CN114361592B - Additive and application thereof in sodium ion battery electrolyte - Google Patents

Additive and application thereof in sodium ion battery electrolyte Download PDF

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Publication number
CN114361592B
CN114361592B CN202111627277.3A CN202111627277A CN114361592B CN 114361592 B CN114361592 B CN 114361592B CN 202111627277 A CN202111627277 A CN 202111627277A CN 114361592 B CN114361592 B CN 114361592B
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sodium
additive
battery electrolyte
carbonate
electrolyte
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CN114361592A (en
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王元杰
薄晋科
曹仕良
田秀君
王文武
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Nanjing Bifeida New Energy Technology Co ltd
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Dalian CBAK Power Battery Co Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

The invention relates to the field of batteries, in particular to an additive, electrolyte and application thereof in improving battery cycle performance. The invention provides an additive for electrolyte, which comprises 1-propyne-3-sodium propyl sulfonate and fluoroethylene carbonate; wherein, based on the total mass of the additive for the electrolyte, the content of the 1-propyne-3-sodium propyl sulfonate is 10-60 percent, and the mass ratio of the 1-propyne-3-sodium propyl sulfonate to the fluoroethylene carbonate is (1-6): (4-9). The additive provided by the invention can form a thin and continuous solid electrolyte membrane on the surface of a hard carbon material in preference to an electrolyte solvent; meanwhile, a certain amount of NaS and NaF with lower impedance and better conductivity are arranged in the membrane, so that the battery is ensured to have certain multiplying power performance. The sodium ion battery using the electrolyte provided by the invention has excellent cycle performance.

