CN116435591B - Lithium ion battery electrode material suitable for working under ultralow temperature condition - Google Patents
Lithium ion battery electrode material suitable for working under ultralow temperature condition Download PDFInfo
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- CN116435591B CN116435591B CN202310448472.2A CN202310448472A CN116435591B CN 116435591 B CN116435591 B CN 116435591B CN 202310448472 A CN202310448472 A CN 202310448472A CN 116435591 B CN116435591 B CN 116435591B
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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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
An electrode material of lithium ion battery suitable for working under ultra-low temperature condition. According to the invention, thionyl chloride is selected as a solvent of the electrolyte, and the freezing point of the thionyl chloride is-110 ℃, so that the lithium cobaltate battery can keep good performance at ultralow temperature. Further, a composite electrolyte LiAlCl is added into the electrolyte 4 And Li (lithium) 2 SO 4 The synergistic effect of the two electrolytes can achieve excellent effects. In addition, mn-doped Li prepared by ion implantation 1.15 CoO 2 The positive electrode material can further improve the capacity achievement rate of the lithium cobalt oxide battery at low temperature. Compared with normal temperature, the capacity achievement rate of the lithium cobaltate battery can exceed 80 percent at ultralow temperature.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium ion battery electrode material suitable for working under ultralow temperature conditions.
Background
Currently, lithium ion batteries are the first battery of choice for portable consumer electronics devices, including cell phones, tablet computers, notebook computers, digital cameras, power tools, and toys, primarily because of their durability, high specific energy, and ability to operate at relatively high power. In recent years, lithium ion batteries are beginning to enter the automobile market as power components of hybrid electric vehicles and pure electric vehicles, and have a huge application prospect in the fields of unmanned planes, unmanned equipment, intelligent products and the like. Among them, lithium cobaltate batteries are one of the most ideal density indexes in the positive electrode materials, and thus have been widely used. However, in the ultra-low temperature use environment of special application fields such as the outdoor, the alpine region and the like, the performance of the lithium ion battery is not ideal. In view of the above, it is necessary to design a lithium ion battery that exhibits excellent performance under ultra-low temperature conditions.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a lithium ion battery electrode material suitable for working under the ultralow temperature condition, and the capacity achievement rate of the battery under the ultralow temperature can exceed 80 percent.
The lithium ion battery electrode material suitable for working under the ultralow temperature condition is characterized in that the lithium ion battery comprises Li 1.15 CoO 2 Positive electrode material, liT i 2 (PO 4 ) 3 Negative electrode material/C and LiAl C l 4 /Li 2 SO 4 Thionyl chloride electrolyte, wherein LiAl C l in the electrolyte 4 And Li (lithium) 2 SO 4 The total concentration of (2) is 1.2mol/L to 4.1mol/L.
Preferably, the lithium ion battery is a lithium cobaltate battery.
Preferably, the Li 1.15 CoO 2 The anode material is prepared by a molten salt method.
Preferably, the Li 1.15 CoO 2 The preparation method of the positive electrode material comprises the following steps: liOH and beta-Co (OH) 2 Grinding according to an atomic ratio, uniformly mixing, heating to 750 ℃ at a rate of 5 ℃/min under an air atmosphere, preserving heat, sintering for about 6.5 hours, and then cooling to room temperature at a rate of 5 ℃/min; washing the sintered material with deionized water, and drying in a drying oven to obtain Li 1.15 CoO 2 And a positive electrode material.
Preferably, the preparation method of the anode material comprises the following steps: coating Li Ti on carbon cloth 2 (PO 4 ) 3 Obtaining Li Ti 2 (PO 4 ) 3 and/C composite material.
Preferably, the coating method is spin coating.
Preferably, the ultra-low temperature refers to a temperature below-50 ℃.
Preferably, the ultra-low temperature refers to a temperature of-55 ℃.
Preferably, the capacity achievement rate of the battery at ultra-low temperature exceeds 80% with respect to normal temperature.
