CN109244335A - A kind of polyimide diaphragm lithium-sulfur cell and preparation method thereof - Google Patents
A kind of polyimide diaphragm lithium-sulfur cell and preparation method thereof Download PDFInfo
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- CN109244335A CN109244335A CN201811287105.4A CN201811287105A CN109244335A CN 109244335 A CN109244335 A CN 109244335A CN 201811287105 A CN201811287105 A CN 201811287105A CN 109244335 A CN109244335 A CN 109244335A
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- lithium
- diaphragm
- sulfur cell
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- positive plate
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000004642 Polyimide Substances 0.000 title claims abstract description 49
- 229920001721 polyimide Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 14
- 239000001989 lithium alloy Substances 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000006258 conductive agent Substances 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 239000002985 plastic film Substances 0.000 claims abstract description 7
- 229920006255 plastic film Polymers 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 238000002347 injection Methods 0.000 claims abstract description 4
- 239000007924 injection Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical group [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 239000003273 ketjen black Substances 0.000 claims description 5
- 239000005030 aluminium foil Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 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
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 238000003475 lamination Methods 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- 229910000676 Si alloy Inorganic materials 0.000 claims description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 2
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical group [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims 1
- 239000002048 multi walled nanotube Substances 0.000 claims 1
- 239000011149 active material Substances 0.000 abstract description 13
- 238000005520 cutting process Methods 0.000 abstract description 3
- 239000004743 Polypropylene Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- FWTXWYXPXGKVJG-UHFFFAOYSA-N atrolactamide Chemical compound NC(=O)C(O)(C)C1=CC=CC=C1 FWTXWYXPXGKVJG-UHFFFAOYSA-N 0.000 description 2
- 229950011225 atrolactamide Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000521 B alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002023 wood Substances 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
-
- 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)
- Materials Engineering (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of polyimide diaphragm lithium-sulfur cells and preparation method thereof, which comprises (1) first mixes sulphur carbon composite, conductive agent, binder, be prepared into slurry, be coated on plus plate current-collecting body, be prepared into positive plate；(2) negative electrode tab is prepared into after cutting metal lithium bands or lithium alloys band；(3) diaphragm is prepared into after cutting polyimide diaphragm；(4) positive plate prepared, diaphragm, negative electrode tab are prepared into battery core, the battery core is put into aluminum plastic film shell, then carry out edge sealing, injection electrolyte, then seal.The invention can effectively improve the active material utilization of lithium-sulfur cell, improve the security performance of lithium-sulfur cell, widen the application field of lithium-sulfur cell, be with a wide range of applications in fields such as portable electronic device, electric vehicle, electric tools.
Description
Technical field
The invention belongs to technical field of chemical power, in particular to a kind of polyimide diaphragm lithium-sulfur cell and its preparation side
Method.
Background technique
Currently, with rapid development of economy, energy crisis and environmental pollution is getting worse is developed and utilized emerging
Green regenerative energy sources and the conversion of colleges and universities' clean energy resource and energy storage technology are extremely urgent.Under the pressure of energy shortage and environmental problem,
Various electronic equipments and new-energy automobile are developed rapidly, lithium ion battery from the nineties in last century realize commercialization with
Come, is widely used to each electronic field and new energy field, however, be limited to the characteristic of lithium ion battery itself, city at present
Lithium ion battery energy density on field is lower and is unable to satisfy requirement of the Novel electric equipment to high-energy density, therefore, opens
The power supply system for sending out new is imperative to meet the needs of various electrical equipments are to high-energy density, high safety performance power supply.
The theoretical energy density of lithium-sulfur cell is up to 2600Wh/kg, is the highest solid-state electricity of energy density being currently known
Pole lithium secondary battery system, and positive electrode sulphur abundance, it is cheap, and toxicity is lower, receives great attention in recent years,
It is considered as most possibly realizing commercialized next-generation lithium secondary battery system.
