CN100487166C - Foam nickel preparing process - Google Patents
Foam nickel preparing process Download PDFInfo
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- CN100487166C CN100487166C CNB2004100275462A CN200410027546A CN100487166C CN 100487166 C CN100487166 C CN 100487166C CN B2004100275462 A CNB2004100275462 A CN B2004100275462A CN 200410027546 A CN200410027546 A CN 200410027546A CN 100487166 C CN100487166 C CN 100487166C
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- nickel
- foam
- making method
- nickel foam
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Abstract
The foam nickel preparing process includes the steps of metallizing polyurethane sponge, electric depositing and final heat treatment. It features the electric depositing step, in which organic additive is added into the electric depositing tank, and the additive consists of chloral hydrate with molecular expression CCl3CH(OH)2 and/or its derivative and has consumption of 0.05-0.25 g/L. The foam nickel preparing process of the present invention is simple and low in cost and can electrode sheet with high strength, less breaking and high quality, suitable for great current discharging and capable of raising the performance of cell.
Description
Technical field
The present invention relates to the making method of battery electrode material, particularly relate to the making method of the foam nickel material that a kind of battery electrode uses.
Background technology
Nickel foam is a kind of material that is used to make battery electrode, and the production technique of regular foam nickel material mainly comprises: earlier with the polyurethane sponge conductionization, carry out galvanic deposit again, heat-treat at last.Wherein, the conductionization processing generally comprises electroless plating, coated with conductive glue and vacuum and plates three kinds; Thermal treatment is normally carried out under 400-1100 ℃ of hydrogen reducing atmosphere condition.Regular foam nickel is as the collector of the positive and negative electrode of battery, because its tensile strength is low, and pole piece easy fracture in battery making processes, the condemnation factor height causes the battery cost of manufacture too high, and is not suitable for heavy-current discharge.For this reason, application number is that the Chinese patent application of 00126771.X discloses a kind of composite particles that adds and carries out composite electrodeposition in the galvanic deposit tank liquor, make the nickel screen surface form the method for uneven surface, the defective of this method is that the composite particles that is added is difficult to be dispersed in the solution, because this composite particles is a metal-powder, its density is bigger than the density of galvanic deposit tank liquor, so can be deposited on the bottom of groove, even thereby add strong mixing, also be difficult to make its homodisperse, therefore make composite particles can not uniform deposition on the nickel foam surface, cause intensity and apparent coarse inequality; Also, metal-powder dissolves owing to can producing in acid electrodeposit liquid, and the less stable of composite particles in solution, so cost is higher.
Summary of the invention
The present invention is intended to effectively address the above problem, and provides a kind of technology simple, and cost is lower, can significantly improve the making method of the nickel foam of battery performance, makes the battery plate intensity height produced, easy fracture not, the low and suitable heavy-current discharge of film-making fraction defective.
For achieving the above object, the invention provides a kind of making method of nickel foam, the step of this method comprises earlier the polyurethane sponge conductionization, carry out galvanic deposit again, heat-treat at last, wherein, in described electrodeposition step, add organic additive in the galvanic deposit tank liquor, this organic additive is that molecular formula is CCl
3CH (OH)
2The Chloral Hydrate or derivatives thereof or the mixture of Chloral Hydrate and its derivative, described organic additive consumption is 0.05-0.25g/L (in every liter of electrodeposit liquid add 0.05-0.25g organic additive).
The preferable amount of described organic additive is 0.1g/L.
The derivative of described Chloral Hydrate is that molecular formula is CCl
3The trichoro-aldehyde of CHO or molecular formula are ClCH
2At least a in the chloroethanal of CHO.
Contribution of the present invention is that it has effectively overcome the deficiencies in the prior art, and provides a kind of technology simple, can significantly improve the method for the making nickel foam of the over-all properties of battery and relative low price.Warp shows that with the simultaneous test that regular foam nickel is done the present invention can obviously improve the intensity, particularly tensile strength of nickel foam.Because intensity improves, and effectively reduces the part rate in battery film-making process, therefore saved production cost.Test also shows, the nickel foam that method of the present invention the is made heavy-current discharge that can suit, thereby improved battery performance.It is simple that the present invention also has technology, easy to implement, and selected additive is stable, characteristics such as good dispersity in solution.
