CN107565097A - Double collector sulphur positive poles and preparation method thereof and the application in lithium-sulfur cell - Google Patents

Double collector sulphur positive poles and preparation method thereof and the application in lithium-sulfur cell Download PDF

Info

Publication number
CN107565097A
CN107565097A CN201710769612.0A CN201710769612A CN107565097A CN 107565097 A CN107565097 A CN 107565097A CN 201710769612 A CN201710769612 A CN 201710769612A CN 107565097 A CN107565097 A CN 107565097A
Authority
CN
China
Prior art keywords
sulphur
lithium
collector
carbon
active
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710769612.0A
Other languages
Chinese (zh)
Inventor
赵金保
张义永
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen University
Original Assignee
Xiamen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiamen University filed Critical Xiamen University
Priority to CN201710769612.0A priority Critical patent/CN107565097A/en
Publication of CN107565097A publication Critical patent/CN107565097A/en
Pending legal-status Critical Current

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

Double collector sulphur positive poles and preparation method thereof and the application in lithium-sulfur cell, are related to electrochemistry.A kind of easy to operate, cheap, high-sulfur area load and the lithium-sulfur cell pair collector sulphur positive poles of high area capacity are provided, and the nonaqueous electrolytic solution lithium-sulfur cell with long-life, high-energy-density using the positive pole is provided.This pair of collector positive pole makees next part fluid by metal foil, and active material is obtained into the sulfur electrode of high-sulfur area load coated on aluminium foil with the method that scraper coats, and then coats one layer of carbon in the above as upper collector.The nonaqueous electrolytic solution lithium-sulfur cell possesses above-mentioned positive pole, negative pole, barrier film and nonaqueous electrolytic solution.

