CN101098002B - Nickel anode material and felt type nickel anode containing the same - Google Patents
Nickel anode material and felt type nickel anode containing the same Download PDFInfo
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- CN101098002B CN101098002B CN2006100907067A CN200610090706A CN101098002B CN 101098002 B CN101098002 B CN 101098002B CN 2006100907067 A CN2006100907067 A CN 2006100907067A CN 200610090706 A CN200610090706 A CN 200610090706A CN 101098002 B CN101098002 B CN 101098002B
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Abstract
The invention relates to a nickel anode material which contains anode active material, conductive agent and hydrophilic adhesive, wherein the anode material also contains staple fiber which average length is shorter than 0.05mm. The adhesive nickel electrode and battery made from the inventive nickel anode material have better circulation property, long service life, stable discharge/charge property, low internal resistance, better 1C discharge/charge property, IEC discharge/charge property, better circulation property, low self-discharge rate, and stable electrode discharge capacity.
Description
Technical field
The invention relates to a kind of nickel positive electrode and contain the nickel positive pole of this positive electrode, especially about a kind of nickel positive electrode and contain the bonded nickel positive pole of this material.
Background technology
Cylinder nickel-based battery positive pole is divided into the nickel positive pole of sintered type and non-sintered type dual mode at present.The preparation method of sintered type electrode comprises that elder generation carries out sintering after applying the mixture of being made up of adhesive and metal nickel powder on the Ni substrate, obtain the nickel porous substrate, then this substrate is handled through operation repeated multiple times such as nickel salt solution dipping, alkalization, made sintered type nickel electrode.This production process complexity, the active material packed density is low.The preparation method of non-sintered type nickel electrode the earliest comprises with the nickel foam being matrix, active material directly is filled in the nickel foam porous body be prepared from.This kind electrode preparation method is simple, owing to adopted highly porous foaming nickel porous body, thereby can high density fill, and makes high-capacity battery, but there are problems such as cost of manufacture height, production efficiency are low in the nickel foam complicated process of preparation.
In order to address the above problem, to have developed and used expanded metal to make the non-sintered type nickel electrode of electrode matrix.For example CN 1317839A discloses a kind of adhered Ni electrode and preparation method thereof, described adhered Ni electrode comprises as one deck perforated metal of conductivity support (collector) and by the nickel hydroxide active material, auxiliary substance such as adhesive and conductive agent mixes the positive electrode of forming, wherein said adhesive is to contain the mixed adhesive that polytetrafluoroethylene and hydrophilic adhesive are formed, described hydrophilic adhesive comprises methylcellulose, carboxymethyl cellulose, at least a in the hydroxypropyl methyl fiber, the consumption of described hydrophilic adhesive is the 0.3-2 weight % of positive electrode dry powder weight, the 1-6 weight % that described polytetrafluoroethylene consumption is anodal dry powder weight.The preparation method of described adhered Ni electrode comprises at room temperature nickel hydroxide active material and conductive agent auxiliary substance is pre-mixed, obtain anodal dry powder batch mixing I, then anodal dry powder batch mixing I is mixed with adhesive and obtain slurry II, slurry II is coated on the perforated metal, and oven dry is removed moisture and is made adhered Ni electrode.Though it is simple that above-mentioned adhered Ni electrode has manufacturing process, no leftover bits are suitable for serialization production, and the electrode alkali resistance that makes is good, electrode reaction is active high, battery discharge voltage is steady, the advantage that life-span is long, but above-mentioned adhered Ni electrode still exists electrochemical reaction resistance higher, self-discharge rate is bigger than normal, cause the electrode discharge capacity low, in the charge and discharge cycles process, active material still has part to come off, cause the short shortcoming of battery service life, and the 1C charge-discharge performance of above-mentioned electrode is relatively poor, and especially large current charge low discharging current performance (being the IEC charge-discharge performance) is relatively poor.
Summary of the invention
The objective of the invention is to come off, cause the short shortcoming of battery service life easily the adhered Ni electrode of provide a kind of active material to be not easy to come off, battery service life is long in order to overcome active material of nickel electrode of the prior art.
Nickel positive electrode provided by the invention contains positive active material, conductive agent and hydrophilic adhesive, and wherein, this positive electrode also contains the short fiber that average length is no more than 0.05 millimeter.
Adhered Ni electrode provided by the invention comprises collector and the positive electrode that loads on the collector, and wherein, described positive electrode is a nickel positive electrode provided by the invention.
