CN103219496B - A kind of manufacture method of cadmium reference electrode for lead acid battery - Google Patents
A kind of manufacture method of cadmium reference electrode for lead acid battery Download PDFInfo
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- CN103219496B CN103219496B CN201210014997.7A CN201210014997A CN103219496B CN 103219496 B CN103219496 B CN 103219496B CN 201210014997 A CN201210014997 A CN 201210014997A CN 103219496 B CN103219496 B CN 103219496B
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- cadmium
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- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 67
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000002253 acid Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 238000009713 electroplating Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000007747 plating Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 13
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 5
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 238000003754 machining Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 2
- 238000012958 reprocessing Methods 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 2
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 2
- FMGSKLZLMKYGDP-USOAJAOKSA-N dehydroepiandrosterone Chemical class C1[C@@H](O)CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC=C21 FMGSKLZLMKYGDP-USOAJAOKSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VMJALCVVAXEWQQ-UHFFFAOYSA-N cadmium sulfamic acid Chemical compound [Cd].S(N)(O)(=O)=O VMJALCVVAXEWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 1
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 1
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The present invention relates to lead-acid accumulator and manufacture field, concretely relate to the manufacture method of a kind of cadmium reference electrode for lead acid battery, including step: select matrix material; Matrix surface is carried out oil removing, oxide film dissolving, cleaning pretreatment; Electroplating bath prepares, including the preparation of electroplate liquid system, the control of bath temperature, plating solution mass transport limitation; Matrix is put into electroplating bath, and its upper end is drawn wire and is connected to DC source cathode end, electroplates, makes matrix be covered with cadmium coater, obtains cadmium coater electrode; Reprocessing for cadmium coater electrode, this invention address that the difficulty of processing existed in tradition cadmium electrode machining is big, cadmium material consumption is many, and be difficult to the problems such as small size type reference electrode, making simple, the purity of cadmium coater is high.
Description
Technical field
The present invention relates to lead-acid accumulator and manufacture field, concretely relate to the manufacture method of a kind of cadmium reference electrode for lead acid battery.
Background technology
Lead-acid accumulator is widely used in commercial production and daily life, and it occupies highly important status and ratio in whole electrochmical power source. In the recent period, along with the electric vehicle industry such as electric automobile, electric bicycle and wind energy, the developing rapidly of solar energy grid-connected power generation system industry, corresponding electrokinetic cell, energy-storage battery market demand are very huge, and its demand growth rate leads over other electrochmical power source.
In lead-acid accumulator research and development and production, what generally detect is the overall work voltage of accumulator, and this cell voltage has contained positive electrical potential difference, negative electricity potential difference, solution and barrier film voltage drop and various ohmic voltage drop. But often need to paying close attention to the potential change situation of negative or positive electrode in accumulator research, to obtain battery important electrode reaction information such as polarization overpotential change in charge and discharge process, and traditional voltage detection method is difficult to meet this requirement. Document has been had to propose to adopt reference electrode to carry out the detection of single electrode potential, such as document " reference electrode application in lead battery the two poles of the earth electrode potential is measured " (Liu Guanglin, " accumulator ", 1988 (1), 24-27), although can adopt Hg/Hg2SO4 reference electrode, Ag/Ag2SO4 reference electrode in lead-acid accumulator is studied, but cadmium electrode is subject to the welcome of battery industry research and production because of advantages such as its making are simple, easy to use, performance is relatively stable.
At present, the manufacture method of cadmium reference electrode: adopting machining manufacture method, owing to the fusing point of cadmium is 320.9 DEG C, when being heated, matter is soft, and reference electrode size is little, it is susceptible to torsional deformation, difficulty when the machining such as lathe big. Additionally, machine-tooled method workload is big, cadmium material consumption is big, it is more serious to waste; Because of potential measurement stability and the requirement ensureing service life, it is necessary to adopting the cadmium of high-purity or ultra-high purity, material cost is high. Additionally, common cadmium reference electrode is relatively large sized, when inside battery is placed, because insufficient space causes use inconvenience, effect is bad.
The present invention proposes a kind of cadmium reference electrode adopting new structure and preparation method thereof, is characterized on suitable conducting base and adopts electro-deposition method to obtain cadmium coater, cadmium coater very high purity, and thickness is controlled, and cadmium material consumption is less, do not waste. Electrode fabrication is simple and easy, easy to use, it is thus achieved that good actual effect, achieves application, it is thus achieved that the real-time electrical potential information of reliable and stable positive and negative electrode in multiple commercial lead battery battery cell in the measurement of both positive and negative polarity current potential.
Summary of the invention
The invention provides the manufacture method of a kind of cadmium reference electrode for lead acid battery, it is intended to adopt on-mechanical processing method to make cadmium reference electrode, the difficulty of processing solving to exist in tradition cadmium electrode machining is big, cadmium material consumption is many, and is difficult to the problems such as small size type reference electrode.