According to the invention, thionyl chloride is selected as a solvent of the electrolyte, and the freezing point of the thionyl chloride is-110 ℃, so that the lithium cobaltate battery can keep good performance at ultralow temperature. Further, a composite electrolyte LiA l C l is added into the electrolyte 4 And Li (lithium) 2 SO 4 The synergistic effect of the two electrolytes can achieve excellent effects. In addition, mn-doped Li prepared by ion implantation 1.15 CoO 2 The positive electrode material can further improve the capacity achievement rate of the lithium cobalt oxide battery at low temperature. Compared with normal temperature, the capacity achievement rate of the lithium cobaltate battery can exceed 80 percent at ultralow temperature.
Detailed Description
The technical effects of the present invention are verified by the following specific examples, but the embodiments of the present invention are not limited thereto.
In the prior art, the preparation method of the lithium cobalt oxide positive electrode material is mature, and the embodiment of the invention adopts a molten salt method to prepare Li CoO 2 The positive electrode material comprises the following specific steps: liOH and beta-Co (OH) 2 Grinding according to an atomic ratio, uniformly mixing, heating to 750 ℃ at a rate of 5 ℃/min under an air atmosphere, preserving heat and sintering for 6.5 hours, and then cooling to room temperature at a rate of 5 ℃/min; washing the sintered material with deionized water, and drying in a drying oven to obtain Li 1.15 CoO 2 And a positive electrode material.
In addition, in the lithium cobaltate battery, li Ti is coated on the carbon cloth 2 (PO 4 ) 3 the/C composite material is used as a battery cathode, wherein the coating method is very mature and is not described herein.
Example 1
The electrolyte composition of the battery is as follows: solvent thionyl chloride, electrolyte LiA l C l 4 And Li (lithium) 2 SO 4 . Wherein LiA l C l 4 At a concentration of 0.6 mol/L, li 2 SO 4 Is 0.6 mol/L.
Example 2
The electrolyte composition of the battery is as follows: solvent thionyl chloride, electrolyte LiA l C l 4 And Li (lithium) 2 SO 4 . Wherein LiA l C l 4 At a concentration of 1.2mol/L, li 2 SO 4 The concentration of (C) was 1.0 mol/L.
Example 3
The electrolyte composition of the battery is as follows: solvent thionyl chloride, electrolyte LiA l C l 4 And Li (lithium) 2 SO 4 . Wherein LiA l C l 4 At a concentration of 1.3 mol/L, li 2 SO 4 The concentration of (C) was 1.8 mol/L.
Example 4
The electrolyte composition of the battery is as follows: solvent thionyl chloride, electrolyte LiA l C l 4 And Li (lithium) 2 SO 4 . Wherein LiA l C l 4 At a concentration of 1.5 mol/L, li 2 SO 4 The concentration of (C) was 1.5 mol/L.
Example 5
The electrolyte composition of the battery is as follows: solvent thionyl chloride, electrolyte LiA l C l 4 And Li (lithium) 2 SO 4 . Wherein LiA l C l 4 At a concentration of 1.9 mol/L, li 2 SO 4 The concentration of (C) was 2.2 mol/L.
Example 6
The electrolyte composition of the battery is as follows: solvent thionyl chloride, electrolyte LiA l C l 4 And Li (lithium) 2 SO 4 . Wherein LiA l C l 4 At a concentration of 1.3 mol/L, li 2 SO 4 The concentration of (C) was 1.8 mol/L. The electrolyte solution same as that of example 3 is selected in this example, but the difference from example 3 is that the positive electrode material is subjected to ion implantation treatment by the following specific method: to be processed into Li 1.15 CoO 2 The anode material is put into metal steam vacuum arc power ion implantation equipment, and metal manganese is selected for Li 1.15 CoO 2 The positive electrode material is subjected to ion implantation, and the Mn ion implantation amount is 5 multiplied by 10 6 i ons/cm 2 。
Comparative example 1
The electrolyte composition of the battery is as follows: solvent thionyl chloride, electrolyte LiA l C l 4 And Li (lithium) 2 SO 4 . Wherein LiA l C l 4 At a concentration of 0.1 mol/L, li 2 SO 4 The concentration of (C) was 0.1 mol/L.
