CN103296283B - Titanium plate with surface being wrapped by Ti4O7 (titanium oxide) membrane and substrate of bipolar lead-acid battery - Google Patents

Titanium plate with surface being wrapped by Ti4O7 (titanium oxide) membrane and substrate of bipolar lead-acid battery Download PDF

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Publication number
CN103296283B
CN103296283B CN201310215533.7A CN201310215533A CN103296283B CN 103296283 B CN103296283 B CN 103296283B CN 201310215533 A CN201310215533 A CN 201310215533A CN 103296283 B CN103296283 B CN 103296283B
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titanium plate
film
surface coating
preparation
titanium
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CN103296283A (en
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王殿龙
周寿斌
郎笑石
于尊奎
黄毅
魏迪
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JIANGSU HUAFU STORAGE NEW TECHNOLOGY Co Ltd
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JIANGSU HUAFU STORAGE NEW TECHNOLOGY Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of a titanium plate with the surface being wrapped by a Ti4O7 (titanium oxide) membrane, and relates to a method for wrapping Ti4O7 membrane on the surface of the titanium plate. By adopting the titanium plate with the surface being wrapped by the Ti4O7 membrane, the problem that the conductivity of an interface is severely influenced by a layer of oxide easily occurring on the surface of the titanium plate when the titanium plate is under the strong acid and strong oxidation condition can be solved. The preparation method comprises the following steps of: mixing Ti(C4H90), C2H5OH, water, a soluble carbon source aqueous solution and diethanol amine, and stirring to obtain sol; coating the sol onto the processed titanium plate, and reducing the titanium plate at a high temperature after being dried to obtain the titanium plate with the surface being wrapped by the Ti4O7 membrane. The Ti4O7 has stronger electron conductivity and stronger stability compared with other titanium oxides, and the composite plate with the surface being wrapped by the Ti4O7 membrane layer is applicable to the substrate of a bipolar lead-acid battery.

Description

A kind of Surface coating has Ti 4o 7the titanium plate of film and the substrate of bipolar lead acid battery made thereof
Technical field
The present invention relates to a kind of Surface coating and have Ti 4o 7the titanium plate of film and the substrate of bipolar lead acid battery made thereof.
Background technology
Titanium has that proportion is little, intensity is high, the anti-corrosion feature such as good, uses it for the substrate of bipolar lead acid battery, can improve specific energy and the service life cycle of battery.But metallic titanium surface easily forms one deck TiO 2, and TiO 2be a kind of nonconducting oxide, therefore can affect the conductivity at interface between titanium-base and active material.There is bibliographical information (exercise question that the people such as Xiaoxia Li delivers on Electrochimical Acta the 55th phase in 2010 5891 ~ 5898 pages is the article of Magneli phase Ti4O7 electrode for oxygen reduction reaction and its implication for zinc-air rechargeable batteries) Ti 4o 7there is good electron conduction and there is very high chemical stability, existence that can be stable for a long time under strong acid, highly basic and strong oxidizing property condition.
Therefore, a kind of Surface coating is needed to have Ti 4o 7the preparation method of the titanium plate of film is to solve the problem.
Summary of the invention
Goal of the invention: the metallic titanium plate that the present invention is directed to prior art strong oxidizing property condition lower surface generation oxide-film and bipolar lead acid battery reactive species interface poorly conductive defect, provide the good Surface coating of a kind of adhesion to have Ti 4o 7the preparation method of the titanium plate of film.
