CN101252204A - Liquid state electrolyte for zinc-nickel secondary batteries and preparing method thereof - Google Patents

Liquid state electrolyte for zinc-nickel secondary batteries and preparing method thereof Download PDF

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CN101252204A
CN101252204A CNA2008100579220A CN200810057922A CN101252204A CN 101252204 A CN101252204 A CN 101252204A CN A2008100579220 A CNA2008100579220 A CN A2008100579220A CN 200810057922 A CN200810057922 A CN 200810057922A CN 101252204 A CN101252204 A CN 101252204A
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liquid electrolyte
zinc
mixture
poly
phosphate
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李林
肖星
周建军
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention belongs to the chemical technical field, relating to electrolyte used on a zinc-nickel secondary cell, in particular to a liquid electrolyte to be used on the zinc-nickel secondary cell and a preparation method for the same. In the method, the corrosion on a zinc electrode by an electrolyte solvent during charging is reduced greatly by adding a polymeric additive into an alkaline electrolyte solution, which restrains the generation of dendrite arms, improves the utilization rate of the electrolyte and prolongs the cycle life of cells.

Description

Be used for liquid electrolyte of zinc-nickel secondary batteries and preparation method thereof
Technical field
The invention belongs to chemical technology field, relate to the electrolyte that is used for zinc-nickel secondary batteries, especially relate to liquid electrolyte that is used for zinc-nickel secondary batteries and preparation method thereof.
Background technology
Along with various portable communication apparatus, laptop computer, the developing rapidly of high-tech products such as digital camera/video camera, these portable electronic products all require supporting with it chemical power source.Performance requirements such as the operating voltage that this class power supply generally need be higher, bigger operating current, the cycle life than long, smaller volume, safety have promoted the development and the technological innovation in rechargeable battery (secondary cell) field greatly.
People are to the existing history that goes up a century of the research of nickel-zinc battery.Zinc-nickel secondary batteries has the following advantages: specific energy height (55～85Wh/kg), specific power big (can surpass 200W/kg), open circuit voltage is up to 1.75V, operating temperature range broadness (20～60 ℃), but large current charge, abundant raw materials and cost are low, can not cause environmental pollution, so be with a wide range of applications as electrical source of power.At present, it is shorter that the major defect of zinc-nickel secondary batteries is that battery recycles the life-span, because it the zinc dendrite growth in use can occur, causes barrier film to be pierced, and causes internal short-circuit of battery, and battery life is ended.
The reason that zinc dendrite generates is mainly due to when discharging, and zinc electrode generates zinc oxide, zinc hydroxide, and these products are dissolved in the highly basic electrolyte in a large number; And when recharging, because the dissolubility of product, most zincate is not deposited on the zinc electrode of porous, and be deposited on electrolyte around and barrier film in, this has produced difficulty with regard to the mass transport process that makes zinc electrode, and on the outer surface of electrode and some point, produce deposit, but not be evenly distributed on the whole surface, the dendritic growth phenomenon formed.The skeleton of zinc metal easily pierces through barrier film from the superficial growth of electrode, and the internal electrical short circuit of formation and nickel electrode makes battery failure.In addition, zincate density is bigger, is tending towards sinking; Along with the carrying out of charge and discharge cycles, electrode top consumes, and a large amount of zinc are deposited on the electrode bottom, and this causes electrode deformation, and electrode deformation reduces effective area, reduces discharge rate, influences battery capacity.
Be used to alleviate the method for dendritic growth at present, comprise three aspects: the active material (US Patent No.4368244, the No.5556720 that change zinc electrode; Jpn Patent JP No.0428160, No.03122235, No.03297057, No.04126356), diagram modification (Jpn Patent JP No.03230480, No.07161375, No.07161376) and improve electrolyte and form (document [1～3]; US PatentNo.5453336, No.54302475; USSR Patent SU No.1457760).Reduce dendrite generation quantity by add additive in electrolyte, the method that improves battery performance is summarized in the table 1.
