CN1062083C - Treatment method for alkali-manganese battery fluid surface - Google Patents

Treatment method for alkali-manganese battery fluid surface Download PDF

Info

Publication number
CN1062083C
CN1062083C CN98112104A CN98112104A CN1062083C CN 1062083 C CN1062083 C CN 1062083C CN 98112104 A CN98112104 A CN 98112104A CN 98112104 A CN98112104 A CN 98112104A CN 1062083 C CN1062083 C CN 1062083C
Authority
CN
China
Prior art keywords
indium
collector
fastener
plating indium
plating
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.)
Expired - Fee Related
Application number
CN98112104A
Other languages
Chinese (zh)
Other versions
CN1204873A (en
Inventor
黎学明
陶长元
张胜涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chongqing University
Original Assignee
Chongqing University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chongqing University filed Critical Chongqing University
Priority to CN98112104A priority Critical patent/CN1062083C/en
Publication of CN1204873A publication Critical patent/CN1204873A/en
Application granted granted Critical
Publication of CN1062083C publication Critical patent/CN1062083C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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

  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to a method for treating the surface of a current collector of an alkaline manganese battery, particularly to a method for the chemical indium plating of the surface of a current collector of an alkaline manganese battery, which realizes the technology for the chemical indium plating of the surface of a current collector of an alkaline manganese battery. The method mainly comprises the steps of pretreatment before the indium plating of a battery current collector, chemical indium plating and post-treatment after plating. The method has the advantages of no substance causing environmental pollution, no need of additional power supplies and direct indium plating on a battery current collector. An indium plated layer on the surface of an obtained current collector has the advantages of uniform distribution, low contact resistance with a zinc anode, and high overpotential of hydrogen evolution. When used for a non-mercury alkaline manganese battery, the current collector can obviously inhibit hydrogen evolution and reduce the liquid leaking rate, so that the sealing performance and storage performance of the battery are enhanced.

