CN113346095A - Button cell with high temperature resistant system - Google Patents

Button cell with high temperature resistant system Download PDF

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Publication number
CN113346095A
CN113346095A CN202110532428.0A CN202110532428A CN113346095A CN 113346095 A CN113346095 A CN 113346095A CN 202110532428 A CN202110532428 A CN 202110532428A CN 113346095 A CN113346095 A CN 113346095A
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temperature resistant
temperature
electrolyte
button cell
negative electrode
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李文荣
赵兵
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Shanghai Sc Graphene Industrial Technology Co ltd
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Shanghai Sc Graphene Industrial 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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/193—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H01M50/437—Glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Cell Separators (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

The invention provides a high-temperature resistant system of a button cell, which belongs to the technical field of electrochemistry and comprises a positive electrode shell, a negative electrode shell, a high-temperature resistant sealing ring, a high-temperature resistant diaphragm and high-temperature resistant electrolyte, wherein the four parts are combined into the high-temperature resistant system, the high-temperature resistant system of the button cell is sequentially assembled by the structural positions of the positive electrode shell, a positive electrode, the high-temperature resistant diaphragm, a negative electrode and the negative electrode shell, the high-temperature resistant sealing ring is embedded in one circle at the edge of the negative electrode shell, and the high-temperature resistant electrolyte is arranged between the positive electrode shell and the negative electrode shell and completely infiltrates the high-temperature resistant diaphragm. The high-temperature resistant system of the button cell has wide adaptability to button cells made of various materials. The lithium/manganese dioxide-carbon fluoride system is used for testing at the temperature of 150 ℃, the voltage lag is small, the discharge voltage platform is stable, and the capacity is not obviously different from the normal-temperature discharge.

Description

Button cell with high temperature resistant system
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a button cell with a high-temperature resistant system.
Background
The internet of things (IoT) is a network composed of physical objects that embed sensors, software, and other technologies so that connections can be established and data exchanged with other devices and systems over the internet. The Internet of things equipment is various in types, and has common household articles and complex industrial appliances. At present, the number of internet of things devices accessing the internet exceeds 70 hundred million, and experts predict that the number will increase to 100 hundred million and 220 hundred million by 2025 in 2020. In the past few years, the internet of things has become one of the most important technologies in the 21 st century. Nowadays, various daily articles can be connected to the internet through embedded equipment, so that seamless communication among people, processes and articles is realized. One of the characteristics of the internet of things is comprehensive sensing, that is, a large amount of technologies such as sensors and radio frequency identification are utilized to acquire information of objects at any time and any place, however, in the industrial field, the agricultural field, the service industry and the public service field, the sensors need to have wide environmental durability, and therefore new requirements are provided for batteries for supplying power to the sensors.
Most button cells are primary cells, which are used in small portable devices that do not have access to external power sources, and also in backup cells for various computer devices. The button cell at present mainly comprises positive and negative cell shells, sealing rings, positive and negative pole pieces, diaphragms and electrolyte, wherein the sealing rings and the diaphragms are made of polypropylene, and the common use temperature range is-10 ℃ to 80 ℃. However, with the development of internet of things (IoT) devices and the increasing use range of IoT devices, the IoT devices in outdoor and special fields require maintenance-free and high reliability, and can stably operate even in severe environments with wide temperature and humidity. Traditional button cell is along with ambient temperature's rising, and the battery can increase from discharging, also has great voltage fluctuation during discharging, and ordinary electrolyte can take place to decompose fast under the high temperature condition, causes the battery performance to worsen rapidly until damaging, and high temperature also can aggravate the ageing of sealing washer and diaphragm simultaneously, shortens battery life.
Lithium hexafluorophosphate (LiPF) is mostly adopted as the electrolyte of the current button cell6) Lithium salt, and a plurality of carbonates are mixed according to a certain proportion to form a solvent. Under the high temperature condition (the temperature is more than or equal to 80 ℃), LiPF6Decomposition occurs to generate Hydrogen Fluoride (HF) and phosphorus Pentafluoride (PF)5). On the one hand, HF can corrode the stainless steel casing of the button cell; on the other hand, HF dissolves an SEI film on the surface of the negative electrode of the secondary battery and generates gas. PF (particle Filter)5It reacts with carbon-oxygen double bonds on the carbonate ester to cause the decomposition of the carbonate ester solvent. The sealing ring and the diaphragm are made of polypropylene materials, and the polypropylene materials can be softened, deformed and aged at high temperature, so that the mechanical property is rapidly reduced, and accidents such as battery leakage, internal short circuit, fire, explosion and the like can be caused.