Table 1 pair dendritic growth plays inhibiting additive agent electrolyte
Additive types List of references or patent
Carbonate List of references [1]
ZnO，(NH 4) 2CS List of references [2]
(CH 3CH 2) 4NBr List of references [3]
Aliphatic acid-alkyl chain hydrocarbon/ester admixture, soap, fatty acid ester USSR Patent SU No.1457760
Hydroxide and hydrofluoride US Patent No.5453336， No.54302475
Though above-mentioned a few class is inorganic/and organics additive can make the dendrite of zinc electrode and being eased of problem on deformation, improve battery to a certain extent and recycled performance, but the adding of these additives, do not solve the problem that the zinc dendrite growth is brought in itself, and these additives dissolubility in alkaline liquid electrolyte is not good.Therefore, need exploitation badly and have more advantageous property, better deliquescent new additive agent.
Document 1, R.Shivkumar, G.Paruthimal Kalaignan and T.Vasudevan " Effect ofadditives on zinc electrodes in alkaline battery systems " J.Power Sources, 199555,53.
Document 2, A.Renuka, A.Veluchamy and N.Venkatakrishnan " Effect ofcarbonate ions on the behaviour of zinc in 30%KOH " J.Power Sources, 199134,381.
Document 3, Z.Baohong, Ch.Meng, X.Dongari and W.Yindong, Ext.Abstr., 46thISE Meet., Xiamen, P.R.China, 1995,2,5～43.
Summary of the invention
The purpose of this invention is to provide a kind of liquid electrolyte that is used for zinc-nickel secondary batteries.
Another object of the present invention provides the preparation method of the liquid electrolyte that is used for zinc-nickel secondary batteries.
The present invention makes an addition to polymeric additive in the alkaline liquid electrolyte, polymer can be adsorbed in the surface of zinc negative material, electrolyte solvent has improved the utilance of electrolyte to the corrosion of zinc electrode material when greatly having reduced charging, has prolonged battery cycle life.The what is more important polymer can make the zinc oxide that zinc electrode produces in the discharge process, inorganic matters such as zinc hydroxide are deposited on the surface of zinc negative electrode material uniformly, rather than in the enrichment of a certain position, simultaneously polymer also can adsorb or desorption at zinc oxide, sedimental surface such as zinc hydroxide, change the chemical property of plane of crystal, the growth rate of driven terms of mechanics controlled oxidation zinc or each crystal face of zinc hydroxide nano particle, thereby, improve the life-span that recycles of zinc-nickel secondary batteries in the formation that fundamentally suppresses zinc dendrite effectively.
And compare with the additive of other electrolyte, the polymeric additive that is added in electrolyte of the present invention does not have corrosivity and toxicity, and wide material sources are easy to get, and are cheap, are easy to large-scale production.
The present invention is used for the liquid electrolyte of zinc-nickel secondary batteries, is made up of polymeric additive and alkaline electrolyte solution.
The polymeric additive total amount that contains in the described liquid electrolyte accounts for 0.1%～10% of liquid electrolyte mass fraction, and preferred polymers additive total amount accounts for 1%～10% of liquid electrolyte mass fraction.
Comprise in the described alkaline electrolyte solution: water, hydroxide, phosphate and fluoride.
Described water comprises deionized water, distilled water or ionized water.
The concentration of described hydroxide in alkaline electrolyte solution is approximately the free alkalinity of 3～10mol/L; Hydroxide is selected from a kind of in NaOH, lithium hydroxide, the potassium hydroxide or greater than a kind of mixture etc.
The concentration of described phosphate in alkaline electrolyte solution is approximately 0.05～0.25mol/L, and phosphate is selected from a kind of in sodium phosphate, potassium phosphate, the lithium phosphate or greater than a kind of mixture etc.; Above-mentioned phosphatic phosphate radical is unit price, divalence or trivalent.
The concentration of described fluoride in alkaline electrolyte solution is approximately 0.01～5mol/L, and fluoride is selected from a kind of in sodium fluoride, lithium fluoride, the potassium fluoride or greater than a kind of mixture etc.
