CN113851727A - Preparation method of solid-state battery ultralow-temperature electrolyte material - Google Patents

Preparation method of solid-state battery ultralow-temperature electrolyte material Download PDF

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Publication number
CN113851727A
CN113851727A CN202111162669.7A CN202111162669A CN113851727A CN 113851727 A CN113851727 A CN 113851727A CN 202111162669 A CN202111162669 A CN 202111162669A CN 113851727 A CN113851727 A CN 113851727A
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solvent
solid
electrolyte material
state battery
temperature
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CN202111162669.7A
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Chinese (zh)
Inventor
徐鸿翔
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Zhengzhou Yingnuo Beisen Energy Technology Co ltd
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Zhengzhou Yingnuo Beisen Energy Technology Co ltd
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Priority to CN202111162669.7A priority Critical patent/CN113851727A/en
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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
    • H01M10/0569—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
    • 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
    • H01M10/0567—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
    • H01M10/056—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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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 discloses a preparation method of a solid-state battery ultralow temperature electrolyte material, which comprises lithium salt, a solvent and an additive; the working efficiency of the lithium ion battery under the low-temperature environment in the low-temperature state is increased through multiple angles, functional groups-NH 2 and/or-COOH are added in the additive and are used for being adsorbed on the surface of vanadium ions, the vanadium ions are dispersed more through electrostatic repulsion, the collision probability is reduced, and the vanadium ions are inhibited from undergoing a condensation reaction to form oligomers; the concentration of the lithium salt is increased to ensure that ions at low temperature also have certain conductivity; the diffusion resistance of Li + in the SEI film is reduced by improving the SEI film, thereby accomplishing the reduction of interfacial diffusion and charge exchange resistance in a low temperature state of the battery.

Description

Preparation method of solid-state battery ultralow-temperature electrolyte material
Technical Field
The invention belongs to the field of battery electrolyte, and particularly relates to a preparation method of an ultralow-temperature electrolyte material of a solid battery.
Background
A lithium ion battery is a secondary battery (rechargeable battery) that mainly operates by movement of lithium ions between a positive electrode and a negative electrode. In the process of charging and discharging, Li + is inserted and extracted back and forth between the two electrodes, and during charging, Li + is extracted from the positive electrode and inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true during discharge.
When the electric automobile is used in northern areas, scientific research and investigation in south Pole areas, aviation and other equipment, the battery is in a low-temperature state for a long time, and the lithium ion battery can have the problems of electrolyte solidification, poor discharge performance, incapability of charging and the like at low temperature.
However, only in the direction of changing the viscosity, the low-temperature condition with higher requirements cannot be met, and therefore, a mode of considering from multiple angles is needed to integrally increase the working efficiency of the lithium ion battery in a low-temperature environment.
Disclosure of Invention
Aiming at the defects, the invention provides a preparation method of a solid-state battery ultralow-temperature electrolyte material, which comprises a lithium salt, a solvent and an additive, wherein the solvent is a mixed solvent of a straight-chain solvent, a cyclic solvent and a VC additive.
Further, the linear solvent is a solvent having a relatively low viscosity and good electrochemical stability, such as DMC, EMC, or the like.
Further, the cyclic solvent is EC.
Further, the dose of VC is 2%.
Further, the additive contains functional groups-NH 2 and/or-COOH.
Further, the molar concentration of the lithium salt in the electrolyte is higher than 1.4mol/L, i.e. the concentration is higher than 16.8%.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the ultralow-temperature electrolyte material for the solid-state battery, the working efficiency of the lithium ion battery in a low-temperature environment in a low-temperature state is increased through multiple angles, functional groups-NH 2 and/or-COOH are added into an additive and used for being adsorbed on the surface of vanadium ions, the vanadium ions are dispersed more through electrostatic repulsion, the collision probability is reduced, and the vanadium ions are inhibited from undergoing a condensation reaction to form oligomers; the concentration of the lithium salt is increased to ensure that ions at low temperature also have certain conductivity; the diffusion resistance of Li + in the SEI film is reduced by improving the SEI film, thereby accomplishing the reduction of interfacial diffusion and charge exchange resistance in a low temperature state of the battery.
Drawings
FIG. 1 shows the molecular structure of the mixed solvent of the present invention.
FIG. 2 shows the basic physical and chemical indexes of the mixed solvent of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the device of the invention will be described more fully hereinafter with reference to the accompanying drawings. Embodiments of the device are given in the figures. However, the apparatus may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Examples
As shown in fig. 1-2, this embodiment provides a method for preparing an ultralow temperature electrolyte material for a solid-state battery, which includes a lithium salt, a solvent and an additive, wherein the solvent is a mixed solvent of a linear solvent, a cyclic solvent and a VC additive, the linear solvent is a solvent having relatively low viscosity and good electrochemical stability, such as DMC and EMC, and the cyclic solvent is EC (molecular structure and basic physicochemical indexes are shown in fig. 1 and 2).
It can be seen that EC has a cyclic structure, and EC can help to form a better and stable SEI film on the negative electrode, and the characteristics of higher melting point (38 ℃) and high viscosity of EC can cause the conductivity of the electrolyte to be lower at low temperature (the ionic conductivity is inversely proportional to the viscosity of the electrolyte) when EC is added too much, thus affecting the low-temperature performance of the electrolyte. The linear solvents, such as DMC, EMC, etc., have relatively low viscosity and good electrochemical stability, so the mixed solvent can improve the low-temperature performance of the lithium ion battery electrolyte, and VC (the VC additive with the dosage of 2% does not significantly change the conductivity of the electrolyte) can be reduced and decomposed in the battery formation process, so a better SEI film can be formed (the porosity and density of the SEI film have significant influence on the performance of the battery, the porosity is too high to prevent the electrolyte from further reacting on the surface of the negative electrode, and the density is too high to significantly hinder the diffusion of Li < + > therein).
When the temperature is reduced, the change of ohmic resistance Rs is relatively small, the diffusion resistance R and the charge exchange resistance Rcte of Li + in the SEI film are greatly changed, and the reduction of the ionic conductivity of the electrolyte is proved not to be the main reason for reducing the low-temperature performance of the battery.
The additive contains functional groups-NH 2 and/or-COOH and is used for being adsorbed on the surface of vanadium ions, so that the vanadium ions are more dispersed through electrostatic repulsion, the collision probability is reduced, and the condensation reaction of the vanadium ions is inhibited to form oligomers.
The molar concentration of the lithium salt in the electrolyte is higher than 1.4mol/L, namely, the concentration is higher than 16.8%, and the higher concentration of the lithium salt is proportional to the concentration of the lithium salt, so that the lithium salt can ensure that the ions have certain conductivity even at low temperature.
It should be noted that the structure of the present invention can be implemented in many different forms, and is not limited to the embodiments, and any equivalent transformation, which is directly or indirectly applied to other related technical fields, such as loading and unloading of other objects, by using the contents of the present specification and the attached drawings, of the ordinary skilled person in the art is included in the protection scope of the present invention.