Description

Additive and application thereof in sodium ion battery electrolyte
Technical Field
The invention relates to the field of batteries, in particular to an additive, electrolyte and application thereof in improving battery cycle performance.
Background
In the 21 st century, lithium batteries were used in many fields such as cellular phones, computers, wearable devices, electric vehicles, two-wheeled bicycles, electric tools, street lamps, and the like. In recent years, consumption of lithium resources has been shown to be large in consumption and rapid in consumption, and the increase in lithium production cannot meet the phenomenon of the increase in consumption: this is because, firstly, lithium resources are limited and exist mainly in spodumene ore and salt lake lithium states, and secondly, winter salt lake lithium cannot extract lithium.
In contrast, sodium is widely available, has a large reserve, is 420 times more expensive than lithium, and is far less expensive than lithium. In recent years, along with the rapid rise of lithium price, the sodium ion battery is expected to be widely focused at a cost which is 30-50% lower than that of the lithium ion battery, and particularly has attractive application prospects in the fields of energy storage, hybrid power and lead-acid battery replacement.
Sodium is the second light alkali metal, similar in chemistry to lithium, but with a sodium ion radius of 0.102nm 34.2% greater than a lithium ion radius of 0.076nm, resulting in sodium ions unsuitable for energy storage in conventional, less-interlayer-spacing graphite negative electrode materials, whereas hard carbon materials are considered to be ideal future negative electrode materials for sodium-ion batteries because of their greater interlayer spacing than graphite. However, it is found that the ester-based electrolyte in the traditional lithium battery, such as Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene Carbonate (PC) and the like, generates a rough, uneven and thicker incomplete solid electrolyte membrane on the surface of the negative electrode of the sodium ion battery, and the solid electrolyte membrane is continuously broken and grown in the battery cycle process, so that the internal resistance of the battery is continuously increased along with the cycle, and the cycle life of the battery is shorter.
Disclosure of Invention
The first object of the invention is to provide an additive for an electrolyte, comprising 1-propyne-3-sodium propyl sulfonate and fluoroethylene carbonate; wherein, based on the total mass of the additive for the electrolyte, the percentage content of the 1-propyne-3-sodium sulfonate propyl ether is 10-60 percent; the mass ratio of the 1-propyne-3-sodium propyl sulfonate to the fluoroethylene carbonate is (1-6): (4-9).
The additive provided by the invention can form a thin and continuous solid electrolyte membrane on the surface of a hard carbon material in preference to an electrolyte solvent, and the main component of the membrane is continuous RCH 2 ONa、RCH 2 SONA is generated by 1-propyne-3-sodium sulfonate propyl ether, and R is alkyl; meanwhile, a certain amount of NaS and NaF with lower impedance and better conductivity are arranged in the membrane, and the NaS and NaF are formed by 1-propyne-3-sodium sulfonate propyl ether and fluoroethylene carbonate, so that the battery is ensured to have certain multiplying power performance.
Preferably, the percentage of the 1-propyne-3-sodium propyl sulfonate is 30-40%.
When the mass percentage of the 1-propyne-3-sodium sulfonate propyl ether in the additive is within the above range, a continuous solid electrolyte film can be formed on the surface of the hard carbon, and the electrolyte film has appropriate impedance, so that the conductivity of the battery can be considered.
As a preferred embodiment, the electrolyte additive comprises the following components in mass ratio (1-6): (4-9) sodium propyl 1-propyne-3-sulfonate and fluoroethylene carbonate, more preferably (3-4): (6-7).
A second object of the present invention is to provide a battery electrolyte comprising the above additive for an electrolyte.
Preferably, the percentage of the additive for the electrolyte is 1 to 3% based on the total mass of the electrolyte for a battery.
Preferably, the battery electrolyte further comprises an organic solvent, wherein the organic solvent comprises the following components in percentage by mass (1-3): cyclic carbonates and chain carbonates of (5-8); the cyclic carbonate is selected from one or two of ethylene carbonate and propylene carbonate; the chain carbonic ester is selected from one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate and methyl propyl carbonate.
Preferably, the battery electrolyte further comprises sodium salt, wherein the sodium salt is selected from one or more of sodium hexafluorophosphate, sodium perchlorate and sodium tetrafluoroborate.
Preferably, the percentage of the sodium salt is 10-20%.
The above-described schemes can be combined by the skilled person in accordance with common knowledge to obtain a preferred scheme of the battery electrolyte of the present invention.
As a preferred scheme, the battery electrolyte comprises the following components in parts by weight:
77-89 parts of organic solvent, 10-20 parts of sodium salt and 1-3 parts of additive for electrolyte.
A third object of the present invention is to provide a battery comprising the above battery electrolyte.
Further, the battery provided by the invention contains the battery electrolyte, and the negative electrode of the battery is made of a hard carbon material.
Preferably, the battery is a sodium ion battery.
The invention has the beneficial effects that: the additive provided by the invention can form a thin and continuous solid electrolyte membrane on the surface of a hard carbon material in preference to an electrolyte solvent; meanwhile, a certain amount of NaS and NaF with lower impedance and better conductivity are arranged in the membrane, so that the battery is ensured to have certain multiplying power performance. The sodium ion battery using the electrolyte provided by the invention has excellent cycle performance.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The examples are not intended to identify the particular technology or conditions, and are either conventional or are carried out according to the technology or conditions described in the literature in this field or are carried out according to the product specifications. The reagents and instruments used, etc. are not identified to the manufacturer and are conventional products available for purchase by regular vendors.
