CN101515642A - Sealed secondary nickel zinc battery cathode and pretreatment method of sealed secondary nickel zinc battery using same - Google Patents
Sealed secondary nickel zinc battery cathode and pretreatment method of sealed secondary nickel zinc battery using same Download PDFInfo
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- CN101515642A CN101515642A CNA2009100428884A CN200910042888A CN101515642A CN 101515642 A CN101515642 A CN 101515642A CN A2009100428884 A CNA2009100428884 A CN A2009100428884A CN 200910042888 A CN200910042888 A CN 200910042888A CN 101515642 A CN101515642 A CN 101515642A
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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
Abstract
The invention relates to a sealed secondary nickel zinc battery cathode and a pretreatment method of sealed secondary nickel zinc battery using the same, wherein, a zinc cathode comprises a cathode current collector and cathode matter applied to the current collector by coating. The cathode matter means zinc active material, a binding agent, a conductive agent and additives contained in the cathode. The pretreatment method comprises battery formation and placing the battery in a certain environment to optimize an internal system of the battery. The method can help that internal matters of the secondary nickel zinc battery have sufficient reaction and reduce selfcorrosion of the zinc cathode in later use so that a battery system can achieve a more satisfactory condition to greatly improve self-discharge performance of the secondary nickel zinc battery. The method can help effectively improve system stability of the secondary nickel zinc battery and reduce self-discharge; and the method has the advantages of being simple and effective and almost increasing no manufacturing cost.
Description
Technical field
The invention belongs to battery and make the field, relate generally to a kind of sealed Zn-Ni secondary battery negative pole, and the series of processing steps of battery before dispatching from the factory after the sealing of using this negative pole, by this step the inside battery system is tended towards stability, and reduce the carrying out of the inner side reaction of battery system, improved the self-discharge performance of battery.
Background technology
In recent years, also more and more higher along with popularizing of digital class mobile device to the requirements such as energy ratio, volume, useful life, big multiplying power discharging and storge quality of portable power source, also to satisfy environmental protection requirement simultaneously.Therefore now worldwide, each producer and scientific research institution are all greatly developing function admirable, pollution-free, low-cost commodity battery.Modal electrokinetic cell has lead acid accumulator in the existing market, lithium ion battery, nickel-cadmium cell, Ni-MH battery etc.But these batteries all have some shortcomings, to such an extent as to restricted their further developing, though wherein the voltage of lithium ion battery is high, but its cost is higher, and fail safe is relatively poor, and preparation technology is complicated, and is very high to environmental requirement during production; The hydrogen bearing alloy cost of Ni-MH battery is also higher, and consistency of battery pack also has much room for improvement; Though nickel-cadmium cell and lead-acid battery have occupied the bigger market share, this two classes energy content of battery density is lower, and the commodity battery generally can only reach 30～50Wh kg
-1The occasion that is not suitable for moving again at a large amount of storing energies of needs is used, harm to environment is comparatively serious again, be not easy to recycle, European Union's waste and old product processing of these batteries of mandatory requirement battery production business burden in addition, these batteries are faced with American-European EUP instruction (" the ecological design instruction of energy-consuming product "), WEEE instruction (" about the waste electronic andelectrical equipment instruction ") and RoHs instruction (" using some harmful substance instruction ") three big barriers about restriction in electronic electric equipment, seriously limited their production development, therefore can not long-range lasting development.
The secondary chemical sources of electric energy of exploitation environment-friendly and green has become when last very necessary and urgent task, and zinc-nickel secondary batteries obtains praising highly with its superior performance, and it has following multiple advantage simultaneously: 1. specific energy height (55-59.8Wh/kg); 2. specific power height (140-200W/kg); 3. open circuit voltage height (1.75V); 4. abundant raw materials cheapness; 5. heavy-current discharge performance is very superior.Therefore zinc-nickel cell is more suitable for the electrical source of power as various mobile communication equipments, small-sized electric instrument, electric bicycle, electric dust collector, electric model and electric mower etc.
Present zinc-nickel cell both domestic and external has begun to realize industrialization recent years through the development of last a century, has had company to release zinc-nickel rectangular cell and sealing cylinder zinc-nickel secondary batteries successively.But develop into today, problems such as the problem that zinc-nickel secondary batteries mainly exists has that self discharge is big, cycle life is short, negative pole dendritic growth and electrode deformation still exist, and negative pole deformation severity wherein, self discharge is serious etc., and problem remains one of topmost factor of present its industrialization of restriction.