The present invention is achieved by the following technical solutions: the manufacture method of a kind of cadmium reference electrode for lead acid battery, including step: select matrix material; Matrix surface is carried out oil removing, oxide film dissolving, cleaning pretreatment; Electroplating bath prepares, and including the preparation of electroplate liquid system, bath temperature control, plating solution mass transport limitation, described bath temperature controls at 20 DEG C��55 DEG C; Matrix is put into electroplating bath, and its upper end is drawn wire and is connected to DC source cathode end, electroplates, makes matrix be covered with cadmium coater, obtains cadmium coater electrode; Reprocess for cadmium coater electrode.
As preferably, step one, described matrix is copper wire or filamentary silver or nickel wire.
As preferably, step 3, magnetic stir bar is set bottom electroplating bath, has magnetic stirring apparatus outside corresponding electroplating bath, for plating solution mass transport limitation.
As preferably, step 3, described bath system adopts acid or neutral or alkaline non-cyanide bath system.
As preferably, step 5, cadmium coater electrode deionized water is fully cleaned, dry, and carry out dehydrogenation.
As preferably, the cadmium coater electrode after being reprocessed, bottom it and top carry out epoxy resin sealing protection together with wire extraction place.
This invention takes above-mentioned corrective measure to carry out, its beneficial effect is notable:
(1) very high purity of cadmium coater in the cadmium reference electrode that electrodeposition process makes, the electrode potential of actually used middle measurement is relatively more accurate, and ruggedness is better;
(2) on matrix, the thickness of cadmium deposition layer is controlled, can change electrodeposition time by desired thickness requirement. Cadmium material consumption is few, does not waste cadmium material, and reference electrode cost of manufacture is low;
(3) cadmium coater is strong with basal body binding force, and the electrode suitability is wide;
(4) method for making its electrode is simple, easy to use.
Accompanying drawing explanation
Fig. 1 is the structural representation of the embodiment of the present invention 1;
Fig. 2 is the structural representation of cadmium coater electrode of the present invention;
In figure, 1 is DC source, and 2 is cadmium positive plate, and 3 is matrix, and 4 is that matrix draws wire, and 5 is electrolysis bath, and 6 is magnetic stir bar, and 7 is magnetic stirring apparatus, and 8 is epoxy sealing layer.
Detailed description of the invention
Below against accompanying drawing, the present invention is further illustrated in conjunction with the embodiments:
Embodiment 1
Shown in reference Fig. 1, the manufacture method of a kind of cadmium reference electrode for lead acid battery, step is:
(1) selecting matrix material is copper wire;
(2) copper wire surface is carried out oil removing, oxide film dissolving, cleaning pretreatment;
(3) electroplating bath prepares: arrange magnetic stir bar bottom electroplating bath, magnetic stirring apparatus is had outside corresponding electroplating bath, magnetic stirring apparatus drives magnetic stir bar stirring, electroplate liquid system adopts acid system, formula is pyrovinic acid cadmium 85g/L, free pyrovinic acid 50g/L, fatty alcohol-polyoxyethylene ether 1.0g/L, gelatin 1.5g/L, the control of bath temperature is 45 DEG C;
(4) copper wire being inserted electroplating bath, its upper end is drawn wire and is connected to the cathode end of DC source, and the cadmium positive plate in electrolysis bath connects the anode output end of power supply, controls cathode-current density, is adjusted to 100A/m2, reached the ability continuing to electroplate in electrolysis bath by the stirring of magnetic stir bar so that copper wire is covered with cadmium coater, i.e. cadmium coater electrode; After testing, in cadmium coater, the content of cadmium is 99.99%.
(5) fully clean for cadmium coater electrode deionized water obtained above, be placed in baking oven dry, and carry out dehydrogenation;
(6) by the cadmium coater electrode after above-mentioned Dehydroepiandrosterone derivative, epoxy resin sealing protection is carried out in bottom and top together with wire extraction place.
Embodiment 2
(1) selecting matrix material is nickel wire;
(2) nickel wire surface is carried out oil removing, oxide film dissolving, cleaning pretreatment;
(3) electroplating bath prepares: arrange magnetic stir bar bottom electroplating bath, magnetic stirring apparatus is had outside corresponding electroplating bath, magnetic stirring apparatus drives magnetic stir bar stirring, electroplate liquid system adopts acid system, formula is sulfamic acid cadmium 40g/L, free amine group sulfonic acid 50g/L, resorcinol 1.5g/L, gelatin 2g/L, bath temperature is 55 DEG C;
(4) nickel wire being inserted electroplating bath, its upper end is drawn wire and is connected to the cathode end of DC source, and the cadmium anode in electrolysis bath connects the anode output end of power supply, controls cathode-current density, is adjusted to 80A/m2, reached the ability continuing to electroplate in electrolysis bath by the stirring of magnetic stir bar so that nickel wire is covered with cadmium coater, i.e. cadmium coater electrode; After testing, in cadmium coater, the content of cadmium is 99.99%.
(5) fully clean for cadmium coater electrode deionized water obtained above, be placed in baking oven dry, and carry out dehydrogenation;
(6) by the cadmium coater electrode after above-mentioned Dehydroepiandrosterone derivative, epoxy resin sealing protection is carried out in bottom and top together with wire extraction place.
