CN201562714U - Button battery with electroplated layer at negative current collection body - Google Patents
Button battery with electroplated layer at negative current collection body Download PDFInfo
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- CN201562714U CN201562714U CN2009201497815U CN200920149781U CN201562714U CN 201562714 U CN201562714 U CN 201562714U CN 2009201497815 U CN2009201497815 U CN 2009201497815U CN 200920149781 U CN200920149781 U CN 200920149781U CN 201562714 U CN201562714 U CN 201562714U
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- layer
- indium
- negative electrode
- electrode collector
- copper
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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 utility model provides a button battery with an electroplated layer at a negative current collection body, comprising a negative current collection body (1), negative zinc gel (2), a diaphragm (3), an insulated seal ring (4), a positive powder cake (5) and a positive shell (6), wherein the diaphragm (3) separates the positive powder cake and the negative zinc gel. The negative current collection body is characterized in that: the inner surface and the outer surface of the negative current collection body (1) are respectively electroplated with a nickel-plated layer (8) which is used as a bottom layer on the inner concave of the negative current collection body; and the nickel-plated layer (8) is also electroplated with an indium layer, a tin layer, an indium alloy layer, a tin alloy layer or an indium-tin alloy layer. The button battery leads the electroplated layer to be more compact and uniform by controlling the current magnitude of electroplating, and provides a mercury-free button buttery which has cheap price as well as more effective, more uniform and thinner electroplated layer, and can more effectively prevent the air inflation and liquid leakage.
Description
Technical field
The utility model relates to alkaline battery, particularly relates to a kind of alkaline non-mercury button battery.
Background technology
Traditional alkaline battery (comprising zinc-manganese dioxide battery and zinc-silver oxide battery etc.), all add mercury, mercury and battery cathode metal produce amalgam, produce hydrogen with reaction between the iron that prevents negative zinc cream and battery cathode negative electrode collector in the battery or the stainless steel basic unit, cause battery inflatable and leakage.In recent years the mankind endeavour to protect environment, and many environmental protection standards and law have successively been released in countries in the world, and wherein various countries are to the use special concern of mercury.Mercury also claims mercury, and toxicity is very high, oral, suck or contact after can cause the damage of brain and liver.
In order to reduce use mercury, alkalescence column type and button cell have been found to electroplate the higher material (as metals such as indium, tin) of hydrogen overpotential to replace mercury in its battery cathode metal surface, successfully prevent reaction between the iron and steel of calamine cream and negative electrode collector in the battery or the stainless steel basic unit and generation hydrogen.But these ways still fail to solve fully problems such as battery inflatable and leakage, and stability, the adverse circumstances of its anti-inflatable, anti-leakage are deposited test and strict destructive testing, and traditional relatively mercurous alkaline battery is all undesirable.Therefore, a lot of researchs at current each electrodeposited coating of negative electrode collector weakness and launch, comprise the nickel coating or the copper layer of the bottom, indium coating, tin coating or each alloy layer of electroplating afterwards has shortcomings such as pin hole and uneven coating be even.
From the electrodeposited coating dissection and analysis, no matter electroplate nickel dam in the present battery cathode collector body, the copper layer, indium layer or tin layer in the re-plating, the indium alloy layer, ashbury metal layer etc., all find the bending part (cutaway view of the negative electrode collector of the button cell that demonstrates with reference to the utility model Fig. 1 in the negative electrode collector, the A position), because the relation of its shape, be difficult to electroplate equably and go up metal level, this problem becomes the weakness of coating, make reaction between the iron and steel of calamine cream and negative electrode collector in the battery or the stainless steel basic unit and generation hydrogen, the phenomenon of battery inflatable and leakage occurred failing to solve fully.
Summary of the invention
The purpose of the utility model patent is to provide a kind of more effective, even, few hole, thinner, low-cost electrodeposited coating, and can more effectively prevents the mercury-free button battery of inflatable and leakage.