The main cause that the self discharge that generally believes at present is big can reduce:
1. the active material activity of zinc negative pole is excessive, and zinc simple substance and oxide thereof are amphiprotic substance.Zinc simple substance dissolves easily in alkaline electrolyte, takes place from corrosion behavior, and separates out hydrogen.Overpotential of hydrogen evolution as battery inner casing metal or collector metal is low more, this corrosion behavior of then easy more generation.And the gas that this corrosion behavior produces not only makes battery leakage occur, the drum end, and make self discharge become big, have a strong impact on battery and use.
2. the cathode pole piece insufficient strength in the long period of soaking process of electrolyte solution, is steeped easily and is rotted, and distortion is by coming off on the zinc negative current collector.
3. the impurity that contains of inside battery, there are other chemical side reactions in unstable or some composition.
For the own discharge performance that solves battery poor, storge quality bad problem, at self discharge produce its method of reason can for:
1. suppress the corrosion liberation of hydrogen behavior of zinc active material in alkaline electrolyte.
2. make the zinc cathode pole piece that mechanical strength is preferably arranged, be not easy shedding.
3. in the zinc negative pole, increase the content of zinc simple substance, and change the ratio of zinc simple substance and zinc oxide, make battery that enough zinc simple substance be arranged behind the formation charging in early stage.
At present, at the problem that zinc-nickel secondary batteries mainly exists, among the patent CN201022083Y, invented the metal shell of zinc-nickel secondary seal battery.This patent is jet-bedding at the bottom of the inner shell of metal shell mainly, to form the gas recombination passage of difform connection, improves gas recombination efficient, climbs problems such as alkali, leakage, the drum end, inflatable to solve battery, and the method has certain effect, but effect is limited.Battery case described in the patent CN101202357 and battery cap all adopt copper or copper alloy shell.Improve the method for battery case by these, though can improve overpotential of hydrogen evolution, manufacturing cost is increased.And in the patent of BYD company, for avoiding the zinc negative pole to contact with battery case, the liberation of hydrogen behavior takes place on internal surface of battery shell, and cylindrical battery pole piece coiling mode designs with battery is opposite usually, is positive pole parcel negative pole, the pole piece coiling mode has following shortcoming like this: the negative pole utilance is lower, and off-capacity, the cycle life of battery is very short, because of negative pole and box hat contact area little, battery can not carry out high rate charge-discharge, and need transform the shell and the battery cap of battery.
In above-mentioned all multi-methods, can play certain effect to improving the zinc-nickel cell self-discharge performance, but effect is limited, complex operation, difficulty, and cost is higher.Therefore, no matter from from production operability or properties of product and cost, all need the zinc-nickel secondary batteries production technology is optimized improvement, the method for seeking simpler use is accelerated its industrialization speed to improve battery performance.
Summary of the invention
The purpose of this invention is to provide a kind of sealed Zn-Ni secondary battery negative pole and use the pre-treating method of the sealed Zn-Ni secondary cell of this negative pole.The present invention is simple to operate, effect is obvious, with low cost, significantly improved the performance of secondary zinc nickle battery.
The objective of the invention is to realize in the following manner.
A kind of sealed Zn-Ni secondary battery negative pole comprises negative current collector and is coated on negative material on the collector with coating method.Negative material comprises zinc active material, binding agent, conductive agent and additive.The quality percentage composition of described each component of negative material is: zinc active material: 88～98%, binding agent: 0.1～5%, electrically conductive graphite: 1～6%, additive: 0.5～1%.
Described zinc active material comprises zinc oxide and zinc powder, and wherein the mass content of zinc powder accounts for 20～40% of negative material quality.
Described zinc active material can also have zincic acid calcium, and the mass content of zincic acid calcium accounts for 6～10% of negative material quality.
Described zinc oxide is medicinal rank, and purity is not less than 99%; Zinc powder is an electrolysis rank zinc powder, and granular size is not less than 300 orders.
Described binding agent is the combination of HPMC and SBR or HPMC+BSS and SBR three's combination; Wherein the mass content of HPMC or HPMC+BSS accounts for 10～40% of binding agent quality; The mass ratio of HPMC and BSS is 1: 1.
Described additive comprises metallic compound and nonmetallic compound.
Described metallic compound is one or more in indium oxide, aluminium oxide, germanate, the stannate; Nonmetallic compound is one or both of glass fibre, ceramic fibre,
Described germanate can be sodium metagermanate, two sodium germanates etc.; Stannate is a sodium stannate etc.
