CN102054994B - Non-corrosive composite electrolyte for zinc manganese dry battery and preparation method thereof - Google Patents
Non-corrosive composite electrolyte for zinc manganese dry battery and preparation method thereof Download PDFInfo
- Publication number
- CN102054994B CN102054994B CN 201010583779 CN201010583779A CN102054994B CN 102054994 B CN102054994 B CN 102054994B CN 201010583779 CN201010583779 CN 201010583779 CN 201010583779 A CN201010583779 A CN 201010583779A CN 102054994 B CN102054994 B CN 102054994B
- Authority
- CN
- China
- Prior art keywords
- zinc
- refining
- composite
- corrosion inhibitor
- reactor
- 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
Classifications
-
- Y02E60/12—
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a non-corrosive composite electrolyte for a zinc manganese dry battery and a preparation method thereof. The composite electrolyte is prepared by uniformly stirring the following three raw materials: more than or equal to 99.5% of refined NH4Cl, more than or equal to 98% of refined ZnCl2, and compound corrosion inhibitor. The refined NH4Cl is prepared through the following steps: adding farm-oriented ammonium chloride and circulating mother liquor into a reaction kettle; heating and dissolving the mixture; removing impurities, filtering, and cooling filtrate till crystallizing at normal temperature; and centrifuging high-purity crystal and drying so as to acquire more than or equal to 99.5% of the refined NH4Cl. The refined ZnCl2 is prepared through the following steps: adding industrial ZnCl2 and water into the reaction kettle; heating and dissolving the mixture; removing impurities; and filtering, concentrating and drying so as to acquire more than or equal to 98% of the refined ZnCl2. The compound corrosion inhibitor comprises the following main components: sodium polyacrylate, esters surface active agent and chelating dispersant. According the invention, the existing electrolyte preparation method is changed, and the electrolyte with a required Baume concentration can be prepared by only directly adding water into solid composite electrolyte. The non-corrosive composite electrolyte and preparation method provided by the invention have the comprehensive effects of convenience, energy-saving property, high efficiency, environmental friendliness and low cost, and can be used for speeding up the mercury-less progress of the zinc manganese dry battery industry.
Description
Technical field
The present invention relates to a kind of non-corrosive composite electrolyte for zinc manganese dry battery and preparation method thereof.
Background technology
Existing zinc-manganese dioxide dry cell electrolyte is to be equipped with electrolyte in Battery Plant through secondary refining again, need buy from small business in all parts of the country the raw material such as LITHIUM BATTERY ammonium chloride, zinc chloride; Battery production enterprise purifies again, be about to the serial refinement treatment processes such as raw material are heated respectively, dissolve, hang zinc metal sheet, add zinc powder, purification, filtration, then prepare the electrolyte (the preparation oar also needs to add in electrolyte mercury 0.1% left and right while sticking with paste) of 2～3 kinds of variable concentrations.Its long processing period, generally need about one month.Processing cost is high, and battery enterprise electrolyte processing cost per ton is 300～500 yuan of left and right approximately, and equipment, place, circulating fund take greatly, brings the repeatedly environmental issues such as the waste residue in refining processing procedure, waste liquid of compact battery level raw material factory, Battery Plant simultaneously.
Summary of the invention
The object of the invention is to overcome above-mentioned defect, a kind of convenience, energy-conservation, efficient, environmental protection, mercuryless and non-corrosive composite electrolyte for zinc manganese dry battery and preparation method thereof cheaply are provided.