Adhered Ni electrode provided by the invention has following advantage:
(1) in the charge and discharge cycles process, positive electrode only is attached on the collector, make battery good cycle, have extended cycle life;
(2), make battery charging and discharging stable performance, internal resistance little by in positive electrode, adding the capacity that cadmium oxide or cadmium hydroxide can also improve battery greatly.
(3) by improvement to adhesive and conductive agent, make nickel electrode have excellent 1C charge-discharge performance, IEC charge-discharge performance and cycle performance, self-discharge rate is low, and the electrode discharge capacity is stable.
Description of drawings
The 1C cycle performance figure of the battery that Fig. 1 makes for the embodiment of the invention 1,4 and Comparative Examples 1;
The IEC cycle performance figure of the battery that Fig. 2 makes for the embodiment of the invention 1,4 and Comparative Examples 1.
Embodiment
According to the present invention, described average length is no more than any short fiber of 0.05 millimeter all can realize purpose of the present invention.The average length of preferred described short fiber is the 0.01-0.05 millimeter, more preferably wherein length be the short fiber of 0.02-0.03 millimeter accounting for 50 weight % of short fiber total amount, be preferably 60-90 weight %.Under the preferable case, the average diameter of described short fiber was no more than for 6 dawn (1 dawn=9 Tekes (tex)), more preferably 0.1-6 dawn.
The fiber that satisfies above-mentioned condition can be one or more in polypropylene (PP), polyethylene (PE), the polyamide (PA).Use above-mentioned short fiber not only can obtain better bonding effect, make positive active material reliablely and stablely attached on the collector, reach the purpose that improves the battery cyclical stability, and because polypropylene (PP), polyethylene (PE), polyamide (PA) short fiber price are lower than polytetrafluoroethylene adhesive, thereby can also reduce production costs.
According to the present invention, although a spot of above-mentioned short fiber and hydrophilic adhesive mating reaction can realize purpose of the present invention, but under the preferable case, dry weight basis with the nickel positive electrode, the content of described short fiber is 0.1-10 weight %, is preferably 0.2-8 weight %, more preferably 0.5-5 weight %, be preferably 0.5-3 weight % again, also be preferably 0.5-2 weight %.Further preferably, with the dry weight basis of nickel positive electrode, the content of positive active material is 45-80 weight %, is preferably 50-65 weight %, more preferably 50-62 weight %; The content of conductive agent is 10-30 weight %, is preferably 15-25 weight %, more preferably 17-23 weight %; The content of described hydrophilic adhesive is 5-35 weight %, is preferably 15-30 weight %.
Described hydrophilic adhesive can be one or more in methylcellulose (MC), carboxymethyl cellulose (CMC), hydroxypropyl methylcellulose (HPMC), hydroxyethylcellulose, the polyvinyl alcohol (PVA).
The inventor also finds, under the identical situation of other conditions, when using average length to be no more than 0.05 millimeter the mixed adhesive of short fiber, hydrophilic adhesive and polytetrafluoroethylene adhesive, the gained battery has more excellent than only using average length to be no more than the mixed adhesive effect of 0.05 millimeter short fiber and hydrophilic adhesive, and the cyclical stability of battery improves 30-60%.Under the preferable case, with the dry weight basis of nickel positive electrode, can also contain the polytetrafluoroethylene adhesive in the described mixed adhesive, the content of preferably polytetrafluoroethylene adhesive is 0.1-1 weight %, more preferably 0.1-0.5 weight %.
Described conductive agent can be the various conductive agents that routine is used for the nickel positive electrode, and as in the compound of graphite, conductive black, nickel powder, copper powder, cobalt powder, cobalt one or more, the compound of described cobalt is preferably cobalt protoxide.The inventor finds, cadmium oxide has excellent conductivity after oxidation in electrode, can further improve anodal capacitance by doping cadmium oxide in conductive agent, improve the utilance of positive active material, reduce the circulation volume decay, reduce self-discharge of battery rate and internal resistance, improve the circulation volume stability, make battery have the excellent charging and discharging performance.Therefore the hybrid conductive agent of one or more in the preferred described conductive agent compound that is graphite, conductive black, nickel powder, copper powder, cobalt powder, cobalt and cadmium oxide, especially preferred conductive agent is the hybrid conductive agent that contains graphite and cadmium oxide, more preferably contains the hybrid conductive agent of graphite, cobalt protoxide and cadmium oxide.
