CN103247822B - Lithium-sulfur secondary battery system - Google Patents
Lithium-sulfur secondary battery system Download PDFInfo
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- CN103247822B CN103247822B CN201210032797.4A CN201210032797A CN103247822B CN 103247822 B CN103247822 B CN 103247822B CN 201210032797 A CN201210032797 A CN 201210032797A CN 103247822 B CN103247822 B CN 103247822B
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Abstract
The present invention discloses a kind of lithium-sulfur secondary battery system, this system comprises positive pole, negative pole and electrolytic solution, wherein, positive active material is carbon sulphur matrix material, negative pole adopts metal lithium sheet, and electrolytic solution be one high salt concentration nonaqueous electrolyte, and described high salt concentration nonaqueous electrolyte comprises lithium salt or sodium salt or lithium sodium mixing salt and non-aqueous organic solvent; The mol ratio of described lithium salt or lithium sodium mixing salt and non-aqueous organic solvent is 2-10 mol/L. The present invention has following significant advantage: owing to this electrolyte system effectively inhibits lithium-sulfur cell many sulfonium ions in charge and discharge process to be dissolved in electrolytic solution, therefore avoid the many sulfonium ions being dissolved in electrolytic solution and produce to shuttle back and forth effect latter stage in charging, thus prevent and overcharge phenomenon, coulombic efficiency is brought up to more than 99%. Thus, cycle performance of battery have also been obtained bigger improvement.
Description
Technical field
The invention belongs to battery technology field, particularly relate to a kind of lithium-sulfur secondary battery system.
Background technology
The anode material for lithium-ion batteries that current commercialization is used mainly concentrates on the embedding oxidate for lithium of transition metal, comprise cobalt, iron, nickel, the oxide compound of manganese and doped compound thereof, but this compounds is by the restriction of self theoretical capacity, its current business-like system theoretical energy density is at about 600Wh/Kg, although industrial level improves constantly, but at present as the power cell of positive electrode material, 200Wh/Kg can be accomplished at most, it will be expected to future reach 300Wh/Kg, but room for promotion is very limited. The positive electrode material of a kind of more high-energy-density is badly in need of in the development of following electromobile.
Lithium-sulfur cell is due to its high specific storage (S81675mAh/g), theoretical energy density can reach 2800Wh/kg, is considered as the direction of following lithium secondary battery development, but due to this system bigger technical barrier of existence, appoint at present and be so in laboratory stage. Its main problem existed cannot effectively suppress intermediate product Li in charge and discharge process2S8��Li2S6��Li2S4It is dissolved in electrolytic solution. Once many sulfonium ions are dissolved in electrolytic solution, serious effect of shuttling back and forth can be produced in process of charging, cause that efficiency for charge-discharge is not high, self-discharge relatively big, thus cause battery performance to worsen, battery life is too short. In addition, effect of shuttling back and forth also can cause going out nonconducting elemental sulfur or polysulfide at conductive agent surface deposition during charging, adds the resistance between conductive agent particle and between conductive agent and collector. And along with discharge and recharge number of times increases, the internal resistance of cell constantly rises, and specific energy declines gradually, and cycle performance of battery worsens rapidly. Therefore, with regard to this system Status of development at present, how to suppress effect of shuttling back and forth, become the key improving this system coulombic efficiency and battery cycle life.
Owing to, in lithium-sulfur cell system, positive active material is the elemental sulfur not containing lithium, and therefore negative pole adopts metallic lithium, therefore safety performance will become the problem that this system following must solve.The major cause causing this system potential safety hazard is owing to negative pole metallic lithium causes Li dendrite to produce owing to lithium deposition is uneven in charge and discharge process, thus easily causes internal short-circuit of battery, causes safety problem.
Summary of the invention
The object of the invention is to there are the problems referred to above for current lithium-sulfur cell, propose to adopt high density lithium salt to be that electrolyte solution system substitutes existing electrolyte system, thus greatly reduce many sulfonium ions solubleness in the electrolytic solution, reach with this and effectively suppress to shuttle back and forth effect, improve the coulombic efficiency of discharge and recharge, it is expected to thoroughly solve the problem of the cycle performance difference of lithium-sulfur cell.
