CN1259741C - Lead dioxide coated carbon material, making method and zinc-nickel battery containing the same - Google Patents
Lead dioxide coated carbon material, making method and zinc-nickel battery containing the same Download PDFInfo
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- CN1259741C CN1259741C CNB021519897A CN02151989A CN1259741C CN 1259741 C CN1259741 C CN 1259741C CN B021519897 A CNB021519897 A CN B021519897A CN 02151989 A CN02151989 A CN 02151989A CN 1259741 C CN1259741 C CN 1259741C
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- zinc
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- carbon element
- lead dioxide
- dioxide coated
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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
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Abstract
The present invention relates to a carbon material which is used as a core and coated by lead dioxide with a weight ratio content of 1% to 80%. The present invention also relates to a manufacturing method in which the carbon material is added in an alkaline solution dissolved with an oxydant, and a solution containing bivalent lead ions is also dropped in the alkaline solution, so that the bivalent lead ions are converted in the alkaline solution into the lead dioxide uniformly attached to the surface of the carbon material. The present invention further relates to a zinc-nickel battery which comprises a Ni (OH) 2 anode, a zinc cathode, an insulator and an alkaline electrolyte solution, wherein the zinc cathode contains the carbon material coated with the lead dioxide. When the zinc-nickel battery is charged for the first time, the PbO2 uniformly attached to the surface of the carbon material is easily converted into a metallic state to suppress hydrogen evolution, enhance the conductivity of the zinc electrode together with the carbon material and improve the high-magnification discharge performance of the battery, so that the battery can bear repeated high-magnification discharge for 200 times.
Description
Technical field
The invention belongs to the rechargeable battery technical field, relate in particular to a kind of modification material with carbon element and manufacture method thereof, also relate to the zinc-nickel cell that contains this material with carbon element as the Zinc-nickel battery negative additive.
Background technology
In recent years, in huge power tool battery and electronic toy Battery Market, the Cd/Ni battery occupies very big share with its good heavy-current discharge performance, but the Cd/Ni battery has pollution to environment, seeks substitute so be necessary for it.
Zinc electrode can be born high-multiplying power discharge, and this has obtained proof in the high magnification zinc-silver oxide cell, but and also high-multiplying power discharge of ickel-cadmium cell, so as long as technological parameter is reasonable, the zinc-nickel cell of being made up of zinc electrode and nickel electrode can stand high-multiplying power discharge.
In disclosed zinc-nickel cell technology at present, also make the battery of the high-multiplying power discharge repeatedly that is specifically designed to electric tool and electronic toy, the especially discharge that leads with 10C at zinc-nickel cell more than 60 ℃ without any company or researcher.Because the instrument battery can be emitted a large amount of heat in use at present, temperature can be increased to more than 60 ℃, and the technology that will be fit to repeatedly high-multiplying power discharge to zinc-nickel cell is the problem of a needs tackling key problem.
In the existing zinc-nickel cell technology, polarize excessive and premature deactivation, can add the oxide of some oxidation-reduction potentials metal positive, as CdO, PbO, Bi than Zn in order to prevent battery negative pole when discharging
2O
3Deng, in primary charging process, these metal oxides can be transformed into metallic state and form conductive network prior to ZnO, but do not participate in discharge when discharging at every turn, like this, the metallic conduction network is kept, and helps to reduce the polarization of zinc negative pole, delays passivation, makes battery can emit more electric weight, simultaneously, these metals have high overpotential of hydrogen evolution, help to reduce separating out of hydrogen, do not add plumbous tetravalent oxide---PbO but mention
2
Have carbon black, graphite are made an addition in the zinc negative pole, as conductive agent.Its effect is the polarization when reducing zinc electrode and discharging and recharging, and intensifier electrode conductivity strengthens the high-rate discharge ability of battery.Its shortcoming is, hydrogen is separated out at carbon material surface easily, and this can cause inner pressure of battery to increase, and increases self discharge.For solving the liberation of hydrogen problem, the someone will have the lead deposit of high overpotential of hydrogen evolution on carbon black or graphite, add to then in the zinc electrode, suppress liberation of hydrogen with this.Must recognize that Pb is deposited on the material with carbon element with metallic state, rather than PbO
2, also must recognize simultaneously, be exposed to the PbO that airborne metallic lead is easy to be oxidized to divalence.