Comparative example 2
The electrolyte composition of the battery is as follows: solvent thionyl chloride, electrolyte LiA l C l 4 And Li (lithium) 2 SO 4 . Wherein LiA l C l 4 At a concentration of 3 mol/L, li 2 SO 4 Is 3 mol/L.
Comparative example 3
The electrolyte composition of the battery is as follows: solvent thionyl chloride, electrolyte LiA l C l 4 . Wherein LiA l C l 4 Is 3.1 mol/L.
Comparative example 4
The electrolyte composition of the battery is as follows: solvent thionyl chloride, electrolyte Li 2 SO 4 . Therein, L i 2 SO 4 Is 3.1 mol/L.
Further, the inventors have carried out the battery electrolytes of examples 1 to 6 and comparative examples 1 to 4 with Li 1.15 CoO 2 Positive electrode material, li Ti 2 (PO 4 ) 3 The negative electrode material/C is formed into a lithium cobaltate battery. Constant current discharge was performed at normal temperature (20 ℃) and-55℃with a current of 1A, and the battery capacity achievement rate at-55℃under ultra-low temperature conditions relative to that at normal temperature conditions was calculated, and the experimental data obtained are shown in Table 1.
Table 1 test data for each test group
| Numbering device | Cell capacity achievement rate/% |
| Example 1 | 73.8 |
| Example 2 | 76.0 |
| Example 3 | 83.1 |
| Example 4 | 81.9 |
| Example 5 | 77.4 |
| Example 6 | 87.1 |
| Comparative example 1 | 56.1 |
| Comparative example 2 | 64.8 |
| Comparative example 3 | 72.2 |
| Comparative example 4 | 75.9 |
As can be seen from Table 1, when the electrolyte LiA l C l 4 And L i 2 SO 4 The capacity achievement rate of the lithium cobaltate battery at ultra-low temperature is more than 70% at a total concentration of 1.2mol/L to 4.1mol/L, and in the most preferred embodiment, 83.1% is achieved, which is satisfactory. Further, as can be seen from comparative example 3, comparative example 3 and comparative example 4, liA l C l 4 And Li (lithium) 2 SO 4 The effect of the combination is obviously better than that of each substance used alone, and the possible reason is that some unknown synergistic effect occurs between the two electrolytes, and the specific mechanism is still to be further studied and is not described herein.
In addition, mn-doped Li prepared by ion implantation method in example 6 1.15 CoO 2 The positive electrode material can further improve the capacity achievement rate of the lithium cobalt oxide battery at low temperature.
It should be noted that, in order to ensure comparability of experimental data, it is necessary to ensure that the conditions (including separator, current collector, casing, etc. of the battery) except for the electrolyte composition in the examples are identical to those in the comparative examples, and thus, the description thereof will not be repeated here.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that modifications and variations can be made without departing from the technical principles of the present invention, and these modifications and variations should also be regarded as the scope of the invention.
Claims (9)
1. The lithium ion battery electrode material suitable for working under the ultralow temperature condition is characterized in that the lithium ion battery comprises Li 1.15 CoO 2 Positive electrode material, liTi 2 (PO 4 ) 3 Negative electrode material/C and LiAlCl 4 /Li 2 SO 4 Thionyl chloride electrolyte, wherein LiAlCl in the electrolyte 4 And Li (lithium) 2 SO 4 The total concentration of (2) is 1.2mol/L to 4.1mol/L.
2. A lithium ion battery electrode material adapted for operation at ultra-low temperatures as in claim 1, wherein said lithium ion battery is a lithium cobalt oxide battery.