Technical scheme of the present invention, a kind of preparation method of non-corrosive composite electrolyte for zinc manganese dry battery, is characterized in that described this corrosion-free composite electrolyte is to adopt refining ammonium chloride, refining zinc chloride and three kinds of raw materials of composite corrosion inhibitor to stir,
The weight proportion of described each raw material is:
The refining ammonium chloride 4-64% of purity >=99.5%
?the refining zinc chloride 34-94% of purity>=98%
Composite corrosion inhibitor 0.1-20%
Above each component percentage composition sum is 100%;
Described composite corrosion inhibitor is that Sodium Polyacrylate, esters surface active agent, chelated dispersants and clean tap water are composited;
Wherein:
Esters surface active agent is alkylolamides phosphate or fatty acid imidazoline quinoline borate, or their combination in any;
Chelated dispersants is ethylenediamine tetra-acetic acid or hexamethylenetetramine or gluconic acid sodium salt or their combination in any;
Concrete steps are as follows:
(1) prepare the refining ammonium chloride of purity >=99.5%:
The ammonium chloride circulating mother liquor is added in reactor, and turn on agitator, drop into NH
4cl content>=97%, SO
4 2-≤ 0.8%, Fe≤0.001%, H
2the agricultural ammonium chloride of O≤0.1% then adds hydrogen peroxide to carry out deironing in reactor, adds charcoal absorption removal heavy metal and organic substance;
Add the barium chloride sulfate radical in reactor, the amount added is metered into by following reaction equation:
Ba
2++SO
4 2－=BaSO
4↓，
Pass into steam simultaneously in reacting kettle jacketing, heat and seethe with excitement to material in 60～80 minutes, 115～130 ℃ of temperature, at high temperature material is emitted and entered the filtering ponds filtration from the reactor bottom, filtrate after filtration enters cooling crystallization pond and carries out crystallisation by cooling to room temperature, enter thickener through cooled material, carry out again centrifugation, simultaneously to crystallized stock on filter cake in centrifuge, add water washing, wash away mother liquor and be adsorbed on the potassium of crystal surface, sodium, the sulfate radical foreign matter ion, obtain wet ammonium product, its moisture≤3.5%, then enter vibration drier, obtain after drying as NH
4cl content>=99.5%, SO
4 2-≤ 0.02%, Fe≤0.0001%, heavy metal≤0.0005%, H
2the qualified products of O≤0.5% are made with extra care ammonium chloride,
(2) prepare the refining zinc chloride of purity >=98%:
To clean running water and add in reactor, turn on agitator, and drop into ZnCl
2>=95%, Fe≤0.001%, the industrial zinc chloride of heavy metal≤0.001%, the concentration of controlling solution is 45
0b é, simultaneously be steam heated to 60～70 ℃ to passing in reacting kettle jacketing, then add the potassium permanganate deironing in reactor, and addition is metered into by following reaction equation:
MnO
4 －+3Fe
2++2H
2O+5OH
－?=?MnO
2↓?+3Fe（OH）
3↓
Control 1.5～2.5 hours reaction time, then carry out filtering and impurity removing; Filtrate after removal of impurities enters the displacement reaction pond, stirs and adds the zinc powder removing heavy metals at normal temperatures, adds the amount of zinc powder, according to metered 1.2 times of following reaction principle, adds:
Cu
2++Zn=Zn
2++Cu
Cd
2++Zn=Zn
2++Cd
Ni
2++Zn=Zn
2++Ni
Pb
2++Zn=Zn
2++Pb
2 hours reaction time.Then carry out filtering and impurity removing, obtain refined liquid after removal of impurities and enter the concentration response still, control 120 ℃ of temperature, concentration response 1～2 hour, controlled concentration 50
0b é, concentrate is put into graphite cuvette and is carried out heat drying, and product is broken and metering packing, make ZnCl after drying
2>=98%, Fe≤0.0005%, the refining zinc chloride product of heavy metal≤0.0005%;
(3) prepare composite corrosion inhibitor:
By molecular weight, be 5000-10000, the chelated dispersants that the polymer that the esters surface active agent that the Sodium Polyacrylate that ratio is 1～10%, ratio are 40～90%, ratio are 1～20%, ratio are 1～20%, ratio are that 10～20% clean tap water add reactor in proportion, stir at normal temperatures, composite is composite corrosion inhibitor; Above each component percentage composition sum is 100%;
The film that the organic surface active molecules of corrosion inhibiter forms at electrode surface has occupied the activity centre that corrosion reaction is carried out, improve the male or female reaction activity, it can not only adsorb also and can desorb, when battery is not used, zinc is in stable potential, the preferential absorption of inhibitor molecular, preferentially to stop zinc to dissolve, plays corrosion inhibition; And, when battery discharge, corrosion inhibiter can break away from zinc surface smoothly, no longer block zinc and dissolve; So the electric discharge initial stage, moment the open circuit voltage ratio have mercury cell slightly low, but continuous discharge can rise, more stable than mercury cell is arranged, and do not affect result of use;
Add chelated dispersants in composite corrosion inhibitor and stop the heavy metal ion deposition, can stop the zinc hydrolytic precipitation, in case form micro cell at the zinc tube inner surface, produce spot corrosion simultaneously;
(4), by above-mentioned refining ammonium chloride, refining zinc chloride and three kinds of raw materials of composite corrosion inhibitor are mixed by weight ratio and are stirred and obtain the non-corrosive composite electrolyte for zinc manganese dry battery product.
