CN108615943A - Sulfur-containing organic solvent electrolyte, lithium-iron disulfide battery and preparation method thereof - Google Patents
Sulfur-containing organic solvent electrolyte, lithium-iron disulfide battery and preparation method thereof Download PDFInfo
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- CN108615943A CN108615943A CN201810432157.XA CN201810432157A CN108615943A CN 108615943 A CN108615943 A CN 108615943A CN 201810432157 A CN201810432157 A CN 201810432157A CN 108615943 A CN108615943 A CN 108615943A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses an organic solvent, and particularly relates to a sulfur-containing organic solvent electrolyte, a lithium-iron disulfide battery adopting the electrolyte, and a preparation method of the lithium-iron disulfide battery. A sulfur-containing organic solvent electrolyte composed of an organic solvent and a lithium salt; the organic solvent is formed by mixing sulfolane and at least one of propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, tetrahydrofuran, 2-methyl tetrahydrofuran, 1,3-dioxolane, 1,2-dimethoxyethane, acetonitrile, dimethyl amide, triphenyl phosphate and gamma-butyrolactone; in the organic solvent, the volume ratio of sulfolane is more than or equal to 33%. The sulfur-containing organic solvent electrolyte improves the high-current discharge performance and the discharge platform of the electrolyte.
Description
Technical Field
The invention relates to an organic solvent, in particular to a sulfur-containing organic solvent electrolyte, a lithium-iron disulfide battery adopting the electrolyte and a preparation method of the lithium-iron disulfide battery.
Background
Li-FeS 2 The battery is FeS 2 A lithium battery in which Li is an anode active material. The working voltage is 1.5V, and the battery is matched with a common electric appliance and can directly replace a standard aqueous solution battery. The battery has the advantages of large specific energy, high capacity and long storage time, has interchangeability with the alkaline zinc-manganese and carbon-zinc primary batteries widely used in the market at present, and can be widely applied to instruments and meters such as cameras, MP3, hearing aids, video cameras, industrial PCs, computer RAMs, CMOS circuit memory supporting power supplies, radio communication, various military communication radio stations, medical equipment, portable communication equipment, timers, counters and the like, and portable electrical equipment such as walkmans and the like. The battery has a huge development prospect because the battery is widely available in the civil market and the industrial market.
The rapid update of diversification and miniaturization of the existing electronic appliances promotes the progress of the battery, and the battery is required to have high specific energy and specific power, long service life, proper price and convenient use. The rapid development of small-sized electric appliances has enabled the market for small-sized civil batteries to multiply the number requirements, and to require a large variety, a long shelf life, a high primary capacity and a small volume. However, the current market condition is that low-grade batteries dominate, and the requirement of heavy load work of electric appliances in the market is far from being met. Existing Li-FeS 2 The discharge performance of the battery is not perfect enough, and the main problems are that the battery capacity is not large, the discharge efficiency is low, and the discharge performance of the battery is relatively poor.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the sulfur-containing organic solvent electrolyte with good discharge performance.
In order to realize the purpose, the invention adopts the following technical scheme:
a sulfur-containing organic solvent electrolyte is composed of an organic solvent and a lithium salt; the organic solvent is formed by mixing sulfolane with at least one of propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 1,2-dimethoxyethane, acetonitrile, dimethyl amide, triphenyl phosphate and gamma-butyrolactone; in the organic solvent, the volume ratio of the sulfolane is more than or equal to 33 percent.
Preferably, in the organic solvent, the volume ratio of the sulfolane is 33-75%, and the volume ratio of the rest organic solvent is 25-67%; the concentration of the lithium salt dissolved in the organic solvent is 0.01-2.5 mol/L.
Preferably, in the organic solvent, the volume ratio of the sulfolane is 33-55%, and the volume ratio of the rest organic solvent is 45-67%; the concentration of the lithium salt dissolved in the organic solvent is 0.01-1.5 mol/L.
