CN109546221B - Wide-temperature-range discharging lithium ion battery electrolyte - Google Patents

Wide-temperature-range discharging lithium ion battery electrolyte Download PDF

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Publication number
CN109546221B
CN109546221B CN201811448641.8A CN201811448641A CN109546221B CN 109546221 B CN109546221 B CN 109546221B CN 201811448641 A CN201811448641 A CN 201811448641A CN 109546221 B CN109546221 B CN 109546221B
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parts
electrolyte
lithium
lithium ion
additive
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CN109546221A (en
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郭少雄
吴玉双
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Fujian Jinde Power Technology Co ltd
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Fujian Jinde Power 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
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/002—Inorganic electrolyte
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The invention belongs to the technical field of lithium ion batteries, and particularly relates to a wide-temperature discharge lithium ion battery electrolyte. The electrolyte consists of electrolyte lithium salt, organic solvent and additive, wherein the electrolyte lithium salt is LiBOB and LiPF6And LiBETI according to the mass ratio of 1:3: 2. The invention uses composite electrolyte lithium bis (oxalato) borate LiBOB and lithium tetrafluoroborate LiPF6LiBETI, and high temperature resistant and low temperature resistant electrolyte additive and organic solvent are added, so that the prepared battery has good discharge effect in the temperature range of-55 ℃ to 95 ℃.

Description

Wide-temperature-range discharging lithium ion battery electrolyte
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a wide-temperature discharge lithium ion battery electrolyte.
Background
A "lithium battery" is a type of battery using a nonaqueous electrolyte solution with lithium metal or a lithium alloy as a negative electrode material. Because the chemical characteristics of lithium metal are very active, the requirements on the environment for processing, storing and using the lithium metal are very high. Since the commercial use of the lithium ion battery in the 90 s of the 20 th century, the lithium ion battery has been rapidly developed with the advantages of high specific energy, high battery voltage, wide working temperature range, long storage life, no memory effect, small self-discharge rate, rapid charge and discharge and the like, and at present, the lithium ion battery is widely applied to electronic products such as mobile phones, notebook computers, digital cameras and the like, and is also gradually widely applied to electric bicycles, model airplanes and electric automobiles as a power battery. Along with the expansion of the application field of lithium ion batteries, the requirements for the performance of the batteries are also continuously improved, and in recent years, the requirements for the temperature tolerance of the lithium batteries in some industrial fields are gradually improved, so that how to improve the performance of the lithium batteries at ultralow temperature and ultrahigh temperature and produce the lithium ion batteries with wide temperature characteristics becomes one of important research directions in the field of the lithium ion batteries.
The current commercial electrolyte mostly adopts a carbonate mixture and electrolyte lithium salt as solventsMainly LiPF6However, LiPF6Easily decomposed by heat and having no high temperature resistance, so that only LiPF is used6Lithium batteries used as electrolytes are generally not adaptable to high temperature environments. However, LiPF6Has excellent low temperature resistance, so the invention uses the composite electrolyte of lithium bis (oxalato) borate LiBOB and lithium tetrafluoroborate LiPF6LiBETI, and high temperature resistant and low temperature resistant electrolyte additive and organic solvent are added, so that the prepared battery has good discharge effect in the temperature range of-55 ℃ to 95 ℃.
Disclosure of Invention
The invention aims to provide a lithium ion battery electrolyte capable of discharging at a wide temperature, which forms a stable, compact and tough SEI film when a lithium ion battery is charged for the first time by changing the type and the proportion of an organic lithium salt and adding an organic solvent and an additive into the electrolyte in proportion, wherein an organic silicon compound R contained in the additive4Si reacts with HF and then water in the electrolyte, and side reactions which damage negative performance and the SEI film are avoided.
In order to achieve the purpose, the invention adopts the following technical scheme:
the electrolyte for the wide-temperature discharge lithium ion battery consists of electrolyte lithium salt, an organic solvent and an additive, wherein the electrolyte lithium salt is LiBOB and LiPF, and the lithium borate is LiBOB6And LiBETI according to the mass ratio of 1:3: 2.
The organic solvent comprises the following raw materials in parts by mass: 1-3 parts of diethyl carbonate DEC, 1-3 parts of dimethyl carbonate DMC, 2-6 parts of fluoroethylene carbonate FEC and 1-3 parts of propylene carbonate PC.
The additive comprises the following raw materials in parts by mass: comprises vinylene carbonate VC 5-10 parts and organosilicon compound R43-6 parts of Si, 1-3 parts of phenyl glycidyl ether, 1-3 parts of ethylene glycol diglycidyl ether, 1-3 parts of neopentyl glycol diglycidyl ether and 1-3 parts of anisole.
The organic solvent and the electrolyte lithium salt are mixed according to the mass ratio of 1:1-1: 2.
The additive and the electrolyte lithium salt are mixed according to the mass ratio of 1:4-1: 6.
The invention has the advantages that:
(1) the invention uses lithium bis (oxalato) borate LiBOB and lithium tetrafluoroborate LiPF6The electrolyte and the LiBETI are mixed according to the mass ratio of 1:3:2, so that single LiPF is formed6Cannot resist high temperature, and the LiBETI can be combined with LiBOB and LiPF6The mixed addition achieves the effect of wide-temperature discharge.
(2) The addition of phenyl glycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether and anisole in the additive can reduce the viscosity of the electrolyte, thereby preventing the phenomenon of conductivity reduction caused by the increase of the viscosity of PC at low temperature.
(3) According to the invention, the unsaturated compound VC is added into the electrolyte additive solution, so that the electrolyte additive solution is easy to reduce on the negative electrode and participates in forming a protective film SEI, the obtained film has good ion permeability and good electronic insulation, lithium ions can enter and exit the negative electrode in the charging and discharging process, but electrons on the negative electrode cannot contact with solvent molecules, the rate capability is improved, and the performances in various aspects such as storage, low-temperature discharging, high-temperature charging and discharging are also improved.
Detailed Description
For further disclosure, but not limitation, the present invention is described in further detail below with reference to examples.
Example 1
(1) Preparation of electrolyte lithium salt: lithium bis (oxalato) borate LiBOB and lithium tetrafluoroborate LiPF6And LiBETI according to the mass ratio of 1:3: 2.
(2) Preparing an organic solvent: diethyl carbonate DEC 1 part, dimethyl carbonate DMC 1 part, fluoroethylene carbonate FEC 2 parts and propylene carbonate PC 1 part are mixed uniformly.
(3) Preparing an additive: vinylene carbonate VC 5 parts and organic silicon compound R43 parts of Si, 1 part of phenyl glycidyl ether, 1 part of ethylene glycol diglycidyl ether, 1 part of neopentyl glycol diglycidyl ether and 1 part of anisole.
(4) And (3) uniformly mixing the organic solvent and the electrolyte lithium salt according to the mass ratio of 1:1, adding 1/4 of the electrolyte lithium salt in mass into the additive prepared in the step (3), uniformly mixing and shaking, and standing for 24 hours.
Example 2
(1) Preparation of electrolyte lithium salt: lithium bis (oxalato) borate LiBOB and lithium tetrafluoroborate LiPF6And LiBETI according to the mass ratio of 1:3: 2.
(2) Preparing an organic solvent: diethyl carbonate DEC 1 part, dimethyl carbonate DMC 2 parts, fluoroethylene carbonate FEC 4 parts and propylene carbonate PC 1 part are mixed uniformly.
(3) Preparing an additive: vinylene carbonate VC 7 parts and organic silicon compound R44 parts of Si, 1 part of phenyl glycidyl ether, 3 parts of ethylene glycol diglycidyl ether, 3 parts of neopentyl glycol diglycidyl ether and 1 part of anisole.
(4) And (3) uniformly mixing the organic solvent and the electrolyte lithium salt according to the mass ratio of 1:2, adding 1/4 of the electrolyte lithium salt in mass into the additive prepared in the step (3), uniformly mixing and shaking, and standing for 24 hours.
Example 3
(1) Preparation of electrolyte lithium salt: lithium bis (oxalato) borate LiBOB and lithium tetrafluoroborate LiPF6And LiBETI according to the mass ratio of 1:3: 2.
(2) Preparing an organic solvent: diethyl carbonate DEC 3 parts, dimethyl carbonate DMC 1 parts, fluoroethylene carbonate FEC 6 parts and propylene carbonate PC 3 parts are mixed uniformly.
(3) Preparing an additive: vinylene carbonate VC 10 parts and organosilicon compound R46 parts of Si, 3 parts of phenyl glycidyl ether, 1 part of ethylene glycol diglycidyl ether, 1 part of neopentyl glycol diglycidyl ether and 3 parts of anisole.
(4) And (3) uniformly mixing the organic solvent and the electrolyte lithium salt according to the mass ratio of 1:2, adding 1/6 of the electrolyte lithium salt in mass into the additive prepared in the step (3), uniformly mixing and shaking, and standing for 24 hours.
The electrolyte prepared in the example 1-3 is injected into a self-made square flexible packaging battery according to the conventional battery manufacturing process, wherein the battery anodeIs 90wt% LiFePO4And 10wt% of conductive carbon black, the negative electrode is artificial graphite, the capacity is 5Ah, and the 0.3C discharge capacity retention rate of the battery at different temperatures is tested. The results are shown in Table 1.
Table 1 examples 1-3 results of cell performance testing
Temperature of -55℃ -20℃ 0℃ 25℃ 55℃ 95℃
Example 1 65% 80% 92% 100% 91% 65%
Example 2 73% 85% 93% 100% 92% 72%
Example 3 71% 81% 92% 100% 89% 62%
As can be seen from Table 1, the samples of examples 1-3 have 100% 0.3C discharge capacity retention at room temperature (25 ℃), 65% -71% 0.3C discharge capacity retention at low temperature of-55 ℃, 62% -72% 0.3C discharge capacity retention at high temperature of 95 ℃, and have the characteristic of wide temperature discharge.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (3)

