CN1104377A - Lithium cell electrolyte and its preparation method - Google Patents
Lithium cell electrolyte and its preparation method Download PDFInfo
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- CN1104377A CN1104377A CN 94114864 CN94114864A CN1104377A CN 1104377 A CN1104377 A CN 1104377A CN 94114864 CN94114864 CN 94114864 CN 94114864 A CN94114864 A CN 94114864A CN 1104377 A CN1104377 A CN 1104377A
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- cyclic ethers
- dioxolane
- compound cyclic
- oxygen
- lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
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- Primary Cells (AREA)
Abstract
There is provided a kind of special electrolyte for lithium-manganese dioxide battery, the solution of the electrolyte is prepared by composite cyclic ether including pentacyclic dioxide, decacyclic tetroxide, dodecyclic tetroxide, hexacyclic dioxide, and 1,2-propylene-carbonic ester, glycol-dimethyl ether added with solute lithium perchlorate, its concentration is 0.l8-1.25 M. The composite cyclic ether is prepared from ethandiol, polyformaldehyde, surfuric acid, urea, sodium carbonate through condensation, dealdehydation, and water elimination. The battery with present electrolyte has large current desnity and improved low temperature performance.
Description
The present invention relates to chemical power source electrolyte, particularly a kind of lithium-manganese dioxide battery special electrolysis liquid and preparation method thereof.
Lithium-manganese dioxide battery is since invention and commercially producing, and the solute of the prescription that its electrolyte is continued to use is a lithium perchlorate, and solvent is that 1.2-propylene glycol carbonic ester adds glycol dimethyl ether, and the concentration of lithium perchlorate in electrolyte is 1M.Adopt the lithium-manganese dioxide battery current density of this electrolyte less, in the time of 20 ℃, can only reach 0.5-1.0mA/cm usually
2; Poor performance at low temperatures, current density drops to 0.1-0.5mA/cm in the time of 0 ℃
2, drop to 0.1mA/cm in the time of-20 ℃
2Below, can not loading in the time of-40 ℃; Because 1.2-propylene glycol carbonic ether trace in acid medium decomposes, also make the battery can not long term storage.
The purpose of this invention is to provide a kind of current density that can improve lithium-manganese dioxide battery, electrolyte of cryogenic property and anti-shelf characteric and preparation method thereof.
For finishing the lithium-manganese dioxide battery special electrolysis liquid that goal of the invention is developed, form by solute lithium perchlorate and double solvents, the concentration of lithium perchlorate in electrolyte is 0.8-1.25M, double solvents comprises the close compound cyclic ethers based on dioxolane of ring diameter, 1.2-propylene glycol carbonic ester, glycol dimethyl ether, and the volume ratio that respectively contains thing is:
Compound cyclic ethers 40-60
1.2-propylene glycol carbonic ester 1-30
Glycol dimethyl ether 1-30
For improving the complexing power of compound cyclic ethers to lithium ion, compound cyclic ethers preferably contains the close dioxolane of ring diameter, four oxygen bull's eyes, four oxygen, 12 rings, these several cyclic ethers of dioxane, and each cyclic ethers volume ratio is:
Dioxolane 80-90
Four oxygen bull's eye 3-6
Four oxygen, 12 ring 1-3
Dioxane 4-8
The preparation method of lithium-manganese dioxide battery special electrolysis liquid of the present invention is: be solute with the lithium perchlorate, with the double solvents preparation electrolyte that comprises compound cyclic ethers based on dioxolane, 1.2-propylene glycol carbonic ester, glycol dimethyl ether, the concentration of lithium perchlorate in electrolyte is 0.8-1.25M; Each inclusion volume ratio of double solvents is:
Compound cyclic ethers 40-60
1.2-propylene glycol carbonic ester 1-30
Glycol dimethyl ether 1-30
The preparation method of the compound cyclic ethers of wherein crucial thing is:
Raw materials used and weight ratio:
Ethylene glycol 55-70
Paraformaldehyde 25-35
Sulfuric acid 0.5-3
Urea 0.1-2.5
Sodium carbonate 0.1-2.5
NaOH 1.0-1.7
Sodium chloride 1.0-1.7
Sodium metal 0.3-3
Preparation method's technological process:
(I) condensation: allocate ethylene glycol, paraformaldehyde, sulfuric acid into distilling apparatus in proportion, and stir evenly, after 35-60 ℃ of liquid temperature reacted 3-5 hour down, condensate liquid is collected in the distillation that heats up, until 65-100 ℃, condensate liquid is compound cyclic ethers crude product, compound cyclic ethers crude product is added with separatory funnel heavy-fluid is discarded after sodium chloride fully stirs.