Description

Treatment method for alkali-manganese battery fluid surface
The invention belongs to alkali-manganese battery fluid surface electroless plating indium processing method.
Alkaline Mn cell is at lay up period, produce hydrogen owing between the battery afflux liquid in zinc anode and the insertion anode electrochemical reaction taking place, cause cell internal pressure to increase, electrolyte is discharged from battery, thereby reduce the leak resistance of battery, can cause also that in some cases battery explosion or explosion accident take place. for mercury-free alkaline manganese dioxide battery, the surface state of battery afflux liquid is particularly evident to producing how much influencing of hydrogen in the battery, must properly address this problem.
U.S. Duracell Co., Ltd proposes a kind of method for preparing the electrochemical cell current-collector in CN1100567A, this method relates to lead plating indium, and then with it drawing-down, the lead of drawing-down is cut into predetermined length, is generally nail shape, as the current-collector in the alkaline battery.Concrete treatment process rules comprise negative electrode purification, anode cleaning, surface active, indium plating, five steps of stretching.But there is following deficiency in this treatment process: adopt the indium anode in (1) electroplating process, one-time investment increases; (2) the battery afflux liquid both ends of the surface there is no the indium layer, can not suppress hydrogen preferably and separate out; (3) need add electroplating power supply.
The objective of the invention is to a kind of treatment method for alkali-manganese battery fluid surface of proposing at above-mentioned the deficiencies in the prior art, this method is according to the chemical plating principle, direct chemical plating indium forms densification in whole collection liquid surface, evenly plates the indium layer, can effectively suppress hydrogen and separate out and prevent the pollution of the environment.
In order to realize the foregoing invention purpose, its technical scheme is on the prior art basis battery afflux liquid to be carried out the chemical plating pre-treatment, and direct chemical is plated indium in the entire cell collection liquid surface, neutralization, drying behind the plating indium.Wherein: 1. electroless plating indium
Purpose be on the entire cell collection liquid surface, form fine and close, evenly, good conductivity, indium layer that overpotential of hydrogen evolution is high, suppress hydrogen and separate out, improve battery storage, leak resistance.
Electroless plating indium solution is by containing 0.005-0.1mol indium salt same the liter in the solution, the 0.05-2mol complexing agent, and 0.5-5mol ammonium chloride, the 0.05-2mol hypophosphite, the 100-150ml concentrated ammonia liquor, surplus is a distilled water.Wherein, complexing agent is the optional 1-5 kind material of selecting in edetate, oxalates, fluoride, citrate, acetate, tartrate, rhodanide, nitrilotriacetic acid, iminodiacetic acid, acetylacetone,2,4-pentanedione, all can wait molal quantity to mix or not to wait molal quantity mixing for each material in the 2-5 kind mixed twine mixture.
The solution compound method be with the complexing agent of amount of calculation, ammonium chloride, hypophosphite, indium salt respectively with adding behind the dissolved in distilled water in the groove, stir, add the concentrated ammonia liquor of amount of calculation again, adding distil water stirs to volume required.
The method of electroless plating indium is that the battery afflux liquid with surface active is immersed in the plating indium groove, can plate one deck indium.Bath temperature is controlled at 10-92 ℃, time 1-60 minute.
Indium salt provides In in the electroless plating indium solution 3+Complexing agent energy and In 3+Form the complex ion of suitable ligancy, make the electroless plating indium layer of formation fine and close more; The reducing agent hypophosphite can and produce In with the indium complex reduction 0, be deposited on the battery current collecting surface; Ammoniacal liquor, ammonium chloride can guarantee that plating solution of indium pH value is alkalescence, makes reducing agent that strong reducing power be arranged.
2. the neutralization behind the plating indium, dried 1) influence electric property in order to suppress the indium layer variable color on the battery afflux liquid, must avoid residual solution to adhere to collection liquid surface with 0.1-1.0mol/L tartaric acid or BAS neutralisation treatment behind the plating indium.The neutralizer temperature is controlled at 15-80 ℃, in and the time be 1-60 minute.After neutralisation treatment, clean with distilled water.2) the plating indium battery afflux liquid after will cleaning up places 50-80 ℃ of hot blast drying.If plating indium collector does not use immediately, must sealing preserve.
