CN107834005A - Preparation method of lithium-selenium battery composite diaphragm - Google Patents
Preparation method of lithium-selenium battery composite diaphragm Download PDFInfo
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- CN107834005A CN107834005A CN201711084020.1A CN201711084020A CN107834005A CN 107834005 A CN107834005 A CN 107834005A CN 201711084020 A CN201711084020 A CN 201711084020A CN 107834005 A CN107834005 A CN 107834005A
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- ZVSWQJGHNTUXDX-UHFFFAOYSA-N lambda1-selanyllithium Chemical compound [Se].[Li] ZVSWQJGHNTUXDX-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 239000006258 conductive agent Substances 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000006255 coating slurry Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 230000004888 barrier function Effects 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 13
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 10
- 235000010413 sodium alginate Nutrition 0.000 claims description 10
- 239000000661 sodium alginate Substances 0.000 claims description 10
- 229940005550 sodium alginate Drugs 0.000 claims description 10
- 238000007581 slurry coating method Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- -1 cdicynanmide Chemical compound 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004964 aerogel Substances 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 239000007767 bonding agent Substances 0.000 claims 1
- 229910021389 graphene Inorganic materials 0.000 claims 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 abstract description 28
- 239000011669 selenium Substances 0.000 abstract description 16
- 229910052711 selenium Inorganic materials 0.000 abstract description 14
- 229910052744 lithium Inorganic materials 0.000 abstract description 13
- 238000002156 mixing Methods 0.000 abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract 1
- 235000011649 selenium Nutrition 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 12
- 238000010345 tape casting Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 8
- 235000019241 carbon black Nutrition 0.000 description 8
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 8
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 4
- 229910013553 LiNO Inorganic materials 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000007974 melamines Chemical class 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000022131 cell cycle Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- ANAXIMBIWHBAHO-UHFFFAOYSA-N dilithium;selenium(2-) Chemical class [Li+].[Li+].[Se-2] ANAXIMBIWHBAHO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 2
- 150000003346 selenoethers Chemical class 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910014276 N-Li Inorganic materials 0.000 description 1
- 229910014326 N—Li Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001912 cyanamides Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a lithium-selenium battery composite diaphragm, which comprises the step of coating slurry on a diaphragm substrate and drying the slurry in vacuum to obtain the composite diaphragm, wherein the slurry is prepared by mixing g-C3N4, a conductive agent and a binder into slurry. The preparation method can effectively prevent the multi-selenide from reciprocating between the lithium cathode and the selenium anode, and obviously improves the cycle performance and the rate capability of the lithium-selenium battery.
Description
Technical field
The present invention relates to field of electrochemical power source, and in particular to a kind of preparation method of lithium selenium cell composite diaphragm.
Background technology
Lithium selenium cell is a kind of new lithium secondary battery system, and, by the use of elemental selenium as positive pole, lithium metal is negative pole, is for it
Based on the battery of the bielectron reaction between cathode of lithium and selenium positive pole, because selenium density is big, good conductivity, current potential is high, has very
High theoretical volume specific capacity, the energy storage of future generation that lithium-selenium cell is expected to be used for including intelligent grid and electric automobile should
In.Compared with metal oxide cathode material, specific capacity is high, compared with sulphur positive pole of the same clan, electric conductivity height, the active material of selenium
Utilization rate is high, capacity attenuation is small, as novel metal lithium secondary battery, has very important scientific research value and application potential.
But there is also some fundamental problems to need to solve, such as the utilization rate of selenium is low, the volumetric expansion after lithiumation, low lithium ion and
Electronics conduction velocity etc..
Different from carbonates electrolyte, in ethers electrolyte (1MLiTFSI DOL/DME solution), the reaction machine of selenium
To manage and reacted for multi-step, selenium is soluble in ethers electrolyte with the more lithium selenides of electric discharge intermediate product that lithium is formed in discharge process,
Selenium positive active material quality is set constantly to reduce, capacity constantly reduces.In addition, the more lithium selenides and the cathode of lithium that are formed react or
Negative terminal surface deposits, and causes battery performance constantly to decline, polarization increase.Therefore need to develop the stable circulation in ethers electrolyte
Lithium-selenium cell.
Mainly from anode composite material is prepared, the pattern and structure that regulate and control positive electrode come current research method
Suppress shuttle effect.Selenium-carbon composite is mainly prepared, by elemental selenium and porous carrier or mesoporous supports Hybrid Heating, from
And elemental selenium is dispersed in the duct of porous carrier or mesoporous supports, there is certain carry to cyclical stability and high rate performance
It is high.