The present invention provides one can fill lithium-sulfur cell system two times, this system comprises positive pole, negative pole and electrolytic solution, wherein, positive active material is carbon sulphur matrix material, negative pole adopts metal lithium sheet, and electrolytic solution be one high salt concentration nonaqueous electrolyte, and described high salt concentration nonaqueous electrolyte comprises lithium salt or sodium salt or lithium sodium mixing salt and non-aqueous organic solvent; The mol ratio of described lithium salt or lithium sodium mixing salt and non-aqueous organic solvent is 3-9 mol/L.
The present invention has following significant advantage:
Owing to this electrolyte system effectively inhibits lithium-sulfur cell many sulfonium ions in charge and discharge process to be dissolved in electrolytic solution, therefore avoid the many sulfonium ions being dissolved in electrolytic solution and produce to shuttle back and forth effect latter stage in charging, thus prevent and overcharge phenomenon, coulombic efficiency is brought up to more than 99%. Thus, cycle performance of battery have also been obtained bigger improvement.
In addition, the porous carbon of high-specific surface area and adding of carbon nanotube, instead of existing conductive additive acetylene black, make conductive additive that a small amount of many sulfonium ions being dissolved in electrolytic solution are also had good adsorption so that system circulates in charge and discharge process and coulombic efficiency gets a promotion further. And by optimizing conductive current collector, adopt coating one layer of carbon on aluminium foil to substitute tradition aluminium foil, improve the interface performance of active substance and collector to a certain extent, it is to increase electroconductibility.
In sum, by adopting the non-water organic electrolyte of high density, and adopt the high specific area carbon (porous carbon or carbon nanotube etc.) that many sulfonium ions have certain adsorption effect as conductive additive, using be coated with one layer of carbon aluminium foil as collector, efficiently solve due in charge and discharge process due to some problems that the dissolving of many sulfonium ions brings so that lithium-sulfur cell chemical property be improved significantly.
Accompanying drawing explanation
Fig. 1 is recycle ratio capacity and the coulombic efficiency figure of embodiment 1 gained, and wherein transverse axis is cycle index (N), and the left longitudinal axis is charging and discharging capacity (mAh/g), and the right longitudinal axis is coulomb efficiency (%); Illustration is this system first week charging and discharging curve figure, and wherein transverse axis is charging and discharging capacity (mAh/g), and the longitudinal axis is charging/discharging voltage (V). Test parameter: constant current is tested, and voltage range 1-3V, charge-discharge magnification is 0.2C.
Fig. 2 is in embodiment 2, adopts the recycle ratio capacity comparison figure of different concns lithium salt electrolyte under charge-discharge magnification 0.2C, and wherein transverse axis is cycle index (N), and the longitudinal axis is charging and discharging capacity (mAh/g);
Fig. 3 is in embodiment 2, adopts the circulation coulombic efficiency comparison diagram of different concns lithium salt electrolyte under charge-discharge magnification 0.2C, and wherein transverse axis is cycle index (N), and the longitudinal axis is coulomb efficiency (%);
Fig. 4 is in embodiment 2, and the carbon sulphur matrix material that employing 1# porous carbon is prepared from and carbon-sulfur ratio are first week charging and discharging curve figure of 5: 5, and wherein transverse axis is charging and discharging capacity (mAh/g), and the longitudinal axis is charging/discharging voltage (V)
Fig. 5 is in embodiment 2, employing 2# porous carbon preparation and carbon-sulfur ratio are respectively first all charging and discharging curve comparison diagrams of the carbon sulphur matrix material of 4: 6,3: 7 and 2: 8 three kinds of proportionings, wherein transverse axis is charging and discharging capacity (mAh/g), and the longitudinal axis is charging/discharging voltage (V).
Fig. 6 is in embodiment 3, and under lithium-sulfur cell charge-discharge magnification 0.1C, first 100 weeks recycle ratio capacity plans, wherein transverse axis is cycle index (N), and the longitudinal axis is charging and discharging capacity (mAh/g).
Fig. 7 is in embodiment 4, and lithium-sulfur cell is recycle ratio capacity plan under different charge-discharge magnification, and wherein transverse axis is cycle index (N), and the longitudinal axis is charging and discharging capacity (mAh/g).
Fig. 8 is in embodiment 5, and lithium-sulfur cell charge-discharge magnification is first week charging and discharging curve figure of 0.2C under the high temperature of 50 degrees Celsius, and wherein transverse axis is charging and discharging capacity (mAh/g), and the longitudinal axis is charging/discharging voltage (V).
