CN102054994A - 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
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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 zinc-manganese dioxide dry cell with there not being corrosion composite electrolyte and preparation method thereof.
Background technology:
Existing zinc-manganese dioxide dry cell electrolyte is to be equipped with electrolyte in Battery Plant again through secondary refining, need buy raw material such as LITHIUM BATTERY ammonium chloride, zinc chloride from small business in all parts of the country; Battery production enterprise purifies once more, be about to serial refinement treatment processes such as raw material heat, dissolve, hang zinc metal sheet more respectively, add zinc powder, purification, filtration, prepare the electrolyte (also needing in electrolyte, add mercury about 0.1% when the preparation oar is stuck with paste) of 2～3 kinds of variable concentrations again.Its long processing period generally needs about one month.The processing cost height, about about 300～500 yuan of battery enterprise electrolyte processing cost per ton, equipment, place, circulating fund take greatly, bring repeatedly environmental issue such as the waste residue in the refinement treatment process, waste liquid of compact battery level raw material factory, Battery Plant simultaneously.
Summary of the invention
The objective of the invention is to overcome above-mentioned defective, provide a kind of convenience, energy-conservation, efficient, environmental protection, mercuryless and cheaply zinc-manganese dioxide dry cell with there not being corrosion composite electrolyte and preparation method thereof.
Technical scheme of the present invention, a kind of zinc-manganese dioxide dry cell be with the preparation method who does not have the corrosion composite electrolyte, it is characterized in that described should nothings corrosion composite electrolyte be to adopt to make with extra care ammonium chloride, make with extra care zinc chloride and three kinds of raw materials of composite corrosion inhibitor and 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%.
More than each component percentage composition sum be 100%,
Described composite corrosion inhibitor is that Sodium Polyacrylate, esters surface active agent, polymer class chelated dispersants and clean tap water are composited;
Described concrete steps comprise:
(1) the refining ammonium chloride of preparation purity 〉=99.5%:
The ammonium chloride circulating mother liquor is added in the reactor, and turn on agitator drops into agricultural ammonium chloride, its NH
4Cl content 〉=97%, SO
4 2-≤ 0.8%, Fe≤0.001%, H
2O≤0.1% adds hydrogen peroxide then and carries out deironing in reactor, add charcoal absorption and remove heavy metal and organic substance;
Deironing principle: H
2O
2+ 2Fe
2++ 2H
+=2Fe
3++ 2H
2O
Fe
3++3H
2O＝Fe(OH)
3↓+3H
+
Add the barium chloride sulfate radical in reactor, the amount of adding is metered into by following reaction equation:
Ba
2++SO
4 2-＝BaSO
4↓，
In reacting kettle jacketing, feed simultaneously steam, heat and seethed with excitement to material in 60～80 minutes, 115～130 ℃ of temperature, at high temperature material is emitted from the reactor bottom and enter the filtering ponds filtration, filtrate filtered enters cooling crystallization pond and carries out crystallisation by cooling to room temperature, enter the stiff device through cooled material, carry out centrifugation again, simultaneously in centrifuge on the filter cake crystallized stock add water washing, flush away mother liquor and be adsorbed on the potassium of crystal surface, sodium, foreign ions such as sulfate radical obtain wet ammonium product, its moisture≤3.5%, enter the vibration drying device then, get the refining ammonium chloride of qualified products after drying, its NH
4Cl content 〉=99.5%, SO
4 2-≤ 0.02%, Fe≤0.0001%, heavy metal≤0.0005%, H
2O≤0.5%;
(2) the refining zinc chloride of preparation purity 〉=98%: with 4.15m
3The cleaning running water adds 5m
3In the reactor, turn on agitator, and drop into industrial zinc chloride 3100Kg, its ZnCl
