CN104577201A - Electrolyte for lithium-carbon fluoride battery - Google Patents
Electrolyte for lithium-carbon fluoride battery Download PDFInfo
- Publication number
- CN104577201A CN104577201A CN201310478283.6A CN201310478283A CN104577201A CN 104577201 A CN104577201 A CN 104577201A CN 201310478283 A CN201310478283 A CN 201310478283A CN 104577201 A CN104577201 A CN 104577201A
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- Prior art keywords
- battery
- lithium
- electrolyte
- solvent
- sulfite
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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
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to an electrolyte for a lithium-carbon fluoride battery. The electrolyte for the lithium-carbon fluoride battery comprises a mixed solution which is formed by lithium salt and a solvent. The lithium for the lithium-carbon fluoride battery is characterized in that the solvent is a sulfur-containing group compound; the concentration of the lithium salt in the mixed solution is 1 plus/minus 0.8mol*L<-1>; the sulfur-containing group compound is one of DMSO, TMS, dimethyl sulfite, diethyl sulfite, glycol sulfite, glycol sulfate, propylene sulfite, propylene sulfate and butylene sulfite. According to the electrolyte, the sulfur-containing group compound is used as a solvent in the electrolyte, so that the electrolyte is in better compatibility with a carbon fluoride positive material; meanwhile, a sulfur-containing group solvent can be used for remarkably improving the conductivity of the electrolyte, reducing the viscosity of the electrolyte and increasing the migration rate of Li<+>, so that the discharging voltage of the lithium-carbon fluoride battery is improved, the discharging current density of the battery is increased and the discharging specific energy of the battery is improved.
Description
Technical field
The invention belongs to lithium battery material technical field, particularly relate to a kind of lithium-fluorocarbons battery electrolytic solution.
Background technology
Lithium metal primary cell is of a great variety, there is higher specific energy and operating voltage, the comparatively ripe system of current development mainly contains lithium-manganese dioxide battery, lithium-thionyl chloride battery, lithium-sulfur dioxide battery etc., and energy density generally can reach 250-350Wh/kg.In recent years, lithium-fluorocarbons battery is because having more high-energy-density advantage and receiving much concern, and the energy density of this battery system can reach 500Wh/kg at present, and still tool has greater room for improvement.The electrolyte be mixed with by electrolyte and solvent is one of important component part of battery, and the performance of its physicochemical property to battery material performance plays vital effect.
At present, the electrolyte of lithium-manganese dioxide battery system mainly continued to use by the electrolyte that lithium-fluorocarbons battery uses, and main formula is: LiClO
4as electrolyte, propene carbonate or glycol dimethyl ether are as solvent.Because manganese dioxide is different from the performance of fluorocarbons, the compatibility of electrolyte of fluorocarbons and lithium-manganese dioxide battery system is poor, the lithium adopting above-mentioned electrolyte to make-fluorocarbons battery not only in discharge process because heat production causes potential safety hazard, and constrain fluorocarbons in the battery to the performance of discharge current density, multiplying power discharging property, discharge voltage plateau and battery energy density, cause lithium-fluorocarbons battery discharge current density, discharge voltage plateau and battery energy density low, multiplying power discharging property is poor.
Summary of the invention
The present invention provides a kind of good with fluorocarbons compatibility for solving in known technology the technical problem that exists, lithium-fluorocarbons battery discharge current density, discharge voltage plateau and energy density can be improved, improve a kind of lithium-fluorocarbons battery electrolytic solution of multiplying power discharging property.
The present invention includes following technical scheme:
A kind of lithium-fluorocarbons battery electrolytic solution, comprises the mixed solution of lithium salts and solvent formation, is characterized in: described solvent is the compound of sulfur-containing group; In described mixed solution, the concentration of lithium salts is 1 ± 0.8moll
-1.
The present invention can also adopt following technical measures:
The compound of described sulfur-containing group is the one of DMSO, TMS, dimethyl sulfite, sulfurous acid diethyl ester, glycol sulfite, ethyl sulfate, propylene sulfite, sulfuric acid propylene, butylene sulfite.
