Journal,2017,327:100-108.
(9)Qian Y.,Liu R.,Wang Q.,et al.Efficient synthesis of hierarchical NiO nanosheets for high-performance flexible all-solid-state supercapacitors[J].J.Mater.Chem.A,2014,2(28):10917-10922.
(10)Ding Y.,Wang Y.,Su L.,et al.Electrospun Co3O4 nanofibers for sensitive and selective glucose detection[J].Biosens Bioelectron,2010,26(2):542-548.
(11)Wang J.Electrochemical glucose biosensors[J].Chem Rev,2008,108(2):814-825.
(12)Xu Y.,Wei J.,Tan L.,et al.A Facile approach to NiCoO2 intimately standing on nitrogen doped graphene sheets by one-step hydrothermal synthesis for supercapacitors[J].Journal of Materials Chemistry A,2015,3(13):7121-7131.
(13)Manjakkal L.,
C.G.,Dang W.,et al.Flexible self-charging supercapacitor based on graphene-Ag-3D graphene foam electrodes[J].Nano Energy,2018,51:604-612.
(14)Luo W.,Li F.,Gaumet J.-J.,et al.Bottom-Up Confined Synthesis of Nanorod-in-Nanotube Structured Sb@N-C for Durable Lithium and Sodium Storage[J].Advanced Energy Materials,2018,8(19).
(15)Zhang Q.,Liang Q.,Zhang Z.,et al.Electromagnetic Shielding Hybrid Nanogenerator for Health Monitoring and Protection[J].Advanced Functional Materials,2018,28(1).
Disclosure of Invention
A material with excellent electrochemical performance and good flexibility is obtained by a simple and efficient preparation method and is applied to the field of wearable energy storage and sensing. Through the research of the application, a self-powered sensing system integrating energy storage and sensing is expected to be constructed on the fabric, and the self-powered sensing system is applied to the field of human health monitoring on a large scale.
The invention provides a preparation method of a nickel-cobalt oxide flexible electrode, which comprises the following steps:
(1) cutting the carbon fiber cloth into rectangular strips with a certain size, and cleaning the surface of the carbon fiber cloth;
(2) preparing hydrophilic carbon fiber cloth CF of a flexible substrate: treating the cleaned carbon fiber cloth in concentrated nitric acid for 8-12h at 60-90 ℃, taking out, cleaning again, and drying in a drying oven at 60-100 ℃ for 8-14 h;
(3) preparing a CF @ NiCo-precursor flexible electrode: in a three-electrode system, a hydrophilic carbon fiber cloth CF with a flexible substrate is used as a working electrode, 25-40mL of mixed solution of cobalt chloride and nickel nitrate is added into an electrolytic bath, and the immersed area of the carbon fiber cloth CF is 1-2cm2(ii) a Taking a saturated calomel electrode SCE as a reference electrode and a platinum sheet as a counter electrode, and carrying out constant potential deposition for 80-100s under the voltage of-1 to-1.5V relative to the SCE electrode; after the constant potential deposition is finished, taking out the carbon fiber cloth CF, cleaning the carbon fiber cloth CF by deionized water, and drying the carbon fiber cloth CF in a drying oven at the temperature of 60-100 ℃ for 8-14 h;
(4) nickel-cobalt oxide flexible electrode CF @ NiCoO2Preparation of @ N-C: preparing 0.1-0.3M Na2HPO40.1-0.2M pyrrole and 0-0.1M NaClO4In a three-electrode system, a CF @ NiCo-precursor flexible electrode is taken as a working electrode, 25-40mL of mixed electroplating solution is added into an electrolytic tank, and the immersed area of the CF @ NiCo-precursor flexible electrode is ensured to be 1-2cm2(ii) a Taking a saturated calomel electrode SCE as a reference electrode, taking a platinum sheet as a counter electrode, and carrying out constant potential deposition for 30-50s at a potential of 0.9-1.1V relative to the SCE electrode; and after the constant potential deposition is finished, taking out the CF @ NiCo-precursor flexible electrode, cleaning the CF @ NiCo-precursor flexible electrode by using deionized water, drying the CF @ NiCo-precursor flexible electrode in an oven at the temperature of 60-100 ℃ for 8-14h, and then placing the CF @ NiCo-precursor flexible electrode in a tube furnace to treat the CF @ NiCo-precursor flexible electrode for 1-2h at the temperature of 450-600.