Alkaline Mn cell is the higher battery product of class in the civilian battery in the world today, it is one of battery kind of giving priority to during China " 95 ", it has superior electric property, it is the most successful high-power battery in the present age, also be the battery of ratio of performance to price the best, be widely used in the electronic installations such as camera, shaver, photoflash lamp, portable radio, beeper, CD player, electronic toy.But present what produce mainly is high mercury or low mercury alkaline Mn cell, and mercury has caused great pollution to environment.In order to protect and to improve the ecological environment, reduce the pollution of mercury to environment, existing mercurous alkaline Mn cell can not satisfy the needs of sustainable economic development strategy, will be replaced by mercury-free alkaline manganese dioxide battery.From on January 1st, 2005, domesticly will forbid producing the alkaline Mn cell of mercury content greater than battery weight 0.0001%, the plating indium collector that " treatment method for alkali-manganese battery fluid surface " that the present invention proposes obtained is particularly suitable for the needs of mercury-free alkaline manganese dioxide battery to high performance battery afflux liquid.
Fig. 1 is a process chart of the present invention.
Embodiment 1
By process chart shown in Figure 1, will be used for alkaline Mn cell (LR No. 5 6) the fastener collector at first plate the indium pre-treatment, to obtain the clean surface.Its method is: 1) chemical polishing
Effect is leveling, to obtain level and smooth, glossy surface.
Polishing fluid consists of: 33% dense H 2SO 4, 5% dense HNO 3, 0.2% dense HCl, 13%CrO 3, surplus is a water.
Compound method is by H 2O, CrO 3, HCl, HNO 3, H 2SO 4Order joins in the predetermined container successively, and stirring gets final product.
The chemical polishing liquid temp is controlled at 20-40 ℃, time 0.2-0.3 minute.The fastener collector is handled the back and is cleaned with running water in polishing fluid.2) oil removing
Effect is a greasy dirt of removing the fastener surface.
It is 1.2%NaOH that degreasing fluid is formed, 2.5%Na 2CO 3, 6.0%Na 3PO 4, 0.8%Na 2SiO 3, surplus is a water.
Compound method be various materials with amount of calculation respectively with mixing behind the 40-80 ℃ of hot water dissolving, add water to volume requiredly, stirring gets final product.
Treatment temperature is 70-80 ℃, and the time thoroughly is as the criterion with oil removing.Clean with hot water (60-80 ℃), cold water after the oil removing.3) etch of fastener
Effect is an oxidation cortex of removing the battery current collecting surface.
Etching solution is by 15% dense HNO 3, 70% dense H 2SO 4, 0.5% dense HCl, surplus is a water.
Compound method is with the water of amount of calculation, HNO 3, HCl mix after again with H 2SO 4Join in the solution, stirring gets final product.
Treatment temperature is 10-35 ℃, time 3-5 minute.Must clean with running water, distilled water after the etch.4) activation on fastener surface is at the dense H of 3-5% 2SO 4Carry out in the solution, purpose is further to remove fastener surface oxide-film as thin as a wafer, makes surface active, guarantees that coating and matrix bond are firm.Treatment conditions are temperature 10-35 ℃, time 20-30 second.After the fastener activation, take out with distilled water and clean, put into the plating solution of indium.
The fastener that will plate the indium pre-treatment then is immersed in that to contain 0.005-0.010mol indium salt, 0.04mol citrate, 0.04mol disodium ethylene diamine tetraacetate, 0.05-0.08mol hypophosphite, 0.7mol ammonium chloride, 100ml concentrated ammonia liquor, surplus in the same liter be in the plating solution of indium of distilled water, handled 10 minutes down in 40-45 ℃, and stir the fastener collector, through the reprocessing of plating indium, can form the thick indium layer of 0.15um.Gained plating indium fastener contact resistance is reduced to 1.70m Ω by the 2.5m Ω before handling, and separates out amounts of hydrogen and be reduced to 0.1ml/ gram zinc powder by the 0.5ml/ gram zinc powder before handling in Belgian mercury less zinc powder, and coating light, densification, spot welding characteristics are good.
LR is pressed in the battery assembling 6The mercury-free alkaline manganese dioxide battery assembly technology carries out, and wherein zinc powder adopts Belgian mercury less zinc powder, and all the other are homemade.Shelve after the battery assembling and a week measure its performance.