The mass content of described nonmetallic compound is no more than 0.5% of negative material gross mass.
The pre-treating method of the sealed Zn-Ni secondary cell of described battery cathode is that the secondary cell after the sealing of blurting out is changed into is deposited processing; Deposit processing procedure for once depositing or secondary is deposited; Once depositing is that the battery after changing into is deposited through a high temperature, and perhaps a normal temperature is deposited; Secondary deposit be with the battery high-temperature after changing into deposit the back normal temperature deposit, high temperature deposit the back high temperature deposit, normal temperature deposit the back high temperature deposit or normal temperature deposit the back normal temperature deposit.
The temperature range that described high temperature is deposited is 30～80 ℃, and be 2～10 days memory time, deposit by the time, cell voltage is not less than 1.5V.
Described normal temperature storage temperature is a room temperature, and be 3～30 days memory time, deposit by the time, cell voltage is not less than 1.4V.
Described high temperature is deposited and normal temperature deposit be battery and discharge fully after, again with the process of depositing after battery 0.1～1C charging 100%～130%.
Described formation process is: the initial charge size of current is 0.1～0.7C, charges to 100%～150% of design capacity, be cooled to room temperature after, the discharging current size is 0.3～0.5C first, discharge cut-off voltage is not less than 1.3V.
The present invention has the following advantages:
1, adds highly purified electrolysis rank zinc powder, reduced the generation of inside battery side reaction, make the content of initial zinc simple substance higher simultaneously, and the activity of several times of zinc powders of electrolysis is different from other zinc powder of general agents level.
2, the zinc-nickel secondary batteries after the present invention also designs sealing changed into carries out the different modes storage of high temperature or normal temperature or a period of time is deposited in the combination of storage mode, make zinc active material and fully reaction such as additive and electrolyte in each in the negative pole, in airtight container, reach than stable status, electrode is stablized, and it is slow that the zinc corrosion behavior becomes; Guaranteed to have all the time on the zinc negative pole active material of capacity simultaneously.Enough make inside battery more stable by above the whole bag of tricks, battery system is optimized.
3, the present invention prevents the mashed shedding of zinc negative pole bubble by the mechanical strength of binder enhancing zinc negative pole, and this binder comprises three kinds of adhesives of HPMC and two kinds of binders of SBR or HPMC+BSS and SBR.
4, this invents used technology technology and is conventional manufacturing technology, and raw materials used is conventional raw material, need not common equipment is transformed, and manufacturing process is simple and convenient
5, this invention operating process is very simple, and cost is lower.
6, the battery performance that obtains by the method manufacturing is good, and its self-discharge performance and discharge performance all improve a lot.
Description of drawings
Fig. 1 is the negative pole piece of battery key diagram;
Fig. 2 for battery when once depositing and secondary deposit change in voltage and residual electricity spirogram.
Embodiment
Below embodiment will the present invention is further illustrated, but can not be interpreted as it is qualification to protection range of the present invention.
Embodiment 1: zinc negative pole preparation process (following each mark is percetage by weight)
The HPMC or the 0.5%HPMC+0.5%BSS that account for negative material quality 1% are placed stirred vessel, add pure water (meter in addition) stirring that is equivalent to negative material quality 25% in addition and obtain viscous liquid after 20 minutes, add again by the zinc oxide that accounts for negative material quality 60%, 20% zinc powder, 8% zincic acid calcium, 6% electrically conductive graphite, 0.25% indium oxide, 0.5% aluminium oxide, the mixed-powder that 0.25% ceramic fibre is formed, continue fast to stir 30 minutes, after treating that each component fully mixes, add to stir continuously and healthily behind the SBR binding agent account for negative material quality 3% and promptly obtain the cathode size that mixes after 10 minutes, slurry is evenly coated on the negative current collector brass screen, obtained smooth smooth cathode pole piece by scraper.To promptly obtain zinc cathode pole piece of the present invention through cutting out appropriate length after the roll-in after the pole piece oven dry.
Contrast scheme one
With account for zinc oxide, 25% zinc powder, 3.5% electrically conductive graphite, 0.25% the indium oxide of negative material quality 67%, the mixed-powder that 0.25% glass fibre is formed joins in the thick liquid that contains HPMC or HPMC+BSS among the embodiment one, after stirring, add the SBR emulsion that accounts for negative material quality 4%, after stirring, smear, drying, roll-in, obtain described zinc cathode pole piece.