The non-corrosive composite electrolyte for zinc manganese dry battery product obtained by said method production.
In sum, this product coordinates novel corrosion inhibitor, is Green Product.The present invention changes the preparation operation method that has zinc-manganese dioxide dry cell enterprise electrolyte now, simplified the preparation operation method of electrolyte, make the preparation that has zinc-manganese dioxide dry cell enterprise electrolyte now only need in composite solid electrolyte, add water, can make the electrolyte of required Baume concentration for direct, make that the preparation of user's electrolyte has conveniently, energy-conservation, efficient, environmental protection and comprehensive effectiveness cheaply, and the mercuryless process of zinc-manganese dioxide dry cell industry is carried out in favourable quickening; Product of the present invention has unique practicality and replicability, is a kind of convenience of being convenient to generally promote at battery industry, energy-conservation, efficient, environmental protection, low-cost completely new product.
Embodiment
A kind of preparation method of non-corrosive composite electrolyte for zinc manganese dry battery, is characterized in that described this corrosion-free composite electrolyte is to adopt refining ammonium chloride, refining zinc chloride and three kinds of raw materials of composite corrosion inhibitor to stir,
The weight proportion of described each raw material is:
The refining ammonium chloride 4-64% of purity >=99.5%
?the refining zinc chloride 34-94% of purity>=98%
Composite corrosion inhibitor 0.1-20%
Above each component percentage composition sum is 100%;
Described composite corrosion inhibitor is that Sodium Polyacrylate, esters surface active agent, chelated dispersants and clean tap water are composited;
Wherein:
Esters surface active agent is alkylolamides phosphate or fatty acid imidazoline quinoline borate, or their combination in any;
Chelated dispersants is ethylenediamine tetra-acetic acid or hexamethylenetetramine or gluconic acid sodium salt or their combination in any;
Concrete steps are as follows:
(1) prepare the refining ammonium chloride of purity >=99.5%:
The ammonium chloride circulating mother liquor is added in reactor, and turn on agitator, drop into NH
4cl content>=97%, SO
4 2-≤ 0.8%, Fe≤0.001%, H
2the agricultural ammonium chloride of O≤0.1% then adds hydrogen peroxide to carry out deironing in reactor, adds charcoal absorption removal heavy metal and organic substance;
Add the barium chloride sulfate radical in reactor, the amount added is metered into by following reaction equation:
Ba
2++SO
4 2－=BaSO
4↓，
Pass into steam simultaneously in reacting kettle jacketing, heat and seethe with excitement to material in 60～80 minutes, 115～130 ℃ of temperature, at high temperature material is emitted and entered the filtering ponds filtration from the reactor bottom, filtrate after filtration enters cooling crystallization pond and carries out crystallisation by cooling to room temperature, enter thickener through cooled material, carry out again centrifugation, simultaneously to crystallized stock on filter cake in centrifuge, add water washing, wash away mother liquor and be adsorbed on the potassium of crystal surface, sodium, the sulfate radical foreign matter ion, obtain wet ammonium product, its moisture≤3.5%, then enter vibration drier, obtain after drying as NH
4cl content>=99.5%, SO
4 2-≤ 0.02%, Fe≤0.0001%, heavy metal≤0.0005%, H
2the qualified products of O≤0.5% are made with extra care ammonium chloride,
(2) prepare the refining zinc chloride of purity >=98%:
To clean running water and add in reactor, turn on agitator, and drop into ZnCl
2>=95%, Fe≤0.001%, the industrial zinc chloride of heavy metal≤0.001%, the concentration of controlling solution is 45
0b é, simultaneously be steam heated to 60～70 ℃ to passing in reacting kettle jacketing, then add the potassium permanganate deironing in reactor, and addition is metered into by following reaction equation:
MnO
4 －+3Fe
2++2H
2O+5OH
－?=?MnO
2↓?+3Fe（OH）
3↓
Control 1.5～2.5 hours reaction time, then carry out filtering and impurity removing; Filtrate after removal of impurities enters the displacement reaction pond, stirs and adds the zinc powder removing heavy metals at normal temperatures, adds the amount of zinc powder, according to metered 1.2 times of following reaction principle, adds:
Cu
2++Zn=Zn
2++Cu
Cd
2++Zn=Zn
2++Cd
Ni
2++Zn=Zn
2++Ni
Pb
2++Zn=Zn
2++Pb
2 hours reaction time.Then carry out filtering and impurity removing, obtain refined liquid after removal of impurities and enter the concentration response still, control 120 ℃ of temperature, concentration response 1～2 hour, controlled concentration 50
0b é, concentrate is put into graphite cuvette and is carried out heat drying, and product is broken and metering packing, make ZnCl after drying
2>=98%, Fe≤0.0005%, the refining zinc chloride product of heavy metal≤0.0005%;
(3) prepare composite corrosion inhibitor:
By molecular weight, be 5000-10000, the chelated dispersants that the polymer that the esters surface active agent that the Sodium Polyacrylate that ratio is 1～10%, ratio are 40～90%, ratio are 1～20%, ratio are 1～20%, ratio are that 10～20% clean tap water add reactor in proportion, stir at normal temperatures, composite is composite corrosion inhibitor; Above each component percentage composition sum is 100%;
The film that the organic surface active molecules of corrosion inhibiter forms at electrode surface has occupied the activity centre that corrosion reaction is carried out, improve the male or female reaction activity, it can not only adsorb also and can desorb, when battery is not used, zinc is in stable potential, the preferential absorption of inhibitor molecular, preferentially to stop zinc to dissolve, plays corrosion inhibition; And, when battery discharge, corrosion inhibiter can break away from zinc surface smoothly, no longer block zinc and dissolve; So the electric discharge initial stage, moment the open circuit voltage ratio have mercury cell slightly low, but continuous discharge can rise, more stable than mercury cell is arranged, and do not affect result of use;
Add chelated dispersants in composite corrosion inhibitor and stop the heavy metal ion deposition, can stop the zinc hydrolytic precipitation, in case form micro cell at the zinc tube inner surface, produce spot corrosion simultaneously;
(4), by above-mentioned refining ammonium chloride, refining zinc chloride and three kinds of raw materials of composite corrosion inhibitor are mixed by weight ratio and are stirred and obtain the non-corrosive composite electrolyte for zinc manganese dry battery product.
Esters surface active agent in the present embodiment in composite corrosion inhibitor is to adopt alkylolamides phosphate and fatty acid imidazoline quinoline borate to be combined (can be also by above-mentioned each lipid surfactant combination in any).The polymer of the composite corrosion inhibitor in the present embodiment is that the employing polymer is the poly anhydride copolymer; The class chelated dispersants is to adopt hexamethylenetetramine and ethylenediamine tetra-acetic acid to be combined (also can by above-mentioned each polymeric type chelating dispersing agent combination in any).
Example 1, I type standard approved product: for S type battery product:
Refining NH
4cl>=58%, refining ZnCl
2>=34%, composite corrosion inhibitor>=0.1%, zinc metal sheet rate of corrosion≤0.1mm/y.
Example 2, II type formula for a product be by the user's request proportioning, for S type battery product:
Refining NH
4cl>=59%, refining ZnCl
2>=34%, composite corrosion inhibitor>=0.1%, zinc metal sheet rate of corrosion≤0.1mm/y.
Example 3, II type formula for a product be by the user's request proportioning, for C type battery product:
Refining NH
4cl>=52%, refining ZnCl
2>=42%, composite corrosion inhibitor>=0.1%, zinc metal sheet rate of corrosion≤0.1mm/y.