Press embodiment 1 and handle the assembled battery of fastener institute, its open circuit voltage is 1.61 volts, and short circuit current is 16.0 amperes, and it is 55.0 minutes that 1 Ω is even put, and it is 15.5 hours that 10 Ω are even put.After storing half a year, open circuit voltage is 1.59 volts, and short circuit current is 14.5 amperes, and it is 35.0 minutes that 1 Ω is even put, and it is 14.1 hours that 10 Ω are even put.Reference examples A
The fastener contact resistance that does not plate the indium processing is 2.5m Ω, and the hydrogen-separating quantity in Belgian mercury less zinc powder is a 0.5ml/ gram zinc powder, and LR is pressed in the battery assembling 6The alkaline Mn cell assembly technology carries out.
The battery of being assembled, its open circuit voltage are 1.60 volts, and short circuit current is 15.8 amperes, and it is 51.0 minutes that 1 Ω is even put, and it is 14.0 hours that 10 Ω are even put.After storing January, battery leakage can't use.Reference examples B
Indium plating forms the thick coating of 0.15um, and gained plating indium fastener contact resistance is 1.73m Ω, and separating out amounts of hydrogen in Belgian mercury less zinc powder is 0.12ml/ gram zinc powder, and coating light, spot welding characteristics are good.
The open circuit voltage of institute's assembled battery is 1.61 volts, and short circuit current is 16.0 amperes, and it is 54.5 minutes that 1 Ω is even put, and it is 15.3 hours that 10 Ω are even put.After storing half a year, open circuit voltage is 1.59 volts, and short circuit current is 14.0 amperes, and it is 34.0 minutes that 1 Ω is even put, and it is 14.0 hours that 10 Ω are even put.
Embodiment 2
Except that complexing agent was made of the 0.10mol citrate, all the other treatment conditions were with embodiment 1.Formed plating indium layer thickness is 0.18um on the collector, and contact resistance is 1.60m Ω, is the 0.15ml/g zinc powder to Belgian mercury less zinc powder hydrogen-separating quantity, coating light, densification.
The LR that is assembled 61.60 volts of mercury-free alkaline manganese dioxide battery open circuit voltages, 15.8 amperes of short circuit currents.After storing half a year, 1.59 volts of open circuit voltages, 14.4 amperes of short circuit currents.
Embodiment 3
The plating solution of indium is formed with embodiment 1, but treatment temperature is 75-85 ℃, and the time is 2 minutes, forms the thick indium layer of 0.20um.Contact resistance is 1.50m Ω, and hydrogen-separating quantity is the 0.08ml/g zinc powder, coating light, densification.
The LR that is assembled 61.62 volts of mercury-free alkaline manganese dioxide battery open circuit voltages, 16.2 amperes of short circuit currents.After storing half a year, 1.60 volts of open circuit voltages, 14.8 amperes of short circuit currents.Embodiment 4
With LR 6Alkaline Mn cell fastener collector at first plates pre-treatment, then fastener is immersed in and contains 0.05-0.10mol indium salt, 0.5mol tartrate, 0.5mol rhodanide, 0.5mol nitrilotriacetic acid, 0.5mol iminodiacetic acid in the same liter, 1-2mol hypophosphite, 2mol ammonium chloride, 150ml concentrated ammonia liquor, surplus are in the plating solution of indium of distilled water.Under 10-20 ℃, handle and to form the thick plating indium layer of 0.10um in 10 minutes.Contact resistance 1.75m Ω, hydrogen-separating quantity 0.12ml/g zinc powder, coating light, densification.
The mercury-free alkaline manganese dioxide battery assembling is the same, 1.60 volts of open circuit voltages, 15.9 amperes of short circuit currents.After storing half a year, 1.59 volts of open circuit voltages, 14.3 amperes of short circuit currents.
Embodiment 5
With embodiment 4, plating indium temperature is 85-92 ℃, and the time is 50 minutes.The plating indium layer thickness that forms is 2.5um, and contact resistance is 1.48m Ω, and hydrogen-separating quantity is the 0.05ml/g zinc powder, the coat binding strength height, and non-scale, no crack performance takes place.
1.62 volts of battery open circuit voltages, 16.3 amperes of short circuit currents., store half a year after, open circuit voltage is 1.60 volts, short circuit current is 14.6 amperes.
Embodiment 6
With LR 6Alkaline Mn cell fastener collector at first plates pre-treatment, then fastener is immersed in and contains 0.01-0.02mol indium salt, 0.2mol fluoride, 0.2mol acetate, 0.2mol citrate, 0.2mol tartrate, 0.2mol acetylacetone,2,4-pentanedione, 0.4-0.8mol hypophosphite, 4mol ammonium chloride, 150ml concentrated ammonia liquor in the same liter, surplus is in the plating solution of indium of distilled water.Handle under 50-60 ℃ and can form the thick plating indium layer of 0.50um in 20 minutes, contact resistance is 1.65m Ω, and hydrogen-separating quantity is the 0.08ml/g zinc powder, coating light, densification.