The current technical scheme is a single targeted solution and does not solve the problem of no high temperature resistance of the button cell integrally and systematically. The existing technology of the heat insulation material layer has the advantages that on one hand, the high temperature capable of being blocked is low, and the high use temperature of some sensors cannot be met. On the other hand, the insulating material layer will add extra volume to the button cell, and this technique is difficult to apply to the sensor due to the strict requirements of the sensor on the volume of the components. The existing high-temperature resistant diaphragm technology only considers whether the mechanical strength of the diaphragm is attenuated at high temperature, and does not consider the matching property of the high-temperature resistant diaphragm to high-temperature resistant electrolyte and the adaptability to different electrolytes. Meanwhile, the sealing ring can be aged at high temperature, and the prior art does not provide a matched option. The existing high-temperature resistant electrolyte technology can not meet the high-temperature environment service temperature required nowadays, and the matching property and the adaptability of the diaphragm need to be considered.
CN109687021A discloses a high-temperature-resistant lithium ion battery non-aqueous electrolyte, which contains a conventional film-forming additive and a high-temperature-resistant additive, wherein the high-temperature-resistant electrolyte contains the conventional film-forming additive and the high-temperature-resistant additive, and the high-temperature-resistant additive can form a film on the surface of a positive electrode material and a negative electrode material by oxidation reduction in preference to a solvent, so that the cracking of a protective film at high temperature is inhibited, the electrolyte and the positive electrode material are prevented from undergoing oxidation reduction reaction, and the service life of the battery is prolonged. CN202839810U discloses a button lithium battery with a high-temperature-resistant diaphragm, which is characterized in that glass fiber is used as the diaphragm, and compared with a common diaphragm, the limit service temperature of the diaphragm is increased from 80 ℃ to 150 ℃. CN108736104A discloses a high temperature resistant battery based on phase change material and heat insulating material, wherein the phase change material layer wraps the outer wall of the battery, the heat insulating layer wraps the outside of the phase change material layer, and the battery is maintained at a proper working temperature through the obstruction of the heat insulating layer and the heat absorption of the phase change material layer. The three patents all improve the high-temperature resistance of the button cell in a certain aspect, but do not take the adaptability among the cell shell, the sealing ring, the diaphragm and the electrolyte into consideration integrally and systematically.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a button cell with a high-temperature resistant system, which has no obvious self-discharge phenomenon after a high-temperature storage aging test, has better initial voltage maintenance and has no influence of high temperature on discharge performance.
The technical scheme of the invention is as follows:
the utility model provides a button cell with high temperature resistant system, includes the battery case that comprises anodal shell and negative pole shell, is equipped with positive pole and negative pole in this battery case, its characterized in that still includes high temperature resistant sealing washer, high temperature resistant diaphragm and high temperature resistant electrolyte, high temperature resistant sealing washer follow negative pole shell edge inlay the round, high temperature resistant diaphragm set up and be in positive pole and negative pole between, high temperature resistant electrolyte be full of the battery case in to soak completely the high temperature resistant diaphragm.
The high-temperature-resistant sealing ring is made of nitrile rubber, silicon rubber or fluororubber. The nitrile rubber can be used at 120 ℃ for a long time, the silicone rubber can be used at 200 ℃ for a long time, the fluororubber can be used at 240 ℃ for a long time, and the three rubbers have good stability in electrolyte.
The high-temperature resistant diaphragm is a glass fiber film with a ceramic coating, a polyimide film with a ceramic coating and an aramid polyamide film with a ceramic coating. The properties of the various separators are shown in Table 1.
