CN106290503A - A kind of silver/silver chloride reference electrode and preparation method thereof - Google Patents
A kind of silver/silver chloride reference electrode and preparation method thereof Download PDFInfo
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- CN106290503A CN106290503A CN201510282229.3A CN201510282229A CN106290503A CN 106290503 A CN106290503 A CN 106290503A CN 201510282229 A CN201510282229 A CN 201510282229A CN 106290503 A CN106290503 A CN 106290503A
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Abstract
The invention provides a kind of silver/silver chloride reference electrode and preparation method thereof.The reference electrode of the present invention includes an outer tube, a bolt, a conductive lead wire rod, a silver electrode and reference salt；Described outer tube be provided with one or two a diameter of 0.1～the micropore of 0.3mm；The material of described bolt and described outer tube is boron nitride.The outer tube of the silver of the present invention/silver chloride reference electrode is that boron nitride powder carries out hot-forming preparing, and described micropore is by getting with the drill bit that sword footpath is 0.1～0.3mm on described outer tube.The silver of the present invention/silver chloride reference electrode, use that temperature range is wide, it is simple and convenient, with low cost to make, stability strong, favorable reproducibility, good reversibility, corrosion-resistant, the response of length in service life, signal is fast, accuracy is high, not Pollution Study system, easy to use, easily stored, be beneficial to industrialized production.The preparation method processing of the silver of the present invention/silver chloride reference electrode is simple, simple and convenient assembly is quick.
Description
Technical field
The present invention relates to a kind of silver/silver chloride reference electrode and preparation method thereof.
Background technology
In electrochemical research and commercial production, high-temperature fusion salt system is all an important field.At chlorine
In compound mixed melting salt system, such as LiCl-KCl, LiCl-NaCl, LiCl-CaCl2And NaCl-MgCl2
Etc. in system, their electrochemistry Quality Research is increasingly paid close attention to by people.At electrochemistry
In Quality Research, in the measurement of the most various electrochemical parameters, three-electrode system is easy to operate because of it,
The data obtained is with a high credibility and enjoys favor.These three-electrode systems are in the measurement of electrochemical parameter, surely
Qualitative by force, favorable reproducibility, service life length reference electrode for measure play vital effect.
But, due in high-temperature molten salt system due in temperature height, high volatility, research process influence factor multiple
The reason such as miscellaneous, so there being the requirement of harshness to the selection of reference electrode.
At present, this area there is no general reference electrode, and the reference electrode of existing main employing has gas to join
Than electrode, metal reference electrode, silver/silver chloride electrode or directly metal platinum or graphite are inserted fuse salt
In false reference electrode.In these reference electrodes, some makes complicated, cost height, and some current potential is stable
Time is short, some poor reproducibility, and some time reaching steady statue before use is long, and some pollution is ground
Studying carefully system, some Applicable temperature is narrow (as quartz can not less than 823K in temperature as reference electrode outer tube
Realizing ion conducting, its temperature range is between 873-1173K), some is the most corrosion-resistant, some
Be weak to variations in temperature, frangible (during such as borosilicate glass as reference electrode outer tube, borosilicate glass
Being easily subject to variations in temperature impact and rupture, some is not easy to store, and so causes reference salt to reveal and draw
Play reference electrode potential drifting, Pollution Study system), thus be all not convenient to use.
Therefore, develop and a kind of use that temperature range is wide, make simple and convenient, with low cost, stability
By force, favorable reproducibility, good reversibility, the response of corrosion-resistant, length in service life, signal is fast, accuracy is high,
Easily stored, not Pollution Study system, reference electrode easy to use, be urgently to be resolved hurrily the asking in this area
Topic.
