CN111224161B - Method for improving low-temperature service performance of lithium ion battery by electrolyte containing additive - Google Patents

Method for improving low-temperature service performance of lithium ion battery by electrolyte containing additive Download PDF

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CN111224161B
CN111224161B CN201811418586.8A CN201811418586A CN111224161B CN 111224161 B CN111224161 B CN 111224161B CN 201811418586 A CN201811418586 A CN 201811418586A CN 111224161 B CN111224161 B CN 111224161B
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electrolyte
lithium ion
ion battery
lithium salt
low
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CN111224161A (en
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马荻
张华民
张洪章
李先锋
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Dalian Institute of Chemical Physics of CAS
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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
    • H01M10/0568—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
    • H01M10/056—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
    • 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 an electrolyte containing an additive for improving the low-temperature performance of an LVP lithium ion battery, which comprises the following components: one or more than two lithium salt additives; the concentration of the lithium salt additive in the electrolyte is 0.5-10 mol/L; solute as electrolyte: LiPF6The concentration of the lithium salt in the electrolyte is 1-20 mol/L; solvent as electrolyte: one or more than two of the linear ester compounds with the following structures, H (CH)2)n‑(C＝O)‑O‑(CH2) mH, wherein m and n are integers, and the value ranges are respectively 10-18 and 11-16; li at low temperature of the electrolyte+Very low binding energy to solvent molecules, Li+The desolvation capacity is enhanced, the charge transfer resistance of an electrode/electrolyte interface is reduced, and the capacity performance and the rate capability of the LVP lithium ion battery are improved.