2〉=95%, Fe≤0.001%, heavy metal≤0.001%, the concentration of control solution is 45 ° of Be, feeds in reacting kettle jacketing simultaneously and is steam heated to 60～70 ℃, adds the potassium permanganate deironing again in reactor, addition is metered into by following reaction equation:
MnO
4 -+3Fe
2++2H
2O+5OH
-＝MnO
2↓+3Fe(OH)
3↓
About controlling reaction time 1.5～2.5 hours, carry out filtering and impurity removing then, the filtrate after the removal of impurities enters the displacement reaction pond, stir at normal temperatures to add the zinc powder removing heavy metals, and the zinc powder addition, extraordinarily go into according to following reaction principle metered 1.2:
Cu
2++Zn＝Zn
2++Cu
Cd
2++Zn＝Zn
2++Cd
Ni
2++Zn＝Zn
2++Ni
Pb
2++Zn＝Zn
2++Pb
About 2 hours reaction time, carry out filtering and impurity removing then, obtain refined liquid after the removal of impurities and enter the concentration response still, about 120 ℃ of control temperature, concentration response 1～2 hour, 50 ° of Be of controlled concentration, concentrate is put into graphite cuvette and is carried out heat drying, broken and the metering packing with product makes refining zinc chloride product after drying; Its ZnCl
2〉=98%, Fe≤0.0005%, heavy metal≤0.0005%;
(3) preparation composite corrosion inhibitor: with molecular weight is 5000-10000, ratio is that 1～10% Sodium Polyacrylate, ratio are that 40～90% esters surface active agent, ratio are that 1～20% polymer class chelated dispersants, ratio are that 10～20% clean tap water add reactor in proportion, stir at normal temperatures, composite is composite corrosion inhibitor;
The organic surface active molecules of corrosion inhibiter has occupied the activity centre that corrosion reaction is carried out at the film that electrode surface forms, improve the male or female reaction activity, it can not only adsorb also and can desorb, promptly when battery does not use, zinc is in stable potential, the preferential adsorption of corrosion inhibiter molecule is dissolved with preferential prevention zinc, plays corrosion inhibition; And when battery discharge, corrosion inhibiter can break away from zinc surface smoothly, no longer blocks the zinc dissolving; So the discharge initial stage, moment the open circuit voltage ratio have mercury cell low slightly, but continuous discharge can rise, and is more stable than mercury cell is arranged, and do not influence result of use.
The compatibility chelated dispersants stops the heavy metal ion deposition, can stop the zinc hydrolytic precipitation simultaneously, produces spot corrosion in case form micro cell at the zinc tube inner surface.
(4) with above-mentioned refining ammonium chloride, refining zinc chloride and three kinds of raw materials of composite corrosion inhibitor mix by weight ratio and stir;
Promptly the zinc-manganese dioxide dry cell that obtains by said method production corrodes the composite electrolyte product with nothing.
Esters surface active agent in the described composite corrosion inhibitor can be the alkylolamides phosphate, or the perfluor phosphate, or perfluoroalkyl ethyoxyl ether alcohol, or fatty acid imidazoline quinoline borate, or their combination in any;
Described polymer class chelated dispersants can be sulfonic acid/acrylic acid/poly anhydride copolymer, or ethylenediamine tetra-acetic acid, or hexamethylenetetramine, or gluconic acid sodium salt, or their combination in any.
In sum, this product cooperates novel corrosion inhibitor, is Green Product.The present invention changes the preparation of existing zinc-manganese dioxide dry cell enterprise electrolyte and uses process, promptly simplify the preparation of electrolyte and used process, make the preparation of existing zinc-manganese dioxide dry cell enterprise electrolyte only need in composite solid electrolyte, to add water, the electrolyte that can make required Baume concentration is for directly using, 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.But product of the present invention has unique practicality and generalization, is a kind of convenience of being convenient to generally to promote at battery industry, energy-conservation, efficient, environmental protection, low-cost completely new product.