Description

Double collector sulphur positive poles and preparation method thereof and the application in lithium-sulfur cell
Technical field
The present invention relates to electrochemistry, more particularly to double collector sulphur positive poles of a kind of high-sulfur area load and preparation method thereof With the application in lithium-sulfur cell.
Background technology
Lithium rechargeable battery is a kind of high efficiency, the electrical energy storage device of high-energy-density, has been widely used in Various small movable electronic equipments.As other battery systems, lithium ion battery mainly by positive electrode, negative material, Barrier film and four big critical material of electrolyte are formed, and the property of material and the performance of lithium ion battery have very important relation. Lithium ion battery is widely used as the power supply of small sized portable communication electronic equipment (such as mobile phone, hand-held computer) at present, its ground Position can not shake.But with the further development (such as requirement of the electric automobile in terms of power source) of society, existing lithium ion Battery system all need to be improved in price, security, specific capacity and power-performance, the plentiful etc. of raw material.Exploitation is more High performance material and corresponding energy storage system are particularly important.
Elemental sulfur, as the positive electrode of lithium-sulfur cell, there is specific capacity height, ABUNDANT NATUREAL RESOURSES, cheap and right A variety of advantages such as environment-friendly.Positive electrode of the sulphur as lithium-sulfur cell, its theoretical specific capacity 1675mAh g-1, it is considered to be ten Divide preferably anode for lithium battery material of future generation;If negative pole uses lithium metal (theoretical specific capacity 3860mAh g-1), formed Lithium-sulfur rechargeable battery theoretical energy density can reach 2680Wh Kg-1, it is preferable high-energy density secondary battery.But lithium The practical application of sulphur battery is limited by following several respects, as the poorly conductive of active material sulphur and its discharging product lithium sulfide, High-dissolvability of the polysulfide ion intermediate in nonaqueous electrolytic solution and diffusion and its caused by shuttle effect and volumetric expansion etc..This A little low-sulfur utilization rates for causing lithium-sulfur cell, low coulombic efficiency, fast capacity decay and short cycle life
To improve the cycle characteristics of lithium-sulfur cell, researchers propose various solutions, as carbon sulphur is compound Material, though these methods make moderate progress to battery performance, the area load amount of its positive active material is relatively low, is generally less than 2mg cm-2, cause its area specific capacity to be less than 3mAh cm-2, do not reach the requirement of existing market.Although recently also it has been proposed that With graphene film, carbon fiber sheet etc. make collector sulfur loaded active material without foil substrate, so as to improve pole piece sulphur active matter The unit area load capacity of matter, but the implementation cost of these methods is higher, is not suitable for mass producing and applies.
The content of the invention
It is an object of the invention to provide with sandwich structure, high unit area sulphur load capacity, high area Specific capacity and excellent cycle performance, and preparation method is simple, is easy to double collector sulphur positive poles and its preparation of large-scale application Method.
Another object of the present invention is to provide double applications of the collector sulphur positive pole in lithium-sulfur cell.
Double collector sulphur positive poles include next part fluid, intermediate active material layer and upper collector;
The next part fluid may be selected from one kind in aluminium foil, nickel foil, aluminum alloy films etc., preferably aluminium foil.
The intermediate active material layer is made up of active material and binding agent, and the mass percent of the active material is 90%~95%, the mass percent of binding agent is 10%~5%, is coated using scraper during coating;The active material is optional From commercialized sulphur simple substance (S8), carbon-sulfur compound, Li2S, at least one of organic carbon sulphur compound etc., is preferably commercialized sulphur Simple substance (S8);The unit area load capacity scope of sulphur simple substance can be 1~16mg cm-2, preferably 7~10mg cm-2.Unit area is born Carrying capacity is too low, then unit area specific capacity is relatively low, it is impossible to meets the needs in market, too high, the cycle characteristics of battery has dropped It is low.
The binding agent may be selected from Kynoar (PVDF), polytetrafluoroethylene (PTFE) (PTFE), sodium carboxymethylcellulose (CMC), at least one of polyvinyl alcohol (PVA), SBR and polyoxyethylene (PEO) etc..
The upper collector is made up of carbon conducting agent and binding agent, and wherein the mass percent of carbon is 80%~95%, And the mass ratio of carbon and intermediate layer sulphur active material is about 1, the method that its painting method selects scraper coating is simple to operation; Carbon in the upper collector, including selected from gas-phase growth of carbon fibre (VGCF), CNT (CNT), graphene, acetylene black etc. The big conductive carbon of at least one of conductive carbon, preferably good conductivity, specific surface area, such as VGCF;It is viscous in the upper collector Knot agent may be selected from least one of PEO, CMC, PVDF, SBR, PVA, PTFE etc., wherein it is preferred that having certain fixed polysulfide The binding agent of ability and preferable lithium ion conductive, such as the ︰ 1 of PEO and CMC mass ratioes 1 combination.