Embodiment 3
Its step and matrix material and embodiment 1 are identical, institute adopts neutral system the difference is that (3) electroplate liquid system, formula is ammonium chloride 180g/L, triacetic acid ammonium 60g/L, sodium ethylene diamine tetracetate 15g/L, cadmium sulfate 45g/L, sodium acetate 30g/L, peptone 0.8g/L, bath temperature is 30 DEG C.
(4) DC power control cathode-current density is 120A/m2. After testing, in cadmium coater, the content of cadmium is 99.99%.
Embodiment 4
Its step and embodiment 1 are identical, and institute is filamentary silver the difference is that selected matrix material, additionally (3) electroplate liquid system employing alkaline system, formula is cadmium sulfate 70g/L, triethanolamine 160g/L, triacetic acid ammonium 40g/L, ammonium sulfate 30g/L, potassium pyrophosphate 40g/L, bath temperature is 20 DEG C.
(4) DC power control cathode-current density is 150A/m2, after testing, in cadmium coater, the content of cadmium is 99.99%. .
Certainly, each constituent content of plating solution formula provided herein is that preferred value, it is also possible to change numerical value and the electroplating time of each reagent according to the thickness needed for cadmium coater.
Listed above is only specific embodiments of the invention, it is clear that the invention is not restricted to above example. All deformation that those of ordinary skill in the art can directly derive from present disclosure or associate, all should belong to protection scope of the present invention.
Claims (3)
1. the manufacture method of a cadmium reference electrode for lead acid battery, it is characterised in that include step:
(1) selecting matrix material, described matrix is copper wire or filamentary silver or nickel wire;
(2) matrix surface is carried out oil removing, oxide film dissolving, cleaning pretreatment;
(3) electroplating bath prepares, including the preparation of electroplate liquid system, bath temperature control, plating solution mass transport limitation, described bath system adopts acid or neutral or alkaline non-cyanide bath system, described bath temperature controls at 20 DEG C��55 DEG C, described plating solution mass transport limitation is arrange magnetic stir bar bottom electroplating bath, has magnetic stirring apparatus outside corresponding electroplating bath;
(4) matrix being put into electroplating bath, its upper end is drawn wire and is connected to DC source cathode end, controls cathode-current density, is adjusted to 100A/m2Or 80A/m2Or 120A/m2Or 150A/m2, electroplate, make matrix be covered with cadmium coater, obtain cadmium coater electrode;
(5) reprocess for cadmium coater electrode.
2. the manufacture method of cadmium reference electrode for lead acid battery according to claim 1, it is characterised in that step (5), fully cleans cadmium coater electrode deionized water, dry, and carries out dehydrogenation.
3. the manufacture method of cadmium reference electrode for lead acid battery according to claim 2, it is characterised in that the cadmium coater electrode after being reprocessed, bottom it and top carry out epoxy resin sealing protection together with wire extraction place.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210014997.7A CN103219496B (en) | 2012-01-18 | 2012-01-18 | A kind of manufacture method of cadmium reference electrode for lead acid battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210014997.7A CN103219496B (en) | 2012-01-18 | 2012-01-18 | A kind of manufacture method of cadmium reference electrode for lead acid battery |
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| CN103219496A CN103219496A (en) | 2013-07-24 |
| CN103219496B true CN103219496B (en) | 2016-06-01 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107783055B (en) * | 2017-09-30 | 2019-12-06 | 超威电源有限公司 | Cadmium reference electrode and manufacturing method thereof |
| CN107807332A (en) * | 2017-10-10 | 2018-03-16 | 超威电源有限公司 | lead-acid battery electrode potential detection device and detection method |
| CN115117487A (en) * | 2022-04-28 | 2022-09-27 | 华北电力科学研究院有限责任公司 | Reference electrode for valve-regulated lead-acid storage battery test and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1212344A (en) * | 1967-02-28 | 1970-11-11 | Int Nickel Ltd | Metal plates for alkaline accumulators |
| CN1250231A (en) * | 1999-09-24 | 2000-04-12 | 国营长虹机器厂 | Manufacture of electrically deposited cadmium electrode |
| CN101082136A (en) * | 2006-05-30 | 2007-12-05 | 比亚迪股份有限公司 | Electroplating liquid for nickel-cadmium battery negative pole and manufacturing method for nickel-cadmium battery negative pole |
-
2012
- 2012-01-18 CN CN201210014997.7A patent/CN103219496B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1212344A (en) * | 1967-02-28 | 1970-11-11 | Int Nickel Ltd | Metal plates for alkaline accumulators |
| CN1250231A (en) * | 1999-09-24 | 2000-04-12 | 国营长虹机器厂 | Manufacture of electrically deposited cadmium electrode |
| CN101082136A (en) * | 2006-05-30 | 2007-12-05 | 比亚迪股份有限公司 | Electroplating liquid for nickel-cadmium battery negative pole and manufacturing method for nickel-cadmium battery negative pole |
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