(II) full gear: the compound cyclic ethers crude product that will discard heavy-fluid adds urea and sodium carbonate is put into the boiling of distilling apparatus Fast Heating, distill out liquid after making it to reflux 6 to 10 hours to boiling range below 95 ℃, the liquid hydro-oxidation sodium that distills out is fully stirred the back leak half with separatory heavy-fluid is discarded.
(III) dealcoholysis, dehydration: the coincidence cyclic ethers that will discard heavy-fluid adds the sodium metal heating to be made it to reflux, distillation after 8 hours, boiling range is 70-85 ℃, the distillation gleanings is for containing the compound cyclic ethers elaboration of dioxolane, four oxygen bull's eyes, four oxygen, 12 rings, dioxane, to be used to prepare the electrolyte of lithium-manganese dioxide battery.
The compound cyclic ethers of purifying with method of the present invention preparation earlier more directly uses with each single cyclic ethers reagent such as dioxolane composite complex loop ether solvents after purifying, not only result of use significantly improves, make electrolyte have good electrical property, and can be significantly reduced to this.
Use the lithium-manganese dioxide battery of electrolyte of the present invention, its current density reaches 3.0-6.0mA/cm in the time of 20 ℃
2, the current density in the time of 0 ℃ is 1.5-3mA/cm
2, the current density in the time of-20 ℃ is 1-2mA/cm
2, the current density in the time of-40 ℃ is 0.5-1mA/cm
2Be much higher than the lithium-manganese dioxide battery that uses existing electrolyte.And the shelf characteric of battery is obviously improved.
Below be embodiments of the invention.
Embodiment one: with 8 liters of close compound cyclic ethers and 6 liters of 1.2-propylene glycol carbonic esters based on dioxolane in ring footpath, 6 liters of glycol dimethyl ethers are hybridly prepared into solvent, adding lithium perchlorate to its concentration again is 0.8M, makes the lithium-manganese dioxide battery special electrolysis liquid.
Embodiment two: 60 liters of close compound cyclic ethers based on dioxolane in ring footpath are mixed with 1 liter of 1.2-propylene glycol carbonic ester and 30 liters of glycol dimethyl ethers, the preparation solvent, adding lithium perchlorate to its concentration again is 1.0M, becomes the lithium-manganese dioxide battery special electrolysis liquid.
Embodiment three, 50 liters of compound cyclic ethers based on dioxolane mixed with 20 liters of 1.2-propylene glycol carbonic esters and 10 liters of glycol dimethyl ethers, and the preparation solvent, adding lithium perchlorate to its concentration again is 1.25M, becomes the lithium-manganese dioxide battery special electrolysis liquid.
Embodiment four, earlier 80 liters of dioxolanes, 6 liter of four oxygen bull's eye, 1 liter of four oxygen 12 ring, 6 liters of dioxane are made into compound cyclic ethers, again with 70 liters of 1.2-propylene glycol carbonic esters, 70 liters of glycol dimethyl ether preparation solvents, adding lithium perchlorate to its concentration again is 0.8M, is made for the lithium-manganese dioxide battery special electrolysis liquid.
Embodiment five, 90 liters of dioxolanes, 5 liter of four oxygen bull's eye, 3 liter of four oxygen 12 ring, 8 liters of dioxane are made into compound cyclic ethers, again with 2 liters of 1.2-propylene glycol carbonic esters and 53 liters of glycol dimethyl ether preparation solvents, adding lithium perchlorate to its concentration then is 1.25M, is made for the lithium-manganese dioxide battery special electrolysis liquid.