May also contain trace impurity etc. in the described alkaline electrolyte solution.
The present invention is used for the preparation method of the liquid electrolyte of zinc-nickel secondary batteries: the mixture of above-mentioned hydroxide, phosphate and fluoride is soluble in water, and stir and make it dissolving, make alkaline electrolyte solution; Then polymeric additive is dissolved in the alkaline electrolyte solution, stirs and make its dissolving, make liquid electrolyte.
The present invention is used for the liquid electrolyte of zinc-nickel secondary batteries, can use in zinc-nickel secondary batteries.Can be positive electrode active materials with the nickel hydroxide for example, be to use in the zinc-nickel secondary batteries of negative active core-shell material with zinc.
The present invention is used for polymeric additive that the liquid electrolyte of zinc-nickel secondary batteries contains for being dispersed in the polymer in the liquid electrolyte; More preferably water-soluble polymer is as polymeric additive.
It is 50～10000 polymer that polymeric additive described in the present invention is the degree of polymerization, and wherein preferred degree of polymerization is 100～10000 polymer.
Polymeric additive among the present invention is selected from a kind of in polyacrylic acid, polyacrylate, polyacrylate, polymethylacrylic acid, polymethacrylates, poly-methyl acrylate, polyether polymer, polyacrylamide base polymer, polyvinylpyrrolidone, polyvinyl alcohol, the poly-polysaccharide or greater than a kind of mixture of polymers etc.
Described polyacrylate is a Poly(Hydroxyethyl Methacrylate) etc.
Described polyacrylate is a Sodium Polyacrylate etc.
Described polymethacrylates is a poly hydroxy ethyl acrylate etc.
Described poly-methyl acrylate is a sodium polymethacrylate etc.
The mixture that described polyethers polymer is polyethylene glycol, polypropylene glycol or polyethylene glycol and polypropylene glycol etc.
Described polyacrylamide base polymer is the mixture of polyacrylamide, poly-(N-N-isopropylacrylamide) or polyacrylamide and poly-(N-N-isopropylacrylamide).
The present invention is by making an addition to polymeric additive in the alkaline electrolyte solution, and electrolyte solvent has suppressed the generation of dendrite to the corrosion of zinc electrode when greatly reducing charging, has improved the utilance of electrolyte, has prolonged the cycle life of battery.
The photo of Fig. 1 is the electron scanning micrograph that does not add 100 rear surfaces of zinc electrode charge and discharge cycles of polymeric additive in the zinc-nickel secondary batteries electrolyte.Fig. 2 to Figure 11 is respectively the electron scanning micrograph on the zinc electrode surface after the embodiment of the invention 1 to embodiment 5 charge and discharge cycles 100 times and the function relation figure of battery capacity and charged period.As seen from the figure, after charge and discharge cycles 100 times, dendrite has obviously appearred in the zinc electrode surface of not adding the zinc-nickel secondary batteries of polymeric additive in the electrolyte.After the electrolyte of polymeric additive of the present invention has been added in use, the zinc electrode surface of zinc-nickel secondary batteries is smoother all, find no dendrite and generate, illustrated that polymeric additive can suppress the generation of dendrite in charge and discharge process, improved the cycle life of zinc-nickel secondary batteries.
The invention will be further described below in conjunction with drawings and Examples, but should not regard limitation of the invention as.
Description of drawings
Fig. 1. do not add the electron scanning micrograph of 100 rear surfaces of zinc electrode charge and discharge cycles of polymeric additive in the electrolyte.
Fig. 2. the electron scanning micrograph on the zinc electrode surface after the embodiment of the invention 1 charge and discharge cycles 100 times.
Fig. 3. the functional relation of the embodiment of the invention 1 battery capacity and charged period.
Fig. 4. the electron scanning micrograph on the zinc electrode surface after the embodiment of the invention 2 charge and discharge cycles 100 times.
Fig. 5. the functional relation of the embodiment of the invention 2 battery capacities and charged period.
Fig. 6. the electron scanning micrograph on the zinc electrode surface after the embodiment of the invention 3 charge and discharge cycles 100 times.