1.62 volts of institute's assemble open circuit voltages, 16.2 amperes of short circuit currents.After storing half a year, open circuit voltage is 1.59 volts, and short circuit current is 14.4 amperes.
Embodiment 7
Plating bath is formed with embodiment 6, and bath temperature is 85-92 ℃, and the processing time is 3 minutes, and the plating indium layer thickness of formation is 0.15um, and contact resistance is 1.71m Ω, and hydrogen-separating quantity is the 0.12ml/g zinc powder, coating light, densification.
1.61 volts of battery open circuit voltages, short circuit current are 16.0 amperes.After storing half a year, 1.59 volts of open circuit voltages, short circuit current are 14.1 amperes.
Embodiment 8
With LR 6Alkaline Mn cell fastener collector at first plates pre-treatment, then fastener is immersed in and contains 0.03-0.06mol indium salt, 0.4mol iminodiacetic acid, 0.4mol oxalates, 0.7-1.4mol hypophosphite, 2mol ammonium chloride, 100ml concentrated ammonia liquor in the same liter, surplus is in the plating solution of indium of distilled water.Handle under 25-35 ℃ and can form the thick plating indium layer of 0.14um in 30 minutes, contact resistance is 1.50m Ω, and hydrogen-separating quantity is the 0.07ml/g zinc powder, coating light, densification.
1.62 volts of institute's assemble open circuit voltages, 16.1 amperes of short circuit currents.After storing half a year, open circuit voltage is 1.59 volts, and short circuit current is 14.4 amperes.Embodiment 9
With LR 6Alkaline Mn cell fastener collector at first plates pre-treatment, then fastener is immersed in and contains 0.04-0.08mol indium salt, 1.5-2.0mol tartrate, 1.2-1.6mol hypophosphite, 1.5mol ammonium chloride, 120ml concentrated ammonia liquor in the same liter, surplus is in the plating solution of indium of distilled water.Handle under 40-50 ℃ and can form the thick plating indium layer of 0.10um in 5 minutes, contact resistance is 1.75m Ω, and hydrogen-separating quantity is the 0.15ml/g zinc powder, coating light, densification.
1.61 volts of institute's assemble open circuit voltages, 16.0 amperes of short circuit currents.After storing half a year, open circuit voltage is 1.59 volts, and short circuit current is 14.1 amperes.
Embodiment 10
With embodiment 9, to handle 5 minutes down at 85-92 ℃, the plating indium layer that the 0.35um that can form is thick, contact resistance are 1.68m Ω, hydrogen-separating quantity is the 0.10ml/g zinc powder, coating light, densification.
1.62 volts of battery open circuit voltages, short circuit current are 16.1 amperes.After storing half a year, 1.59 volts of open circuit voltages, short circuit current are 14.3 amperes.
Embodiment 11
With LR 6Alkaline Mn cell fastener collector at first plates pre-treatment, then fastener is immersed in and contains 0.02-0.05mol indium salt, 0.06-0.15mol tartrate, 0.18-0.45mol citrate, 0.80-1.2mol hypophosphite, 1.2mol ammonium chloride, 100ml concentrated ammonia liquor in the same liter, surplus is in the plating solution of indium of distilled water.Handle under 60-70 ℃ and can form the thick plating indium layer of 0.18um in 15 minutes, contact resistance is 1.70m Ω, and hydrogen-separating quantity is the 0.10ml/g zinc powder, coating light, densification.
1.61 volts of institute's assemble open circuit voltages, 16.0 amperes of short circuit currents.After storing half a year, open circuit voltage is 1.59 volts, and short circuit current is 14.1 amperes.
Embodiment 12
With LR 6Alkaline Mn cell fastener collector at first plates pre-treatment, then fastener is immersed in and contains 0.005-0.010mol indium salt, 0.02-0.04mol oxalates, 0.09-0.18mol citrate, 0.05-0.10mol rhodanide, 0.40-0.60mol hypophosphite, 0.8mol ammonium chloride, 100ml concentrated ammonia liquor in the same liter, surplus is in the plating solution of indium of distilled water.Handle under 35-45 ℃ and can form the thick plating indium layer of 0.10um in 5 minutes, contact resistance is 1.73m Ω, and hydrogen-separating quantity is the 0.14ml/g zinc powder, coating light, densification.
1.60 volts of institute's assemble open circuit voltages, 15.9 amperes of short circuit currents.After storing half a year, open circuit voltage is 1.59 volts, and short circuit current is 14.2 amperes.
As mentioned above, when adopting the handled collector of the present invention, make cell negative electrode material, can obtain the mercury-free alkaline manganese dioxide battery that hydrogen-separating quantity is few, leak resistance good, internal resistance is little in conjunction with mercury less zinc powder.