Further, in the technical scheme, the carbon fiber cloth in the step (1) is cut into 1-3cm2A rectangular strip of (a); the method for cleaning the surface of the carbon fiber cloth comprises the following steps: and (3) carrying out ultrasonic treatment on the carbon fiber cloth in deionized water, ethanol and propanol for 15-30min in sequence.
Further, in the above technical solution, the preparation method of the mixed solution of cobalt chloride and nickel nitrate in step (3) is: 10-20g of CoCl2·6H2O and 10-20g of Ni (NO)3)2·6H2O additiveAdding the mixture into deionized water, and fixing the volume by using a 500mL volumetric flask to obtain a mixed solution of cobalt chloride and nickel nitrate.
The invention also provides the nickel-cobalt oxide flexible electrode prepared by the preparation method.
The invention also provides application of the nickel-cobalt oxide flexible electrode in preparation of a flexible solid-state supercapacitor.
Further, in the above technical scheme, the flexible solid-state supercapacitor takes a nickel-cobalt oxide flexible electrode as a positive electrode, nitrogen-doped carbon of carbon fiber as a negative electrode, and PVA/KOH as an electrolyte.
Further, in the above technical scheme, the preparation method of the nitrogen-doped carbon of the carbon fiber comprises the following steps: configuring 0.1-0.3M Na2HPO40.1-0.2M pyrrole with 0-0.1M NaClO4In a three-electrode system, a saturated calomel electrode SCE is used as a reference electrode, a platinum sheet is used as a counter electrode, a hydrophilic carbon fiber cloth CF is used as a working electrode, 25-40mL of mixed electroplating solution is added into an electrolytic tank, and the immersed area of the hydrophilic carbon fiber cloth CF is 1-2cm2(ii) a Constant potential deposition is carried out for 1.5-2h at a potential of 0.9-1.1V relative to the SCE electrode; and taking out the carbon fiber cloth CF after the constant potential deposition is finished, washing the carbon fiber cloth CF by deionized water, drying the carbon fiber cloth CF in an oven at the temperature of 60-100 ℃ for 8-14h, and then placing the carbon fiber cloth CF into a tube furnace to be treated at the temperature of 450-600 ℃ for 1-2h under the argon atmosphere to obtain the nitrogen-doped carbon of the carbon fiber.
The invention also provides application of the nickel-cobalt oxide flexible electrode in preparation of a wearable glucose sensor.
Further, in the technical scheme, a nickel-cobalt oxide flexible electrode is used as a working electrode, a conductive silver paste coated carbon fiber is used as a reference electrode, and a carbon fiber cloth CF is used as a counter electrode, so that the wearable glucose sensor is assembled; the assembled wearable glucose sensor can be woven and integrated on a textile for use, wherein the textile comprises a head band and clothes.
Further, in the above technical scheme, the preparation method of the carbon fiber coated with the conductive silver paste comprises the following steps: coating the surface of the cleaned carbon fiber to a thickness of 1-2cm2Drying the silver paste in an oven at 60-80 DEG CCuring for 1.5-2h, and drying to obtain reference electrode.
The nickel-cobalt oxide of the invention is used as a multi-metal mixed oxide, and the electric conductivity and the redox activity of the nickel-cobalt oxide are far higher than those of nickel oxide or cobalt oxide due to the coexistence of nickel and cobalt.
The glucose sensor based on the metal oxide has the advantages of good stability, low cost, simple and convenient preparation process and the like. In the detection process, the metal oxide and the glucose are subjected to redox reaction, and the glucose concentration is detected by detecting the magnitude of corresponding current. Such enzyme-free glucose sensors have more stable properties and simpler manufacturing procedures.
