CN108808090B - High-safety self-blocking lithium battery electrolyte and lithium battery - Google Patents

High-safety self-blocking lithium battery electrolyte and lithium battery Download PDF

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CN108808090B
CN108808090B CN201810777432.1A CN201810777432A CN108808090B CN 108808090 B CN108808090 B CN 108808090B CN 201810777432 A CN201810777432 A CN 201810777432A CN 108808090 B CN108808090 B CN 108808090B
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electrolyte
lithium battery
battery
carbonate
self
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CN108808090A (en
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黄昌玥
沈志鸿
邢雪坤
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Kunshan Synergy Energy Technology Co ltd
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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
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • 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
    • 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
    • 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
    • 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

Abstract

The invention discloses a high-safety self-blocking lithium battery electrolyte, which comprises lithium salt, an organic solvent and an additive, wherein the additive comprises 1-5% of fluoroethylene carbonate, 1-3% of 1, 3-propane sultone, 0.5-3% of methylene disulfonate, 0.5-3% of tri (trimethyl alkane) borate enzyme and 3-10% of fluorobenzene in percentage by mass of the electrolyte, and the organic solvent is a carbonate solvent. The invention can generate self-destruction behavior to cause termination reaction for the battery in a discharge state (0% SOC) and a room temperature storage time of more than 1 year or a temperature of more than 55 ℃ in the discharge state, thereby improving the safety of the product.