Main product currently as lithium-sulfur cell diaphragm material is micro- using U.S. Celgard as the polyethylene (PE) of representative
The polyolefins such as pore membrane, polypropylene (PP) microporous barrier and polypropylene, polyethylene/polypropylene (PP/PE/PP) three layers of microporous compound film
Diaphragm, however, the absorbent of polyolefins diaphragm is limited, and safety is poor, is more than 70 DEG C in battery temperature, diaphragm micro-hole
It may turn off, influence the normal work of battery, when battery temperature is more than 150 DEG C, diaphragm can melt, and cause positive/negative plate direct
Contact may cause on fire or explosion, will lead to serious safety concerns so as to cause battery short circuit.Compared to polyolefin every
Film, polyimide diaphragm have excellent heat-resisting quantity and good absorbent, are resistant to 350 DEG C of high temperature, therefore, with PI every
Film makees the diaphragm of lithium-sulfur cell, is more advantageous to the absorption of electrolyte, is conducive to the active material utilization for improving lithium-sulfur cell, separately
Outside, when battery temperature is higher, the contraction damage of diaphragm will not occur, so as to improve the safety of lithium-sulfur cell.
Summary of the invention
The technical problem to be solved by the present invention is providing a kind of polyimide diaphragm lithium-sulfur cell and preparation method thereof, mention
The active material utilization of high lithium-sulfur cell improves the security performance of lithium-sulfur cell, widens the application field of lithium-sulfur cell.
In order to solve the above-mentioned technical problem, the adopted technical solution is that:
The present invention proposes a kind of polyimide diaphragm lithium-sulfur cell, the battery include diaphragm, positive plate, negative electrode tab and
Electrolyte, which is characterized in that the diaphragm is polyimide diaphragm；The positive plate material includes sulphur carbon composite, conduction
Agent, binder；The negative electrode tab material is lithium metal or lithium alloys；The electrolyte is the electrolysis containing lithium salts and organic solvent
Liquid includes additive in the electrolyte.
The present invention also proposes a kind of preparation method of polyimide diaphragm lithium-sulfur cell, the battery by diaphragm, positive plate,
Negative electrode tab and electrolyte composition, which is characterized in that the diaphragm is polyimide diaphragm；The positive plate material includes sulphur carbon
Composite material, conductive agent, binder；The negative electrode tab material is lithium metal or lithium alloys；The electrolyte be containing lithium salts and
The electrolyte of organic solvent, wherein containing additive in the electrolyte；The preparation method comprises the following steps: (1) it is described just
The preparation of pole piece: first sulphur carbon composite, conductive agent, binder are mixed, slurry is prepared into, is then coated on the slurry
On plus plate current-collecting body, drying, roll-in, cut, be dried in vacuo after be prepared into positive plate；(2) preparation of the negative electrode tab: will be golden
Category lithium band or lithium alloys band are prepared into negative electrode tab after cutting；(3) it the preparation of the diaphragm: is made after polyimide diaphragm is cut
For at diaphragm；(4) battery assembly step: by the positive plate prepared, diaphragm, negative electrode tab is rolled or lamination is prepared into battery core,
The battery core is put into aluminum plastic film shell, then carries out edge sealing, injection electrolyte, then seal.
The present invention realizes following beneficial technical effect:
The present invention uses diaphragm of the polyimide diaphragm as lithium-sulfur cell, uses high performance sulphur carbon composite wood on anode
Expect a part as blended anode material, lithium metal or lithium alloys is used on cathode, and use and contain the organic of additive
Electrolyte can effectively improve the active material utilization of lithium-sulfur cell, improve the security performance of lithium-sulfur cell, widen lithium sulphur electricity
The application field in pond is with a wide range of applications in fields such as portable electronic device, electric vehicle, electric tools.