Claims (2)
1. the preparation method of a non-corrosive composite electrolyte for zinc manganese dry battery, is characterized in that described this corrosion-free composite electrolyte is to adopt refining ammonium chloride, refining zinc chloride and three kinds of raw materials of composite corrosion inhibitor to stir,
The weight proportion of described each raw material is:
The refining ammonium chloride 4-64% of purity >=99.5%
?the refining zinc chloride 34-94% of purity>=98%
Composite corrosion inhibitor 0.1-20%
Above each component percentage composition sum is 100%;
Described composite corrosion inhibitor is that Sodium Polyacrylate, esters surface active agent, chelated dispersants and clean tap water are composited;
Wherein:
Esters surface active agent is alkylolamides phosphate or fatty acid imidazoline quinoline borate, or their combination in any;
Chelated dispersants is ethylenediamine tetra-acetic acid or hexamethylenetetramine or gluconic acid sodium salt or their combination in any;
Concrete steps are as follows:
(1) prepare the refining ammonium chloride of purity >=99.5%:
The ammonium chloride circulating mother liquor is added in reactor, and turn on agitator, drop into NH
4cl content>=97%, SO
4 2-≤ 0.8%, Fe≤0.001%, H
2the agricultural ammonium chloride of O≤0.1% then adds hydrogen peroxide to carry out deironing in reactor, adds charcoal absorption removal heavy metal and organic substance;
Add the barium chloride sulfate radical in reactor, the amount added is metered into by following reaction equation:
Ba
2++SO
4 2－=BaSO
4↓，
Pass into steam simultaneously in reacting kettle jacketing, heat and seethe with excitement to material in 60～80 minutes, 115～130 ℃ of temperature, at high temperature material is emitted and entered the filtering ponds filtration from the reactor bottom, filtrate after filtration enters cooling crystallization pond and carries out crystallisation by cooling to room temperature, enter thickener through cooled material, carry out again centrifugation, simultaneously to crystallized stock on filter cake in centrifuge, add water washing, wash away mother liquor and be adsorbed on the potassium of crystal surface, sodium, the sulfate radical foreign matter ion, obtain wet ammonium product, its moisture≤3.5%, then enter vibration drier, obtain after drying as NH
4cl content>=99.5%, SO
4 2-≤ 0.02%, Fe≤0.0001%, heavy metal≤0.0005%, H
2the qualified products of O≤0.5% are made with extra care ammonium chloride,
(2) prepare the refining zinc chloride of purity >=98%:
To clean running water and add in reactor, turn on agitator, and drop into ZnCl
2>=95%, Fe≤0.001%, the industrial zinc chloride of heavy metal≤0.001%, the concentration of controlling solution is 45
0b é, simultaneously be steam heated to 60～70 ℃ to passing in reacting kettle jacketing, then add the potassium permanganate deironing in reactor, and addition is metered into by following reaction equation:
MnO
4 －+3Fe
2++2H
2O+5OH
－?=?MnO
2↓?+3Fe（OH）
3↓
Control 1.5～2.5 hours reaction time, then carry out filtering and impurity removing; Filtrate after removal of impurities enters the displacement reaction pond, stirs and adds the zinc powder removing heavy metals at normal temperatures, adds the amount of zinc powder, according to metered 1.2 times of following reaction principle, adds:
Cu
2++Zn=Zn
2++Cu
Cd
2++Zn=Zn
2++Cd
Ni
2++Zn=Zn
2++Ni
Pb
2++Zn=Zn
2++Pb
2 hours reaction time, then carry out filtering and impurity removing, obtain refined liquid after removal of impurities and enter the concentration response still, control 120 ℃ of temperature, concentration response 1～2 hour, controlled concentration 50
0b é, concentrate is put into graphite cuvette and is carried out heat drying, and product is broken and metering packing, make ZnCl after drying
2>=98%, Fe≤0.0005%, the refining zinc chloride product of heavy metal≤0.0005%;
(3) prepare composite corrosion inhibitor:
By molecular weight, be 5000-10000, the chelated dispersants that the polymer that the esters surface active agent that the Sodium Polyacrylate that ratio is 1～10%, ratio are 40～90%, ratio are 1～20%, ratio are 1～20%, ratio are that 10～20% clean tap water add reactor in proportion, stir at normal temperatures, composite is composite corrosion inhibitor; Above each component percentage composition sum is 100%;
The film that the organic surface active molecules of corrosion inhibiter forms at electrode surface has occupied the activity centre that corrosion reaction is carried out, improve the male or female reaction activity, it can not only adsorb also and can desorb, when battery is not used, zinc is in stable potential, the preferential absorption of inhibitor molecular, preferentially to stop zinc to dissolve, plays corrosion inhibition; And, when battery discharge, corrosion inhibiter can break away from zinc surface smoothly, no longer block zinc and dissolve; So the electric discharge initial stage, moment the open circuit voltage ratio have mercury cell slightly low, but continuous discharge can rise, more stable than mercury cell is arranged, and do not affect result of use;
Add chelated dispersants in composite corrosion inhibitor and stop the heavy metal ion deposition, can stop the zinc hydrolytic precipitation, in case form micro cell at the zinc tube inner surface, produce spot corrosion simultaneously;
(4), by above-mentioned refining ammonium chloride, refining zinc chloride and three kinds of raw materials of composite corrosion inhibitor are mixed by weight ratio and are stirred and obtain the non-corrosive composite electrolyte for zinc manganese dry battery product.
2. the non-corrosive composite electrolyte for zinc manganese dry battery that the method for claim 1 is produced.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010583779 CN102054994B (en) | 2010-12-10 | 2010-12-10 | Non-corrosive composite electrolyte for zinc manganese dry battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010583779 CN102054994B (en) | 2010-12-10 | 2010-12-10 | Non-corrosive composite electrolyte for zinc manganese dry battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102054994A CN102054994A (en) | 2011-05-11 |
| CN102054994B true CN102054994B (en) | 2013-06-19 |
Family
ID=43959114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010583779 Active CN102054994B (en) | 2010-12-10 | 2010-12-10 | Non-corrosive composite electrolyte for zinc manganese dry battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102054994B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102392255B (en) * | 2011-10-10 | 2013-04-03 | 南昌航空大学 | Preparation method of sodium polyacrylate dispersing imidazoline corrosion inhibitor |
| CN103762374B (en) * | 2014-01-10 | 2016-01-20 | 宁波豪生电池有限公司 | The preparation method of high-energy environment-friendlybattery battery electrolyte and equipment thereof |
| CN104332663B (en) * | 2014-09-07 | 2016-08-10 | 桂林理工大学 | Electrolyte and preparation method containing 4-Nitrobenzol diazanyl contracting p-carboxybenzaldehyde PEG400 laurate surfactant |
| CN104201427B (en) * | 2014-09-07 | 2016-08-24 | 桂林理工大学 | Electrolyte containing phenylhydrazine contracting p-carboxybenzaldehyde PEG400 laurate surfactant and preparation method thereof |
| CN105449237A (en) * | 2015-11-25 | 2016-03-30 | 四川长虹新能源科技股份有限公司 | Alkaline dry battery |
| AU2018292510B2 (en) | 2017-06-27 | 2020-07-16 | Ecolab Usa Inc. | Non-phosphorous transition metal control in laundry applications |
| CN107634266B (en) * | 2017-08-18 | 2019-12-10 | 上海交通大学 | Flame-retardant electrolyte for zinc secondary battery |
| CN109616677B (en) * | 2018-12-10 | 2020-11-10 | 杭州长命电池有限公司 | Paste-type mercury-free battery slurry and preparation method thereof |
| CN110600756A (en) * | 2019-08-29 | 2019-12-20 | 佛山市佳盈电池有限公司 | Preparation method of zinc-manganese battery electrolyte |
| CN114122533B (en) * | 2020-08-28 | 2024-04-12 | 中国科学院上海硅酸盐研究所 | Multifunctional composite electrolyte for neutral or weak acid zinc-based battery |
| CN113583185A (en) * | 2021-08-27 | 2021-11-02 | 石河子大学 | Adsorbent with hierarchical porous network structure and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122521A (en) * | 1994-11-04 | 1996-05-15 | 郝进生 | Rapid purification process for zinc-manganese dry-cell celectrolyte |