Advantageous effects of the invention
1. CF @ NiCoO based on carbon fiber2The preparation method of the @ N-C flexible electrode can develop a general preparation mode of the flexible electrode with the active substance. Based on CF @ NiCoO2The process for preparing the supercapacitor and the glucose sensor by using the @ N-C is simple, excellent in performance and low in cost, and has high economic benefit.
2. The flexible solid-state supercapacitor obtained based on the manufacturing process shows excellent cycle stability and rate performance, and has no obvious influence on the performance after being bent for many times when being used as a wearable electronic device.
3. The prepared glucose sensor shows excellent sensing performance and has higher sensitivity.
Drawings
FIG. 1 is a drawing showing CF @ NiCoO in example 12The preparation schematic diagram (a) of the @ N-C flexible electrode, and performance graphs of cyclic voltammetry test (b), constant current charge and discharge test (C) and cyclic stability test (d).
FIG. 2 is a representation of CF @ NiCoO in example 12Kinetic analysis of @ N-C Flexible electrode, in which CF @ NiCoO2B value (a), 1mV s of @ N-C at different potentials-1CF @ NiCoO at sweeping speed2Capacitive contribution current comparison plot (b), 2mV s of @ N-C-1CF @ NiCoO at sweeping speed2Capacitive contribution current comparison plot (C) of @ N-C, CF @ NiCoO at different sweep speeds2The capacitive contribution of @ N-C accounts for histogram (d).
Fig. 3 is a performance graph of cyclic voltammetry test (a), constant current charge and discharge test (b), electrochemical impedance test (c) and cyclic stability test (d) of the flexible solid-state supercapacitor in example 2.
Fig. 4 is performance test graphs of the flexible solid-state supercapacitor in different bending states and performance stability test graphs after bending for multiple times in example 2, where in the flexible solid-state supercapacitor in a bending state (a), the cyclic voltammogram of the flexible solid-state supercapacitor in different deformation states (bending, twisting, and normal) (b), the capacitance retention rate of the flexible solid-state supercapacitor during 10000 times of bending (c), and the cyclic voltammogram of the flexible solid-state supercapacitor after bending for 0 times, 5000 times, and 10000 times (d).
FIG. 5 is a graph of cyclic voltammetry and time-current curves based on CF @ NiCoO for a glucose sensor at different glucose concentrations in example 32@ N-C glucose sensor at 20mV s-1Cyclic voltammograms (a) without glucose (black curve) and with 5mM glucose (red curve) at sweep rate, glucose sensors at 20mV s-1The cyclic voltammogram (b) at sweep rate was added 1mM glucose at a time in the range of 0-7mM, the glucose sensor corresponding to the i-t curve for 0mM to 7mM glucose in 1mM (c), linear relationship (d) for the glucose sensors collected at 150 s.
FIG. 6 shows the cyclic voltammogram of the wearable glucose sensor in example 4 at different glucose concentrations (a), the current-time curve of the glucose sensor (in the concentration range of 0-7 mM) (b), and the linear relationship of the glucose concentration at 200 seconds (c).
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
Example 1
Cutting carbon fiber cloth into 2cm2The rectangular strips were sequentially subjected to ultrasonic treatment in deionized water, ethanol and propanol for 15min to clean the surface of the carbon fiber cloth. Treating the cleaned carbon fiber cloth in concentrated nitric acid at the temperature of 80 ℃ for 12 hours, and taking outThen sequentially carrying out ultrasonic treatment in deionized water, ethanol and propanol for 15min for cleaning treatment, and drying in a 60 ℃ oven for 12h to obtain the hydrophilic carbon fiber Cloth (CF) serving as the flexible substrate.