But the duct of poromerics or mesoporous material is minimum, the above method be difficult to make elemental selenium fully and evenly into
Micropore canals, and the elemental selenium for being introduced into duct makes blockage of the micro orifice, it is difficult to make more elemental seleniums well into poromerics or
Inside mesoporous material, cause elemental selenium can not be uniformly compound with carrier, and the pore volume of poromerics or mesoporous material is small, load
Measure it is low, suppress shuttle effect effect need further to be improved.
The content of the invention
Based on technical problem existing for background technology, the present invention proposes a kind of preparation side of lithium selenium cell composite diaphragm
Method, can effectively hinder more selenides to be shuttled in cathode of lithium and the positive interpolar of selenium, significantly improve lithium selenium cell cycle performance and
High rate performance.
A kind of preparation method of lithium selenium cell composite diaphragm proposed by the present invention, it is true to be included in coating slurry in diaphragm matrix
Composite diaphragm is obtained after sky drying, the slurry is mixed into slurry and obtained by g-C3N4, conductive agent, binding agent.
Preferably, the one kind of the preparation method of the g-C3N4 in hard template method, soft template method, template-free method.
Preferably, the g-C3N4 is entered with least one of urea, cyanamide, cdicynanmide, melamine for presoma
It is prepared by row.
Preferably, the conductive agent is selected from conductive black, CNT, carbon nano-fiber, acetylene black, charcoal-aero gel, stone
At least one of black alkene.
Preferably, the binding agent in sodium alginate, gelatin, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose at least
It is a kind of.
Preferably, the mass ratio of the g-C3N4 and conductive agent are 8-1：1-8.
Preferably, the mass ratio of the conductive agent and binding agent is 8-1：1.
Preferably, the diaphragm matrix is in PE barrier films, PP barrier films, PP/PE/PP barrier films, PI barrier films, nonwoven cloth diaphragm
At least one.
Preferably, a diameter of 15-25mm of the composite diaphragm.
Preferably, the thickness of the diaphragm matrix is 16-40 μm.
Preferably, the thickness of the slurry coating is 5-20 μm.
Preferably, the temperature of the vacuum drying is 50-90 DEG C, time 12-24h.
Compared with prior art, the beneficial effects of the present invention are：
1) present invention process is simple and convenient to operate, and is advantageous to industrialized production.
2) present invention is coated in g-C3N4 as slurry on barrier film so that and composite diaphragm contains abundant functional group,
G-C3N4 empty places can form pyridine-N-Li keys, in g-C3N4 and Li2Also C-Se keys can be formed between Se, to more selenides
With extraordinary suction-operated, it can effectively suppress in lithium selenium cell charge and discharge process caused more plasma seleniums in selenium positive pole and lithium
Shuttle effect between negative pole, and then significantly improve the cycle performance and high rate performance of lithium selenium cell.
3) g-C3N4 of micro-dimension is used the mechanical strength of barrier film to be improved, for coating paste to ensure it in the present invention
To the limitation function of polysulfide during long-time circulates.
Brief description of the drawings
Fig. 1 is g-C3N4 of the present invention XRD.
Fig. 2 is the test result schematic diagram of button cell cycle performance in test example of the present invention.
Embodiment
Below, technical scheme is described in detail by specific embodiment.
Embodiment 1
A kind of preparation method of lithium selenium cell composite diaphragm, it is included in diaphragm matrix after coating slurry after vacuum drying and obtains
To composite diaphragm, the slurry is mixed into slurry and obtained by g-C3N4, conductive agent, binding agent.
Embodiment 2
1g melamines are taken to be positioned in alumina crucible, with 3 DEG C/min-1Programming rate be warming up to 550 DEG C, insulation 2
Hour, yellow product g-C3N4, the g-C3N4 XRD are obtained as shown in figure 1, diffraction maximum generation at wherein 13.1 ° and 27.3 °
Table g-C3N4 (100) and (002) crystal face.
It is 6 in mass ratio by g-C3N4, Super P conductive carbon blacks and sodium alginate：3：1 ratio mixing, addition go from
Sub- water, stir to obtain slurry using high speed machine, the slurry is coated on the original bases of barrier film Celgard 2400 with knife coating
On body, vacuum drying 24h obtains composite diaphragm at a temperature of 60 DEG C；
Wherein, a diameter of 15mm of the composite diaphragm；
The thickness of the diaphragm matrix is 40 μm；
The thickness of the slurry coating is 5 μm.