Preferably, the polyimide film with the ceramic coating takes the polyimide film as a substrate, and a layer of yttrium-doped zirconia inorganic ceramic coating is coated on the surface of the polyimide film. The ceramic coating is prepared by adopting a dip-coating or blade-coating process, and the coating slurry is prepared by ultrafine ceramic particles (99.99 percent, the particle size is 0.1-1.0 mu m), a binder, a solvent and a surfactant according to a certain proportion. Preferably, the ultra-fine ceramic particles: adhesive: surfactant 80: 15: 5; the solvent is deionized water, and 1-10 wt% of binder is prepared from homogeneous water-based binders such as sodium carboxymethylcellulose (CMC), Styrene Butadiene Rubber (SBR), hydroxypropyl methylcellulose (HPMC) and the like; the surfactant is polyvinyl alcohol (PEO) or polyethylene glycol (PEG) or sodium hexadecyl sulfonate.
TABLE 1
Figure BDA0003068423490000041
As a further preferable aspect of the present invention, the high temperature resistant electrolytic solution includes a high temperature resistant electrolyte lithium salt and a high temperature resistant non-aqueous organic solvent.
As a further preferred aspect of the present invention, the high temperature resistant electrolyte lithium salt is lithium bistrifluoromethanesulfonylimide (LiTFSI) and lithium tetrafluoroborate (LiBF)4) At least one of (1). LiTFSI and LiPF4All have good thermal stability, are not easy to decompose at the temperature of 150 ℃, and have no corrosion effect on the anode aluminum current collector under higher voltage.
In a further preferred embodiment of the present invention, the concentration of the high-temperature resistant electrolyte lithium salt is 0.5mol/L to 1 mol/L.
As a further preferred aspect of the present invention, the high temperature-resistant non-aqueous organic solvent is Propylene Carbonate (PC). The electrolyte has the molecular weight of 102.09, the relative density of 1.2047, the melting point of-49.2 ℃, the boiling point of 238.4 ℃, the flash point of 128 ℃ and the relative dielectric constant (under the condition of 25 ℃) of 66.1, is a polar solvent, can bear less severe light, heat and chemical change environments when being used as a battery electrolyte, and has higher ionic conductivity under the condition of high temperature.
The invention has the following beneficial effects:
1) the system comprehensively considers the mutual adaptability of different parts at different use temperatures and the incompatible condition of each part, and avoids the occurrence of the barrel effect. The core of the button cell high-temperature resistant system is a high-temperature resistant sealing ring, a high-temperature resistant diaphragm and high-temperature resistant electrolyte. On one hand, each component has high temperature resistance and can not melt or decompose at high temperature. On the other hand, the lithium salt has good solubility in the solvent, the electrolyte has high ionic conductivity at high temperature, the electrolyte has good wettability to the diaphragm, and the sealing ring is inert to the electrolyte. The heat stability and the ionic conductivity of the electrolyte, the high-temperature resistance and the inertia of the sealing ring to the electrolyte, the high-temperature resistance of the diaphragm and the infiltration performance of the electrolyte are comprehensively considered.
2) The button cell has wide adaptability to button cells made of various types of materials. The lithium/manganese dioxide-carbon fluoride system is used for testing at the temperature of 150 ℃, the voltage lag is small, the discharge voltage platform is stable, and the capacity is not obviously different from the normal-temperature discharge.
Drawings
FIG. 1 is a high temperature resistant constant current discharge test chart in test example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A high-temperature resistant system of a button battery comprises a positive electrode shell, a negative electrode shell, a high-temperature resistant sealing ring, a high-temperature resistant diaphragm and high-temperature resistant electrolyte. The button type battery high-temperature resistant system is assembled by sequentially arranging a positive electrode shell, a positive electrode, a high-temperature resistant diaphragm, a negative electrode and a negative electrode shell, the high-temperature resistant sealing ring is embedded in the edge circle of the negative electrode shell, and the high-temperature resistant diaphragm is completely immersed in the high-temperature resistant electrolyte between the positive electrode shell and the negative electrode shell. The anode shell and the cathode shell are made of 316 stainless steel, the high-temperature-resistant sealing ring is made of silicon rubber, the high-temperature-resistant diaphragm is a ceramic coating glass fiber membrane, the high-temperature-resistant electrolyte is 0.5mol/L lithium bistrifluoromethane sulfimide (LiTFSI) serving as an electrolyte, and the solvent is Propylene Carbonate (PC).
