CN107017376A - A kind of Ti3C2Tx/Nafion/Celgard composite diaphragms - Google Patents
A kind of Ti3C2Tx/Nafion/Celgard composite diaphragms Download PDFInfo
- Publication number
- CN107017376A CN107017376A CN201710225974.3A CN201710225974A CN107017376A CN 107017376 A CN107017376 A CN 107017376A CN 201710225974 A CN201710225974 A CN 201710225974A CN 107017376 A CN107017376 A CN 107017376A
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- Prior art keywords
- nafion
- celgard
- layers
- lithium
- powder
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
-
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
-
- 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)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of Ti3C2Tx/ Nafion/Celgard composite diaphragms, including Celgard barrier films and the Ti on its surface3C2Tx/ Nafion layers of composition, described Ti3C2Tx/ Nafion layers of thickness is 1~10 μm, described Ti3C2TxTi in/Nafion layers3C2TxMass ratio with Nafion is 0.05 0.5：1.Ti3C2TxTi in/Nafion layers3C2TxOn T be F groups or OH groups, it is highly polar group with the F groups on Nafion membrane, strong chemisorbed can be formed to the polysulfide formed in charge and discharge process, polysulfide can be effectively prevented to reach negative pole through barrier film, the generation of shuttle effect is reduced, the life-span of lithium-sulfur cell is improved.
Description
Technical field
The present invention relates to lithium-sulfur cell field, more particularly to a kind of lithium-sulfur cell barrier film.
Background technology
Lithium-sulfur cell is that, using lithium metal as negative pole, elemental sulfur is the battery system of positive pole.Lithium-sulfur cell have two put
Level platform（About 2.4 V and 2.1 V）, but its electrochemical reaction mechanism is more complicated.Lithium-sulfur cell has specific energy high
（2600 Wh/kg）, specific capacity it is high（1675 mAh/g）, low cost and other advantages, it is considered to be very promising a new generation's electricity
Pond.But at present the problems such as there is low active material utilization, low cycle life and poor security, this seriously governs lithium
The development of sulphur battery.Causing the main cause of above mentioned problem has the following aspects：（1）Elemental sulfur is electronics and ion insulation
Body, room-temperature conductivity is low（5×10-30S·cm-1）, because the sulphur without ionic state is present, thus it is tired as positive electrode activation
It is difficult；（2）The high poly- many lithium sulfide Li of state produced in electrode process2Sn（8 ＞ n >=4）It is soluble in electrolyte, positive and negative
Concentration difference is formed between pole, negative pole is moved in the presence of concentration gradient, the high poly- many lithium sulfides of state are reduced into low by lithium metal
The poly- many lithium sulfides of state.The progress of reaction more than, the oligomeric many lithium sulfides of state are assembled in negative pole, finally formed between electrodes
Concentration difference, moves to positive pole and is oxidized to the high many lithium sulfides of poly- state again.This phenomenon is referred to as shuttle effect, reduces sulphur activity
The utilization rate of material.While insoluble Li2S and Li2S2Cathode of lithium surface is deposited on, lithium-sulfur cell is further degrading
Performance；（3）React final product Li2S is equally electronic body, can be deposited on sulfur electrode, and lithium ion vulcanizes in solid-state
Migration velocity is slow in lithium, makes electrochemical reaction kinetic rate slack-off；（4）Sulphur and final product Li2S density is different, works as sulphur
Rear volumetric expansion about 79% is lithiated, Li is easily caused2S efflorescence, causes the safety problem of lithium-sulfur cell.Above-mentioned not enough restriction
The development of lithium-sulfur cell, this is also the Important Problems that current lithium-sulfur cell research needs to solve.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of Ti3C2Tx/ Nafion/Celgard composite diaphragms, including business
With Celgard barrier films and the Ti on its surface3C2Tx/ Nafion layers of composition, described Ti3C2Tx/ Nafion layers of thickness be 1~
10 μm, described Ti3C2TxTi in/Nafion layers3C2TxMass ratio with Nafion is 0.05-0.5：1.
The present invention provides a kind of Ti3C2TxThe preparation method of/Nafion/Celgard composite diaphragms is as follows：
（1）By Ti3AlC2Ceramic powders, which are put into hydrofluoric acid, to be corroded, and solution adds deionized water and carries out centrifugal treating after corrosion,
Then sediment is dried, obtains the lamellar Ti of stacking3C2TxPowder；
（2）By Ti3C2TxPowder adds ultrasonic disperse in Nafion solution, the suspension of formation, then suspension be applied to
A kind of Ti is obtained on Celgard barrier films, after vacuum drying3C2Tx/ Nafion/Celgard composite diaphragms.