Embodiment
The following example is to further explanation of the present invention and explanation, and the present invention is not constituted any limitation.
The present invention is the production technique to regular foam nickel, i.e. polyurethane sponge conductionization → galvanic deposit → heat treated improvement, and its main points are in the galvanic deposit stage, add organic additive in the galvanic deposit tank liquor, this organic additive is that molecular formula is CCl
3CH (OH)
2The Chloral Hydrate or derivatives thereof or the mixture of Chloral Hydrate and its derivative.
In the above-mentioned technology, the polyurethane sponge conductionization can adopt routine techniquess such as coated with conductive glue, electroless plating or vacuum plating.
Galvanic deposit is to electroplating through the polyurethane sponge of conductionization processing, and sulfate system or thionamic acid salt system are adopted in galvanic deposit, and can adopt one-level plating mode or multistage plating mode.Major technique measure of the present invention is to add a kind of organic additive in the galvanic deposit tank liquor, and this organic additive is that molecular formula is CCl
3CH (OH)
2The Chloral Hydrate or derivatives thereof or the mixture of Chloral Hydrate and its derivative, the addition of additive is 0.05-0.25g/L.The derivative of Chloral Hydrate is that molecular formula is CCl
3The trichoro-aldehyde of CHO or molecular formula are ClCH
2The chloroethanal of CHO or both mixtures.Additive of the present invention can significantly improve the formation speed of nucleus in electrodeposition process, make electric force lines distribution even, thereby acquisition crystal grain is careful, arrangement is tight, even partly bright coating, and can significantly improve the intensity of nickel foam.
Thermal treatment then is to remove polyurethane skeleton under 400-1100 ℃ of hydrogen reducing atmosphere, makes the high strength nickel foam.
By the following examples the present invention is made more specific description.
Embodiment 1
Get continuous polyurethane sponge (aperture 110PP, thickness 1.9mm, width 1000mm) two volumes, each 50m conduction, be designated I, II respectively, conductionization is to adopt the coated with conductive adhesive process, I, II be gluing under identical conditions, wherein, the solid content of glue is that 7-10%, pH value are that 10-11, temperature are that 10-30 ℃, viscosity are 5-20mPas; Then I is put into regular foam nickel and carry out galvanic deposit with galvanic deposition cell liquid, II is put into galvanic deposit tank liquor of the present invention (promptly add organic additive Chloral Hydrate of the present invention with electrodeposit liquid at regular foam nickel, addition is 0.05g/L) in carry out galvanic deposit, during galvanic deposit except that above-mentioned condition other conditionally completes identical; At last with the I after the galvanic deposit, II thermal treatment under the same conditions.To call I in the following text is that regular foam nickel, II are the high strength nickel foam.
The processing parameter of regular foam electrodeposition of nickel tank liquor is as follows:
Single nickel salt (NiSO
47H
2O) 200-250 (g/L)
Nickelous chloride (NiCl
26H
2O) 30-45 (g/L)
Boric acid (H
3BO
3) 30-45 (g/L)
pH 3.8-4.4
Temperature 45-60 ℃
Galvanic deposit tank liquor processing parameter is as follows in the nickel foam making method of the present invention:
Single nickel salt (NiSO
47H
2O) 200-250 (g/L)
Nickelous chloride (NiCl
26H
2O) 30-45 (g/L)
Boric acid (H
3BO
3) 30-45 (g/L)
Additive 0.05 (g/L)
pH 3.8-4.4
Temperature 45-60 ℃
Get nickel foam II and the regular foam nickel I that the invention described above obtains and do the physicochemical property test, result such as table 1:
Table 1
Performance I II
Thickness (mm) 1.9 1.9
Area density (g/m
2) 430 ± 25 430 ± 25
Aperture 110 110
Endwise tensile strength (N/mm) 2.3 2.8
Transverse tensile strength (N/mm) 1.9 2.3
Snappiness (inferior) 99
Nickel (%) 99.3 99.2
Iron (ppm) 38 30
Copper (ppm) 40 45
Manganese (ppm) 15 18
Sulphur (ppm) 30 25
Carbon (ppm) 100 110
Can find out that from table 1 its performance of nickel foam that obtains by making method of the present invention is significantly better than regular foam nickel, particularly its tensile strength.
