Polymer electrolyte, half cell for electrochemical measurements, and the use thereof

Abstract

A polymer electrolyte for an electrochemical half cell, in particular for a reference half cell, contains a polymer which as a first monomer component contains at least one alkyl methacrylate. The alkyl methacrylate has a substituted alkyl group with from three to seven carbon atoms and at least two substituents. The aforementioned substituents are selected from the group comprising OR1 and NR2R3, in which R1, R2 and R3 are selected from the group comprising hydrogen, methyl, and ethyl, on the condition that the substituted alkyl group contains the substituent OH at most once.

Description

RELATED APPLICATIONS

[0001] This application claims priority under 35 U.S.C. §119 to German Patent Application No. 10214035.9 filed in Germany on Mar. 27, 2002, the entire content of which is hereby incorporated by reference.

BACKGROUND

[0002] 1. Field of the Invention

[0003] The invention relates to a polymer electrolyte, to a half cell, and to uses of the half cell and of the polymer electrolyte.

[0004] 2. Prior Art

[0005] Numerous half cells for electrochemical measurements, such as potentiometric or amperometric measurements, are known. In particular, such half cells can be embodied as reference electrodes, which are used in combination with potentiometric or amperometric sensors. In such reference electrodes, it is imporant that they output as constant a reference potential as possible.

[0006] In one type of reference electrodes, there is a fluid reference electrolyte, such as an aqueous potassium chloride solution, which can be brought into contact with a fluid measuring medium via a liquid connection (also known as a “liquid junction”). To avoid or reduce an unwanted mass transfer between the measuring medium and the reference electrolyte, the liquid junction is typically designed as a more or less porous diaphragm. One disadvantage of such liquid junctions, however, is that soiling or even plugging up of the pores can occur, which can lead to considerable faulty potentials and possibly interruptions.

[0007] In another type of reference electrodes, instead of the diaphragm, a single opening or a plurality of openings is provided, as a result of which the aforementioned problem of soiling can be largely avoided. However, this embodiment means that instead of the otherwise usual fluid or gel-like reference electrolyte, a non-flowable reference electrolyte is used, to prevent the reference electrolyte from flowing out. A polymer electrolyte in the form of a hydrogel, which for instance contains a saturated aqueous potassium chloride solution and preferably additionally suspended potassium chloride is especially well suited for this purpose.

[0008] In European Patent Disclosure EP 1124132 A1, which is hereby incorporated by reference in its entirety, a reference electrode of this generic type is described which contains a polymer electrolyte that contains a polymer on the basis of monomers selected from N-substituted acrylamides and/or methacrylates. For instance, the methacrylate is a methacrylate with at least two hydroxy groups, and in particular 2,3-dihydroxypropyl methacrylate.

SUMMARY

[0009] An object of the invention is to furnish further polymer electrolytes which are especially well suited for electrochemical half cells and in particular for reference half cells. Other objects of the invention are to furnish an improved half cell and to disclose uses of the half cell and of the polymer electrolytes.

[0010] The polymer electrolytes of the invention contain a polymer which as a first monomer component contains at least one alkyl methacrylate. The aforementioned alkyl methacrylate has a substituted alkyl group with from three to seven carbon atoms and at least two substituents, and the aforementioned substituents are selected from the group comprising OR1 and NR2R3, and R1, R2 and R3 are selected from the group comprising hydrogen, methyl, and ethyl, on the condition that the substituted alkyl group contains the substituent OH at most once. By a suitable selection of the substituents in the aforementioned range, the properties of the polymer electrolyte, in particular its polarity and hence its resistance and stability to water or to polar or apolar solvents, can be adapted accordingly to the intended area of use. Moreover, the polymer electrolytes of the invention are distinguished by good resistance and stability to acids.

[0011] The half cell of the invention, which can be used as a component in potentiometric or amperometric sensors, contains one of the polymer electrolytes of the invention. The polymer electrolyte of the invention can also be used as a solid-phase electrolyte in a battery half cell.

[0012] Exemplary embodiments are directed to the substituted alkyl group of the alkyl methacrylate intended as the first monomer component. According to exemplary embodiments, the substituted alkyl group is a 3-amino-2-hydroxypropyl or a 2-amino-3-hydroxypropyl. Moreover, in accordance in exemplary embodiments, the substituted alkyl group may be a 3-diethylamino-2-hydroxypropyl, a 3-ethoxy-2-hydroxypropyl, a 3-methoxy-2-hydroxypropyl, or a 3- methylamino-2-hydroxypropyl. Furthermore, according to exemplary embodiments, the substituted alkyl group can be a —CH2—CH2OH—CH2—NR2R3 or a —CH2—CH2—NR2R3—CH2OH, in which R2 and R3, are as described above. Also, the substituted alkyl group can be a —CH2—CH2OH—CH2—OR4 or a —CH2—CH2—OR4—CH2OH, in which R4 is a methyl or ethyl. However, a mixture of alkyl methacrylates of the type named above can also be contemplated as the first monomer component.

