CN104715871A - Method for treating high-temperature oxide skin on surface of lithium thionyl chloride battery insulator - Google Patents
Method for treating high-temperature oxide skin on surface of lithium thionyl chloride battery insulator Download PDFInfo
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- CN104715871A CN104715871A CN201510079570.9A CN201510079570A CN104715871A CN 104715871 A CN104715871 A CN 104715871A CN 201510079570 A CN201510079570 A CN 201510079570A CN 104715871 A CN104715871 A CN 104715871A
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- thionyl chloride
- lithium thionyl
- chloride cell
- high temperature
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Abstract
The invention discloses a method for treating high-temperature oxide skin on the surface of a lithium thionyl chloride battery insulator. The method includes the following steps that firstly, the lithium thionyl chloride battery insulator to be treated is placed in acid liquor, and the oxide skin on the surface of the lithium thionyl chloride battery insulator is removed; secondly, ultrasonic cleaning is adopted for the lithium thionyl chloride battery insulator treated in the first step, and dust and dead-angle oxide skin on the surface of the lithium thionyl chloride battery insulator are removed; thirdly, the lithium thionyl chloride battery insulator retreated in the second step is subjected to passivating treatment, and a corrosion-resistant passive film is formed on the surface of the lithium thionyl chloride battery insulator. According to the method for treating the high-temperature oxide skin on the surface of the lithium thionyl chloride battery insulator, the reaction speed is moderate, control is easy, the oxide skin is cleaned away completely, and acid cleaning consistency is good.
Description
Technical field
The invention belongs to technical field of surface, be specifically related to a kind of lithium thionyl chloride cell insulator surface high temperature scale processing method.
Background technology
Lithium thionyl chloride cell is the battery that in current chemical power source, specific energy is the highest, possesses the feature of long term storage energy, is widely used in intellectual water meter, ammeter, in the low energy consumption industrial equipments such as gas meter, flow meter.The surface appearance of its key components and parts---glass sealing insulator cover group plays vital effect for the performance of its performance.The sub-battery insulator of lithium is assembled, at N by 304 stainless steel cover plates, Pyrex base and 4J28 stem stem in graphite jig
2form through 1020 DEG C of high temperature sealings by fusing under gas shielded.The grey black oxide skin of its Surface Creation and matrix adhesive force extremely strong, not only have a strong impact on presentation quality and the performance of product, to following process and use also very unfavorable.
The sub-battery insulator high temperature scale of lithium is the mixture of the high temperature sintering product of 304 stainless steels and kovar alloy 4J28.At present, surface treatment method in the industry for this product does not still have comparatively mature and stable process, simultaneously main cause removes totally by the oxide skin that two states and composition are not quite similar by same solution or method, and will to ensure that two kinds of matrixes do not weather be very difficult.If surface treatment is improper, not only waste of manpower, material resources, financial resources, the greater loss such as also likely finally cause that insulator surface spot corrosion, dimension overproof are even scrapped.Therefore, explore a kind of simple and practical surface treatment method and there is theoretical research value widely and actual production meaning.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provide a kind of reaction speed moderate, be easy to control, clean up and pickling consistency good lithium thionyl chloride cell insulator surface high temperature scale processing method.
For solving the problems of the technologies described above, the technical solution used in the present invention is, a kind of lithium thionyl chloride cell insulator surface high temperature scale processing method, comprises the following steps:
Step one, pending lithium thionyl chloride cell insulator is positioned in acid solution, removes the oxide skin on its surface;
Step 2, in step one process after lithium thionyl chloride cell insulator take Ultrasonic Cleaning, remove its surperficial dust and dead angle oxide skin;
Step 3, the thionyl chloride battery insulator after reprocessing in step 2 is carried out Passivation Treatment, make its surface form corrosion resistant passivating film.
Further, the acid solution in step one is H
2sO
4, HNO
3with the mixed liquor of HF.
Further, also H is comprised in the acid solution in step one
3pO
4.