Technical scheme: for solving the problems of the technologies described above, substrate of bipolar lead acid battery of the present invention and preparation method thereof adopts following technical scheme:
A kind of Surface coating has Ti 4o 7the preparation method of the titanium plate of film, comprises the following steps:
1), Ti(C is taken according to the volume ratio of 38:65:5:5:5 4h 9o) 4, C 2h 5oH, H 2o, the solubility carbon source aqueous solution and diethanol amine, get a part of C 2h 5oH also adds Ti(C wherein 4h 9o) 4, obtain Ti(C 4h 9o) 4ethanolic solution, by remaining C 2h 5oH, H 2o, the solubility carbon source aqueous solution and diethanol amine are fully mixed to get the first mixed solution, then under stirring, the first mixed solution are joined Ti(C 4h 9o) 4ethanolic solution in, continue stirring 1 ~ 2h until in dissolved colloidal state, obtain colloidal sol;
2), titanium plate is soaked 1 ~ 2h in aqueous slkali, by the titanium plate crossed through aqueous slkali soaking, clean up in distilled water, after cleaned titanium plate is soaked 2 ~ 3 minutes in the second mixed solution of nitric acid, hydrogen peroxide and hydrofluoric acid, titanium plate distilled water is cleaned up and dries;
3) colloidal sol, by step 1) obtained is coated to through step 2) on the titanium plate that processed, putting into drying box, is dry 30 ~ 90min under the condition of 50 ~ 100 DEG C in temperature;
4) the titanium plate, by step 3) obtained is placed in heating furnace, in argon atmospher, furnace temperature is risen to 100 ~ 300 DEG C of pre-burning 1 ~ 3 h;
5), by the titanium plate through step 4) preheating, in argon atmospher, furnace temperature is risen to 800 ~ 1200 DEG C of reduction 1 ~ 3h, then naturally cool with stove, obtaining Surface coating has Ti 4o 7the titanium plate of film.
Further, in the carbon source of solubility described in the step 1) aqueous solution, carbon content is 5 ~ 50mol/L.
Further, the carbon source of solubility described in the step 1) aqueous solution is C 12h 11o 22the aqueous solution, C 6h 6the O aqueous solution or sucrose solution.
Further, step 2) described in the thickness of titanium plate be 0.05-1mm.
Further, step 2) described in the concentration of nitric acid be 5 ~ 10ml/L, the concentration of described hydrogen peroxide is 10 ~ 15ml/L, and described hydrofluoric acid concentration is 5 ~ 10ml/L.
Further, Ti described in step 5) 4o 7the thickness of film is 0.01-0.5mm.
Further, step 2) described in aqueous slkali be saturated sodium carbonate liquor.
Further, mixing speed described in step 1) is 200-300 rev/min.
The invention also discloses a kind of Surface coating and have Ti 4o 7the titanium plate of film, described Surface coating has Ti 4o 7the titanium plate of film adopts Surface coating as above to have Ti 4o 7the preparation method of the titanium plate of film prepares.
Beneficial effect: Surface coating of the present invention has Ti 4o 7the preparation method of the titanium plate of film by sol-gal process at titanium plate Surface coating one deck Ti 4o 7film.In implementation process, gained colloidal sol dimensionally stable, is coated to titanium plate surface by colloidal sol, makes titanium plate surface more even, Ti 4o 7the production process of material is carried out on titanium plate surface, improves Ti so greatly 4o 7the adhesion of film and titanium plate.The Ti obtained 4o 7material microstructure is also more even.
The invention also discloses a kind of substrate of bipolar lead acid battery, described substrate adopts Surface coating as above to have Ti 4o 7the titanium plate of film is made.One deck Ti at titanium plate Surface coating 4o 7film, Ti 4o 7the coated pickling metal titanium plate surface uniform of film, adhesion are good, the Ti obtained 4o 7material microstructure is also relatively more even, this titanium plate is used for the substrate of bipolar lead acid battery, can improves and the adhesion of active material and interface electron conduction.
Accompanying drawing explanation
The XRD figure of the titanium plate surfacing that Fig. 1 embodiment 1 obtains;
What Fig. 2 embodiment 1 was obtained is coated with Ti 4o 7the stereoscan photograph on the titanium plate surface of film.
Embodiment
Below in conjunction with the drawings and specific embodiments, illustrate the present invention further, these embodiments should be understood only be not used in for illustration of the present invention and limit the scope of the invention, after having read the present invention, the amendment of those skilled in the art to the various equivalent form of value of the present invention has all fallen within the application's claims limited range.