Contrast scheme two
With account for zinc oxide, 30% zinc powder, 2% electrically conductive graphite, 0.25% indium oxide, 0.25% the sodium metagermanate of negative material quality 65%, the mixed-powder that 0.25% glass fibre is formed joins in the thick liquid that contains HPMC or HPMC+BSS among the embodiment one, after stirring, add the SBR emulsion that accounts for negative material quality 2.25%, after stirring, smear, drying, roll-in, obtain described zinc cathode pole piece.
Embodiment 2: the changing into of zinc-nickel secondary batteries, high temperature are deposited and are added normal temperature and deposit
With the zinc-nickel secondary batteries of good seal by 0.1C current charges 12 hours, be cooled to room temperature after, the 0.3C current discharge is to the lower voltage limit of 1.3V, so that battery changes into fully.Use the 1C current charges after 1.1 hours on this battery that changes into, place among 70 ℃ of baking ovens, every day recording voltage, after 2～10 days, treat to stop to deposit after its voltage drops to 1.5V, use the 1C current charges to carry out normal temperature after 1.1 hours again behind the cool to room temperature and deposit, every day, recording voltage was treated after 3～30 days to stop when voltage is reduced to 1.5V depositing.Battery 1C charging 100% is got final product.
Contrast scheme one
With the zinc-nickel secondary batteries of good seal by 0.2C current charges 6 hours, be cooled to room temperature after, the 0.3C current discharge is to the lower voltage limit of 1.3V, so that battery changes into fully.This battery that changes into, is placed among 50 ℃ of baking ovens after 1.1 hours with the 1C current charges, and every day, recording voltage after 2～10 days, was treated to stop to deposit after its voltage drops to 1.5V, used the 1C current charges to get final product to design capacity 100% behind the cool to room temperature.
Embodiment 3: the battery performance test condition
Discharge and recharge system and battery storing explanation (is example with the 400mAh battery):
1. self-discharge of battery performance test system: battery filled with the 400mA electric current set aside to normal temperature after 70 minutes, deposit dual mode with normal temperature and high temperature then and carry out the self discharge test.
2 normal temperature are that room temperature is deposited, and every day, the recording voltage value was emitted dump energy with the 0.5C electric current after 30 days.Discharge cut-off voltage is set to 1.4V.
3 high temperature deposit methods are: with battery with 1C fill set aside to normal temperature after 70 minutes after, battery is placed 60 ℃ of baking ovens, taking out battery every day and put to the normal temperature measuring voltage 7 days, was that lower limit is emitted all dump energies with 1.4V on tester after being placed into normal temperature after 7 days.
Claims (13)
1, a kind of sealed Zn-Ni secondary battery negative pole comprises negative current collector and is coated on negative material on the collector with coating method that negative material comprises zinc active material, binding agent, conductive agent and additive; It is characterized in that the quality percentage composition of described each component of negative material is: zinc active material: 88～98%, binding agent: 0.1～5%, electrically conductive graphite: 1～6%, additive: 0.5～1%.
2, a kind of sealed Zn-Ni secondary battery negative pole according to claim 1 is characterized in that described zinc active material comprises zinc oxide and zinc powder, and wherein the mass content of zinc powder accounts for 20～40% of negative material quality.
3, a kind of sealed Zn-Ni secondary battery negative pole according to claim 1 and 2, it is characterized in that, described zinc active material comprises zinc oxide, zinc powder and zincic acid calcium, wherein the mass content of zinc powder accounts for the 20-40% of negative material quality, and the mass content of zincic acid calcium accounts for 6～10% of negative material quality.
4, a kind of sealed Zn-Ni secondary battery negative pole according to claim 3 is characterized in that described zinc oxide is medicinal rank, and purity is not less than 99%; Zinc powder is the electrolysis rank, and granular size is not less than 300 orders.
5, a kind of sealed Zn-Ni secondary battery negative pole according to claim 1 is characterized in that, described binding agent is the combination of HPMC and SBR or HPMC+BSS and SBR three's combination; Wherein the mass content of HPMC or HPMC+BSS accounts for 10～40% of binding agent quality; The mass ratio of HPMC and BSS is 1: 1.
6, a kind of sealed Zn-Ni secondary battery negative pole according to claim 1 is characterized in that described additive comprises metallic compound and nonmetallic compound.
