CN112285183A - Membrane-free all-solid-state ion selective electrode and preparation method and application thereof - Google Patents
Membrane-free all-solid-state ion selective electrode and preparation method and application thereof Download PDFInfo
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- 150000002500 ions Chemical class 0.000 claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001514 detection method Methods 0.000 claims abstract description 14
- 239000010405 anode material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 4
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
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- Chemical Kinetics & Catalysis (AREA)
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- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
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Abstract
The invention discloses a membrane-free all-solid-state ion selective electrode and a preparation method and application thereof. The lithium ion anode material is selected from at least one of lithium iron phosphate and lithium manganate. The membrane-free all-solid-state ion selective electrode disclosed by the invention shows excellent lithium ion selectivity, potential long-term stability and detection limit, and also shows excellent stability and Nernst response in artificial plasma detection. Because the ion selective membrane is not contained, the mechanical property of the electrode is improved, and the electrode is suitable for preparing a miniaturized electrode and has strong feasibility; and the raw materials are easy to prepare and can be produced in large quantity, so that the method is very suitable for industrial application in clinical diagnosis.
Description
Technical Field
The invention relates to the field of electrochemistry, in particular to a membrane-free all-solid-state ion selective electrode and a preparation method and application thereof.
Background
With the progress of science and technology and the rapid development of economy, people increasingly demand personal health and health monitoring systems, so that researchers have paid extensive attention to the design and development of novel sensing devices. The electrochemical sensor has wide application prospect due to the characteristics of portability, high sensitivity, low energy consumption and high monitoring efficiency. Among them, potentiometric sensors, especially Ion Selective Electrodes (ISEs), are one of the most attractive electrochemical sensors.
In recent years, all-solid-state ion selective electrodes (SC-ISEs) have attracted wide attention in the field of clinical analysis, and have the advantages of being easy to miniaturize, portable, and capable of being produced in mass, and the like, so that the life of people is more convenient. Such devices require 3S principle of sensors-high selectivity, high sensitivity, high stability. In addition to this, good reproducibility and fast response time are also crucial for constructing sensors with excellent performance. A typical SC-ISEs device includes an Ion Selective Membrane (ISM) for specifically recognizing ions and creating a stable membrane potential and an all-solid-state switching layer material for stabilizing the potential of SC-ISEs. The earliest solid state switching layer materials were conductive polymers and their derivatives, which have large redox capacitance; in addition, carbon materials with high capacitance and good hydrophobicity are another type of solid transition layer, such as carbon nanotubes, fullerenes, graphene and the like and derivatives thereof.
Bipolar disorder, also known as bipolar disorder, is a disorganized disorder in which patients with abnormal shifts in mood, energy and activity levels are common. Nowadays, lithium salt-containing drugs are widely used for the treatment of bipolar disorder and other affective disorders, and are effective in the blood of humans at concentrations ranging from 0.5 to 1.5mM, below which the drug will not work and above which damage to the kidneys may occur. Thus for Li in human blood+The detection of the concentration content is very urgent and necessary. The traditional detection means needs complex pretreatment procedures and has the problems of high pollution and high energy consumption, and SC-ISEs have the characteristics of Li due to the portability, easy operation, low cost, quick result output and the like+The field of concentration detection is attracting attention. However, the SC-ISEs that are mainstream at present have a series of disadvantages: (1) the ISM has poor mechanical strength, and the ISM may be detached or damaged during long-term use; (2) the composition of the ISM risks leaking into the analysis liquid; (3) ISM is poor in biocompatibility, and when the material is applied to a flexible wearable analysis sensor (such as human sweat ion online analysis), the material can directly contact the skin, so that toxicity risks are caused; (4) the water layer is easy to appear between the ISM and the solid switching layer, and the electricity is reducedBit stability; (5) the ISM component contains very expensive ionophores, which makes the cost prohibitive. Therefore, constructing a new generation of all-solid-state ion-selective electrodes that are stable and repeatable currently faces a significant challenge.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Accordingly, a first object of the present invention is to provide a membrane-free all-solid-state ion-selective electrode which does not include an ion-selective membrane (ISM) and can avoid problems such as damage and leakage caused by the ISM.