Concrete real execution mode
A kind of zinc-manganese dioxide dry cell is with the preparation method who does not have the corrosion composite electrolyte, and it is characterized in that described should nothings corrosion composite electrolyte be to adopt to make with extra care ammonium chloride, make with extra care zinc chloride and three kinds of raw materials of composite corrosion inhibitor and 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%.
More than each component percentage composition sum be 100%,
Described composite corrosion inhibitor is that Sodium Polyacrylate, esters surface active agent, polymer class chelated dispersants and clean tap water are composited;
Described concrete steps comprise:
(1) the refining ammonium chloride of preparation purity 〉=99.5%:
With 4.2m
3The ammonium chloride circulating mother liquor adds 5m
3Reactor in, turn on agitator drops into agricultural ammonium chloride 1200Kg, its NH
4Cl content 〉=97%, SO
4 2-≤ 0.8%, Fe≤0.001%, H
2O≤0.1% adds hydrogen peroxide 1000ml left and right sides deironing then in reactor, add active carbon 1～3Kg absorption and remove heavy metal and organic substance;
Deironing principle: H
2O
2+ 2Fe
2++ 2H
+=2Fe
3++ 2H
2O
Fe
3++3H
2O＝Fe(OH)
3↓+3H
+
Add the barium chloride sulfate radical in reactor, the amount of adding is metered into by following reaction equation:
Ba
2++SO
4 2-＝BaSO
4↓，
In reacting kettle jacketing, feed simultaneously steam, heat and seethed with excitement to material in 60～80 minutes, 115～130 ℃ of temperature, at high temperature material is emitted from the reactor bottom and enter the filtering ponds filtration, filtrate filtered enters cooling crystallization pond and carries out crystallisation by cooling to room temperature, enter the stiff device through cooled material, carry out centrifugation again, simultaneously in centrifuge on the filter cake crystallized stock add water washing, flush away mother liquor and be adsorbed on the potassium of crystal surface, sodium, foreign ions such as sulfate radical obtain wet ammonium product, its moisture≤3.5%, enter the vibration drying device then, get qualified products refining ammonium chloride, i.e. NH after drying
4Cl content 〉=99.5%, SO
4 2-≤ 0.02%, Fe≤0.0001%, heavy metal≤0.0005%, H
2O≤0.5%;
(2) the refining zinc chloride of preparation purity 〉=98%: with 4.15m
3The cleaning running water adds 5m
3In the reactor, turn on agitator, and drop into industrial zinc chloride 3100Kg, its ZnCl
2〉=95%, Fe≤0.001%, heavy metal≤0.001%, the concentration of control solution is 45 ° of Be, feeds in reacting kettle jacketing simultaneously and is steam heated to 60～70 ℃, adds the potassium permanganate deironing again in reactor, addition is metered into by following reaction equation:
MnO
4 -+3Fe
2++2H
2O+5OH
-＝MnO
2↓+3Fe(OH)
3↓
About controlling reaction time 1.5～2.5 hours, carry out filtering and impurity removing then, the filtrate after the removal of impurities enters the displacement reaction pond, stir at normal temperatures to add the zinc powder removing heavy metals, and the zinc powder addition, extraordinarily go into according to following reaction principle metered 1.2:
Cu
2++Zn＝Zn
2++Cu
Cd
2++Zn＝Zn
2++Cd
Ni
2++Zn＝Zn
2++Ni
Pb
2++Zn＝Zn
2++Pb
About 2 hours reaction time, carry out filtering and impurity removing then, obtain refined liquid after the removal of impurities and enter the concentration response still, about 120 ℃ of control temperature, concentration response 1～2 hour, 50 ° of Be of controlled concentration, concentrate is put into graphite cuvette and is carried out heat drying, broken and the metering packing with product makes refining zinc chloride product after drying; Its ZnCl
2〉=98%, Fe≤0.0005%, heavy metal≤0.0005%.