3. A lithium ion battery electrode material suitable for operation under ultra-low temperature conditions as defined in claim 1, wherein said Li 1.15 CoO 2 The anode material is prepared by a molten salt method.
4. A lithium ion battery electrode material suitable for operation under ultra-low temperature conditions as defined in claim 1, wherein said Li 1.15 CoO 2 The preparation method of the positive electrode material comprises the following steps: liOH and beta-Co (OH) 2 Grinding according to an atomic ratio, uniformly mixing, heating to 750 ℃ at a speed of 5 ℃/min under an air atmosphere, preserving heat, sintering for about 6.5 hours, and then cooling to room temperature at a speed of 5 ℃/min; washing the sintered material with deionized water, and drying in a drying oven to obtain Li 1.15 CoO 2 And a positive electrode material.
5. A lithium ion battery electrode material suitable for operation at ultra-low temperatures as in claim 1, wherein the negative electrode material is prepared by a process comprising: coating LiTi on carbon cloth 2 (PO 4 ) 3 Obtaining LiTi 2 (PO 4 ) 3 and/C composite material.
6. A lithium ion battery electrode material adapted for operation at ultra-low temperatures according to claim 5, wherein the coating method is spin coating.
7. A lithium ion battery electrode material adapted for operation at ultra-low temperatures as defined in claim 5, wherein said ultra-low temperature is less than-50 ℃.
8. A lithium ion battery electrode material according to claim 5, adapted for operation at ultra-low temperatures, wherein the ultra-low temperature is-55 ℃.
9. A lithium ion battery electrode material according to claim 8, wherein the capacity achievement rate of the battery at ultra-low temperature is more than 80% with respect to normal temperature.
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| CA1165813A (en) * | 1980-05-08 | 1984-04-17 | Michael J. Domeniconi | Electrochemical cell and electrolytic solution therefor |
| CN1893164A (en) * | 2005-07-08 | 2007-01-10 | 黄穗阳 | Active electrolyte double V lithium polymerization cell |
| CN101783413A (en) * | 2003-09-23 | 2010-07-21 | 冈瑟·汉比特泽 | Method for manufacturing electrochemical cell |
| CN105720235A (en) * | 2016-04-05 | 2016-06-29 | 惠州亿纬锂能股份有限公司 | Cathode, preparation method thereof and lithium battery employing cathode |
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| US20030157409A1 (en) * | 2002-02-21 | 2003-08-21 | Sui-Yang Huang | Polymer lithium battery with ionic electrolyte |
| US11177500B2 (en) * | 2017-01-17 | 2021-11-16 | Sila Nanotechnologies, Inc. | Electrolytes for improved performance of cells with high-capacity anodes based on micron-scale moderate volume-changing particles |
| US11264659B2 (en) * | 2019-08-20 | 2022-03-01 | Uchicago Argonne, Llc | Rechargeable lithium-hydroxide based non-aqueous lithium oxygen batteries |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1165813A (en) * | 1980-05-08 | 1984-04-17 | Michael J. Domeniconi | Electrochemical cell and electrolytic solution therefor |
| CN101783413A (en) * | 2003-09-23 | 2010-07-21 | 冈瑟·汉比特泽 | Method for manufacturing electrochemical cell |
| CN1893164A (en) * | 2005-07-08 | 2007-01-10 | 黄穗阳 | Active electrolyte double V lithium polymerization cell |
| CN105720235A (en) * | 2016-04-05 | 2016-06-29 | 惠州亿纬锂能股份有限公司 | Cathode, preparation method thereof and lithium battery employing cathode |
Non-Patent Citations (1)
| Title |
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| Electrochemical performance of LiAlCl 4 /SOCl 2 electrolyte with 2, 2’-bipyridine in Li/SOCl 2 batteries;Honggang Zhao;《Int. J. Electrochem. Sci.》;全文 * |
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