Preparing an aqueous solution of cobalt chloride and nickel nitrate, and adding 15g of CoCl2·6H2O and 18g of Ni (NO)3)2·6H2O was added to deionized water and made to volume with a 500mL volumetric flask. In a three-electrode system, carbon fiber Cloth (CF) is used as a working electrode, 25mL of prepared mixed solution of cobalt chloride and nickel nitrate is added into an electrolytic bath, and the immersion area of the carbon fiber cloth is ensured to be 1-2cm2. Saturated Calomel Electrode (SCE) is used as reference electrode, Pt sheet is used as counter electrode, and constant potential deposition is carried out for 100s under the voltage of-1V relative to SCE electrode. And after the constant potential deposition is finished, taking out the carbon fiber cloth, cleaning the carbon fiber cloth by using deionized water, and drying the carbon fiber cloth in an oven at 60 ℃ overnight to obtain the CF @ NiCo-precursor flexible electrode.
Configuring 0.1-0.3M Na2HPO40.1-0.2M pyrrole with 0-0.1M NaClO4The mixed plating solution of (1). In a three-electrode system, a CF @ NiCo-precursor flexible electrode is used as a working electrode, 25mL of prepared electroplating solution is added into an electrolytic tank, and the immersed area of the CF @ NiCo-precursor flexible electrode is ensured to be 1-2cm2. Saturated Calomel Electrode (SCE) was used as a reference electrode and a platinum plate as a counter electrode, and potentiostatic deposition was performed for 50s at a potential of 0.9V relative to the SCE electrode. After the potentiostatic deposition was completed, the CF @ NiCo-precursor flexible electrode was taken out, washed with deionized water, and dried in an oven at 60 ℃ overnight. The dried sample is put into a tube furnace to be processed for 2 hours at 450 ℃ in the argon atmosphere to obtain the target material CF @ NiCoO2@ N-C. Electrochemical performance tests were performed in 1M KOH solutions.
As shown in FIG. 1, FIG. 1(a) is CF @ NiCoO in example 12Schematic diagram of the preparation of @ N-C flexible electrode. Meanwhile, the performance of the electrode was analyzed by cyclic voltammetry in fig. 1(b) and constant current charge and discharge in fig. 1(c), and the charge and discharge curves in the graph show better capacitance and excellent rate performance. The cycling stability test in figure 1(d) that follows also demonstrates its excellent stability. Further counter electrodeKinetic Process analysis, FIG. 2(a) shows CF @ NiCoO2@ N-C b values at different potentials. The received b value was 0.7 at a peak potential of 0.35V, indicating that the potential is mainly diffusion-controlled. Meanwhile, at potentials higher or lower than 0.35V, the b value is in the range of 0.8-1.0, indicating mainly capacitive control. Further studies were used to quantitatively distinguish capacitance contributions at various CV curve scan rates. FIG. 2(b) is 1mV s-1CF @ NiCoO at sweeping speed2Graph comparing the capacitive contribution current of @ N-C, FIG. 2(C) is 2mV s-1CF @ NiCoO at sweeping speed2The capacitance of @ N-C contributes to the current contrast plot. FIG. 2(d) is a CF @ NiCoO at different sweep rates2The capacitive contribution of @ N-C is proportional to the histogram. It can be seen intuitively that as the scan rate is increased from 1mV s-1Increase to 50mV s-1The capacitance contribution increases with increasing scan rate, indicating that the surface capacitance process dominates the electrochemical reaction at high scan rates. The CF @ NiCoO is well explained by analyzing its redox process using surface control and diffusion control2The reason why the @ N-C material has excellent rate capability.
Example 2
The carbon fiber cloth was treated in the same manner as described in example 1 to obtain hydrophilic carbon fiber Cloth (CF) as a flexible substrate.
