CN106531927A - Application of porous separator in lithium ion battery - Google Patents

Application of porous separator in lithium ion battery Download PDF

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Publication number
CN106531927A
CN106531927A CN201510573548.XA CN201510573548A CN106531927A CN 106531927 A CN106531927 A CN 106531927A CN 201510573548 A CN201510573548 A CN 201510573548A CN 106531927 A CN106531927 A CN 106531927A
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pei
pvp
lithium ion
solution
polyetherimide
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CN106531927B (en
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史丁秦
李先锋
张华民
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Dalian Institute of Chemical Physics of CAS
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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
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • 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
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to application of a porous separator in a lithium ion battery, in particular to application of the porous separator in the field of the lithium ion battery. The porous separator is a blended solution formed from polyetherimide and polyvinylpyrrolidone and is prepared by a humidity phase inversion method, wherein the mass ratio of the polyetherimide to the polyvinylpyrrolidone is (10-40):(1-30), the pore diameter is 10-1,000 nanometers, and the porosity is 45-85%. The blended porous separator prepared according to the invention is good in lyophilicity, high in thermal stability, uniform in pore distribution, high in porosity and adjustable in pore diameter, the preparation method is simple and controllable, and mass production is easily achieved; and more importantly, the available range of the separator for the lithium ion battery is expanded.

