CN102780003B - Method for reducing contact resistance of electrode - Google Patents
Method for reducing contact resistance of electrode Download PDFInfo
- Publication number
- CN102780003B CN102780003B CN201210285849.9A CN201210285849A CN102780003B CN 102780003 B CN102780003 B CN 102780003B CN 201210285849 A CN201210285849 A CN 201210285849A CN 102780003 B CN102780003 B CN 102780003B
- Authority
- CN
- China
- Prior art keywords
- battery
- potassium
- butadiene
- electrode
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for reducing contact resistance of an electrode. The technical scheme is as follows: the negative plate of a battery is prepared by adopting fluorinated styrene butadiene latex as an adhesive, wherein a method for preparing the fluorinated styrene butadiene latex comprises the following steps of: orderly adding de-ionized water, lauryl mercaptan, potassium oleate, potassium chloride, divinyl benzene and potassium peroxydisulfate to a polymeric kettle; performing replacement by using nitrogen; increasing the temperature to 60-70 DEG C after stirring for 30 minutes, dropwise adding styrene to the polymeric kettle and simultaneously introducing butadiene and tetrafluoroethylene gases, and stirring for reaction. The method adopts the fluorinated styrene butadiene latex as the negative adhesive so that the contact resistance of the electrode is reduced, and simultaneously, the internal pressure of the battery is reduced and the cycle life of the battery is prolonged; as a result, the battery is high in overcharge resistance, high in discharge platform and good in capacity recovery.
Description
Technical field
The invention belongs to field of batteries, be specifically related to a kind of method that reduces alkaline battery electrode microcosmic contact resistance.
Background technology
The performance such as internal resistance and cycle life of battery, as the important indicator of evaluating alkaline battery, is the key factor of its development of restriction always.It has been generally acknowledged that alkaline battery lost efficacy in two steps, be first that solution resistance Rs increases because electrolyte in barrier film becomes dry, thereby battery performance is declined, it is to be restored by again noting alkali that this early stage decline changes; Secondly, electrode surface inactivation increases reaction impedance Rt, thereby causes voltage characteristic and capacity loss, and it is irreversible that this species impoverishment changes, and then has accelerated alkaline battery inefficacy.Increase so the main cause of alkaline battery electrode performance degradation is impedance Rt, Electrodes and electrode reaction resistance increase.Electrodes, comprises the resistance between electrode active material and collector, and resistance between active material particle; Electrodes reduces, and battery performance will significantly promote, and is the research emphasis of this area therefore reduce Electrodes always.
Summary of the invention
The object of this invention is to provide a kind of method of preparing negative plate and reduce electrode microcosmic contact resistance to fluoridize butadiene-styrene latex as negative pole binding agent.
The technical solution used in the present invention is: a kind of method that reduces Electrodes: be to adopt to fluoridize butadiene-styrene latex and prepare negative plate as negative pole binding agent.
The described preparation method who fluoridizes butadiene-styrene latex is as follows: in polymeric kettle, add successively deionized water, lauryl mercaptan, potassium oleate, potassium chloride, divinylbenzene and potassium peroxydisulfate, with nitrogen replacement, stir and be warming up to 60-70 DEG C after 30 minutes, in polymeric kettle, slowly splash into styrene, and pass into butadiene and tetrafluoroethene gas, stirring reaction
simultaneously.
Above-mentioned raw material mass mixture ratio is as follows:
70 ~ 100 parts of butadiene, 10 ~ 20 parts of styrene,
2 ~ 3 parts of divinylbenzenes, 3 ~ 4 parts of potassium oleates,
0.2 ~ 0.4 part of lauryl mercaptan, 0.5 ~ 1 part, potassium chloride,
60 ~ 100 parts of deionized waters, 0.1 ~ 0.3 part of potassium peroxydisulfate,
3 ~ 20 parts, tetrafluoroethene.
Prepared by the present invention fluoridizes butadiene-styrene latex (FSBR) by tetrafluoroethene, and butadiene and styrene make through copolymerization.
beneficial effect of the present invention:because fluorochemical monomer has excellent chemical stability and unique oily hydrophobicity performance of hating, therefore, butadiene-styrene latex not only retained butadiene-styrene latex (SBR) cohesive force that prepared by the present invention fluoridize is strong, the performance such as pliability good, acid-fast alkali-proof, and owing to containing fluorine, its glued membrane surface has the hydrophobic region of the point-like of random dispersion on microcosmic, wetting glued membrane surface can form stable vapor-liquid equilibrium state, and the medium that is applicable to very much carrying out gas-liquid type chemical reaction is provided.The present invention's employing is fluoridized butadiene-styrene latex and is made negative pole binding agent, can reduce the resistance between electrode active material and collector, and resistance between active material particle is reduced, thereby having reduced the contact resistance of electrode, the battery that adopts method of the present invention to prepare, has obviously reduced the internal resistance of cell and interior pressure, improve the cycle life of battery, overcharging resisting ability is strong, and discharge platform is high, and capacity restoration is good.