Detailed description of the invention
Fig. 1 is the flow chart of the preparation method of polyimide diaphragm lithium-sulfur cell of the invention；
Fig. 2 is the putting as the lithium-sulfur cell of diaphragm using polyimides (PI) and Celgard2325 respectively of the embodiment of the present invention 1
Electric curve comparison figure.
Specific embodiment
Below by specific embodiment, present invention is further described in detail, but these embodiments are only that citing
Illustrate, the scope of the present invention is not defined.
Polyimide diaphragm lithium-sulfur cell of the invention, is made of diaphragm, positive plate, negative electrode tab and electrolyte, wherein
Diaphragm is polyimide diaphragm；The positive plate material includes sulphur carbon composite, conductive agent, binder；Negative electrode tab material is
Lithium metal or lithium alloys；Electrolyte is the electrolyte containing lithium salts and organic solvent, contains additive in electrolyte.
As shown in Fig. 1, polyimide diaphragm lithium-sulfur cell preparation method the following steps are included:
(1) preparation of positive plate: first mixing sulphur carbon composite, conductive agent, binder, be prepared into slurry, then will
The slurry is coated on plus plate current-collecting body, drying, roll-in, cut, be dried in vacuo after be prepared into positive plate；
(2) preparation of negative electrode tab: negative electrode tab is prepared into after metal lithium bands or lithium alloys band are cut；
(3) diaphragm the preparation of diaphragm: is prepared into after polyimide diaphragm is cut；
(4) battery assembly: first by the positive plate prepared, diaphragm, negative electrode tab is rolled or lamination is prepared into battery core, will
The battery core is put into aluminum plastic film shell, then carries out edge sealing, injection electrolyte, then seal.
Wherein, the temperature range of baking oven is 55 DEG C~65 DEG C in drying course, the temperature of vacuum tank in process of vacuum drying
Range is 50 DEG C~60 DEG C.
Wherein, for the polyimide diaphragm with a thickness of 20 μm~40 μm, aperture is 0.02 μm~0.06 μm, and porosity is
70%~90%.
Wherein, the mass content ratio of sulphur is 50%~90% in the sulphur carbon composite.
Wherein, the carbon in the sulphur carbon composite is Ketjen black, active carbon, Cabot carbon black, carbon nanotube, multi wall carbon
One of nanotube or two or more mixing.
Wherein, the lithium alloys are one of lithium boron alloy, lithium-aluminium alloy, Li-Si alloy.
Wherein the lithium content of the lithium alloys is 70%~95%.
Wherein, lithium salts is LiClO in the electrolyte4、LiBF4、LiPF6、LiAsF6、LiCF3SO3、LiN(CF3SO2)2In
One or more kinds of mixing, lithium salt is 0.5mol/L~5.0mol/L；Organic solvent is 1,3- in the electrolyte
The mixed solvent of dioxolane, glycol dimethyl ether, volume ratio are 1:1~1:5；The electrolysis additive is LiNO3、
LiBOB、P2S5One or more kinds of mixing, additive concentration is 0.1mol/L~0.5mol/L.
Wherein, sulphur carbon composite in the step (1), conductive agent, binder mass ratio be 70%~85%:
5%~20%:10%.
Wherein, the conductive agent is the mixing of one or more of acetylene black, graphite powder, graphene, Super P；
The binder is Kynoar, polytetrafluoroethylene (PTFE), sodium alginate, gelatin, cyclodextrin, acrylonitrile multiple copolymer, carboxylic first
One or more kinds of mixing of base sodium cellulosate and butadiene-styrene rubber.
Wherein, the collector of the positive plate be aluminium foil, the positive plate with a thickness of 12 μm~20 μm.
Illustrate the preparation method of polyimide diaphragm lithium-sulfur cell of the present invention with reference to embodiments.
