CN1141516A - Method for mfg. secondary alkaline cccumulator electrode - Google Patents
Method for mfg. secondary alkaline cccumulator electrode Download PDFInfo
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- CN1141516A CN1141516A CN95108271A CN95108271A CN1141516A CN 1141516 A CN1141516 A CN 1141516A CN 95108271 A CN95108271 A CN 95108271A CN 95108271 A CN95108271 A CN 95108271A CN 1141516 A CN1141516 A CN 1141516A
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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 method for mfg. electrode of alkaline secondary cell. Said method doesn't use the traditional mfg. process of conductive-base alkali secondary cell electrode, and uses the conductive fibre whose weight is 3-60 wt% (related to total weight of electrode piece), diameter (D) is 2-100 mcirometers and L/D is greater than or equal to 5, active material and additive, and uniformly mixes them so as to make them into positive and negative electrodes of the cell.
Description
The invention belongs to the secondary alkaline cccumulator electrode manufacture method.
As everyone knows, the manufacturing of traditional secondary alkaline cccumulator electrode all is, sintering bonding active material or is filled on the conductive substrates.Conductive substrates has nickel strap with holes, nickel plating steel band with holes, nickel screen, nickel fibre felt, carbon fiber felt and foaming nickel etc.
The manufacture method of secondary alkaline cccumulator electrode mainly contains following several at present:
1. active material is sintered on the conductive substrates.For example, AB
2The type alloy sintering is to collection
On the fluid (U.S.Pat.No.4,728,586 and U.S.Pat.No.4,716,088).
2. active material is bonded on the conductive substrates.
2.1 active material is bonded on the conductive substrates with plastic adhesive.For example, use the PTFE powder
Hydrogen storing alloy powder by thermo-compression bonding (Japanese Unexamined to collector
Patent Publication (KOKAI) No.64069/1986); Alloyed powder with
Plastic binder is mixed into cream, is coated onto and dries rolling forming (Japanese on the collector
Unexamined?Patent?Publication?No.16470/86?and?European
Patent?No.0284063A1)。
2.2 metal dust is made binding agent active material is bonded on the conductive substrates.For example use a large amount of
Metal nickel powder is molded into active material on the conductive substrates.
3. active material is filled on the foaming nickel substrate.For example the hydrogen storing alloy powder and the PVA aqueous solution
Be mixed into cream, be applied to three-dimensional conductive substrates (as foaming nickel) then and go up (Japanese Un-
examined?Patent?Publication(KOKAI)No.233967/1986?and
European?Patent?No.0271043A1)。
The electrode that sintering process is made, long working life, resistance is little.But this arts demand high temperature and complex device, and the electrode of making is very crisp.
Adhered method for making its electrode is simple, and equipment needed thereby is uncomplicated.The electrode pliability is good, but the electrode working life is short, and resistance is bigger, and high rate during charging-discharging is poor.If will reduce the electrode internal resistance, then need to increase a large amount of conductive agents, electrode capacity can be suffered a loss like this.
Active material directly is filled on the three-dimensional conductive substrates (as the foaming nickel substrate) and makes electrode, simplified production technology and equipment, but the electrodes conduct ability made from the method is unsatisfactory.In addition, the pliability of electrode is relatively poor.
In sum, all electrode manufacturing methods have all adopted conductive substrates, and the whole bag of tricks all has pluses and minuses.Except that three-dimensional conductive substrates, with the electrode three-dimensional structure of other substrate fabrication shown in Fig. 2 A and 2B.25 effects of playing water conservancy diversion and skeleton of conductor, and the effect of afflux seems not enough from the active material particle.In fact for the very tight battery of assembling,, do not need skeleton to support as takeup type lean solution battery.In addition, the active material 24 on the matrix 25 is very easy to come off, and has shortened electrode life.Though adopt three-dimensional conductive substrates to simplify Processes and apparatus, can not improve the conductive capability of electrode.
The object of the present invention is to provide a kind of method of making secondary alkaline cccumulator electrode, the electrode made of method has higher specific energy thus, good large current density characteristic and long working life.