Manganese dioxide-carbon fluoride is used as a battery anode, a metal lithium sheet is used as a battery cathode, 0.5mol/L LiTFSI in PC is used as a high-temperature resistant electrolyte, and a high-temperature resistant button cell system is used in a low-water-oxygen environment (H)2O＜1ppm，O2Less than 1ppm) assembling the battery by using the structure positions of the positive electrode shell, the positive electrode, the high-temperature resistant diaphragm, the negative electrode and the negative electrode shell, wherein the high-temperature resistant sealing ring is embedded in the edge of the negative electrode shell for a circle, and the high-temperature resistant electrolyte is between the positive electrode and the negative electrode and completely infiltrates the high-temperature resistant diaphragm.
Example 2
A high-temperature resistant system of a button battery comprises a positive electrode shell, a negative electrode shell, a high-temperature resistant sealing ring, a high-temperature resistant diaphragm and high-temperature resistant electrolyte. The button type battery high-temperature resistant system is assembled by sequentially arranging a positive electrode shell, a positive electrode, a high-temperature resistant diaphragm, a negative electrode and a negative electrode shell, the high-temperature resistant sealing ring is embedded in the edge circle of the negative electrode shell, and the high-temperature resistant diaphragm is completely immersed in the high-temperature resistant electrolyte between the positive electrode shell and the negative electrode shell. Wherein the positive electrode shell and the negative electrode shell are made of 316 stainless steel, the high-temperature resistant sealing ring is made of nitrile rubber, the high-temperature resistant diaphragm is a ceramic coating glass fiber film, and the high-temperature resistant electrolyte is 1mol/L lithium tetrafluoroborate (LiBF)4) As the electrolyte, the solvent was Propylene Carbonate (PC).
Manganese dioxide-carbon fluoride is taken as the battery anode, a metal lithium sheet is taken as the battery cathode, and1mol/L LiBF is adopted4in PC as high temperature resistant electrolyte, using high temperature resistant button cell system in low water oxygen environment (H)2O＜1ppm，O2Less than 1ppm) assembling the battery at the structural positions of a positive electrode shell, a positive electrode, a high-temperature resistant diaphragm, a negative electrode and a negative electrode shell, wherein a high-temperature resistant sealing ring is embedded at the edge of the negative electrode shell for a circleThe high-temperature resistant electrolyte is arranged between the anode and the cathode and completely infiltrates the high-temperature resistant diaphragm.
Example 3
A high-temperature resistant system of a button battery comprises a positive electrode shell, a negative electrode shell, a high-temperature resistant sealing ring, a high-temperature resistant diaphragm and high-temperature resistant electrolyte. The button type battery high-temperature resistant system is assembled by sequentially arranging a positive electrode shell, a positive electrode, a high-temperature resistant diaphragm, a negative electrode and a negative electrode shell, the high-temperature resistant sealing ring is embedded in the edge circle of the negative electrode shell, and the high-temperature resistant diaphragm is completely immersed in the high-temperature resistant electrolyte between the positive electrode shell and the negative electrode shell. The anode shell and the cathode shell are made of 316 stainless steel, the high-temperature-resistant sealing ring is made of silicon rubber, the high-temperature-resistant diaphragm is a ceramic coating polyimide film, the high-temperature-resistant electrolyte is 0.5mol/L lithium bis (trifluoromethane) sulfonyl imide (LiTFSI) serving as an electrolyte, and the solvent is Propylene Carbonate (PC).
Manganese dioxide-carbon fluoride is used as a battery anode, a metal lithium sheet is used as a battery cathode, 0.5mol/L LiTFSI in PC is used as a high-temperature resistant electrolyte, and a high-temperature resistant button cell system is used in a low-water-oxygen environment (H)2O＜1ppm，O2Less than 1ppm) assembling the battery by using the structure positions of the positive electrode shell, the positive electrode, the high-temperature resistant diaphragm, the negative electrode and the negative electrode shell, wherein the high-temperature resistant sealing ring is embedded in the edge of the negative electrode shell for a circle, and the high-temperature resistant electrolyte is between the positive electrode and the negative electrode and completely infiltrates the high-temperature resistant diaphragm.