Embodiment 3
1g melamines are taken to be positioned in alumina crucible, with 3 DEG C/min-1Programming rate be warming up to 550 DEG C, insulation 2
Hour, obtain yellow product g-C3N4.
It is 4 in mass ratio by g-C3N4, Super P conductive carbon blacks and sodium alginate：5：1 ratio mixing, addition go from
Sub- water, stir to obtain slurry using high speed machine, the slurry is coated on the original bases of barrier film Celgard 2400 with knife coating
On body, vacuum drying 24h obtains composite diaphragm at a temperature of 60 DEG C；
Wherein, a diameter of 19mm of the composite diaphragm；
The thickness of the diaphragm matrix is 25 μm；
The thickness of the slurry coating is 15 μm.
Embodiment 4
1g melamines are taken to be positioned in alumina crucible, with 3 DEG C/min-1Programming rate be warming up to 550 DEG C, insulation 2
Hour, obtain yellow product g-C3N4.
It is 8 in mass ratio by g-C3N4, Super P conductive carbon blacks and sodium alginate：1：1 ratio mixing, addition go from
Sub- water, stir to obtain slurry using high speed machine, the slurry is coated on the original bases of barrier film Celgard 2400 with knife coating
On body, vacuum drying 24h obtains composite diaphragm at a temperature of 60 DEG C；
Wherein, a diameter of 25mm of the composite diaphragm；
The thickness of the diaphragm matrix is 16 μm；
The thickness of the slurry coating is 20 μm.
Embodiment 5
1g melamines are taken to be positioned in alumina crucible, with 3 DEG C/min-1Programming rate be warming up to 550 DEG C, insulation 2
Hour, obtain yellow product g-C3N4.
It is 2 in mass ratio by g-C3N4, Super P conductive carbon blacks and sodium alginate：7：1 ratio mixing, addition go from
Sub- water, stir to obtain slurry using high speed machine, the slurry is coated on the original bases of barrier film Celgard 2400 with knife coating
On body, vacuum drying 24h obtains composite diaphragm at a temperature of 60 DEG C；
Wherein, a diameter of 20mm of the composite diaphragm；
The thickness of the diaphragm matrix is 30 μm；
The thickness of the slurry coating is 10 μm.
Embodiment 6
1g cyanamides are taken to be positioned in alumina crucible, with 3 DEG C/min-1Programming rate be warming up to 550 DEG C, insulation 2 is small
When, obtain yellow product g-C3N4.
It is 1 in mass ratio by g-C3N4, CNT and gelatin：8：1 ratio mixing, adds deionized water, using height
Fast mechanical agitation obtains slurry, the slurry is coated on the original matrixes of barrier film Celgard 2400 with knife coating, at 50 DEG C
At a temperature of be dried in vacuo 15h obtain composite diaphragm；
Wherein, a diameter of 22mm of the composite diaphragm；
The thickness of the diaphragm matrix is 20 μm；
The thickness of the slurry coating is 9 μm.
Embodiment 7
1g urea is taken to be positioned in alumina crucible, with 3 DEG C/min-1Programming rate be warming up to 550 DEG C, be incubated 2 hours,
Obtain yellow product g-C3N4.
It is 5 in mass ratio by g-C3N4, acetylene black and sodium carboxymethylcellulose：4：1 ratio mixing, adds deionization
Water, stir to obtain slurry using high speed machine, the slurry is coated on the original matrixes of barrier film Celgard 2400 with knife coating
On, vacuum drying 12h obtains composite diaphragm at a temperature of 90 DEG C；
Wherein, a diameter of 16mm of the composite diaphragm；
The thickness of the diaphragm matrix is 36 μm；
The thickness of the slurry coating is 18 μm.
Test example 1
Selenium positive pole is prepared by active material of selenium powder：It is in mass ratio by selenium powder, Super P conductive carbon blacks and sodium alginate
7：2：1 ratio mixing, is added deionized water, is stirred to obtain slurry using high speed machine, coated the slurry with knife coating
In on aluminium foil, 24h is dried in vacuo at a temperature of 60 DEG C.