Configuration 0.2M Na2HPO40.1M pyrrole with 0.05M NaClO4In a three-electrode system, a Saturated Calomel Electrode (SCE) is used as a reference electrode, a Pt sheet is used as a counter electrode, hydrophilic carbon fiber cloth is used as a working electrode, 25mL of prepared electroplating solution is added into an electrolytic tank, and the immersion area of the hydrophilic carbon fiber cloth is ensured to be 1-2cm2. Potentiostatic deposition was carried out for 1.5h at a potential of 0.9V relative to the SCE electrode. And taking out the carbon fiber cloth after the constant potential deposition is finished, washing the carbon fiber cloth by deionized water, and drying the carbon fiber cloth in an oven at 60 ℃ overnight. And (3) putting the dried sample into a tubular furnace, and treating for 2h at 450 ℃ in an argon atmosphere to obtain a target material CF @ N-C serving as a cathode material of the super capacitor. CF @ NiCoO prepared as in example 12@ N-C as the positive electrode of a supercapacitor, CF @ N-C prepared in example 2 as the negative electrode material of a supercapacitor, the electrode was immersed in PVAnd taking out the A/KOH solid electrolyte after the A/KOH solid electrolyte is fully soaked, and assembling the two electrodes into a complete flexible solid asymmetric supercapacitor in a right-facing way.
FIG. 3(a) is a cyclic voltammetry test chart of the solid-state supercapacitor in example 2, wherein the cyclic voltammetry curve area increases with the increase of the scan rate, and the scan rate is 100mV s-1In the process, the shape of the cyclic voltammetry curve does not show great change, and no obvious polarization phenomenon exists. Fig. 3(b) is a constant current charge and discharge test chart of the solid-state supercapacitor at different current densities, and the device is subjected to constant current charge and discharge tests at different current densities to obtain substantially symmetrical charge and discharge curves. Fig. 3(c) is an electrochemical impedance test chart of the solid-state supercapacitor, and the intersection point of the nyquist curve and the X-axis, namely, the Equivalent Series Resistance (ESR), is only 3.1 Ω, which indicates that ions between the active material and the electrolyte can be rapidly transferred. Fig. 3(d) is a cycle stability test chart of the solid-state supercapacitor, showing excellent cycle stability and capacity retention rate.
Fig. 4 is a performance test chart of the flexible solid-state supercapacitor in example 2 in different bending states and a performance stability test chart after multiple bending. Wherein (a) is the flexible solid-state supercapacitor in a bending state, and the prepared device has excellent flexibility and the bending does not cause irreversible damage to the device. (b) For cyclic voltammograms of the flexible solid-state supercapacitor in different deformation states (bending, twisting and normal), it can be observed that cyclic voltammograms do not change greatly in different states, which indicates that the cyclic voltammograms do not have obvious influence on the performance of the device in different bending states. (c) The capacitance retention rate of the flexible solid-state supercapacitor during 10000 times of bending is shown in the figure, after 10000 times of bending, the device still maintains 95% of specific capacitance, and the result shows that the prepared device has excellent flexibility and stability after bending. (d) The cyclic voltammograms of the flexible solid-state supercapacitor after being bent for 0 time, 5000 times and 10000 times further prove the intentional mechanical stability of the device, and show the application prospect of the device in intelligent wearable electronic equipment.
Example 3
To prepare the prepared CF @ NiCoO2The glucose sensor is based on the @ N-C flexible electrode and utilizes a traditional three-electrode system. The glucose sensor is based on prepared CF @ NiCoO2The @ N-C flexible electrode was a Working Electrode (WE), the Pt sheet was a Counter Electrode (CE), and the Hg/HgO electrode was a Reference Electrode (RE), and the samples were placed in a 25mL electrolytic cell, 10mL of a 1M KOH solution was added as an electrolyte, and glucose (0mM, 1mM, 2mM, 3mM, 4mM, 5mM, 6mM, and 7mM) was measured at different concentrations. The results of the experiment are shown in FIG. 5.
