CN105470518A - Lithium sulfur battery sulfur cathode slurry and preparation method thereof, preparation method of lithium sulfur battery - Google Patents
Lithium sulfur battery sulfur cathode slurry and preparation method thereof, preparation method of lithium sulfur battery Download PDFInfo
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- CN105470518A CN105470518A CN201510829455.9A CN201510829455A CN105470518A CN 105470518 A CN105470518 A CN 105470518A CN 201510829455 A CN201510829455 A CN 201510829455A CN 105470518 A CN105470518 A CN 105470518A
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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
- 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
- H01M4/622—Binders being polymers
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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
- H01M10/052—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
- H01M10/058—Construction or manufacture
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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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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a lithium sulfur battery sulfur cathode slurry, wherein Arabic gum is taken as a binding agent of elemental sulfur and a conducting agent, and water is taken as a solvent. The low-cost, safe and green Arabic gum is taken as the binding agent of a lithium sulfur secondary battery cathode material, so that the electrochemical performance of sulfur cathode is obviously improved. Moreover, the invention also provides a preparation method of the lithium sulfur battery sulfur cathode slurry and a preparation method of a lithium sulfur battery.
Description
Technical field
The present invention relates to a kind of lithium sulfur battery anode material, more particularly, is a kind of sulfur electrode of modification, and the preparation method of lithium-sulfur cell.
Background technology
It is high that lithium ion battery has energy density, the advantages such as self discharge is little, memory-less effect, operating temperature range are wide, have extended cycle life, be the good secondary cell system of current combination property, and be widely used on the portable electric appts such as mobile phone, digital camera and notebook computer.But along with the development of electronic electric equipment, the rise of electric automobile and hybrid vehicle especially in recent years, conventional lithium ion battery has more and more been difficult to meet the demand of people for the energy content of battery.Conventional lithium ion battery positive electrode based on transition metal oxide (as LiCoO
2, LiMnO
2and LiFePO
4deng), although have advantages such as having extended cycle life, fail safe is good, be subject to the restriction of its relatively low theoretical specific capacity, be difficult to meet the demand of electrokinetic cell to high-energy-density.Lithium-sulfur cell take elemental sulfur as positive pole, and lithium metal is the battery system of negative pole.Elemental sulfur has 1675mAhg
-1theoretical specific capacity, corresponding lithium-sulfur cell has 2600Whkg
-1theoretical specific energy, it is nearly about 10 times that current commercial Li-ion battery reality can reach, the wide material sources of active material sulphur, cheap simultaneously, environmental friendliness, therefore lithium-sulfur cell is considered to one of most potentiality a new generation high energy energy storage system (see Manthiram, A., S.H.Chung, andC.Zu, Lithium-sulfurbatteries:progressandprospects [J] .AdvMater, 2015.27 (12): 1980-2006.).Although lithium-sulfur cell has so tempting advantage, this system still also exists some problems, causes its commercialization process slow.These problems comprise sulphur and reduzate Li
2electronics, the ionic conductivity of S are poor, charge and discharge process electrode change in volume is large, intermediate product in the electrolytic solution there is dissolubility and adjoint " effect of shuttling back and forth " etc., cause the cycle life of lithium-sulfur cell poor (see Fang, X.andH.Peng, Arevolutioninelectrodes:recentprogressinrechargeablelith ium-sulfurbatteries [J] .Small, 2015.11 (13): 1488-511.).In recent years, all kinds of sulphur carbon composite material is synthesized, and effectively improve the chemical property of lithium-sulfur cell, then the complicated and special construction material with carbon element of costliness is prepared and is not suitable for suitability for industrialized production, and adopts multifunctional binder to be expected to simply and effectively reach the object promoting battery performance.In the battery, binding agent is generally be bonded on collector by active material, is used to the structural intergrity of maintenance electrode, guarantees electronics path in charge and discharge process, ensureing the macromolecular material that battery normally runs, is the vital factor affecting battery performance.The present binding agent for lithium sulfur battery anode material is still based on traditional Kynoar (PVDF).
Arabic gum is also referred to as gum arabic, derive from the trunk exudant of the Acacia Pterostyrax of pulse family, primarily of high molecular polysaccharide and protein composition, comprise pectinose, galactolipin, glucuronic acid, hydroxyproline, serine etc., molecular weight is generally 22-30 about ten thousand, wide material sources, cheap, environmental protection.(see: D.Renard, L.Lavenant-Gourgeon, M.C.Ralet, C.Sanchez, Biomacromolecules2006,7,2637.).
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of cheap, safety and environmental protection, be easy to industrialization, the lithium-sulfur cell sulphur anode sizing agent of sulphur positive pole chemical property can be significantly improved;
Another object of the present invention is to provide the preparation method of above-mentioned lithium-sulfur cell sulphur anode sizing agent;
Another object of the present invention is to provide the above-mentioned method utilizing above-mentioned lithium-sulphur cell positive electrode to prepare lithium-sulfur cell.
A kind of lithium-sulfur cell sulphur anode sizing agent, using Arabic gum as the binding agent of elemental sulfur and conductive agent, uses water as solvent.
Preferably, described conductive agent is carbon black conductive agent; Preferred SuperP, SuperS, carbon nano-tube or graphite agent.
Preferably, the weight ratio of described superP and elemental sulfur is 1:(1-9); Preferred 1:3.
Preferably, described Arabic gum: elemental sulfur: the mass ratio of conductive agent is 0.2:(0.4-0.6): (0.05-0.4), the best is 0.2:0.2:0.6.
Preferably, the proportionate relationship of described Arabic gum and water is 0.2g/2.5ml.
The preparation method of above-mentioned lithium-sulfur cell sulphur anode sizing agent, binding agent dissolving be scattered in water and form binder solution, by elemental sulfur and conductive agent, grinding evenly, adds in binder solution, is stirred to and mixes.
A preparation method for lithium-sulfur cell, comprises the steps:
1) aluminium foil is cleaned with deionized water and acetone successively, dry;
2) above-mentioned slurry is poured on the aluminium foil after cleaning-drying, equably slurry is coated in the hair side of aluminium foil with scraper, dry;
3) by step 2) dried aluminium foil takes out, as the anode electrode sheet of battery.
4) the positive electrode pole piece of described drying is transferred in glove box, is to electrode with metal lithium sheet, is assembled into button cell, add electrolyte, by the battery seal of assembling, leave standstill 3h.
Preferably, described step 1) in, aluminium foil is cut into the disk that diameter is 14mm, described step 3) in, be cut into the disk that diameter is 14mm, described step 4 after taking out dry aluminium foil) in, metal lithium sheet diameter is 15.8mm.
Preferably, described step 2) in, the process of described drying adopts the method for first vacuumize constant pressure and dry again; Preferably, vacuum drying temperature is 60 DEG C, drying time is 8h; Preferably, the temperature of constant pressure and dry is 80 DEG C, drying time is 2h.
Preferably, described step 2) in, the use thickness of scraper is 150 ~ 600 μm.
Preferably, described step 4) in, described electrolyte is: with two trifluoromethanesulfonimide lithiums (LiTFSI) of 1M for electric conducting lithium salt, volume ratio is DME (the glycol dimethyl ether)/DOL (1 of 1:1,3-dioxolanes) be solvent, and add the LiNO of 1%
3for additive.
Preferably, the addition of described electrolyte is 50 μ l/mgS.
Beneficial effect of the present invention:
The present invention utilizes Arabic gum that is cheap, safe green to be the agent of lithium-sulfur rechargeable battery anode material binding, combines cleverly and utilizes environmental protection the most and cheap solvent--water, significantly improve the chemical property of sulphur positive pole.Therefore lithium sulfur battery anode material binding agent of the present invention has higher cost performance and good market using value.Arabic gum is a kind of safe and harmless thickener, has water-soluble, can make binding agent with water, avoids the use that employing conventional binders is toxic organic solvents, makes electrode production process environmental protection more.Using Arabic gum as positive electrode binding agent, more even and tough electrode structure can be provided, and the good elasticity of Arabic gum can buffer electrode change in volume.Meanwhile, functional group abundant on Arabic gum can form chemical bonding with sulphur positive pole discharge and recharge intermediate product polysulfide ion, effectively suppresses the dissolving of polysulfide ion and shuttles back and forth.Utilize the dual-use function of Arabic gum physics and chemistry two aspect, significantly improve the cycle performance of lithium-sulfur cell.The contrast that concrete effect analysis refers to embodiment below detects analysis.
Accompanying drawing explanation
Fig. 1 is the circulation comparison diagram of battery in embodiment 1,2,3, and show with Arabic gum when being binding agent in figure, sulphur positive pole shows higher capacity and more stable cyclical stability;
Fig. 2 is electrode surface electromicroscopic photograph in embodiment 3 and element S, C element distribution, and show with Arabic gum when being positive electrode binder in figure, electrode has uniform structure and activity species distribution; Wherein: Fig. 2 a is electrode surface electromicroscopic photograph; Fig. 2 b is C element distribution map; Fig. 2 c is S distribution diagram of element;
Fig. 3 is the cycle performance of battery figure in embodiment 5, when being presented at sulphur carbon ratio in figure up to 3:1, is that the sulphur positive pole of binding agent has very high capability retention and cycle life with Arabic gum;
Fig. 4 is the cycle performance of battery in embodiment 7,8,9, shows in figure, is that the sulphur positive pole of binding agent is still have higher energy density and good cycle performance in high-sulfur carrying capacity with Arabic gum;
Fig. 5 is the change curve of cycle performance along with electrode active material sulphur carbon content of battery of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
Embodiment 1:
Taking 0.2g Kynoar (PVDF) adds in measuring cup, measures 2.5mlN-methyl pyrrolidone (NMP) and adds measuring cup, stirring and dissolving.Weigh 0.4gsuperP and 0.4g sublimed sulfur, grinding evenly, adds measuring cup.Stir 12h, be uniformly dispersed.By aluminium foil successively with deionized water and acetone cleaning, then dry under vacuum.Aluminium foil after cleaning-drying is cut into the disk of diameter 14mm, weighs and be designated as weight 1.The slurry mixed is poured on the aluminium foil after cleaning-drying, equably slurry is coated in the hair side of aluminium foil with scraper 150 μm of faces.Coated aluminium foil is placed with vacuum drying chamber, 60 DEG C of vacuumize 8h, 80 DEG C of constant pressure and dry 2h, take out and pole piece be cut into the disk of diameter 14mm, weighing, be designated as weight 2.Weight 2 deducts the quality that weight 1 is coating on pole piece, is designated as weight 3, calculates the weight of active material in the ratio of addition, is designated as weight 4.The pole piece of drying is transferred in glove box, with metal lithium sheet for become CR2025 button cell to electrode assembling.Wherein electrolyte is with the LiTFSI of 1M for electric conducting lithium salt, and volume ratio is the DME/DOL of 1:1 is solvent, and adds the LiNO of 1%
3for additive.By the battery seal of assembling, leave standstill 3h.The battery left standstill is carried out electrochemical property test on charge-discharge test instrument.Wherein electric current is 1675mA/g* weight 4*0.2, and test voltage scope is 1.8-2.6V.
Embodiment 2:
Taking 0.2g gelatin (gelatin) adds in measuring cup, measures 2.5ml deionized water and adds measuring cup, stirring and dissolving.Weigh 0.4gsuperP and 0.4g sublimed sulfur, grinding evenly, adds measuring cup.Stir 12h, be uniformly dispersed.By aluminium foil successively with deionized water and acetone cleaning, then dry under vacuum.Aluminium foil after cleaning-drying is cut into the disk of diameter 14mm, weighs and be designated as weight 1.The slurry mixed is poured on the aluminium foil after cleaning-drying, equably slurry is coated in the hair side of aluminium foil with scraper 150 μm.The aluminium foil that coats is placed with vacuum drying chamber, 60 DEG C of vacuumize 8h, 80 DEG C of constant pressure and dry 2h, take out and pole piece be cut into the disk of 14mm, weighing, be designated as weight 2.Weight 2 deducts the quality that weight 1 is coating on pole piece, is designated as weight 3, calculates the weight of active material in the ratio of addition, is designated as weight 4.By the transfer of the pole piece of drying as in glove box, with metal lithium sheet for become CR2025 button cell to electrode assembling.Wherein electrolyte is with the LiTFSI of 1M for electric conducting lithium salt, and volume ratio is the DME/DOL of 1:1 is solvent, and adds the LiNO of 1%
3for additive.By the battery seal of assembling, leave standstill 3h.The battery left standstill is carried out electrochemical property test on charge-discharge test instrument.Wherein electric current is 1675mA/g* weight 4*0.2, and test voltage scope is 1.8-2.6V.
Embodiment 3:
Taking 0.2g Arabic gum (GA) adds in measuring cup, measures 2.5ml deionized water and adds measuring cup, stirring and dissolving.Weigh 0.4gsuperP and 0.4g sublimed sulfur, grinding evenly, adds measuring cup.Stir 12h, be uniformly dispersed.By aluminium foil successively with deionized water and acetone cleaning, then dry under vacuum.Aluminium foil after cleaning-drying is cut into the disk of diameter 14mm, weighs and be designated as weight 1.The slurry mixed is poured on the aluminium foil after cleaning-drying, equably slurry is coated in the hair side of aluminium foil with scraper 150 μm.The aluminium foil that coats is placed with vacuum drying chamber, 60 DEG C of vacuumize 8h, 80 DEG C of constant pressure and dry 2h, take out and pole piece be cut into the disk of 14mm, weighing, be designated as weight 2.Weight 2 deducts the quality that weight 1 is coating on pole piece, is designated as weight 3, calculates the weight of active material in the ratio of addition, is designated as weight 4.By the transfer of the pole piece of drying as in glove box, with metal lithium sheet for become CR2025 button cell to electrode assembling.Wherein electrolyte is with the LiTFSI of 1M for electric conducting lithium salt, and volume ratio is the DME/DOL of 1:1 is solvent, and adds the LiNO of 1%
3for additive.By the battery seal of assembling, leave standstill 3h.The battery left standstill is carried out electrochemical property test on charge-discharge test instrument.Wherein electric current is 1675mA/g* weight 4*0.2, and test voltage scope is 1.8-2.6V.
See Fig. 1, for the circulation comparison diagram of battery in embodiment 1,2,3, show with Arabic gum when being binding agent in figure, sulphur positive pole shows higher capacity and better cyclical stability, its actual specific discharge capacity is 1380mAh/g, and reach after 50 times in cycle-index, battery capacity drives gesture without significant change, in chronic steady state, battery still keeps high electric discharge ratio capacitance to be 1200mAh/g.
Fig. 2 is electrode surface electromicroscopic photograph in embodiment 3 and element S, C element distribution, shows with Arabic gum when being positive electrode binder in figure, and electrode has clicks structure and activity species distribution uniformly.
Embodiment 4:
Taking 0.2g Arabic gum adds in measuring cup, measures 2.5ml deionized water and adds measuring cup, stirring and dissolving.Weigh 0.267gsuperP and 0.533g sublimed sulfur, grinding evenly, adds measuring cup.Stir 12h, be uniformly dispersed.By aluminium foil successively with deionized water and acetone cleaning, then dry under vacuum.Aluminium foil after cleaning-drying is cut into the disk of diameter 14mm, weighs and be designated as weight 1.The slurry mixed is poured on the aluminium foil after cleaning-drying, equably slurry is coated in the hair side of aluminium foil with scraper 150 μm.The aluminium foil that coats is placed with vacuum drying chamber, 60 DEG C of vacuumize 8h, 80 DEG C of constant pressure and dry 2h, take out and pole piece be cut into the disk of 14mm, weighing, be designated as weight 2.Weight 2 deducts the quality that weight 1 is coating on pole piece, is designated as weight 3, calculates the weight of active material in the ratio of addition, is designated as weight 4.By the transfer of the pole piece of drying as in glove box, with metal lithium sheet for become CR2025 button cell to electrode assembling.Wherein electrolyte is with the LiTFSI of 1M for electric conducting lithium salt, and volume ratio is the DME/DOL of 1:1 is solvent, and adds the LiNO of 1%
3for additive.By the battery seal of assembling, leave standstill 3h.The battery left standstill is carried out electrochemical property test on charge-discharge test instrument.Wherein electric current is 1675mA/g* weight 4*0.2, and test voltage scope is 1.8-2.6V.Along with the raising of sulfur content, electrode energy density is improved.
Embodiment 5:
Taking 0.2g Arabic gum adds in measuring cup, measures 2.5ml deionized water and adds measuring cup, stirring and dissolving.Weigh 0.2gsuperP and 0.6g sublimed sulfur, grinding evenly, adds measuring cup.Stir 12h, be uniformly dispersed.By aluminium foil successively with deionized water and acetone cleaning, then dry under vacuum.Aluminium foil after cleaning-drying is cut into the disk of diameter 14mm, weighs and be designated as weight 1.The slurry mixed is poured on the aluminium foil after cleaning-drying, equably slurry is coated in the hair side of aluminium foil with scraper 150 μm.The aluminium foil that coats is placed with vacuum drying chamber, 60 DEG C of vacuumize 8h, 80 DEG C of constant pressure and dry 2h, take out and pole piece be cut into the disk of 14mm, weighing, be designated as weight 2.Weight 2 deducts the quality that weight 1 is coating on pole piece, is designated as weight 3, calculates the weight of active material in the ratio of addition, is designated as weight 4.By the transfer of the pole piece of drying as in glove box, with metal lithium sheet for become CR2025 button cell to electrode assembling.Wherein electrolyte is with the LiTFSI of 1M for electric conducting lithium salt, and volume ratio is the DME/DOL of 1:1 is solvent, and adds the LiNO of 1%
3for additive.By the battery seal of assembling, leave standstill 3h.The battery left standstill is carried out electrochemical property test on charge-discharge test instrument.Wherein electric current is 1675mA/g* weight 4*0.2, and test voltage scope is 1.8-2.6V.
Along with sulfur content improves further, cause active material utilization and electrode specific capacity to decrease, but battery energy density and cyclical stability are improved significantly.Fig. 3 display with Arabic gum be the sulphur positive pole of binding agent in sulphur carbon ratio for still showing excellent cycle performance during 3:1.Wherein the initial capacity of sulfur electrode is 1200mAh/g, and the capacity of the second circle battery reduces to 900mAh/g, gos up to 858mAh/g and keep stablizing after continuing reduction, and after 500 circle circulations, battery is still kept above the capacity of 800mAh/g.
Embodiment 6:
Taking 0.2g Arabic gum adds in measuring cup, measures 2.5ml deionized water and adds measuring cup, stirring and dissolving.Weigh 0.05gsuperP and 0.45g sublimed sulfur, grinding evenly, adds measuring cup.Stir 12h, be uniformly dispersed.By aluminium foil successively with deionized water and acetone cleaning, then dry under vacuum.Aluminium foil after cleaning-drying is cut into the disk of diameter 14mm, weighs and be designated as weight 1.The slurry mixed is poured on the aluminium foil after cleaning-drying, equably slurry is coated in the hair side of aluminium foil with scraper 150 μm.The aluminium foil that coats is placed with vacuum drying chamber, 60 DEG C of vacuumize 8h, 80 DEG C of constant pressure and dry 2h, take out and pole piece be cut into the disk of 14mm, weighing, be designated as weight 2.Weight 2 deducts the quality that weight 1 is coating on pole piece, is designated as weight 3, calculates the weight of active material in the ratio of addition, is designated as weight 4.By the transfer of the pole piece of drying as in glove box, with metal lithium sheet for become CR2025 button cell to electrode assembling.Wherein electrolyte is with the LiTFSI of 1M for electric conducting lithium salt, and volume ratio is the DME/DOL of 1:1 is solvent, and adds the LiNO of 1%
3for additive.By the battery seal of assembling, leave standstill 3h.The battery left standstill is carried out electrochemical property test on charge-discharge test instrument.Wherein electric current is 1675mA/g* weight 4*0.2, and test voltage scope is 1.8-2.6V.
Fig. 5 shows the change of cycle performance along with electrode active material sulphur carbon content of battery, and the cycle performance of battery also shows corresponding change.When sulphur carbon content is 1:1, the initial capacity of battery is 1450mAh/g, and after the circulation of 500 circles, it still maintains the capacity of nearly 900mAh/g.When in battery, sulphur carbon content is respectively 2:1, the 3:1 even content of sulphur are 90%, and after the circulations of 500 circles, battery capacity is respectively 784,618 and 405mAh/g.That is along with sulphur carbon ratio improves further, the conductivity of electrode reduces further, specific capacity decreases, find after deliberation, be (1-9) in sulphur carbon ratio: when 1, along with the rising of sulphur carbon ratio, the circulation volume of battery is basicly stable, downslide amount is little, stable not more than the circulation volume of battery after 9:1.When sulphur carbon ratio is 3:1, can the high activity of holding electrode, make again battery have good circulation volume and excellent cyclical stability.
Embodiment 7:
Taking 0.2g Arabic gum adds in measuring cup, measures 2.5ml deionized water and adds measuring cup, stirring and dissolving.Weigh 0.2gsuperP and 0.6g sublimed sulfur, grinding evenly, adds measuring cup.Stir 12h, be uniformly dispersed.By aluminium foil successively with deionized water and acetone cleaning, then dry under vacuum.Aluminium foil after cleaning-drying is cut into the disk of diameter 14mm, weighs and be designated as weight 1.The slurry mixed is poured on the aluminium foil after cleaning-drying, equably slurry is coated in the hair side of aluminium foil with scraper 250 μm.The aluminium foil that coats is placed with vacuum drying chamber, 60 DEG C of vacuumize 8h, 80 DEG C of constant pressure and dry 2h, take out and pole piece be cut into the disk of 14mm, weighing, be designated as weight 2.Weight 2 deducts the quality that weight 1 is coating on pole piece, is designated as weight 3, calculates the weight of active material in the ratio of addition, is designated as weight 4.By controlling the number of times being coated in material on pole piece, be such as respectively 1 time, 2 times, 3 coatings even repeatedly, effectively control the content of active material on pole piece, namely when other amount part is constant, control the sulphur carrying capacity of pole piece.As the cycle performance of sulphur positive pole when different sulphur carrying capacity that Fig. 4 display take Arabic gum as binding agent.Take Arabic gum as the sulphur positive pole of binding agent be 4.4mg/cm in sulphur carrying capacity
2time still show good capacity and cyclical stability.
Be the preferred embodiments of the present invention in above embodiment, elemental sulfur is wherein not limited to sublimed sulfur, can also substitute with other elemental sulfur; And conductive agent, be not limited to superP, superS, graphite agent etc. also can be used to substitute.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment to invention has been detailed description, for a person skilled in the art, it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a lithium-sulfur cell sulphur anode sizing agent, is characterized in that: using Arabic gum as the binding agent of elemental sulfur and conductive agent, use water as solvent.
2. lithium-sulfur cell sulphur anode sizing agent according to claim 1, is characterized in that: described conductive agent is carbon black conductive agent; Preferred SuperP, SuperS, carbon nano-tube or graphite agent.
3. lithium-sulfur cell sulphur anode sizing agent according to claim 2, is characterized in that: the weight ratio of described superP and elemental sulfur is 1:(1-9); Preferred 1:3.
4. lithium-sulfur cell sulphur anode sizing agent according to claim 1, is characterized in that: described Arabic gum: elemental sulfur: the mass ratio of conductive agent is 0.2:(0.4-0.6): (0.05-0.4), is preferably 0.2:0.2:0.6.
5. lithium-sulfur cell sulphur anode sizing agent according to claim 1, is characterized in that: the proportionate relationship of described Arabic gum and water is 0.2g/2.5ml.
6. a preparation method for the lithium-sulfur cell sulphur anode sizing agent that one of claim 1 to 5 is described, is characterized in that: binding agent dissolving be scattered in water and form binder solution, by elemental sulfur and conductive agent, grinding evenly, add in binder solution, be stirred to and mix.
7. a preparation method for lithium-sulfur cell, is characterized in that: comprise the steps:
1) aluminium foil is cleaned with deionized water and acetone successively, dry;
2) slurry described in any one of claim 1-5 is poured on the aluminium foil after cleaning-drying, equably slurry is coated in the hair side of aluminium foil with scraper, dry;
3) by step 2) dried aluminium foil takes out, as the anode electrode sheet of battery.
4) the anode electrode sheet of described drying is transferred in glove box, is to electrode with metal lithium sheet, is assembled into button cell, add electrolyte, by the battery seal of assembling, leave standstill 3h;
Preferably, described step 1) in, aluminium foil is cut into the disk that diameter is 14mm, described step 3) in, be cut into the disk that diameter is 14mm, described step 4 after taking out dry aluminium foil) in, metal lithium sheet diameter is 15.8mm.
8. the preparation method of lithium-sulfur cell according to claim 7, is characterized in that: described step 2) in, dry process adopts the method for first vacuumize constant pressure and dry again; Preferably, vacuum drying temperature is 60 DEG C, drying time is 8h; Preferably, the temperature of constant pressure and dry is 80 DEG C, drying time is 2h.
9. the preparation method of lithium-sulfur cell according to claim 7, is characterized in that: described step 2) in, the use thickness of scraper is 150 ~ 600 μm.
10. the preparation method of lithium-sulfur cell according to claim 7, it is characterized in that: described step 4) in, described electrolyte is: with two trifluoromethanesulfonimide lithiums of 1M for electric conducting lithium salt, and volume ratio is the DME/DOL of 1:1 is solvent, and adds the LiNO of 1%
3for additive; Preferably, the addition of described electrolyte is 50 μ l/mgS.
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| CN108493411A (en) * | 2018-03-14 | 2018-09-04 | 东华大学 | Lithium sulfur battery anode material and cationic lithium-sulfur cell binder |
| CN108511695A (en) * | 2017-02-24 | 2018-09-07 | 天津大学 | Lithium-sulfur cell based on sulphur nitrogen auto-dope positive electrode active materials |
| CN109378430A (en) * | 2018-09-21 | 2019-02-22 | 天津大学 | A kind of lithium-sulfur cell polymer barrier layer material and preparation method |
| CN111082054A (en) * | 2018-10-22 | 2020-04-28 | 中南大学 | Lithium-sulfur battery positive electrode material, positive electrode, preparation and application thereof |
| WO2020097672A1 (en) | 2018-11-12 | 2020-05-22 | Monash University | Method of producing thick sulphur cathodes for li-s batteries |
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| CN108511695A (en) * | 2017-02-24 | 2018-09-07 | 天津大学 | Lithium-sulfur cell based on sulphur nitrogen auto-dope positive electrode active materials |
| CN108493411A (en) * | 2018-03-14 | 2018-09-04 | 东华大学 | Lithium sulfur battery anode material and cationic lithium-sulfur cell binder |
| CN109378430A (en) * | 2018-09-21 | 2019-02-22 | 天津大学 | A kind of lithium-sulfur cell polymer barrier layer material and preparation method |
| CN111082054A (en) * | 2018-10-22 | 2020-04-28 | 中南大学 | Lithium-sulfur battery positive electrode material, positive electrode, preparation and application thereof |
| CN111082054B (en) * | 2018-10-22 | 2021-04-20 | 中南大学 | Lithium-sulfur battery positive electrode material, positive electrode, preparation and application thereof |
| WO2020097672A1 (en) | 2018-11-12 | 2020-05-22 | Monash University | Method of producing thick sulphur cathodes for li-s batteries |
| CN111769282A (en) * | 2020-06-22 | 2020-10-13 | 上海交通大学 | Application method of water-based binder in magnesium-sulfur battery |
| WO2022114650A1 (en) * | 2020-11-27 | 2022-06-02 | 주식회사 엘지에너지솔루션 | Binder composition for manufacturing lithium-sulfur battery cathode, and lithium-sulfur battery cathode manufactured therefrom |
| CN112898949A (en) * | 2021-01-19 | 2021-06-04 | 华南农业大学 | Lithium-sulfur battery containing plant juice-based binder |
| WO2023140607A1 (en) * | 2022-01-20 | 2023-07-27 | 주식회사 엘지에너지솔루션 | Binder composition for manufacturing lithium secondary battery cathode, and lithium secondary battery cathode manufactured thereby |
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