Embodiment six, 85 liters of dioxolanes, 3 liter of four oxygen bull's eye, 2 liter of four oxygen 12 ring, 4 liters of dioxane are made into compound cyclic ethers, be mixed into solvent with 43 liters of 1.2-propylene glycol carbonic esters, 22 liters of glycol dimethyl ethers again, adding lithium perchlorate to concentration then is 1.0M, is made for the lithium-manganese dioxide battery special electrolysis liquid.
Embodiment seven, are the compound cyclic ethers of feedstock production with 55 kilograms of ethylene glycol, 35 kilograms of paraformaldehydes, 3 kilograms of sulfuric acid, 2.5 kilograms of urea, 1 kilogram of sodium carbonate, 1.7 kilograms of NaOH, 1 kilogram of sodium chloride, 2 kilograms of sodium metals earlier.
(I) condensation: ethylene glycol, paraformaldehyde, sulfuric acid are put into distilling apparatus and stirred evenly, after 35-60 ℃ of liquid temperature reacted 3-5 hour down, condensate liquid is collected in the distillation that heats up, until 65-100 ℃, condensate liquid is compound cyclic ethers crude product, compound cyclic ethers crude product is added with separatory funnel heavy-fluid is discarded after sodium chloride fully stirs.
(II) full gear: the compound cyclic ethers crude product that will discard heavy-fluid adds urea and sodium carbonate is put into the boiling of distilling apparatus Fast Heating, distills out liquid after making it to reflux 6 to 10 hours, and hydro-oxidation sodium fully stirs the back and with separatory funnel heavy-fluid discarded.
(III) dealcoholysis, dehydration: the compound cyclic ethers that will discard heavy-fluid adds the sodium metal heating to be made it to reflux, distillation after 8 hours, and boiling range is 70-80 ℃, the distillation gleanings is for containing the compound cyclic ethers elaboration of dioxolane, four oxygen bull's eyes, four oxygen, 12 rings, dioxane.
Get 8 liters of compound cyclic ethers elaboration and 6 liters of 1.2-propylene glycol carbonic esters, 6 liters of glycol dimethyl ethers are mixed into solvent, adding lithium perchlorate to its concentration again is 0.8M, becomes lithium-manganese dioxide battery electrolyte.
Embodiment 8, prepare compound cyclic ethers elaboration with 70 kilograms of ethylene glycol, 25 kilograms of paraformaldehydes, 0.5 kilogram of sulfuric acid, 0.1 kilogram of urea, 0.1 kilogram of sodium carbonate, 1 kilogram of NaOH, 1.7 kilograms of sodium chloride, 0.3 kilogram of sodium metal by embodiment seven steps (I) (II) (III) earlier.
Get 60 liters of compound cyclic ethers elaboration and 1 liter of 1.2-propylene glycol carbonic ester, 30 liters of glycol dimethyl ethers are mixed into solvent, adding lithium perchlorate to its concentration again is 1.0M, becomes lithium-manganese dioxide battery electrolyte.
Embodiment nine, are that raw material is prepared compound cyclic ethers elaboration by embodiment seven steps (I) (II) (III) with 60 kilograms of ethylene glycol, 30 kilograms of paraformaldehydes, 2 kilograms of sulfuric acid, 1.5 kilograms of urea, 2.5 kilograms of sodium carbonate, 1.5 kilograms of NaOH, 1.3 kilograms of sodium chloride, 1 kilogram of sodium metal earlier.
Get 50 liters of compound cyclic ethers elaboration and 20 liters of 1.2-propylene glycol carbonic esters, 10 liters of glycol dimethyl ethers are mixed into solvent, adding lithium perchlorate to its concentration again is 1.25M, becomes lithium-manganese dioxide battery electrolyte.