FIG. 5(a) is CF @ NiCoO2@ N-C glucose sensor at 20mV s-1The cyclic voltammograms at sweep rate with no glucose (black curve) and with 5mM glucose (red curve) show a significant redox reaction with glucose from 0.4V (vs. Hg/Hgo) compared to 0mM glucose in the presence of 5mM glucose. FIG. 5(b) shows the glucose sensor at 20mV s-1The electrocatalytic current increases proportionally in the CV curve as the glucose concentration increases proportionally with each 1mM glucose addition in the 0-7mM range at sweep rate. FIG. 5(c) is a graph of current versus time for a glucose sensor corresponding to 0mM to 7mM glucose, with an increase of 1mM, with the current tending to increase with increasing glucose concentration. FIG. 5(d) is a linear relationship of the glucose sensor collected under 150s, which shows that the glucose sensor has excellent linear relationship and sensitivity, and has practical application value.
Example 4
To prepare the prepared CF @ NiCoO2And constructing a wearable glucose sensor based on the @ N-C flexible electrode. The wearable glucose sensor consists of a three-electrode system, and textile of common clothes is selected as a flexible substrate of the three electrodes. The prepared CF @ NiCoO of example 12Cutting the flexible electrode at a thickness of 1-2cm2The rectangle of (a) serves as the working electrode of the glucose sensor. The carbon fiber after washing (the washing method was the same as that of the carbon fiber cloth in example 1) was cut into 1-2cm2Is coated with 1-2cm of2The silver paste is put into a 60 ℃ oven for drying and curing for 2h, and the silver paste is used as a reference electrode after drying. Carbon fiber after cleaningCutting into 1-2cm pieces2As a counter electrode to build a wearable glucose sensor. The constructed wearable glucose sensor can be woven and integrated on textiles such as a headband, clothes and the like. Glucose (0mM, 1mM, 2mM, 3mM, 4mM, 5mM, 6mM, 7mM) was detected at various concentrations using a 1M KOH solution as an electrolyte. The results of the experiment are shown in FIG. 6.
Fig. 6(a) is a cyclic voltammogram of a wearable glucose sensor at different glucose concentrations showing a pair of distinct redox peaks. FIG. 6(b) is a current-time curve (in the concentration range of 0-7 mM) of a glucose sensor, the current increasing with increasing glucose concentration. FIG. 6(c) is a linear relationship of different glucose concentrations at 200 seconds, which visually shows that the glucose sensor has excellent linear relationship and sensitivity, and has practical application value.
Claims (10)
1. The preparation method of the nickel-cobalt oxide flexible electrode is characterized by comprising the following steps of:
(1) cutting the carbon fiber cloth into rectangular strips with a certain size, and cleaning the surface of the carbon fiber cloth;
(2) preparing hydrophilic carbon fiber cloth CF of a flexible substrate: treating the cleaned carbon fiber cloth in concentrated nitric acid for 8-12h at 60-90 ℃, taking out, cleaning again, and drying in a drying oven at 60-100 ℃ for 8-14 h;
(3) preparing a CF @ NiCo-precursor flexible electrode: in a three-electrode system, a hydrophilic carbon fiber cloth CF with a flexible substrate is used as a working electrode, 25-40mL of mixed solution of cobalt chloride and nickel nitrate is added into an electrolytic bath, and the immersed area of the carbon fiber cloth CF is 1-2cm2(ii) a Taking a saturated calomel electrode SCE as a reference electrode and a platinum sheet as a counter electrode, and carrying out constant potential deposition for 80-100s under the voltage of-1 to-1.5V relative to the SCE electrode; after the constant potential deposition is finished, taking out the carbon fiber cloth CF, cleaning the carbon fiber cloth CF by deionized water, and drying the carbon fiber cloth CF in an oven at the temperature of 60-100 ℃ for 12-14 h;
(4) nickel-cobalt oxide flexible electrode CF @ NiCoO2Preparation of @ N-C: preparing 0.1-0.3M Na2HPO40.1-0.2M pyrrole and 0-0.1M NaClO4In a three-electrode system, a CF @ NiCo-precursor flexible electrode is taken as a working electrode, 25-40mL of mixed electroplating solution is added into an electrolytic tank, and the immersed area of the CF @ NiCo-precursor flexible electrode is ensured to be 1-2cm2(ii) a Taking a saturated calomel electrode SCE as a reference electrode, taking a platinum sheet as a counter electrode, and carrying out constant potential deposition for 30-50s at a potential of 0.9-1.1V relative to the SCE electrode; and after the constant potential deposition is finished, taking out the CF @ NiCo-precursor flexible electrode, cleaning the CF @ NiCo-precursor flexible electrode by using deionized water, drying the CF @ NiCo-precursor flexible electrode in an oven at the temperature of 60-80 ℃ for 8-14h, and then placing the CF @ NiCo-precursor flexible electrode in a tube furnace to treat the CF @ NiCo-precursor flexible electrode at the temperature of 450-600 ℃ for 1-2.