Description

Method for improving low-temperature service performance of lithium ion battery by electrolyte containing additive
Technical Field
The invention relates to the field of low-temperature lithium ion batteries, in particular to a low-temperature electrolyte of a lithium ion battery.
Background
Lithium ion batteries have been widely used in many fields, such as electronic devices and hybrid electric vehicles, due to their advantages of high energy density, high power density, long cycle life, flexibility, portability, etc., and become an energy storage technology with the greatest application prospect in the field of new energy. With the increasing expansion of the application range of the lithium ion battery, especially the application in the fields of electric vehicles, aerospace and military industry, the lithium ion battery has higher requirements on the low-temperature charge and discharge performance, but the lithium ion battery has poor charge and discharge performance in a low-temperature environment, especially below-thirty degrees, the common lithium ion battery cannot be used basically, and if the low-temperature performance of the lithium ion battery is improved, the application of the lithium ion battery in more fields can be developed more greatly.
Polyanionic materials are a series of compounds containing tetrahedral or octahedral anionic structural units connected by stronger covalent bondsThe polyanion type anode material has a crystal structure completely different from that of the metal oxide and excellent performances due to the formation of a three-dimensional network structure. Among them, Lithium Vanadium Phosphate (LVP) having a monoclinic structure belongs to Nassicon type compounds, and has P21The/n-type space structure group enables lithium ions to realize three-dimensional diffusion in crystal lattices, has good rate capability and low-temperature capability better than the diffusion modes of LiFePO4, LiMn2O4, LiCoO2 and the like, and has rich vanadium ore resources in China, so that the LVP is more suitable for being applied to low-temperature lithium ion batteries.
The electrolyte is used as a medium for conducting ions and electrons, is one of important components of the battery, the composition of the electrolyte has great influence on the normal-temperature performance, particularly the low-temperature performance of the battery, and the improvement of the low-temperature performance of the lithium ion battery by improving the components of the electrolyte (including lithium salt, solvent and additives) is a more effective method, so that the development of the low-temperature electrolyte for the lithium ion battery is very important. The main reason for the poor low temperature performance of lithium ion batteries is the excessive charge transfer resistance (Rct), which results from: the method comprises the following steps of (1) desolvating Li +, penetrating through an SEI (solid electrolyte interface) film of an electrode/electrolyte interface, and (3) accepting electrons when Li + is embedded into the electrode, wherein the desolvation process before the Li + is embedded into the electrode is a main reason for increasing Rct. The desolvation capacity of Li + is greatly related to the type of the solvent, solvent molecules can tightly surround Li + after the lithium salt is dissociated, and particularly the combination energy of Li + and the solvent molecules is high at low temperature, so that the desolvation effect of Li + is reduced, and the battery has poor capacity and rate performance at low temperature. The solvation effect of solvent molecules on Li + is related to the structure of the solvent molecules, and the solvation effect of the solvent molecules on Li + is reduced by screening the solvent with a special structure, so that the aim of improving the low-temperature performance of the lithium ion battery is fulfilled.
Disclosure of Invention
The invention aims to provide an electrolyte for improving the low-temperature performance of an LVP lithium ion battery, wherein the binding energy of Li & lt + & gt and solvent molecules in the electrolyte is extremely low at-40 ℃, so that the Li & lt + & gt desolvation capacity is remarkably enhanced, and the charge transfer resistance of an electrode/electrolyte interface is reduced, thereby improving the capacity and rate capability of the battery.
In order to achieve the purpose, the invention adopts the following specific scheme:
the low-temperature electrolyte for the LVP lithium ion battery comprises the following components:
1. solvent as electrolyte: one or more than two of the linear ester compounds with the following structures, H (CH)2)n-(C＝O)-O-(CH2)mH, wherein m and n are integers, and the value ranges of n is 10-18, m is 11-16, preferably n is 12-15, and m is 13-14;
2. solute as electrolyte: LiPF6The concentration of the lithium salt in the electrolyte is 1-20 mol/L;
3. as an additive of the electrolyte: one or more than two lithium salt additives; the concentration of the lithium salt additive in the electrolyte is 0.5-10 mol/L
The concentration of the lithium salt in the electrolyte is preferably 10-15 mol/L;
the concentration of the lithium salt additive in the electrolyte is preferably 5-10 mol/L;
the lithium salt additive comprises one or more than two of the following components: LiBr, LiI, LiBF4LiBOB, LiDFOB, LiFSI, LiTFSI; among them, preferred is LiBF4One or more of LiI and LiBr.
The electrolyte is used for LVP lithium ion batteries, and the temperature of the electrolyte is-50 to-30 ℃.
The invention has the beneficial effects that:
the electrolyte is applied to the lithium ion battery, and the low-temperature service performance of the lithium ion battery is remarkably improved, because the lithium salt in the electrolyte has higher dissociation degree in the ultra-long straight-chain solvent molecules, and the solvent molecules and Li are reduced+The binding energy of (1) is such that the anions dissociated from the lithium salt additive in the electrolyte are preferentially bound to the lithium ions, thereby greatly reducing Li+Increase of Li at Low temperatures+Desolvation ability and can form a negative electrode having high Li content+The conductive SEI film reduces the resistance of the SEI film, so that the LVP lithium ion battery is at the low temperature of-40 DEG CThe product has good capacity and rate capability.
Attached table:
table 1: the embodiment 1-2 is the calculation of the binding energy of the negative and positive ions and the solvent molecules of the electrolyte at the normal temperature of 25 ℃ and the low temperature of minus 40 ℃;