Embodiment 1:
The preparation of positive plate: by the sulphur of sulfur content 60%/Ketjen black composite material, acetylene black, sodium carboxymethylcellulose, fourth
Atrolactamide 80%:10%:4%:6% in mass ratio mixing, makees solvent with deionized water, prepares slurry, be then coated on thickness
For on 18 μm of aluminium foils, the preliminary drying in 60 DEG C of baking oven, then through roll-in, cut-parts, in 60 DEG C of vacuum ovens it is dry for 24 hours, preparation
At positive plate.
Negative electrode tab uses metal lithium bands, and the capacity ratio of positive and negative anodes active material is 1:1.5；Diaphragm uses with a thickness of 25 μm
Polyimide diaphragm.By positive plate, diaphragm, negative electrode tab winding preparation battery core, it is then placed in edge sealing in the aluminum plastic film of forming, is infused
Enter 1.0mol/L LiN (CF3SO2)2+ DOL/DME (v/v=1:1)+0.1mol/L LiNO3Electrolyte, then seal, that is, it is prepared into
Polyimide diaphragm lithium-sulfur cell.
In order to carry out performance comparison, it is prepared for the flexible package lithium-sulfur cell that diaphragm is Celgard2325 in the same way.
Performance test: by the lithium-sulfur cell of PI diaphragm and Celgard2325 diaphragm respectively with 0.1C multiplying power discharging, electric discharge is cut
Only voltage is 1.5V, and the specific discharge capacity of PI diaphragm lithium-sulfur cell is 1505.6mAh/g, active material utilization 90%；
The specific discharge capacity of Celgard2325 diaphragm lithium-sulfur cell is 1446.9mAh/g, active material utilization 86%.
Embodiment 2:
The preparation of positive plate: the sulphur of sulfur content 70%/Ketjen black composite material, acetylene black, Kynoar are pressed into quality
It is mixed than 85%:5%:10%, makees solvent with N-Methyl pyrrolidone, prepare slurry, be then coated on the aluminium with a thickness of 18 μm
On foil, the preliminary drying in 60 DEG C of baking oven, then through roll-in, cut-parts, in 60 DEG C of vacuum ovens it is dry for 24 hours, be prepared into positive plate.
Negative electrode tab uses metal lithium bands, and the capacity ratio of positive and negative anodes active material is 1:1.5；Diaphragm uses with a thickness of 25 μm
Polyimide diaphragm.By positive plate, diaphragm, negative electrode tab winding preparation battery core, it is then placed in edge sealing in the aluminum plastic film of forming, is infused
Enter 1.0mol/L LiN (CF3SO2)2+ DOL/DME (v/v=1:2)+0.2mol/L LiNO3Electrolyte, then seal, that is, it is prepared into
Polyimide diaphragm lithium-sulfur cell.
In order to carry out performance comparison, it is prepared for the flexible package lithium-sulfur cell that diaphragm is Celgard2325 in the same way.
Referring to Fig. 2, performance test: the lithium-sulfur cell of PI diaphragm and Celgard2325 diaphragm is put respectively with 0.1C multiplying power
Electricity, the specific discharge capacity of discharge cut-off voltage 1.5V, PI diaphragm lithium-sulfur cell are 1321.5mAh/g, active material utilization
It is 79%；The specific discharge capacity of Celgard2325 diaphragm lithium-sulfur cell is 1201.4mAh/g, active material utilization 72%.
Embodiment 3:
The preparation of positive plate: by the sulphur of sulfur content 80%/Ketjen black composite material, acetylene black, sodium carboxymethylcellulose, fourth
Atrolactamide 75%:15%:5%:5% in mass ratio mixing, makees solvent with deionized water, prepares slurry, be then coated on thickness
For on 18 μm of aluminium foils, the preliminary drying in 60 DEG C of baking oven, then through roll-in, cut-parts, in 60 DEG C of vacuum ovens it is dry for 24 hours, preparation
At positive plate.
Negative electrode tab uses metal lithium bands, and the capacity ratio of positive and negative anodes active material is 1:1.5；Diaphragm uses with a thickness of 25 μm
Polyimide diaphragm.By positive plate, diaphragm, negative electrode tab winding preparation battery core, it is then placed in edge sealing in the aluminum plastic film of forming, is infused
Enter 0.6mol/L LiN (CF3SO2)2+ DOL/DME (v/v=1:1)+0.2mol/L LiNO3Electrolyte, then seal, that is, it is prepared into
Polyimide diaphragm lithium-sulfur cell.
In order to carry out performance comparison, it is prepared for the flexible package lithium-sulfur cell that diaphragm is Celgard2325 in the same way.
Performance test: by the lithium-sulfur cell of PI diaphragm and Celgard2325 diaphragm respectively with 0.1C multiplying power discharging, electric discharge is cut
Only voltage is 1.5V, and the specific discharge capacity of PI diaphragm lithium-sulfur cell is 1226.5mAh/g, active material utilization 73%；
The specific discharge capacity of Celgard2325 diaphragm lithium-sulfur cell is 1185.7mAh/g, active material utilization 70%.
Although the present invention has chosen preferable embodiment and discloses as above, it is not intended to limit the present invention.Obviously, it is not necessarily to here
Also all embodiments can not be exhaustive.Any this field researcher without departing from the spirit and scope of the present invention,
The design method and content that all can be used in embodiment disclosed above are changed and are modified to research approach of the invention, because
This, all contents without departing from the present invention program, research essence according to the present invention is to any simple made by above-described embodiment
Modification, Parameters variation and modification, belong to the protection scope of the present invention program.
Claims (10)
1. a kind of polyimide diaphragm lithium-sulfur cell, the battery includes diaphragm, positive plate, negative electrode tab and electrolyte, spy
Sign is that the diaphragm is polyimide diaphragm；The positive plate material includes sulphur carbon composite, conductive agent, binder；Institute
Stating negative electrode tab material is lithium metal or lithium alloys；The electrolyte is the electrolyte containing lithium salts and organic solvent, the electrolysis
It include additive in liquid.
2. polyimide diaphragm lithium-sulfur cell according to claim 1, it is characterised in that: the polyimide diaphragm thickness
It is 20 μm~40 μm, aperture is 0.02 μm~0.06 μm, and porosity is 70%~90%.
3. polyimide diaphragm lithium-sulfur cell according to claim 1, it is characterised in that: sulphur in the sulphur carbon composite
Mass content ratio be 50%~90%.
4. polyimide diaphragm lithium-sulfur cell according to claim 3, it is characterised in that: in the sulphur carbon composite
Carbon is one of Ketjen black, active carbon, Cabot carbon black, carbon nanotube, multi-walled carbon nanotube or two or more mixing.
5. polyimide diaphragm lithium-sulfur cell according to claim 1, it is characterised in that: the lithium alloys are lithium boron conjunction
One of gold, lithium-aluminium alloy, Li-Si alloy, wherein the lithium content of the lithium alloys is 70%~95%.
6. polyimide diaphragm lithium-sulfur cell according to claim 1, it is characterised in that: the lithium salts in the electrolyte is
LiClO4、LiBF4、LiPF6、LiAsF6、LiCF3SO3、LiN(CF3SO2)2One or more of mixing, lithium salt is
0.5mol/L~5.0mol/L；Organic solvent is the mixed solvent of 1,3- dioxolane, glycol dimethyl ether in the electrolyte,
The two volume ratio is 1:1~1:5；The additive of the electrolyte is LiNO3、LiBOB、P2S5One or more it is mixed
It closes, additive concentration is 0.1mol/L~0.5mol/L.
7. polyimide diaphragm lithium-sulfur cell according to claim 1, it is characterised in that: wherein, sulphur carbon composite is led
Electric agent, binder mass ratio be 70%~85%:5%~20%:10%.