Specifically, the membrane-free all-solid-state ion selective electrode of the invention is composed of an electrode substrate and a loaded lithium ion positive electrode material loaded on the electrode substrate.
The lithium ion anode material is selected from lithium iron phosphate (LiFePO)4(LFP) and lithium manganate LiMn2O4(LMO).
The loading capacity of the lithium ion anode material is 0.2-0.4 mg-cm-2。
The electrode substrate is selected from a Glassy Carbon Electrode (GCE).
The second purpose of the invention is to provide a preparation method of a membrane-free all-solid-state ion selective electrode, which comprises the following steps: and coating the lithium ion anode material on an electrode substrate to obtain the membrane-free all-solid-state ion selective electrode.
The coating method can adopt a general coating method, for example, a lithium ion anode material is dispersed in a solvent to obtain a dispersion liquid, then the dispersion liquid is dripped on an electrode substrate, and the film-free all-solid-state ion selective electrode is obtained after drying.
The third purpose of the invention is to provide the application of the membrane-free all-solid-state ion selective electrode in lithium ion detection, especially in the lithium ion detection in plasma.
It is a further object of the present invention to provide a sensor comprising the above membrane-free all-solid-state ion-selective electrode.
Compared with the prior art, the invention has the following beneficial effects:
the membrane-free all-solid-state ion selective electrode disclosed by the invention shows excellent lithium ion selectivity, potential long-term stability and detection limit, and also shows excellent stability and Nernst response in artificial plasma detection. Because the ion selective membrane is not contained, the mechanical property of the electrode is improved, and the electrode is suitable for preparing a miniaturized electrode and has strong feasibility; and the raw materials are easy to prepare and can be produced in large quantity, so that the method is very suitable for industrial application in clinical diagnosis.
Drawings
FIG. 1 shows a GCE/LFP electrode and a GCE/LFP/ISM electrode pair Li+A response curve (a) and a water layer test curve (b);
FIG. 2 shows the results of 12-day potential stability test of GCE/LFP electrodes;
FIG. 3 shows the electrode pairs of GCE/LMO, GCE/LCO and GCE/LNCMO for Li+The response curve of (a);
FIG. 4 is the selectivity coefficient values of three electrodes GCE/LMO, GCE/LFP and GCE/LFP/ISM;
FIG. 5 shows Li in artificial plasma for GCE/LMO and GCE/LMO/ISM electrodes+And responding to the situation.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
The following examples used drug sources as follows:
lithium iron phosphate (LiFePO)4) Lithium ionophore VI, potassium tetrakis (pentafluorophenyl) borate (KTpFPB), polyvinyl chloride (PVC), diisooctyl sebacate (bis (2-ethylhexyl) sebacate, DOS), Tetrahydrofuran (THF), polyvinylidene fluoride resin (poly (vinylidenefluoride), PVDF), lithium chloride, sodium chloride, potassium chloride, commercially available from sigma-ori limited; disodium hydrogen phosphate, sodium dihydrogen phosphate, calcium chloride, urea, glucose were purchased from enokay chemical agents ltd; magnesium chloride, N-methylpyrrolidone (NMP), was purchased from Shanghai Michelin Biochemical Co., Ltd. Lithium manganate (LiMn)2O4) Lithium cobaltate (LiCoO)2) Purchased from alfa epsa chemical limited. LiNixCoyMnzO2(x + y + z ═ 1) belongs to the self-synthesis preparation.
Example 1
A membrane-free all-solid-state ion selective electrode is prepared by the following steps:
0.3 mu m Al is used for glassy carbon electrode2O3Polishing the polishing powder on nylon cloth, cleaning, and adding 0.05 μm Al2O3Polishing with polishing powder, and washing with clear water and ethanol for several times.
Mixing LiFePO4Grinding the powder in a mortar for 3min, and mixing the powder with PVDF according to a mass ratio of 8: 2, dispersing in NMP solution, and ultrasonically dispersing for 2h to obtain LiFePO4A dispersion with a concentration of 70 mg/ml.
Dripping 10 mu L of dispersion liquid on a treated glassy carbon electrode, and coating LiFePO on the electrode4The loading capacity on the glassy carbon electrode is about 0.3mg cm-2. And finally, drying in an oven at 60 ℃ for 2h to obtain the membrane-free all-solid-state ion selective electrode which is marked as a GCE/LFP electrode.