The making method of getting the invention described above obtains each 10000 of nickel foam II and regular foam nickel I, battery plate manufacture craft routinely, under the same conditions, coating, oven dry, scraping blade, roller-compaction, it makes fraction defective such as table 2 when producing 10000 battery plates:
Table 2
Nickel foam sign input sum (sheet) is disconnected, sliver number (sheet) fraction defective
I 10000 70 0.7％
II 10000 23 0.23％
Can find out that from table 2 the nickel foam film-making fraction defective that obtains by making method of the present invention is starkly lower than regular foam nickel.
Embodiment 2
By Chloral Hydrate addition in 1 described change galvanic deposit tank liquor of the present invention of embodiment is 0.1g/L, and other processing condition are constant.
The making method of getting the invention described above obtains nickel foam II and regular foam nickel I does the physicochemical property test, result such as table 3:
Table 3
Performance I II
Thickness (mm) 1.9 1.9
Area density (g/m
2) 430 ± 25 430 ± 25
Aperture 110 110
Endwise tensile strength (N/mm) 2.3 3.1
Transverse tensile strength (N/mm) 1.9 2.5
Snappiness (inferior) 99
Nickel (%) 99.3 99.15
Iron (ppm) 38 41
Copper (ppm) 40 38
Manganese (ppm) 15 20
Sulphur (ppm) 30 19
Carbon (ppm) 100 90
Can find out from table 3, obtain its performance of nickel foam significantly better than regular foam nickel by making method of the present invention, particularly its tensile strength.
The making method of getting the invention described above obtains each 10000 of nickel foam II and regular foam nickel I, battery plate manufacture craft routinely, under the same conditions, coating, oven dry, scraping blade, roller-compaction, it makes fraction defective such as table 4 when producing 10000 battery plates:
Table 4
Nickel foam sign input sum (sheet) is disconnected, sliver number (sheet) fraction defective
I 10000 75 0.75％
II 10000 13 0.13％
Can find out from table 4, obtain nickel foam film-making fraction defective by making method of the present invention and be starkly lower than regular foam nickel.
Embodiment 3
By Chloral Hydrate addition in 1 described change galvanic deposit tank liquor of the present invention of embodiment is 0.25g/L, and other processing condition are constant.
The making method of getting the invention described above obtains nickel foam II and regular foam nickel I does the physicochemical property test, result such as table 5:
Table 5
Performance I II
Thickness (mm) 1.9 1.9
Area density (g/m
2) 430 ± 25 430 ± 25
Aperture 110 110
Endwise tensile strength (N/mm) 2.3 3.0
Transverse tensile strength (N/mm) 1.9 2.3
Snappiness (inferior) 99
Nickel (%) 99.3 99.3
Iron (ppm) 38 35
Copper (ppm) 40 49
Manganese (ppm) 15 20
Sulphur (ppm) 30 25
Carbon (ppm) 100 105
Can find out from table 5, obtain its performance of nickel foam significantly better than regular foam nickel by making method of the present invention, particularly its tensile strength.
Get each 10000 of the high strength nickel foam II of the invention described above and regular foam nickel I, battery plate manufacture craft routinely, under the same conditions, and coating, oven dry, scraping blade, roller-compaction, it makes fraction defective such as table 6 when producing 10000 battery plates:
Table 6
Nickel foam sign input sum (sheet) is disconnected, sliver number (sheet) fraction defective
I 10000 80 0.8％
II 10000 20 0.2％
Can find out from table 6, obtain nickel foam film-making fraction defective by making method of the present invention and be starkly lower than regular foam nickel.