A kind of negative electrode collector has the button cell of electrodeposited coating, comprising: negative electrode collector 1, negative zinc cream 2, barrier film 3, insulated enclosure circle 4, anodal muffin 5 and anodal housing 6; Anodal muffin 5 is filled in the bottom of anodal housing 6, barrier film 3 is arranged on the anodal muffin, separates anodal muffin and negative zinc cream, and negative zinc cream 2 is filled in the recess of negative electrode collector 1, above-mentioned insulated enclosure circle 4 is arranged between negative electrode collector 1 and the anodal housing 6, it is characterized in that:
The interior outside of negative electrode collector 1 is electroplate with nickel coating 8 as bottom, on the inner concave of negative electrode collector, also is electroplate with one deck indium layer, tin layer, indium alloy layer, ashbury metal layer or indium-ashbury metal layer 10 on nickel coating 8.
On the inner concave of negative electrode collector, between nickel coating 8 and indium layer, tin layer, indium alloy layer, ashbury metal layer or indium-ashbury metal layer 10, also be electroplate with layer of copper layer or copper-bearing alloy layer 9.
Above-mentioned copper-bearing alloy layer 9 is pltine layer or Guillaume metal layer.
Above-mentioned copper layer or copper-bearing alloy layer 9 and indium layer, tin layer, indium alloy layer, ashbury metal layer or indium-ashbury metal layer 10 is covered to the negative electrode collector outer surface by negative electrode collector 1 inner concave and does not exceed negative electrode collector end face 11.
Above-mentioned nickel coating 8, the thickness of copper layer or copper-bearing alloy layer 9 and indium layer, tin layer, indium alloy layer, ashbury metal layer or indium-ashbury metal layer 10 are respectively between 0.1 μ m to 5 μ m.
The thickness of above-mentioned copper layer or copper-bearing alloy layer 9 and indium layer, tin layer, indium alloy layer, ashbury metal layer or indium-ashbury metal layer 10 is respectively between 0.1 μ m to 2 μ m.
Described anodal muffin 5 is the mixture of manganese dioxide or manganese dioxide and silver oxide.
Described negative zinc cream 2 contains indium oxide or indium hydroxide, and is filled in the negative electrode collector recess.
Negative electrode collector is made by one deck iron plate or stainless steel substrates, and periphery has the U-shaped revers turn part.
Has the electrolyte that increases electrical conductivity in the electrolyte.
Be directly proportional with the size of electric current according to Faraday's law (Faraday ' s Law) rate of reduction of metal.Yet if metallic reducing speed is too fast, in the time of can causing on the metal deposition plating piece, outer surface reduction speed is comparatively fast shut the hole, forms in the hole and stays hole, causes coating not dense, and is unequal and hole arranged.
Therefore, the utility model patent is added the electrolyte that increases electrical conductivity by (1); (2) reduce electroplating current and make that electrodeposited coating is more even, fine and close, thinner to overcome phenomenons such as prior art battery inflatable and leakage.
The utility model advantage and effect compared with the prior art is:
(1) added the electrolysis mass-energy that increases electrical conductivity and improved concentration of metal ions, improved the transfer rate of metal ion greatly, helped and take enough metal ions to response location.It is concavo-convex and irregular particularly to work as the plating piece shape, when electroplating, shape its current potential of diverse location concavo-convex and difform plating piece is different, high potential electroplated metal layer or alloy-layer thickening, electronegative potential electroplated metal layer or alloy-layer attenuation, cause uneven metal level or alloy-layer, thereby become the weakness of electrodeposited coating.Add the then effective head it off of the electrolyte that increases electrical conductivity, electroplated out uniform coating.
(2) discover by using reduced-current to electroplate, and interpolation increases the electrolyte of electrical conductivity, can effectively reduce the speed of metallic reducing, make the metal or alloy deposit filling in each electrodeposited coating (comprise nickel dam, copper layer, and the indium layer in the re-plating thereafter, tin layer, indium alloy layer, ashbury metal layer etc.) structure reach even distribution and not contain any space.