Making the zinc cathode size and then making in the process of zinc negative pole, the use of some bonding agents is indispensable, and these bonding agents comprise CMC, HPMC, PTFE and PVA etc.When making additive making cathode size with metallic aluminum, (comprise the metallic lead PbO that autoxidation generates in air) because Pb and can make the water absorption of bonding agents such as CMC, HPMC and difficulties in dispersion, make cathode size to prepare, thereby can't make negative plate with lower-cost slurry legal system.That is to say, if contain the oxides, divalent PbO of metallic lead or aluminium in the additive, then can not contain CMC or HPMC in Pei Zhi the cathode size, otherwise the high-rate discharge ability of zinc-nickel cell is had a greatly reduced quality, can make zinc electrode lack enough electrolyte solutions because lack water absorbing agents such as CMC and HPMC, thereby enough hydroxyl (OH can't be provided
-) to deal with the need of discharge, when the high magnification heavy-current discharge, very easily cause the zinc electrode passivation especially and battery can not put.
Facts have proved PbO
2Can not make CMC, HPMC that difficulties in dispersion takes place, and in first time charging process, PbO
2Also the same with other metal oxide above-mentioned, be easy to change into metallic state.
Summary of the invention
The present invention will solve zinc-nickel cell and be fit to the technical problem of high-multiplying power discharge repeatedly, and primary and foremost purpose is to improve the negative pole electric conductivity and suppress liberation of hydrogen, provides as the modification material with carbon element of a kind of lead dioxide coated of Zinc-nickel battery negative additive to realize for this reason.
A kind of material with carbon element of lead dioxide coated is a nuclear with the material with carbon element, and brown lead oxide is coated on its top layer, and wherein brown lead oxide weight ratio content is 1%-80%, is that 25%-50% is preferred with content.
Material with carbon element wherein can be crystalline state carbon such as various graphite, amorphous carbon such as carbon black and acetylene black, or various transition state carbon.
Further aim of the present invention provides a kind of material with carbon element manufacture method of lead dioxide coated of as above-mentioned description.
Material with carbon element manufacture method of the present invention realizes in the following way:
In being dissolved with the alkaline solution of oxidant, add material with carbon element, splash into the solution that contains lead then, make lead in alkaline solution, change into the surface that brown lead oxide is attached to material with carbon element equably.
Alkali in the alkaline solution wherein can be NaOH, KOH or both mixtures with any mixed.
Lead wherein can be provided by lead salt such as lead acetate or plumbi nitras, or plumbous oxides, divalent and hydroxide provide.
Wherein under alkali condition oxidant to the lead oxidizing potential for just, lead can be oxidized to PbO
2, hypochlorous sodium or hydrogen peroxide are preferred.
Further object of the present invention provides a kind of zinc-nickel cell, and high-multiplying power discharge substitutes ickel-cadmium cell repeatedly, reduces the pollution to environment.
The invention provides a kind of zinc-nickel cell, comprise one with Ni (OH)
2Be main positive electrode, by a kind of positive pole of wettability microporous barrier parcel, one is the negative pole of main active substances with the Zinc material, a kind of spacer, a kind of alkaline electrolyte solution is characterized in that: described zinc negative pole contains the material with carbon element as the lead dioxide coated of above-mentioned description.
Wherein the material with carbon element of lead dioxide coated accounts for negative pole total weight 0.1%-10%.
Wherein the anodal wettability microporous barrier of parcel is selected from as polyethylene radiation grafting films such as CN-1000, CN-2000, CN-2020, or the three cellulose acetate membrane of handling through saponification, or any as in wettability polyethylene such as wettability Celgard film or the microporous polypropylene membrane.
Wherein cathode capacitance be electric capacity of anode 1.2-3 doubly, doubly serve as preferred with 2-3.
Wherein spacer is nylon nonwoven fabrics or polypropylene non-woven fabric or vinylon felt.
Alkaline electrolyte solution wherein contains one or more among electrolyte KOH, NaOH and the LiOH, and the weight content of electrolyte in solution is 15%-45%, is preferred with 20%-35%.
Wherein negative current collector is the punched copper tape that is made through punching by red copper or filtter gold, and preferred surface contains the punched copper tape of Pb, Sn or Pb-Sn alloy layer.