Fig. 7. the functional relation of the embodiment of the invention 3 battery capacities and charged period.
Fig. 8. the electron scanning micrograph on the zinc electrode surface after the embodiment of the invention 4 charge and discharge cycles 100 times.
Fig. 9. the functional relation of the embodiment of the invention 4 battery capacities and charged period.
Figure 10. the electron scanning micrograph on the zinc electrode surface after the embodiment of the invention 5 charge and discharge cycles 100 times.
Figure 11. the functional relation of the embodiment of the invention 5 battery capacities and charged period.
Embodiment
Embodiment 1
With 28g Na 2HPO 4, 23g KF, the mixture of 5g LiF and 112g KOH joins in the 1L deionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.To wherein adding 8g polyacrylic acid (degree of polymerization is 80) additive, stir and make its dissolving then, prepare liquid electrolyte.This liquid electrolyte is used for zinc-nickel secondary batteries, and the scanning electron microscopy on the zinc electrode surface after the charge and discharge cycles 100 times the results are shown in Figure 2, and battery capacity the results are shown in Figure 3 with what the charged period changed.
Embodiment 2
With 12g NaH 2PO 4, 29g KF, the mixture of 112g KOH and 80g NaOH joins in the 1L deionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.To wherein adding 15g sodium polymethacrylate (degree of polymerization is 600) additive, stir and make its dissolving then, prepare liquid electrolyte.This liquid electrolyte is used for zinc-nickel secondary batteries, and the scanning electron microscopy on the zinc electrode surface after the charge and discharge cycles 100 times the results are shown in Figure 4, and battery capacity the results are shown in Figure 5 with what the charged period changed.
Embodiment 3
With 12g NaH 2PO 4, the mixture of 29g KF and 168g KOH joins in the 1L ionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.To wherein adding 10g poly hydroxy ethyl acrylate (degree of polymerization is 2000) additive, stir and make its dissolving then, prepare liquid electrolyte.This liquid electrolyte is used for zinc-nickel secondary batteries, and the scanning electron microscopy on the zinc electrode surface after the charge and discharge cycles 100 times the results are shown in Figure 6, and battery capacity the results are shown in Figure 7 with what the charged period changed.
Embodiment 4
With 12g NaH 2PO 4, 29g KF, the mixture of 56g KOH and 72g LiOH joins in the 1L deionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.To the mixed additive that wherein adds 30g polymethylacrylic acid (degree of polymerization is 400) and 1g Poly(Hydroxyethyl Methacrylate) (degree of polymerization is 60), stir and make its dissolving then, prepare liquid electrolyte.This liquid electrolyte is used for zinc-nickel secondary batteries, and the scanning electron microscopy on the zinc electrode surface after the charge and discharge cycles 100 times the results are shown in Figure 8, and battery capacity the results are shown in Figure 9 with what the charged period changed.
Embodiment 5
With 14g NaH 2PO 4, 29g KF, the mixture of 112g KOH and 80g NaOH joins in the 1L distilled water, stirs and makes its dissolving, makes alkaline electrolyte solution.To wherein adding 15g polymethylacrylic acid (degree of polymerization is 1000) additive, stir and make its dissolving then, prepare liquid electrolyte.This liquid electrolyte is used for zinc-nickel secondary batteries, and the scanning electron microscopy on the zinc electrode surface after the charge and discharge cycles 100 times the results are shown in Figure 10, and battery capacity the results are shown in Figure 11 with what the charged period changed.
Embodiment 6
With 36g NaH 2PO 4, 6g KF, 5g LiF, the mixture of 80g NaOH and 48g LiOH joins in the 1L ionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.To wherein adding 50g polyethylene glycol (degree of polymerization is 500) additive, stir and make its dissolving then, prepare liquid electrolyte.
Embodiment 7
With 28g Na 2HPO 4, 23g KF, the mixture of 5g LiF and 112g KOH joins in the 1L deionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.To wherein adding 8g Sodium Polyacrylate (degree of polymerization is 1000) additive, stir and make its dissolving then, prepare liquid electrolyte.