Further, H
2sO
4, HNO
350 ~ 100g/L, 40 ~ 80g/L, 20 ~ 50g/L is respectively with the concentration of HF.
Further, H
3pO
4concentration be 40 ~ 100g/L.
Further, also comprise corrosion inhibiter in acid solution, described corrosion inhibiter is methenamine or sulfamic acid, and the content of described corrosion inhibiter is 0.5 ~ 3g/L.
Further, pending lithium thionyl chloride cell insulator is positioned over before in acid solution, also needs its surface removal greasy dirt, and fully wetting to it.
Further, before Passivation Treatment, also need to carry out mechanical polishing to lithium thionyl chloride cell insulator, to remove residue.
Further, before carrying out mechanical polishing, adopt Ultrasonic Cleaning, to remove piece surface dust and dead angle oxide skin.
Further, concentration is adopted to be the HNO of 300 ~ 700g/L in described step 3
3carry out Passivation Treatment.
A kind of lithium thionyl chloride cell insulator surface of the present invention high temperature scale processing method, adopt the mode that pickling, mechanical polishing and Passivation Treatment combine, and have employed Ultrasonic Cleaning, achieve without dead angle, omnibearing surface treatment, selected acid solution can the oxide skin of dissolving lithium thionyl chloride battery insulator surface well.Achieve the oxide skin adopting single acid solution simultaneously can process different parts and save operation, save cost.The acid solution good stability adopted, process hourly velocity is moderate.Handled good product consistency.Meanwhile, operating environment is comparatively safe.Generate the salt of nitrose and salt acids after dissolving, the salt of generation is soluble, is convenient to cleaning.
Accompanying drawing explanation
Fig. 1 is that 304 stainless steel cover plates are at N
2the X-Ray diffracting spectrum of oxide skin in gas.
Fig. 2 is that 4J28 stem stem is at N
2the X-Ray diffracting spectrum of oxide skin in gas.
Fig. 3 is the X-Ray diffracting spectrum of 304 stainless steels oxide in atmosphere.
Fig. 4 is sealing-in curve synoptic diagram.
Fig. 5 is 304 stainless steel cover plate high-temperature oxide tissue topography figure;
Wherein: the microscopic appearance figure of cover plate frontside oxide when a is protective gas abundance;
B is the not enough and cover plate backside oxide be close to graphite jig of protective gas, microstructure morphology figure.
Fig. 6 is 4J28 stem stem high-temperature oxide tissue topography figure;
Wherein: a is that the position oxide tissue topography be close to graphite schemes;
B is the position oxide tissue topography figure not having graphite jig to protect.
Embodiment
A kind of lithium thionyl chloride cell insulator surface of the present invention high temperature scale processing method, comprises following steps successively:
Pending lithium thionyl chloride cell insulator is positioned over before in acid solution, to its surface removal greasy dirt, and fully wetting to it; At room temperature, pending lithium thionyl chloride cell insulator is positioned in acid solution, removes the oxide skin on its surface; Take Ultrasonic Cleaning 10 ~ 15min, remove dust and the dead angle oxide skin on its surface; Mechanical polishing is carried out to lithium thionyl chloride cell insulator, to remove residue; Carry out Passivation Treatment 30 ~ 60min, wherein, adopt concentration to be the HNO of 300 ~ 700g/L
3carry out Passivation Treatment, make its surface form corrosion resistant passivating film; Adopt the water of flowing to clean up, and then dried, bake out temperature is 60 ~ 100 DEG C.
A kind of lithium thionyl chloride cell insulator surface of the present invention high temperature scale processing method, adopt the mode that pickling, mechanical polishing and Passivation Treatment combine, and in processing procedure, have employed Ultrasonic Cleaning, piece surface greasy dirt is removed before pickling, and fully wetting to it, when ensureing pickling, acid solution can contact with high temperature scale well, and after wipe oil, decrease the pollution to acid solution in cleaning process, can acid solution be reused.Adopt ultrasonic cleaning after pickling, removing piece surface dust and dead angle oxide skin, then mechanical polishing, abrasive material, to piece surface rubbing down, is removed residue, is made surface smoothing, light, to facilitate Passivation Treatment, make piece surface form corrosion resistant passivating film.Passivating film has blocked the contact of matrix and extraneous wet environment, and prevent matrix to be etched, secondary gets rusty.