Described lithium salts is LiBF
4, LiPF
6, LiAsF
6, LiClO
4, LiBOB, LiDFOB, LiCF
3sO
3, LiN (SO
2cF
3), LiC (SO
2cF
3)
3in one or more mixture.
The advantage that the present invention has and good effect:
1, the present invention adopts the compound of sulfur-containing group as the solvent in electrolyte, and electrolyte and fluorocarbons positive electrode can be made to have better compatibility, and meanwhile, sulfur-containing group solvent can significantly improve the conductivity of electrolyte, reduces electrolyte viscosity, improves Li
+migration rate, thus improve the discharge voltage of lithium-fluorocarbons battery, improve battery discharge current density, promote the electric discharge specific energy of battery.
2, the present invention adopts and carries out mixed preparing lithium-fluorocarbons battery electrolyte containing element sulphur solvent and organic and inorganic anion electrolyte lithium salt, can improve discharge voltage plateau further, improve the specific energy that discharges.
3, the present invention makes simply, practical, has a wide range of applications.
Accompanying drawing explanation
The electrolyte of Fig. 1 to be DMSO of the present invention be solvent is assembled into the discharge curve comparison diagram that battery and commercially available lithium-manganese dioxide battery electrolyte are assembled into battery;
Fig. 2 is the discharge curve that sulfolane base of the present invention is solvent, LiCLO4 is lithium salts electrolyte is assembled into battery;
The electrolyte that Fig. 3 is DMSO of the present invention is solvent, LiTFSI is lithium salts is assembled into the discharge curve that battery carries out different multiplying;
Fig. 4 is impedance spectrum resolution chart before and after battery discharge in Fig. 3.
Embodiment
For summary of the invention of the present invention, Characteristic can be disclosed further, be also described in detail as follows by reference to the accompanying drawings especially exemplified by following instance.
A kind of lithium-fluorocarbons battery electrolytic solution, comprises the mixed solution of lithium salts and solvent formation, is characterized in: described solvent is the compound of sulfur-containing group; In described mixed solution, the concentration of lithium salts is 1 ± 0.8moll
-1.
The compound of described sulfur-containing group is the one of DMSO, TMS, dimethyl sulfite, sulfurous acid diethyl ester, glycol sulfite, ethyl sulfate, propylene sulfite, sulfuric acid propylene, butylene sulfite.
Described lithium salts is LiBF
4, LiPF
6, LiAsF
6, LiClO
4, LiBOB, LiDFOB, LiCF
3sO
3, LiN (SO
2cF
3), LiC (SO
2cF
3)
3in one or more mixture.
Manufacturing process of the present invention
Embodiment 1:
(1), in the room temperature glove box being full of argon gas, take the LiPF of 3.038g respectively
6with the DMSO of 25g;
(2) the LiPF will taken
6be placed in the volumetric flask of 20ml, drip DMSO solvent to 2/3rds places of volumetric flask, shake up until lithium salts dissolves completely gently, form mixed solution;
(3) continue instillation DMSO to volumetric flask graduation mark place, rock volumetric flask, mix to solution, make LiPF in mixed solution
6concentration reach 1moll
-1, namely form lithium-fluorocarbons battery electrolyte.
Embodiment 2:
(1), in the room temperature glove box being full of argon gas, take the LiClO of 2.128g respectively
4with the DMSO of 25g;
(2) the LiClO will taken
4be placed in the volumetric flask of 20ml, drip DMSO solvent to 2/3rds places of volumetric flask, shake up until lithium salts dissolves completely gently, form mixed solution;
(3) continue instillation DMSO to volumetric flask graduation mark place, rock volumetric flask, mix to solution, make LiClO in mixed solution
4concentration reach 1moll
-1, namely form lithium-fluorocarbons battery electrolyte.