[0013] According to exemplary emboidments, the polymer contains, as a further monomer component, a hydroxyalkyl methacrylate, which is preferably 2-hydroxyethyl methacrylate and/or 3-hydroxypropyl methacrylate. With this further monomer component, the polarity of the polymer electrolyte can advantageously be varied, and by a choice of the quantity ratio of the further monomer component to the first monomer component, the polarity is adjustable over a wide range.

[0014] Exemplary embodiments can be used in conjunction with a half cell with a glass housing. Because the polymer contains, as an additional monomer component, a silylated alkyl methacrylate, preferably 3-(trimethoxysilyl)propyl methacrylate, an adhesion of the polymer electrolyte to the glass housing is achieved, as a result of which a longer service life of the half cell and in particular better resistance to pressure and washing out is attained.

[0015] Exemplary embodiments are directed to a polymer electrolyte. This polymer electrolyte can additionally contain a concentrated aqueous solution of a salt or salt mixture, which is indicated for use in polar measuring media. The polymer electrolyte can contain a mixture of an organic solvent and an aqueous solution of a salt and is accordingly predominantly usable for less-polar measuring media. The organic solvent is selected from the group comprising glycerine, ethylene glycol, methanol, ethanol, N-propanol, isopropanol, acetone, and mixtures thereof. It is especially advantageous if the salt is additionally in the form of a suspension. As a result of the increased salt content, a longer resistance of the half cell to washing out of the salt as a result of the contact with the measuring medium is achieved. On the other hand, the progressive depletion of the salt caused by the washing out can be readily ascertained visually from the developing washing-out or depletion front, which forms the boundary between a region of the polymer electrolyte that is clouded by the salt suspension and a region of the polymer electrolyte that is more clear because the salt suspension is no longer present there. For instance, the aforementioned salt is selected from the group comprising potassium chloride, sodium chloride, lithium chloride, potassium nitrate, potassium perchlorate, sodium formiate, lithium acetate, lithium sulfate, ammonium chloride, methylammonium chloride, dimethylammonium chloride, trimethylammonium chloride, and mixtures thereof. This salt can, however, also be a further ionic organic halide, for instance. This salt can also form a redox system.

[0016] The half cell can have an open liquid junction between the polymer electrolyte and a surrounding medium—as a rule, a measuring medium or a fluid specimen. This embodiment is possible because the polymer electrolyte is essentially in solid form and accordingly cannot escape from the open liquid junction. By dispensing with a diaphragm, unwanted interfering potentials in the region of the liquid junction can be largely avoided.

BRIEF DESCRIPTION OF THE DRAWING

[0017] The sole drawing FIGURE schematically shows a reference electrode for electrochemical measurements in longitudinal section.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The reference electrode shown in the drawing has a tubular housing 2, made from glass or plastic, whose lower end 4, in the example shown, is immersed in a measuring medium 6. The interior of the housing 2 is filled with a polymer electrolyte 8, in which a lead-off element 10 is immersed. The lead-off element is formed for instance by a chlorinated silver wire, which is extended to the outside through an upper cap part 12 of the housing 2. An opening 14 in the vicinity of the lower end 4 serves as liquid junction between the polymer electrolyte 8 and the measuring medium 6.

[0019] The polymer electrolyte 8 is advantageously formed in the interior of the housing 2; first the requisite educts, and in particular the corresponding monomer components, are introduced into the interior, and after that a polymerization is performed. In this reaction, a solidification takes place, so that the polymer electrolyte 8 formed cannot escape from the opening 14.

[0020] Besides the reference electrode shown in the drawing, other embodiments are possible. In particular, the reference electrode can be combined with a measuring electrode, for instance a pH electrode, to form a single-rod measurement chain, in a manner known per se. However, still other types of electrochemical half cells can be equipped with the polymer electrolyte, for instance for amperometric measurements. The polymer electrolyte can also be used as a solid-phase electrolyte in a battery half cell.