Aforesaid zinc-nickel cell, preferred structure is: described negative plate, the spacer that is enclosed with the positive plate of wettability microporous barrier and is between the both positive and negative polarity forms electrode cores in the mode of reeling, described pole piece is received and kept in battery steel shell, be provided with anodal drainage band in the described positive pole, anodal drainage tape welding is connected on nickel plating box hat bottom, be provided with negative pole drainage band in the described negative pole, negative pole drainage tape welding is connected on the battery cap, be provided with between the outside of electrode cores and the inboard of battery case that one deck made by PVC material or polytetrafluoroethylmaterial material, be used to the hydrophobic insulating barrier that prevents that negative pole from contacting with battery steel shell, be marked with quantitative alkaline electrolyte solution and sealing in the described battery steel shell.
Details are as follows for the manufacture method of zinc-nickel cell:
Batchings such as the lead dioxide coated material with carbon element that will produce with said method and zinc oxide, mercury less zinc powder, calcium hydroxide also mix with mixing apparatus.
Said mixture and HPMC, CMC, PTFE, PVA and deionized water are stirred into by a certain percentage the slurry of thickness.
Again above-mentioned slurry is invested on the punched copper tape that is coated with Pb, Sn or Pb-Sn alloy layer by tensile pulp machine.
Process oven dry, roll-in, cut-parts are also welded the negative pole that the drainage band makes battery.
Ball-type nickel hydroxide, cobalt protoxide, conductive carbon black and bonding agent PTFE, CMC and deionized water are stirred into slurry according to a certain percentage and be coated onto on the foaming nickel that is welded with the drainage band, make the positive pole of battery through oven dry, roll-in, cut-parts.
Form pole piece with up-coiler coiling multi-turn and receive and keep in the cylindrical battery box hat across slider being enclosed with the positive pole of wettability microporous barrier and negative pole.
With the semi-finished product that make through spot welding, jet-bedding, notes electrolyte with seal and make cylindrical zinc nickel-based battery described in the invention.
In the first time of the battery of making charging process, evenly be attached to the PbO of carbon material surface
2Be easy to change into metallic state, play the effect that suppresses liberation of hydrogen, strengthen the conductivity of zinc electrode simultaneously with material with carbon element, improve the high-rate discharge ability of battery, make battery can stand repeatedly high-multiplying power discharge, reach 200 times.
Description of drawings
The XRD figure of Fig. 1 embodiment of the invention 1 product
The SEM figure of Fig. 2 embodiment of the invention 1 product
The SEM figure of Fig. 3 embodiment of the invention 2 products
Embodiment
The present invention is described in detail below in conjunction with drawings and Examples:
Embodiment 1
Get 6 gram NaClO solution and 2 gram NaOH wiring solution-forming 250ml, 4.8 gram graphite are added in the alkaline NaClO solution, constantly stir.Other gets 3.04 gram lead acetates and is made into 100ml solution, and the lead acetate drips of solution is added in the alkaline NaClO solution.After reaction is finished the solution suction filtration is also used deionized water wash, drying.Product characterizes with XRD, SEM, sees Fig. 1 and Fig. 2.
Embodiment 2
Get 12 gram NaClO solution and 4 gram NaOH wiring solution-forming 250ml, 4.8 gram graphite are added in the alkaline NaClO solution, constantly stir.Other gets 7.6 gram lead acetate 100ml solution, and the lead acetate drips of solution is added in the alkaline NaClO solution.After reaction is finished the solution suction filtration is also used deionized water wash, drying.Product characterizes with SEM, sees Fig. 3.
Embodiment 3
Be taken at lead dioxide coated graphite 5 grams of producing among the embodiment 1, Belgian mercury less zinc powder 16 grams, zinc oxide 59 grams, calcium hydroxide 10 grams mix with mixing apparatus.
Said mixture is become the slurry of thickness with 4 gram PTFE, 0.6 gram PVA, 0.5 gram HPMC and 40 gram deionized water and stirring.Again above-mentioned slurry is invested the thick 0.07mm that is coated with the Pb-Sn alloy layer by tensile pulp machine, on the punched copper tape of wide 33.5mm.Process oven dry, roll-in, cut-parts are also welded the negative pole that the drainage band makes long 220mm.