Claims (3)
1, a kind of lithium-manganese dioxide battery special electrolysis liquid, form by solute lithium perchlorate and double solvents, the concentration that it is characterized in that said solute lithium perchlorate is 0.8-1.25M, double solvents comprises compound cyclic ethers, propylene glycol carbonic ester, the glycol dimethyl ether based on dioxolane, and the volume ratio that respectively contains thing is:
Compound cyclic ethers 40-60 based on dioxolane
1.2-propylene glycol carbonic ester 1-30
Glycol dimethyl ether 1-30
2, lithium-manganese dioxide battery special electrolysis liquid according to claim 1 is characterized in that said compound cyclic ethers contains dioxolane, four oxygen bull's eyes, four oxygen, 12 rings, dioxane, and each cyclic ethers volume ratio is:
Dioxolane 80-90
Four oxygen bull's eye 3-6
Four oxygen, 12 ring 1-3
Dioxane 4-8
3, a kind of preparation method of lithium-manganese dioxide battery special electrolysis liquid is characterized in that:
Solute lithium perchlorate concentration is 0.8-1.25M in a, the electrolyte;
B, double solvents comprise compound cyclic ethers, 1.2-propylene glycol carbonic ester, glycol dimethyl ether, and each inclusion volume ratio is:
Compound cyclic ethers 40-60 based on dioxolane
1.2-propylene glycol carbonic ester 1-30
Glycol dimethyl ether 1-30
C, wherein the preparation method based on the compound cyclic ethers of dioxolane is:
Raw material and weight ratio:
Ethylene glycol 55-70
Paraformaldehyde 25-35
Sulfuric acid 0.5-3
Urea 0.1-2.5
Sodium carbonate 0.1-2.5
NaOH 1.0-1.7
Sodium chloride 1.0-1.7
Sodium metal 0.3-3
Technological process:
(I) condensation: allocate ethylene glycol, paraformaldehyde, carbonic acid into distilling apparatus in proportion, and stir evenly, after 35-60 ℃ of liquid temperature reacted 3-5 hour down, condensate liquid is collected in the distillation that heats up, until 65-100 ℃, condensate liquid is compound cyclic ethers crude product, compound cyclic ethers crude product is added with separatory funnel heavy-fluid is discarded after sodium chloride fully stirs.
(II) full gear: the compound cyclic ethers crude product that will discard heavy-fluid adds urea and sodium carbonate is put into the boiling of distilling apparatus Fast Heating, distill out liquid after making it to reflux 6 to 10 hours to boiling range below 95 ℃, the liquid hydro-oxidation sodium that distills out is fully stirred the back leak half with separatory heavy-fluid is discarded.
(III) dealcoholysis, dehydration: the coincidence cyclic ethers that will discard heavy-fluid adds the sodium metal heating to be made it to reflux, distillation after 8 hours, and boiling range is 70-85 ℃, the distillation gleanings is for containing the compound cyclic ethers elaboration of dioxolane, four oxygen bull's eyes, four oxygen, 12 rings, dioxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94114864 CN1104377A (en) | 1994-08-15 | 1994-08-15 | Lithium cell electrolyte and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94114864 CN1104377A (en) | 1994-08-15 | 1994-08-15 | Lithium cell electrolyte and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1104377A true CN1104377A (en) | 1995-06-28 |
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| CN 94114864 Pending CN1104377A (en) | 1994-08-15 | 1994-08-15 | Lithium cell electrolyte and its preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314960C (en) * | 2004-12-10 | 2007-05-09 | 张家港市国泰华荣化工新材料有限公司 | Method for measurement of solvent in lithium ion battery electrolyte |
| CN101174697B (en) * | 2007-11-21 | 2010-12-08 | 天津和平安耐高能电池科技有限公司 | Minitype lithium-manganese dioxide battery electrolyte |
| CN113248468A (en) * | 2021-06-28 | 2021-08-13 | 苏州百灵威超精细材料有限公司 | 12-crown ether-4 lithium salt complex and preparation method and application thereof |
-
1994
- 1994-08-15 CN CN 94114864 patent/CN1104377A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314960C (en) * | 2004-12-10 | 2007-05-09 | 张家港市国泰华荣化工新材料有限公司 | Method for measurement of solvent in lithium ion battery electrolyte |
| CN101174697B (en) * | 2007-11-21 | 2010-12-08 | 天津和平安耐高能电池科技有限公司 | Minitype lithium-manganese dioxide battery electrolyte |
| CN113248468A (en) * | 2021-06-28 | 2021-08-13 | 苏州百灵威超精细材料有限公司 | 12-crown ether-4 lithium salt complex and preparation method and application thereof |
| CN113248468B (en) * | 2021-06-28 | 2021-10-19 | 苏州百灵威超精细材料有限公司 | 12-crown ether-4 lithium salt complex and preparation method and application thereof |
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