[0021] Production of Preferred Polymer Electrolytes

[0022] For producing preferred polymer electrolytes, monomer solutions with a composition shown in Table 1 were mixed with a powder mixture shown in Table 2 and other additives shown in Table 3 and homogenized with cooling at 15 to 20° C. The mixtures thus obtained were introduced into electrodes with a tubular glass housing. By ensuing heat treatment of the filled electrodes, polymerization was initiated, which led to the formation of the polymer electrolytes.

TABLE 1
Monomer Solution
Substance                        Proportion by weight
Aminohydroxypropyl methacrylate (AHPMA) 8 to 12%
Hydroxypropyl methacrylate (HPMA) 4 to 6%
Hydroxyethyl methacrylate (HEMA) 6 to 8%
Silylpropyl methacrylate         ca. 0.1%
N,N,N′,N′-tetramethylethlyenediamine (TEMED) ca. 0.2%
Glycerine                        ca. 30%
Powder mixture                   (according to Table 2)
Additives                        (according to Table 3)
Water                            15 to 20%

[0023]

TABLE 2
Powder Mixture
Substance                        Proportion by weight
Potassium chloride with 2% aerosil 25 to 30%
Silica gel H60                   3 to 5%

[0024]

TABLE 3
Additives
Substance                        Proportion by weight
Methylene-bis-acrylamide (MBA)   ca. 0.5%
Ammonium persulfate              ca. 0.05%
2,2′-Azo-bis(2-(2-imidazolin-2-yl)propane) ca. 0.05%
dihydrochloride (WAKO 44)

[0025] The first monomer component, designated above as aminohydroxypropyl methacrylate (AHPMA), is a mixture of the two isomers 3-amino-2-hydroxypropyl methacrylate and 2-amino-3-hydroxypropyl methacrylate, which can be produced for instance by reacting glycidyl methacrylate (2,3-epoxypropyl methacrylate) with ammonia in an isomer ratio of approximately 9:1. WAKO 44 is a radical former that is used as an azo initiator for polymerization reactions. TEMED is a starter compound for the polymerization of acryl and methacryl derivatives. Silica gel and aerosil are used to improve the consistency of the polymer and to adsorb interfering substances, such as electrode poisons, from the measuring medium.

[0026] The polymer electrolytes described above are distinguished by excellent stability to acids, water, and both polar and apolar solvents. Accordingly, these polymer electrolytes can be used in the most various types of measuring media.

[0027] Further Exemplary Embodiments

[0028] For particular areas of use, the properties of the polymer electrolytes can be optimized specifically, as documented by the exemplary embodiments that follow.

TABLE 4
Composition of Example 1
Proportion by Weight
Monomer
3-Amino-2-hydroxypropyl methacrylate 15%
3-(Trimethyloxysilyl)propyl      1%
methacrylate
Cross-linking agent              2%
Fillers
KCl                              25%
Silicic acid                     5%
Solvents
Water                            22%
Glycerine                        30%

[0029]

TABLE 5
Composition of Example 2
Proportion by Weight
Monomer
3-Diethylamino-2-hydroxypropyl 20%
methacrylate
3-(Trimethyloxysilyl)propyl    1%
methacrylate
Cross-linking agent            5%
Fillers
KCl                            12%
Silicic acid                   8%
Solvents
Water                          16%
Glycerine                      38%

[0030]

TABLE 6
Composition of Example 3
Proportion by Weight
Monomer
3-Ethoxy-2-hydroxypropyl    18%
methacrylate
3-(Trimethyloxysilyl)propyl 1%
methacrylate
Cross-linking agent         3%
Fillers
KCl                         20%
Silicic acid                5%
Solvents
Water                       20%
Glycerine                   33%

[0031]

TABLE 7
Composition of Example 4
Proportion by Weight
Monomer
3-Methoxy-2-hydroxypropyl   19%
methacrylate
3-(Trimethyloxysilyl)propyl 1%
methacrylate
Cross-linking agent         3%
Fillers
KCl                         15%
Silicic acid                6%
Solvents
Water                       21%
Glycerine                   35%

[0032]

TABLE 8
Composition of Example 5
Proportion by Weight
Monomer
3-Methylamino-2-hydroxypropyl 14%
methacrylate
3-(Trimethyloxysilyl)propyl   1%
methacrylate
Hydroxypropyl methacrylate    4%
Cross-linking agent           5%
Fillers
KCl                           20%
Silicic acid                  5%
Solvents
Water                         15%
Glycerine                     36%

[0033] All the polymer electrolytes described above here have good stability to acids; other properties are listed in Table 9.