Preferably, in the organic solvent, the volume ratio of the sulfolane is 33-45%, and the volume ratio of the rest organic solvent is 55-67%; the concentration of the lithium salt dissolved in the organic solvent is 0.01-1.5 mol/L.
Preferably, the lithium salt is at least one of lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium iodide, lithium nitrate, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonylimide and lithium bisoxalato borate.
Has the advantages that: the sulfur-containing organic solvent electrolyte consists of an organic solvent and lithium salt, wherein the organic solvent is formed by mixing the raw materials, particularly in the organic solvent, the volume ratio of sulfolane is more than or equal to 33%, and the high-current discharge performance and the discharge platform of the electrolyte are improved.
The invention also provides a lithium-iron disulfide battery with good discharge performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium-iron disulfide battery comprises a battery shell, a battery core arranged in the battery shell, and the sulfur-containing organic solvent electrolyte injected into the battery shell.
Preferably, the battery cell comprises a positive plate, a negative plate and a diaphragm; the positive plate is prepared by coating positive active slurry on a metal strip material matrix.
The positive active slurry comprises the following raw materials in parts by weight:
wherein the average particle size of the iron disulfide powder is 30-44 μm, and the inherent pH value is 2.0-6.0;
the binder is any one of CMC (carboxymethyl cellulose), PTFE (polytetrafluoroethylene) and PVDF (polyvinylidene fluoride);
the conductive agent is any one of carbon black, acetylene black, conductive graphite and metal powder.
Preferably, the iron disulfide powder has an average particle diameter of 30 to 44 μm and an intrinsic pH of 2.0 to 6.0.
Preferably, the first main group element compound is at least one of lithium carbonate, sodium carbonate, potassium carbonate, sodium silicate and lithium titanate.
Preferably, the negative electrode plate is a metal lithium strip or a lithium aluminum alloy strip.
Has the advantages that: due to the adoption of the sulfur-containing organic solvent electrolyte, the high-current discharge performance and the discharge platform of the battery are improved; and the anode plate prepared by the raw materials has large discharge capacity and long discharge time. Compared with the traditional alkaline manganese and zinc-manganese batteries, the battery has more excellent high-current discharge performance; the degree of discharge hysteresis is reduced compared to conventional lithium-iron disulfide batteries. In addition, the battery has good high-low temperature discharge performance, and the application range of the battery is expanded.
The invention also provides a preparation method of the lithium-iron disulfide battery, which comprises the following steps:
preparing an organic solvent electrolyte, namely mixing various raw materials in proportion according to the proportion of the raw materials;
preparing a positive plate: adding various raw materials into a solvent according to the raw material ratio, then adding a dispersing agent, uniformly stirring, and obtaining positive active material slurry after the dispersing is finished; coating the prepared positive active material slurry on a metal strip material substrate, and drying to remove the solvent to obtain a positive plate;
preparing an electric core: winding the prepared positive plate, the negative plate and the diaphragm under the environment that the relative humidity is lower than 2% to form a battery plate group;
preparation of lithium-iron disulfide batteries: and placing the prepared battery core into a battery shell, then injecting the prepared organic solvent electrolyte, and finally sealing the opening to immediately finish the preparation of the lithium-iron disulfide battery.
Specifically, the solvent is N-methyl-2-pyrrolidone; the dispersant is absolute ethyl alcohol or isopropanol.
Has the advantages that: by adopting the preparation method, the lithium-iron disulfide battery with high discharge platform, long discharge time, large discharge capacity and wide application range is simply and conveniently prepared.
Drawings
FIG. 1 is a graph of 2A discharge at room temperature for lithium-iron disulfide cells prepared in examples 1-4;
FIG. 2 is a graph of 1A discharge at room temperature for lithium-iron disulfide cells prepared in examples 1-4;
figure 3 is a graph of the discharge at room temperature of 0.3A for lithium-iron disulfide cells prepared in examples 1-4;
fig. 4 is a graph of discharge curves of the lithium-iron disulfide batteries prepared in examples 1 to 4 at 60 ℃ in an environment of 2A;
figure 5 is a graph of the discharge of the lithium-iron disulfide batteries prepared in examples 1-4 at 0.3A in an environment of 40 c.