According to this invention, the conductive fiber of active material and 3～60wt% (with respect to the electrode gross weight) (D:2～100 μ m, L/D 〉=5) is mixed, shaped electrode then, and do not adopt traditional conductive substrates.
The present invention---the manufacture method of no conventional conductive basal electrode, principal character is 3～60wt% conductive fiber of (being equivalent to the electrode gross weight) (D:2～100 μ m, L/D 〉=5) and active material fully mix, the direct forming electrode, and do not adopt the conventional conductive substrate, as Ni net, nickel strap with holes, nickel plating steel band with holes etc.According to the present invention, it is even that conductive fiber and active material and other are added material mixing, and shown in Figure 1A, conductive fiber 11 forms tridimensional networks, and active material 12 is bundled together with adding material 13, and press molding electrode then is shown in Figure 1B.
Because the present invention makes electrode and does not adopt conventional conductive substrates, so can reduce electrode weight, improve the pole piece gravimetric specific energy, the adding of conductive fiber simultaneously, in electrode, form the space network shown in Figure 1B, it has better conductive capability than conventional conductive substrate on the one hand, has reduced the electrode internal resistance, improves active material utilization; On the other hand, this space network tightly encases active material, has prolonged electrode life.In addition, do not lead substrate,, make the battery assembly yield improve, and this may for using barrier film thinner, that resistance is littler to provide in alkaline secondary cell as nickel screen, nickel strap with holes etc. because pole piece shown in Figure 1B has traditional electrical.
Above-mentioned described active material comprises: hydrogen storing alloy powder, Ni (OH)
2Powder (or NiOOH powder), CdO powder, MnO
2Powder.Adding material comprises: pore former, conductive agent and binding agents such as graphite powder, acetylene black, Co powder, CoO powder, nickel powder and various resins.
Above-mentioned used conductive fiber can be carbon fiber, graphite fibre, also can be nickel fiber type metal fiber or conductive plastics fiber, and these fibers will be used for the electrode manufacturing, must stablize in electrolyte.Fibre diameter D is between 2～100 μ m, if too little, intensity is too low; If too big, be difficult to reach the purpose of improving electrode performance.Fibre length and diameter ratio L/D answer 〉=5, and too weak point then can not wrap active material effectively.Consumption is selected in 3～60wt% (with respect to the pole piece gross weight).Poor less than the 3wt% electrode conductivuty, and it is difficult to be shaped; Greater than 60wt%, then can reduce activity substance filling amount, electrode capacity is low.
The present invention uses the method for conductive fiber in electrode is made, bad to conductivity, the electric conductivity that particularly non-conductive or semi-conducting material is made the electrode of electrode active material has great improvement.Obviously, the electrode to tradition has conductive substrates if add conductive fiber in active material, improves the electrodes conduct ability too greatly.Example one:
According to the present invention, we have made hydrogen storage alloy negative.Alloyed powder consist of MmNi
4.2Mn
0.3-Al
0.3Co
0.2, average grain diameter is 50 μ m.A certain amount of alloyed powder and 10wt%Ni fiber (diameter D:10 μ m, length diameter ratio mean value L/D=100), 4wt%PTFE powder, 1wt% acetylene black mixing and stirring (all with respect to the pole piece gross weight), become structure shown in Figure 1A, die forming is made electrode shown in Figure 1B then, the about 150kgf/cm of molding pressure
2, pole piece is of a size of 110 * 40 * 0.38mm.It is the polyamide nonwoven fabrics that positive pole is used sintering oxidation nickel electrode, barrier film.Positive and negative electrode is wound as utmost point group, packs in the plating Ni box hat, inject the electrolyte that consists of 5NKOH+1NLiOH, make the cylindrical Experimental cell A of about 1100mAh.Earlier with 0.2CA constant current charge 7h, 0.2CA constant-current discharge to the system of discharging and recharging of 1.0V charges and discharge circulation, make battery capacity stable, under 20 ± 5 ℃, lead constant current charge 1.5h then with 1C, stop 1h, lead constant-current discharge to 1.0V, in the examination charge and discharge process with 1C, the situation of change of battery terminal voltage is seen shown in Fig. 3 curve a.