With 92 gram ball-type nickel hydroxides, 7 gram cobalt protoxides, 11 gram conductive carbon blacks and 4 gram PTFE, 0.2 gram CMC and 40 gram deionized water and stirring pulp things and be coated onto on the foaming nickel that is welded with the drainage band, make the positive pole of the wide 32mm of long 200mm through oven dry, roll-in, cut-parts.
The positive pole of battery and negative pole are formed pole piece with up-coiler coiling multi-turn and receive and keep in the SC battery steel shell across slider.The semi-finished product that make are contained through spot welding, jet-bedding, injection 25% KOH and 1.5% LiOH electrolyte and seal and make SC type column like zinc nickel-based battery of the present invention, be numbered 1.
Battery is changed into the back with 800mA charging 2 hours, and 15A is discharged to 1.2V and carries out loop test, when discharge capacity of the cell reduce to initial discharge capacity 70% the time stop test.
Embodiment 4
Be taken at lead dioxide coated carbon black 5 grams of producing among the embodiment 2, other condition and embodiment 3 identical making batteries are numbered 2, press the test of embodiment 3 same procedure.
Comparative Examples
Zinc oxide by identical weight replaces the lead dioxide coated material with carbon element, and other condition and embodiment 3 identical making batteries are numbered 3, presses the test of embodiment 3 same procedure.
Test result such as following table one for above-mentioned zinc-nickel cell:
Table one SC type sealed Zn-Ni cycle performance of battery (0.5C fills 2hrs, and 10C is put to 1.2V)
| Battery | Nominal capacity (mAh) | Discharging current (A) | Cut-off condition (mAh) | Cycle life (inferior) | ||
| On average | The highest | Scope | ||||
| 1 | 1500 | 15 | 1050 | 105 | 174 | 100-174 |
| 2 | 1500 | 15 | 1050 | 160 | 201 | 136-201 |
| 3 | 1300 | 13 | 910 | 45 | 50 | 35-50 |
Above-mentioned test result shows, utilizes the zinc-nickel cell of lead dioxide coated material with carbon element preparation of the present invention all to be better than conventional zinc nickel-based battery, effect highly significant greatly in the cycle life of capacity, 10C multiplying power discharging.
After the invention has been described by embodiment, be appreciated that those skilled in the art on the basis of having read this specification, obviously can make various changes to the present invention.Therefore, be noted that content of the present invention disclosed herein has been believed to comprise the above-mentioned various changes that will make, they belong within subsidiary claims scope.
Claims (19)
1, a kind of material with carbon element of lead dioxide coated is characterized in that: be nuclear with the material with carbon element, brown lead oxide is coated on its top layer, and wherein brown lead oxide weight ratio content is 1%-80%.
2, the material with carbon element of lead dioxide coated according to claim 1, wherein brown lead oxide weight ratio content is for 25%-50%.
3, the material with carbon element of lead dioxide coated according to claim 1, material with carbon element wherein are one or more in crystalline state carbon, amorphous carbon, the various transition state carbon.
4, as the material with carbon element manufacture method of lead dioxide coated as described in the claim 1 to 3 any, it is characterized in that: in being dissolved with the alkaline solution of oxidant, add material with carbon element, splash into the solution that contains lead then, make lead in alkaline solution, change into the surface that brown lead oxide is attached to material with carbon element.
5, the material with carbon element manufacture method of lead dioxide coated according to claim 4, the alkali in the alkaline solution wherein are NaOH, KOH or both mixtures with any mixed.
6, the material with carbon element manufacture method of lead dioxide coated according to claim 4, lead is wherein provided by lead salt or plumbous oxides, divalent and in the hydroxide one or more.
7, the material with carbon element manufacture method of lead dioxide coated according to claim 4, wherein under alkali condition oxidant to the lead oxidizing potential for just, lead can be oxidized to PbO
2
8, the material with carbon element manufacture method of lead dioxide coated according to claim 7, oxidant wherein is clorox or hydrogen peroxide.
9, a kind of zinc-nickel cell comprises one with Ni (OH)
2Main positive electrode, positive pole by a kind of wettability microporous barrier parcel, one is the negative pole of main active substances with the Zinc material, a kind of spacer, a kind of alkaline electrolyte solution is characterized in that: described zinc negative pole contains the material with carbon element just like any described lead dioxide coated in the claim 1 to 3.
10, zinc-nickel cell according to claim 9, wherein the material with carbon element of lead dioxide coated accounts for negative pole total weight 0.1%-10%.