Under the preferable case, be benchmark with the total amount of conductive agent, the content of cadmium oxide is 5-40 weight %, is preferably 3-20 weight %, more preferably 3-15 weight %.More preferably under the situation, be benchmark with the total amount of conductive agent, the content of graphite is 30-70 weight %, is preferably 35-65 weight %; The content of cobalt protoxide is 20-55 weight %, is preferably 25-50 weight %.Preferred described graphite is that mean particle diameter is no more than 12 microns flaky graphite, and the specific area of described cobalt protoxide preferably is not less than 12 meters squared per gram, more preferably the 15-30 meters squared per gram; The specific area of cadmium oxide is the 1-5 meters squared per gram, preferred 2.1-3.1 meters squared per gram.The conductive agent that satisfies above-mentioned condition can further improve the utilance of positive active material, reduces the circulation volume decay, reduces self-discharge of battery rate and internal resistance, improves the circulation volume stability, makes battery have more excellent charging and discharging performance.
According to the present invention, described positive active material can be to well known to a person skilled in the art various nickel positive active materials, as amorphous nickel hydroxide or ball-type nickel hydroxide.
The present invention has no particular limits the collector of described nickel positive pole, can adopt the collector of all available nickel positive poles known in the art.
Nickel positive electrode provided by the invention can adopt prepared in various methods of the prior art to obtain with the nickel positive pole that contains this material, and different is the above-mentioned composition of composition employing the present invention of positive electrode.For example, can be in the preparation process of positive electrode earlier with positive active material, conductive agent mixes, form positive electrode dry powder, simultaneously hydrophilic adhesive is dissolved in the water form binder solution after, again with the polypropylene polypropylene fiber in the adhesive, polytetrafluoroethylene and positive electrode dry powder blend are even, be prepared into the positive electrode slurry, the viscosity that the addition of solvent can be coated with according to the slurry of the nickel positive pole that will prepare and the requirement of operability are adjusted flexibly, described solvent can be an all kinds of solvents of the prior art, as water, water-soluble solvent or their mixture, described water-soluble solvent comprises that carbon number is the lower alcohol of 1-6, acetone, N, dinethylformamide etc.The preferred water as solvent of the present invention.The uniform positive electrode slurry coating that will make then is bonded in a kind of matrix both sides in copper mesh as plus plate current-collecting body, foaming nickel or the nickel plated steel strip, dry after cut, roll-in can make nickel positive pole of the present invention.
Nickel electrode provided by the invention is the alkaline nickel positive pole, can be assembled into nickel-based battery with NI-G negative pole, hydrogen-storage alloy negative plate, zinc negative pole.
The following examples will the present invention is described further.
Embodiment 1
Present embodiment is used to illustrate nickel positive electrode provided by the invention and nickel positive pole.
Ball-shape nickel hydroxide, the cobalt protoxide of 8.5 weight portions, 18.0 weight portion graphite, the 1.0 weight portion cadmium oxide mixing and stirring of 72.5 weight portions are become anodal dry powder.Simultaneously with 10.0 weight portion methylcellulose, 15.0 weight portion carboxymethyl cellulose, 1.6 the weight portion hydroxypropyl methyl fiber is soluble in water, (average length is 0.025 millimeter with 0.8 weight portion polypropylene (PP) short fiber then, average diameter was 3.5 dawn, length is the 80 weight % that account for the short fiber total amount between the 0.02-0.03 millimeter), 0.4 weight portion polytetrafluoroethylene and above-mentioned anodal dry powder add wherein, obtain uniform nickel positive electrode slurry after mixing, then this slurry is evenly applied and be bonded to nickel plated steel strip matrix both sides, after the drying, roll-in cuts into 66 millimeters * 39.0 millimeters * 0.70 millimeter nickel positive pole.The content of positive active material is 3.0 grams.
Embodiment 2
Present embodiment is used to illustrate nickel positive electrode provided by the invention and nickel positive pole.