As a comparison,, be pressed on the punching nickel strap of thick 0.05mm, make the experiment pole piece that is of a size of 110 * 40 * 0.38mm, shown in Fig. 2 B identical alloyed powder, 4wt%PTFE powder, 1wt% acetylene black mixing and stirring.Adopt identical positive pole, barrier film and electrolyte, be assembled into the Ni-MH battery B of the about 1100mAh of capacity.Equally, with 0.2CA constant current charge 7h, the 0.2CA constant-current discharge is to the system that charges and discharge of 1.0V earlier, make battery capacity stable, under 20 ± 5 ℃, lead constant current charge 1.5h then, stop 1h with 1C, lead constant-current discharge to 1.0V with 1C, investigate the variation of battery terminal voltage, shown in Fig. 3 curve b.
Storage hydrogen negative plate by above-mentioned two kinds of technologies difference manufacturing dimension, 40 * 40 * 0.38mm.Investigate them with the attenuation that discharges and recharges number of times increase capacity.Experimental electrode is placed on (the nickel oxide electrode capacity is at least 2 times of capacity of negative plates) between two bigger sintering oxidation nickel electrodes, makes barrier film with the vinylon nonwoven fabrics, clamps utmost point group with the porous poly (methyl methacrylate) plate again.Electrolyte is the 6NKOH+1NLiOH aqueous solution, and reference electrode is the Hg/HgO electrode.Under 20 ± 5 ℃ of environment, lead constant current charge 1.5h with 1C, 1C leads constant-current discharge and experimentizes to cathode voltage-600mV (vs.Hg/HgO).Electrolyte is changed in every circulation 50 times.
Fig. 4 has indicated two kinds of hydrogen-bearing alloy electrodes with the attenuation that discharges and recharges number of times increase capacity.Curve e is a hydrogen-storage electrode capacity attenuation situation constructed in accordance; Curve f is the hydrogen-storage electrode capacity attenuation situation with the conventional method preparation.Example two:
Constructed in accordance Ni-Cd, Ni-MH, Ni-H
2Deng the alkaline secondary cell nickel oxyhydroxide.Be average grain diameter Ni (OH) about 50 μ m at first
2Powder and 10wt%Ni fiber (D:10 μ m, L/D=100), 1.5wt%PVA (aqueous solution), 1wt% acetylene black, 2wt% expanded graphite (all with respect to the pole piece gross weight) mixing and stirring become paste, clamp-on then in the mould, make pole piece 140 ℃ of following oven dry, the demoulding, roll extrusion.Experiment pole piece size 73 * 40 * 0.72mm, the spot welding lug.Negative pole use capacity is the plastic bonding formula hydrogen-storage electrode of 1400～1600 mAh, and barrier film polyamide nonwoven fabrics in the nickel plating box hat of packing into behind the coiling, injects the 5NKOH+1NLiOH aqueous solution, makes Ni-MH Experimental cell E.With 0.2CA constant current charge 7h, the 0.2CA constant-current discharge charges and discharge to 1.0V earlier, after the capacity for the treatment of is stable, leads constant current charge 1.5h with 1C under 20 ± 5 ℃ of conditions, stops 1h, and 1C leads constant-current discharge to 1.0V, and Fig. 5 curve g is seen in the variation of examination battery terminal voltage.