Example 4
A high-temperature resistant system of a button battery comprises a positive electrode shell, a negative electrode shell, a high-temperature resistant sealing ring, a high-temperature resistant diaphragm and high-temperature resistant electrolyte. The button type battery high-temperature resistant system is assembled by sequentially arranging a positive electrode shell, a positive electrode, a high-temperature resistant diaphragm, a negative electrode and a negative electrode shell, the high-temperature resistant sealing ring is embedded in the edge circle of the negative electrode shell, and the high-temperature resistant diaphragm is completely immersed in the high-temperature resistant electrolyte between the positive electrode shell and the negative electrode shell. Wherein the positive electrode shell and the negative electrode shell are made of 316 stainless steel, the high-temperature-resistant sealing ring is made of nitrile rubber, the high-temperature-resistant diaphragm is a ceramic coating polyimide film, and the high-temperature-resistant electrolyte is 0.5mol/L lithium bistrifluoromethanesulfonylimide (LiTFSI) mixed with 1mol/L lithium tetrafluoroborate (LiBF)4) As electrolyte, solventIs Propylene Carbonate (PC).
Manganese dioxide-carbon fluoride is taken as the battery anode, a metal lithium sheet is taken as the battery cathode, 0.5mol/L LiTFSI and1mol/L LiBF are adopted4in PC as high temperature resistant electrolyte, using high temperature resistant button cell system in low water oxygen environment (H)2O＜1ppm，O2Less than 1ppm) assembling the battery by using the structure positions of the positive electrode shell, the positive electrode, the high-temperature resistant diaphragm, the negative electrode and the negative electrode shell, wherein the high-temperature resistant sealing ring is embedded in the edge of the negative electrode shell for a circle, and the high-temperature resistant electrolyte is between the positive electrode and the negative electrode and completely infiltrates the high-temperature resistant diaphragm.
Example 5
A high-temperature resistant system of a button battery comprises a positive electrode shell, a negative electrode shell, a high-temperature resistant sealing ring, a high-temperature resistant diaphragm and high-temperature resistant electrolyte. The button type battery high-temperature resistant system is assembled by sequentially arranging a positive electrode shell, a positive electrode, a high-temperature resistant diaphragm, a negative electrode and a negative electrode shell, the high-temperature resistant sealing ring is embedded in the edge circle of the negative electrode shell, and the high-temperature resistant diaphragm is completely immersed in the high-temperature resistant electrolyte between the positive electrode shell and the negative electrode shell. The anode shell and the cathode shell are made of 316 stainless steel, the high-temperature-resistant sealing ring is made of fluororubber, the high-temperature-resistant diaphragm is a ceramic coating aramid polyamide film, the high-temperature-resistant electrolyte is 0.5mol/L lithium bistrifluoromethanesulfonylimide (LiTFSI) serving as an electrolyte, and the solvent is Propylene Carbonate (PC).
Manganese dioxide-carbon fluoride is used as a battery anode, a metal lithium sheet is used as a battery cathode, 0.5mol/L LiTFSI in PC is used as a high-temperature resistant electrolyte, and a high-temperature resistant button cell system is used in a low-water-oxygen environment (H)2O＜1ppm，O2Less than 1ppm) assembling the battery by using the structure positions of the positive electrode shell, the positive electrode, the high-temperature resistant diaphragm, the negative electrode and the negative electrode shell, wherein the high-temperature resistant sealing ring is embedded in the edge of the negative electrode shell for a circle, and the high-temperature resistant electrolyte is between the positive electrode and the negative electrode and completely infiltrates the high-temperature resistant diaphragm.
Comparative example 1
The test was carried out using a commercially available CR2032 cell case, the seal ring being of polypropylene (PP), and the diaphragm being a commercially available Celgard2500 diaphragm (PP) and a commercially available electrolyte. Wherein the sealing ring is made of polypropylene, the diaphragm is made of polypropylene, and the electrolyteLithium hexafluorophosphate (LiPF) at 1mol/L6) As the electrolyte, the solvents are Ethylene Carbonate (EC) and dimethyl carbonate (DMC).
Manganese dioxide-carbon fluoride is used as a battery anode, a metal lithium sheet is used as a battery cathode, and1mol/L LiPF6in EC: DMC 1:1 vol% as electrolyte in low water oxygen environment (H)2O＜1ppm，O2Less than 1ppm) assembling the battery by using the structural positions of the positive electrode shell, the positive electrode, the diaphragm, the negative electrode and the negative electrode shell, wherein the PP sealing ring is embedded in the edge of the negative electrode shell for a circle, and the electrolyte is arranged between the positive electrode and the negative electrode and completely infiltrates the diaphragm. After the assembled battery is kept stand for 12 hours, the assembled battery is transferred to a thermostat with the temperature of 150 ℃, and the PP sealing ring can be observed to be softened at the temperature of 120 ℃, so that the battery cannot be effectively sealed and electrolyte seeps out. And then the battery is transferred into a glove box for disassembly, so that the softening deformation of the PP diaphragm can be found, the contact of the positive and negative pole pieces can not be effectively separated to prevent short circuit, and the phenomenon of electrolyte lithium salt precipitation can be found.