TABLE 9
Properties of the Polymer Electrolytes Investigated
Example	Polarity	Area of Use	KCl Solution
1	Strong	Water; no organic	Supersaturated
		solvents
2	Medium-	Water; polar	Supersaturated
	strong	organic solvents
3	Very weak	Apolar organic	Supersaturated
		solvents
4	Medium-	Polar organic	Saturated
	weak	solvents
5	Weak	Polar and apolar	Supersaturated
		organic solvents

[0034] Individually, the following properties were also ascertained. The polymer electrolyte of Example 1 is stable to water but not to organic solvents. The polymer electrolyte of Example 2 is suitable for use with water and polar solvents. The polymer electrolyte of Example 4, compared to that of Example 3, has a shorter service life. The polymer electrolyte of Example 5 is especially well suited, because of its stability, for use with any organic solvents.

[0035] It will be appreciated by those skilled in the art that the present invention can be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The presently disclosed embodiments are therefore considered in all respects to be illustrative and not restricted. The scope of the invention is indicated by the appended claims rather than the foregoing description and all changes that come within the meaning and range and equivalence thereof are intended to be embraced thereon.

Claims

1. A polymer electrolyte for an electrochemical half cell, comprising: a polymer which as a first monomer component contains at least one alkyl methacrylate, wherein the alkyl methacrylate has a substituted alkyl group with from three to seven carbon atoms and at least two substituents, and the substituents are selected from a group comprising OR1 and NR2R3, and R1, R2 and R3 are selected from a group comprising hydrogen, methyl, and ethyl, on a condition that the substituted alkyl group contains a substituent OH at most once.

2. The polymer electrolyte of claim 1, wherein the substituted alkyl group is a 3-amino-2-hydroxypropyl.

3. The polymer electrolyte of claim 1, wherein the substituted alkyl group is a 2-amino-3-hydroxypropyl.

4. The polymer electrolyte of claim 1, wherein the substituted alkyl group is a 3-diethylamino-2-hydroxypropyl.

5. The polymer electrolyte of claim 1, wherein the substituted alkyl group is a 3-ethoxy-2-hydroxypropyl.

6. The polymer electrolyte of claim 1, wherein the substituted alkyl group is a 3-methoxy-2-hydroxypropyl.

7. The polymer electrolyte of claim 1, wherein the substituted alkyl group is a 3-methylamino-2-hydroxypropyl.

8. The polymer electrolyte of claim 1, wherein the substituted alkyl group is a —CH2—CH2OH—CH2—NR2R3 or a —CH2—CH2—NR2R3—CH2OH, in which R2 and R3 are as defined in claim 1.

9. The polymer electrolyte of claim 1, wherein the substituted alkyl group is a —CH2—CH2OH—CH2—OR4 or a —CH2—CH2—OR4—CH2OH, in which R4 is a methyl or ethyl.

10. The polymer electrolyte of claim 1, wherein the polymer contains, as a further monomer component, a hydroxyalkyl methacrylate.

11. The polymer electrolyte of claim 1, wherein the polymer contains, as an additional monomer component, a silylated alkyl methacrylate, preferably 3-(trimethoxysilyl)propyl methacrylate.

12. The polymer electrolyte of claim 1, wherein it additionally contains a concentrated aqueous solution of a salt or salt mixture.

13. The polymer electrolyte of claim 1, wherein it additionally contains a mixture of an organic solvent and an aqueous solution of a salt.

14. The polymer electrolyte of claim 13, wherein the organic solvent is selected from the group comprising glycerine, ethylene glycol, methanol, ethanol, N-propanol, isopropanol, acetone, and mixtures thereof.

15. The polymer electrolyte of claim 12, wherein the salt is additionally in the form of a suspension.

16. The polymer electrolyte of claim 12, wherein the salt is selected from the group comprising potassium chloride, sodium chloride, lithium chloride, potassium nitrate, potassium perchlorate, sodium formiate, lithium acetate, lithium sulfate, ammonium chloride, methylammonium chloride, dimethylammonium chloride, trimethylammonium chloride, and mixtures thereof.

17. A half cell for electrochemical measurements, comprising: a polymer electrolyte according to claim 1.

18. The half cell of claim 17, comprising: an open liquid junction between the polymer electrolyte and a surrounding medium.

19. The use of the half cell of claim 17, as a component in potentiometric or amperometric sensors.

20. The use of the polymer electrolyte of claim 1, as a solid-phase electrolyte in a battery half cell.

21. The polymer electrolyte of claim 1, wherein the electrochemical half cell is a reference half cell.

22. The polymer electrolyte of claim 1, wherein the polymer contains, as a further monomer component, a 2-hydroxyethyl methacrylate and/or 3-hydroxypropyl methacrylate.