As a comparison, with Ni same as described above (OH)
2Powder, 1.5wt%PVA (aqueous solution), 1wt% acetylene black, 2wt% expanded graphite (all with respect to the pole piece gross weight) mix, and make paste, then this cream are coated on the punching nickel strap drying, rolling forming, spot welding lug.The experiment pole piece is of a size of 73 * 40 * 0.72mm.Negative pole adopts the hydrogen-bearing alloy electrode of 1400～1600mAh, and barrier film is the polyamide nonwoven fabrics, and coiling poling group in the nickel plating box hat of packing into, is injected the 5NKOH+1NLiOH aqueous solution, makes Experimental cell F.With 0.2CA constant current charge 7h, the 0.2CA constant-current discharge charges and discharge to 1.0V earlier, after the capacity for the treatment of is stable, under 20 ± 5 ℃ of conditions, leads constant current charge 1.5h with 1C, stops 1h, and 1C leads constant-current discharge to 1.0V, investigates terminal voltage and changes, and sees Fig. 5 curve h.
Figure 1A shows the tridimensional network after conductive fiber, active material and additive mix.
Figure 1B shows the electrode structure by conductive fiber, active material and additive direct forming.
The electrode structure of two-sided year active material of the conductive substrates that Fig. 2 A is traditional.
The conductive substrates single face that Fig. 2 B is traditional carries the electrode structure of active material.
After the Ni-MH secondary battery negative pole that Fig. 3 adopts conventional conductive substrate method and the inventive method to make is assembled into battery with identical positive pole respectively, the situation of change of battery charging and discharging terminal voltage.
Fig. 4 adopt Ni-MH secondary battery negative pole that conventional conductive substrate method and the inventive method make respectively with identical excessive positive pole under the rich solution condition, capacity changes with discharging and recharging number of times.
The Ni (OH) that Fig. 5 adopts the inventive method and conventional conductive substrate method to make
2After anodal and identical excessive MH electrode is assembled into battery, the variation of battery terminal voltage in charge and discharge process.
Claims (5)
1. the present invention is a kind of secondary alkaline cccumulator electrode manufacture method, it is characterized in that not using the conventional conductive substrate, but conductive fiber is mixed with active material, conductive agent, binding agent, pore former, stirs, and makes battery electrode.The conventional conductive substrate refers to: nickel screen, nickel strap with holes, nickel plating steel band with holes, nickel fibre felt, carbon fiber felt, foaming nickel.Active material comprises: hydrogen storing alloy powder, Ni (OH)
2(or NiOOH) powder, CdO powder and MnO
2Powder.
2. secondary alkaline cccumulator electrode manufacture method described in the claim 1 comprises conductive fiber and active material, additive mixing and stirring, directly makes electrode, and does not need the conventional conductive substrate.
3. conductive fiber described in the claim 1 comprises: carbon fiber, graphite fibre and the alkaline-resisting plastic optical fibre of various conduction, metallic fiber.
4. conductive fiber addition described in the claim 1 is 3～60wt% (with respect to the electrode gross weight).
5. conductive fiber diameter D:2～100 μ m in the claim 3, length-to-diameter L/D 〉=5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95108271A CN1141516A (en) | 1995-07-25 | 1995-07-25 | Method for mfg. secondary alkaline cccumulator electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95108271A CN1141516A (en) | 1995-07-25 | 1995-07-25 | Method for mfg. secondary alkaline cccumulator electrode |
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|---|---|
| CN1141516A true CN1141516A (en) | 1997-01-29 |
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|---|---|---|---|
| CN95108271A Pending CN1141516A (en) | 1995-07-25 | 1995-07-25 | Method for mfg. secondary alkaline cccumulator electrode |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101226830B (en) * | 2007-12-28 | 2011-03-30 | 上海奥威科技开发有限公司 | Electrochemical capacitor electrode and manufacturing method thereof |
| CN108886161A (en) * | 2016-04-07 | 2018-11-23 | Jenax股份有限公司 | The manufacturing method of electrode assemblies and electrode assemblies and battery |
-
1995
- 1995-07-25 CN CN95108271A patent/CN1141516A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101226830B (en) * | 2007-12-28 | 2011-03-30 | 上海奥威科技开发有限公司 | Electrochemical capacitor electrode and manufacturing method thereof |
| CN108886161A (en) * | 2016-04-07 | 2018-11-23 | Jenax股份有限公司 | The manufacturing method of electrode assemblies and electrode assemblies and battery |
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