Description

A kind of application of porous septum in lithium ion battery
Technical field
The present invention provides a kind of battery blending porous septum, more particularly to its application in field of lithium ion battery.
Background technology
The renewable energy power generations such as wind energy, solar energy are affected by season, meteorological and regional condition, with significantly not connecting Continuous, unstability.The power fluctuation for sending is larger, and controllability is poor.And then greater impact will likely be produced to electrical network.Therefore, With the rapid emergence of the regenerative resources such as wind energy, solar energy and intelligent grid industry, energy storage technology becomes Jiao for attracting the attention of millions of people Point.Extensive energy storage technology is considered as the strategic technology for supporting regenerative resource popularization, obtains national governments and business circles Highest attention.
Energy storage technology includes two big class of physics energy storage and chemical energy storage.Physics energy storage includes draw water energy storage, compressed air storage Energy, flywheel energy storage etc..Chemical energy storage mainly includes lead-acid battery, sodium-sulphur battery, flow battery and lithium ion battery etc..But it is each The application that kind of energy storage technology has which suitable, be adapted to extensive energy storage chemical energy storage technology mainly include flow battery, Sodium-sulphur battery, lead-acid battery, lithium ion battery.Consider the pluses and minuses of various energy storage technologies, flow battery and lithium-ion electric Pond energy storage technology is received more broadly to be paid close attention to.
No matter in flow battery or lithium ion battery, barrier film is the important component part of battery, in battery cost Proportion is higher, therefore, development cost is low, performance is high and the battery diaphragm that has a safety feature, is to reduce battery cost, lifting One of important channel of battery performance.
Research finds that Polyetherimide (abbreviation PEI) is one of optimal polymer of combination property, and PEI has very strong High-temperature stability, even the PEI of non-reinforcing type, still with good toughness and intensity, with excellent mechanical performance, electricity absolutely Edge performance, radiation-resistant property, high-low temperature resistant and anti-wear performance.PEI also has good anti-flammability, anti-chemical reaction and electric insulation Characteristic.PEI also has very low shrinkage factor and the direction mechanical property such as good.And polyvinylpyrrolidone (PVP) has very Good dissolubility, very soluble in water and most of organic solvent, this is also provided and has played positive for the preparation of porous septum Effect.
The content of the invention
In order to achieve the above object, the present invention adopt the following technical scheme that it is as follows,
Porous septum is the blend solution formed by Polyetherimide and polyvinylpyrrolidone, by humidity phase inversion It is prepared from, one or more wherein in polysulfones, polyimides, PAEK, polyether sulfone, Polyetherimide, it is and poly- The mass ratio of vinylpyrrolidone is (10-40)：(1-30), aperture 10-1000nm, porosity 45-85%.
The preparation method of battery porous septum, its raw material for adopting include Polyetherimide and polyvinylpyrrolidine Ketone；
The porous composite film can be prepared as follows：
1) Polyetherimide is dissolved in organic solvent, is to stir more than 1 hour between 10-40 DEG C in temperature, obtains molten Liquid；
2) PVP is added into step 1) in configured good solution, it is to stir more than 1 hour between 10-40 DEG C in temperature, obtains To mixed solution；In mixed solution the mass concentration of Polyetherimide be 10-40% between, PVP mass concentrations be 1-30% it Between；
3) mixed solution is coated on flat board, using humidity phase inversion mixed solution masking, temperature 10-50 DEG C, Relative humidity 60-100%, 3-20 minutes humidity inversion of phases time.
The organic solvent can be one or more in DMSO, DMAC, NMP, DMF.
The beneficial outcomes of the present invention：
1st, polyvinylpyrrolidone (PVP) has good dissolubility, very soluble in water and most of organic solvent, Porous septum has good pore-creating function in preparing, and this is also provided and played positive effect for the preparation of porous septum；
2nd, improve the heat stability of barrier film.
3rd, pollution is not produced to environment in barrier film preparation process.
4th, a large amount of apertures are distributed with the porous septum, and the even aperture distribution and controllable of barrier film are bent between Kong Yukong Folding connection, can extend the service life of battery.
5th, the present invention has expanded the species and use range of lithium ion battery film.
Description of the drawings
Fig. 1 PEI and PVP blended porous membrane plane electron microscopes；
Fig. 2 PEI and PVP blended porous membrane section electron microscopes；
Fig. 3 PEI and coulombic efficiency of the PVP blended porous membranes in 0.5C and specific discharge capacity design sketch；
Fig. 4 PEI and PVP blended porous membranes specific discharge capacity comparison diagram in 0.5C with business-like Celgard films.
Specific embodiment
Below example is that the present invention is further illustrated, and is not to limit the scope of the present invention.
Embodiment 1
The PEI of 10g is dissolved in 39gNMP, is 25 DEG C in experimental temperature and is stirred 2 hours, obtain PEI solution.
The PVP of 1g is added in configured good PEI solution, is 25 DEG C in experimental temperature and is stirred 2 hours, obtain PEI, It is 10 that PVP mixed solutions, wherein PEI mass concentrations are the mass ratio that 20%, PVP mass concentrations are 2%, PEI and PVP:1.
Will be PEI, PVP mixed solution for obtaining static 10 hours.
Using humidity phase inversion static good PEI, PVP mixed solution masking, 40 DEG C of experimental temperature, test relatively wet Degree 90%, experimental period 8 minutes.
The film by made by carries out porosity test about 54%；Contact angle is tested, and is as a result 44.4o.The film by made by enters Row heat stability testing, as a result within 200 DEG C without metamorphosis.Then, using the porous composite film assembling lithium ion for preparing Battery, the discharge and recharge under conditions of 0.5C.The coulombic efficiency of battery is 99.9%, and specific discharge capacity is 148mAh/g.
Embodiment 2
The PEI of 8g is dissolved in 40gNMP, is 25 DEG C in experimental temperature and is stirred 2 hours, obtain PEI solution.
The PVP of 2g is added in configured good PEI solution, is 25 DEG C in experimental temperature and is stirred 2 hours, obtain PEI, It is 4 that PVP mixed solutions, wherein PEI mass concentrations are the mass ratio that 16%, PVP mass concentrations are 4%, PEI and PVP:1.
Will be PEI, PVP mixed solution for obtaining static 10 hours.
Using humidity phase inversion static good PEI, PVP mixed solution masking, 40 DEG C of experimental temperature, test relatively wet Degree 90%, experimental period 8 minutes.
The film by made by carries out porosity test about 58%；Contact angle is tested, and is as a result 43.8o.The film by made by enters Row heat stability testing, as a result within 200 DEG C without metamorphosis.Then, using the porous composite film assembling lithium ion for preparing Battery, test condition are same as Example 1.The coulombic efficiency of battery is 99.6%, and specific discharge capacity is 155mAh/g.
Embodiment 3
The PEI of 10g is dissolved in 37.5gNMP, is 25 DEG C in experimental temperature and is stirred 2 hours, obtain PEI solution.
The PVP of 2.5g is added in configured good PEI solution, is 25 DEG C in experimental temperature and is stirred 2 hours, obtain PEI, It is 4 that PVP mixed solutions, wherein PEI mass concentrations are the mass ratio that 20%, PVP mass concentrations are 5%, PEI and PVP:1.
Will be PEI, PVP mixed solution for obtaining static 10 hours.
Using humidity phase inversion static good PEI, PVP mixed solution masking, 40 DEG C of experimental temperature, test relatively wet Degree 90%, experimental period 8 minutes.
The film by made by carries out porosity test about 60%；Contact angle is tested, and is as a result 40.7o.The film by made by enters Row heat stability testing, as a result within 200 DEG C without metamorphosis.Then, using the porous composite film assembling lithium ion for preparing Battery, test condition are same as Example 1.The coulombic efficiency of battery is 99.9%, and specific discharge capacity is 153mAh/g.
Embodiment 4
The PEI of 12.5g is dissolved in 35gNMP, is 25 DEG C in experimental temperature and is stirred 2 hours, obtain PEI solution.
The PVP of 5g is added in configured good PEI solution, is 25 DEG C in experimental temperature and is stirred 2 hours, obtain PEI, It is 5 that PVP mixed solutions, wherein PEI mass concentrations are the mass ratio that 25%, PVP mass concentrations are 10%, PEI and PVP:2.
Will be PEI, PVP mixed solution for obtaining static 10 hours.
Using humidity phase inversion static good PEI, PVP mixed solution masking, 40 DEG C of experimental temperature, test relatively wet Degree 90%, experimental period 8 minutes.
The film by made by carries out porosity test about 74%；Contact angle is tested, and is as a result 38.7o.The film by made by enters Row heat stability testing, as a result within 200 DEG C without metamorphosis.Then, using the porous composite film assembling lithium ion for preparing Battery, test condition are same as Example 1.The coulombic efficiency of battery is 99.9%, and specific discharge capacity is 152mAh/g.
Embodiment 5
The PEI of 12.5g is dissolved in 35gNMP, is 25 DEG C in experimental temperature and is stirred 2 hours, obtain PEI solution.
The PVP of 10g is added in configured good PEI solution, is 25 DEG C in experimental temperature and is stirred 2 hours, obtain PEI, It is 5 that PVP mixed solutions, wherein PEI mass concentrations are the mass ratio that 25%, PVP mass concentrations are 20%, PEI and PVP:4.
Will be PEI, PVP mixed solution for obtaining static 10 hours.
Using humidity phase inversion static good PEI, PVP mixed solution masking, 40 DEG C of experimental temperature, test relatively wet Degree 90%, experimental period 8 minutes.
The film by made by carries out porosity test about 82%；Contact angle is tested, and is as a result 36.7o.The film by made by enters Row heat stability testing, as a result within 200 DEG C without metamorphosis.Then, using the porous composite film assembling lithium ion for preparing Battery, test condition are same as Example 1.The coulombic efficiency of battery is 99.9%, and specific discharge capacity is 153mAh/g.
Comparative example 1
The PEI of 10g is dissolved in 40gNMP, is 25 DEG C in experimental temperature and is stirred 2 hours, obtain PEI solution.
Wherein PEI mass concentrations were 20%, by the PEI solution stands that obtain 10 hours.
Using humidity phase inversion static good PEI solution film-formings, 40 DEG C of experimental temperature, relative humidity 90% is tested, Experimental period 8 minutes.
The film by made by carries out porosity test about 44%；Contact angle is tested, and is as a result 47.7o.The film by made by enters Row heat stability testing, as a result within 200 DEG C without metamorphosis.Then, using the porous composite film assembling lithium ion for preparing Battery, test condition are same as Example 1.The coulombic efficiency of battery is 99.9%, and specific discharge capacity is 145mAh/g.
Comparative example 2
The PEI of 12.5g is dissolved in 37.5gNMP, is 25 DEG C in experimental temperature and is stirred 2 hours, obtain PEI solution.
Wherein PEI mass concentrations were 25%, by the PEI solution stands that obtain 10 hours.
Using humidity phase inversion static good PEI solution film-formings, 40 DEG C of experimental temperature, relative humidity 90% is tested, Experimental period 8 minutes.
The film by made by carries out porosity test about 38%；Contact angle is tested, and is as a result 53.4 °.The film by made by enters Row heat stability testing, as a result within 200 DEG C without metamorphosis.Then, using the porous composite film assembling lithium ion for preparing Battery, test condition are same as Example 1.The coulombic efficiency of battery is 99.9%, and specific discharge capacity is 143mAh/g.
Comparative example 3
Business-like Celgard films are carried out into contact angle test, is as a result 50 °.The porosity of business-like Celgard films 41% or so.Business-like Celgard films are carried out into heat stability testing, and when as a result 100 DEG C are reached for temperature, film form is received Contracting is obvious, and with the rising of temperature, when temperature reaches 200 DEG C, film melts completely.Using business-like Celgard films group Dress lithium ion battery, test condition are same as Example 1.The coulombic efficiency of battery is 99.2%, and specific discharge capacity is 140mAh/ g。
In sum, from contact angle test result it is found that the made film lyophily of the present invention is significantly improved, make electrolysis Liquid energy is fully infiltrated in membrane surface, illustrates the addition of PVP, effectively improves the hydrophilic of porous septum.Survey from heat stability Test result is it is found that the heat stability of present invention raising film, improves the safety of battery.From in battery testing data, The performance of the made film of the present invention is suitable with business-like film properties.