In order to more advantageously compare the difference in effect of the additives, the same sodium salt and organic solvent were used in the electrolytes of the following examples, and in fact, the sodium salt and organic solvent were used as long as they were within the range defined in the present invention, all had the effects mentioned in the present invention.
Example 1
The present example provides an additive for an electrolyte, which contains 1-propyne-3-sodium propyl sulfonate and fluoroethylene carbonate in a mass ratio of 1:9.
The embodiment further provides an electrolyte containing the additive, which comprises the following formula: 17g of sodium hexafluorophosphate, 30g of ethylene carbonate, 50g of dimethyl carbonate, 0.3g of 1-propyne-3-sulfonic acid sodium propyl ether and 2.7g of fluoroethylene carbonate.
The preparation method comprises mixing the above materials.
Example 2
The present example provides an additive for an electrolyte, which contains 1-propyne-3-sodium propyl sulfonate and fluoroethylene carbonate in a mass ratio of 1:4.
The embodiment further provides an electrolyte containing the additive, which comprises the following formula: 17g of sodium hexafluorophosphate, 30g of ethylene carbonate, 50g of dimethyl carbonate, 0.6g of 1-propyne-3-sulfonic acid sodium propyl ether and 2.4g of fluoroethylene carbonate.
The preparation method comprises mixing the above materials.
Example 3
The present example provides an additive for an electrolyte, which contains 1-propyne-3-sodium propyl sulfonate and fluoroethylene carbonate in a mass ratio of 3:7.
The embodiment further provides an electrolyte containing the additive, which comprises the following formula: 17g of sodium hexafluorophosphate, 30g of ethylene carbonate, 50g of dimethyl carbonate, 0.9g of 1-propyne-3-sodium propyl sulfonate and 2.1g of fluoroethylene carbonate.
The preparation method comprises mixing the above materials.
Example 4
The present example provides an additive for an electrolyte, which contains 1-propyne-3-sodium propyl sulfonate and fluoroethylene carbonate in a mass ratio of 2:3.
The embodiment further provides an electrolyte containing the additive, which comprises the following formula: 17g of sodium hexafluorophosphate, 30g of ethylene carbonate, 50g of dimethyl carbonate, 1.2g of 1-propyne-3-sulfonic acid sodium propyl ether and 1.8g of fluoroethylene carbonate.
The preparation method comprises mixing the above materials.
Example 5
The present example provides an additive for an electrolyte, which contains 1-propyne-3-sodium propyl sulfonate and fluoroethylene carbonate in a mass ratio of 1:1.
The embodiment further provides an electrolyte containing the additive, which comprises the following formula: 17g of sodium hexafluorophosphate, 30g of ethylene carbonate, 50g of dimethyl carbonate, 1.5g of 1-propyne-3-sulfonic acid sodium propyl ether and 1.5g of fluoroethylene carbonate.
The preparation method comprises mixing the above materials.
Example 6
The present example provides an additive for an electrolyte, which contains 1-propyne-3-sodium propyl sulfonate and fluoroethylene carbonate in a mass ratio of 3:2.
The embodiment further provides an electrolyte containing the additive, which comprises the following formula: 17g of sodium hexafluorophosphate, 30g of ethylene carbonate, 50g of dimethyl carbonate, 1.8g of 1-propyne-3-sulfonic acid sodium propyl ether and 1.2g of fluoroethylene carbonate.
The preparation method comprises mixing the above materials.
Example 7
The present example provides an additive for an electrolyte, which contains 1-propyne-3-sodium propyl sulfonate and fluoroethylene carbonate in a mass ratio of 3:2.
The embodiment further provides an electrolyte containing the additive, which comprises the following formula: 17g of sodium hexafluorophosphate, 30g of ethylene carbonate, 25g of methyl ethyl carbonate, 25g of dimethyl carbonate, 1.8g of 1-propyne-3-sulfonic acid sodium propyl ether and 1.2g of fluoroethylene carbonate.
The preparation method comprises mixing the above materials.
Comparative example 1
This comparative example provides an electrolyte which differs from example 3 only in that: fluoroethylene carbonate and 1-propyne-3-sodium propyl sulfonate are not added;
the formula is as follows: 17g of sodium hexafluorophosphate, 31.125g of ethylene carbonate and 51.875g of dimethyl carbonate.
The preparation method comprises mixing the above materials.
Comparative example 2
This comparative example provides an electrolyte which differs from example 3 only in that: only 1-propyne-3-sodium sulfonate propyl ether is added, and fluoroethylene carbonate is not added;
the formula is as follows: 17g of sodium hexafluorophosphate, 30.79g of ethylene carbonate, 51.31g of dimethyl carbonate and 0.9g of 1-propyne-3-sulfonic acid sodium propyl ether.
The preparation method comprises mixing the above materials.
Comparative example 3
This comparative example provides an electrolyte which differs from example 3 only in that: only fluoroethylene carbonate is added, and 1-propyne-3-sodium propyl sulfonate is not added;
the formula is as follows: 17g of sodium hexafluorophosphate, 30.338g of ethylene carbonate, 50.562g of dimethyl carbonate and 2.1g of fluoroethylene carbonate.
The preparation method comprises mixing the above materials.
Performance verification
The electrolytes of examples and comparative examples were injected into 26650-1.8Ah sodium ion battery cells (positive vanadium sodium phosphate, negative hard carbon) to prepare batteries.
And (3) carrying out cycle test on the prepared battery, cycling for 1000 times, recording the discharge capacity of the first battery and the 1000 th battery, and calculating the discharge retention rate. Discharge retention = first discharge capacity/1000 th discharge capacity 100%, and the results are shown in table 1.
TABLE 1 discharge retention results
Project Discharge retention rate
Example 1 71.2%
Example 2 86.5%
Example 3 95.3%
Example 4 94.6%
Example 5 86.9%
Example 6 77.8%
Example 7 80.2%
Comparative example 1 23.8%
Comparative example 2 85.7%
Comparative example 3 38.6%
The proportion of the 1-propyne-3-sodium sulfonate propyl ether added in the additive is 30-40% in comparison with examples 1-6, the sodium ion battery has the most excellent cycle performance, and the 1-propyne-3-sodium sulfonate propyl ether can greatly improve the cycle life of the sodium ion battery in comparison with examples 1-3, and the 1-propyne-3-sodium sulfonate propyl ether and fluoroethylene carbonate are combined to have better cycle life.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (12)