8. polyimide diaphragm lithium-sulfur cell according to claim 1, it is characterised in that: the conductive agent be acetylene black,
One or more of graphite powder, graphene, SuperP mixing；The binder be Kynoar, polytetrafluoroethylene (PTFE),
Sodium alginate, gelatin, cyclodextrin, acrylonitrile multiple copolymer, sodium carboxymethylcellulose and butadiene-styrene rubber it is one or two kinds of with
Upper mixing.
9. polyimide diaphragm lithium-sulfur cell according to claim 1, it is characterised in that: the collector of the positive plate is
Aluminium foil, the positive plate with a thickness of 12 μm~20 μm.
10. a kind of preparation method of polyimide diaphragm lithium-sulfur cell, the battery is by diaphragm, positive plate, negative electrode tab and electricity
Solve liquid composition, which is characterized in that the diaphragm is polyimide diaphragm；The positive plate material includes sulphur carbon composite, leads
Electric agent, binder；The negative electrode tab material is lithium metal or lithium alloys；The electrolyte is the electricity containing lithium salts and organic solvent
Liquid is solved, includes additive in the electrolyte；
The preparation method comprises the following steps:
(1) preparation of the positive plate: first mixing sulphur carbon composite, conductive agent, binder, be prepared into slurry, then will
The slurry is coated on plus plate current-collecting body, drying, roll-in, cut, be dried in vacuo after be prepared into positive plate；
(2) preparation of the negative electrode tab: negative electrode tab is prepared into after metal lithium bands or lithium alloys band are cut；
(3) diaphragm the preparation of the diaphragm: is prepared into after polyimide diaphragm is cut；
(4) battery assembly step: by the positive plate prepared, diaphragm, negative electrode tab is rolled or lamination is prepared into battery core, will be described
Battery core is put into aluminum plastic film shell, then carries out edge sealing, injection electrolyte, then seal.
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Cited By (3)
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| CN111446418A (en) * | 2020-04-17 | 2020-07-24 | 中国航发北京航空材料研究院 | High-sulfur-loading-capacity lithium-sulfur battery positive plate and preparation method thereof |
| CN111792646A (en) * | 2020-07-21 | 2020-10-20 | 苏州华赢新能源材料科技有限公司 | Polyimide modified nano silicon negative electrode material and preparation method and application thereof |
| CN115692693A (en) * | 2022-11-22 | 2023-02-03 | 江苏正力新能电池技术有限公司 | A lithium-sulfur battery positive electrode material, its preparation method and lithium-sulfur battery |
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| CN108134033A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of application of porous septum in lithium-sulfur cell |
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| CN104538668A (en) * | 2014-12-25 | 2015-04-22 | 贵州梅岭电源有限公司 | Lithium ion battery with relatively high safety and preparation method thereof |
| CN106252572A (en) * | 2016-09-09 | 2016-12-21 | 贵州梅岭电源有限公司 | A kind of energy-density lithium ion battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111446418A (en) * | 2020-04-17 | 2020-07-24 | 中国航发北京航空材料研究院 | High-sulfur-loading-capacity lithium-sulfur battery positive plate and preparation method thereof |
| CN111446418B (en) * | 2020-04-17 | 2021-08-03 | 中国航发北京航空材料研究院 | A high-sulfur-loaded lithium-sulfur battery positive electrode sheet and preparation method thereof |
| CN111792646A (en) * | 2020-07-21 | 2020-10-20 | 苏州华赢新能源材料科技有限公司 | Polyimide modified nano silicon negative electrode material and preparation method and application thereof |
| CN111792646B (en) * | 2020-07-21 | 2022-04-08 | 苏州华赢新能源材料科技有限公司 | Polyimide modified nano silicon negative electrode material and preparation method and application thereof |
| CN115692693A (en) * | 2022-11-22 | 2023-02-03 | 江苏正力新能电池技术有限公司 | A lithium-sulfur battery positive electrode material, its preparation method and lithium-sulfur battery |
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