(3) plating after the above improvement of use, coating is obviously more even, fine and close than prior art, the pin hole rate is few.Because effect is showing, need not to use thickness coating, can plate thinner coating, particularly the thickness of copper layer or copper-bearing alloy layer 9 and indium layer, tin layer, indium alloy layer, ashbury metal layer or indium-ashbury metal layer 10 more can be less than 1 μ m, is thin than prior art each electrodeposited coating 1 μ m to 10 μ m on negative electrode collector.New technology can be used still less material, economizes on resources more, reduces cost.Research also finds that flash plating is more winning in the uniformity and the quality of stability of control coating than thickness coating, more can solve phenomenons such as prior art battery inflatable and leakage.
(4) the utility model has used the low current galvanoplastic to realize flash plating 0.1 μ m to 3 μ m, uses electric current to be lower than 1dm
2/ A is (by 0.05 to 1dm
2/ A), the electroplating current 1 that uses than prior art is to 3dm
2/ A is little.Low current galvanoplastic of the present utility model not only effectively electroplate out evenly, fine and close, coating that the pin hole rate is few and thin, simultaneously, and energy savings, very environmental protection.
Description of drawings
Fig. 1 is the structural representation of the utility model negative electrode collector;
Fig. 2 is the coating structure schematic diagram of the utility model negative electrode collector;
Fig. 3 is the structural representation of the utility model mercury-free button battery.
Embodiment
, its negative electrode collector lower below in conjunction with accompanying drawing detailed description the utility model cost has coating average, fine and close, that the pin hole rate is few, thinner, and can more effectively prevent the mercury-free button battery of inflatable and leakage.
For solve prior art just (1) coating inequality, not fine and close, the pin hole rate is many; (2) special in problems such as the A of negative electrode collector inner concave parts, add the electrolyte that increases electrical conductivity by (1); (2) control electroplating current size makes electrodeposited coating finer and close, even, overcomes phenomenons such as prior art battery inflatable and leakage.
Embodiment one
As shown in Figure 2, the thinner nickel coating 8 that is less than 5 μ m of last layer is electroplated in the interior outside of negative electrode collector 1, on the inner concave of negative electrode collector 1, and the thinner tin layer 10 that is less than 1 μ m of re-plating last layer on nickel coating 8.Two-layer electrodeposited coating is all by using electroplating solution pH≤2, the control electroplating current in 0.05 to 1dm
2Between/the A, and add the electrolyte (content accounts between the electroplating solution total content 0.02% to 1%) that increases electrical conductivity is done plating in electroplating solution modification method.
Embodiment two
The present embodiment two is identical with the plating improvement method of embodiment one, the thinner nickel coating 8 that is less than 2 μ m of last layer is electroplated in the interior outside of negative electrode collector 1, on the inner concave of negative electrode collector 1, the thinner indium layer 10 that is less than 1.5 μ m of re-plating last layer on nickel coating 8.
Embodiment three
As shown in Figure 2, the thinner nickel coating 8 that is less than 3.5 μ m of last layer is electroplated in the interior outside of negative electrode collector 1, on the inner concave of negative electrode collector 1, electroplate copper layer or cupric (〉=75%) alloy-layer 9 that last layer is less than 1 μ m on nickel coating 8, the re-plating last layer is less than 1 μ m tin layer 10 on copper layer or the copper-bearing alloy layer 9.Three layers of electrodeposited coating are all by using electroplating solution pH≤2, the control electroplating current in 0.05 to 1dm
2Between/the A, and add the electrolyte (content accounts between the electroplating solution total content 0.02% to 1%) that increases electrical conductivity and in electroplating solution, make to electroplate modification method.
Embodiment four
The present embodiment four is identical with the plating improvement method of embodiment three, as shown in Figure 2, the thinner nickel coating 8 that is less than 3.5 μ m of last layer is electroplated in the interior outside of negative electrode collector 1, on the inner concave of negative electrode collector 1, electroplate copper layer or cupric (〉=75%) alloy-layer 9 that last layer is less than 0.5 μ m on nickel coating 8, copper layer or copper-bearing alloy layer 9 re-plating last layer are less than 0.5 μ m indium layer 10.
Embodiment five
The present embodiment five is identical with the plating improvement method of embodiment three, as shown in Figure 2, it is the nickel coating 8 of 0.1 μ m that the interior outside of negative electrode collector 1 is electroplated last layer thinner, on the inner concave of negative electrode collector 1, on nickel coating 8, electroplate copper layer or cupric (〉=75%) alloy-layer 9 of last layer 0.1 μ m, re-plating last layer 0.1 μ m indium-ashbury metal layer 10 on copper layer or the copper-bearing alloy layer 9.
