CN106876637A - A kind of Ti3C2Tx/PVDF/Celgard composite diaphragms - Google Patents

A kind of Ti3C2Tx/PVDF/Celgard composite diaphragms Download PDF

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Publication number
CN106876637A
CN106876637A CN201710225973.9A CN201710225973A CN106876637A CN 106876637 A CN106876637 A CN 106876637A CN 201710225973 A CN201710225973 A CN 201710225973A CN 106876637 A CN106876637 A CN 106876637A
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China
Prior art keywords
pvdf
celgard
lithium
hours
solution
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CN201710225973.9A
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钟玲珑
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Shenzhen Pei Cheng Technology Co Ltd
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Shenzhen Pei Cheng Technology Co Ltd
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Priority to CN201710225973.9A priority Critical patent/CN106876637A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • 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)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a kind of Ti3C2Tx/ PVDF/Celgard composite diaphragms, including commercial Celgard barrier films and its surface Ti3C2Tx/ PVDF layers of composition, described Ti3C2Tx/ PVDF layers of thickness is 1~10 μm, described Ti3C2TxTi in/PVDF layers3C2TxIt is 1 with the mass ratio of PVDF：0.01‑0.1.Ti3C2TxOn T be F groups or OH groups, highly polar group is, strong chemisorbed can be formed to the polysulfide formed in charge and discharge process, can effectively prevent polysulfide from reaching negative pole through barrier film, the generation of shuttle effect is reduced, the life-span of lithium-sulfur cell is improved.