1. An additive for sodium ion battery electrolyte is characterized by comprising 1-propyne-3-sodium propyl sulfonate and fluoroethylene carbonate;
wherein, based on the total mass of the additive for the sodium ion battery electrolyte, the percentage content of the 1-propyne-3-sodium sulfonate propyl ether is 10-60%;
the mass ratio of the 1-propyne-3-sodium propyl sulfonate to the fluoroethylene carbonate is (1-6): (4-9).
2. The additive for sodium ion battery electrolyte according to claim 1, wherein the percentage content of 1-propyne-3-sodium propyl sulfonate is 30 to 40% based on the total mass of the additive for sodium ion battery electrolyte.
3. A battery electrolyte comprising the additive for a sodium ion battery electrolyte according to claim 1 or 2.
4. The battery electrolyte according to claim 3, wherein the percentage of the additive for a sodium ion battery electrolyte is 1 to 3% based on the total mass of the battery electrolyte.
5. The battery electrolyte according to claim 3 or 4, further comprising an organic solvent; the organic solvent comprises the following components in percentage by mass (1-3): cyclic carbonates and chain carbonates of (5-8);
the cyclic carbonate is selected from one or two of ethylene carbonate and propylene carbonate;
the chain carbonic ester is selected from one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate and methyl propyl carbonate.
6. The battery electrolyte according to claim 3 or 4, further comprising a sodium salt selected from one or more of sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate.
7. The battery electrolyte according to claim 5, further comprising a sodium salt selected from one or more of sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate.
8. The battery electrolyte of claim 6 wherein the percentage of sodium salt is 10-20% based on the total mass of the battery electrolyte.
9. The battery electrolyte of claim 7 wherein the percentage of sodium salt is 10-20% based on the total mass of the battery electrolyte.
10. The battery electrolyte according to claim 9, which comprises the following components in parts by weight: 77-89 parts of organic solvent, 10-20 parts of sodium salt and 1-3 parts of additive for electrolyte.
11. A battery comprising the battery electrolyte according to any one of claims 3 to 10, and a negative electrode made of a hard carbon material.
12. The battery according to claim 11, characterized in that it is a sodium ion battery.
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Publication number Priority date Publication date Assignee Title
JP2001357874A (en) * 2000-06-13 2001-12-26 Shin Kobe Electric Mach Co Ltd Nonaqueous electrolyte secondary battery
WO2013045561A1 (en) * 2011-09-30 2013-04-04 Westfälische Wilhelms-Universität Münster Electrochemical cell
JP2017117684A (en) * 2015-12-25 2017-06-29 セントラル硝子株式会社 Electrolytic solution for nonaqueous electrolyte battery, and nonaqueous electrolyte battery using the same
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Address after: 211399 Factory Building No. 6, Phase II, Standard Factory Building, No. 86 Shuanggao Road, Economic Development Zone, Gaochun District, Nanjing City, Jiangsu Province

Patentee after: Nanjing Bifeida New Energy Technology Co.,Ltd.

Address before: 116450 No. 11, East Rose Street, Huayuankou Economic Zone, Dalian City, Liaoning Province

Patentee before: DALIAN CBAK POWER BATTERY CO.,LTD.