Brief description of the drawings
Fig. 1 is the three-electrode electro Chemical impedance spectrogram of the binding agent negative plate that is respectively FSBR-1, FSBR-2, SBR.
Fig. 2 is the cycle life curve chart of AAA type nickel-hydrogen secondary cell.
Embodiment
embodiment 1fluoridize the preparation of butadiene-styrene latex FSBR-1
In polymerization autoclave, add successively deionized water 800g, lauryl mercaptan 3g, potassium oleate 35g, potassium chloride 8g, divinylbenzene 25g, potassium peroxydisulfate 2g, uses nitrogen replacement 3 times, stirs and is warming up to 60 degree after 30 minutes.In polymeric kettle, slowly splash into styrene 150g, and pass into butadiene 850g and tetrafluoroethene gas 38g simultaneously, start reaction.Solid content (determination of solid content is referring to GB2958-82) is measured in timing, and cessation reaction while being greater than 99% to monomer conversion, must fluoridize butadiene-styrene latex FSBR-1.
Adopt quartzy oxygen bottle to decompose and fluoridize butadiene-styrene latex FSBR-1, under medium-acetone, make indicator with haematine, in lanthanum nitrate titration test copolymer, fluorine content is 2.3%.
embodiment 2fluoridize the preparation of butadiene-styrene latex FSBR-2
In polymerization autoclave, add successively deionized water 800g, lauryl mercaptan 3g, potassium oleate 35g, potassium chloride 8g, divinylbenzene 25g, potassium peroxydisulfate 2g, uses nitrogen replacement 3 times, stirs and is warming up to 70 degree after 30 minutes.In polymeric kettle, slowly splash into styrene 150g, and pass into butadiene 850g and tetrafluoroethene gas 187g simultaneously, start reaction.Solid content (determination of solid content is referring to GB2958-82) is measured in timing, and cessation reaction while being greater than 99% to monomer conversion, must fluoridize butadiene-styrene latex FSBR-2.
Adopt quartzy oxygen bottle to decompose and fluoridize butadiene-styrene latex FSBR-2, under medium-acetone, make indicator with haematine, in lanthanum nitrate titration test copolymer, fluorine content is 11.2%.
embodiment 3a kind of method that reduces Electrodes
Prepare negative plate to fluoridize butadiene-styrene latex as negative pole binding agent, concrete grammar is as follows:
(1) preparation of negative plate
Get hydrogen storing alloy powder 1000g, sodium carboxymethylcellulose (CMC) 3 g, conductive black (C) 3 g, binding agent (FSBR-1 or FSBR-2 or SBR) 15 g, then add deionized water 180 g, stir 3 h, mix and make slurry, evenly be coated on the nickel plated steel strip that thickness is 0.06mm, after oven dry through roll-in, roll film, cutting is of a size of 76.5mm × 36mm × 0.24mm, makes negative plate.
(2) electrochemical impedance Performance Ratio
Experimental technique: test adopts three-electrode system, the negative plate that work electrode is above-mentioned preparation, area is 10mm × 10mm × 0.24mm.Reference electrode is Hg/HgO electrode, is platinum electrode to electrode.Electrolyte is potassium hydroxide (KOH), NaOH (NaOH), lithium hydroxide (LiOH) mixed electrolytic solution of mass percentage concentration 20%, and density is 1.0 ~ 1.5g/cm
3, test result as shown in Figure 1.
As can be seen from Figure 1, the semicircle of the high frequency region of its impedance spectrum of electrode that contains FSBR is significantly less than SBR electrode, illustrate that FSBR has reduced the contact resistance between alloying pellet and collector and between alloying pellet, reduced Electrodes, so method of the present invention is having obvious effect aspect the internal resistance of control battery microcosmic.
embodiment 4taking alkaline nickel-hydrogen battery as example, adopt FSBR to do the battery performance evaluation of negative pole binding agent
(1) preparation of Ni-MH battery
(1) preparation of negative plate
Get hydrogen storing alloy powder 1000 g, sodium carboxymethylcellulose (CMC) 3 g, conductive black (C) 3 g, binding agent (FSBR-1 or FSBR-2 or SBR) 15 g, then add deionized water 180 g, stir 3 h, mix and make slurry, evenly be coated on the nickel plated steel strip that thickness is 0.06mm, after oven dry through roll-in, roll film, cutting is of a size of 76.5mm × 36mm × 0.24mm, makes negative plate.