Example 2
This example provides a membrane-free all-solid-state ion-selective electrode, and the only difference between the preparation method of the electrode and that of example 1 is that LiFePO4Replacement by LiMn of equal mass2O4(LMO), the resulting membrane-free all-solid-state ion-selective electrode is labeled as a GCE/LMO electrode.
Comparative example 1
This comparative example provides a membrane-free all-solid-state ion-selective electrode whose preparation process differs from that of example 1 only in that LiFePO is used4Replacement by equal mass LiCoO2(LCO), the resulting membrane-free all-solid-state ion-selective electrode is labeled as a GCE/LCO electrode.
Comparative example 2
This comparative example provides a membrane-free all-solid-state ion-selective electrode whose preparation process differs from that of example 1 only in that LiFePO is used4Replacing by equal-mass ternary nickel cobalt lithium manganate LiNixCoyMnzO2(x + y + z ═ 1) (LNCMO), and the resulting membrane-free all-solid-state ion-selective electrode was labeled as a GCE/LNCMO electrode.
Comparative example 3
The comparative example provides a conventional membrane-bearing all-solid-state ion-selective electrode, the method of preparation comprising the steps of:
32.9mg of PVC, 65.7mg of DOS, 1mg of lithium ionophore VI and 0.4mg of KTpFPB were dissolved in 1mL of THF to form an ISM solution. 50 μ L of ISM solution was applied dropwise to the GCE/LFP electrode of example 1 and allowed to dry overnight at room temperature to give a membrane-containing all-solid ion-selective electrode labeled GCE/LFP/ISM.
Alternatively, 32.9mg PVC, 65.7mg DOS, 1mg lithium ionophore VI and 0.4mg KTpFPB were dissolved in 1mL THF to form an ISM solution. 50 μ L of ISM solution was applied dropwise to the GCE/LMO electrode of example 2, which was dried overnight at room temperature to give a membrane-bearing all-solid ion-selective electrode, labeled GCE/LMO/ISM.
Performance detection
The electrodes of examples 1 and 2 and comparative examples 1 to 3 were subjected to electrochemical performance measurement. It should be noted that all electrodes were at 10 f prior to the ion response test-3Soaking in M LiCl solution for 24h, and then soaking in 10-7Soaking in M LiCl solution for 4 h; other electrochemical tests are carried out by soaking in 0.1M LiCl solution for 24 h.
(1) The electrode response and stability of the GCE/LFP and GCE/LFP/ISM electrodes were compared using an electrochemical open circuit potential test method.
The specific test method comprises the following steps: testing a series of Li by taking a GCE/LFP electrode or a GCE/LFP/ISM electrode as a working electrode and taking a platinum wire and a saturated calomel electrode as a counter electrode and a reference electrode respectively+Concentration (from 10)-7To 10-1M) to obtain the open-circuit potential of the working electrode pair Li+Response curve (FIG. 1a, a in abscissaLi +Represents Li+Activity); water layer test method: the working electrode was first tested for open circuit potential in 0.1M LiCl solution, after which the test solution was changed to 0.1M NaCl solution and finally tested again in 0.1M LiCl solution (fig. 1 b).
It can be seen from FIG. 1a that the GCE/LFP electrode exhibits a Nernst response slope (53.3. + -. 0.1mV/dec and 60.5. + -. 0.2mV/dec) and a detection limit (10) similar to those of the GCE/LFP/ISM electrode-4.5M and 10-4.7M). Testing the koji from the aqueous layerAs can be seen in the line, the GCE/LFP electrode had no significant water layer formation, which might benefit from its two-phase interface response, less than the three-phase interface of the GCE/LFP/ISM electrode, which had potential drifts by 157.1 μ V/h and 366.5 μ V/h, respectively. These results all illustrate the superiority of the membraneless all-solid-state ion-selective electrode.
(2) The long-term stability of the potential of the electrode was analyzed using an electrochemical open circuit potential test to obtain a 12-day potential stability test for the GCE/LFP electrode (FIG. 2). As can be seen from the figure, the GCE/LFP electrode is placed in a 0.1M LiCl solution, the stability of the electrode is tested, and the potential drift of the electrode within 12 days is 52 muV/h, so that the electrode has good stability.