The preparation method of double collector sulphur positive poles comprises the following steps:
1) sulfur electrode of unit area high-sulfur load capacity is prepared;
In step 1), the specific method of the sulfur electrode for preparing unit area high-sulfur load capacity can be:By sulphur activity Material and binding agent, which are added in dispersant, to be stirred, and the slurry of gained is applied directly on collector by the method coated with scraper, 24h is dried in 60 DEG C of vacuum drying oven, obtains sulfur electrode;The sulphur active material is selected from commercialization sulphur powder, and the binding agent can Using PVDF;The mass percent of the sulphur active material can be 90%~95%, and the mass percent of binding agent can be 10% ~5%.It is preferred that the mass percent of sulphur active material is 95%, the mass percent of binding agent is 5%;The dispersant is optional The dispersant commonly used from lithium ion batteries such as N- first class pyrrolidones (NMP), tetrahydrofuran, ethanol, preferably NMP;The activity The coated weight of material can control the concentration of slurry to control according to the amount of added NMP dispersants;The sulphur active material list Plane product load capacity can be 1~16mg cm-2.It is preferred that 7~10mg cm-2.Too low, unit area specific capacity is relatively low, it is impossible to meets The needs in market, the cycle characteristics of battery decreases when too high.
2) upper collector is prepared;
In step 2), the specific method of collector can be in the preparation:First selected carbon and binding agent are added to Stirred in dispersant, gained slurry is applied directly in step 1) on the sulfur electrode of gained with scraper coating, vacuum drying, obtained Double collector sulphur positive poles;The carbon is preferably commercialized VGCF, and the mass ratio of the binding agent can be 1 ︰ 1 PEO and CMC mixing Binding agent;The mass percent of the carbon can be 80%~95%, and the mass ratio of carbon and intermediate layer sulphur active material is 1, excellent The content for selecting carbon is 90%;The dispersant may be selected from deionized water, N- first class pyrrolidones (NMP), tetrahydrofuran, ethanol etc. The conventional dispersant of lithium ion battery, the selected preferred deionized water of binding agent is dispersant.
Double collector sulphur positive poles can be applied in lithium-sulfur cell.
The lithium-sulfur cell includes double collector positive pole, negative pole, barrier film and nonaqueous electrolytic solutions.The lithium-sulfur cell is one kind Non-aqueous electrolyte secondary lithium-sulfur cell, as long as there is double collector positive poles, other inscapes are not particularly limited, can To use the inscape same with existing known nonaqueous electrolytic solution secondary battery.The negative pole includes negative electrode active material, The negative electrode active material includes one of material, Zinc-lithium alloy material and lithium metal of lithium insertion.Wrapped between the positive pole and negative pole Containing barrier film and nonaqueous electrolytic solution.Electrolyte between lithium-sulfur cell both positive and negative polarity is mainly played by conducting lithium ions to transmit electric charge Effect.Electrolyte needs have a good wellability with electrode, electrolyte lithium salt have wherein good dissolubility and from Electron conductivity, operating temperature to battery, than importants such as energy, cycle efficieny, security performances.And barrier film therein It is to separate the both positive and negative polarity active material of battery, avoids any electron stream of positive and negative interpolar directly by avoiding battery short circuit;Ion The out-of-date resistance that circulates is as small as possible, uses apertured polymeric film in most lithium ion batteries at present.The nonaqueous electrolytic solution Solvent be that molecular formula is R (CH2CH2O)n- R' more ethers, wherein, n=1~£ 6, R and R' are methyl or ethyl.
Electrolyte includes electrolytic salt and organic solvent and additive.Wherein electrolytic salt is selected from lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), hexafluoroarsenate lithium (LiAsF6), lithium perchlorate (LiClO4), trifluoromethanesulfonic acid lithium (CF3SO3Li), double (trifluoromethyl) sulfimide lithium (LiN (S02CF3)2) in one kind and combinations thereof;It is wherein organic The nonaqueous solvents of the preferred high-k of solvent.Because sulfide (the particularly inductor of elemental sulfur) is in the electrolysis of carbonates Solvation is not easy in liquid, discharge and recharge is generally difficult in the electrolyte that this kind of solvent is formed, so more ethers R (CH2CH2O)n-R' (n=1-6;R and R' is methyl or ethyl etc.) it is preferable, particularly dimethyl ether tetraethylene glycol (TEGDME), glycol dimethyl ether (DME), 1,3- dioxolanes (DOL) etc. are that stability is good it is furthermore preferred that these solvents are high to polysulfide solubility.
In addition, a small amount of addition of carbonate-containing class is feasible.Wherein, it is recommended to use dielectric constant is more than 30 ester, As the ester of high-k, for example, ethylene carbonate, propene carbonate, butylene, gamma-butyrolacton, sulphur can be enumerated One kind in class ester (ethylene glycol sulfide etc.) etc., preferably cyclic ester, ethylene carbonate, vinylene carbonate, propene carbonate, The cyclic carbonates such as butylene are particularly preferred.In addition to above-mentioned organic solvent, dimethyl carbonate, carbonic acid two can be used Ethyl ester, methyl ethyl carbonate etc. are the polarity linear carbonate of the low viscosity of representative, aliphatic branched chain type carbonats compound;Have Mixed solvent of the preferred cyclic carbonate of solvent (particularly ethylene carbonate) with linear carbonate.