Description

A kind of Ti3C2Tx/ PVDF/Celgard composite diaphragms
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, with lithium metal as negative pole, elemental sulfur is the battery system of positive pole.Lithium-sulfur cell is put with two 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 the problems such as there is low active material utilization, low cycle life and poor security at present, 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）, it is because the sulphur without ionic state is present thus tired as positive electrode activation It is difficult；（2）The many lithium sulfide Li of high poly- 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 poly- many lithium sulfides of state high are reduced into low by lithium metal The poly- many lithium sulfides of state.The carrying out of reaction more than, the oligomeric many lithium sulfides of state are assembled in negative pole, are finally formed between electrodes Concentration difference, moves to positive pole and is oxidized to many lithium sulfides of poly- state high 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）Reaction 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 Li2The density of S is different, works as sulphur Rear volumetric expansion about 79% is lithiated, Li is easily caused2The efflorescence of S, 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/ PVDF/Celgard composite diaphragms, including commercialization The Ti of Celgard barrier films and its surface3C2Tx/ PVDF layers of composition, described Ti3C2Tx/ PVDF layers of thickness is 1~10 μm, institute The Ti for stating3C2TxTi in/PVDF layers3C2TxIt is 1 with the mass ratio of PVDF：0.01-0.1.
The present invention provides a kind of Ti3C2TxThe preparation method of/PVDF/Celgard composite diaphragms is as follows：
（1）By Ti3AlC2Ceramic powders corrode in being put into hydrofluoric acid, and solution addition deionized water carries out centrifugal treating after corrosion, Then sediment is dried, obtains the lamellar Ti of stacking3C2TxPowder；
（2）PVDF is added in 1-METHYLPYRROLIDONE, stirring and dissolving, forms PVDF solution；
（3）By Ti3C2TxMechanical agitation is uniform during powder is added to PVDF solution, the slurry of formation, then slurry is coated to On Celgard barrier films, Ti is obtained after vacuum drying3C2Tx/ PVDF/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）Middle PVDF is 1 with the mass ratio of 1-METHYLPYRROLIDONE:10-100, mixing time is 1-12 hours；
Step（3）Middle Ti3C2TxIt is 1 with the mass ratio of PVDF：0.01-0.1, mixing time is 1-12 hours；
The present invention has the advantages that： Ti3C2TxOn T be-F groups or-OH groups, be highly polar group, can be right The polysulfide formed in charge and discharge process forms strong chemisorbed, can effectively prevent polysulfide from being reached through barrier film Negative pole, reduces the generation of shuttle effect, improves the life-span of lithium-sulfur cell.
Brief description of the drawings
Fig. 1 is Ti of the invention3C2Tx/ PVDF/Celgard composite separator structure schematic diagrames.
Fig. 2 is Ti of the invention3C2Tx/ PVDF/Celgard composite diaphragm preparation flow figures.
Fig. 3 is Ti of the invention3C2TxThe cycle life figure of/PVDF/Celgard composite diaphragms.
Wherein, 1 is Ti3C2Tx/ PVDF layers, 2 is Celgard barrier films.
Specific embodiment
Below in conjunction with the accompanying drawings, preferably embodiment of the invention is described in further detail：
Embodiment 1
（1）By Ti3AlC2Ceramic powders corrode 24h in being put into the hydrofluoric acid that mass concentration is 20%, and solution is added after corrosion Deionized water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
（2）1g PVDF are added in 100g 1-METHYLPYRROLIDONEs, stirring dissolves it in 1 hour, form PVDF solution；
（3）By 100g Ti3C2TxMechanical agitation is well mixed 12 hours it during powder is added to PVDF solution, the slurry of formation Material, then slurry is coated on Celgard barrier films, Ti is obtained after vacuum drying3C2Tx/ PVDF/Celgard composite diaphragms.
Embodiment 2
（1）By Ti3AlC2Ceramic powders corrode 4h in being put into the hydrofluoric acid that mass concentration is 50%, and solution is added and gone after corrosion Ionized water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
（2）1g PVDF are added in 10g 1-METHYLPYRROLIDONEs, stirring dissolves it in 12 hours, form PVDF solution；
（3）By 10gTi3C2TxMechanical agitation is well mixed 1 hour it during powder is added to PVDF solution, the slurry of formation, then Slurry is coated on Celgard barrier films, Ti is obtained after vacuum drying3C2Tx/ PVDF/Celgard composite diaphragms.
Embodiment 3
（1）By Ti3AlC2Ceramic powders corrode 20h in being put into the hydrofluoric acid that mass concentration is 30%, and solution is added after corrosion Deionized water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
（2）1g PVDF are added in 50g 1-METHYLPYRROLIDONEs, stirring dissolves it in 6 hours, form PVDF solution；
（3）By 50gTi3C2TxMechanical agitation is well mixed 6 hours it during powder is added to PVDF solution, the slurry of formation, then Slurry is coated on Celgard barrier films, Ti is obtained after vacuum drying3C2Tx/ PVDF/Celgard composite diaphragms.
Embodiment 4
（1）By Ti3AlC2Ceramic powders corrode 15h in being put into the hydrofluoric acid that mass concentration is 40%, and solution is added after corrosion Deionized water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
（2）1g PVDF are added in 80g 1-METHYLPYRROLIDONEs, stirring dissolves it in 3 hours, form PVDF solution；
（3）By 30gTi3C2TxMechanical agitation is well mixed 3 hours it during powder is added to PVDF solution, the slurry of formation, then Slurry is coated on Celgard barrier films, Ti is obtained after vacuum drying3C2Tx/ PVDF/Celgard composite diaphragms.
Embodiment 5
（1）By Ti3AlC2Ceramic powders corrode 13h in being put into the hydrofluoric acid that mass concentration is 35%, and solution is added after corrosion Deionized water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
（2）1g PVDF are added in 30g 1-METHYLPYRROLIDONEs, stirring dissolves it in 10 hours, form PVDF solution；
（3）By 80gTi3C2TxMechanical agitation is well mixed 9 hours it during powder is added to PVDF solution, the slurry of formation, then Slurry is coated on Celgard barrier films, Ti is obtained after vacuum drying3C2Tx/ PVDF/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 Mix in NMP, be coated on aluminium foil as electrode film, metal lithium sheet be to electrode, composite diaphragm prepared by embodiment 1 as every Film, the LiTFSI/DOL-DME (volume ratios 1 of 1mol/L:1) it is electrolyte, the LiNO3 of 1mol/L 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.
It is lithium-sulfur cell barrier film that comparative example uses Celgard barrier films, 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.As can be seen from the figure Capacity still possesses the 63% of initial capacity after composite diaphragm prepared by the present invention carries out 400 discharge and recharges, and comparative example is used Celgard barrier films are assembled into lithium-sulfur cell, and to enter be the 40% of initial capacity to capacity after carrying out 200 circulations, illustrates 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 Specific implementation of the 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 be all considered as belonging to of the invention Protection domain.