By the use of lithium metal as negative pole, electrolyte is 1mol/L LiTFSI (double trifluoromethanesulfonimide lithiums)/DOL-DME,
Wherein, LiTFSI and DOL-DME volume ratio is 1：1, also contain 0.5mol/L LiNO in electrolyte3；It is made with embodiment 2
Composite diaphragm coated side face positive pole, be assembled into button cell.
The cycle performance that battery is carried out to the button cell under 0.5C current density is tested, as a result such as Fig. 2 institutes
Show.
As shown in Figure 2：The first circle discharge capacity of the button cell is 642mAh/g, and first circle coulombic efficiency is 94%, is followed
After ring 100 encloses, remain to keep 447mAh/g specific capacity；Under the different current density such as 0.1C, 0.2C, 0.5C, 1C, 2C
The high rate performance of battery is tested, reversible specific capacity is respectively 627mAh g-1、582mAh/g、523mAh/g、484mAh/g、
443mAh/g；After high rate cyclic, when electric current returns to 0.1C, specific discharge capacity remains able to reach 557mAh/g,
It can be seen that the button cell shows excellent high rate performance and the excellent stability of electrode.
Test example 2
Selenium positive pole is prepared by active material of selenium powder：It is in mass ratio by selenium powder, Super P conductive carbon blacks and sodium alginate
7.5：1.5：1 ratio mixing, is added deionized water, is stirred to obtain slurry using high speed machine, with knife coating by the slurry
Coated on aluminium foil, 24h is dried in vacuo at a temperature of 60 DEG C.
By the use of lithium metal as negative pole, electrolyte is 1mol/L LiTFSI (double trifluoromethanesulfonimide lithiums)/DOL-DME,
Wherein, LiTFSI and DOL-DME volume ratio is 1：1, also contain 0.5mol/L LiNO in electrolyte3；It is made with embodiment 3
Composite diaphragm coated side face positive pole, be assembled into button cell.
Under 0.5C current density to the button cell carry out battery cycle performance test, as a result for：The button
The first circle discharge capacity of formula battery is 631mAh/g, and first circle coulombic efficiency is 92%, after the circle of circulation 100, remains to keep 418mAh/
G specific capacity, the high rate performance of battery is tested under the different current density such as 0.1C, 0.2C, 0.5C, 1C, 2C, in putting for 2C
Under electric density, remain to keep 411mAh/g.
Test example 3
Selenium positive pole is prepared by active material of selenium powder：It is in mass ratio by selenium powder, Super P conductive carbon blacks and sodium alginate
8：1：1 ratio mixing, is added deionized water, is stirred to obtain slurry using high speed machine, coated the slurry with knife coating
In on aluminium foil, 24h is dried in vacuo at a temperature of 60 DEG C.
By the use of lithium metal as negative pole, electrolyte is 1mol/L LiTFSI (double trifluoromethanesulfonimide lithiums)/DOL-DME,
Wherein, LiTFSI and DOL-DME volume ratio is 1：1, also contain 0.5mol/L LiNO in electrolyte3；It is made with embodiment 4
Composite diaphragm coated side face positive pole, be assembled into button cell.
Under 0.5C current density to the button cell carry out battery cycle performance test, as a result for：The button
The first circle discharge capacity of formula battery is 627mAh/g, and first circle coulombic efficiency is 91%, after the circle of circulation 100, remains to keep 382mAh/
G specific capacity, the high rate performance of battery is tested under the different current density such as 0.1C, 0.2C, 0.5C, 1C, 2C, in putting for 2C
Under electric density, remain to keep 373mAh/g.
Test example 4
Selenium positive pole is prepared by active material of selenium powder：It is in mass ratio by selenium powder, Super P conductive carbon blacks and sodium alginate
7：2：1 ratio mixing, is added deionized water, is stirred to obtain slurry using high speed machine, coated the slurry with knife coating
In on aluminium foil, 24h is dried in vacuo at a temperature of 60 DEG C.
By the use of lithium metal as negative pole, electrolyte is 1mol/L LiTFSI (double trifluoromethanesulfonimide lithiums)/DOL-DME,
Wherein, LiTFSI and DOL-DME volume ratio is 1：1, also contain 0.5mol/L LiNO in electrolyte3；It is made with embodiment 5
Composite diaphragm coated side face positive pole, be assembled into button cell.