Refer to shown in Fig. 1 and Fig. 2, Surface coating of the present invention has Ti 4o 7the preparation method of the titanium plate of film, comprises the following steps:
1), Ti(C is taken according to the volume ratio of 38:65:5:5:5 4h 9o) 4, C 2h 5oH, H 2o, the solubility carbon source aqueous solution and diethanol amine, get a part of C 2h 5oH also adds Ti(C wherein 4h 9o) 4, obtain Ti(C 4h 9o) 4ethanolic solution, by remaining C 2h 5oH, H 2o, the solubility carbon source aqueous solution and diethanol amine are fully mixed to get the first mixed solution, then under stirring (mixing speed: 200-300 rev/min), the first mixed solution are joined Ti(C 4h 9o) 4ethanolic solution in, continue to stir (mixing speed: 200-300 rev/min) 1 ~ 2h until in dissolved colloidal state, obtain colloidal sol; Wherein, in the solubility carbon source aqueous solution, carbon content is 5 ~ 50mol/L, and the solubility carbon source aqueous solution can be C 12h 11o 22the aqueous solution, C 6h 6the O aqueous solution or sucrose solution.
2), titanium plate is soaked 1 ~ 2h in aqueous slkali, by the titanium plate crossed through aqueous slkali soaking, clean up in distilled water, after cleaned titanium plate is soaked 2 ~ 3 minutes in the second mixed solution of nitric acid, hydrogen peroxide and hydrofluoric acid, titanium plate distilled water is cleaned up and dries; Wherein, the thickness of titanium plate is 0.05-1mm.The concentration of nitric acid is 5 ~ 10ml/L, and the concentration of hydrogen peroxide is 10 ~ 15ml/L, and hydrofluoric acid concentration is 5 ~ 10ml/L.Wherein, in the present invention, aqueous slkali is saturated sodium carbonate liquor.
3) colloidal sol, by step 1) obtained is coated to through step 2) on the titanium plate that processed, putting into drying box, is dry 30 ~ 90min under the condition of 50 ~ 100 DEG C in temperature;
4) the titanium plate, by step 3) obtained is placed in heating furnace, in argon atmospher, furnace temperature is risen to 100 ~ 300 DEG C of pre-burning 1 ~ 3 h;
5), by the titanium plate through step 4) preheating, in argon atmospher, furnace temperature is risen to 800 ~ 1200 DEG C of reduction 1 ~ 3h, then naturally cool with stove, obtaining Surface coating has Ti 4o 7the titanium plate of film.Wherein, Ti 4o 7the thickness of film is 0.01-0.5mm.
Wherein, the argon gas used by the present invention is the argon gas of volumn concentration >=99.995%.
The invention also discloses a kind of Surface coating and have Ti 4o 7the titanium plate of film, Surface coating has Ti 4o 7the titanium plate of film adopts Surface coating as above to have Ti 4o 7the preparation method of the titanium plate of film prepares.
The invention also discloses a kind of substrate of bipolar lead acid battery, substrate adopts Surface coating as above to have Ti 4o 7the titanium plate of film is made.
embodiment 1
A1, take the Ti(C of 7.6ml 4h 9o) 4, 13ml C 2h 5the H of OH, 1ml 2o, 1ml's is the diethanol amine of the aqueous sucrose solution of 20mol/L, 1ml according to carbon content calculating concentration;
A2, by the C of 6ml in steps A 1 2h 5oH joins the Ti(C of 7.6ml 4h 9o) 4in obtain Ti(C 4h 9o) 4ethanolic solution, at the C of remaining 7ml 2h 5oH adds the H of 1ml 2o, 1ml's is the aqueous sucrose solution of 20mol/L and the diethanol amine of 1ml according to carbon content calculating concentration, and under magnetic agitation condition (mixing speed: 250 revs/min), this mixed solution is joined Ti (C 4h 9o) 4ethanolic solution in, magnetic agitation (mixing speed: 250 revs/min) obtains colloidal sol until above-mentioned solution is dissolved colloidal state in 1.5 hours at normal temperatures;
A3, by after the sand papering of titanium plate different thicknesses, it is soaked 1.5h in aqueous slkali, cleaned up in distilled water by the titanium plate crossed through aqueous slkali soaking, wherein, aqueous slkali is saturated sodium carbonate solution.Be soak 2.5 minutes in the mixed solution of the nitric acid of 10ml/L, the hydrogen peroxide of 15ml/L and 5ml/L hydrofluoric acid in concentration by cleaned titanium plate, after having red gas to emerge, titanium plate distilled water cleaned up and dries;
A4, be coated on the titanium plate of step 3 process by colloidal sol in steps A 2, putting into drying box, is dry 30min under the condition of 75 DEG C in temperature;
A5, titanium plate steps A 4 obtained are placed in tube furnace, in the protective atmosphere of argon gas, furnace temperature are risen to 200 DEG C, pre-burning 2h;
A6, after steps A 5 presintering process completes, in the protective atmosphere of argon gas, furnace temperature is risen to 900 DEG C, high temperature reduction 1h, then naturally cool with stove, obtaining Surface coating has Ti 4o 7the titanium plate of film.