Test example 1
The button cell high temperature resistant system prepared in example 1 was tested at 150 ℃ using a lithium/manganese dioxide-carbon fluoride system, and the specific test conditions were as follows: the high-temperature thermostat is used to maintain the test environment temperature at 150 ℃, and the micro-current battery test equipment is used to perform 0.1C constant current discharge test on the battery, and the result is shown in figure 1. as can be seen from figure 1, the voltage lag is small, the discharge voltage platform is stable, and the capacity is not obviously different from the normal-temperature discharge.
Test example 2
The high temperature systems of the button cells prepared in examples 1 to 5 were subjected to performance tests, and the results are shown in Table 2.
TABLE 2
Group of Specific capacity (mAh/g) Discharging voltage platform (V) High temperature storage Property (V)
Example 1 853 2.57 2.88
Example 2 817 2.58 2.90
Example 3 781 2.51 2.83
Example 4 790 2.49 2.78
Example 5 730 2.45 2.74
Wherein the high temperature storage property is expressed as an initial voltage property after storage at 150 ℃ for 1 month.
After the battery is subjected to a high-temperature storage aging test, the battery has no obvious self-discharge phenomenon, the initial voltage is kept better, and the discharge performance is not influenced by high temperature.
Compared with the prior art, the high-temperature resistant system of the button cell comprises the high-temperature resistant sealing ring, the high-temperature resistant diaphragm and the high-temperature resistant electrolyte, the system comprehensively considers the mutual adaptability of different parts at different use temperatures and the incompatible condition of each part, and avoids the occurrence of the wooden barrel effect. And the battery has wide adaptability to button batteries of various types of materials. The lithium/manganese dioxide-carbon fluoride system is used for testing at the temperature of 150 ℃, the voltage lag is small, the discharge voltage platform is stable, and the capacity is not obviously different from the normal-temperature discharge.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (7)

1. A button cell with a high-temperature resistant system comprises a cell shell consisting of an anode shell and a cathode shell, wherein an anode and a cathode are arranged in the cell shell;
the high-temperature resistant sealing ring is made of nitrile rubber, silicon rubber or fluororubber;
the high-temperature resistant diaphragm is a glass fiber film with a ceramic coating, a polyimide film with a ceramic coating or an aramid fiber polyimide film with a ceramic coating.
2. The button cell with a high temperature resistant system according to claim 1, wherein the high temperature resistant electrolyte comprises a high temperature resistant electrolyte lithium salt and a high temperature resistant non-aqueous organic solvent.
3. Button cell with high temperature system according to claim 2, characterized in that the lithium salt of the high temperature electrolyte is bis (trifluoromethanesulphonimide)Lithium (LiTFSI) and lithium tetrafluoroborate (LiPF)4) At least one of (1).
4. The button cell with the high-temperature resistant system according to claim 2, wherein the concentration of the substance of the high-temperature resistant electrolyte lithium salt is 0.5mol/L to 1 mol/L.
5. The button cell with a high temperature resistant system according to claim 2, wherein the high temperature resistant non-aqueous organic solvent is Propylene Carbonate (PC).
6. The button cell with the high temperature resistant system according to claim 1, wherein the polyimide film with the ceramic coating is a polyimide film as a substrate, and an yttrium-doped zirconia inorganic ceramic coating is coated on the surface of the polyimide film.
7. The button cell refractory temperature system of claim 6, wherein the inorganic ceramic coating is selected from alumina (Al)2O3) Silicon dioxide (SiO)2) Magnesium hydroxide (Mg (OH)2) Yttrium doped zirconia (Y-ZrO)2) At least one of (1).
CN202110532428.0A 2021-05-17 2021-05-17 Button cell with high temperature resistant system Pending CN113346095A (en)

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Application publication date: 20210903