Embodiment 3:
(1), in the room temperature glove box being full of argon gas, take the DMSO of LiTFSI and 25g of 5.742g respectively;
(2) the LiTFSI taken is placed in the volumetric flask of 20ml, drips DMSO solvent to 2/3rds places of volumetric flask, shake up until lithium salts dissolves completely gently, form mixed solution;
(3) continue instillation DMSO to volumetric flask graduation mark place, rock volumetric flask, mix to solution, make the concentration of LiTFSI in mixed solution reach 1moll
-1, namely form lithium-fluorocarbons battery electrolyte.
Embodiment 4:
(1), in the room temperature glove box being full of argon gas, take the LiCLO of 2.66g respectively
4with the solvent sulfolane of 25g;
(2) the LiCLO will taken
4be placed in the volumetric flask of 25ml, drip sulfolane solvent to 2/3rds places of volumetric flask, shake up until lithium salts dissolves completely gently, form mixed solution;
(3) continue instillation sulfolane to volumetric flask graduation mark place, rock volumetric flask, mix to solution, make LiCLO in mixed solution
4concentration reach 1moll
-1, namely form lithium-fluorocarbons battery electrolyte.
Comparative example
Commercially available lithium-manganese dioxide battery electrolyte, primary solvent is propene carbonate, glycol dimethyl ether, and electrolyte lithium salt is lithium perchlorate, and lithium salt is 1moll
-1.
Make lithium-fluorocarbons battery:
Under room temperature, fluorographite positive electrode, conductive agent SP, bonding agent polyvinylidene fluoride (PVDF) are carried out homogenate according to the ratio of 85:7:8, solvent is METHYLPYRROLIDONE (NMP), solid content is 25%, evenly be coated on the thick aluminium foil of 0.02mm, through oven dry, roll-in, cut-parts, make the fluorocarbons electrode film of Φ 16mm;
Positive pole is unified adopts fluorocarbons electrode film, and negative pole adopts metal lithium electrode, and electrolyte adopts the electrolyte in embodiment 1, embodiment 2, embodiment 3, embodiment 4 and comparative example to produce CR2430 lithium-fluorocarbons battery respectively successively.The battery that the battery that the battery that the battery that in embodiment 1, electrolyte makes is 1# battery, electrolyte makes in embodiment 2 is 2# battery, electrolyte makes in embodiment 3 is 3# battery, electrolyte makes in embodiment 4 is the battery that in 4# battery, comparative example, electrolyte makes is 5# battery.
Battery multiplying power discharging and testing impedance test:
1,1# battery, 2# battery, 3# battery and 5# battery multiplying power discharging test:
1# battery, 2# battery, 3# battery and 5# battery being completed after shelving 24 hours, is 0.1C at discharge-rate, and discharge cut-off voltage is carry out discharge test, test result discharge curve as shown in Figure 1 under 1.5 laid shoot parts; 1# battery, 2# battery, 3# battery are the battery of the electrolyte assembling of DMSO solvent, and discharge platform is 2.7 volts; 5# battery is the battery of commercially available lithium-manganese dioxide battery electrolyte assembling, and discharge platform is 2.5 volts, and platform voltage improves 0.2 volt; Result of the test shows, lithium-fluorocarbons battery that the electrolyte adopting the present invention to make is made improves discharge voltage plateau and electric discharge specific energy.
2,4# battery multiplying power discharging test:
Being completed by above-mentioned 4# battery after shelving 24 hours, is 0.1C at discharge-rate, and discharge cut-off voltage is carry out discharge test, test result discharge curve as shown in Figure 2 under 1.5 laid shoot parts; From accompanying drawing 2, although the viscosity of solvent sulfolane is slightly large, after mixing with lithium perchlorate, 0.1C still can release the specific discharge capacity of 786.6mAh/g, and visible sulfur-containing group solvent can significantly improve the conductivity of electrolyte, improves Li
+migration rate, effectively improve the multiplying power discharging property of battery.