Wherein, the argon gas used by the present invention is the argon gas of volumn concentration >=99.995%.
Through measuring, Ti 4o 7the thickness of film is 0.25mm, and the thickness of titanium plate is 0.5mm.
The XRD figure of the titanium plate surfacing that embodiment 1 obtains as shown in Figure 1.Fig. 1 is Ti 4o 7the diffraction maximum of XRD, can find out that from XRD spectra all strong diffraction maximums are all Ti 4o 7xRD characteristic peak, the coated material of pickling metal titanium plate is Ti 4o 7material.
Embodiment 1 is coated with Ti 4o 7the stereoscan photograph on the titanium plate surface of film, as shown in Figure 2.As can be seen from Figure 2 the pattern of surfacing is cellular and is similar to spherical in shape.Microscopic appearance is relatively more even, and granular size is unanimous on the whole.Effectively can improve Ti like this 4o 7with the adhesion of active material.
Therefore by the present invention, one deck Ti at titanium plate Surface coating 4o 7film, is used for the substrate of bipolar lead acid battery by this titanium plate, can improve and the adhesion of active material and interface electron conduction.
embodiment 2
B1, take the Ti(C of 7.6ml 4h 9o) 4, 13ml C 2h 5the H of OH, 1ml 2o, 1ml's is the C of 5mol/L according to carbon content calculating concentration 12h 11o 22the aqueous solution, the diethanol amine of 1ml;
B2, by the C of 6ml in step B1 2h 5oH joins the Ti(C of 7.6ml 4h 9o) 4in obtain Ti(C 4h 9o) 4ethanolic solution, at the C of remaining 7ml 2h 5oH adds the H of 1ml 2o, 1ml's is the aqueous sucrose solution of 20mol/L and the diethanol amine of 1ml according to carbon content calculating concentration, and under magnetic agitation condition (mixing speed: 300 revs/min), this mixed solution is joined Ti (C 4h 9o) 4ethanolic solution in, magnetic agitation (mixing speed: 300 revs/min) obtains colloidal sol until above-mentioned solution is dissolved colloidal state in 1 hour at normal temperatures;
B3, by after the sand papering of titanium plate different thicknesses, it is soaked 1h in aqueous slkali, cleaned up in distilled water by the titanium plate crossed through aqueous slkali soaking, wherein, aqueous slkali is saturated sodium carbonate solution.Be soak 3 minutes in the mixed solution of the nitric acid of 5ml/L, the hydrogen peroxide of 10ml/L and 5ml/L hydrofluoric acid in concentration by cleaned titanium plate, after having red gas to emerge, titanium plate distilled water cleaned up and dries;
B4, be coated on the titanium plate of step B3 process by colloidal sol in step B2, putting into drying box, is dry 90min under the condition of 50 DEG C in temperature;
B5, the titanium plate obtained by step B4 are placed in tube furnace, in the protective atmosphere of argon gas, furnace temperature are risen to 100 DEG C, pre-burning 3h;
B6, after step B5 presintering process completes, in the protective atmosphere of argon gas, furnace temperature is risen to 800 DEG C, high temperature reduction 3h, then naturally cool with stove, obtaining Surface coating has Ti 4o 7the titanium plate of film.