Embodiment
Embodiment 1
Lithium-sulfur cell system simulated battery, concrete making processes is as follows:
Positive electrode material and pole piece making processes thereof:
Carbon sulphur matrix material adopts the concrete parameter of 2# porous carbon as follows: specific surface area (m2/g): 1431, mean pore size (nm): 3.8, pore volume (cc/g): 1.58
Positive electrode material preparation process is as follows:
Porous carbon 2# is mixed with weight percent 4: 6 with elemental sulfur powder, by composite material closed for above carbon sulphur and airtight fill in argon Glass tubing, and by this raw material thermal treatment 24 hours under 155 degree.
Take a certain amount of carbon sulphur matrix material, carbon nanotube and polyvinylidene difluoride (PVDF) (PVDF) respectively according to weight percent 8: 1: 1, it is dispersion agent taking pyrrolidone, is uniformly mixed. Adopt the aluminium foil of surface-coated one layer of carbon as collector, mixed slurry be coated on collector uniformly, with post-drying and be cut into the pole piece that shape is identical with area. Cathode pole piece adopts metal lithium sheet.
Electrolyte system:
Electrolytic solution adopts organic electrolyte DOL: DME=1: 1, and electrolyte concentration is respectively 7mol/LLiTFSI, and gained electrolytic solution water-content is lower than 10ppm.
Battery assembling employing standard button cell CR2032, barrier film is glass fibre. Whole assembling process completes in the argon gas glove box of moisture content lower than 0.5ppm. Adopting constant current charge-discharge, under 0.2C electric current, charging/discharging voltage scope is that 1-3V tests.
As shown in Figure 1, have employed high density lithium salt system 7mol/LLiTFSI (DOL: DME=1: 1), system electrolytic solution, battery performance is excellent, major embodiment average coulombic efficiencies is greater than 99.5%, and within 90 weeks, Posterior circle charging capacity maintenance rate can reach 81.2%.
Embodiment 2
Lithium-sulfur cell system simulated battery, concrete making processes is as follows:
Positive electrode material and pole piece making processes thereof:
Carbon sulphur matrix material adopts the concrete parameter of 1# porous carbon as follows: specific surface area (m2/g): 671, mean pore size (nm): 2.5, pore volume (cc/g): 0.77
Carbon sulphur matrix material adopts the concrete parameter of 2# porous carbon as follows: specific surface area (m2/g): 1431, mean pore size (nm): 3.8, pore volume (cc/g): 1.58
Positive electrode material preparation process is as follows:
Porous carbon 1# is mixed with weight percent 5: 5 with elemental sulfur powder, porous carbon 2# is mixed with weight percent 4: 6,3: 7,2: 8 respectively with elemental sulfur powder, by composite material closed for above four kinds of carbon sulphur and airtight fill in argon Glass tubing, and by this raw material thermal treatment 24 hours under 155 degree.
Take a certain amount of carbon sulphur matrix material, acetylene black and polyvinylidene difluoride (PVDF) (PVDF) respectively according to weight percent 8: 1: 1, it is dispersion agent taking pyrrolidone, is uniformly mixed. Using aluminium foil as collector, mixed slurry is coated on collector uniformly, with post-drying and be cut into the pole piece that shape is identical with area. Cathode pole piece adopts metal lithium sheet.
Electrolyte system:
Electrolytic solution adopts organic electrolyte DOL: DME=1: 1, electrolyte concentration is respectively 2,4,5,6mol/LLiTFSI, gained electrolytic solution water-content is lower than 10ppm.
Battery assembling employing standard button cell CR2032, barrier film is glass fibre. Whole assembling process completes in the argon gas glove box of moisture content lower than 0.5ppm. Adopt constant current charge-discharge, under 0.2C multiplying power, battery is tested.
As shown in Figures 2 and 3, when other positive and negative electrode are identical with assembled condition, adopt 1# porous carbon compound 5: 5, along with the raising of lithium salt, the chemical property of battery is significantly improved, it is mainly manifested in cycle performance and coulombic efficiency aspect, and when lithium salt is when volume ratio and weight ratio are all greater than solvent (6mol/L), electrochemistry is improved especially obvious.
In addition, Fig. 4 and Fig. 5 is first all charging and discharging curves of four described in embodiment a kind carbon sulphur matrix material, charging and discharging currents is set to 0.2C, charging/discharging voltage scope is: 1.5-2.8V, by contrast, specific storage is unified adopts elemental sulfur to calculate, contrast two figure can find, increase along with containing sulphur content, contained by system, effective active matter is more many, and composite theory specific storage increases thereupon, but due to sulphur be megohmite, the membership that adds in a large number of sulphur causes material actual specific capacity to decline to a certain extent, and chemical property worsens. As shown in Figure 5, compared with Fig. 4, owing to 2# porous carbon carrying active substance sulphur content is higher, and compound specific storage is the highest under 4: 6 ratios.