Description

High-safety self-blocking lithium battery electrolyte and lithium battery
Technical Field
The invention relates to a high-safety self-blocking lithium battery electrolyte and a lithium battery, and belongs to the technical field of lithium ion secondary batteries.
Background
In response to the energy demand and the development of electronic products, the safety of lithium ion secondary batteries has been a very important issue for all researchers and manufacturers in recent years, especially for 3C mobile products in recent years, but the batteries are rapidly developed, but the battery charging explosion and combustion behaviors are often generated, and some problems of these electronic products are that the battery manufacturers themselves are not proper in management and protection behaviors and not good in design, which leads to the safety problem of high risk in use for consumers. The invention mainly relates to the improvement of a lithium battery formula, and aims to solve the problem that after a consumer does not use a battery for a long time, the lithium in the battery is possibly deposited when the battery is reused due to the variation in the battery, so that the internal short circuit of the battery is guided, high heat is generated, and the failure with a certain probability is caused.
Disclosure of Invention
The invention aims to provide a lithium battery electrolyte and a lithium battery, which can improve the safety of the battery.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the lithium battery electrolyte with high safety and self-blocking comprises a lithium salt, an organic solvent and an additive, wherein the additive comprises 1-5% of fluoroethylene carbonate, 1-3% of 1, 3-propane sultone, 0.5-3% of methylene methane disulfonate, 0.5-3% of tri (trimethyl alkane) borate enzyme and 3-10% of fluorobenzene in percentage by mass of the electrolyte, and the organic solvent is a carbonate solvent.
The additive was 2% fluoroethylene carbonate, 3%1, 3-propane sultone, 1% methylene methanedisulfonate, 1% tris (trimethylalkane) borate enzyme and 10% fluorobenzene.
The concentration of the lithium salt is 1M-1.3M.
The lithium salt is L iPF6。
The organic solvent is ethylene carbonate EC, propylene carbonate PC, diethyl carbonate DEC, ethyl methyl carbonate EMC, dimethyl carbonate DMC or propyl propionate PP.
A lithium battery comprises a positive electrode, a negative electrode, an isolating membrane, electrolyte and a conductive handle, wherein the electrolyte is adopted.
The invention achieves the following beneficial effects: the electrolyte can be used as a battery through a further activation process, the performance of the manufactured battery is equivalent to that of a common battery, the battery has the advantages of capacity of controlling gas generation under a full power state at a high temperature of 60 ℃, low cost and the like, and the battery can be self-destroyed only under a discharge state (0% SOC) and a room temperature storage time of more than 1 year or a discharge state stored at a temperature of more than 55 ℃, so that the charging behavior of the battery is blocked.
Drawings
FIG. 1 is a schematic diagram of a cell according to an embodiment of the present invention;
FIG. 2 is a graph of the discharge rate of a cell of an example of the present invention over 500 cycles at room temperature of 23. + -. 3 ℃;
FIG. 3 is a graph of the discharge rate of a battery of an embodiment of the present invention at a high temperature of 60. + -. 3 ℃ over 300 cycles;
FIG. 4 is a graph of the storage of example cells of different capacities of the present invention after disassembly at room temperature for 60 days;
fig. 5 shows the storage of the batteries of the embodiments of the present invention with different capacities after disassembly for 60 days at high temperature.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
This example was carried out using a cell of type AHB412434 as the experimental cell, shown in fig. 1 as a body figure, dimensioned with the first/second digit as a thickness of 4.1mm, dimensioned with the third/fourth digit as a width of 24mm, dimensioned with the fifth/sixth digit as a length of 34mm, and a nominal capacity of the cell of 380mAh,
the internal design of the battery mainly comprises five types of positive electrodes, negative electrodes, isolating membranes, electrolyte and conductive handles, and the positive electrode material can be selected from conventional positive electrode active materials, such as: lithium cobalt oxide, lithium iron phosphate, lithium manganese oxide, ternary materials, and the like, but not limited to this range, wherein the negative electrode material is a conventional negative electrode active material, such as: natural graphite, artificial graphite, micro-carbon spherical graphite, silicon carbon and the like, but is not limited by the range; the separator material is a microporous material, for example: the electrolyte is selected from conventional lithium salts, the solvent is selected from carbonate solvents, the additive is shown in the following table 1, the effect is not good when the content of the additive is too low, and the excessive content is shown in the right side of the table 1.
TABLE 1 description of additives in the electrolyte
Figure BDA0001731698440000031
L iCoO is selected as the anode material in the embodiment2The negative electrode adopts graphite series, the electrolyte is a main solvent EC/PC/EMC/PP commonly used in high voltage, and the lithium salt is 1.3M L iPF6The resulting cell was tested with the additive being 2% fluoroethylene carbonate, 3%1, 3-propane sultone, 1% methylene methanedisulfonate, 1% tris (trimethyleneboronic acid) enzyme and 10% fluorobenzeneThe performance of the battery at room temperature and high temperature is shown in fig. 2 and fig. 3, the battery still has a good service life level of more than 88% after being repeatedly charged and discharged for 500 cycles at room temperature, and the battery still has a good service life level of more than 84% after being repeatedly charged and discharged for 300 cycles at a severe high temperature of 60 ℃, and simultaneously passes a safety test of U L1642, as shown in table 2, the battery has the performance of high safety and thermal stability as a whole.
Table 2 shows the results of the safety test of the batteries of the examples
Figure BDA0001731698440000041
Tables 3 and 4 below are control tables of blocking performance for long-term (eight weeks), room temperature (25 ℃) and high temperature (60 ℃) for the examples and the control (the control is a commercially available electrolyte, most commonly used with the formulation EC/PC/DEC/EMC + 1% PS + 1% FEC +1.0M L iPF6), respectively.
TABLE 3 comparison of results stored at room temperature for eight weeks
Figure BDA0001731698440000051
TABLE 4 comparison of results of eight weeks storage at high temperature
Figure BDA0001731698440000071
Under the condition of 0-50% SOC storage for 60 days at room temperature, the results of the reference product and the examples show that the comparative product shows quite good battery behavior with little difference of the capacitance loss and the recovery result, but the comparative product shows one-time capacitance loss difference compared with the examples because only a trace amount of the positive electrode film-forming protective agent is added to cause capacitance loss and recovery with 100% SOC storage behavior.
In addition, the battery of the embodiment shows a quite good battery behavior under the voltage of a discharge state (0% SOC) and 50-100% SOC storage under another condition of 60 ℃ for 60 days at high temperature, while the comparative product causes the problems that the battery can not recover the electric capacity and the battery generates gas under the storage of 100% SOC, and in addition, the voltage shows a result of nearly 0V under the storage of 0% SOC for 60 days at high temperature, so that the battery can not have a reversible behavior completely after recharging, and the formula of the invention also shows that the battery can play a role indeed.
From the results, it is observed that the example battery generated the self-destruction and destruction reaction described in the present invention under the state of 0% SOC that can simulate the consumer's non-use for a long time, using the results of 60 days at high temperature, and the battery was not charged and discharged. The present invention is illustrated by using high temperature as an example, and in order to simulate the temperature effect and the time effect according to the law of thermodynamics, it can be estimated that the limited destruction reaction will occur if the consumer normally does not use the battery at room temperature for more than about 1-1.5 years.
Table 5 below shows the results of the batteries of examples and comparative examples with different battery capacities stored for 7 days under high temperature (65 ℃) and high humidity (95% RH), the test shows the results by accelerating the chemical cross-linking reaction generated inside the battery using the accelerated verification method, and the examples with different battery capacities all show the self-destruction (reduction) behavior with the internal resistance and the thickness variation of the voltage within the standard range when a part of the capacity is retained, whereas the 0% SOC shows the self-destruction (reduction) behavior.
Table 5 shows the storage results of the examples and the control products with different battery capacities under different voltage conditions
Figure BDA0001731698440000091
The additive adopted by the invention also synchronously considers the reduction potential of the negative electrode and designs the reaction potential of the additive, the cross-linking reaction is carried out at high temperature, and because the reaction is related to the additive, the fluorine substituent groups in the battery can be increased by controlling different addition ratios, and the groups have strong electron-withdrawing capability, so the reduction potential is easy to occur, and the high acidity is easy to generate under the discharge state voltage, and the temperature effect, namely L iPF6 is higher than 60 ℃, so that the Lewis acid is decomposed, the SEI film is greatly damaged to generate a trace amount of gas, the surface of the negative electrode is indirectly corroded and finally stripped, and the self-destruction function of the battery is further induced.
The lithium battery prepared by the electrolyte is stored at a high temperature for a period of time, as shown in figure 5, as long as the voltage is lower than 0% SOC (about 3V) in a discharge state, the acidity of the additive is increased under the high-temperature storage, so that the negative electrode material is damaged, the structural phase change is caused, an irreversible barrier layer is formed on the surface of the negative electrode, the voltage is reduced to 0V, the internal electrode also has a stripping self-destruction gas production effect, and the combustion problem cannot occur due to electrode stripping in the aspect of safety.
The additive combination adopted in the scheme has a self-blocking function, and also has a lithium ion carrying function due to the fact that a carbonate solvent is selected to be blended with the additive.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (5)