(3) Other lithium ion battery positive electrode materials (example 2, comparative example 1, and comparative example 2) were tested for Li using an electrochemical open circuit potential method+Obtaining the GCE/LMO, GCE/LCO and GCE/LNCMO electrode pair Li+(FIG. 3, the numerical value on the graph in FIG. 3 represents log a)Li +). As can be seen in FIG. 3, the GCE/LCO electrode and the GCE/LNCMO electrode couple Li+None of the Nernst responses, and the GCE/LMO electrode showed good response with a corresponding slope of 56.2. + -. 0.4 mV/dec.
(4) The electrochemical open-circuit potential test method is used to obtain the interference ions (Na) of different electrodes at different concentrations+,K+,Ca2+,Mg2+) Observing whether the electrode has response or not, and then calculating respective selectivity coefficients to obtain the selectivity coefficient values of three electrodes of GCE/LMO, GCE/LFP and GCE/LFP/ISM as shown in FIG. 4. The GCE/LFP and GCE/LMO electrode pairs Li are illustrated+All with good selectivity, especially with monovalent Na+And K+The selectivity coefficient of the membrane is close to or even exceeds that of GCE/LFP/ISM with the membrane. For bivalent Ca2+And Mg2+Although the selectivity coefficient is weaker than that of the electrode with the membrane, the selectivity is satisfactory for the analysis of the actual sample.
(6) The GCE/LMO electrode is made into a sensor for testing Li of the GCE/LMO electrode in artificial plasma+Responding, and comparing with GCE/LMO/ISM electrode, and testing concentration range is 0.1-10 mM.The components of the artificial plasma are as follows: 137.7mM NaCl, 2.1mM Na2HPO4，2.1mM NaH2PO4，4.3mM KCl，2.5mM CaCl2，1.1mM MgCl22.5mM urea and 4.7mM glucose.
The test results are shown in fig. 5. As can be seen from FIG. 5, the GCE/LMO electrode had good Li in the artificial plasma+In response, the response slope reached 54.8mV/dec, with a corresponding slope of only 30.2mV/dec for the GCE/LMO/ISM electrode. The test results reflect that the film-free GCE/LMO electrode can effectively identify Li compared with the all-solid-state ion selective electrode containing the polymer film+Effective recognition of Li in artificial plasma+Can effectively solve the problem of being influenced by easily interfered ions, especially from Na+Interference, unstable potential, etc. The preparation method of the membrane-free all-solid-state ion selective electrode system based on the lithium ion battery cathode material is simple and convenient, has low cost, and is very suitable for being industrially applied to clinical detection of Li in blood+。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A membraneless all-solid-state ion-selective electrode, characterized in that: the lithium ion battery comprises an electrode substrate and a lithium ion positive electrode material loaded on the electrode substrate.
2. The membrane-free all-solid-state ion-selective electrode of claim 1, wherein: the lithium ion anode material is selected from at least one of lithium iron phosphate and lithium manganate.
3. The membrane-free all-solid-state ion-selective electrode of claim 1, wherein: the loading capacity of the lithium ion anode material is 0.2-0.4 mg-cm-2。
4. A method for preparing the membrane-free all-solid-state ion-selective electrode according to any one of claims 1 to 3, wherein the method comprises the following steps: the method comprises the following steps: and coating the lithium ion anode material on an electrode substrate to obtain the membrane-free all-solid-state ion selective electrode.
5. The method according to claim 4, wherein: the coating method comprises the following steps: dispersing the lithium ion anode material in a solvent to obtain a dispersion liquid, then dripping the dispersion liquid on an electrode substrate, and drying to obtain the membrane-free all-solid-state ion selective electrode.
6. Use of the membrane-free all-solid-state ion-selective electrode according to any one of claims 1 to 3 in lithium ion detection.
7. Use of the membrane-free all-solid-state ion-selective electrode according to any one of claims 1 to 3 in the detection of lithium ions in plasma.
8. A sensor, characterized by: comprising the membrane-free all-solid-state ion-selective electrode according to any one of claims 1 to 3.
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