(3) preparation composite corrosion inhibitor: with molecular weight is 5000-10000, ratio is that 1～10% Sodium Polyacrylate, ratio are that 40～90% esters surface active agent, ratio are that 1～20% polymer class chelated dispersants, ratio are that 10～20% clean tap water add reactor in proportion, stir at normal temperatures, composite is composite corrosion inhibitor;
The organic surface active molecules of corrosion inhibiter has occupied the activity centre that corrosion reaction is carried out at the film that electrode surface forms, improve the male or female reaction activity, it can not only adsorb also and can desorb, promptly when battery storing, zinc is in stable potential, the preferential adsorption of corrosion inhibiter molecule is dissolved with preferential prevention zinc, plays corrosion inhibition; And when battery discharge, corrosion inhibiter can break away from zinc surface smoothly, no longer blocks the zinc dissolving; So the discharge initial stage, moment the open circuit voltage ratio have mercury cell low slightly, but continuous discharge can rise, and is more stable than mercury cell is arranged, and do not influence result of use;
The compatibility chelated dispersants stops the heavy metal ion deposition, can stop the zinc hydrolytic precipitation simultaneously, produces spot corrosion in case form micro cell at the zinc tube inner surface;
(4) above-mentioned refining ammonium chloride, refining zinc chloride and three kinds of raw materials of composite corrosion inhibitor are mixed by weight ratio and stir and promptly get zinc-manganese dioxide dry cell with there not being the composite electrolyte of corrosion product.Promptly obtained zinc-manganese dioxide dry cell with there not being corrosion composite electrolyte product by said method production.
Esters surface active agent in the described composite corrosion inhibitor can be the alkylolamides phosphate, or the perfluor phosphate, or perfluoroalkyl ethyoxyl ether alcohol, or fatty acid imidazoline quinoline borate, or their combination in any.Described polymer class chelated dispersants can be sulfonic acid/acrylic acid/poly anhydride copolymer, or ethylenediamine tetra-acetic acid, or hexamethylenetetramine, or gluconic acid sodium salt, or their combination in any.
Esters surface active agent in the present embodiment in the composite corrosion inhibitor is to adopt alkylolamides phosphate and fatty acid imidazoline quinoline borate to make up (also can be by above-mentioned each lipid surfactant combination in any).The polymer class chelated dispersants of the composite corrosion inhibitor in the present embodiment is to adopt sulfonic acid/acrylic acid/poly anhydride copolymer and ethylenediamine tetra-acetic acid to make up (also can close the dispersant combination in any by above-mentioned each polymeric type huge legendary turtle).
Example 1, I type standard approved product: be used for S type battery product:
Refining NH
4Cl 〉=62%, refining ZnCl
2〉=36%, composite corrosion inhibitor 〉=0.1%, zinc metal sheet rate of corrosion≤0.1mm/y.
Example 2, II type formula for a product are used for S type battery product by the user's request proportioning:
Refining NH
4Cl 〉=64%, 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 are used for C type battery product by the user's request proportioning:
Refining NH
4Cl 〉=54%, refining ZnCl
2〉=44%, composite corrosion inhibitor 〉=0.1%, zinc metal sheet rate of corrosion≤0.1mm/y.
Claims (3)
1. a zinc-manganese dioxide dry cell is with the preparation method who does not have the corrosion composite electrolyte, and it is characterized in that described should nothings corrosion composite electrolyte be to adopt to make with extra care ammonium chloride, make with extra care zinc chloride and three kinds of raw materials of composite corrosion inhibitor and 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%.