Embodiment 4
By Chloral Hydrate addition in 1 described change galvanic deposit tank liquor of the present invention of embodiment is 0.3g/L, and other processing condition are constant.
The making method of getting the invention described above obtains nickel foam II and regular foam nickel I does the physicochemical property test, result such as table 7:
Table 7
Performance I II
Thickness (mm) 1.9 1.9
Area density (g/m
2) 430 ± 25 430 ± 25
Aperture 110 110
Endwise tensile strength (N/mm) 2.3 3.0
Transverse tensile strength (N/mm) 1.9 2.2
Snappiness (inferior) 99
Nickel (%) 99.3 99.18
Iron (ppm) 38 30
Copper (ppm) 40 45
Manganese (ppm) 15 28
Sulphur (ppm) 30 29
Carbon (ppm) 100 112
Can find out from table 7, obtain its performance of nickel foam significantly better than regular foam nickel by making method of the present invention, its tensile strength particularly, but compare performance with embodiment 3 and do not have notable difference, additive amount is not obviously improved performance after surpassing 0.25g/L, so the additive amount upper limit is advisable at 0.25g/L.
The making method of getting the invention described above obtains each 10000 of nickel foam II and regular foam nickel I, battery plate manufacture craft routinely, under the same conditions, coating, oven dry, scraping blade, roller-compaction, it makes fraction defective such as table 8 when producing 10000 battery plates:
Table 8
Nickel foam sign input sum (sheet) is disconnected, sliver number (sheet) fraction defective
I 10000 70 0.7％
II 10000 23 0.23％
Can find out from table 8, obtain nickel foam film-making fraction defective by making method of the present invention and be starkly lower than regular foam nickel.There is not notable difference but compare the film-making fraction defective, so additive amount is not obviously improved performance after surpassing 0.25g/L with embodiment 3. the additive amount upper limit is advisable at 0.25g/L.
Embodiment 5
By Chloral Hydrate addition in 1 described change galvanic deposit tank liquor of the present invention of embodiment is 0.04g/L, and other processing condition are constant.
The making method of getting the invention described above obtains nickel foam II and regular foam nickel I does the physicochemical property test, result such as table 9:
Table 9
Performance I II
Thickness (mm) 1.9 1.9
Area density (g/m
2) 430 ± 25 430 ± 25
Aperture 110 110
Endwise tensile strength (N/mm) 2.3 2.4
Transverse tensile strength (N/mm) 1.9 2.1
Snappiness (inferior) 99
Nickel (%) 99.3 99.35
Iron (ppm) 38 40
Copper (ppm) 40 50
Manganese (ppm) 15 10
Sulphur (ppm) 30 15
Carbon (ppm) 100 110
Can find out from table 9, obtain its performance of nickel foam by making method of the present invention and be better than regular foam nickel slightly, but its intensity and embodiment 1 relatively differ bigger, so additive capacity tensile strength raising to nickel foam when 0.04g/L is little, so the additive amount lower limit is good at 0.05g/L.
The making method of getting the invention described above obtains each 10000 of nickel foam II and regular foam nickel I, battery plate manufacture craft routinely, under the same conditions, coating, oven dry, scraping blade, roller-compaction, it makes fraction defective such as table 10 when producing 10000 battery plates:
Table 10
Nickel foam sign input sum (sheet) is disconnected, sliver number (sheet) fraction defective (sheet)
I 10000 58 0.58％
II 10000 69 0.69％
Can find out from table 10, obtain a little higher than regular foam nickel of nickel foam film-making fraction defective by making method of the present invention.Add-on is improved little when 0.04g/L to the film-making fraction defective, so the additive amount lower limit is good at 0.05g/L.
The foregoing description is the result show, adds additive of the present invention in electrodeposit liquid, and additive amount can obviously improve the intensity of nickel foam when 0.05-0.25g/L, reduce the battery plate fracture rate, reduces the battery cost of manufacture.And produce and to realize that cost is low.