Claims (3)

1. application of a kind of porous septum in lithium ion battery, it is characterised in that：
Porous septum is the blend solution formed by Polyetherimide and polyvinylpyrrolidone, is prepared by humidity phase inversion Form, wherein Polyetherimide is (10-40) with the mass ratio of polyvinylpyrrolidone：(1-30), aperture 10-1000nm, hole Gap rate 45-85%.
2. application according to claim 1, the porous composite film are prepared as follows：
1) Polyetherimide is dissolved in organic solvent, is to stir more than 1 hour between 10-40 DEG C in temperature, obtains solution；
2) PVP is added into step 1) in configured good solution, it is to stir more than 1 hour between 10-40 DEG C in temperature, is mixed Close solution；In mixed solution, the mass concentration of Polyetherimide is that, between 10-40%, PVP mass concentrations are between 1-30%；
3) mixed solution is coated on flat board, using humidity phase inversion mixed solution masking, temperature 10-50 DEG C, relatively Humidity 60-100%, 3-20 minutes humidity inversion of phases time.
3. application according to claim 2, it is characterised in that：
The organic solvent can be one or more in DMSO, DMAC, NMP, DMF.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111732754A (en) * 2020-07-02 2020-10-02 四川大学 Three-dimensional scaffold with multistage holes, three-dimensional functional scaffold and preparation method thereof

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