More than each component percentage composition sum be 100%,
Described composite corrosion inhibitor is that Sodium Polyacrylate, esters surface active agent, polymer class chelated dispersants and clean tap water are composited;
Described concrete steps comprise:
(1) the refining ammonium chloride of preparation purity 〉=99.5%:
The ammonium chloride circulating mother liquor is added in the reactor, and turn on agitator drops into agricultural ammonium chloride, its NH
4Cl content 〉=97%, SO
4 2-≤ 0.8%, Fe≤0.001%, H
2O≤0.1% adds hydrogen peroxide then and carries out deironing in reactor, add charcoal absorption and remove heavy metal and organic substance;
Add the barium chloride sulfate radical in reactor, the amount of adding is metered into by following reaction equation:
Ba
2++SO
4 2-＝BaSO
4↓，
In reacting kettle jacketing, feed simultaneously steam, heat and seethed with excitement to material in 60～80 minutes, 115～130 ℃ of temperature, at high temperature material is emitted from the reactor bottom and enter the filtering ponds filtration, filtrate filtered enters cooling crystallization pond and carries out crystallisation by cooling to room temperature, enter the stiff device through cooled material, carry out centrifugation again, simultaneously in centrifuge on the filter cake crystallized stock add water washing, flush away mother liquor and be adsorbed on the potassium of crystal surface, sodium, foreign ions such as sulfate radical obtain wet ammonium product, its moisture≤3.5%, enter the vibration drying device then, get qualified products refining ammonium chloride, i.e. NH after drying
4Cl content 〉=99.5%, SO
4 2-≤ 0.02%, Fe≤0.0001%, heavy metal≤0.0005%, H
2O≤0.5%;
(2) the refining zinc chloride of preparation purity 〉=98%:
To clean running water and add in the reactor, turn on agitator, and drop into industrial zinc chloride, its ZnCl
2〉=95%, Fe≤0.001%, heavy metal≤0.001%, the concentration of control solution is 45 ° of Be, feeds in reacting kettle jacketing simultaneously and is steam heated to 60～70 ℃, adds the potassium permanganate deironing again in reactor, addition is metered into by following reaction equation:
MnO
4 -+3Fe
2++2H
2O+5OH
-＝MnO
2↓+3Fe(OH)
3↓
About controlling reaction time 1.5～2.5 hours, carry out filtering and impurity removing then.Filtrate after the removal of impurities enters the displacement reaction pond, stirs at normal temperatures to add the zinc powder removing heavy metals, adds the amount of zinc powder, extraordinarily goes into according to following reaction principle metered 1.2:
Cu
2++Zn＝Zn
2++Cu
Cd
2++Zn＝Zn
2++Cd
Ni
2++Zn＝Zn
2++Ni
Pb
2++Zn＝Zn
2++Pb
About 2 hours reaction time.Carry out filtering and impurity removing then, obtain refined liquid after the removal of impurities and enter the concentration response still, about 120 ℃ of control temperature, concentration response 1～2 hour, 50 ° of Be of controlled concentration, concentrate is put into graphite cuvette and is carried out heat drying, broken and the metering packing with product makes refining zinc chloride product, i.e. ZnCl after drying
2〉=98%, Fe≤0.0005%, heavy metal≤0.0005%;
(3) preparation composite corrosion inhibitor:
With molecular weight is 5000-10000, ratio is that 1～10% Sodium Polyacrylate, ratio are that 40～90% esters surface active agent, ratio are that 1～20% polymer class chelated dispersants, ratio are that 10～20% clean tap water add reactor in proportion, stir at normal temperatures, composite is composite corrosion inhibitor;
The organic surface active molecules of corrosion inhibiter has occupied the activity centre that corrosion reaction is carried out at the film that electrode surface forms, improve the male or female reaction activity, it can not only adsorb also and can desorb, promptly when battery does not use, zinc is in stable potential, the preferential adsorption of corrosion inhibiter molecule is dissolved with preferential prevention zinc, plays corrosion inhibition; And when battery discharge, corrosion inhibiter can break away from zinc surface smoothly, no longer blocks the zinc dissolving; So the discharge initial stage, moment the open circuit voltage ratio have mercury cell low slightly, but continuous discharge can rise, and is more stable than mercury cell is arranged, and do not influence result of use;
The compatibility chelated dispersants stops the heavy metal ion deposition, can stop the zinc hydrolytic precipitation simultaneously, produces spot corrosion in case form micro cell at the zinc tube inner surface;
(4) with above-mentioned refining ammonium chloride, refining zinc chloride and three kinds of raw materials of composite corrosion inhibitor mix by weight ratio and stir and promptly get zinc-manganese dioxide dry cell with there not being the composite electrolyte of corrosion product.