In addition, in addition to above-mentioned nonaqueous solvents, the chains such as chain-like alkyl esters, the trimethyl phosphates such as methyl propionate can be used Phosphotriester;The nitrile solvents such as 3- methoxypropionitriles;The branched chain type compound with ehter bond using dendrimer as representative Deng nonaqueous solvents (organic solvent).
In addition, it can also use fluorine solvent.
As fluorine solvent, for example, H (CF can be enumerated2)2OCH3、C4F9OCH3、H(CF2)2OCH2CH3、H(CF2)2OCH2CF3、H(CF2)2CH2O(CF2)2H etc. or CF3CHFCF2OCH3、CF3CHFCF2OCH2CH3Etc. (the perfluor alkane of linear chain structure Base) alkyl ether, i.e. 2- trifluoromethyls hexafluoro propyl methyl ether, 2- trifluoromethyl hexafluoro propyl group ether, 2- trifluoromethyl hexafluoro propyl group Propyl ether, 3- trifluoromethyl octafluoros butyl methyl ether, 3- trifluoromethyl octafluoro butyl ether, 3- trifluoromethyl octafluoro butyl propyl ether, 4- The fluorine amyl group methyl ether of trifluoromethyl ten, the fluorine amyl group ether of 4- trifluoromethyls ten, the fluorine amyl group propyl ether of 4- trifluoromethyls ten, 5- trifluoromethyls Ten difluoro hexyl methyl ethers, the difluoro hexyl ether of 5- trifluoromethyls ten, the difluoro hexyl propyl ether of 5- trifluoromethyls ten, 6- trifluoromethyls ten Tetrafluoro heptyl methyl ether, the tetrafluoro heptyl ether of 6- trifluoromethyls ten, the tetrafluoro heptyl propyl ether of 6- trifluoromethyls ten, 7- trifluoromethyls 16 Fluorine octyl group methyl ether, the hexafluoro octyl group ether of 7- trifluoromethyls ten, the hexafluoro octyl group propyl ether of 7- trifluoromethyls ten etc..
In addition, above-mentioned different (perfluoroalkyl) alkyl ether and (perfluoroalkyl) alkyl ether of above-mentioned linear chain structure can be also used in combination.
To lift lithium-sulfur cell performance, discharge and recharge activation is carried out after lithium-sulfur cell is prepared, including early stage some is followed The charge and discharge that the ring cycle first carries out smaller current density is electro-active, then carry out larger current density charge-discharge test charge and discharge it is electro-active Program.
To lift lithium-sulfur cell performance, charge condition is adjusted in charge and discharge cycles, constant volume is carried out to battery Charging, the electrochemical reaction for constraining battery are carried out under polysulfide ion state.Obtain fabulous cycle performance and capability retention.
Nonaqueous electrolytic solution secondary battery provided by the invention, due to high power capacity, battery behavior is good, can be used as hand The secondary cell of driving power in the removable information-based instrument such as machine, notebook computer, and it is also used as electric automobile Or the various machines such as hybrid electric vehicle power supply and utilize extensively.
The metal collector that double collector positive poles of the present invention are commonly used by using lithium battery makees next part fluid, and carbon-coating is made Upper collector.Upper and lower collector tightly presses close to sulphur active material layer, as electronic conductor, accelerates being transferred to for electronics from top to down Sulphur active material layer, there is provided the electronics needed for cell electrochemical reaction;Intermediate active material can be buffered as physical barrier Layer volumetric expansion, prevent active material peeling and maintain electrode it is complete.In addition, upper collector can effectively limit it is poly- Sulphion intermediate, and the diffusion of lithium ion is not influenceed, so as to suppress shuttle effect and improve the stable circulation of battery Property.Wherein VGCF and PEO are negatively charged, can suppress the diffusion of polysulfide ion by Coulomb repulsion, and PEO in the electrolytic solution can Gel state is formed, so as to reduce the pore size of VGCF formation, preferably suppresses the diffusion of polysulfide ion, PEO is lithium again The good conductor of ion, so not interfering with the transmission of lithium ion.
In summary, double collector positive poles can provide the electronics and lithium ion of abundance, so that it is guaranteed that active material sulphur Mutual conversion between discharging product lithium sulfide.So the battery of this pair of collector positive pole is with higher specific capacity and preferably Cycle performance.Above all the sulphur active unit area load amount of this pair of collector electrode is high, can obtain pole High area specific capacity (> 3mAh cm-2), and the preparation method of electrode is simple to operation, and raw material are easy to get, implementation cost It is low, there are the potentiality of large-scale application.And by this pair of collector positive pole with lithium-sulfur cell widely used negative material, every Film, nonaqueous electrolytic solution etc. form high performance lithium-sulfur cell, achieve the achievement of the present invention.
Brief description of the drawings
Fig. 1 is the first circle charging and discharging curve of 1~4 pair of collector positive pole of embodiment.In Fig. 1, curve a is 5.4mg cm-2, Curve b is 3.67mg cm-2, curve c is 3.10mg cm-2, curve d is 2.03mg cm-2
Fig. 2 is the capacity circulating figure of 1 pair of collector positive pole of embodiment.