Step（1）The concentration of middle hydrofluoric acid is 20%-50%, and the time of corrosion is 4-24 hours;
Step（2）The mass fraction of middle Nafion solution is 5%, and ultrasonic time is 1-5 hours, Ti3C2TxThe addition of powder is
The quality 0.25-2.5% of Nafion solution；
The present invention has the advantages that： Ti3C2TxTi in/Nafion layers3C2TxOn T be-F groups or-OH groups,
It is highly polar group with the-F groups on Nafion membrane, strong change can be formed to the polysulfide formed in charge and discharge process
Absorption is learned, can effectively prevent polysulfide from reaching negative pole through barrier film, the generation of shuttle effect is reduced, lithium-sulfur cell is improved
Life-span.
Brief description of the drawings
Fig. 1 is the Ti of the present invention3C2Tx/ Nafion/Celgard composite separator structure schematic diagrames.
Fig. 2 is the Ti of the present invention3C2Tx/ Nafion/Celgard composite diaphragm preparation flow figures.
Fig. 3 is the Ti of the present invention3C2TxThe cycle life figure of/Nafion/Celgard composite diaphragms.
Wherein, 1 is Ti3C2Tx/ Nafion layers, 2 be Celgard barrier films.
Embodiment
Below in conjunction with the accompanying drawings, the preferably embodiment to the present invention is described in further detail：
Embodiment 1
（1）By Ti3AlC2Ceramic powders, which are put into the hydrofluoric acid that mass concentration is 20%, corrodes solution addition after 24h, corrosion
Deionized water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
（2）By 0.025gTi3C2TxPowder is added to ultrasonic disperse, ultrasonic time in the Nafion solution that 10g mass fractions are 5%
For 1 hour, the suspension of formation, then suspension be applied on Celgard barrier films, Ti is obtained after vacuum drying3C2Tx/
Nafion/Celgard composite diaphragms.
Embodiment 2
（1）By Ti3AlC2Ceramic powders are put into mass concentration and gone to corrode solution addition after 4h, corrosion in 50% hydrofluoric acid
Ionized water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
（2）By 0.25gTi3C2TxPowder is added to ultrasonic disperse, ultrasonic time in the Nafion solution that 10g mass fractions are 5%
For 5 hours, the suspension of formation, then suspension be applied on Celgard barrier films, Ti is obtained after vacuum drying3C2Tx/
Nafion/Celgard composite diaphragms.
Embodiment 3
（1）By Ti3AlC2Ceramic powders, which are put into the hydrofluoric acid that mass concentration is 30%, corrodes solution addition after 20h, corrosion
Deionized water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
（2）By 0.05gTi3C2TxPowder is added to ultrasonic disperse, ultrasonic time in the Nafion solution that 10g mass fractions are 5%
For 2 hours, the suspension of formation, then suspension be applied on Celgard barrier films, Ti is obtained after vacuum drying3C2Tx/
Nafion/Celgard composite diaphragms.
Embodiment 4
（1）By Ti3AlC2Ceramic powders, which are put into the hydrofluoric acid that mass concentration is 40%, corrodes solution addition after 15h, corrosion
Deionized water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
（2）By 0.1gTi3C2TxPowder is added to ultrasonic disperse in the Nafion solution that 10g mass fractions are 5%, and ultrasonic time is
3 hours, the suspension of formation, then suspension be applied on Celgard barrier films, Ti is obtained after vacuum drying3C2Tx/Nafion/
Celgard composite diaphragms.
Embodiment 5
（1）By Ti3AlC2Ceramic powders, which are put into the hydrofluoric acid that mass concentration is 35%, corrodes solution addition after 13h, corrosion
Deionized water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
（2）By 0.2gTi3C2TxPowder is added to ultrasonic disperse in the Nafion solution that 10g mass fractions are 5%, and ultrasonic time is
4 hours, the suspension of formation, then suspension be applied on Celgard barrier films, Ti is obtained after vacuum drying3C2Tx/Nafion/
Celgard composite diaphragms.
The preparation and performance test of lithium-sulfur cell；By sulphur simple substance material, acetylene black and PVDF in mass ratio 70：20：10
Mixed in NMP, it is electrode film to be coated on aluminium foil, metal lithium sheet be to electrode, composite diaphragm prepared by embodiment 1 as every
Film, 1mol/L LiTFSI/DOL-DME (volume ratios 1:1) it is electrolyte, 1mol/L LiNO3 is additive, full of Ar hands
Button cell is assembled into casing, constant current charge-discharge test is carried out using Land battery test systems.Charging/discharging voltage scope is
1-3V, current density is 0.5C.