Embodiment 8
With 12g NaH 2PO 4, 29g KF, the mixture of 112g KOH and 80g NaOH joins in the 1L deionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.To the additive that wherein adds 1g polyethylene glycol (degree of polymerization is 20) and 1g polypropylene glycol (degree of polymerization is 90), stir and make its dissolving then, prepare liquid electrolyte.
Embodiment 9
With 12g NaH 2PO 4, the mixture of 29g KF and 168g KOH joins in the 1L distilled water, stirs and makes its dissolving, makes alkaline electrolyte solution.To wherein adding 10g polyvinylpyrrolidone (degree of polymerization is 2000) additive, stir and make its dissolving then, prepare liquid electrolyte.
Embodiment 10
With 12g NaH 2PO 4, 29g KF, the mixture of 56g KOH and 72g LiOH joins in the 1L distilled water, stirs and makes its dissolving, makes alkaline electrolyte solution.To wherein adding 9g Poly(Hydroxyethyl Methacrylate) (degree of polymerization is 500) additive, stir and make its dissolving then, prepare liquid electrolyte.
Embodiment 11
With 36g NaH 2PO 4, 12g KF, 5g LiF, the mixture of 80g NaOH and 48g LiOH joins in the 1L deionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.To wherein adding poly-(N-N-isopropylacrylamide) (degree of polymerization is 8000) additive of 70g, stir and make its dissolving then, prepare liquid electrolyte.
Embodiment 12
With 28g Na 2HPO 4, 23g KF, the mixture of 5g LiF and 112g KOH joins in the 1L deionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.To wherein adding poly-(N-N-isopropylacrylamide) (degree of polymerization is 6000) additive of 8g polyacrylamide (degree of polymerization is 900) and 50g, stir and make its dissolving then, prepare liquid electrolyte.
Embodiment 13
With 12g NaH 2PO 4, 29g KF, the mixture of 118g KOH and 80g NaOH joins in the 1L ionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.To wherein adding 25g polyvinylpyrrolidone (degree of polymerization is 4000) additive, stir and make its dissolving then, prepare liquid electrolyte.
Embodiment 14
With 12g NaH 2PO 4, the mixture of 29g KF and 168g KOH joins in the 1L ionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.To wherein adding 53g polyvinyl alcohol (degree of polymerization is 3500) additive, stir and make its dissolving then, prepare liquid electrolyte.
Embodiment 15
With 12g NaH 2PO 4, 26g KF, the mixture of 56g KOH and 78g LiOH joins in the 1L deionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.To wherein adding 30g carboxymethyl cellulose (degree of polymerization is 1300) additive, stir and make its dissolving then, prepare liquid electrolyte.
Embodiment 16
With 36g NaH 2PO 4, 12g KF, 5g LiF, the mixture of 80g NaOH and 48g LiOH joins in the 1L deionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.To wherein adding 50g polyvinyl alcohol (degree of polymerization is 8000) and 30g carboxymethyl cellulose (degree of polymerization is 1300) additive, stir and make its dissolving then, prepare liquid electrolyte.
Embodiment 17
With 28g Na 2HPO 4, 23g KF, the mixture of 5g LiF and 112g KOH joins in the 1L deionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.To wherein adding 50g polyvinyl alcohol (degree of polymerization is 2600), 30g polyacrylamide (degree of polymerization is 7000) and 8g polyacrylic acid (degree of polymerization is 120) additive, stir and make its dissolving then, prepare liquid electrolyte.
Embodiment 18
With 12g NaH 2PO 4, 29g KF, the mixture of 112g KOH and 80g NaOH joins in the 1L ionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.Then to wherein adding poly-(N-N-isopropylacrylamide) (degree of polymerization is 1900) additive of 50g polyethylene glycol (degree of polymerization is 600), 10g poly hydroxy ethyl acrylate (degree of polymerization is 3000), 2g polyvinylpyrrolidone (degree of polymerization is 4500) and 20g, stirring makes its dissolving, prepares liquid electrolyte.