1. The wide-temperature discharge lithium ion battery electrolyte is characterized in that: the electrolyte consists of electrolyte lithium salt, organic solvent and additive, wherein the electrolyte lithium salt is LiBOB and LiPF, and the LiBOB and the LiPF are lithium bis (oxalato-borate)6Mixing the powder and LiBETI according to the mass ratio of 1:3: 2; the organic solvent comprises the following raw materials in parts by mass: 1-3 parts of diethyl carbonate DEC, 1-3 parts of dimethyl carbonate DMC, 2-6 parts of fluoroethylene carbonate FEC and 1-3 parts of propylene carbonate PC; the additive comprises the following raw materials in parts by mass: comprises vinylene carbonate VC 5-10 parts and organosilicon compound R43-6 parts of Si, 1-3 parts of phenyl glycidyl ether, 1-3 parts of ethylene glycol diglycidyl ether, 1-3 parts of neopentyl glycol diglycidyl ether and 1-3 parts of anisole.
2. The wide temperature discharge lithium ion battery electrolyte of claim 1, wherein the organic solvent is mixed with the electrolyte lithium salt in a mass ratio of 1:1 to 1: 2.
3. The wide temperature discharge lithium ion battery electrolyte of claim 1, wherein the additive is mixed with the electrolyte lithium salt in a mass ratio of 1:4 to 1: 6.
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