Ball-shape nickel hydroxide, the cobalt protoxide of 8.7 weight portions, 15.0 weight portion graphite, the 1.5 weight portion cadmium oxide mixing and stirring of 74.8 weight portions are become anodal dry powder.Simultaneously with 10 weight portion methylcellulose, 10 weight portion carboxymethyl celluloses, 4.0 the weight portion hydroxypropyl methyl fiber is soluble in water, (average length is 0.020 millimeter with 1.0 weight portion polypropylene (PP) short fibers then, average diameter was 5.5 dawn, length is the 40 weight % that account for the short fiber total amount between the 0.02-0.03 millimeter), 0.5 weight portion polytetrafluoroethylene and above-mentioned anodal dry powder add wherein, obtain uniform nickel positive electrode slurry after mixing, then this slurry is evenly applied and be bonded to nickel plated steel strip matrix both sides, after the drying, cut into 66 millimeters * 39.0 millimeters nickel positive pole, pass through roll-in again, obtain thickness and be 0.70 millimeter nickel positive electrode plate.The content of positive active material is 3.0 grams.
Embodiment 3
Present embodiment is used to illustrate nickel positive electrode provided by the invention and nickel positive pole.
Ball-shape nickel hydroxide, the cobalt protoxide of 8.9 weight portions, 16.0 weight portion graphite, the 1.8 weight portion cadmium oxide mixing and stirring of 73.3 weight portions are become anodal dry powder.Simultaneously with 5 weight portion methylcellulose, 10 weight portion carboxymethyl celluloses, 10 weight portion hydroxypropyl methyl fibers are soluble in water, (average length is 0.035 millimeter with 1.6 weight account polyethylenes (PE) short fiber then, average diameter was 1.5 dawn, length is the 90 weight % that account for the short fiber total amount between the 0.02-0.03 millimeter), 0.4 weight portion polytetrafluoroethylene and above-mentioned anodal dry powder add wherein, obtain uniform nickel positive electrode slurry after mixing, then this slurry is evenly applied and be bonded to nickel plated steel strip matrix both sides, after the drying, cut into 66 millimeters * 39.0 millimeters nickel positive pole, pass through roll-in again, obtain thickness and be 0.70 millimeter nickel positive electrode plate.The content of positive active material is 3.0 grams.
Embodiment 4
Present embodiment is used to illustrate nickel positive electrode provided by the invention and nickel positive pole.
Ball-shape nickel hydroxide, the cobalt protoxide of 9.0 weight portions, 13.0 weight portion graphite, the 3.0 weight portion cadmium oxide mixing and stirring of 75.0 weight portions are become anodal dry powder.Simultaneously with 10 weight portion methylcellulose, 10 weight portion carboxymethyl celluloses, 2 weight portion hydroxypropyl methyl fibers are soluble in water, (average length is 0.020 millimeter with 1.3 weight parts of polyamide short fibers then, average diameter was 2.5 dawn, length is the 70 weight % that account for the short fiber total amount between the 0.02-0.03 millimeter), 0.5 weight portion polytetrafluoroethylene and above-mentioned anodal dry powder add wherein, obtain uniform nickel positive electrode slurry after mixing, then this slurry is evenly applied and be bonded to nickel plated steel strip matrix both sides, after the drying, cut into 66 millimeters * 39.0 millimeters nickel positive pole, pass through roll-in again, obtain thickness and be 0.70 millimeter nickel positive electrode plate.The content of positive active material is 3.0 grams.
Embodiment 5
Present embodiment is used to illustrate nickel positive electrode provided by the invention and nickel positive pole.
Ball-shape nickel hydroxide, the cobalt protoxide of 11.0 weight portions, 12.0 weight portion graphite, the 2.0 weight portion cadmium oxide mixing and stirring of 75.0 weight portions are become anodal dry powder.Simultaneously with 20.0 weight portion methylcellulose, 15.0 weight portion carboxymethyl cellulose, 6.0 the weight portion carboxymethyl cellulose is soluble in water, (average length is 0.050 millimeter with 1.8 weight portion polypropylene (PP) short fibers then, average diameter was 5.5 dawn, length is the 70 weight % that account for the short fiber total amount between the 0.02-0.03 millimeter), 0.3 weight portion polytetrafluoroethylene and above-mentioned anodal dry powder add wherein, obtain uniform nickel positive electrode slurry after mixing, then this slurry is evenly applied and be bonded to nickel plated steel strip matrix both sides, after the drying, cut into 66 millimeters * 39.0 millimeters nickel positive pole, pass through roll-in again, obtain thickness and be 0.70 millimeter nickel positive electrode plate.The content of positive active material is 3.0 grams.
Embodiment 6
Present embodiment is used to illustrate nickel positive electrode provided by the invention and nickel positive pole.