Summary of the invention
The technical problem to be solved in the present invention is to overcome in prior art three-electrode system at chloride
During the electrochemical parameter of mixed melting salt system is measured, reference electrode makes complexity, cost is high, current potential is steady
Fix time reach before short, poor reproducibility, use the time length of steady statue, Pollution Study system, some
Applicable temperature is narrow, be weak to burn into be weak to variations in temperature, frangible, be not convenient to use, be unfavorable for store,
It is unfavorable for the defects such as industrialized production, and provides a kind of silver/silver chloride reference electrode and preparation method thereof.
The silver of the present invention/silver chloride reference electrode, use temperature range is wide, it is simple and convenient, with low cost to make,
Stability is strong, favorable reproducibility, good reversibility, corrosion-resistant, the response of length in service life, signal is fast, accurately
Property high, not Pollution Study system, easy to use, easily stored, be beneficial to industrialized production.The present invention's
The preparation method processing of silver/silver chloride reference electrode is simple, simple and convenient assembly is quick.The reference electrode of the present invention
It is applicable to the electrochemistry Quality Research of the chloride mixed melting salt system of 673～1153K.
The present invention solves above-mentioned technical barrier the most by the following technical programs.
The invention provides a kind of silver/silver chloride reference electrode, it includes a bolt, an outer tube, a conduction
Lead-in wire rod, a silver electrode and reference salt；It is provided with female thread at the one end open of described outer tube；Described outer tube
The other end close, and to be provided with one or two straight position apart from this end 10～20mm in the axial direction
Footpath is the micropore of 0.1～0.3mm；The inside of described bolt is provided with the internal cavity at through two ends；In described
Cavity is provided with female thread；The outside of described conductive lead wire rod one end is provided with external screw thread；Described conductive lead wire
The other end of rod is connected with one end of described silver electrode；The other end of described silver electrode is positioned at described reference salt
In；The external screw thread of described bolt and the female thread of described outer tube match；The outer spiral shell of described conductive lead wire rod
The female thread of stricture of vagina and described bolt matches；Described reference salt is muriatic mixed with other containing silver chloride
Close salt；The material of described bolt and described outer tube is boron nitride.
It is preferred that the position of described micropore is positioned at blind end 13mm～18mm of described outer tube.
It is preferred that the thickness of described micropore is less than the thickness of described outer tube；More preferably, described reference salt
Melt temperature is when 623～773K, and the thickness of described micropore is 0.1～0.2mm, melting of described reference salt
Melting temperature when 773～1073K, the thickness of described micropore is 0.2～0.3mm.
Usually, according to common sense in the field, the excellent and described silver electrode of described conductive lead wire is connected, be in order to
Playing the purpose of current lead-through, therefore, described connected mode is as the criterion not loosen.
It is preferred that described outer tube and described bolt total length after screwing is no less than 3cm；It is more preferably
3～10cm；Such as 5cm.
It is preferred that the overall diameter of described outer tube is 5～20mm, such as 12mm.
It is preferred that the thickness of described outer tube is 2～5mm, such as 3mm.
It is preferred that the female thread of described bolt is left-handed, external screw thread is dextrorotation；Or, described bolt
Female thread be dextrorotation, external screw thread be left-handed.
It is preferred that the pitch of the female thread of described bolt is 0.5～1.5mm.
It is preferred that the externally threaded pitch of described bolt is 0.5～1.5mm.
It is preferred that the blind end of described outer tube, it is internal is step structure or pyramidal structure, and distance
The nearer one end of outer tube end is less inner-diameter end.
It is preferred that the less internal diameter of described step structure is 1～2mm, larger interior diameter is 3～4mm；
And a length of the 6～8mm of the part of the less internal diameter of described step structure.
It is preferred that the material of described conductive lead wire rod is one or more in copper, nickel and ferrum；More preferably,
The material of described conductive lead wire rod is copper.
It is preferred that a length of the 3～4cm of described conductive lead wire rod.
It is preferred that a diameter of the 1 of described silver electrode～2mm.
It is preferred that a length of the 4 of described silver electrode～5cm.