Under 0.5C current density to the button cell carry out battery cycle performance test, as a result for：The button
The first circle discharge capacity of formula battery is 640mAh/g, and first circle coulombic efficiency is 94%, after the circle of circulation 100, remains to keep 435mAh/
G specific capacity, the high rate performance of battery is tested under the different current density such as 0.1C, 0.2C, 0.5C, 1C, 2C, in putting for 2C
Under electric density, remain to keep 426mAh/g.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of lithium selenium cell composite diaphragm, is included in diaphragm matrix and is answered after coating slurry vacuum drying
Close barrier film, it is characterised in that the slurry is mixed into slurry and obtained by g-C3N4, conductive agent, binding agent.
2. the preparation method of lithium selenium cell composite diaphragm according to claim 1, it is characterised in that the preparation of the g-C3N4
The one kind of method in hard template method, soft template method, template-free method.
3. the preparation method of lithium selenium cell composite diaphragm according to claim 1 or claim 2, it is characterised in that the g-C3N4 with
At least one of urea, cyanamide, cdicynanmide, melamine are prepared by presoma.
4. according to the preparation method of any one of the claim 1-3 lithium selenium cell composite diaphragms, it is characterised in that the conduction
Agent is selected from least one of conductive black, CNT, carbon nano-fiber, acetylene black, charcoal-aero gel, graphene.
5. according to the preparation method of any one of the claim 1-4 lithium selenium cell composite diaphragms, it is characterised in that the bonding
Agent is selected from least one of sodium alginate, gelatin, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose.
6. according to the preparation method of any one of the claim 1-5 lithium selenium cell composite diaphragms, it is characterised in that the g-
The mass ratio of C3N4 and conductive agent is 8-1：1-8.
7. according to the preparation method of any one of the claim 1-6 lithium selenium cell composite diaphragms, it is characterised in that the conduction
The mass ratio of agent and binding agent is 8-1：1.
8. according to the preparation method of any one of the claim 1-7 lithium selenium cell composite diaphragms, it is characterised in that the barrier film
Matrix is selected from least one of PE barrier films, PP barrier films, PP/PE/PP barrier films, PI barrier films, nonwoven cloth diaphragm.
9. according to the preparation method of any one of the claim 1-8 lithium selenium cell composite diaphragms, it is characterised in that described compound
A diameter of 15-25mm of barrier film；Preferably, the thickness of the diaphragm matrix is 16-40 μm；Preferably, the slurry coating
Thickness is 5-20 μm.
10. according to the preparation method of any one of the claim 1-9 lithium selenium cell composite diaphragms, it is characterised in that described true
The temperature of sky drying is 50-90 DEG C, time 12-24h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108767175A (en) * | 2018-06-29 | 2018-11-06 | 青岛科技大学 | A kind of preparation method of lithium-sulfur cell diaphragm |
| CN109704303A (en) * | 2018-12-03 | 2019-05-03 | 江苏理工学院 | A kind of compound biomass carbon material and its preparation and the application in lithium selenium cell coated separator |
| CN111740076A (en) * | 2020-06-22 | 2020-10-02 | 珠海冠宇电池股份有限公司 | Preparation method of nitrogen-doped, boron-doped or phosphorus-doped graphitized carbon nitride material |
| CN111785971A (en) * | 2020-07-17 | 2020-10-16 | 扬州大学 | MWCNT/PCN/Co3O4Preparation method of composite nano material and lithium-sulfur battery positive electrode material |
| CN112751140A (en) * | 2019-10-16 | 2021-05-04 | 珠海冠宇电池股份有限公司 | Diaphragm functional coating material for improving liquid retention capacity and safety performance of lithium ion battery electrolyte |
| CN114927827A (en) * | 2022-05-27 | 2022-08-19 | 山东海科创新研究院有限公司 | Composite diaphragm for lithium-selenium battery, preparation method of composite diaphragm and lithium-selenium battery |
| CN115441123A (en) * | 2022-10-14 | 2022-12-06 | 贺州学院 | High-liquid-absorption-rate and high-flame-retardance battery diaphragm and preparation method thereof |