Embodiment 3
Lithium-sulfur cell system simulated battery, detailed process is as follows:
Positive electrode material and pole piece making processes thereof:
Carbon sulphur matrix material preparation process is as follows: mixed with weight percent 5: 5 with sulphur powder by porous carbon 1#, closes and fills in argon Glass tubing with airtight, and under 155 degree, this raw material is processed 24 hours.
Take a certain amount of carbon sulphur matrix material, sodium alginate and acetylene black respectively according to weight percent 7: 2: 1, it is dispersion agent taking deionized water, is uniformly mixed. Using aluminium foil as collector, mixed slurry is coated on collector uniformly, with post-drying and be cut into the pole piece that shape is identical with area. Cathode pole piece adopts metal lithium sheet.
Electrolyte system:
Electrolytic solution adopts organic electrolyte DOL: DME=1: 1, and ionogen is 6mol/LLiTFSI, and gained electrolytic solution water-content is lower than 10ppm.
Battery assembling employing standard button cell CR2032, barrier film is glass fibre. Whole assembling process completes in the argon gas glove box of moisture content lower than 0.5ppm. Adopt constant current charge-discharge, under 0.1C multiplying power, battery is tested.
As shown in Figure 6, employing sodium alginate is the carbon sulphur matrix material of tackiness agent, and under the electrolyte of high density lithium salt, has good cycle performance.
Embodiment 4
Lithium-sulfur cell system simulated battery, concrete making processes is as follows:
Positive electrode material and pole piece making processes thereof:
Carbon sulphur matrix material adopts the concrete parameter of 2# porous carbon as follows: specific surface area (m2/g): 1431, mean pore size (nm): 3.8, pore volume (cc/g): 1.58
Positive electrode material preparation process is as follows:
Porous carbon 2# is mixed with weight percent 4: 6 with elemental sulfur powder, by composite material closed for above carbon sulphur and airtight fill in argon Glass tubing, and by this raw material thermal treatment 24 hours under 155 degree.
Take a certain amount of carbon sulphur matrix material, porous carbon 2# and polyvinylidene difluoride (PVDF) (PVDF) respectively according to weight percent 8: 1: 1, it is dispersion agent taking pyrrolidone, is uniformly mixed. Adopt the aluminium foil of surface-coated one layer of carbon as collector, mixed slurry be coated on collector uniformly, with post-drying and be cut into the pole piece that shape is identical with area.Cathode pole piece adopts metal lithium sheet.
Electrolyte system:
Electrolytic solution adopts organic electrolyte DOL: DME=1: 1, and electrolyte concentration is respectively 6mol/LLiTFSI, and gained electrolytic solution water-content is lower than 10ppm.
Battery assembling employing standard button cell CR2032, barrier film is glass fibre. Whole assembling process completes in the argon gas glove box of moisture content lower than 0.5ppm. Adopt constant current charge-discharge, battery is tested.
As shown in Figure 7, this system have employed high density lithium salt system 6mol/LLiTFSI (DOL: DME=1: 1) system electrolytic solution, gained battery high rate performance is excellent, and charging specific storage can reach first week 0.2C (1333mAh/g), the 11 week 0.5C (1120mAh/g), the 21 week 1C (965mAh/g), the 31 week 2C (677mAh/g) and the 41 week 5C (274mAh/g) respectively successively.
Embodiment 5
High lithium salt electrolyte system and low lithium salt system apply to lithium-sulfur cell system contrast experiment:
High lithium salt electrolyte system:
Electrolytic solution adopts organic solvent DOL: DME=1: 1, and ionogen is 10mol/LLiTFSI, and gained electrolytic solution water-content is lower than 10ppm.
Lithium-sulfur cell system simulated battery, detailed process is as follows:
Positive electrode material and pole piece making processes thereof:
Carbon sulphur matrix material preparation process is as follows: mixed with weight percent 4: 6 with sulphur powder by porous carbon, closes and fills in argon Glass tubing with airtight, and under 155 degrees Celsius, this raw material is processed 24 hours.