Embodiment 19
With 12g NaH 2PO 4, the mixture of 29g KF and 168g KOH joins in the 1L distilled water, stirs and makes its dissolving, makes alkaline electrolyte solution.Then to wherein adding 2g polypropylene glycol (degree of polymerization is 20), 5g polyvinyl alcohol (degree of polymerization is 850), 10g Sodium Polyacrylate (degree of polymerization is 4600), 2g polyvinylpyrrolidone (degree of polymerization is 9000) and 8g water soluble starch (degree of polymerization is 550) additive, stirring makes its dissolving, prepares liquid electrolyte.
Embodiment 20
With 12g NaH 2PO 4, 29g KF, the mixture of 6g KOH and 72g LiOH joins in the 1L distilled water, stirs and makes its dissolving, makes alkaline electrolyte solution.Then to wherein adding 2g polypropylene glycol (degree of polymerization is 10), poly-(N-N-isopropylacrylamide) (degree of polymerization is 200) of 2g, 2g polyvinyl alcohol (degree of polymerization is 900), 2g polymethylacrylic acid (degree of polymerization is 6700), 2g polyvinylpyrrolidone (degree of polymerization is 10000) and 2g water soluble starch (degree of polymerization is 550) additive, stirring makes its dissolving, prepares liquid electrolyte.
Embodiment 21
With 36g NaH 2PO 4, 6g KF, 5g LiF, the mixture of 80g NaOH and 48g LiOH joins in the 1L deionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.To wherein adding poly-(N-N-isopropylacrylamide) (degree of polymerization is 2000) additive of 5g polypropylene glycol (degree of polymerization is 2000), 0.3g polyethylene glycol (degree of polymerization is 2000) and 0.2g, stir and make its dissolving then, prepare liquid electrolyte.
Embodiment 22
With 28g Na 2HPO 4, 23g KF, the mixture of 5g LiF and 112g KOH joins in the 1L ionized water, stirs and makes its dissolving, makes alkaline electrolyte solution.Then to wherein adding 0.5g polypropylene glycol (degree of polymerization is 100), 0.5g polyethylene glycol (degree of polymerization is 500), 0.2g polymethylacrylic acid (degree of polymerization is 2000), 0.3g Poly(Hydroxyethyl Methacrylate) (degree of polymerization is 8000) additive, stirring makes its dissolving, prepares liquid electrolyte.

Claims (10)

1. liquid electrolyte that is used for zinc-nickel secondary batteries, it is characterized in that: this liquid electrolyte is made up of polymeric additive and alkaline electrolyte solution.
2. liquid electrolyte according to claim 1 is characterized in that: the polymeric additive total amount that contains in the described liquid electrolyte accounts for 0.1%～10% of liquid electrolyte mass fraction.
3. liquid electrolyte according to claim 2 is characterized in that: the polymeric additive total amount that contains in the described liquid electrolyte accounts for 1%～10% of liquid electrolyte mass fraction.
4. liquid electrolyte according to claim 1 is characterized in that: comprise in the described alkaline electrolyte solution: water, hydroxide, phosphate and fluoride.
5. liquid electrolyte according to claim 4 is characterized in that: described water is deionized water, distilled water or ionized water;
The concentration of described hydroxide in alkaline electrolyte solution is the free alkalinity of 3～10mol/L; Hydroxide is selected from a kind of in NaOH, lithium hydroxide, the potassium hydroxide or greater than a kind of mixture;
The concentration of described phosphate in alkaline electrolyte solution is 0.05～0.25mol/L, and phosphate is selected from a kind of in sodium phosphate, potassium phosphate, the lithium phosphate or greater than a kind of mixture; Above-mentioned phosphatic phosphate radical is unit price, divalence or trivalent;
The concentration of described fluoride in alkaline electrolyte solution is 0.01～5mol/L, and fluoride is selected from a kind of in sodium fluoride, lithium fluoride, the potassium fluoride or greater than a kind of mixture.