3, the electric discharge of 3# battery different multiplying condition and the testing impedance test of electric discharge front and back:
By above-mentioned 3# battery respectively with 0.1C, 0.5C and 1C multiplying power discharging, discharge cut-off voltage is carry out discharge test, test result discharge curve as shown in Figure 3 under 1.5 laid shoot parts; Carry out impedance spectrum test with defeated power forceful electric power chem workstation, amplitude is 5mv/s, and frequency range is 0.01 ~ 10
6hZ, carry out testing impedance to before and after the electric discharge of 3# battery different multiplying, the impedance magnitude comparing result of test as shown in Figure 4.The data of Fig. 3 and Fig. 4 show, the battery impedance after electric discharge is significantly less than the battery impedance before electric discharge, and test shows that sulfur-containing group solvent can significantly improve the conductivity of electrolyte, reduce electrolyte viscosity, improve Li
+migration rate, thus improve the discharge voltage of lithium-fluorocarbons battery, improve battery discharge current density, promote the electric discharge specific energy of battery.
Although be described the preferred embodiments of the present invention by reference to the accompanying drawings above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not departing under the ambit that present inventive concept and claim protect, a lot of form can also be made.These all belong within protection scope of the present invention.
Claims (3)
1. lithium-fluorocarbons battery electrolytic solution, comprises the mixed solution of lithium salts and solvent formation, it is characterized in that: described solvent is the compound of sulfur-containing group; In described mixed solution, the concentration of lithium salts is 1 ± 0.8moll
-1.
2. a kind of lithium-fluorocarbons battery electrolytic solution according to claim 1, is characterized in that: the compound of described sulfur-containing group is the one of DMSO, TMS, dimethyl sulfite, sulfurous acid diethyl ester, glycol sulfite, ethyl sulfate, propylene sulfite, sulfuric acid propylene, butylene sulfite.
3. a kind of lithium-fluorocarbons battery electrolytic solution according to claim 1, is characterized in that: described lithium salts is LiBF
4, LiPF
6, LiAsF
6, LiClO
4, LiBOB, LiDFOB, LiCF
3sO
3, LiN (SO
2cF
3), LiC (SO
2cF
3)
3in one or more mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310478283.6A CN104577201A (en) | 2013-10-14 | 2013-10-14 | Electrolyte for lithium-carbon fluoride battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310478283.6A CN104577201A (en) | 2013-10-14 | 2013-10-14 | Electrolyte for lithium-carbon fluoride battery |
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| Publication Number | Publication Date |
|---|---|
| CN104577201A true CN104577201A (en) | 2015-04-29 |
Family
ID=53092758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310478283.6A Pending CN104577201A (en) | 2013-10-14 | 2013-10-14 | Electrolyte for lithium-carbon fluoride battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450365A (en) * | 2016-07-22 | 2017-02-22 | 惠州市惠德瑞锂电科技股份有限公司 | Anticorrosive electrolyte of lithium battery and obtained lithium primary battery |
| CN107706433A (en) * | 2016-08-08 | 2018-02-16 | 中国电子科技集团公司第十八研究所 | A kind of lithium fluorocarbon battery sulfur-bearing electrolyte and its application |
| CN114551979A (en) * | 2022-02-22 | 2022-05-27 | 厦门永力鑫新能源科技有限公司 | Electrolyte and galvanic cell using same |
| US11489205B2 (en) | 2017-11-15 | 2022-11-01 | Xiamen University | Primary lithium battery |
-
2013
- 2013-10-14 CN CN201310478283.6A patent/CN104577201A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450365A (en) * | 2016-07-22 | 2017-02-22 | 惠州市惠德瑞锂电科技股份有限公司 | Anticorrosive electrolyte of lithium battery and obtained lithium primary battery |
| CN107706433A (en) * | 2016-08-08 | 2018-02-16 | 中国电子科技集团公司第十八研究所 | A kind of lithium fluorocarbon battery sulfur-bearing electrolyte and its application |
| US11489205B2 (en) | 2017-11-15 | 2022-11-01 | Xiamen University | Primary lithium battery |
| CN114551979A (en) * | 2022-02-22 | 2022-05-27 | 厦门永力鑫新能源科技有限公司 | Electrolyte and galvanic cell using same |
| CN114551979B (en) * | 2022-02-22 | 2023-11-07 | 厦门永力鑫新能源科技有限公司 | Electrolyte and primary cell using same |
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Application publication date: 20150429 |