Take a certain amount of carbon sulphur matrix material, acetylene black and polyvinylidene difluoride (PVDF) (PVDF) respectively according to weight percent 8: 1: 1, it is dispersion agent taking pyrrolidone, is uniformly mixed. Using aluminium foil as collector, mixed slurry is coated on collector uniformly, with post-drying and be cut into the pole piece that shape is identical with area. Cathode pole piece adopts metal lithium sheet.
Battery assembling employing standard button cell CR2032, barrier film is glass fibre. Whole assembling process completes in the argon gas glove box of moisture content lower than 0.5ppm.
Adopting constant current charge-discharge, in constant temperature high-low temperature chamber, under 0.2C multiplying power, battery is tested by constant temperature 50 degrees Celsius. As shown in Figure 8, have employed the lithium-sulfur cell of ether class system electrolytic solution (10mol/L) of superelevation lithium salt, can well work under high temperature, first all charging and discharging curves are normal, polarize less, well inhibiting and overcharge phenomenon due to what effect of shuttling back and forth caused, specific storage is close to design capacity.
Embodiment 6
Lithium-sulfur cell system simulated battery, detailed process is as follows:
Positive electrode material and pole piece making processes thereof:
Carbon sulphur matrix material preparation process is as follows: acetylene black mixed with weight percent 4: 6 with sulphur powder, closes and fills in argon Glass tubing with airtight, and under 155 degree, this raw material is processed 24 hours.
Take a certain amount of carbon sulphur matrix material, acetylene black and polyvinylidene difluoride (PVDF) (PVDF) respectively according to weight percent 8: 1: 1, it is dispersion agent taking pyrrolidone, is uniformly mixed. Sticky as collector using graphite, mixed slurry is coated on collector uniformly, with post-drying and be cut into the pole piece that shape is identical with area. Cathode pole piece adopts metal lithium sheet.
Electrolyte system:
1# electrolytic solution adopts organic electrolyte diglycol ethylene dme (DGM), and ionogen is 6mol/LLiFSI, and gained electrolytic solution water-content is lower than 10ppm.
2# electrolytic solution adopts organic electrolyte diglycol ethylene dme (DGM), and ionogen is 5mol/LLiTFSI, and gained electrolytic solution water-content is lower than 10ppm.
3# electrolytic solution adopts organic electrolyte contracting contracting TRIGLYME (TGDME), and ionogen is 4mol/LLiFSI, and gained electrolytic solution water-content is lower than 10ppm.
4# electrolytic solution adopts organic electrolyte contracting tetraethyleneglycol dimethyl ether (TEGDME), and ionogen is 3mol/LLiTFSI, and gained electrolytic solution water-content is lower than 10ppm.
5# electrolytic solution adopts organic electrolyte dimethyl sulfoxide (DMSO) (DMSO), and ionogen is 6mol/LLiTFSI, and gained electrolytic solution water-content is lower than 10ppm.
6# electrolytic solution adopts organic electrolyte DOL: DME=1: 1 (volume ratio), and ionogen is 3mol/LLiTFSI and 3mol/LNaFSI, and gained electrolytic solution water-content is lower than 10ppm.
Battery assembling employing standard button cell CR2032, barrier film is glass fibre. Whole assembling process completes in the argon gas glove box of moisture content lower than 0.5ppm. Adopt constant current charge-discharge, under 0.2C multiplying power, battery is tested.
Above embodiment result is as shown in the table:
As seen from the results in Table 1, the electrolyte system of high lithium salt, has same effect after adopting other organic solvents, and therefore, for lithium-sulfur cell system, the raising of battery performance is had general suitable effect by high lithium salt.
In above-described embodiment, only list minority non-aqueous organic solvent in claim book, certainly, it is also possible to be selected from ether class, sulfone class, sulfuric ester, alkane oxygen silicon class, nitrile class one or more mixtures any and replace.
Above-mentioned ether organic solvent comprises ring-type ether and chain shape ether two class; Wherein, ring-type ether comprises tetrahydrofuran (THF) (THF), 2-methyltetrahydrofuran (2-MeTHF), 1,3-dioxolanes (DOL) or 4-methyl-1,3-dioxy pentamethylene (4-MeDOL); Chain shape ether comprises Methylal(dimethoxymethane) (DMM), 1,2-glycol dimethyl ether (DME), 1,2-Propanal dimethyl acetal (DMP), diglycol ethylene dme (DGDME), contracting TRIGLYME (TGDME) or contracting tetraethyleneglycol dimethyl ether (TEGDME).