6. according to claim 1,2 or 3 described liquid electrolytes, it is characterized in that: described polymeric additive is to be dispersed in the liquid electrolyte.
7. liquid electrolyte according to claim 6 is characterized in that: described polymeric additive is that the degree of polymerization is 50～10000 polymer.
8. liquid electrolyte according to claim 7 is characterized in that: described polymeric additive is selected from a kind of in polyacrylic acid, polyacrylate, polyacrylate, polymethylacrylic acid, polymethacrylates, poly-methyl acrylate, polyether polymer, polyacrylamide base polymer, polyvinylpyrrolidone, polyvinyl alcohol, the poly-polysaccharide or greater than a kind of mixture of polymers.
9. liquid electrolyte according to claim 8 is characterized in that: described polyacrylate is a Poly(Hydroxyethyl Methacrylate);
Described polyacrylate is a Sodium Polyacrylate;
Described polymethacrylates is a poly hydroxy ethyl acrylate;
Described poly-methyl acrylate is a sodium polymethacrylate;
Described polyethers polymer is the mixture of polyethylene glycol, polypropylene glycol or polyethylene glycol and polypropylene glycol;
Described polyacrylamide base polymer is the mixture of polyacrylamide, poly-(N-N-isopropylacrylamide) or polyacrylamide and poly-(N-N-isopropylacrylamide).
10. preparation method according to each described liquid electrolyte of claim 1～9 is characterized in that: the mixture of hydroxide, phosphate and fluoride is soluble in water, and stir and make it dissolving, make alkaline electrolyte solution; Then polymeric additive is dissolved in the alkaline electrolyte solution, stirs and make its dissolving, make liquid electrolyte.
CNA2008100579220A 2008-02-21 2008-02-21 Liquid state electrolyte for zinc-nickel secondary batteries and preparing method thereof Pending CN101252204A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102790239A (en) * 2012-08-30 2012-11-21 上海锦众信息科技有限公司 Zinc-silver battery electrolyte preparation method
CN102832419A (en) * 2012-08-30 2012-12-19 上海锦众信息科技有限公司 Preparation method of electrolyte of alkaline zinc battery
CN109818086A (en) * 2017-11-22 2019-05-28 王明煜 A kind of zinc-nickel cell alkaline gelled electrolyte and preparation method thereof, application
CN110010982A (en) * 2018-01-05 2019-07-12 苏州宝时得电动工具有限公司 Battery
CN110212137A (en) * 2019-05-29 2019-09-06 常州优特科新能源科技有限公司 A kind of preparation method and application of zinc system alkaline battery diaphragm
CN111463499A (en) * 2020-03-18 2020-07-28 山东合泰新能源有限公司 Electrolyte for secondary zinc-nickel battery
CN114094205A (en) * 2021-10-27 2022-02-25 山东合泰新能源有限公司 Colloidal electrolyte and preparation method and application thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102790239A (en) * 2012-08-30 2012-11-21 上海锦众信息科技有限公司 Zinc-silver battery electrolyte preparation method
CN102832419A (en) * 2012-08-30 2012-12-19 上海锦众信息科技有限公司 Preparation method of electrolyte of alkaline zinc battery
CN109818086A (en) * 2017-11-22 2019-05-28 王明煜 A kind of zinc-nickel cell alkaline gelled electrolyte and preparation method thereof, application
CN110010982A (en) * 2018-01-05 2019-07-12 苏州宝时得电动工具有限公司 Battery
CN110212137A (en) * 2019-05-29 2019-09-06 常州优特科新能源科技有限公司 A kind of preparation method and application of zinc system alkaline battery diaphragm
CN111463499A (en) * 2020-03-18 2020-07-28 山东合泰新能源有限公司 Electrolyte for secondary zinc-nickel battery
CN111463499B (en) * 2020-03-18 2021-12-28 山东合泰新能源有限公司 Electrolyte for secondary zinc-nickel battery
CN114094205A (en) * 2021-10-27 2022-02-25 山东合泰新能源有限公司 Colloidal electrolyte and preparation method and application thereof

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