Adopt the lithium thionyl chloride cell insulator that as above step process is pending, the component of the acid solution adopted in processing procedure is as shown in table 1:
Table 1 specific embodiment
Lithium thionyl chloride cell insulator (all size) used in experiment, at meshbeltfurnace through 1020 DEG C high temperature sinterings forms after being assembled by 304 stainless steel cover plates, 4J28 kovar alloy stem stem and Pyrex base.Its chemical element content is as shown in table 2.
Table 2 technical grade 304 stainless steel and 4J28 alloying element content
304 stainless steels are containing multiple elements such as Fe, Cr, Ni, Mn, C, Si, P, S, and belong to austenite (Fe-Cr-Ni) stainless steel, crystal structure is face-centred cubic ferrous alloy, all very complicated in oxidation kinetics or in oxidation type.4J28 kovar alloy is a kind of special expansion steel, basically identical with 55 stainless steels (1Cr28) composition, belongs to a kind of ferrite (Fe-Cr) stainless steel, and owing to greatly improving containing Cr amount, its decay resistance is also eager to excel than 304.
Insulator is at N
2oxide phase composition under protection, the composition of sealing alloy oxide-film and state, outside the Pass having with material composition, also relevant with oxidation technology.To the sub-battery insulator of lithium at N
2the lower high-temperature oxide generated of protection carries out X-ray analysis, and as shown in Figure 1, the high temperature scale of cover plate is NiO
2, CrO
3, FeOCr
2o
3, FeOCr
2o3Fe
2o
3deng dense form product, very complicated.
4J28 stem stem is at N
2under gas shielded, the high temperature scale of Surface Creation is Fe-Cr solid solution, Cr
2n, FeCr
2o
4, Cr
23c
6deng dense form oxide.As shown in Figure 2.
And the oxide skin that stainless steel generates in atmosphere generally only comprises α-Fe, Fe
3o
4or Fe
3-yo
4phase, in addition, according to Ellingham Richardson diagram, in the scope of room temperature to 1600 DEG C, the standard free energy of formation of chromium oxide is all lower than the oxide of iron, and chromium is easier than iron to be combined with oxygen.XRD detects and shows, chromium element is not with Cr
2o
3exist mutually, and with Fe
3-ycr
yo
4exist mutually, as shown in Figure 3.
Insulator is at N
2oxidation kinetics under protection, tests high-sintering process curve that lithium thionyl chloride cell insulator used experiences as shown in Figure 4.304 stainless steel cover plates and 4J28 stem stem always experience such oxidation kinetics process in sealing-in process: be one from room temperature to 900 DEG C and be oxidized the incubation period, along with the rising of temperature, oxide skin slowly increases, and at soak, oxide skin obviously increases; From room temperature to most sealing temperature, Cr
2o
3standard generate lower than the oxide of Fe, Fe can be caused
3-ycr
yo
4exist; And within the scope of 650 ~ 1100 DEG C, M
23c
6just 950 DEG C of precipitations.
M
23c
6generation be at 950-980 DEG C, when protective gas is not enough, metal and graphite react, and produce intercrystalline corrosion, cause selective oxidation to increase the weight of, and in this and actual production during protective gas deficiency, insulator occurs that " the black bar phenomenon " of a large amount of stem stem is very identical.So avoid its generation not only can reduce surface-treated difficulty, be also a kind of protection to material itself simultaneously.