Detailed Description
In order to more fully understand the technical content of the present invention, the technical solution of the present invention will be further described and illustrated with reference to the following specific embodiments, but not limited thereto.
Example 1
A lithium-iron disulfide battery comprises a battery shell, an electric core arranged in the battery shell, and sulfur-containing organic solvent electrolyte injected into the battery shell;
specifically, the sulfur-containing organic solvent electrolyte consists of an organic solvent and a lithium salt;
more specifically, the organic solvent is formed by mixing 35% by volume of sulfolane and 65% by volume of 1,3-Dioxolane (DOL); the lithium salt is lithium bistrifluoromethanesulfonylimide, and the molar concentration of the lithium salt dissolved in the organic solvent is 1.0Mol/L.
Specifically, the battery cell comprises a positive plate, a negative plate and a diaphragm; the positive plate is prepared by coating positive active slurry on a metal strip material matrix.
More specifically, the positive active slurry comprises the following raw materials in parts by weight:
more specifically, the negative electrode sheet is a metallic lithium ribbon.
The specific manufacturing process of the lithium-iron disulfide battery comprises the following steps:
a. preparing sulfur-containing organic solvent electrolyte according to the raw material proportion of the sulfur-containing organic solvent;
b. sieving iron disulfide powder with a 325-mesh sieve, then sieving with a 500-mesh sieve, mixing the raw materials into a solvent N-methyl-2-pyrrolidone according to the raw material proportion of the positive active slurry, and then adding absolute ethyl alcohol and uniformly stirring to obtain the positive active slurry; then coating the dispersed positive active substance slurry on a metal strip material matrix, drying to remove the solvent, and rolling to obtain a positive plate; cutting the positive plate into corresponding size and shape according to actual requirements;
c. winding the prepared positive plate, the negative plate and the diaphragm under the environment that the relative humidity is lower than 2% to form a battery plate group;
d. and (3) putting the prepared battery core into a battery shell, then injecting the prepared organic solvent electrolyte, and finally sealing the battery shell to immediately finish the preparation of the lithium-iron disulfide battery.
Example 2
The composition and preparation of the positive plate of the lithium-iron disulfide battery in the embodiment are the same as those in embodiment 1, except that the sulfur-containing organic solvent electrolyte is prepared by mixing 35% by volume of sulfolane and 65% by volume of 1,3-Dioxolane (DOL); the lithium salt is a mixture of lithium bistrifluoromethane sulfonyl imide and lithium iodide, the molar ratio of the lithium bistrifluoromethane sulfonyl imide to the lithium iodide is 1:2, and the total molar concentration of the lithium bistrifluoromethane sulfonyl imide and the lithium iodide after the lithium bistrifluoromethane sulfonyl imide and the lithium iodide are dissolved in an organic solvent is 1.0Mol/L.
Example 3
The composition and preparation of the positive plate of the lithium-iron disulfide battery in the embodiment are the same as those in embodiment 1, except that the sulfur-containing organic solvent electrolyte is prepared by mixing 35% by volume of sulfolane and 65% by volume of 1,3-Dioxolane (DOL); the lithium salt is a mixture of lithium bistrifluoromethane sulfonyl imide and lithium iodide, the molar ratio of the lithium bistrifluoromethane sulfonyl imide to the lithium iodide is 1:4, and the total molar concentration of the lithium bistrifluoromethane sulfonyl imide and the lithium iodide after the lithium bistrifluoromethane sulfonyl imide and the lithium iodide are dissolved in an organic solvent is 1.0Mol/L.