Wherein, the argon gas used by the present invention is the argon gas of volumn concentration >=99.995%.
Through measuring, Ti 4o 7the thickness of film is 0.01mm, and the thickness of titanium plate is 0.05mm.
What embodiment 2 obtained is coated with Ti 4o 7the character of the titanium plate of film is with embodiment 1.
embodiment 3
C1, take the Ti(C of 7.6ml 4h 9o) 4, 13ml C 2h 5the H of OH, 1ml 2o, 1ml's is the C of 50mol/L according to carbon content calculating concentration 6h 6the O aqueous solution, the diethanol amine of 1ml;
C2, by the C of 6ml in step C1 2h 5oH joins the Ti(C of 7.6ml 4h 9o) 4in obtain Ti(C 4h 9o) 4ethanolic solution, at the C of remaining 7ml 2h 5oH adds the H of 1ml 2o, 1ml's is the aqueous sucrose solution of 20mol/L and the diethanol amine of 1ml according to carbon content calculating concentration, and this mixed solution is joined Ti (C by (mixing speed: 200 revs/min) under magnetic agitation condition 4h 9o) 4ethanolic solution in, magnetic agitation (mixing speed: 200 revs/min) obtains colloidal sol until above-mentioned solution is dissolved colloidal state in 2 hours at normal temperatures;
C3, by after the sand papering of titanium plate different thicknesses, it is soaked 2h in aqueous slkali, cleaned up in distilled water by the titanium plate crossed through aqueous slkali soaking, wherein, aqueous slkali is saturated sodium carbonate solution.Be soak 2 minutes in the mixed solution of the nitric acid of 10ml/L, the hydrogen peroxide of 15ml/L and 10ml/L hydrofluoric acid in concentration by cleaned titanium plate, after having red gas to emerge, titanium plate distilled water cleaned up and dries;
C4, be coated on the titanium plate of step C3 process by colloidal sol in step C2, putting into drying box, is dry 30min under the condition of 100 DEG C in temperature;
C5, the titanium plate obtained by step C4 are placed in tube furnace, in the protective atmosphere of argon gas, furnace temperature are risen to 300 DEG C, pre-burning 1h;
C6, after step C5 presintering process completes, in the protective atmosphere of argon gas, furnace temperature is risen to 1200 DEG C, high temperature reduction 1h, then naturally cool with stove, obtaining Surface coating has Ti 4o 7the titanium plate of film.
Wherein, the argon gas used by the present invention is the argon gas of volumn concentration >=99.995%.
Through measuring, Ti 4o 7the thickness of film is 0.5mm, and the thickness of titanium plate is 1mm.
What embodiment 3 obtained is coated with Ti 4o 7the character of the titanium plate of film is with embodiment 1.
Of the present invention by sol-gal process at titanium plate Surface coating one deck Ti 4o 7film.In implementation process, gained colloidal sol dimensionally stable, is coated to titanium plate surface by colloidal sol, makes titanium plate surface more even, Ti 4o 7the production process of material is carried out on titanium plate surface, improves Ti so greatly 4o 7the adhesion of film and titanium plate.

Claims (9)

1. a Surface coating has Ti 4o 7the preparation method of the titanium plate of film, is characterized in that, comprise the following steps:
1), Ti (C is taken according to the volume ratio of 38:65:5:5:5 4h 9o) 4, C 2h 5oH, H 2o, the solubility carbon source aqueous solution and diethanol amine, get a part of C 2h 5oH also adds Ti (C wherein 4h 9o) 4, obtain Ti (C 4h 9o) 4ethanolic solution, by remaining C 2h 5oH, H 2o, the solubility carbon source aqueous solution and diethanol amine are fully mixed to get the first mixed solution, and in the described solubility carbon source aqueous solution, carbon content is 5 ~ 50mol/L, then under stirring, the first mixed solution is joined Ti (C 4h 9o) 4ethanolic solution in, continue stirring 1 ~ 2h until in dissolved colloidal state, obtain colloidal sol;
2), titanium plate is soaked 1 ~ 2h in aqueous slkali, by the titanium plate crossed through aqueous slkali soaking, clean up in distilled water, after cleaned titanium plate is soaked 2 ~ 3 minutes in the second mixed solution of nitric acid, hydrogen peroxide and hydrofluoric acid, titanium plate distilled water is cleaned up and dries;
3), by step 1) colloidal sol that obtains is coated to through step 2) on the titanium plate that processed, putting into drying box, is dry 30 ~ 90min under the condition of 50 ~ 100 DEG C in temperature;
4), by step 3) the titanium plate that obtains is placed in heating furnace, in argon atmospher, furnace temperature risen to 100 ~ 300 DEG C of pre-burning 1 ~ 3h;
5), will through step 4) the titanium plate of preheating, in argon atmospher, furnace temperature is risen to 800 ~ 1200 DEG C of reduction 1 ~ 3h, then naturally cool with stove, obtaining Surface coating has Ti 4o 7the titanium plate of film.