7, a kind of sealed Zn-Ni secondary battery negative pole according to claim 6 is characterized in that, described metallic compound is one or more in indium oxide, aluminium oxide, germanate, the stannate; Described nonmetallic compound is one or both of glass fibre, ceramic fibre.
8, according to claim 6 or 7 described a kind of sealed Zn-Ni secondary battery negative poles, it is characterized in that the mass content of described nonmetallic compound is no more than 0.5% of negative material quality.
9, using the pre-treating method of the sealed Zn-Ni secondary cell of the described battery cathode of claim 1, is that the secondary cell after the described sealing of blurting out is changed into is deposited processing; It is characterized in that the described processing procedure of depositing is for once depositing or secondary is deposited; Described once depositing is that the battery after changing into is deposited through a high temperature, and perhaps a normal temperature is deposited; Described secondary deposit be with the battery high-temperature after changing into deposit the back normal temperature deposit, high temperature deposit the back high temperature deposit, normal temperature deposit the back high temperature deposit or normal temperature deposit the back normal temperature deposit.
10, the pre-treating method of the sealed Zn-Ni secondary cell of battery cathode according to claim 9 is characterized in that, the temperature range that described high temperature is deposited is 30～80 ℃, and be 2～10 days memory time, deposit by the time, cell voltage is not less than 1.5V.
11, the pre-treating method of the sealed Zn-Ni secondary cell of battery cathode according to claim 9 is characterized in that, described normal temperature storage temperature is a room temperature, and be 3～30 days memory time, deposit by the time, cell voltage is not less than 1.4V.
12, the pre-treating method of the sealed Zn-Ni secondary cell of battery cathode according to claim 9, it is characterized in that, described high temperature is deposited and normal temperature deposit be battery and discharge fully after, again with the process of depositing after battery 0.1～1C charging 100%～130%.
13, the pre-treating method of the sealed Zn-Ni secondary cell of battery cathode according to claim 9, it is characterized in that, described formation process is: the initial charge size of current is 0.1～0.7C, charge to 100%～150% of design capacity, after being cooled to room temperature, the discharging current size is 0.3～0.5C first, and discharge cut-off voltage is not less than 1.3V.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106935865A (en) * | 2017-05-12 | 2017-07-07 | 吉林唯圣能源科技开发有限公司 | A kind of GND and preparation method thereof, zinc-nickel cell |
| CN108963241A (en) * | 2017-05-19 | 2018-12-07 | 苏州宝时得电动工具有限公司 | battery, battery pack and uninterruptible power supply |
| CN110364692A (en) * | 2018-04-10 | 2019-10-22 | 中国科学院上海硅酸盐研究所 | Composite zinc cathode with multiphase material |
| CN110364732A (en) * | 2018-04-10 | 2019-10-22 | 中国科学院上海硅酸盐研究所 | With the compound zinc load and preparation method and application of inorganic functional decorative layer in a kind of water system battery |
| CN111370781A (en) * | 2020-03-16 | 2020-07-03 | 河南创力新能源科技股份有限公司 | Tin-based compound iron-nickel battery additive and iron-nickel battery based on additive |
-
2009
- 2009-03-18 CN CNA2009100428884A patent/CN101515642A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106935865A (en) * | 2017-05-12 | 2017-07-07 | 吉林唯圣能源科技开发有限公司 | A kind of GND and preparation method thereof, zinc-nickel cell |
| CN106935865B (en) * | 2017-05-12 | 2023-04-18 | 中塑新材料技术(吉林)有限公司 | Battery cathode, preparation method thereof and zinc-nickel battery |
| CN108963241A (en) * | 2017-05-19 | 2018-12-07 | 苏州宝时得电动工具有限公司 | battery, battery pack and uninterruptible power supply |
| CN108963241B (en) * | 2017-05-19 | 2021-07-13 | 苏州宝时得电动工具有限公司 | Battery, battery pack and uninterruptible power supply |
| CN110364692A (en) * | 2018-04-10 | 2019-10-22 | 中国科学院上海硅酸盐研究所 | Composite zinc cathode with multiphase material |
| CN110364732A (en) * | 2018-04-10 | 2019-10-22 | 中国科学院上海硅酸盐研究所 | With the compound zinc load and preparation method and application of inorganic functional decorative layer in a kind of water system battery |
| CN111370781A (en) * | 2020-03-16 | 2020-07-03 | 河南创力新能源科技股份有限公司 | Tin-based compound iron-nickel battery additive and iron-nickel battery based on additive |
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Open date: 20090826 |