Insulator high temperature scale microstructure morphology, utilizes ESEM to observe lid surface oxide, as shown in Figure 5, wherein, the microscopic appearance figure of cover plate frontside oxide when a is protective gas abundance, can find out that even tissue is consistent, particle loosens; B is the not enough and microstructure morphology figure of the cover plate backside oxide be close to graphite jig of protective gas, and microstructure morphology presents netted, and oxidizing process exists a large amount of intercrystalline corrosion phenomenon, and the phenomenon such as blackspot, stain macroscopically appears in cover plate.
Equally, observe stem stem oxide on surface, as shown in Figure 6, wherein, a is that the position oxide tissue topography be close to graphite schemes, and the position oxide skin be close to graphite presents black, tissue looseness, removes than being easier to; B is the position oxide tissue topography figure not having graphite jig to protect, and the position not having graphite jig to protect then presents grey black, organizes relatively fine and close.This is, because stem stem reacts with graphite when protective gas deficiency, intercrystalline corrosion phenomenon occurs, and not by the place that graphite is protected, if protective gas is sufficient, also can form fine and close oxide skin.
By repeatedly testing and little, middle batch pilot plant test, adopt mix acid liquor of the present invention to clean very clean, pickling consistency is good.Adopt in embodiment 3 and embodiment 7, oxide skin is dissolved gradually in acid solution, come off; Reaction speed is moderate, is easy to control; Do not corrode matrix, can not make dimension overproof, the consistency of handled product is good.Embodiment 3 is compared with embodiment 7, and after adding corrosion inhibiter in acid solution, reaction speed is more easy to control, the good stability of acid solution.
In mix acid liquor of the present invention, the performance of various acid is as follows:
Sulfuric acid: strong oxidizing property, has light enhancing effect, is applicable to austenitic stainless steel.
Nitric acid: hydrogen-oxygen voltinism, dissolved oxygen compound, simultaneously by passivation.
Phosphoric acid: viscosity modifier, forms mucous membrane in metal surface, improves surface brightness, reduces sulfuric acid to the corrosion rate of matrix, has passivation, protection matrix.
In acid solution, various acid has certain proportioning, just can play the effect of dissolved oxygen skin, if the content of sulfuric acid is too high, easily causes excessive erosion, and too low, response speed is slow.The too high levels of hydrofluoric acid, etching glass, have harm to insulator air-tightness, content is too low, and Scavenging activity is inadequate, does not reach the object of clean cleaning., there is brightness in the too high levels of nitric acid, reduces pickling effect on the contrary, and content is too low, easily causes excessive erosion.Phosphoric acid can regulate the viscosity of acid solution, forms mucous membrane in metal surface, improves the brightness on surface, can reduce the corrosion rate of salt sulfuric acid to matrix simultaneously, have passivation, plays the effect of protection matrix.Adding of corrosion inhibiter, make the speed in acid cleaning process more easy to control, and ensure that fail safe.
Claims (10)
1. a lithium thionyl chloride cell insulator surface high temperature scale processing method, is characterized in that, comprise the following steps:
Step one, pending lithium thionyl chloride cell insulator is positioned in acid solution, removes the oxide skin on its surface;
Step 2, in step one process after lithium thionyl chloride cell insulator take Ultrasonic Cleaning, remove its surperficial dust and dead angle oxide skin;
Step 3, the thionyl chloride battery insulator after reprocessing in step 2 is carried out Passivation Treatment, make its surface form corrosion resistant passivating film.
2., according to a kind of lithium thionyl chloride cell insulator surface high temperature scale processing method according to claim 1, it is characterized in that, the acid solution in described step one is H
2sO
4, HNO
3with the mixed liquor of HF.
3., according to a kind of lithium thionyl chloride cell insulator surface high temperature scale processing method according to claim 2, it is characterized in that, in the acid solution in described step one, also comprise H
3pO
4.
4., according to a kind of lithium thionyl chloride cell insulator surface high temperature scale processing method according to claim 3, it is characterized in that described H
2sO
4, HNO
350 ~ 100g/L, 40 ~ 80g/L, 20 ~ 50g/L is respectively with the concentration of HF.