Ball-shape nickel hydroxide, the cobalt protoxide of 12.0 weight portions, 9.0 weight portion graphite, the 4.0 weight portion cadmium oxide mixing and stirring of 75.0 weight portions are become anodal dry powder.Simultaneously with 20.0 weight portion methylcellulose, 15.0 weight portion carboxymethyl cellulose, 6.5 the weight portion carboxymethyl cellulose is soluble in water, (average length is 0.015 millimeter with 2.0 weight parts of polyamide short fibers then, average diameter was 4.5 dawn, length is the 80 weight % that account for the short fiber total amount between the 0.02-0.03 millimeter) and above-mentioned anodal dry powder adding is wherein, obtain uniform nickel positive electrode slurry after mixing, then this slurry is evenly applied and be bonded to nickel plated steel strip matrix both sides, after the drying, cut into 66 millimeters * 39.0 millimeters nickel positive pole, pass through roll-in again, obtain thickness and be 0.70 millimeter nickel positive electrode plate.The content of positive active material is 3.0 grams.
Embodiment 7
Present embodiment is used to illustrate nickel positive electrode provided by the invention and nickel positive pole.
Ball-shape nickel hydroxide, the cobalt protoxide of 8.0 weight portions, 19.0 weight portion graphite, the 0.9 weight portion cadmium oxide mixing and stirring of 72.1 weight portions are become anodal dry powder.Simultaneously with 10.0 weight portion methylcellulose, 10.0 weight portion carboxymethyl cellulose, 6.0 the weight portion hydroxypropyl methyl fiber is soluble in water, (average length is 0.025 millimeter with 0.6 weight account polyethylene (PE) short fiber then, average diameter was 1.5 dawn, length is the 80 weight % that account for the short fiber total amount between the 0.02-0.03 millimeter), 0.3 weight portion polytetrafluoroethylene and above-mentioned anodal dry powder add wherein, obtain uniform nickel positive electrode slurry after mixing, then this slurry is evenly applied and be bonded to nickel plated steel strip matrix both sides, after the drying, cut into 66 millimeters * 39.0 millimeters nickel positive pole, pass through roll-in again, obtain thickness and be 0.70 millimeter nickel positive electrode plate.The content of positive active material is 3.0 grams.
Embodiment 8
Present embodiment is used to illustrate nickel positive electrode provided by the invention and nickel positive pole.
Ball-shape nickel hydroxide, the cobalt protoxide of 7.0 weight portions, 20.0 weight portion graphite, the 1.1 weight portion cadmium oxide mixing and stirring of 71.9 weight portions are become anodal dry powder.Simultaneously with 10 weight portion methylcellulose, 10 weight portion carboxymethyl celluloses, 10 weight portion hydroxypropyl methyl fibers are soluble in water, (average length is 0.025 millimeter with 2.4 weight portion polypropylene (PP) short fibers then, average diameter was 3.5 dawn, length is the 70 weight % that account for the short fiber total amount between the 0.02-0.03 millimeter), 0.9 weight portion polytetrafluoroethylene and above-mentioned anodal dry powder add wherein, obtain uniform nickel positive electrode slurry after mixing, then this slurry is evenly applied and be bonded to nickel plated steel strip matrix both sides, after the drying, cut into 66 millimeters * 39.0 millimeters nickel positive pole, pass through roll-in again, obtain thickness and be 0.70 millimeter nickel positive electrode plate.The content of positive active material is 3.0 grams.
Embodiment 9
Present embodiment is used to illustrate nickel positive electrode provided by the invention and nickel positive pole.
Ball-shape nickel hydroxide, the cobalt protoxide of 8.9 weight portions, the 16 weight portion graphite mixing and stirring of 75.1 weight portions are become anodal dry powder.Simultaneously with 5 weight portion methylcellulose, 10 weight portion carboxymethyl celluloses, 10 weight portion hydroxypropyl methyl fibers are soluble in water, (average length is 0.025 millimeter with 1.6 weight portion polypropylene (PP) short fibers then, average diameter was 3.5 dawn, length is the 80 weight % that account for the short fiber total amount between the 0.02-0.03 millimeter), 0.4 weight portion polytetrafluoroethylene and above-mentioned anodal dry powder add wherein, obtain uniform nickel positive electrode slurry after mixing, then this slurry is evenly applied and be bonded to nickel plated steel strip matrix both sides, after the drying, cut into 66 millimeters * 39.0 millimeters nickel positive pole, pass through roll-in again, obtain thickness and be 0.70 millimeter nickel positive electrode plate.The content of positive active material is 3.0 grams.