Fig. 3 is the capacity circulating figure of 2 pairs of collector positive poles of embodiment.
Fig. 4 is the capacity circulating figure of 3 pairs of collector positive poles of embodiment.
Fig. 5 is the capacity circulating figure of 4 pairs of collector positive poles of embodiment.
Fig. 6 is the capacity circulating figure of 7 pairs of collector positive poles of embodiment.
Embodiment
By embodiment, the invention will be further described below in conjunction with the accompanying drawings.
In the following description, what " % " was not specifically noted is mass percent.
Embodiment 1
It is prepared by double collector positive poles:The binding agent PVDF of 9 parts by weight is dissolved in the Solvents N-methyl pyrroles of 91 parts by weight Obtained cohesive agent dispersing liquid in alkanone (NMP);With solvent NMP by the commercialization sulphur powder of 95 parts by weight and the bonding of 55 parts by weight Agent solution mixes 1h or longer time, is prepared into active material powdery pulp;Above-mentioned slurry is by scraper for coating in thickness In 10 μm of aluminum foil current collector, the electrode plates after coating dry 24h in 60 DEG C of vacuum drying oven and remove solvent, obtain bright sulfur electricity Pole.The VGCF of 90 parts by weight, the PEO of 5 parts by weight and 5 parts by weight CMC are mixed, are mixed with deionized water as dispersant 1h or longer time are stirred, is prepared into the powdery pulp containing binding agent, bright sulfur electricity of the slurry as scraper for coating obtained by above-mentioned On extremely, the electrode plates after coating dry 24h in 60 DEG C of vacuum drying oven and remove solvent, obtain double collector positive poles.Wherein The unit area load capacity of sulphur is 5.40mg cm-2, the mass ratio of VGCF and active material sulphur is about 1.
It is prepared by battery:Battery is carried out with double collector positive poles and lithium metal piece the composition button cell of above-mentioned gained Evaluation.The preparation method of battery is as follows:In the glove box of argon gas atmosphere, according to double collector anode pole pieces, three layers it is porous every Film (PP/PE/PP), waterleaf paper, the laminated structure of lithium an- ode, add electrolyte (1M two (trifluoromethane sulfonic acid) imines Lithium (LiTFSI)-DOL/DME (1/1 volume ratio)) button cell is assembled into, and the property of battery is tested in battery test system Can, discharge and recharge blanking voltage is 1.8~2.6V, and discharge and recharge condition is that first circle charging and discharging currents density is 50mA g-1, Ran Hou 100mA g-1Carry out charge and discharge cycles.Battery charging and discharging curve and cycle characteristics are shown in Fig. 1 and 2.
Embodiment 2~6
Embodiment 2~6 prepares double collector positive poles, different sulphur units using with the same steps described in embodiment 1 Area load amount, respectively 2.03mg cm-2、3.10mg cm-2、3.67mg cm-2,~7mg cm-2With~16mg cm-2, and Lithium-sulfur cell is fabricated to same as Example 1ly to be evaluated.
As can be seen that the battery of double collector positive poles has preferable electrochemical properties, the utilization of the active material of battery Rate and area specific capacity are all very high.Other sulphur unit area load capacity is less than 7mg cm-2In the range of, battery is in 100 circulations Capability retention afterwards (encloses) more than 90% relative to second, more than 7mg cm-2When, because resistance increases, it compares battery Capacity and cycle characteristics are deteriorated, and coulombic efficiency reduces.Fig. 3 provides the capacity circulating figure of 2 pairs of collector positive poles of embodiment;Fig. 4 gives Go out the capacity circulating figure of 3 pairs of collector positive poles of embodiment;Fig. 5 provides the capacity circulating figure of 4 pairs of collector positive poles of embodiment.
Embodiment 7
It is identical with the condition of embodiment 1, double collector electrodes are made with similarity condition and battery is made and is evaluated.Only It is test condition difference, its discharge and recharge blanking voltage is 1.8~3.0V, and discharge and recharge condition is that first circle charging and discharging currents density is 50mA g-1, then in 100mA g-1Carry out constant volume charging and constant-current discharge circulation.Fig. 6 provides 7 pairs of collector positive poles of embodiment Capacity circulating figure.
Embodiment 8
It is identical with the condition of embodiment 1, double collector electrodes are made with similarity condition and battery is made and is evaluated.Only It is carbonizable substance have been changed into CNT by VGCF.
Embodiment 9
It is identical with the condition of embodiment 1, double collector electrodes are made with similarity condition and battery is made and is evaluated.Only It is carbonizable substance have been changed into graphene by VGCF.
Comparative example 1
In double collector positive pole pole preparation process of embodiment 1, in addition to the PVDF of binding agent respective amount is substituted, with Embodiment 1 is equally prepared for lithium sulphur button cell and evaluated.
Comparative example 2
In double collector positive pole pole preparation process of embodiment 1, in addition to the CMC of binding agent respective amount substitutes PEO, Lithium sulphur button cell is prepared for similarly to Example 1 and is evaluated.
Comparative example 3
In double collector positive pole pole preparation process of embodiment 1, in addition to the PEO of binding agent respective amount substitutes CMC, Lithium sulphur button cell is prepared for similarly to Example 1 and is evaluated.

Claims (10)

1. pair collector sulphur positive pole, it is characterised in that include next part fluid, intermediate active material layer and upper collector.
2. double collector sulphur positive poles as claimed in claim 1, it is characterised in that the next part fluid is selected from aluminium foil, nickel foil, aluminium and closed One kind in gold thin film, preferably aluminium foil.
3. double collector sulphur positive poles as claimed in claim 1, it is characterised in that the intermediate active material layer by active material and Intermediate active material binding agent forms;The mass percent of the active material is 90%~95%, and intermediate active material bonds The mass percent of agent is 10%~5%, is coated using scraper during coating;The active material may be selected from sulphur simple substance (S8), carbon Sulfur compound, Li2S, at least one of organic carbon sulphur compound, preferably sulphur simple substance (S8);The unit area load capacity of sulphur simple substance Scope can be 1~16mg cm-2, preferably 7~10mg cm-2;The intermediate active material binding agent may be selected from Kynoar, At least one of polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, polyvinyl alcohol, SBR and polyoxyethylene.
4. double collector sulphur positive poles as claimed in claim 1, it is characterised in that the upper collector is by carbon conducting agent and upper collection Fluid binder forms, and the carbon mass percent in carbon conducting agent is 80%~95%, the carbon in the carbon conducting agent with The mass ratio of intermediate layer sulphur active material is 1;Carbon in the upper collector, including selected from gas-phase growth of carbon fibre, carbon nanometer At least one of pipe, graphene, acetylene black conductive carbon, the preferably big conductive carbon of good conductivity, specific surface area, such as vapor phase growth Carbon fiber;Binding agent in the upper collector may be selected from least one of PEO, CMC, PVDF, SBR, PVA, PTFE, wherein It is preferred that there is the binding agent of certain fixed polysulfide ability and preferable lithium ion conductive, such as the ︰ 1 of PEO and CMC mass ratioes 1 Combination.
5. the preparation method of double collector sulphur positive poles as claimed in claim 1, it is characterised in that comprise the following steps:
1) sulfur electrode of unit area high-sulfur load capacity is prepared;
2) upper collector is prepared.
6. the preparation method of double collector sulphur positive poles as claimed in claim 5, it is characterised in that described to prepare list in step 1) The specific method of sulfur electrode of plane product high-sulfur load capacity is:Sulphur active material and binding agent are added in dispersant and stirred, is used The slurry of gained is applied directly on collector by the method for scraper coating, and 24h is dried in 60 DEG C of vacuum drying oven, obtains sulphur electricity Pole.
7. the preparation method of double collector sulphur positive poles as claimed in claim 6, it is characterised in that the sulphur active material is selected from business Industry sulphur powder, the binding agent use PVDF;The mass percent of the sulphur active material is 90%~95%, the matter of binding agent It is 10%~5% to measure percentage.It is preferred that the mass percent of sulphur active material is 95%, the mass percent of binding agent is 5%; The dispersant may be selected from the conventional dispersant of N- first class pyrrolidones, tetrahydrofuran, ethanol lithium ion battery, preferably N- first class Pyrrolidones NMP;The coated weight of the active material can control the concentration of slurry to control according to the amount of added NMP dispersants System;The sulphur active unit area load amount can be 1~16mg cm-2, preferably 7~10mg cm-2
8. the preparation method of double collector sulphur positive poles as claimed in claim 5, it is characterised in that in step 2), in the preparation The specific method of collector is:First selected carbon and binding agent are added in dispersant and stirred, is coated with scraper and starches gained Material is applied directly in step 1) on the sulfur electrode of gained, vacuum drying, obtains double collector sulphur positive poles;The carbon is preferably commercialized VGCF, the mass ratio of the binding agent can be 1 ︰ 1 PEO and CMC hybrid adhesive;The mass percent of the carbon can be 80%~95%, and the mass ratio of carbon and intermediate layer sulphur active material is 1, preferably the content of carbon is 90%;The dispersant can The dispersant commonly used selected from lithium ion batteries such as deionized water, N- first class pyrrolidones, tetrahydrofuran, ethanol, selected binding agent It is preferred that deionized water is dispersant.
9. double collector sulphur positive poles are applied in lithium-sulfur cell as claimed in claim 1.
10. application as claimed in claim 9, it is characterised in that the lithium-sulfur cell include double collector positive poles, negative pole, barrier film and Nonaqueous electrolytic solution;The lithium-sulfur cell is non-aqueous electrolyte secondary lithium-sulfur cell;The negative pole includes negative electrode active material, described Negative electrode active material includes one of material, Zinc-lithium alloy material and lithium metal of lithium insertion;The solvent of the nonaqueous electrolytic solution is point Minor is R (CH2CH2O)n- R' more ethers, wherein, n=1~£ 6, R and R' are methyl or ethyl;
The nonaqueous electrolytic solution includes electrolytic salt, organic solvent and additive, and wherein electrolytic salt is selected from lithium hexafluoro phosphate, and four At least one of lithium fluoroborate, hexafluoroarsenate lithium, lithium perchlorate, trifluoromethanesulfonic acid lithium, double (trifluoromethyl) sulfimide lithiums; Organic solvent is nonaqueous solvents;Preferable more ethers R (CH2CH2O) n-R', n=1~6;R and R' is methyl or ethyl, is particularly Dimethyl ether tetraethylene glycol, glycol dimethyl ether, one kind in 1,3- dioxolane;It is preferred that carbonate-containing class, dielectric constant be 30 with On ester, carbonate-containing class be ethylene carbonate, propene carbonate, butylene, gamma-butyrolacton, sulphur class ester (ethylene glycol sulphur Compound) in one kind, preferred cyclic ester, ethylene carbonate, vinylene carbonate, propene carbonate, butylene, ring-type carbon One kind in acid esters;Can use dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate for the low viscosity of representative polarity chain carbon Acid esters, aliphatic branched chain type carbonats compound;The mixed solvent of the preferred cyclic carbonate of organic solvent and linear carbonate, Or ethylene carbonate and the mixed solvent of linear carbonate;Using methyl propionate, trimethyl phosphate, 3- methoxypropionitriles;It is described Methyl propionate is chain-like alkyl esters, and the trimethyl phosphate is chain phosphotriester, and the 3- methoxypropionitriles are that nitrile is molten Agent;The branched chain type compound nonaqueous solvents with ehter bond using dendrimer as representative;Or using fluorine solvent, the fluorine Class solvent is selected from (perfluoroalkyl) alkyl ether of linear chain structure, and (perfluoroalkyl) alkyl ether of the linear chain structure is selected from H (CF2)2OCH3、C4F9OCH3、H(CF2)2OCH2CH3、H(CF2)2OCH2CF3、H(CF2)2CH2O(CF2)2H、CF3CHFCF2OCH3、 CF3CHFCF2OCH2CH3In one kind, i.e. 2- trifluoromethyls hexafluoro propyl methyl ether, 2- trifluoromethyl hexafluoro propyl group ether, 2- tri- Methyl fluoride hexafluoro propyl group propyl ether, 3- trifluoromethyl octafluoros butyl methyl ether, 3- trifluoromethyl octafluoro butyl ether, 3- trifluoromethyls eight Fluorine butyl propyl ether, the fluorine amyl group methyl ether of 4- trifluoromethyls ten, the fluorine amyl group ether of 4- trifluoromethyls ten, the fluorine amyl group third of 4- trifluoromethyls ten Ether, the difluoro hexyl methyl ether of 5- trifluoromethyls ten, the difluoro hexyl ether of 5- trifluoromethyls ten, the difluoro hexyl third of 5- trifluoromethyls ten Ether, the tetrafluoro heptyl methyl ether of 6- trifluoromethyls ten, the tetrafluoro heptyl ether of 6- trifluoromethyls ten, the tetrafluoro heptyl third of 6- trifluoromethyls ten Ether, the hexafluoro octyl group methyl ether of 7- trifluoromethyls ten, the hexafluoro octyl group ether of 7- trifluoromethyls ten, the hexafluoro octyl group propyl ether of 7- trifluoromethyls ten In one kind.
CN201710769612.0A 2017-08-31 2017-08-31 Double collector sulphur positive poles and preparation method thereof and the application in lithium-sulfur cell Pending CN107565097A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710769612.0A CN107565097A (en) 2017-08-31 2017-08-31 Double collector sulphur positive poles and preparation method thereof and the application in lithium-sulfur cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710769612.0A CN107565097A (en) 2017-08-31 2017-08-31 Double collector sulphur positive poles and preparation method thereof and the application in lithium-sulfur cell

