CN104795592A - Polymer lithium-sulfur battery and preparation method thereof - Google Patents
Polymer lithium-sulfur battery and preparation method thereof Download PDFInfo
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- CN104795592A CN104795592A CN201510200961.1A CN201510200961A CN104795592A CN 104795592 A CN104795592 A CN 104795592A CN 201510200961 A CN201510200961 A CN 201510200961A CN 104795592 A CN104795592 A CN 104795592A
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- 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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- 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
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a polymer lithium-sulfur battery and a preparation method thereof. The polymer lithium-sulfur battery comprises a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises a sulfur-based active substance, a conductive agent and a binder; the negative electrode comprises an active substance, the conductive agent and the binder; the electrolyte is a polymer electrolyte and comprises a combination of a solid solvent and a liquid solvent, lithium salt, a crosslinking monomer and an initiator. According to the invention, the prepared polymer lithium-sulfur battery is high in energy density and safety performance, stable in chemical performance, low in production cost, less in polarization in the charge and discharge processes, and stable in capacity, and has good application prospects.
Description
Technical field
The invention belongs to polymer lithium sulphur cell manufacturing techniques field, particularly relate to a kind of new polymers battery and application thereof.
Background technology
Mankind's modern life be unable to do without moveable chemical power source, lithium ion battery is widely used in all kinds of Miniature Portable Unit owing to having the advantages such as environmental friendliness, operating voltage is high, specific capacity is large and have extended cycle life, and becomes the extremely potential novel green chemical power source in the world today.But along with the raising of life taste, people propose higher demand to mobile electrical appliance: gentlier, thinner, less, more lasting; Therefore as the power supply unit of these portable power sources, to the requirement also corresponding increase of lithium ion battery.But the lithium ion battery of traditional form has been difficult to meet the requirements of people for chemical power source, the lithium ion battery of future generation of high-energy-density is in the middle of the upsurge of extensive exploitation, lithium-sulfur cell as by the good lithium ion battery of new generation of industrial circle and academia gradually favor by people.But lithium-sulfur cell on stream the problems that expose to the open air out be also badly in need of solving: such as, sulphur is as the dissolving, in addition of intermediate product polysulfide in its lower electronic conductivity of positive active material, cyclic process, and the change in volume of sulfur electrode in doff lithium process is all the main cause of restriction lithium-sulfur cell development.
In the last few years, in order to solve the problem, people prepare various dimensions, multiple dimensioned new carbon is mated with sulphur.Although novel carbon-sulfur composite material effectively can improve the electronic conductivity of sulphur, and suppresses the dissolving of polysulfide to a certain extent, nanoscale new carbon complicated process of preparation, and reduce the energy density of overall sulfur electrode.Therefore, other method improving lithium-sulfur cell performance is in the middle of developing gradually.Wang [ChemElectroChem, 2015,2 (1): 22-36.] etc. people thinks and adopts polymer dielectric effectively to suppress polysulfide to dissolve in lithium-sulfur cell, thus the materials such as the lithium sulfide that repeatedly generates in negative terminal surface after dissolving of the sulphur loss reduced in cyclic process and polysulfide.But its conductivity of the polymer dielectric that traditional lithium battery generally uses is low, the compatible problem of complicated process of preparation and the interface poor when mating with sulfur electrode all become polymer lithium-sulfur cell exploitation in technological difficulties.
The method of in-situ polymerization is adopted electrolyte and electrode to be carried out mating and effectively can reduce inside battery interface impedance problem, but the low subject matter remaining polymer dielectric and apply in lithium-sulfur cell of conductivity.Therefore, how to take into account the compatible problem in interface in the conductivity improving polymer dielectric simultaneously, develop the polymer lithium-sulfur cell of stable performance, high power density, high-energy-density, being the important topic in lithium-sulfur cell field, is also current lithium-sulfur cell commercialized development technical barrier urgently to be resolved hurrily.
Summary of the invention
In order to solve above technical problem, the invention provides the polymer lithium-sulfur cell of a kind of stable performance, high power density, high-energy-density.
A kind of polymer lithium-sulfur cell, comprising:
Positive pole: sulfenyl active material, conductive agent, binding agent;
Negative pole: active material, conductive agent, binding agent;
Electrolyte: adopt polymer dielectric, comprise solid solvent and liquid flux combination, lithium salts, cross-linking monomer and initator;
Described cross-linking monomer comprises following structure:
wherein R
1, R
2linear alkyl chain for carbon number 1-20, the linear alkyl chain containing ether-oxygen bond, alkyl chain containing side base and the segment containing single phenyl ring wherein a kind of, wherein n>=2.This cross-linking monomer is purchased in E.I.Du Pont Company.
Preferably, described polymer dielectric is characterized in that, by weight percentage, described cross-linking monomer is 0.5-20%; Described initator is 0.001-5%; Described lithium salts is 1-20%, and surplus is solid-liquid solvent.
Preferably, in described positive pole, by weight percentage, sulfenyl active material accounts for the 70-99% of whole anode pole piece; Conductive agent accounts for the 0.5-20% of whole anode pole piece; Binding agent accounts for the 0.5-20% of whole anode pole piece.
Preferably, in described negative pole, by weight percentage, active material accounts for the 70-100% of whole cathode pole piece; Conductive agent accounts for the 0.5-20% of whole cathode pole piece; Conductive agent accounts for the 0.5-20% of whole cathode pole piece;
Preferably, in described positive pole, described positive pole sulfenyl active material is elemental sulfur, polysulfide (Li
2s
n), at least one in organic sulfur compound and sulphur carbon composite; Conductive agent adopts at least one in acetylene black, conductive black, Ketjen black, electrically conductive graphite, Graphene, carbon nano-tube; Binding agent adopts at least one in Kynoar, polyvinyl alcohol, polytetrafluoroethylene, sodium carboxymethylcellulose, polyolefin, polyurethane, butadiene-styrene rubber, acrylonitrile multiple copolymer.
Preferably, active material in described negative pole adopts lithium metal, or embedding lithium compound, lithium metal or prelithiation graphite, embedding lithium Si-C composite material, at least one in embedding lithium tin carbon composite; Conductive agent adopts at least one in acetylene black, conductive black, Ketjen black, electrically conductive graphite, Graphene, carbon nano-tube.
Preferably, described solid-liquid solvent is the mixture of solid solvent and liquid flux; Described liquid flux adopts at least one in ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, oxolane, glycol dimethyl ether, tetraethyleneglycol dimethyl ether and DOX; Described solid solvent: at least one in ethylene carbonate, diphenyl carbonate, di-tert-butyl dicarbonate, malononitrile, succinonitrile, stearonitrile and isophthalodinitrile.
Preferably, described lithium salts adopts lithium hexafluoro phosphate, two (trifluoromethane sulfonic acid) imine lithium, three (trimethyl fluoride sulfonyl) lithium methide, dioxalic acid lithium borate, at least one of three (pentafluoroethyl group) three in lithium fluophosphate.
Accordingly, the present invention also provides a kind of preparation method of polymer lithium-sulfur cell, it is characterized in that, comprises the following steps:
Steps A: the preparation of solid polymer electrolyte presoma: cross-linking monomer, lithium salts, initator are mixed after adding solid-liquid solvent, obtained solid polymer electrolyte presoma;
Step B: by barrier film, positive pole diaphragm and cathode membrane after glove box is assembled into naked battery core, enter shell or bag, obtains treating fluid injection battery core;
Step C: solid polymer electrolyte presoma obtained for steps A is injected and seals after fluid injection battery core, after diaphragm fully infiltrates, trigger monomer polymerization in 2-24 hour is heated at 0.1-10Pa, 50-100 DEG C, fabricated in situ solid polymer electrolyte, carry out successively changing into, shaping, after degasification operation, prepare shaping after battery.
Polymer lithium sulphur battery energy density prepared by the present invention is high, security performance is high, stable chemical performance, production cost are low, in charge and discharge process, have less polarization, and capacity keeps stable, has good application prospect.
Accompanying drawing explanation
Fig. 1 is the outward appearance photo of polymer dielectric prepared by the present invention.
Fig. 2 is in the polymer dielectric prepared of the present invention, active function groups number and its conductivity and the relation first between reversible specific capacity in polymerization single polymerization monomer.Number of monomers accounts for 5% of whole precursor solution gross mass.
Fig. 3 is polymer dielectric thermogravimetric curve figure in air atmosphere prepared by the present invention.
Fig. 4 is the cycle performance of polymer lithium-sulfur cell under 0.5C/0.5C current density prepared by the present invention.
Fig. 5 is the high rate performance of polymer lithium-sulfur cell under different current density prepared by the present invention.
Embodiment
Below in conjunction with accompanying drawing, preferably embodiment of the present invention is described in further detail:
Embodiment 1
Step 1) take following component by following relationship between quality, by weight, ethoxyquin tetramethylol methane tetraacrylate: ethylene carbonate: diethyl carbonate: methyl ethyl carbonate: lithium hexafluoro phosphate: lauroyl peroxide=5:30:20:30:14.9:0.1.By ethylene carbonate, diethyl carbonate, methyl ethyl carbonate, mix, add lithium hexafluoro phosphate afterwards, then ethoxyquin tetramethylol methane tetraacrylate, lauroyl peroxide are added above-mentioned electrolyte and obtain polymer dielectric presoma;
Step 2) prepare and treat fluid injection battery core: according to weight ratio, nano-sulfur powder: acetylene black: Kynoar is that the ratio of 70:25:5 takes anode pole piece material; According to weight ratio, lithium intercalated graphite: acetylene black: Kynoar is that the ratio of 90:5:5 takes cathode pole piece material, through stirring, apply, cold pressing, itemize, the operation such as welding obtain pole piece to be spooled, reel together with barrier film more afterwards and obtain naked battery core, use aluminum plastic film to carry out top side seal for packaging bag, toast in vacuum drying oven afterwards.
Polymer dielectric presoma obtained for steps A injects and seals after fluid injection battery core by step 3, after diaphragm fully infiltrates, in 2Pa, heating trigger monomer polymerization in 4 hours at 80 DEG C, fabricated in situ polymer dielectric, carry out successively changing into, shaping, after degasification operation, prepare shaping after battery.
Embodiment 2
Step 1) take following component by following relationship between quality, according to weight ratio, double pentaerythritol methacrylate: glycol dimethyl ether: DOX: base two (trifluoromethane sulfonic acid) imine lithium: azodiisobutyronitrile=3:40:40:30:14.9:0.1.Glycol dimethyl ether, DOX are mixed, adds base two (trifluoromethane sulfonic acid) imine lithium afterwards, then double pentaerythritol methacrylate, azodiisobutyronitrile are added above-mentioned electrolyte and obtain polymer dielectric presoma;
Step 2) prepare and treat fluid injection battery core: according to weight ratio, sulphur carbon composite: carbon nano-tube: polytetrafluoroethylene is that the ratio of 70:25:5 takes anode pole piece material, through stirring, apply, cold pressing, itemize, the operation such as welding obtain pole piece to be spooled, reel together with barrier film and lithium sheet more afterwards and obtain naked battery core, use aluminum plastic film to carry out top side seal for packaging bag, toast in vacuum drying oven afterwards.
Polymer dielectric presoma obtained for steps A injects and seals after fluid injection battery core by step 3, after diaphragm fully infiltrates, in 0.5Pa, heating trigger monomer polymerization in 4 hours at 70 DEG C, fabricated in situ solid polymer electrolyte, carry out successively changing into, shaping, after degasification operation, prepare shaping after battery.
Embodiment 3
Step 1) take following component by following relationship between quality, according to weight ratio, succinonitrile: acrylonitrile replacing for polyvinyl alcohol: lithium hexafluoro phosphate: boron trifluoride=75:10:14.9:0.1.By succinonitrile heating and melting at 50 DEG C, acrylonitrile replacing for polyvinyl alcohol, lithium hexafluoro phosphate, boron trifluoride are mixed after adding nitrile melt, obtained full solid state polymer electrolyte presoma;
Step 2) prepare and treat fluid injection battery core: according to organic sulfur compound: Graphene: sodium carboxymethylcellulose is that the ratio of 70:25:5 takes anode pole piece material; According to embedding lithium Si-C composite material: Graphene: sodium carboxymethylcellulose is that the ratio of 90:5:5 takes cathode pole piece material, mixed through stirring, applying, cold pressing, itemize, the operation such as welding obtain pole piece to be spooled, reel together with barrier film more afterwards and obtain naked battery core, use aluminum plastic film to carry out top side seal for packaging bag, toast in vacuum drying oven afterwards.
Polymer dielectric presoma obtained for steps A injects and seals after fluid injection battery core by step 3, after diaphragm fully infiltrates, in 4Pa, heating 24 hours at 80 DEG C, fabricated in situ solid polymer electrolyte, carry out successively changing into, shaping, after degasification operation, prepare shaping after battery.
Comparative example 1
Preparation liquid electrolyte: take following component by following mass ratio relation stand-by: glycol dimethyl ether: 1,3-dioxolanes=50:50, add base two (trifluoromethane sulfonic acid) imine lithium afterwards again, obtaining base two (trifluoromethane sulfonic acid) imine lithium concentration is the electrolyte of 1mol/L.
Fluid injection battery core is treated in preparation: with nano-sulfur powder for active material, add conductive agent, bonding agent again, through stirring, apply, cold pressing, itemize, the operation such as welding obtain pole piece to be spooled, reel together with barrier film and lithium sheet more afterwards and obtain naked battery core, use aluminum plastic film to carry out top side seal for packaging bag, toast in vacuum drying oven afterwards.
Fluid injection and anode ring forming: above-mentioned electrolyte is injected the battery core after baking, leave standstill until electrolyte fully infiltrates whole diaphragm, then carry out changing into, shaping, the operation such as degasification, finally obtain shaping after battery.
Embodiment 1-3 and comparative example 1 are tested as follows:
Volume test: carry out volume test by the battery core of following flow process to each embodiment and comparative example in 25 DEG C of environment: leave standstill 3min; 0.1C constant current is put a little to 1.5V; Leave standstill 3min; 0.1C constant current charge obtains discharge capacity first to 3.0V; Volume test is completed after leaving standstill 3min.
Multiplying power is tested: in 25 DEG C of environment, carry out multiplying power test by the battery core of following flow process to each embodiment and comparative example:
Drift bolt is tested: completely fill by the battery core of following flow process by each embodiment and comparative example in 25 DEG C of environment: leave standstill 3min; 0.1C constant-current discharge is to 1.5V, and constant voltage charge is to 0.05C; Be fixed on special drift bolt fixture afterwards, the iron nail that uses diameter to be 2.5mm, with the speed of 10mm/s through battery core central authorities, statistics battery core is caught fire quantity; Simultaneously in the process of drift bolt, the heating curve of monitoring drift bolt position, records the maximum of T of not catching fire in battery core heating curve
max.
Performance is as shown in table 1:
Table 1
Fig. 1 is the outward appearance photo of polymer dielectric prepared by the present invention, is rendered as white gels shape; Fig. 2 shows that its polymer dielectric conductivity and first reversible specific capacity increase with the increase of active function groups number in polymerization single polymerization monomer when monomer ratio one timing in precursor solution.
Polymer lithium-sulfur cell prepared by the present invention, Room-temperature-conductivity of Polymer Electrolyte can up to 10
-2s/cm, first charge-discharge reversible capacity reaches 1150mAh/g; Fig. 3 shows that polymer dielectric prepared by the present invention is heated to 300 DEG C of mass losses 11.5% in air atmosphere, and conventional electrolysis liquid is 300 DEG C of losses 46.2% in contrast to this, shows that gel polymer electrolyte has good thermal stability; Fig. 4 shows the charge-discharge performance figure of polymer lithium-sulfur cell under 0.5C/0.5C current density prepared by the present invention, after 300 circulations, capacity is not almost decayed, battery polarization is little, coulombic efficiency can reach more than 99%, Fig. 5 is the circulation curve chart of polymer lithium-sulfur cell prepared by the present invention, under more than 90%, the 5C current density that under 2C current density, reversible capacity still can play under 0.1C, reversible capacity still can play more than 60% under 0.1C.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (9)
1. a polymer lithium-sulfur cell, is characterized in that, comprising:
Positive pole: sulfenyl active material, conductive agent, binding agent;
Negative pole: active material, conductive agent, binding agent;
Electrolyte: adopt polymer dielectric, described polymer dielectric comprises solid-liquid solvent, lithium salts, cross-linking monomer and initator;
Described cross-linking monomer comprises following structure:
wherein R
1, R
2linear alkyl chain for carbon number 1-20, the linear alkyl chain containing ether-oxygen bond, alkyl chain containing side base and the segment containing single phenyl ring wherein a kind of, wherein n>=2.
2. polymer lithium-sulfur cell as claimed in claim 1, it is characterized in that, by weight percentage, described cross-linking monomer is 0.5-20% to described polymer dielectric; Described initator is 0.001-5%; Described lithium salts is 1-20%, and surplus is solid-liquid solvent.
3. polymer lithium-sulfur cell as claimed in claim 1, it is characterized in that, in described positive pole, by weight percentage, sulfenyl active material accounts for the 70-99% of whole anode pole piece; Conductive agent accounts for the 0.5-20% of whole anode pole piece; Binding agent accounts for the 0.5-20% of whole anode pole piece.
4. polymer lithium-sulfur cell as claimed in claim 1, it is characterized in that, in described negative pole, by weight percentage, active material accounts for the 70-100% of whole cathode pole piece; Conductive agent accounts for the 0.5-20% of whole cathode pole piece; Conductive agent accounts for the 0.5-20% of whole cathode pole piece.
5. polymer lithium-sulfur cell as claimed in claim 1, it is characterized in that, in described positive pole, described positive pole sulfenyl active material is at least one in elemental sulfur, polysulfide, organic sulfur compound and sulphur carbon composite; Conductive agent adopts at least one in acetylene black, conductive black, Ketjen black, electrically conductive graphite, Graphene, carbon nano-tube; Binding agent adopts at least one in Kynoar, polyvinyl alcohol, polytetrafluoroethylene, sodium carboxymethylcellulose, polyolefin, polyurethane, butadiene-styrene rubber, acrylonitrile multiple copolymer.
6. polymer lithium-sulfur cell as claimed in claim 1, is characterized in that, the active material in described negative pole adopts lithium metal, or embedding lithium compound, lithium metal or prelithiation graphite, embedding lithium Si-C composite material, at least one in embedding lithium tin carbon composite; Conductive agent adopts at least one in acetylene black, conductive black, Ketjen black, electrically conductive graphite, Graphene, carbon nano-tube.
7. polymer lithium-sulfur cell as claimed in claim 1, it is characterized in that, described solid-liquid solvent is made up of solid solvent and liquid flux; Described liquid flux adopts at least one in ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, oxolane, glycol dimethyl ether, tetraethyleneglycol dimethyl ether and DOX; Described solid solvent: at least one in ethylene carbonate, diphenyl carbonate, di-tert-butyl dicarbonate, malononitrile, succinonitrile, stearonitrile and isophthalodinitrile.
8. polymer lithium-sulfur cell as claimed in claim 1, it is characterized in that, described lithium salts adopts lithium hexafluoro phosphate, two (trifluoromethane sulfonic acid) imine lithium, three (trimethyl fluoride sulfonyl) lithium methide, dioxalic acid lithium borate, at least one of three (pentafluoroethyl group) three in lithium fluophosphate.
9. prepare a polymer lithium-sulfur cell as claimed in claim 1, it is characterized in that, comprise the following steps:
Steps A: the preparation of solid polymer electrolyte presoma: cross-linking monomer, lithium salts, initator are mixed after adding solid-liquid solvent, obtained solid polymer electrolyte presoma;
Step B: by barrier film, positive pole diaphragm and cathode membrane after glove box is assembled into naked battery core, enter shell or bag, obtains treating fluid injection battery core;
Step C: solid polymer electrolyte presoma obtained for steps A is injected and seals after fluid injection battery core, after diaphragm fully infiltrates, trigger monomer polymerization in 2-24 hour is heated at 0.1-10Pa, 50-100 DEG C, fabricated in situ solid polymer electrolyte, carry out successively changing into, shaping, after degasification operation, prepare shaping after battery.
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| CN109873199B (en) * | 2017-12-01 | 2021-11-16 | 中国科学院大连化学物理研究所 | Polymer dispersion liquid and application thereof |
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| CN115241541A (en) * | 2022-08-04 | 2022-10-25 | 中国人民解放军军事科学院防化研究院 | Preparation method of in-situ thermal polymerization solid lithium-sulfur battery |
| CN115241541B (en) * | 2022-08-04 | 2024-04-05 | 中国人民解放军军事科学院防化研究院 | Preparation method of in-situ thermal polymerization solid-state lithium sulfur battery |
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