Claims (8)

1. treatment method for alkali-manganese battery fluid surface is characterized in that may further comprise the steps: preliminary treatment before the electroless plating indium:
Collector is carried out chemical polishing, oil removing, etch, surface active; Electroless plating indium:
Preparation electroless plating indium solution:
Contain 0.005-0.1mol indium salt in the solution same the liter, the 0.05-2mol complexing agent, 0.5-5mol ammonium chloride, the 0.05-2mol hypophosphite, the 100-150ml concentrated ammonia liquor, surplus is a distilled water;
At first the complexing agent of amount of calculation, ammonium chloride, hypophosphite, indium salt are added in the groove after with dissolved in distilled water, stir;
The concentrated ammonia liquor that adds amount of calculation then, and adding distil water stirs to desired volume; Wherein, complexing agent is the optional 1-5 kind material of selecting in edetate, oxalates, fluoride, citrate, acetate, tartrate, rhodanide, nitrilotriacetic acid, iminodiacetic acid, acetylacetone,2,4-pentanedione, all can wait molal quantity to mix or not to wait molal quantity mixing for each material in the 2-5 kind mixed twine mixture;
Electroless plating indium:
To immerse in the electroless plating indium liquid through the battery afflux liquid after the pre-treatment of plating indium, plating indium liquid temp is controlled at 10-92 ℃, time 1-60 minute; Neutralization, dried behind the plating indium:
Collector behind the plating indium is immersed in 0.1-1mol/L tartaric acid or the BAS, and the neutralizer temperature is controlled at 15-80 ℃, time 1-60 minute;
Place 50-80 ℃ of hot blast to dry up the plating indium collector after the neutralisation treatment.
2. treatment method for alkali-manganese battery fluid surface according to claim 1, the electroless plating indium liquid that it is characterized in that alkaline Mn cell fastener collector are samely to rise that to contain 0.005-0.010mol indium salt, 0.04mol citrate, 0.04mol disodium ethylene diamine tetraacetate, 0.05-0.08mol hypophosphite, 0.7mol ammonium chloride, 100ml concentrated ammonia liquor, surplus in the solution be distilled water.Place 40-45 ℃ plating indium liquid to handle 10 minutes pretreated fastener collector before the plating indium, and in plating indium process, stir the fastener collector.
3. treatment method for alkali-manganese battery fluid surface according to claim 1, the electroless plating indium liquid that it is characterized in that alkaline Mn cell fastener collector is that same the liter contained 0.05-0.10mol indium salt, 0.5mol tartrate, 0.5mol rhodanide, 0.5mol nitrilotriacetic acid, 0.5mol iminodiacetic acid in the solution, 1-2mol hypophosphite, 2mol ammonium chloride, 150ml concentrated ammonia liquor, surplus are distilled water.Place 10-20 ℃ plating indium liquid to handle 10 minutes pretreated fastener collector before the plating indium, and in plating indium process, stir the fastener collector.
4. treatment method for alkali-manganese battery fluid surface according to claim 1, the electroless plating indium liquid that it is characterized in that alkaline Mn cell fastener collector is that same the liter contained 0.01-0.02mol indium salt .2mol fluoride, 0.2mol acetate, 0.2mol citrate, 0.2mol tartrate, 0.2mol acetylacetone,2,4-pentanedione, 0.4-0.8mol hypophosphite, 4mol ammonium chloride, 150ml concentrated ammonia liquor in the solution, and surplus is a distilled water; Place 50-60 ℃ plating indium liquid to handle 20 minutes pretreated fastener collector before the plating indium, and in plating indium process, stir the fastener collector.
5. treatment method for alkali-manganese battery fluid surface according to claim 1, the electroless plating indium liquid that it is characterized in that alkaline Mn cell fastener collector is that same the liter contained 0.03-0.06mol indium salt, 0.4mol iminodiacetic acid, 0.4mol oxalates, 0.7-1.4mol hypophosphite, 2mol ammonium chloride, 100ml concentrated ammonia liquor in the solution, and surplus is a distilled water; Place 25-35 ℃ plating indium liquid to handle 30 minutes pretreated fastener collector before the plating indium, and in plating indium process, stir the fastener collector.
6. treatment method for alkali-manganese battery fluid surface according to claim 1, the electroless plating indium liquid that it is characterized in that alkaline Mn cell fastener collector is that same the liter contained 0.04-0.08mol indium salt, 1.5-2.0mol tartrate, 1.2-1.6mol hypophosphite, 1.5mol ammonium chloride, 120ml concentrated ammonia liquor in the solution, and surplus is a distilled water; Place 40-50 ℃ plating indium liquid to handle 5 minutes pretreated fastener collector before the plating indium, and in plating indium process, stir the fastener collector.
7. treatment method for alkali-manganese battery fluid surface according to claim 1, the electroless plating indium liquid that it is characterized in that alkaline Mn cell fastener collector is that same the liter contained 0.02-0.05mol indium salt, 0.06-0.15mol tartrate, 0.18-0.45mol citrate, 0.80-1.2mol hypophosphite, 1.2mol ammonium chloride, 100ml concentrated ammonia liquor in the solution, and surplus is a distilled water; Place 60-70 ℃ plating indium liquid to handle 15 minutes pretreated fastener collector before the plating indium, and in plating indium process, stir the fastener collector.
8. treatment method for alkali-manganese battery fluid surface according to claim 1, the electroless plating indium liquid that it is characterized in that alkaline Mn cell fastener collector is that same the liter contained 0.005-0.010mol indium salt, 0.02-0.04mol oxalates, 0.09-0.18mol citrate, 0.05-0.10mol rhodanide, 0.40-0.60mol hypophosphite, 0.8mol ammonium chloride, 100ml concentrated ammonia liquor in the solution, and surplus is a distilled water; Place 35-45 ℃ plating indium liquid to handle 5 minutes pretreated fastener collector before the plating indium, and in plating indium process, stir the fastener collector.
CN98112104A 1998-06-18 1998-06-18 Treatment method for alkali-manganese battery fluid surface Expired - Fee Related CN1062083C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN98112104A CN1062083C (en) 1998-06-18 1998-06-18 Treatment method for alkali-manganese battery fluid surface