It is preferred that described reference salt is dry salt.
It is preferred that described reference salt is the reference salt through dehydration and deoxidation pretreatment.
It is preferred that the particle diameter that described reference salt is when room temperature is 100～200 mesh.
Usually, other described chlorides, the ratio of the amount of its kind and the material between them be with
Muriatic kind in the fuse salt system that reference electrode is to be studied and the ratio phase one of the amount of material
Cause.
Other described chlorides can be the various conventional chlorinating thing in this area in addition to silver chloride.Preferably
Ground, other chlorides described are containing lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride and chlorine
Change in barium two or more；It is more preferably lithium chloride and potassium chloride, or lithium chloride and sodium chloride.
It is preferred that the consumption of described silver chloride is 1～15%, percentage ratio be silver chloride molal quantity relative to
The percentage ratio of muriatic total molal quantity in salt-mixture；It is more preferably 2～10%.
During it is preferred that other chlorides described are lithium chloride and potassium chloride, described lithium chloride: described
Potassium chloride: the mol ratio of described silver chloride is (38～40): (14～16): 1；Other chlorides described
During for lithium chloride and sodium chloride；Described lithium chloride: described sodium chloride: the mol ratio of described silver chloride is
(48～50): (10～12): 1.
It is preferred that the store method of described silver/silver chloride reference electrode is for being dried, keeping in Dark Place；More preferably
For keeping in Dark Place in glove box.
Present invention also offers the preparation method of a kind of described silver/silver chloride reference electrode, it comprises following step
Rapid:
S1, carries out hot-forming by boron nitride powder, prepares described outer tube, and uses sword on described outer tube
Footpath be 0.1～0.3mm drill bit get described micropore；
S2, is placed in described reference salt in described outer tube；
S3, is attached one end of described silver electrode with described conductive lead wire rod；
S4；Excellent for described conductive lead wire and described bolt is screwed；
Finally described bolt is screwed with described outer tube；
Wherein, S2 must be after S1 order, and S1, S2, S3 and S4 are in other combinations sequentially not
Limit.
It is preferred that the method that the drill bit that described sword footpath is 0.1～0.3mm gets described micropore uses manual
Hold bit bore.
It is preferred that described sword footpath is 0.1mm.
It is preferred that described drill bit is tungsten bur.
It is preferred that described hot-forming temperature is 1600～2000 DEG C；It is more preferably 1800 DEG C.
It is preferred that described hot-forming pressure is 25～35MPa；It is more preferably 30MPa.
It is preferred that the method that the excellent and described silver electrode of described conductive lead wire is connected is in following three kinds of methods
A kind of:
Method one, described silver electrode are wound in described conductive lead wire this end of rod；
The end face of this end of method two, described conductive lead wire rod is provided with a hole, the one of described silver electrode
End is placed in described hole；
Method three, described conductive lead wire rod are provided with the axial internal cavity at through two ends, and described silver electrode is inserted
Enter in described axial internal cavity, and containing female thread and to be perpendicular to it axial one on described conductive lead wire rod
The transverse passageway in direction, described transverse passageway is through to described axially from the outer surface of described conductive lead wire rod
Internal cavity；Described transverse passageway is rotary with containing externally threaded cross bolts, to fasten described silver electrode.
According to general knowledge, the effect of described transverse passageway is in order to make described filamentary silver and described conductive lead wire rod
Being completely embedded unlikely loosening, the internal diameter of the most described transverse passageway and thread pitch need not be particularly limited to,
Can be realized this act on.
During it is preferred that the thickness of described micropore is less than the thickness of described outer tube, " get described micro-described
Hole " carry out before, first the wall of described micro well locations and neighbouring outer tube is polished thinning.
Usually, described polishing uses machine tool to carry out conventional polishing.
Usually, recessed at this on outer tube after polishing.
In the present invention, described room temperature refers to that ambient temperature is 10～35 DEG C.