table 2: comparative examples 1-2 are the calculation of the binding energy of the negative and positive ions and the solvent molecules of the electrolyte at the normal temperature of 25 ℃ and the low temperature of-40 ℃;
table 3: example 3 and comparative example 3 are the specific discharge capacity of the LVP lithium ion battery of 0.2C at 25 ℃ at normal temperature and the specific discharge capacity of 0.2C-2C at-40 ℃ at low temperature;
Detailed Description
Example 1
The electrolyte lithium salt is LiPF6, and the concentration of the lithium salt in the electrolyte is 1 mol/L; the solvent is H (CH2) n- (C ═ O) -O- (CH2) mH, wherein n is 12, m is 13, the lithium salt additive is LiI, and the concentration is 0.5 mol/L; calculating the binding energy of anions and cations in the Electrolyte and solvent molecules at 25 ℃ and-40 ℃ by adopting a Gering's Advanced Electrolyte Model method;
the test results are shown in table 1.
Example 2
The electrolyte lithium salt is LiPF6, and the concentration of the lithium salt in the electrolyte is 10 mol/L; the solvent is H (CH2) n- (C ═ O) -O- (CH2) mH, wherein n is 12, m is 13, the lithium salt additive is LiI, and the concentration is 5 mol/L; calculating the binding energy of anions and cations in the Electrolyte and solvent molecules at 25 ℃ and-40 ℃ by adopting a Gering's Advanced Electrolyte Model method;
the test results are shown in table 1.
Example 3
The electrolyte lithium salt is LiPF6, and the concentration of the lithium salt in the electrolyte is 10 mol/L; the solvent is H (CH2) n- (C ═ O) -O- (CH2) mH, wherein n is 12, m is 13, the lithium salt additive is LiI, and the concentration is 5 mol/L; (ii) a
The positive electrode of the lithium ion battery is prepared as follows: li3V2(PO4)3Dissolving the conductive carbon black and the binder in a mass ratio of 8:1:1 in a proper amount of N-methyl pyrrolidone, uniformly mixing, coating the mixture into an electrode film with the thickness of 0.15mm by using a wet film preparation device, and drying in vacuumAfter drying, the pieces were cut into pieces of 12mm in diameter with a microtome, weighed and the mass of the active substance calculated. Meanwhile, a lithium sheet was used as a negative electrode, Celgard 2500 was used as a separator, 50 μ l of an electrolyte was added, a button cell was assembled in a glove box filled with argon gas, and then the assembled cell was subjected to an electrochemical test. Inspecting the capacity performance and rate performance of the battery at the normal temperature of 25 ℃ and the low temperature of-40 ℃;
the test results are shown in table 3.
Comparative example 1
The electrolyte lithium salt is LiPF6, and the concentration of the lithium salt in the electrolyte is 1 mol/L; the solvent is methyl acetate; the lithium salt additive is LiI, the concentration is 0.5mol/L, and the binding energy of anions and cations in the Electrolyte and solvent molecules at 25 ℃ and-40 ℃ is calculated by adopting a Gering's Advanced electric cell Model method;
the test results are shown in table 2.
Comparative example 2
The electrolyte lithium salt is LiPF6, and the concentration of the lithium salt in the electrolyte is 10 mol/L; the solvent is methyl acetate; the lithium salt additive is LiI, the concentration is 5mol/L, and the binding energy of anions and cations in the Electrolyte and solvent molecules at 25 ℃ and-40 ℃ is calculated by adopting a Gering's Advanced electric Model method;
the test results are shown in table 2.
Comparative example 3
The electrolyte lithium salt is LiPF6, and the concentration of the lithium salt in the electrolyte is 10 mol/L; the solvent is methyl acetate; the lithium salt additive is LiI, the concentration is 5mol/L, and the binding energy of anions and cations in the Electrolyte and solvent molecules at 25 ℃ and-40 ℃ is calculated by adopting a Gering's Advanced electric Model method;
the positive electrode of the lithium ion battery is prepared as follows: li3V2(PO4)3Dissolving the conductive carbon black and the binder in a proper amount of N-methyl pyrrolidone at a mass ratio of 8:1:1, uniformly mixing, coating into an electrode film with the thickness of 0.15mm by using a wet film preparation device, cutting into electrode slices with the diameter of 12mm by using a slicing machine after vacuum drying, weighing, and calculating the mass of the active substance. Meanwhile, a lithium plate is used as a negative electrode, Celgard 2500 is used as a diaphragm, and 50 microliter of electrolyte is addedThe button cells were assembled in an argon-filled glove box and the assembled cells were subjected to electrochemical testing. Table 3 examines the capacity performance and rate performance of the battery at normal temperature of 25 ℃ and low temperature of-40 ℃;
as can be seen from the combination of tables 1 and 2, compared with the comparative example, the solvent molecules selected for the electrolyte have higher solubility of lithium salt, the higher the concentration of lithium salt is, the lower the binding energy of lithium salt and solvent is, the anions after dissociation of the lithium salt additive in the electrolyte are preferentially combined with lithium ions, and the Li is reduced+Increase of Li at Low temperatures+The desolvation capability enables the LVP lithium ion battery to have good capacity and rate capability at the low temperature of-40 ℃. The conventional solvent is selected for the comparative example, and even if the lithium salt additive is added, the solubility of the lithium salt in the electrolyte is low, the solvation effect of the electrolyte cannot be solved, and the specific discharge capacity of the battery is low.
TABLE 1
Figure BDA0001880056290000041
TABLE 2
Figure BDA0001880056290000051
TABLE 3
Figure BDA0001880056290000052

Claims (1)

1. A method for improving the low-temperature service performance of a lithium ion battery by adopting electrolyte containing an additive is characterized in that:
the electrolyte comprises a solvent of the electrolyte, a solute of the electrolyte and an additive of the electrolyte;
solvent as electrolyte: one or more than two of the linear ester compounds with the following structures, H (CH)2)n-(C=O)-O-(CH2) mH, wherein m, n are wholeThe number ranges of n = 10-18 and m = 11-16 respectively;
solute as electrolyte: LiPF6The concentration of the lithium salt in the electrolyte is 10-15 mol/L;
as an additive of the electrolyte: LiBF4One or more than two of LiI and LiBr, wherein the concentration is 5-10 mol/L;
the electrolyte is used for a lithium vanadium phosphate LVP lithium ion battery with a monoclinic structure, and the temperature of the electrolyte is between 50 ℃ below zero and 30 ℃ below zero.
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