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN98112104A CN1062083C (en) 1998-06-18 1998-06-18 Treatment method for alkali-manganese battery fluid surface

Publications (2)

Publication Number Publication Date
CN1204873A CN1204873A (en) 1999-01-13
CN1062083C true CN1062083C (en) 2001-02-14

Family

ID=5221983

Family Applications (1)

Application Number Title Priority Date Filing Date
CN98112104A Expired - Fee Related CN1062083C (en) 1998-06-18 1998-06-18 Treatment method for alkali-manganese battery fluid surface

Country Status (1)

Country Link
CN (1) CN1062083C (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102082274B (en) * 2010-12-09 2013-04-10 襄樊学院 Surface treatment process of battery current collector
CN102500581A (en) * 2011-09-27 2012-06-20 余姚市中盛电子科技有限公司 Cleaning process of copper needle of alkaline Zn/MnO2 battery
CN103474669B (en) * 2013-08-20 2016-01-20 胡伟康 Anode current collector structure in cylindrical zinc-air battery and manufacturing method thereof
CN107634227B (en) * 2017-08-21 2020-07-03 清华大学 Aluminum current collector and method for manufacturing the same, and lithium secondary battery and method for manufacturing the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06275280A (en) * 1993-03-18 1994-09-30 Matsushita Electric Ind Co Ltd Alkaline battery
CN1100567A (en) * 1993-06-02 1995-03-22 杜拉塞尔公司 Method of p reparing current collectors for electrochemical cells

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06275280A (en) * 1993-03-18 1994-09-30 Matsushita Electric Ind Co Ltd Alkaline battery
CN1100567A (en) * 1993-06-02 1995-03-22 杜拉塞尔公司 Method of p reparing current collectors for electrochemical cells

Also Published As

Publication number Publication date
CN1204873A (en) 1999-01-13

Similar Documents

Publication Publication Date Title
CN1294663C (en) Plus plate active material of chargable lithium-sulphur battery and its preparation method
CN103474644B (en) There is lithium titanate composite electrode material and the preparation method of fluoride surface coating layer
CN111916744A (en) Liquid metal composite cathode of zinc ion battery and preparation method and application thereof
CN110600747A (en) Flexible three-dimensional layered MXene @ indium composite film and preparation method and application thereof
CN112635698B (en) Negative pole piece of zinc secondary battery and preparation method and application thereof
CN103682357A (en) Graphene composite electrode material and preparation method thereof, lead-carbon battery negative electrode lead plaster and preparation method thereof as well as lead-carbon battery
CN1320681C (en) Long time stored nickel-hydrogen battery and mfg. method thereof
CN112687967A (en) Zinc ion battery and power utilization device using same
CN1062083C (en) Treatment method for alkali-manganese battery fluid surface
CN1231984C (en) Electrode material and preparation method thereof
CN1741304A (en) Metal oxide electrode material for producing adulterant utilizing electro-deposition-heat treatment technology
CN108987678B (en) Preparation method of lead-acid storage battery electrode containing lead-tin/graphene composite coating
CN113314773A (en) Aqueous zinc ion battery electrolyte and preparation method and application thereof
CN1152444C (en) Indium plating method for copper nail of negative current collector of mercury-free alkaline zinc-manganese dioxide battery
CN113054256A (en) Electrolyte additive, electrolyte and sodium ion battery
CN1492080A (en) Process for preparing nickel hydroxide material using electric deposition method
CN1260603A (en) Zinc-manganese battery
CN113991086B (en) Zinc ion battery negative electrode composite material and preparation method and application thereof
CN1095209C (en) Substrate for alkaline storage battery, process for producing the same and alkaline storage battery
JPH0773060B2 (en) Secondary battery
CN114050261A (en) Preparation method of zinc-based battery negative electrode material
CN1211085A (en) Electrode for alkali accumulator and its producing method and alkaline accumulator
CN1179436C (en) Nickel positive active material and nickel-hydrogen accumulator
CN112038699A (en) Method for improving stability of electrolyte of lithium iron phosphate battery and manufacturing method of battery
CN111430699A (en) Positive electrode material of lithium-sulfur battery, preparation method of positive electrode material and lithium-sulfur battery

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee