CN109962199A - A kind of production method of the polyurethane diaphragm for lithium-sulfur cell - Google Patents
A kind of production method of the polyurethane diaphragm for lithium-sulfur cell Download PDFInfo
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- CN109962199A CN109962199A CN201711436526.4A CN201711436526A CN109962199A CN 109962199 A CN109962199 A CN 109962199A CN 201711436526 A CN201711436526 A CN 201711436526A CN 109962199 A CN109962199 A CN 109962199A
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- polyurethane
- production method
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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
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- 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 Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of production method of polyurethane diaphragm for lithium-sulfur cell, method includes heating '-diphenylmethane diisocyanate and polytetramethylene ether diol in the environment of anaerobic performed polymer is made；Performed polymer made from step 1, is dissolved in solvent and is added ethylenediamine by step 2 and double trifluoromethanesulfonimide lithiums obtain polymer emulsion, is then poured polymer emulsion to film on glass plate and drying, is obtained polyurethane prefabricated membrane；Obtained polyurethane prefabricated membrane is soaked into electrolyte and activates to obtain polyurethane diaphragm by step 3.
Description
Technical field
The present invention relates to cell manufacturing techniques field, particularly a kind of production of the polyurethane diaphragm for lithium-sulfur cell
Method.
Background technique
Lithium-sulfur cell theoretical capacity is high, and it is a kind of new type lithium ion battery that energy density is big, and anode uses rich reserves
Elemental sulfur, have the characteristics that cheap, environmental-friendly, but the popularization and application of lithium-sulfur cell at present receive its " shuttle effect "
Inhibition.So-called " shuttle effect ", i.e., in charge and discharge process, intermediate product polysulfide Li2Sn(2≤n≤8) are soluble in electricity
Liquid is solved, is shuttled to cathode, this not only results in active material loss, reduces the discharge capacity of battery, and shuttle to cathode
Polysulfide can also be reacted with lithium, generate dead lithium (Li2S and Li2S2) it is covered on negative terminal surface, reduce the transmission speed of lithium ion
Rate.
The aperture of single-layer polypropylene seperation film about 17nm cannot stop the shuttle of polysulfide, patent document CN
106129455 A are coated in polyalkene diaphragm surface using graphene oxide, alleviate more sulphur by way of increasing physical barriers
The shuttle of compound, but the coat easily peels off in cyclic process, its mechanism of action is caused to fail.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of production method of polyurethane diaphragm for lithium-sulfur cell,
Polysulfide can be stopped using polyurethane diaphragm produced by the present invention, shuttle effect is effectively relieved.The present invention is using as follows
What scheme was realized:
A kind of production method of the polyurethane diaphragm for lithium-sulfur cell, includes the following steps,
'-diphenylmethane diisocyanate and polytetramethylene ether diol are heated in the environment of anaerobic and are made pre- by step 1
Aggressiveness；
Performed polymer made from step 1, is dissolved in solvent and is added ethylenediamine by step 2 and double fluoroform sulphonyl are sub-
Amine lithium obtains polymer emulsion, then pours polymer emulsion on glass plate and dry, obtains polyurethane prefabricated membrane；
Obtained polyurethane prefabricated membrane is soaked into electrolyte and activates to obtain polyurethane diaphragm by step 3.
Preferably, in the step 1, the molar ratio of '-diphenylmethane diisocyanate and polytetramethylene ether diol is 1~
0.01:1。
It is highly preferred that in the step 1, by '-diphenylmethane diisocyanate and polytetramethylene ether diol in anaerobic ring
It is heated to 60~100 DEG C in border, and stirs 1~5h, performed polymer is made.
It is highly preferred that in the step 1, reaction condition N2Atmosphere or inert gas atmosphere.
Preferably, in the step 2, the reaction condition of performed polymer and ethylenediamine, double trifluoromethanesulfonimide lithiums is 60
~100 DEG C, 0~5h of mixing time.
Preferably, in the step 2, the reaction temperature that polymer emulsion is made is 40~50 DEG C.
Preferably, in the step 2, the solvent is acetone.
Preferably, in the step 2, substrate is glass plate or ceramic wafer.
Preferably, in the step 2, drying time of polymer emulsion is 5~for 24 hours.
Preferably, in the step 3, electrolyte is double trifluoromethanesulfonimide lithium electrolytes.
It is highly preferred that the solvent of double trifluoromethanesulfonimide lithium electrolytes is 1,3- dioxy in the step 3
Penta ring/glycol dimethyl ether, 1,3-dioxolane and glycol dimethyl ether are 1:1 by volume in the solvent.
In the present invention, using the polyurethane diaphragm of any of the above-described production method production, surface and ontology are equal
Even compact texture, electrolyte can only be transmitted along the hydrophilic radical on intensive strand gap and strand, can be effective
The shuttle for inhibiting polysulfide, improves the chemical property of lithium-sulfur cell.
Further, the present invention using any of the above-described production method production polyurethane diaphragm, aperture is 0.5~
1.0nm, the polyurethane membrane configuration is close, and there is only strand gaps, and shuttle effect can be effectively relieved.
Detailed description of the invention
Fig. 1 is the contact angle test comparison diagram of polyurethane diaphragm and existing polypropylene diaphragm made from the embodiment of the present invention 1；
Fig. 2 is the head of lithium-sulfur cell made of polyurethane diaphragm made from the embodiment of the present invention 1 and existing polypropylene diaphragm
Secondary discharge capacity comparison diagram.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
A kind of production method of the polyurethane diaphragm for lithium-sulfur cell, includes the following steps:
Step 1 adds '-diphenylmethane diisocyanate and polytetramethylene ether diol (PTMEG) in the environment of anaerobic
The obtained performed polymer of heat；
Performed polymer made from step 1, is dissolved in solvent and is added ethylenediamine by step 2 and double fluoroform sulphonyl are sub-
Amine lithium obtains polymer emulsion, then pours polymer emulsion on glass plate and dry, obtains polyurethane prefabricated membrane；
Obtained polyurethane prefabricated membrane is soaked into electrolyte and activates to obtain polyurethane diaphragm by step 3.
Further, in step 1, reaction condition is 60~100 DEG C, 1~5h of mixing time.
Further, in step 1, reaction condition is oxygen-free environment, preferably N2Atmosphere or other inert gas atmospheres.
Further, in step 2, performed polymer and ethylenediamine, double trifluoromethanesulfonimide lithiums reaction condition be 60~
100 DEG C, 0~5h of mixing time.
Further, in step 2, the solvent is acetone.
Further, in step 2, the substrate of selection can be glass plate or ceramic wafer.
Further, in step 2, the condition that the performed polymer is dissolved in solvent is 40~50 DEG C.
Further, in step 2, drying time of polymer emulsion is 5~for 24 hours.
Further, in step 3, electrolyte is double trifluoromethanesulfonimide lithium electrolytes.
Further, in step 3, the solvent of the LiTFSI electrolyte is 1,3-dioxolane (DOL)/ethylene glycol two
Methyl ether (DME), DOL and DME is 1:1 by volume in solvent.
Embodiment 1
By raw material '-diphenylmethane diisocyanate (MDI) and polytetramethylene ether diol (PTMEG) dehydration, and according to
The proportion that the molar ratio of MDI:PTMEG is 1.008:1 is added in flask, is passed through N2It is protected, stirs 2h under the conditions of 80 DEG C,
Obtain performed polymer.
Performed polymer is cooled to room temperature, is stirred, and sequentially add acetone, ethylenediamine and double trifluoromethanesulfonimide lithiums
(LiTFS), wherein performed polymer: acetone: ethylenediamine: the weight ratio of LiTFS is 55:10:25:10, is warming up to 80 DEG C of stirring 1h, obtains
Polymer emulsion；Resulting polymer emulsion is poured on smooth glass plate, film is carried out using automatic spray device, then is placed in
Dry 12h, obtains polyurethane prefabricated membrane in vacuum drying box.
Resulting polyurethane prefabricated membrane is soaked into electrolyte and is activated, electrolyte is 1M LiTFSI, and solvent is
DOL/DME solvent, wherein DOL and DME is 1:1 by volume in solvent, obtains polyurethane diaphragm.
Embodiment 2
By raw material MDI and PTMEG dehydration, and it is added and burns according to the proportion that the molar ratio of MDI:PTMEG is 1.005:1
In bottle, it is passed through N2It is protected, stirs 2h under the conditions of 85 DEG C, obtain performed polymer.
Performed polymer is cooled to room temperature, is stirred, and sequentially add acetone, ethylenediamine and LiTFS, wherein performed polymer: acetone:
Ethylenediamine: the weight ratio of LiTFS is 55:10:25:10, is warming up to 80 DEG C of stirring 1h, obtains polymer emulsion；It will be resulting poly-
It closes object lotion and pours on smooth glass plate and film is carried out using automatic spray device, then be placed in vacuum drying box dry 12h, obtain
Polyurethane prefabricated membrane.
Resulting polyurethane prefabricated membrane is soaked into LiTFSI electrolyte and is activated, polyurethane diaphragm is obtained.
Embodiment 3
Flask is added by raw material MDI and PTMEG dehydration, and according to the proportion that the molar ratio of MDI:PTMEG is 0.8:1
In, it is passed through N2It is protected, stirs 1h under the conditions of 90 DEG C, obtain performed polymer.
Performed polymer is cooled to room temperature, is stirred, and sequentially add acetone, ethylenediamine and LiTFS, wherein performed polymer: acetone:
Ethylenediamine: the feed weight ratio of LiTFS is 55:10:25:10, is warming up to 90 DEG C of stirring 1h, obtains polymer emulsion；It will be resulting
Polymer emulsion pours on smooth glass plate and carries out film using automatic spray device, then is placed in vacuum drying box dry 18h,
Obtain polyurethane prefabricated membrane.
Resulting polyurethane prefabricated membrane is soaked into electrolyte and is activated, electrolyte is 1M LiTFSI, and solvent is
DOL/DME solvent, wherein DOL and DME is 1:1 by volume in solvent, obtains polyurethane diaphragm.
In above-described embodiment 1~3, polyurethane obtained is made of soft segment and hard section two parts, wherein soft segment be from
- the O-R of PTMEG '-O-, hard section are the-CONH-R-NHCO-NH-R from MDI "-NH-CONH-R-NHCO-.
Further, polyurethane diaphragm made from embodiment 1 is tested, control group is existing polypropylene diaphragm.
The surface that 20 μ L electrolyte are dropped to polyurethane diaphragm and polypropylene diaphragm respectively, is measured, such as using contact angle tester
Fig. 1 has found that the contact angle of electrolyte and polypropylene diaphragm is about 32 °, and electrolyte can then be sprawled completely in polyurethane membrane surface
It opens, contact angle illustrates parent of the polyurethane diaphragm to the lyophily of electrolysis fluidity better than polypropylene diaphragm to electrolyte close to 0 °
Fluidity, this is conducive to electrolyte and quickly moistens diaphragm, increases the lyophily of diaphragm, guarantees that lithium ion quickly passes in diaphragm
It is defeated.
Further, polyurethane diaphragm made from embodiment 1 and existing polypropylene diaphragm are respectively used to lithium-sulfur cell
Assembly, wherein the positive electrode of battery include S/C composite material, acetylene black and PVDF, cathode is lithium piece, electrolyte 1M
LiTFSI/DOL/DME(1:1,v/v).Polyurethane diaphragm cell obtained and polypropylene diaphragm battery are carried out to electricity at 0.2C
Chemical property test, battery testing voltage range is 1.7~2.8V.If Fig. 2 is that polyurethane diaphragm and polypropylene diaphragm are answered respectively
When for lithium-sulfur cell, the comparison of first charge-discharge capacity under 0.2C.Wherein the corresponding discharge capacity of polyurethane diaphragm is
1033mAh/g is higher than the corresponding capacity of polypropylene diaphragm (907mAh/g).And the voltage difference between polyurethane diaphragm charge and discharge platform
It is smaller, illustrate that the corresponding battery polarization of polyurethane diaphragm is smaller, illustrates that shuttle effect has been effectively relieved in polyurethane diaphragm, shuttle extremely
The polysulfide of cathode is less, and side reaction is less, the dead lithium (Li of negative terminal surface2S and Li2S2) less, lithium ion transport is very fast.
And as the study found that the gap aperture of strand is about 0.8nm in polyurethane membrane configuration made from embodiment 1, also into one
Step card polyurethane diaphragm alleviates shuttle effect.
In further test, polyurethane diaphragm made from embodiment 2 and embodiment 3 similarly have than polypropylene every
The more excellent lyophily of film, manufactured lithium-sulfur cell discharge capacity are above 1000mAh/g.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with scope of protection of the claims
Subject to.
Claims (10)
1. a kind of production method of the polyurethane diaphragm for lithium-sulfur cell, which is characterized in that the production method includes as follows
Step:
'-diphenylmethane diisocyanate and polytetramethylene ether diol are heated in oxygen-free environment and performed polymer are made by step 1；
Performed polymer made from the step 1, is dissolved in solvent and is added ethylenediamine by step 2 and double fluoroform sulphonyl are sub-
Amine lithium obtains polymer emulsion, then pours the polymer emulsion to film on substrate and drying, obtains polyurethane prefabricated membrane；
The obtained polyurethane prefabricated membrane is soaked into electrolyte and activates to obtain polyurethane diaphragm by step 3.
2. manufacturing method according to claim 1, which is characterized in that in the step 1, '-diphenylmethane diisocyanate
Molar ratio with polytetramethylene ether diol is 1~0.01:1.
3. production method according to claim 1 or 2, which is characterized in that in the step 1, by two isocyanide of diphenyl-methane
Acid esters and polytetramethylene ether diol are heated to 60~100 DEG C in oxygen-free environment, and stir 1~5h, and performed polymer is made.
4. production method according to claim 1 or 2, which is characterized in that in the step 1, oxygen-free environment N2Atmosphere
Or other inert gas atmospheres.
5. production method according to claim 1 or 2, which is characterized in that in the step 2, performed polymer and ethylenediamine,
The reaction temperature of double trifluoromethanesulfonimide lithiums is 60~100 DEG C, 0~5h of mixing time.
6. production method according to claim 1 or 2, which is characterized in that in the step 2, polymer emulsion is made
Reaction temperature is 40~50 DEG C, drying time of polymer emulsion is 5~for 24 hours.
7. production method according to claim 1 or 2, which is characterized in that in the step 2, solvent is acetone, substrate
For glass plate or ceramic wafer.
8. manufacturing method according to claim 1, which is characterized in that in the step 3, electrolyte is double fluoroforms
Sulfimide lithium electrolyte.
9. production method according to claim 8, which is characterized in that in the step 3, double trifluoromethanesulfonimides
The solvent of lithium electrolyte is 1,3-dioxolane/glycol dimethyl ether, 1,3-dioxolane and glycol dinitrate in the solvent
Ether is 1:1 by volume.
10. a kind of polyurethane diaphragm is made, which is characterized in that the polyurethane using any the method for claim 1~10
The aperture of diaphragm is 0.5~1.0nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711436526.4A CN109962199A (en) | 2017-12-26 | 2017-12-26 | A kind of production method of the polyurethane diaphragm for lithium-sulfur cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711436526.4A CN109962199A (en) | 2017-12-26 | 2017-12-26 | A kind of production method of the polyurethane diaphragm for lithium-sulfur cell |
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| CN109962199A true CN109962199A (en) | 2019-07-02 |
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| CN201711436526.4A Pending CN109962199A (en) | 2017-12-26 | 2017-12-26 | A kind of production method of the polyurethane diaphragm for lithium-sulfur cell |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111704708A (en) * | 2020-06-08 | 2020-09-25 | 广州市乐基智能科技有限公司 | Preparation method of cross-linked polyurethane binder and application of cross-linked polyurethane binder in field of lithium batteries |
| CN114437620A (en) * | 2021-12-30 | 2022-05-06 | 广东粤港澳大湾区黄埔材料研究院 | Polyurethane coating, lithium ion battery diaphragm and lithium ion battery |
| CN114976482A (en) * | 2022-04-28 | 2022-08-30 | 清华大学山西清洁能源研究院 | Lithium-sulfur battery diaphragm, preparation method thereof and lithium-sulfur battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101090164A (en) * | 2007-07-12 | 2007-12-19 | 武汉大学 | Polymer lithium secondary battery and preparation method thereof |
-
2017
- 2017-12-26 CN CN201711436526.4A patent/CN109962199A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101090164A (en) * | 2007-07-12 | 2007-12-19 | 武汉大学 | Polymer lithium secondary battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MOHANLAL DIGAR AND TEN-CHIN WEN: "Ionic Conductivity and Morphological Study of a Thermoplastic Polyurethane Based Electrolyte Comprising of Mixed Soft Segments", 《POLYMER JOURNAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111704708A (en) * | 2020-06-08 | 2020-09-25 | 广州市乐基智能科技有限公司 | Preparation method of cross-linked polyurethane binder and application of cross-linked polyurethane binder in field of lithium batteries |
| CN114437620A (en) * | 2021-12-30 | 2022-05-06 | 广东粤港澳大湾区黄埔材料研究院 | Polyurethane coating, lithium ion battery diaphragm and lithium ion battery |
| CN114976482A (en) * | 2022-04-28 | 2022-08-30 | 清华大学山西清洁能源研究院 | Lithium-sulfur battery diaphragm, preparation method thereof and lithium-sulfur battery |
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