Claims (3)
1, a kind of making method of nickel foam, its step comprise that elder generation with the polyurethane sponge conductionization, carries out galvanic deposit again, heat-treat at last, it is characterized in that, in described electrodeposition step, add organic additive in the galvanic deposit tank liquor, this organic additive is that molecular formula is CCl
3CH (OH)
2The Chloral Hydrate or derivatives thereof or the mixture of Chloral Hydrate and its derivative, described additive amount is 0.05-0.25g/L.
2, the making method of nickel foam as claimed in claim 1 is characterized in that, the preferable amount of described organic additive is 0.1g/L.
3, the making method of nickel foam as claimed in claim 1 is characterized in that, the derivative of described Chloral Hydrate is that molecular formula is CCl
3The trichoro-aldehyde of CHO or molecular formula are ClCH
2At least a in the chloroethanal of CHO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100275462A CN100487166C (en) | 2004-06-07 | 2004-06-07 | Foam nickel preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100275462A CN100487166C (en) | 2004-06-07 | 2004-06-07 | Foam nickel preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1706991A CN1706991A (en) | 2005-12-14 |
| CN100487166C true CN100487166C (en) | 2009-05-13 |
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ID=35581094
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100275462A Expired - Fee Related CN100487166C (en) | 2004-06-07 | 2004-06-07 | Foam nickel preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100487166C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101431885B (en) * | 2008-12-18 | 2011-06-29 | 浙江三元电子科技有限公司 | All-directional conductive foam and producing method thereof |
| CN101481467B (en) * | 2009-02-03 | 2011-05-25 | 深圳市长园特发科技有限公司 | Preparations of conductive sponge and conductive latex solution |
| CN105585818B (en) * | 2014-10-22 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of nickel modified polyurethane doping epoxy resin seismic physical model material and preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3528894A (en) * | 1966-08-25 | 1970-09-15 | M & T Chemicals Inc | Method of electrodepositing corrosion resistant coating |
| US4441969A (en) * | 1982-03-29 | 1984-04-10 | Omi International Corporation | Coumarin process and nickel electroplating bath |
| CN1361311A (en) * | 2000-12-28 | 2002-07-31 | 长沙力元新材料股份有限公司 | Foamed nickel material with superhigh binding force and its prepn |
-
2004
- 2004-06-07 CN CNB2004100275462A patent/CN100487166C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3528894A (en) * | 1966-08-25 | 1970-09-15 | M & T Chemicals Inc | Method of electrodepositing corrosion resistant coating |
| US4441969A (en) * | 1982-03-29 | 1984-04-10 | Omi International Corporation | Coumarin process and nickel electroplating bath |
| CN1361311A (en) * | 2000-12-28 | 2002-07-31 | 长沙力元新材料股份有限公司 | Foamed nickel material with superhigh binding force and its prepn |
Non-Patent Citations (2)
| Title |
|---|
| 泡沫镍的制备工艺及性能参数. 汤宏伟，陈宗璋，钟发平.电池工业，第7卷第6期. 2002 |
| 泡沫镍的制备工艺及性能参数. 汤宏伟，陈宗璋，钟发平.电池工业，第7卷第6期. 2002 * |
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|---|---|
| CN1706991A (en) | 2005-12-14 |
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|---|---|---|---|
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| SE01 | Entry into force of request for substantive examination | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Huizhou Biyadi Industry Co., Ltd Assignor: Biyadi Co., Ltd. Contract fulfillment period: 2008.4.25 to 2012.11.19 contract change Contract record no.: 2008440000069 Denomination of invention: Foam nickel preparing process License type: General permission Record date: 2008.5.4 |
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Free format text: COMMON LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.4.25 TO 2012.11.19 Name of requester: HUIZHOU BIYADI INDUSTRY CO.,LTD. Effective date: 20080504 |
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Granted publication date: 20090513 Termination date: 20160607 |