Example 4
The composition and preparation of the positive plate of the lithium-iron disulfide battery in the embodiment are the same as those in embodiment 1, except that the sulfur-containing organic solvent electrolyte is prepared by mixing 45% by volume of sulfolane and 55% by volume of 1,3-Dioxolane (DOL); the lithium salt is a mixture of lithium bistrifluoromethane sulfonyl imide and lithium iodide, the molar ratio of the lithium bistrifluoromethane sulfonyl imide to the lithium iodide is 1:4, and the total molar concentration of the lithium bistrifluoromethane sulfonyl imide and the lithium iodide after the lithium bistrifluoromethane sulfonyl imide and the lithium iodide are dissolved in an organic solvent is 1.0Mol/L.
Performance test experiment
From each of examples 1-4, 5 lithium-iron disulfide cells were selected, labeled as cell a, cell B, cell C, and cell D, respectively.
Test experiment 1
One battery a, one battery B, one battery C, and one battery D were selected respectively to perform a 2A discharge experiment at room temperature, and the obtained discharge curves are shown in fig. 1.
It is evident from fig. 1 that the discharge plateau for 4 cells was about 1.25V and the discharge capacity was greater than 2800mAh when discharged at 2A at room temperature.
Test experiment 2
One battery a, one battery B, one battery C, and one battery D were selected respectively to perform a 1A discharge experiment at room temperature, and the obtained discharge curves are shown in fig. 2.
It is evident from fig. 2 that the discharge plateau of 4 cells was about 1.30V and the discharge capacity was greater than 2900mAh at 1A discharge at room temperature.
Test experiment 3
One battery a, one battery B, one battery C, and one battery D were selected respectively to perform a 0.3A discharge experiment at room temperature, and the obtained discharge curves are shown in fig. 3.
It is evident from fig. 3 that the discharge plateau for 4 cells was about 1.40V and the discharge capacity was greater than 3000mAh at 0.3A discharge at room temperature.
Test experiment 4
One battery a, one battery B, one battery C, and one battery D were selected respectively to perform a 2A discharge experiment at a high temperature of 60 ℃, and the obtained discharge curves are shown in fig. 4.
It is evident from fig. 4 that the discharge plateau of 4 cells was about 1.20-1.40V and the discharge capacity was greater than 2700mAh when 2A was discharged at 60 c.
Test experiment 5
One battery A, one battery B, one battery C and one battery D are respectively selected to carry out 0.3A discharge experiments at the low temperature of minus 40 ℃, and the obtained discharge curves are shown in figure 5.
Obviously, as can be seen from fig. 5, when 0.3A is discharged at a low temperature of-40 ℃, the discharge plateau of 4 batteries is about 1.1V, and the discharge capacity is 50% -75% of the discharge capacity at normal temperature.
In conclusion: the lithium-iron disulfide battery provided by the invention has the advantages of high discharge capacity, excellent high and low temperature discharge performance, and is very suitable for electrical appliances under heavy load and severe environment.
The technical contents of the present invention are further illustrated by the examples only for the convenience of the reader, but the embodiments of the present invention are not limited thereto, and any technical extension or re-creation based on the present invention is protected by the present invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A sulfur-containing organic solvent electrolyte is characterized by comprising an organic solvent and a lithium salt; the organic solvent is formed by mixing sulfolane and at least one of propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, tetrahydrofuran, 2-methyl tetrahydrofuran, 1,3-dioxolane, 1,2-dimethoxyethane, acetonitrile, dimethyl amide, triphenyl phosphate and gamma-butyrolactone; in the organic solvent, the volume ratio of the sulfolane is more than or equal to 33 percent.
2. The sulfur-containing organic solvent electrolyte according to claim 1, wherein the organic solvent contains sulfolane 33 to 75% by volume, and the remaining organic solvent contains 25 to 67% by volume; the concentration of the lithium salt dissolved in the organic solvent is 0.01-2.5 mol/L.
3. The sulfur-containing organic solvent electrolyte according to claim 2, wherein the organic solvent contains sulfolane 33 to 55% by volume, and the remaining organic solvent contains 45 to 67% by volume; the concentration of the lithium salt dissolved in the organic solvent is 0.01-1.5 mol/L.