Publications (1)

Publication Number Publication Date
CN107565097A true CN107565097A (en) 2018-01-09

Family

ID=60978483

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710769612.0A Pending CN107565097A (en) 2017-08-31 2017-08-31 Double collector sulphur positive poles and preparation method thereof and the application in lithium-sulfur cell

Country Status (1)

Country Link
CN (1) CN107565097A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108493411A (en) * 2018-03-14 2018-09-04 东华大学 Lithium sulfur battery anode material and cationic lithium-sulfur cell binder
CN108666533A (en) * 2018-05-16 2018-10-16 清华大学深圳研究生院 A kind of preparation method and application of lithium-sulfur cell sulfur electrode
CN110931714A (en) * 2019-12-12 2020-03-27 中国科学院过程工程研究所 Preparation and application of PEO-based film coated silicon-carbon electrode

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YIYONG ZHANG等: "High sulfur loading lithium–sulfur batteries based on a upper current collector electrode with lithium-ion conductive polymers", 《JOURNAL OF MATERIALS CHEMISTRY A》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108493411A (en) * 2018-03-14 2018-09-04 东华大学 Lithium sulfur battery anode material and cationic lithium-sulfur cell binder
CN108666533A (en) * 2018-05-16 2018-10-16 清华大学深圳研究生院 A kind of preparation method and application of lithium-sulfur cell sulfur electrode
CN110931714A (en) * 2019-12-12 2020-03-27 中国科学院过程工程研究所 Preparation and application of PEO-based film coated silicon-carbon electrode

Similar Documents

Publication Publication Date Title
KR101363442B1 (en) Electrolyte for electrochemical device, electrolyte solution using same, and non-aqueous electrolyte battery
CN103247822B (en) Lithium-sulfur secondary battery system
CN104037418A (en) Lithium ion battery anode film, preparation and application thereof
CN104835961A (en) Transition metal sulfide coated with carbon, preparation method and application
CN107565097A (en) Double collector sulphur positive poles and preparation method thereof and the application in lithium-sulfur cell
KR20140004773A (en) Polyimide capacitance battery and manufacturing method thereof
CN108630979B (en) Secondary battery based on calcium ions and preparation method thereof
Xu et al. Sulfonyl-based polyimide cathode for lithium and sodium secondary batteries: Enhancing the cycling performance by the electrolyte
CN107251287B (en) Organic lithium battery
KR20150083381A (en) Rechargeable lithium battery
CN108615941B (en) Additive for preventing thermal runaway and application thereof in secondary lithium metal battery
CN103367791A (en) Novel lithium ion battery
CN103915622A (en) Transition metal sulfide negative electrode active material, corresponding negative electrode and corresponding cell
CN105845978A (en) Lithium-ion battery
CN101017918A (en) Electrolyte of the lithium ion battery for ultra-low temperature discharge and its lithium ion battery
JP2016051600A (en) Nonaqueous electrolytic solution for power storage device
CN111342133A (en) Novel non-aqueous electrolyte for lithium ion battery and lithium ion battery
KR101198295B1 (en) A forming method of anode active material layer of a lithium secondary battery, and an anode of lithium secondary battery formed therefrom and a lithium secondary battery having the same
CN105009346B (en) Electrolyte for lithium secondary battery and the lithium secondary battery comprising it
CN109616611A (en) A kind of lithium-sulfur family mixed energy storage system
JP4811070B2 (en) Non-aqueous electrolyte battery electrolyte, electrolyte and non-aqueous electrolyte battery
CN111600073A (en) Lithium ion battery electrolyte
CN108352571B (en) Nonaqueous electrolyte for secondary battery and secondary battery
JP2008071624A (en) Lithium polymer battery
JP2015062154A (en) Lithium ion secondary battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20180109