11, zinc-nickel cell according to claim 9, wherein the anodal wettability microporous barrier of parcel is selected from polyethylene radiation grafting film, or the three cellulose acetate membrane of handling through saponification, but or any in the wettability polyethylene microporous polypropylene membrane.
12, zinc-nickel cell according to claim 9, wherein cathode capacitance be electric capacity of anode 1.2-3 doubly.
13, zinc-nickel cell according to claim 12, wherein cathode capacitance be electric capacity of anode 2-3 doubly.
14, zinc-nickel cell according to claim 9, wherein spacer is nylon nonwoven fabrics or polypropylene non-woven fabric or vinylon felt.
15, zinc-nickel cell according to claim 9, alkaline electrolyte solution wherein contains one or more among electrolyte KOH, NaOH and the LiOH, and the weight content of electrolyte in solution is 15%-45%.
16, zinc-nickel cell according to claim 15, the weight content of electrolyte wherein in solution is 20%-35%.
17, zinc-nickel cell according to claim 9, wherein negative current collector is the punched copper tape that is made through punching by red copper or filtter gold.
18, zinc-nickel cell according to claim 17, wherein negative current collector is the punched copper tape that Pb, Sn or Pb-Sn alloy layer are contained in the surface.
19, zinc-nickel cell according to claim 9, it is characterized in that: described negative plate, the spacer that is enclosed with the positive plate of wettability microporous barrier and is between the both positive and negative polarity forms electrode cores in the mode of reeling, described pole piece is received and kept in battery steel shell, be provided with anodal drainage band in the described positive pole, anodal drainage tape welding is connected on nickel plating box hat bottom, be provided with negative pole drainage band in the described negative pole, negative pole drainage tape welding is connected on the battery cap, be provided with between the outside of electrode cores and the inboard of battery case that one deck made by PVC material or polytetrafluoroethylmaterial material, be used to the hydrophobic insulating barrier that prevents that negative pole from contacting with battery steel shell, be marked with quantitative alkaline electrolyte solution and sealing in the described battery steel shell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021519897A CN1259741C (en) | 2002-11-19 | 2002-11-19 | Lead dioxide coated carbon material, making method and zinc-nickel battery containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021519897A CN1259741C (en) | 2002-11-19 | 2002-11-19 | Lead dioxide coated carbon material, making method and zinc-nickel battery containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1501530A CN1501530A (en) | 2004-06-02 |
| CN1259741C true CN1259741C (en) | 2006-06-14 |
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| CNB021519897A Expired - Fee Related CN1259741C (en) | 2002-11-19 | 2002-11-19 | Lead dioxide coated carbon material, making method and zinc-nickel battery containing the same |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100449823C (en) | 2005-01-28 | 2009-01-07 | 比亚迪股份有限公司 | Zinc negative pole used for secondary zinc-nickel battery and preperative method and secondary zinc-nickel battery containing the same zinc negative pole |
| CN101824639B (en) * | 2010-04-30 | 2011-08-17 | 浙江汇同电源有限公司 | Anode of electrodeposition device for recovery of lead-acid battery and manufacturing method thereof |
| CN102208694A (en) * | 2011-05-16 | 2011-10-05 | 卢国骥 | Flat zinc-nickel secondary battery with replaceable polar plates and electrolyte |
| CN102263250A (en) * | 2011-06-22 | 2011-11-30 | 吉林汇能科技有限公司 | Lead-acid cell composite negative plate |
| CN102242269A (en) * | 2011-06-30 | 2011-11-16 | 长春黄金研究院 | Method for selectively recovering lead from pregnant solution containing cyanides and heavy metals |
| CN103022472B (en) * | 2012-12-17 | 2015-03-11 | 湖南丰日电源电气股份有限公司 | Large-power zinc-nickel mixed battery cathode slurry and preparation method thereof |
| CN103008653B (en) * | 2012-12-31 | 2015-05-27 | 株洲冶炼集团股份有限公司 | Carbon coated lead composite material and preparation method thereof |
| CN104900881A (en) * | 2015-06-09 | 2015-09-09 | 海宁美达瑞新材料科技有限公司 | Lead-doped modified lithium ion battery composite positive electrode material and preparation method thereof |
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2002
- 2002-11-19 CN CNB021519897A patent/CN1259741C/en not_active Expired - Fee Related
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