4. The sulfur-containing organic solvent electrolyte according to claim 3, wherein the organic solvent contains sulfolane 33 to 45% by volume and the remaining organic solvent 55 to 67% by volume; the concentration of the lithium salt dissolved in the organic solvent is 0.01-1.5 mol/L.
5. The sulfur-containing organic solvent electrolyte according to any one of claims 1 to 4, wherein the lithium salt is at least one of lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium iodide, lithium nitrate, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonylimide, and lithium bisoxalato borate.
6. A lithium-iron disulfide battery comprising a battery casing, a cell disposed within the battery casing, and the sulfur-containing organic solvent electrolyte of claim 5 impregnated into the battery casing.
7. The lithium-iron disulfide battery of claim 6, wherein the cell comprises a positive plate, a negative plate, and a separator; the positive plate is prepared by coating positive active slurry on a metal strip material substrate; the positive active slurry comprises the following raw materials in parts by weight:
wherein the average particle size of the iron disulfide powder is 30-44 μm, and the inherent pH value is 2.0-6.0;
the binder is any one of CMC, PTFE and PVDF;
the conductive agent is any one of carbon black, acetylene black, conductive graphite and metal powder.
8. The lithium-iron disulfide cell of claim 7 wherein the first main group element compound is at least one of lithium carbonate, sodium carbonate, potassium carbonate, sodium silicate, and lithium titanate.
9. The lithium-iron disulfide battery of claim 7 wherein the negative plate is a strip of lithium metal or lithium aluminum alloy.
10. A method for the preparation of a lithium-iron disulfide cell as claimed in any of claims 6 to 9, comprising the steps of:
preparing an organic solvent electrolyte, namely mixing various raw materials in proportion according to the proportion of the raw materials;
preparing a positive plate: adding various raw materials into a solvent according to the raw material ratio, then adding a dispersing agent, uniformly stirring, and obtaining positive active material slurry after the dispersing is finished; coating the prepared positive active material slurry on a metal strip material substrate, and drying to remove the solvent to obtain a positive plate;
preparing an electric core: winding the prepared positive plate, the negative plate and the diaphragm under the environment that the relative humidity is lower than 2% to form a battery plate group;
preparation of lithium-iron disulfide batteries: and placing the prepared battery core into a battery shell, then injecting the prepared organic solvent electrolyte, and finally sealing the opening to immediately finish the preparation of the lithium-iron disulfide battery.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110265722A (en) * | 2019-06-14 | 2019-09-20 | 中国科学院长春应用化学研究所 | A kind of Dual-ion cell electrolyte and application |
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| US3907597A (en) * | 1974-09-27 | 1975-09-23 | Union Carbide Corp | Nonaqueous cell having an electrolyte containing sulfolane or an alkyl-substituted derivative thereof |
| CN101911353A (en) * | 2008-01-23 | 2010-12-08 | 吉列公司 | Lithium cell |
| CN102024953A (en) * | 2010-11-06 | 2011-04-20 | 广州市鹏辉电池有限公司 | Positive electrode material of lithium-iron disulfide battery and battery |
| US20130089792A1 (en) * | 2009-11-24 | 2013-04-11 | The Gillette Company | Electrochemical cells with improved separator and electrolyte |
-
2018
- 2018-05-08 CN CN201810432157.XA patent/CN108615943A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907597A (en) * | 1974-09-27 | 1975-09-23 | Union Carbide Corp | Nonaqueous cell having an electrolyte containing sulfolane or an alkyl-substituted derivative thereof |
| CN101911353A (en) * | 2008-01-23 | 2010-12-08 | 吉列公司 | Lithium cell |
| US20130089792A1 (en) * | 2009-11-24 | 2013-04-11 | The Gillette Company | Electrochemical cells with improved separator and electrolyte |
| CN102024953A (en) * | 2010-11-06 | 2011-04-20 | 广州市鹏辉电池有限公司 | Positive electrode material of lithium-iron disulfide battery and battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110265722A (en) * | 2019-06-14 | 2019-09-20 | 中国科学院长春应用化学研究所 | A kind of Dual-ion cell electrolyte and application |
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