Comparative example uses Celgard barrier films for lithium-sulfur cell barrier film, and other conditions are same as described above.
Fig. 3 is the cycle life figure that composite diaphragm prepared by the embodiment of the present invention 1 is assembled into lithium-sulfur cell.Can be with from figure
Find out that capacity still possesses the 73% of initial capacity after composite diaphragm 400 discharge and recharges of progress prepared by the present invention, and comparative example is used
Celgard barrier films are assembled into lithium-sulfur cell, carry out capacity after 200 circulations and enter for the 40% of initial capacity, illustrate the composite diaphragm
Shuttle effect can effectively be suppressed, the life-span of sulphur battery is improved.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to assert
The specific implementation of the present invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of not departing from present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the present invention's
Protection domain.
Claims (5)
1. a kind of Ti3C2Tx/ Nafion/Celgard composite diaphragms, including Celgard barrier films and the Ti on its surface3C2Tx/
Nafion layers of composition, described Ti3C2Tx/ Nafion layers of thickness is 1~10 μm, described Ti3C2TxIn/Nafion layers
Ti3C2TxMass ratio with Nafion is 0.05-0.5：1.
2. one kind prepares Ti as claimed in claim 13C2TxThe preparation method of/Nafion/Celgard composite diaphragms, its feature
It is, including following steps：
Step（1）：By Ti3AlC2Ceramic powders, which are put into hydrofluoric acid, to be corroded, and solution adds deionized water and centrifuged after corrosion
Processing, then sediment is dried, obtain the lamellar Ti of stacking3C2TxPowder；
Step（2）：By Ti3C2TxPowder adds ultrasonic disperse in Nafion solution, the suspension of formation, then suspension is coated
Onto Celgard barrier films, Ti is obtained after vacuum drying3C2Tx/ Nafion/Celgard composite diaphragms.
3. method as claimed in claim 2, it is characterised in that the step（1）The concentration of middle hydrofluoric acid is 20%-50%, rotten
The time of erosion is 4-24 hours.
4. method as claimed in claim 2, it is characterised in that step（2）The mass fraction of middle Nafion solution is 5%, ultrasound
Time is 1-5 hours.
5. method as claimed in claim 2, it is characterised in that Ti3C2TxThe addition of powder is the quality of Nafion solution
0.25-2.5%。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710225974.3A CN107017376A (en) | 2017-04-08 | 2017-04-08 | A kind of Ti3C2Tx/Nafion/Celgard composite diaphragms |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710225974.3A CN107017376A (en) | 2017-04-08 | 2017-04-08 | A kind of Ti3C2Tx/Nafion/Celgard composite diaphragms |
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| Publication Number | Publication Date |
|---|---|
| CN107017376A true CN107017376A (en) | 2017-08-04 |
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|---|---|---|---|
| CN201710225974.3A Pending CN107017376A (en) | 2017-04-08 | 2017-04-08 | A kind of Ti3C2Tx/Nafion/Celgard composite diaphragms |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018184237A1 (en) * | 2017-04-08 | 2018-10-11 | 深圳市佩成科技有限责任公司 | Ti3c2tx/nafion/celgard composite separator |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105993093A (en) * | 2013-12-03 | 2016-10-05 | 株式会社爱发科 | Lithium sulfur secondary battery |
| CN106062995A (en) * | 2014-02-19 | 2016-10-26 | 巴斯夫欧洲公司 | Electrode protection using a composite comprising an electrolyte-inhibiting ion conductor |
-
2017
- 2017-04-08 CN CN201710225974.3A patent/CN107017376A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105993093A (en) * | 2013-12-03 | 2016-10-05 | 株式会社爱发科 | Lithium sulfur secondary battery |
| CN106062995A (en) * | 2014-02-19 | 2016-10-26 | 巴斯夫欧洲公司 | Electrode protection using a composite comprising an electrolyte-inhibiting ion conductor |
Non-Patent Citations (2)
| Title |
|---|
| JIANJUN SONG ET AL.: ""Immobilizing Polysulfides withMXene-Functionalized Separators for Stable Lithium-Sulfur Batteries"", 《APPLIED MATERIALS & INTERFACES》 * |
| JIA-QI HUANG ET AL.，: ""Ionic shield for polysulfides towards highly-stable lithium–sulfur batteries"", 《ENERGY & ENVIRONMENTAL SCIENCE》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018184237A1 (en) * | 2017-04-08 | 2018-10-11 | 深圳市佩成科技有限责任公司 | Ti3c2tx/nafion/celgard composite separator |
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Application publication date: 20170804 |
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