Embodiment six
Be the contrast scheme, use existing electroplating technology scheme to be electroplate with one the interior outside of negative electrode collector 1, on the inner concave of negative electrode collector 1, on nickel coating 8, electroplate last layer greater than 1 μ m tin layer 10 greater than 3 μ m nickel coatings 8.
Embodiment seven
Be the contrast scheme, use existing electroplating technology scheme to be electroplate with one 3 μ m nickel coatings 8 the interior outside of negative electrode collector 1, on the inner concave of negative electrode collector 1, electroplate the copper layer 9 of last layer greater than 1 μ m on nickel coating 8, the re-plating last layer is greater than the indium layer 10 of 1 μ m on the copper layer 9.
Above-mentioned seven embodiments produce negative electrode collector 1 described in the utility model as shown in Figure 1, can be made by one deck iron plate or stainless steel substrates, and its periphery has U-shaped revers turn part 7.
Above-mentioned seven embodiments produce negative electrode collector 1 described in the utility model as shown in Figure 2, and described two-layer coating 9 and coating 10 are covered to the negative electrode collector outer surface by negative electrode collector 1 inner concave and do not exceed negative electrode collector end face 11.Described negative electrode collector 1 each coating 8～10 its thickness can be between 0.1 μ m to 10 μ m.
Further, described negative electrode collector 1 each coating 8～10 its thickness can be respectively between 0.1 μ m to 5 μ m.
Further again, described negative electrode collector 1 each coating 8～10 its thickness can be respectively between 0.1 μ m to 2 μ m.
The produced negative electrode collector 1 of above-mentioned seven embodiments can manufacture the L1154 mercury-free button battery, comprises as shown in Figure 3: negative electrode collector 1, negative zinc cream 2, barrier film 3, insulated enclosure circle 4, anodal muffin 5 and anodal housing 6.Described anodal muffin 5 is the mixture of manganese dioxide or manganese dioxide and silver oxide, and anodal muffin 5 is filled in the bottom of anodal housing 6, and barrier film 3 is arranged on the anodal muffin, separates anodal muffin and negative zinc cream.Described negative zinc cream 2 contains indium oxide or indium hydroxide, and negative zinc cream 2 is filled in the recess of negative electrode collector 1, and negative electrode collector 1 back-off is on barrier film 3.Negative electrode collector 1 periphery has U-shaped revers turn part 7, between above-mentioned revers turn part and the anodal housing 6 insulated enclosure circle 4 is installed, and all is coated with inside and outside the above-mentioned insulated enclosure circle 4 and is soaked with thick glue, does sealing and uses.
The produced L1154 mercury-free button battery of above-mentioned seven embodiments is done leakage (2) 45 ℃ of high temperature storages of test leakage in 20 days, 40 days, 60 days test by (1) IEC standard; (3) 60 ℃ of high temperature storages leakage in 20 days, 40 days, 60 days test; Find that seven embodiments are all by IEC basic leakage test and 45 ℃ of storage leakage tests in 20 days, 40 days, 60 days.Under worse storage environment, embodiment one, two, three, four and five can be by 60 ℃ of storage leakage tests in 20 and 40 days.And embodiment three, four reaches just before dawn and can test by 60 ℃ of storage leakages in 60 days.Above embodiment has clearly demonstrated after negative electrode collector 1 has used the electro-plating method of improvement, coating is thinner, uses electric current still less, saves resource and cost greatly, and can more effectively improve problems such as prior art inflatable and leakage, in strict leakage test, better performance be arranged.
Those of ordinary skills can make various improvement in the scope that does not exceed the utility model spirit under prompting of the present utility model, protection range of the present utility model is as the criterion with claim.