1. The lithium battery electrolyte with high safety and self-blocking comprises a lithium salt, an organic solvent and an additive, and is characterized in that the additive comprises 2% of fluoroethylene carbonate, 3% of 1, 3-propane sultone, 1% of methylene methane disulfonate, 1% of tri (trimethyl alkane) borate and 10% of fluorobenzene in percentage by mass of the electrolyte, and the organic solvent is a carbonate solvent.
2. The electrolyte for a lithium battery having high safety self-blocking according to claim 1, wherein the concentration of the lithium salt is 1M to 1.3M.
3. The electrolyte for a lithium battery with high safety and self-blocking of claim 2, wherein the lithium salt is L iPF6。
4. The electrolyte for lithium battery of claim 1, wherein the organic solvent is selected from the group consisting of Ethylene Carbonate (EC), Propylene Carbonate (PC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), and Propyl Propionate (PP).
5. A lithium battery comprising a positive electrode, a negative electrode, a separator, an electrolyte and a conductive handle, characterized in that the electrolyte according to any one of claims 1 to 4 is used.
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CN102064344A (en) * 2010-12-21 2011-05-18 东莞市杉杉电池材料有限公司 Novel electrolyte for power battery
CN102983354A (en) * 2011-09-05 2013-03-20 轻工业化学电源研究所 Nonaqueous electrolyte solution for improving lithium ion battery cycling stability
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CN103078138B (en) * 2013-02-03 2016-07-06 宁德新能源科技有限公司 high-voltage lithium ion battery and electrolyte thereof
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