On the basis of meeting common sense in the field, above-mentioned each optimum condition, can combination in any, i.e. get Ben Fa
Bright each preferred embodiments.
Agents useful for same of the present invention and raw material are the most commercially.
The most progressive effect of the present invention is:
(1) reference electrode prepared by the present invention has that response signal is fast, soaks in fuse salt 1 hour
In can carry out electro-chemical test；Stability is high, at experiment test in 223 hours, and potential drifting
Less than 20mV；Reproduction performance is good, with OCP between batch reference electrode made less than 5mV；Accurate
Really property is high, to test lithium chloride decomposition voltage for object of study test value and literature value error less than 10
mV。
(2) prepared by the present invention, reference electrode conducting mechanism is the micro channel that ion passes through outer tube lower end,
Using in high-temperature chlorine compound salt-mixture system will not Pollution Study system.
(3) the reference electrode use boron nitride ceramic material prepared by the present invention is as reference electrode outer tube,
High temperature resistant, the fused salt corrosion of resistance to chloride, will not rupture in the case of suddenly cold and hot, prepared reference electricity
Stabilizer pole performance is good.
(4) reference electrode prepared by the present invention is when bottom internal diameter is related to trapezoidal, due to operationally
In reference salt, most of silver chloride are deposited in melted reference salt with supersaturation dissolved state, therefore outer tube
Bottom part can accommodate the AgCl of excess, when AgCl amount loss in interior reference salt, bottom excess
AgCl can supplement in time, keeps the stability of reference electrode；And trapezoidal design can subtract again
The consumption of few AgCl, reference electrode design is the most economical.
(5) reference electrode made by the present invention uses compressing boron nitride ceramic material to make outer tube,
Outer tube quality is softer, it is easy to processing, and other fitment material are easy to get, and processing is simple, simple and convenient assembly, quick,
Easily stored, beneficially industrialized production.
(6) reference electrode prepared by the present invention is long for shelf life.
Accompanying drawing explanation
Fig. 1 is the structural representation of silver/silver chloride reference electrode obtained in embodiment 1；Wherein 1
For outer tube；2 is bolt；3 is silver electrode；4 is micropore；5 is step structure；6 is conductive lead wire
Rod；7 is reference salt；8 is cross bolts.
Fig. 2 is in test different time lithium analysis in the reference electrode stability test example in effect example 1
Different time points cyclic voltammetry figure when going out potential drifting.
Fig. 3 is the partial enlarged drawing of Fig. 2.
Fig. 4 be the lithium deposition potential in the reference electrode stability test example in effect example 1 in time
Variation diagram.
Fig. 5 is the reference of two present invention in the reference electrode repeatability test case in effect example 1
Interelectrode OCP test figure.
Fig. 6 is to be the ginseng of two present invention in the reference electrode reversibility test case in effect example 1
Than cyclic voltammetry figure between electrode.
Fig. 7 is that the reference electrode in effect example 1 tests lithium chloride in LiCl-KCl molten salt system
Theoretical decomposition voltage figure.
Detailed description of the invention
Further illustrate the present invention below by the mode of embodiment, but the most therefore limit the present invention to
Among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to often
Rule method and condition, or select according to catalogue.
Embodiment 1
A kind of boron nitride sleeve using bottom to be equipped with micropore encapsulation is through the chlorination of dehydration and deoxidation pretreatment
The method that Ag/AgCl reference electrode prepared by lithium-potassium chloride-silver chloride reference salt, comprises the following steps:
(1) length 50mm is produced, the boron nitride sleeve (i.e. outer tube 1) of diameter 12mm.
This boron nitride sleeve is hot-forming (temperature 1800 DEG C, pressure 30MPa), and raw material is boron nitride powder
End.Sleeve bottom internal diameter stepped (i.e. step structure 5), internal diameter is that a segment length of 7mm is
39mm, internal diameter be 4mm mono-segment length be 8mm, distance bottom seal end 13mm at use drill bit
Sword footpath is the micropore (i.e. micropore 4) that the tungsten bur of 0.1mm beats a diameter of 0.1mm；Ferrule openings end
Containing female thread；
(2) accurately weighing thing mass ratio is the lithium chloride of 56.05:38.95:5, potassium chloride, silver chloride
Totally 10 grams, under 573K, drying under reduced pressure is after 3 hours, standby after grinding；Weigh the dried chlorine of 0.8g
Change lithium-potassium chloride-silver chloride reference salt 7 to put in boron nitride sleeve；
(3) filamentary silver (i.e. silver electrode 3) of a diameter of 1mm, a length of 5cm is taken, and diameter 4mm,
The copper rod (i.e. conductive lead wire rod 6) of a length of 4cm, copper rod has diameter 1mm, the axle at through two ends
To internal cavity, and copper rod one end has external screw thread, the other end to have the groove can being connected with conduction instrument end,
This trench bottom position the most on the lower, copper rod has a transverse passageway；This transverse passageway is through from copper rod outer surface
To axial internal cavity；Transverse passageway has female thread.Filamentary silver and transverse passageway is filled in the axial internal cavity of copper rod
The bolt (i.e. cross bolts 8) that interior screw-in one screw thread is supporting, threaded bolt contacts filamentary silver also screws and makes fastening filamentary silver
Do not loosen.Copper rod contains externally threaded one end and one end (i.e. bolt 2) on female bolt
Screwing, this bolt 2 other end contains external screw thread；
(4), bolt 2 is screwed in containing externally threaded one end the opening of boron nitride sleeve, can prepare
One good silver/silver chloride reference electrode.
Silver/silver chloride reference electrode obtained according to the method described above, its structure is as it is shown in figure 1, its structure
Including bolt 2, outer tube 1, conductive lead wire rod 6, step structure 5, silver electrode 3,
Reference salt 7 and cross bolts 8；It is provided with female thread at the one end open of described outer tube；Described outer tube another
One end is closed, and position apart from this end 13mm is provided with the micro-of an a diameter of 0.1mm in the axial direction
Hole 4；The inside of described bolt is provided with the internal cavity at through two ends；Described internal cavity is provided with female thread；
The outside of described conductive lead wire rod one end is provided with external screw thread；Described conductive lead wire rod the other end have can with lead
The groove that electricity instrument end connects, on the copper rod of this trench bottom position the most on the lower, has a transverse passageway；
This transverse passageway is from through to the axial internal cavity of copper rod outer surface；Transverse passageway has female thread；Transverse passageway
The bolt (i.e. cross bolts 8) that interior screw-in one screw thread is supporting, threaded bolt contacts filamentary silver also screws and makes fastening filamentary silver
Do not loosen；One end of described silver electrode is placed in described hole；The other end of described silver electrode is positioned at described
In reference salt；The external screw thread of described bolt screws mutually with the female thread of described outer tube；Described conductive lead wire rod
External screw thread screw mutually with the female thread of described bolt；Described reference salt is silver chloride, lithium chloride and chlorination
The salt-mixture of potassium；Described bolt and described outer tube are boron nitride insulating ceramics；Described outer pipe bottom interior
The stepped structure in footpath 5.
Reference electrode made by the present invention uses compressing boron nitride ceramic material to do outer tube, outer tube matter
Ground is softer, it is easy to processing, and other fitment material are easy to get, and processing is simple, simple and convenient assembly, quick, it is easy to
Store, beneficially industrialized production.
Effect example 1
The lithium chloride 91.9 grams that dehydration and deoxidation of learning from else's experience processes, puts into after 111.9 grams of mix homogeneously of potassium chloride
Proceed in the lump in electric furnace after in graphite crucible.Test being inserted with the electric furnace cover Sealed electric oven of various electrodes.
In burner hearth, logical high-purity argon gas is to eliminate air in burner hearth, and maintains argon gas atmosphere in burner hearth all the time.
Heating schedule is set, after 90 minutes are warmed up to 723K, by working electrode (diameter 1mm tungsten filament),
To electrode (diameter 5mm carbon-point) with according to two boron nitride sleeves prepared by the method for embodiment 1
Ag/AgCl reference electrode is inserted into the following certain altitude of fused salt liquid level and carries out electrochemical measurement.Electrochemistry is surveyed
Examination platform AUTOLAB 302N.
1) stability test
Keep reference electrode to be immersed in molten salt system always, use the precipitation of cyclic voltammetric method test lithium
Current potential, thus determine the stability of reference electrode.Cyclic voltammetric voltage scan range is set for-2.63-0
V, sweep speed 0.1V/s.From the beginning of reference electrode soaks fused salt internal latter 0.5 hour, measure continuously
Using 223 hours lithium deposition potential situations of change, result is shown in Fig. 2, Fig. 3 and Fig. 4, and wherein Fig. 3 is
The partial enlarged drawing of Fig. 2.By Fig. 2 and Fig. 3 can be seen that after reference electrode soaks 1.5 hours,
The display reference electrode stable performance of CV curve.As shown in Figure 4, extend soak time to 122 hours,
Lithium deposition potential positive excursion 10mV；In the range of between at this moment, reference electrode is believable.Continue to extend
Reference electrode uses time to 223 hours, lithium deposition potential positive excursion 20mV, now reference electrode
Error occurs.Visible, reference electrode prepared by the present invention has that response signal is fast, soaks in fuse salt
Electro-chemical test can be carried out in 1 hour；Stability is high, at experiment test in 223 hours, and electricity
Position drift is less than 20mV.Further, the reference electrode prepared by the present invention uses boron nitride ceramic material to make
For reference electrode outer tube, high temperature resistant, the fused salt corrosion of resistance to chloride, will not break in the case of suddenly cold and hot
Splitting, prepared reference electrode stability is good, such as, sends out above-mentioned that is in the present embodiment of room temperature
Bright reference electrode is inserted directly in the molten salt system of 923K temperature, and reference electrode will not rupture.
And, reference electrode prepared by the present invention is when bottom internal diameter is related to trapezoidal, due to operationally reference
In salt, most of silver chloride are deposited in melted reference salt with supersaturation dissolved state, therefore outer tube bottom
Part can accommodate the AgCl of excess, when AgCl amount loss in interior reference salt, and the AgCl of bottom excess
Can supplement in time, keep the stability of reference electrode；And trapezoidal design can reduce again AgCl
Consumption, reference electrode design the most economical.
2) repeatability test
Using two self-control reference electrodes in one as working electrode, other one as reference electrode,
Using graphite electrode as to electrode.The OCP (Fig. 5) of two reference electrodes of test.Soak at electrode
OCP about 5mV between two reference electrodes in one hour, hereafter uses the 103 of the time at electrode
In hour, as shown in Fig. 5 dotted line frame, the OCP between two reference electrodes maintains 3-4mV
Between.Visible, it is good, with open circuit electricity between batch reference electrode made that the reference electrode of the present invention reappears performance
Position is less than 5mV.
3) reversibility test case
Take wherein one self-control boron nitride sleeve reference electrode as working electrode, an other boron nitride set
Pipe reference electrode is as reference electrode, using graphite rod as to electrode.CV curve under test system comes
The reversibility of the reference electrode prepared by judgement, result is shown in Fig. 6.As can be seen from Figure 6 at-0.5V-0.5V
Potential range in, positive and negative both direction scanning curve be completely superposed.
4) accuracy test case
With tungsten filament as working electrode, carbon-point is to electrode, makes Ag/AgCl reference electrode by oneself.To work electricity
Pole applies-50mA operating current 10s, the most instantaneous applying electric current that removes, and now can record Li+/Li
Vs Ag/AgCl electromotive force.Same method applies the operating current 10s of 100mA to working electrode, then
Suddenly remove electric current, Cl2/Cl-Vs Ag/AgCl electromotive force can be recorded.Two electromotive force absolute value sums are i.e.
It it is the theoretical decomposition voltage of lithium chloride under this system.Experimental result is as it is shown in fig. 7, record lithium chloride 723
The theoretical decomposition voltage of K is 3.665V.Visible, the reference electrode accuracy of the present invention is high, with test
Lithium chloride decomposition voltage is that (literature values is in 3.722V (673K) for object of study test value and literature value
And between 3.646V (773K)) error is less than 10mV.
5) to test system molten salt system contamination test case
LiCl-KCl fused salt after soaking at a temperature of 450 DEG C 223 hours of prepared reference electrode is taken
Sample, and use ICP-AES to be analyzed test silver element content therein, to judge through long-time
Immersion, whether the silver ion in reference electrode leaks in body fused salt.Testing result is silver element
Concentration is less than the Monitoring lower-cut of instrument less than 0.1ppm, the i.e. silver element concentration in body fused salt.It is visible,
Prepared by the present invention, reference electrode conducting mechanism is the micro channel that ion passes through outer tube lower end, in high-temperature chlorine
Using in compound salt-mixture system will not Pollution Study system.
6) test case electrode life
Preserve, without any in being placed on glove box after being taken out from fused salt by used reference electrode
Processing after placing 30 days, reference electrode property retention is constant.The above-mentioned store method of reference electrode,
Reusing in same molten salt system 10 times, reference electrode property retention is constant.
Claims (10)
1. silver/silver chloride reference electrode, it is characterised in that it include a bolt, an outer tube, one
Conductive lead wire rod, a silver electrode and reference salt；It is provided with female thread at the one end open of described outer tube；Described
The other end of outer tube is closed, and position apart from this end 10～20mm is provided with one or two in the axial direction
Individual a diameter of 0.1～the micropore of 0.3mm；The inside of described bolt is provided with the internal cavity at through two ends；Institute
State internal cavity and be provided with female thread；The outside of described conductive lead wire rod one end is provided with external screw thread；Described conduction
The other end of lead-in wire rod is connected with one end of described silver electrode；The other end of described silver electrode is positioned at described ginseng
Ratio is in salt；The external screw thread of described bolt and the female thread of described outer tube match；Described conductive lead wire rod
The female thread of external screw thread and described bolt matches；Described reference salt is containing silver chloride and other chlorides
Salt-mixture；The material of described bolt and described outer tube is boron nitride.
2. silver/silver chloride reference electrode as claimed in claim 1, it is characterised in that: described micropore
Position is positioned at blind end 13mm～18mm of described outer tube；And/or, the thickness of described micropore
Less than the thickness of described outer tube.
3. silver/silver chloride reference electrode as claimed in claim 2, it is characterised in that: described reference salt
Melt temperature when 623～773K, the thickness of described micropore is 0.1～0.2mm, described reference salt
Melt temperature is when 773～1073K, and the thickness of described micropore is 0.2～0.3mm.
4. silver/silver chloride reference electrode as claimed in claim 1, it is characterised in that: described outer tube
Blind end, it is internal is step structure or pyramidal structure, and is relatively apart from one end that outer tube end is nearer
Little inner-diameter end.
5. silver/silver chloride reference electrode as claimed in claim 4, it is characterised in that: described stepped
The less internal diameter of structure is 1～2mm, and larger interior diameter is 3～4mm；And described step structure is less
A length of the 6 of the part of internal diameter～8mm.
6. silver/silver chloride reference electrode as claimed in claim 1, it is characterised in that:
Described outer tube and described bolt total length after screwing is no less than 3cm；
And/or, the overall diameter of described outer tube is 5～20mm；
And/or, the thickness of described outer tube is 2～5mm；
And/or, the material of described conductive lead wire rod is one or more in copper, nickel and ferrum；
And/or, the female thread of described bolt be left-handed, external screw thread be dextrorotation；Or, described bolt interior
Screw thread be dextrorotation, external screw thread be left-handed；
And/or, the pitch of the female thread of described bolt is 0.5～1.5mm；
And/or, the externally threaded pitch of described bolt is 0.5～1.5mm；
And/or, a length of the 3～4cm of described conductive lead wire rod；
And/or, a diameter of the 1 of described silver electrode～2mm；
And/or, a length of the 4 of described silver electrode～5cm；
And/or, described reference salt is dry salt；
And/or, the described reference salt particle diameter when room temperature is 100～200 mesh；
And/or, other chlorides described are containing lithium chloride, sodium chloride, potassium chloride, magnesium chloride, chlorination
Two or more in calcium and barium chloride；
And/or, the consumption of described silver chloride is 1～15%, percentage ratio be silver chloride molal quantity relative to
The percentage ratio of muriatic total molal quantity in salt-mixture.
7. silver/silver chloride reference electrode as claimed in claim 6, it is characterised in that: described conduction is drawn
The material of bar is copper；And/or, when other chlorides described are lithium chloride and potassium chloride, described chlorination
Lithium: described potassium chloride: the mol ratio of described silver chloride is (38～40): (14～16): 1；Described
When other chlorides are lithium chloride and sodium chloride；Described lithium chloride: described sodium chloride: described silver chloride
Mol ratio is (48～50): (10～12): 1.
8. a preparation method for silver/silver chloride reference electrode as according to any one of claim 1～7,
It is characterized in that, it comprises the steps of:
S1, carries out hot-forming by boron nitride powder, prepares described outer tube, and uses sword on described outer tube
Footpath be 0.1～0.3mm drill bit get described micropore；
S2, is placed in described reference salt in described outer tube；
S3, is attached one end of described silver electrode with described conductive lead wire rod；
S4；Excellent for described conductive lead wire and described bolt is screwed；
Finally described bolt is screwed with described outer tube；
Wherein, S2 must be after S1 order, and S1, S2, S3 and S4 are in other combinations sequentially not
Limit.
9. the preparation method of silver/silver chloride reference electrode as claimed in claim 8, it is characterised in that:
Described sword footpath be 0.1～0.3mm drill bit get the method for described micropore and use and manual hold drill bit
Boring；
And/or, described drill bit is tungsten bur；
And/or, described hot-forming temperature is 1600～2000 DEG C；
And/or, described hot-forming pressure is 25～35MPa；
And/or, when the thickness of described micropore is less than the thickness of described outer tube, described " getting described micropore "
Before carrying out, first the wall of described micro well locations and neighbouring outer tube is polished thinning；
And/or, the method that the excellent and described silver electrode of described conductive lead wire is connected is in following three kinds of methods
Kind:
Method one, described silver electrode are wound in described conductive lead wire this end of rod；
The end face of this end of method two, described conductive lead wire rod is provided with a hole, the one of described silver electrode
End is placed in described hole；
Method three, described conductive lead wire rod are provided with the axial internal cavity at through two ends, and described silver electrode is inserted
Enter in described axial internal cavity, and containing female thread and to be perpendicular to it axial one on described conductive lead wire rod
The transverse passageway in direction, described transverse passageway is through to described axially from the outer surface of described conductive lead wire rod
Internal cavity；Described transverse passageway is rotary with containing externally threaded cross bolts, to fasten described silver electrode.
10. the preparation method of silver/silver chloride reference electrode as claimed in claim 9, it is characterised in that: institute
Stating sword footpath is 0.1mm；Described hot-forming temperature is 1800 DEG C；Described hot-forming pressure is
30MPa。
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