Claims (9)
1. a negative electrode collector has the button cell of electrodeposited coating, comprising: negative electrode collector (1), negative zinc cream (2), barrier film (3), insulated enclosure circle (4), anodal muffin (5) and anodal housing (6); Anodal muffin (5) is filled in the bottom of anodal housing (6), barrier film (3) is arranged on the anodal muffin, separate anodal muffin and negative zinc cream, negative zinc cream (2) is filled in the recess of negative electrode collector (1), above-mentioned insulated enclosure circle (4) is arranged between negative electrode collector (1) and the anodal housing (6), it is characterized in that:
The interior outside of negative electrode collector (1) is electroplate with nickel coating (8) as bottom, on the inner concave of negative electrode collector, also is electroplate with one deck indium layer, tin layer, indium alloy layer, ashbury metal layer or indium-ashbury metal layer (10) on nickel coating (8).
2. button cell according to claim 1 is characterized in that:
On the inner concave of negative electrode collector, between nickel coating (8) and indium layer, tin layer, indium alloy layer, ashbury metal layer or indium-ashbury metal layer (10), also be electroplate with layer of copper layer or copper-bearing alloy layer (9).
3. button cell according to claim 2 is characterized in that:
Above-mentioned copper-bearing alloy layer (9) is pltine layer or Guillaume metal layer.
4. button cell according to claim 1 and 2 is characterized in that:
Above-mentioned copper layer or copper-bearing alloy layer (9) and indium layer, tin layer, indium alloy layer, ashbury metal layer or indium-ashbury metal layer (10) is covered to the negative electrode collector outer surface by negative electrode collector (1) inner concave and does not exceed negative electrode collector end face (11).
5. button cell according to claim 1 and 2 is characterized in that:
Above-mentioned nickel coating (8), the thickness of copper layer or copper-bearing alloy layer (9) and indium layer, tin layer, indium alloy layer, ashbury metal layer or indium-ashbury metal layer (10) are respectively between 0.1 μ m to 5 μ m.
6. button cell according to claim 1 and 2 is characterized in that:
The thickness of above-mentioned copper layer or copper-bearing alloy layer (9) and indium layer, tin layer, indium alloy layer, ashbury metal layer or indium-ashbury metal layer (10) is respectively between 0.1 μ m to 2 μ m.
7. button cell according to claim 1 is characterized in that:
Described negative zinc cream (2) contains indium oxide or indium hydroxide, and is filled in negative electrode collector (1) recess.
8. button cell according to claim 1 is characterized in that:
Negative electrode collector (1) is made by one deck iron plate or stainless steel substrates, and periphery has U-shaped revers turn part (7).
9. button cell according to claim 1 is characterized in that:
Has the electrolyte that increases electrical conductivity in the electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009201497815U CN201562714U (en) | 2009-06-18 | 2009-06-18 | Button battery with electroplated layer at negative current collection body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009201497815U CN201562714U (en) | 2009-06-18 | 2009-06-18 | Button battery with electroplated layer at negative current collection body |
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| Publication Number | Publication Date |
|---|---|
| CN201562714U true CN201562714U (en) | 2010-08-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009201497815U Expired - Lifetime CN201562714U (en) | 2009-06-18 | 2009-06-18 | Button battery with electroplated layer at negative current collection body |
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| CN (1) | CN201562714U (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103866359A (en) * | 2014-03-25 | 2014-06-18 | 株洲永盛电池材料有限公司 | Mercury-free button cell negative electrode cover material and preparation method thereof |
| CN110364645A (en) * | 2019-06-18 | 2019-10-22 | 深圳清华大学研究院 | Mercury-free button cells cathode cover material and its preparation method and application |
-
2009
- 2009-06-18 CN CN2009201497815U patent/CN201562714U/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103866359A (en) * | 2014-03-25 | 2014-06-18 | 株洲永盛电池材料有限公司 | Mercury-free button cell negative electrode cover material and preparation method thereof |
| CN103866359B (en) * | 2014-03-25 | 2016-04-06 | 湖南永盛新材料股份有限公司 | Mercury-free button cell negative electrode cover material and preparation method thereof |
| CN110364645A (en) * | 2019-06-18 | 2019-10-22 | 深圳清华大学研究院 | Mercury-free button cells cathode cover material and its preparation method and application |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20100825 |
|
| CX01 | Expiry of patent term |