Comparative Examples 1
This Comparative Examples is used to illustrate the nickel positive electrode and the nickel positive pole of prior art.
Ball-shape nickel hydroxide, the cobalt protoxide of 8.9 weight portions, the 16 weight portion graphite mixing and stirring of 75.1 weight portions are become anodal dry powder.Simultaneously that 5 weight portion methylcellulose, 10 weight portion carboxymethyl celluloses, 10 weight portion hydroxypropyl methyl fibers are soluble in water, then 2.0 weight portion polytetrafluoroethylene and above-mentioned anodal dry powder are added wherein, obtain uniform nickel positive electrode slurry after mixing, then this slurry is evenly applied and be bonded to nickel plated steel strip matrix both sides, after the drying, cut into 66 millimeters * 39.0 millimeters nickel positive pole, pass through roll-in again, obtain thickness and be 0.70 millimeter nickel positive electrode plate.The content of positive active material is 3.0 grams.
Battery performance test
The nickel that the foregoing description 1-9 and Comparative Examples 1 are made is anodal to be assembled into AA type battery with cadmium cathode, discharges and recharges activation then, and the battery numbering is respectively A1-A9 and B1.Above-mentioned battery is carried out following performance test respectively:
(1) circulation volume test: above-mentioned battery was charged 75 minutes with 1C (600 milliamperes), shelved after the charging 15 minutes, 1C (600 milliamperes) is discharged to 1.0 volts, draw the 1C discharge capacity of each battery, note is made the 1st circulation volume, as stated above to identical battery charge and discharge N time, be called the N circulation, obtaining the N circulation volume, is the 10th circulation as charging and discharging the 10th time, obtains the 10th circulation volume.Table 1 has provided the circulation volume under the different circulations.And battery A1, A4 that embodiment 1,4 and Comparative Examples 1 are made and cyclic discharge capacity and the cycle-index mapping of B1, obtain the cycle performance figure of battery, wherein abscissa is cycle-index (inferior), ordinate is discharge capacity (MAH);
(2) self-discharge of battery rate test: above-mentioned battery through the circulation volume test was placed 7 days in 60 ℃ of environment, at room temperature shelved then 30 minutes, use 1C (600 milliamperes) to be discharged to 1.0 volts afterwards, draw each self-discharge of battery rate.The results are shown in Table shown in 1;
(3) test of battery charge attitude internal resistance: above-mentioned battery with 1C (600 milliamperes) charging 75 minutes, was shelved after the charging 30 minutes, surveyed the internal resistance of battery charge attitude then, draw each battery charge attitude internal resistance.The result is as shown in table 1;
(4) IEC (international standard) cycle performance test: with 0.1C (60 milliamperes) charging 960 minutes, shelved after the charging 15 minutes, 0.2C (120 milliamperes) is discharged to 1.0 volts, draws the IEC cycle life capacity of each battery.The result is as shown in table 1.
Table 1
| Test event | A1 | A2 | A3 | A4 | A5 | A6 | A7 | A8 | A9 | B1 |
| 1C discharge capacity (MAH) | 675 | 689. | 696 | 687 | 689 | 698 | 679 | 689 | 704 | 691 |
| Charging state internal resistance (ohm) | 21.3 | 21.2 | 22.5 | 23.6 | 23.1 | 20.0 | 21.4 | 20.7 | 26.3 | 30.3 |
| 7 |
24.2％ | 22.5％ | 23.5％ | 23.15 | 24.0％ | 22.3％ | 23.2％ | 21.0％ | 33.3％ | 36.8％ |
| The 10th circulation volume (MAH) | 653 | 688 | 698 | 688 | 689 | 694 | 686 | 669 | 666 | 666 |
| The 50th circulation volume (MAH) | 669 | 688 | 696 | 689 | 687 | 693 | 685 | 672 | 660 | 669 |
| The 100th circulation volume (MAH) | 668 | 687 | 695 | 685 | 698 | 692 | 686 | 673 | 656 | 667 |
| The 150th circulation volume (MAH) | 668 | 688 | 695 | 684 | 692 | 690 | 687 | 668 | 651 | 663 |
| The 200th circulation volume (MAH) | 666 | 686 | 690 | 680 | 690 | 691 | 689 | 670 | 640 | 669 |
| The 300th circulation volume (MAH) | 670 | 683 | 693 | 675 | 687 | 693 | 684 | 665 | 632 | 433 |
| The 450th circulation volume (MAH) | 680 | 682.1 | 670 | 672 | 678 | 677.6 | 683 | 664 | 600 | 0 |
By table 1 data and Fig. 1 as can be seen, contain the conductive agent that average length is no more than the adhesive of 0.05 millimeter short fiber and contains cadmium oxide owing to adopt, thereby adopt positive electrode of the present invention to have excellent 1C circulation and IEC cycle performance, discharge performance capacity height, cycle life are good, and discharge performance is lasting, stable.Check find that active material and the combining closely property of matrix of the battery A1-A9 that embodiment 1-9 makes is good, and the active material of the battery B1 that Comparative Examples 1 makes has part to come off through dissection.