| CN1673455A (en) * | 2005-03-14 | 2005-09-28 | 河北科技大学 | Mercury-free slurry laminated paper containing polymer solid electrolyte for zinc-manganese battery |
| CN101271968A (en) * | 2008-05-16 | 2008-09-24 | 辽源市鸿图纸业有限公司 | Mercury-free diaphragm paper for laminated cell |
-
2010
- 2010-12-10 CN CN 201010583779 patent/CN102054994B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122521A (en) * | 1994-11-04 | 1996-05-15 | 郝进生 | Rapid purification process for zinc-manganese dry-cell celectrolyte |
| CN1673455A (en) * | 2005-03-14 | 2005-09-28 | 河北科技大学 | Mercury-free slurry laminated paper containing polymer solid electrolyte for zinc-manganese battery |
| CN101271968A (en) * | 2008-05-16 | 2008-09-24 | 辽源市鸿图纸业有限公司 | Mercury-free diaphragm paper for laminated cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102054994A (en) | 2011-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102054994B (en) | Non-corrosive composite electrolyte for zinc manganese dry battery and preparation method thereof | |
| CN101724756A (en) | Phosphorus and silicon removing method of vanadium-contained clinker leaching liquor | |
| CN104628206A (en) | Recycling technique of lithium iron phosphate production wastewater | |
| CN100482577C (en) | Preparation for battery level lithium dihydrogen phosphate | |
| CN103588229A (en) | Production method for magnesium sulfate by using purple waste acid solution obtained in production of anthraquinone | |
| CN101885498A (en) | Method for preparing high-purity magnesium sulfate | |
| CN105129838A (en) | Method for producing copper sulphate by using copper-containing waste solution of PCB circuit board plant | |
| CN103058235A (en) | Method of removing calcium with magnesium sulfate and high-purity magnesium sulfate | |
| CN101058536B (en) | Method of preparing ultramicro ferrous oxalate | |
| CN102320635A (en) | Comprehensive utilization method of waste sulfuric acid of sulfonated products | |
| JP2019131448A (en) | Method for producing lithium hydroxide | |
| CN1491898A (en) | Process for preparinbg vanadylic sulfate and use | |
| CN102627307A (en) | Solid aluminum sulfate and production process thereof | |
| CN101671838A (en) | Method for preparing electronic-grade high-purity stannous methanesulfonate solution | |
| CN112607751B (en) | Method for re-dissolving, freezing and purifying mixed salt containing arsenic, sodium sulfite and sodium sulfate | |
| CN105271406B (en) | A kind of preparation method of sodium metavanadate | |
| CN112209858B (en) | Preparation method of 2- [ [ tri (hydroxymethyl) methyl ] amino ] ethanesulfonic acid | |
| CN103771367B (en) | A kind of stirred crystallization produces the method for electron-level phosphoric acid | |
| CN101885495A (en) | Method for preparing high-purity anhydrous sodium carbonate | |
| WO2013000255A1 (en) | Use of combination of polyphosphoric acid and metallic zinc in decolorizing of tetraacetyl ethylene diamine mother liquid | |
| CN106395758A (en) | A method of producing high-purity sodium sulfide | |
| CN106542971B (en) | A kind of synthesis technology of the bromo- beta naphthal of 6- | |
| CN100352774C (en) | Method of removing silicon in artificial rutile mether liquor | |
| CN110498431A (en) | A kind of preparation method of high-purity spherical shape potassium chloride | |
| CN103754843B (en) | A kind of baffle crystallization produces the method for electron-level phosphoric acid |
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 | ||
| CP03 | Change of name, title or address |
Address after: 410600 room 1402, Jinzhou Avenue venture building, Jing Jing District, Changsha, Hunan, Ningxiang Patentee after: Hunan Jianghai Environmental Protection Industry Co Ltd Address before: 412000 Hunan Province, Zhuzhou city Lusong District Sports Road No. 1 Yinfeng building 2-1003 Patentee before: Zhuzhou Jianghai Environmental Protection Co., Ltd. |
|
| CP03 | Change of name, title or address |