5., according to a kind of lithium thionyl chloride cell insulator surface high temperature scale processing method according to claim 4, it is characterized in that, described H
3pO
4concentration be 40 ~ 100g/L.
6. according to a kind of lithium thionyl chloride cell insulator surface high temperature scale processing method described in claim 1,2,3,4 or 5, it is characterized in that, also comprise corrosion inhibiter in described acid solution, described corrosion inhibiter is methenamine or sulfamic acid, and the content of described corrosion inhibiter is 0.5 ~ 3g/L.
7. according to a kind of lithium thionyl chloride cell insulator surface high temperature scale processing method described in claim 1,2,3,4 or 5, it is characterized in that, pending lithium thionyl chloride cell insulator is positioned over before in acid solution, also needs its surface removal greasy dirt, and fully wetting to it.
8. according to a kind of lithium thionyl chloride cell insulator surface high temperature scale processing method described in claim 1,2,3,4 or 5, it is characterized in that, before Passivation Treatment, also need to carry out mechanical polishing to lithium thionyl chloride cell insulator, to remove residue.
9. according to a kind of lithium thionyl chloride cell insulator surface high temperature scale processing method described in claim 1,2,3,4 or 5, it is characterized in that, before carrying out mechanical polishing, adopt Ultrasonic Cleaning, to remove piece surface dust and dead angle oxide skin.
10. according to a kind of lithium thionyl chloride cell insulator surface high temperature scale processing method described in claim 1,2,3,4 or 5, it is characterized in that, in step 3, adopt concentration to be the HNO of 300 ~ 700g/L
3carry out Passivation Treatment.
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Citations (4)
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|---|---|---|---|---|
| JPS53138928A (en) * | 1977-05-10 | 1978-12-04 | Kobe Steel Ltd | Pickling liquid for stainless steel and elongating method for life thereof |
| CN1124788A (en) * | 1994-05-04 | 1996-06-19 | 孙永春 | Pickling paste for stainless steel |
| EP1050605A2 (en) * | 1999-05-03 | 2000-11-08 | Henkel Kommanditgesellschaft auf Aktien | Process for pickling stainless steel in the absence of nitric acid and in the presence of chloride ions |
| CN1718865A (en) * | 2005-07-05 | 2006-01-11 | 何明威 | Method of removing oxidized skin on hot rolling nickel stainless steel material |
-
2015
- 2015-02-13 CN CN201510079570.9A patent/CN104715871B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53138928A (en) * | 1977-05-10 | 1978-12-04 | Kobe Steel Ltd | Pickling liquid for stainless steel and elongating method for life thereof |
| CN1124788A (en) * | 1994-05-04 | 1996-06-19 | 孙永春 | Pickling paste for stainless steel |
| EP1050605A2 (en) * | 1999-05-03 | 2000-11-08 | Henkel Kommanditgesellschaft auf Aktien | Process for pickling stainless steel in the absence of nitric acid and in the presence of chloride ions |
| CN1718865A (en) * | 2005-07-05 | 2006-01-11 | 何明威 | Method of removing oxidized skin on hot rolling nickel stainless steel material |
Non-Patent Citations (2)
| Title |
|---|
| 方刚: "不锈钢的电解抛光及钝化", 《电镀与精饰》 * |
| 林百春: "不锈钢表面处理:酸洗、钝化与抛光", 《材料开发与应用》 * |
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Address after: 710021 No. 15, West Section of Xijin Road, Jingwei Industrial Park, Xi'an Economic and Technological Development Zone, Shaanxi Province Patentee after: Xi'an Taijin Xinneng Technology Co.,Ltd. Address before: 710021 No. 15, West Section of Xijin Road, Jingwei Industrial Park, Xi'an Economic and Technological Development Zone, Shaanxi Province Patentee before: XI'AN TAIJIN INDUSTRIAL ELECTROCHEMICAL TECHNOLOGY Co.,Ltd. |
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