(2) positive plate preparation
Get and cover cobalt Ni (OH)
2995 g, sodium carboxymethylcellulose (CMC) 10 g, yittrium oxide (Y
2o
3) 5 g, deionized water 280 g, mix and make slurry, be evenly coated in nickel foam, dry rear roll-in, roll film, be cut to and be of a size of 50mm × 36mm × 0.6mm, make positive plate.
(3) battery assembling
With polypropylene (PP) diaphragm paper of sulfonation, thickness is 0.12 mm, prepared positive plate and negative plate are separated, being wound into cylindrical shape is inserted in the AAA battery case that diameter is 10.2 mm, positive plate is weldingly connected by lug and positive electrode cap, negative pole directly contacts with battery case, injects after electrolyte, and battery is sealed, changes into, packed.Wherein electrolyte is potassium hydroxide (KOH), NaOH (NaOH), lithium hydroxide (LiOH) mixed electrolytic solution of mass percentage concentration 20%, and density is 1.0 ~ 1.5g/cm
3, addition is 1.13 ~ 1.16 g.
(2) contrast experiment of electrical property
(1) cycle life test
Experimental technique: full battery testing: 730 mA constant current charge 72 min, shelve 30 min, 730 mA constant-current discharge to 1.0 V, so circulation, until discharge capacity is initial capacity 80%, investigates cycle life.Test result is in table 1 and Fig. 2:
Table 1 the cyclic lifetime test results
| Binding agent | Initial capacity (mAh) | End capacity (mAh) | Life-span week number (n) |
| SBR | 679.3 | 543.5 | 297 |
| FSBR-1 | 684.5 | 549.1 | 395 |
| FSBR-2 | 688.3 | 556.6 | 372 |
Can be found out by table 1 and Fig. 2, nickel-hydrogen secondary cell has added after FSBR binding agent, and capacity attenuation is than adding the obviously slack-off of SBR, illustrate that FSBR adds to after negative plate, the good reversibility of battery, in charge and discharge process, the utilance of active material is higher, has extended the useful life of battery;
(2) capacity restoration test
Experimental technique: full battery testing: 146 mA constant-current discharge to 1.0 V, battery is put into 65 DEG C of insulating boxs and within 28 days, take out afterwards test, 146 mA constant current charge 360 min, shelve 30 min, 146 mA constant-current discharge to 1.0 V.Test result is in table 2:
Table 2 capacity restoration test result
| Binding agent | Initial capacity (mAh) | Recovery capacity (mAh) | Capacity restoration rate |
| SBR | 708.4 | 673.8 | 95.10% |
| FSBR-1 | 719.8 | 707.4 | 98.30% |
| FSBR-2 | 716.1 | 705.7 | 98.55% |
(3) charged maintenance test
Experimental technique: full battery testing: 146 mA constant current charge 6 h, battery is put into 45 DEG C of insulating boxs and within 28 days, take out afterwards test, with 146 mA constant-current discharge to 1.0 V, test result is in table 3:
The charged maintenance test result of table 3
| Binding agent | Initial capacity (mAh) | Residual capacity (mAh) | Charged conservation rate |
| SBR | 731.4 | 547.7 | 74.88% |
| FSBR-1 | 727.1 | 564.3 | 77.61% |
| FSBR-2 | 726.1 | 559.3 | 77.03% |
(4) overcharge test
Experimental technique: full battery testing: whether after 1C current charges 2 h, drip phenolphthalein indicator at battery cap place, observing cell row pore has the exhaust phenomenon of leakage;
Finding after tested, all there is not leakage situation in the battery that contains FSBR, is 4.5% containing the battery leakage rate of SBR.
In sum, the battery that adopts method of the present invention to prepare, has extended cycle life, and charged conservation rate is high, and capacity restoration is good, and overcharging resisting ability is strong.