Claims (10)
1. nickel positive electrode that is used for adhered Ni electrode, this positive electrode contains positive active material, conductive agent and hydrophilic adhesive, it is characterized in that, this positive electrode also contains the short fiber that average length is the 0.01-0.05 millimeter, dry weight basis with the nickel positive electrode, the content of described short fiber is 0.1-10 weight %, described short fiber is a polyethylene, in polypropylene or the polyamide one or more, described hydrophilic adhesive is selected from methylcellulose, carboxymethyl cellulose, hydroxypropyl methyl fiber, hydroxyethylcellulose, in the polyvinyl alcohol one or more.
2. nickel positive electrode according to claim 1, with the dry weight basis of nickel positive electrode, the content of described positive active material is 45-80 weight %, and the content of described conductive agent is 10-30 weight %, and the content of described hydrophilic adhesive is 5-35 weight %.
3. nickel positive electrode according to claim 2, wherein, dry weight basis with the nickel positive electrode, the content of described positive active material is 50-65 weight %, the content of conductive agent is 15-25 weight %, the content of described short fiber is 0.5-2 weight %, and the content of described hydrophilic adhesive is 15-30 weight %.
4. nickel positive electrode according to claim 1 wherein, is a benchmark with the total amount of short fiber, and length is that the content of the short fiber of 0.02-0.03 millimeter is 60-90 weight %.
5. nickel positive electrode according to claim 1, wherein, the average diameter of described short fiber is the 0.1-0.6 dawn.
6. nickel positive electrode according to claim 1, wherein, described positive electrode also contains the polytetrafluoroethylene adhesive, and with the dry weight basis of nickel positive electrode, the content of described polytetrafluoroethylene adhesive is 0.1-0.5 weight %.
7. nickel positive electrode according to claim 1, wherein, described conductive agent is the hybrid conductive agent of one or more and cadmium oxide in graphite, conductive black, nickel powder, copper powder, cobalt powder, cobalt protoxide, the cobalt oxide.
8. nickel positive electrode according to claim 7 wherein, is a benchmark with the total amount of conductive agent, and the content of cadmium oxide is 3-20 weight %.
9. nickel positive electrode according to claim 1, wherein, described positive active material is a ball-shape nickel hydroxide.
10. bonded nickel positive pole, this positive pole comprise collector and load on positive electrode on the collector that wherein, described positive electrode is any described nickel positive electrode among the claim 1-9.
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| CN101615667B (en) * | 2008-06-26 | 2012-01-04 | 上海比亚迪有限公司 | Method and device for preparing battery pole piece |
| JP6296075B2 (en) * | 2016-02-15 | 2018-03-20 | トヨタ自動車株式会社 | Electrode plate manufacturing method |
| CN111987292B (en) * | 2020-08-14 | 2022-07-08 | 湖南格瑞普新能源有限公司 | Nickel-hydrogen battery wet method cathode process added with short fibers |
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| CN1099908A (en) * | 1993-08-29 | 1995-03-08 | 哈尔滨工业大学 | Nickel electrode binding and preparing method |
| CN1317839A (en) * | 2000-04-12 | 2001-10-17 | 深圳市比亚迪实业有限公司 | Adhered Ni electrode and its making method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1099908A (en) * | 1993-08-29 | 1995-03-08 | 哈尔滨工业大学 | Nickel electrode binding and preparing method |
| CN1317839A (en) * | 2000-04-12 | 2001-10-17 | 深圳市比亚迪实业有限公司 | Adhered Ni electrode and its making method |
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| CN101098002A (en) | 2008-01-02 |
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