Claims (5)

1. a kind of Ti3C2Tx/ PVDF/Celgard composite diaphragms, including commercial Celgard barrier films and its surface Ti3C2Tx/ PVDF layers of composition, described Ti3C2Tx/ PVDF layers of thickness is 1~10 μm, described Ti3C2TxTi in/PVDF layers3C2TxWith The mass ratio of PVDF is 1：0.01-0.1.
2. a kind of Ti as claimed in claim 13C2TxThe preparation method of/PVDF/Celgard composite diaphragms, it is characterised in that Including following steps：
Step（1）By Ti3AlC2Ceramic powders corrode in being put into hydrofluoric acid, and solution addition deionized water is carried out at centrifugation after corrosion Reason, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
Step（2）PVDF is added in 1-METHYLPYRROLIDONE, stirring and dissolving, forms PVDF solution；
Step（3）By Ti3C2TxMechanical agitation is uniform during powder is added to PVDF solution, the slurry of formation, then slurry is coated to On Celgard barrier films, Ti after vacuum drying3C2Tx/ PVDF/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 the step（2）The matter of middle PVDF and 1-METHYLPYRROLIDONE Amount is than being 1:10-100, mixing time is 1-12 hours.
5. method as claimed in claim 2, it is characterised in that the step（3）Middle Ti3C2TxIt is 1 with the mass ratio of PVDF： 0.01-0.1, mixing time is 1-12 hours.
CN201710225973.9A 2017-04-08 2017-04-08 A kind of Ti3C2Tx/PVDF/Celgard composite diaphragms Pending CN106876637A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107369801A (en) * 2017-06-29 2017-11-21 华南理工大学 A kind of MXene modifications composite diaphragm and preparation method thereof and the application in lithium-sulfur cell
CN112864527A (en) * 2021-04-02 2021-05-28 衢州德联环保科技有限公司 Preparation method of Mxene/PVDF lithium-sulfur battery diaphragm

Citations (3)

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Publication number Priority date Publication date Assignee Title
CN105990552A (en) * 2015-02-04 2016-10-05 中国科学院苏州纳米技术与纳米仿生研究所 Composite diaphragm used for lithium-sulfur battery, preparation method and application thereof
CN106082313A (en) * 2016-05-31 2016-11-09 陕西科技大学 The preparation method of bar-shaped tin ash/two-dimensional nano titanium carbide composite
CN106098394A (en) * 2016-05-31 2016-11-09 西安交通大学 Two-dimensional layer N doping Ti3c2" paper " nano composite material and preparation method thereof and the method preparing combination electrode with this material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105990552A (en) * 2015-02-04 2016-10-05 中国科学院苏州纳米技术与纳米仿生研究所 Composite diaphragm used for lithium-sulfur battery, preparation method and application thereof
CN106082313A (en) * 2016-05-31 2016-11-09 陕西科技大学 The preparation method of bar-shaped tin ash/two-dimensional nano titanium carbide composite
CN106098394A (en) * 2016-05-31 2016-11-09 西安交通大学 Two-dimensional layer N doping Ti3c2" paper " nano composite material and preparation method thereof and the method preparing combination electrode with this material

Non-Patent Citations (1)

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Title
JIANJUN SONG,ET AL.: ""Immobilizing Polysulfides withMXene-Functionalized Separators for Stable Lithium-Sulfur Batteries"", 《APPLIED MATERIALS & INTERFACES》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107369801A (en) * 2017-06-29 2017-11-21 华南理工大学 A kind of MXene modifications composite diaphragm and preparation method thereof and the application in lithium-sulfur cell
CN107369801B (en) * 2017-06-29 2020-02-18 华南理工大学 MXene modified composite diaphragm, preparation method thereof and application thereof in lithium-sulfur battery
CN112864527A (en) * 2021-04-02 2021-05-28 衢州德联环保科技有限公司 Preparation method of Mxene/PVDF lithium-sulfur battery diaphragm
CN112864527B (en) * 2021-04-02 2022-12-09 福建康墨新能源科技有限公司 Preparation method of Mxene/PVDF lithium-sulfur battery diaphragm

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Application publication date: 20170620