Claims (1)
1. reduce a method for Electrodes, it is characterized in that adopting and fluoridize butadiene-styrene latex and prepare negative plate as negative pole binding agent; The described preparation method who fluoridizes butadiene-styrene latex is as follows: in polymeric kettle, add successively deionized water, lauryl mercaptan, potassium oleate, potassium chloride, divinylbenzene and potassium peroxydisulfate, with nitrogen replacement, stir and be warming up to 60-70 DEG C after 30 minutes, in polymeric kettle, slowly splash into styrene, and pass into butadiene and tetrafluoroethene gas, stirring reaction simultaneously; Wherein raw material mass mixture ratio used is as follows:
70 ~ 100 parts of butadiene, 10 ~ 20 parts of styrene,
2 ~ 3 parts of divinylbenzenes, 3 ~ 4 parts of potassium oleates,
0.2 ~ 0.4 part of lauryl mercaptan, 0.5 ~ 1 part, potassium chloride,
60 ~ 100 parts of deionized waters, 0.1 ~ 0.3 part of potassium peroxydisulfate,
3 ~ 20 parts, tetrafluoroethene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210285849.9A CN102780003B (en) | 2012-08-13 | 2012-08-13 | Method for reducing contact resistance of electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210285849.9A CN102780003B (en) | 2012-08-13 | 2012-08-13 | Method for reducing contact resistance of electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102780003A CN102780003A (en) | 2012-11-14 |
| CN102780003B true CN102780003B (en) | 2014-06-04 |
Family
ID=47124840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210285849.9A Active CN102780003B (en) | 2012-08-13 | 2012-08-13 | Method for reducing contact resistance of electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102780003B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104362303B (en) * | 2014-10-30 | 2017-02-15 | 陕西德飞新能源科技有限公司大荔分公司 | Preparation method for negative electrode piece of nickel hydrogen power battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1452649A (en) * | 2000-04-26 | 2003-10-29 | 3M创新有限公司 | Latex adhesive with coating enhancer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4682401B2 (en) * | 2000-07-31 | 2011-05-11 | 日本ゼオン株式会社 | Secondary battery electrode binder, secondary battery electrode and secondary battery |
-
2012
- 2012-08-13 CN CN201210285849.9A patent/CN102780003B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1452649A (en) * | 2000-04-26 | 2003-10-29 | 3M创新有限公司 | Latex adhesive with coating enhancer |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2002-42819A 2002.02.08 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102780003A (en) | 2012-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Streich et al. | Online electrochemical mass spectrometry of high energy lithium nickel cobalt manganese oxide/graphite half-and full-cells with ethylene carbonate and fluoroethylene carbonate based electrolytes | |
| CN108767233B (en) | Large-capacity long-life double-bag type hydrogen-nickel battery | |
| CN107994207B (en) | Lithium ion battery and cathode plate thereof | |
| JP2008529224A (en) | Zinc cathode for zinc-nickel secondary battery, method for producing the same, and zinc-nickel secondary battery including the zinc cathode | |
| CN111048846A (en) | Nickel-zinc battery | |
| CN102780003B (en) | Method for reducing contact resistance of electrode | |
| CN100459271C (en) | Method for making alkali secondary cell | |
| JPS62139255A (en) | Manufacture of hydrogen absorbing electrode | |
| Cha et al. | Comparative experimental study of gas evolution and gas consumption reactions in sealed Ni–Cd and Ni–MH cells | |
| JP2014139880A (en) | Separator for alkaline electrolyte secondary battery, alkaline electrolyte secondary battery, and method for manufacturing alkaline electrolyte secondary battery | |
| CN101640272B (en) | Anode material of alkaline secondary battery, anode and alkaline secondary battery | |
| CN110544797A (en) | Water-containing solid electrolyte and electric energy storage equipment thereof | |
| JP5557385B2 (en) | Energy storage device with proton as insertion species | |
| CN1558462A (en) | Sealed basic Ni-Cd secondary cell | |
| CN210379221U (en) | Battery diaphragm coated with hydrophobic coating and nickel-hydrogen battery using same | |
| JP2808679B2 (en) | Formation method of sealed alkaline storage battery using hydrogen storage alloy negative electrode | |
| Berg et al. | Recent progress on Li-O2 batteries at PSI | |
| JP2010282744A (en) | Alkaline dry battery | |
| CN115295779A (en) | Nickel electrode preparation method, nickel electrode and nickel-metal hydride battery | |
| CN106602048B (en) | A kind of resistance to deep discharge nickel-metal hydride battery and preparation method thereof | |
| CN100517816C (en) | Composite partile, nickel-hydrogen secondary cell negative-pole and cell and method for making same | |
| JP6955686B2 (en) | Power storage element | |
| CN117253997A (en) | Negative electrode piece, preparation method thereof and nickel-hydrogen battery | |
| KR100882375B1 (en) | Large Capacity Rectangular Sealed ??-?? secondary battery | |
| KR20020002301A (en) | Hydrogen Absorbing Alloy Electrode, Method of Fabricating The Same and Alkaline Storage Battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: 114051 Anshan city in Liaoning Province mountain Anqian Road No. 751 Patentee after: Liaoning nine Yi Energy Technology Co., Ltd. Address before: No. 269 Liaoning nine Yi energy Polytron Technologies Inc in Liaoning province 114051 city of Anshan high tech Zone Anqian Road Patentee before: Liaoning Jiuyi Energy Technology Co.,Ltd. |