2. The production method according to claim 1, wherein the carbon fiber cloth in the step (1) is cut to 1 to 3cm2A rectangular strip of (a); the method for cleaning the surface of the carbon fiber cloth comprises the following steps: and (3) carrying out ultrasonic treatment on the carbon fiber cloth in deionized water, ethanol and propanol for 15-30min in sequence.
3. The preparation method according to claim 1, wherein the mixed solution of cobalt chloride and nickel nitrate in the step (3) is prepared by: 10-20g of CoCl2·6H2O and 10-20g of Ni (NO)3)2·6H2And adding O into deionized water, and fixing the volume by using a 500mL volumetric flask to obtain a mixed solution of cobalt chloride and nickel nitrate.
4. The nickel cobalt oxide flexible electrode prepared by the preparation method of any one of claims 1 to 3.
5. Use of the nickel cobalt oxide flexible electrode of claim 4 in the manufacture of a flexible solid state supercapacitor.
6. The use of claim 5, wherein the flexible solid-state supercapacitor is characterized in that the nickel-cobalt oxide flexible electrode is used as a positive electrode, the nitrogen-doped carbon of the carbon fiber is used as a negative electrode, and the PVA/KOH is used as an electrolyte.
7. According to the claimsThe application of claim 5, wherein the preparation method of the nitrogen-doped carbon of the carbon fiber comprises the following steps: configuring 0.1-0.3M Na2HPO40.1-0.2M pyrrole with 0-0.1M NaClO4In a three-electrode system, a saturated calomel electrode SCE is used as a reference electrode, a platinum sheet is used as a counter electrode, a hydrophilic carbon fiber cloth CF is used as a working electrode, 25-40mL of mixed electroplating solution is added into an electrolytic tank, and the immersed area of the hydrophilic carbon fiber cloth CF is 1-2cm2(ii) a Constant potential deposition is carried out for 1.5-2h at a potential of 0.9-1.1V relative to the SCE electrode; and taking out the carbon fiber cloth CF after the constant potential deposition is finished, washing the carbon fiber cloth CF by deionized water, drying the carbon fiber cloth CF in an oven at the temperature of 60-100 ℃ for 8-14h, and then placing the carbon fiber cloth CF into a tube furnace to be treated at the temperature of 450-600 ℃ for 1-2h under the argon atmosphere to obtain the nitrogen-doped carbon of the carbon fiber.
8. Use of the nickel cobalt oxide flexible electrode of claim 4 in the manufacture of a wearable glucose sensor.
9. The use of claim 8, wherein a nickel cobalt oxide flexible electrode is used as a working electrode, a conductive silver paste coated carbon fiber is used as a reference electrode, and a carbon fiber cloth CF is used as a counter electrode, to assemble a wearable glucose sensor; the assembled wearable glucose sensor can be woven and integrated on a textile for use, wherein the textile comprises a head band and clothes.
10. The use according to claim 9, wherein the conductive silver paste coated carbon fiber is prepared by the following method: coating the surface of the cleaned carbon fiber to a thickness of 1-2cm2Drying and curing the silver paste in an oven at 60-80 ℃ for 1.5-2h, and using the dried silver paste as a reference electrode.
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