2. Surface coating as claimed in claim 1 has Ti 4o 7the preparation method of the titanium plate of film, is characterized in that, step 1) described in the solubility carbon source aqueous solution be C 12h 11o 22the aqueous solution or C 6h 6the O aqueous solution.
3. Surface coating as claimed in claim 1 has Ti 4o 7the preparation method of the titanium plate of film, is characterized in that, step 2) described in the thickness of titanium plate be 0.05-1mm.
4. Surface coating as claimed in claim 1 has Ti 4o 7the preparation method of the titanium plate of film, is characterized in that, step 2) described in the concentration of nitric acid be 5 ~ 10ml/L, the concentration of described hydrogen peroxide is 10 ~ 15ml/L, and described hydrofluoric acid concentration is 5 ~ 10ml/L.
5. Surface coating as claimed in claim 1 has Ti 4o 7the preparation method of the titanium plate of film, is characterized in that, step 5) described in Ti 4o 7the thickness of film is 0.01-0.5mm.
6. Surface coating as claimed in claim 1 has Ti 4o 7the preparation method of the titanium plate of film, is characterized in that, step 2) described in aqueous slkali be saturated sodium carbonate liquor.
7. Surface coating as claimed in claim 1 has Ti 4o 7the preparation method of the titanium plate of film, is characterized in that, step 1) described in mixing speed be 200-300 rev/min.
8. a Surface coating has Ti 4o 7the titanium plate of film, is characterized in that, described Surface coating has Ti 4o 7the titanium plate of film adopts the Surface coating as described in any one of claim 1-7 to have Ti 4o 7the preparation method of the titanium plate of film prepares.
9. a substrate for bipolar lead acid battery, is characterized in that, described substrate adopts Surface coating as claimed in claim 8 to have Ti 4o 7the titanium plate of film is made.
CN201310215533.7A 2013-06-03 2013-06-03 Titanium plate with surface being wrapped by Ti4O7 (titanium oxide) membrane and substrate of bipolar lead-acid battery Active CN103296283B (en)

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CN104218245B (en) * 2014-04-24 2016-09-28 江苏华富储能新技术股份有限公司 A kind of preparation method of titanium/Asia titanium oxide/lead composite base plate
CN103985878A (en) * 2014-05-17 2014-08-13 湘潭赛虎电池有限责任公司 Bipolar grid of lead-acid storage battery and manufacturing method of bipolar grid
CN104591342B (en) * 2014-11-10 2017-04-05 牛军峰 For the Ti/Ebonex/PbO of advanced treatment of wastewater2The preparation method of electrode
CN105552314B (en) * 2015-12-08 2017-09-26 哈尔滨工业大学 A kind of preparation method of high reliability bipolar plates for bipolarity lead accumulator
CN106997952B (en) * 2016-01-22 2020-10-27 中国电力科学研究院 Lead-carbon battery positive electrode additive and preparation method thereof
CN105800683B (en) * 2016-02-24 2017-06-13 北京交通大学 A kind of one-dimensional array formula TiOxThe preparation method of nano material
CN110272097B (en) * 2019-07-01 2022-03-15 长春光华环保有限责任公司 Titanium suboxide multi-dimensional coating electrode and preparation method thereof

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