Claims (6)

1. The preparation method of the solid-state battery ultralow-temperature electrolyte material comprises lithium salt, solvent and additive, and is characterized in that: the solvent is a mixed solvent of a straight-chain solvent, a cyclic solvent and a VC additive.
2. The method for preparing an ultralow temperature electrolyte material for a solid-state battery according to claim 1, wherein the method comprises the following steps: the linear solvent is a solvent having a relatively low viscosity and good electrochemical stability, such as DMC, EMC, or the like.
3. The method for preparing an ultralow temperature electrolyte material for a solid-state battery according to claim 1, wherein the method comprises the following steps: the cyclic solvent is EC.
4. The method for preparing an ultralow temperature electrolyte material for a solid-state battery according to claim 1, wherein the method comprises the following steps: the dose of VC is 2%.
5. The method for preparing an ultralow temperature electrolyte material for a solid-state battery according to claim 1, wherein the method comprises the following steps: the additive contains functional groups-NH 2 and/or-COOH.
6. The method for preparing an ultralow temperature electrolyte material for a solid-state battery according to claim 1, wherein the method comprises the following steps: the molar concentration of the lithium salt in the electrolyte is higher than 1.4mol/L, i.e. the concentration is higher than 16.8%.
CN202111162669.7A 2021-09-30 2021-09-30 Preparation method of solid-state battery ultralow-temperature electrolyte material Pending CN113851727A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101252207A (en) * 2008-04-02 2008-08-27 中南大学 Low temperature electrolyte for lithium ion battery
CN103078136A (en) * 2012-12-03 2013-05-01 湖州创亚动力电池材料有限公司 Low-temperature rate lithium ion battery electrolyte
CN103151560A (en) * 2013-02-05 2013-06-12 东莞新能源科技有限公司 Lithium ion battery electrolyte solution and its additive
CN104810551A (en) * 2014-07-09 2015-07-29 万向A一二三系统有限公司 Lithium-ion power battery electrolyte for high/low temperature environment
CN110518284A (en) * 2018-05-22 2019-11-29 比亚迪股份有限公司 A kind of nonaqueous electrolytic solution, battery and electric vehicle containing the nonaqueous electrolytic solution
CN112271338A (en) * 2020-11-27 2021-01-26 凯博能源科技有限公司 Electrolyte and lithium ion battery containing same
CN112909341A (en) * 2021-01-11 2021-06-04 电子科技大学 Lithium ion battery electrolyte, preparation method thereof, lithium ion battery and electric vehicle

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101252207A (en) * 2008-04-02 2008-08-27 中南大学 Low temperature electrolyte for lithium ion battery
CN103078136A (en) * 2012-12-03 2013-05-01 湖州创亚动力电池材料有限公司 Low-temperature rate lithium ion battery electrolyte
CN103151560A (en) * 2013-02-05 2013-06-12 东莞新能源科技有限公司 Lithium ion battery electrolyte solution and its additive
CN104810551A (en) * 2014-07-09 2015-07-29 万向A一二三系统有限公司 Lithium-ion power battery electrolyte for high/low temperature environment
CN110518284A (en) * 2018-05-22 2019-11-29 比亚迪股份有限公司 A kind of nonaqueous electrolytic solution, battery and electric vehicle containing the nonaqueous electrolytic solution
CN112271338A (en) * 2020-11-27 2021-01-26 凯博能源科技有限公司 Electrolyte and lithium ion battery containing same
CN112909341A (en) * 2021-01-11 2021-06-04 电子科技大学 Lithium ion battery electrolyte, preparation method thereof, lithium ion battery and electric vehicle

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