| CN115513605A (en) * | 2022-10-17 | 2022-12-23 | 北京化工大学 | Lithium-sulfur battery diaphragm based on functional carbon material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104638219A (en) * | 2015-02-11 | 2015-05-20 | 中南大学 | Composite diaphragm for lithium-selenium battery and preparation method of composite diaphragm |
| CN104986742A (en) * | 2015-06-29 | 2015-10-21 | 济南大学 | Bead-chain-like graphitized carbon nitride nano material and preparation method thereof |
| CN105679983A (en) * | 2016-03-11 | 2016-06-15 | 中南大学 | Modified diaphragm and preparation method and application therefor |
| US20160233487A1 (en) * | 2015-02-06 | 2016-08-11 | Mitsubishi Chemical Corporation | Pnictide containing catalysts for electrochemical conversion reactions and methods of use |
| CN106744742A (en) * | 2016-11-11 | 2017-05-31 | 天津大学 | Many shell graphite phase carbon nitride hollow nano-spheres and its synthetic method and application |
| CN107204414A (en) * | 2016-03-18 | 2017-09-26 | 东北师范大学 | It is a kind of that the method that barrier film prepares high-performance lithium-sulfur cell is modified based on rich nitrogen molecular |
-
2017
- 2017-11-07 CN CN201711084020.1A patent/CN107834005A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160233487A1 (en) * | 2015-02-06 | 2016-08-11 | Mitsubishi Chemical Corporation | Pnictide containing catalysts for electrochemical conversion reactions and methods of use |
| CN104638219A (en) * | 2015-02-11 | 2015-05-20 | 中南大学 | Composite diaphragm for lithium-selenium battery and preparation method of composite diaphragm |
| CN104986742A (en) * | 2015-06-29 | 2015-10-21 | 济南大学 | Bead-chain-like graphitized carbon nitride nano material and preparation method thereof |
| CN105679983A (en) * | 2016-03-11 | 2016-06-15 | 中南大学 | Modified diaphragm and preparation method and application therefor |
| CN107204414A (en) * | 2016-03-18 | 2017-09-26 | 东北师范大学 | It is a kind of that the method that barrier film prepares high-performance lithium-sulfur cell is modified based on rich nitrogen molecular |
| CN106744742A (en) * | 2016-11-11 | 2017-05-31 | 天津大学 | Many shell graphite phase carbon nitride hollow nano-spheres and its synthetic method and application |
Non-Patent Citations (1)
| Title |
|---|
| 李静等: "锂硒电池及碳/硒电极：机遇与挑战", 《新型炭材料》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108767175A (en) * | 2018-06-29 | 2018-11-06 | 青岛科技大学 | A kind of preparation method of lithium-sulfur cell diaphragm |
| CN109704303A (en) * | 2018-12-03 | 2019-05-03 | 江苏理工学院 | A kind of compound biomass carbon material and its preparation and the application in lithium selenium cell coated separator |
| CN112751140A (en) * | 2019-10-16 | 2021-05-04 | 珠海冠宇电池股份有限公司 | Diaphragm functional coating material for improving liquid retention capacity and safety performance of lithium ion battery electrolyte |
| CN112751140B (en) * | 2019-10-16 | 2023-09-15 | 珠海冠宇电池股份有限公司 | Diaphragm functional coating material for improving liquid retention capacity and safety performance of lithium ion battery electrolyte |
| CN111740076A (en) * | 2020-06-22 | 2020-10-02 | 珠海冠宇电池股份有限公司 | Preparation method of nitrogen-doped, boron-doped or phosphorus-doped graphitized carbon nitride material |
| CN111785971A (en) * | 2020-07-17 | 2020-10-16 | 扬州大学 | MWCNT/PCN/Co3O4Preparation method of composite nano material and lithium-sulfur battery positive electrode material |
| CN114927827A (en) * | 2022-05-27 | 2022-08-19 | 山东海科创新研究院有限公司 | Composite diaphragm for lithium-selenium battery, preparation method of composite diaphragm and lithium-selenium battery |
| CN115441123A (en) * | 2022-10-14 | 2022-12-06 | 贺州学院 | High-liquid-absorption-rate and high-flame-retardance battery diaphragm and preparation method thereof |
| CN115441123B (en) * | 2022-10-14 | 2024-03-08 | 贺州学院 | High-liquid-absorption and high-flame-retardance battery diaphragm and preparation method thereof |
| CN115513605A (en) * | 2022-10-17 | 2022-12-23 | 北京化工大学 | Lithium-sulfur battery diaphragm based on functional carbon material and preparation method and application thereof |
| CN115513605B (en) * | 2022-10-17 | 2024-03-08 | 北京化工大学 | Lithium-sulfur battery diaphragm based on functional carbon material, and preparation method and application thereof |
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Application publication date: 20180323 |