2. the zinc-manganese dioxide dry cell of the method for claim 1 production is with there not being the corrosion composite electrolyte.
3. zinc-manganese dioxide dry cell as claimed in claim 1 is characterized in that with there not being the preparation method of corroding composite electrolyte:
Esters surface active agent in the described composite corrosion inhibitor can be the alkylolamides phosphate, or the perfluor phosphate, or perfluoroalkyl ethyoxyl ether alcohol, or fatty acid imidazoline quinoline borate, or their combination in any;
In the described composite corrosion inhibitor the polymer class chelated dispersants can be sulfonic acid/acrylic acid/poly anhydride copolymer, or ethylenediamine tetra-acetic acid, or hexamethylenetetramine, or gluconic acid sodium salt, or their combination in any.
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|---|---|---|---|
| CN 201010583779 CN102054994B (en) | 2010-12-10 | 2010-12-10 | Non-corrosive composite electrolyte for zinc manganese dry battery and preparation method thereof |
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| CN102392255A (en) * | 2011-10-10 | 2012-03-28 | 南昌航空大学 | Preparation method of sodium polyacrylate dispersing imidazoline corrosion inhibitor |
| CN103762374A (en) * | 2014-01-10 | 2014-04-30 | 宁波豪生电池有限公司 | Preparation method and preparation device of high-energy environment-friendly battery electrolyte |
| CN104201427A (en) * | 2014-09-07 | 2014-12-10 | 桂林理工大学 | Electrolyte containing phenylhydrazine reduction 4-formylbenzoic acid polyethylene glycol 400 laurate surfactant and preparation method of electrolyte |
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| CN102392255B (en) * | 2011-10-10 | 2013-04-03 | 南昌航空大学 | Preparation method of sodium polyacrylate dispersing imidazoline corrosion inhibitor |
| CN102392255A (en) * | 2011-10-10 | 2012-03-28 | 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 |
| CN103762374A (en) * | 2014-01-10 | 2014-04-30 | 宁波豪生电池有限公司 | Preparation method and preparation device of high-energy environment-friendly battery electrolyte |
| 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 |
| CN104332663A (en) * | 2014-09-07 | 2015-02-04 | 桂林理工大学 | Electrolyte containing 4-nitrophenylhydrazine 4-carboxybenzaldehyde polyethylene glycol 400 laurate acetal surfactant, and its preparation method |
| 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 |
| CN104201427A (en) * | 2014-09-07 | 2014-12-10 | 桂林理工大学 | Electrolyte containing phenylhydrazine reduction 4-formylbenzoic acid polyethylene glycol 400 laurate surfactant and preparation method of electrolyte |
| 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 |
| US10472596B2 (en) | 2017-06-27 | 2019-11-12 | Ecolab Usa Inc. | Non-phosphorous transition metal control in laundry applications |
| CN107634266A (en) * | 2017-08-18 | 2018-01-26 | 上海交通大学 | A kind of MH secondary battery flame-retardant electrolyte |
| CN109616677A (en) * | 2018-12-10 | 2019-04-12 | 杭州长命电池有限公司 | Paste-type mercury-free battery slurry and preparation method thereof |
| 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 |
| CN114122533A (en) * | 2020-08-28 | 2022-03-01 | 中国科学院上海硅酸盐研究所 | Multifunctional composite electrolyte of neutral or weak acid zinc-based battery |
| 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 |
| CN113097518A (en) * | 2021-03-18 | 2021-07-09 | 苏州柔能纳米科技有限公司 | Electrolyte for flexible neutral zinc-manganese dioxide battery and preparation method thereof |
| 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 |
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