Above-mentioned sulfone class organic solvent comprises dimethyl sulfoxide (DMSO) (DMSO), tetramethylene sulfone (TMSO) or dimethyl sulfone (MSM).
Above-mentioned sulfuric acid ester organic solvent comprises methyl sulfate, sulfovinic acid, methyl-sulfate and ethyl sulfate.
Above-mentioned alkane oxygen silicon class organic solvent has and comprises chemical structure as follows: SiR1R2R3R4, wherein, substituent R1��R2��R3��R4Identical or different, it is selected from hydrogen atom and carbon atom independently of one another, and carbon atom is stated as the saturated of 1-10 or unsaturated alkyl and OCxF2x+1-yHy��OCOCxF2x+1-yHy��OSO2CxF2x+1-yHyWith the polymeric groups based on oxyethyl group, wherein, x is the integer of 1-10, y be greater than zero integer, and 2x+1-y is more than or equal to zero; Or, substituent R1��R2��R3��R4Identical or different, independently of one another by F, CxF2x+1-yHy��OCxF2x+1-yHy��OCOCxF2x+1-yHy�� OSO2CxF2x+1-yHy��N(CxF2x+1-yHy)2Not replacing monosubstituted or polysubstituted aryl, described aryl is phenyl and (or) how base, or is by F, CxF2x+1-yHy��OCxF2x+1-yHy��OCOCxF2x+1-yHy��OSO2CxF2x+1-yHy��N(CxF2x+1-yHy)2Not replacing monosubstituted or polysubstituted aromatic heterocyclic radical, described heterocyclic radical is pyridyl, pyridyl and (or) pyrimidyl; Wherein, x is the integer of 1-10, y be greater than zero integer, and 2x+1-y is more than or equal to zero.
Above-mentioned alkane oxygen silicon class organic solvent is selected from tetramethoxy-silicane, ethyl triethoxy silicane oxygen alkane, ethyl triacetyl oxygen radical siloxane, diphenylmethyl oxygen radical siloxane, silicoheptane oxygen alkyl fluoride RF for methane sulfonates, and mixture.
Above-mentioned nitrile class organic solvent comprises propionitrile, propane dinitrile, methoxyacetonitrile, 3-methoxypropionitrile and mixture thereof.
In addition, the positive pole of the embodiment of the present invention comprises active substance, conductive additive and tackiness agent;Wherein, active substance is that carbon-sulfur compound is formed. In embodiments of the present invention, positive pole only lists porous carbon as carbon source, certainly, it is also possible to one or more mixtures such as the carbon of employing acetylene black, graphite, Graphene, porous carbon, carbon nanotube, carbon fiber, N doping are formed.
Above-mentioned conductive additive is mainly formed with carbon material, in embodiments of the present invention, only list acetylene black, carbon nanotube and porous carbon, naturally it is also possible to be that one or more mixtures such as carbon of acetylene black, graphite, Graphene, porous carbon, carbon nanotube, carbon fiber, N doping are formed.
Above-mentioned tackiness agent can be aqueous adhesive sodium alginate, carboxymethyl cellulose (CMC), polytetrafluoroethylene PTFE wherein one or more mixtures formation, it is also possible to be non-aqueous adhesive polyvinylidene difluoride (PVDF) (PVDF).
In addition, the lithium salt of the embodiment of the present invention or sodium salt only list LiTFSI, LiFSI and NaTFSI, certainly, it is also possible to be selected from LiNO3��NaNO3��LiCl��NaCl��LiBr��NaBr��LiI��NaI��Li2CO3��Na2CO3��Li2SO��Na2SO4��LiCF3SO3��NaCF3SO3��LiC4F9SO3��NaC4F9SO3��LiN(CxF2x+1SO2)(CyF2y+1SO2) or NaN (CxF2x+1SO2)(CyF2y+1SO2), wherein, x and y is natural number, LiBFz(CF3)4-z��NaBFz(CF3)4-z, the wherein natural number of z��4, LiC (SO2CF3)3��NaC(SO2CF3)3��LiPFa(CF3)6-a��NaPFa(CF3)6-a��LiPFb(C2F5)6-b��NaPFb(C2F5)6-b��LiPFc(iso-C3F7)6-c��NaPFC. (iso-C3F7)6-c, wherein a, b, c��6 natural number.
Claims (14)
1. a lithium-sulfur secondary battery system, this system comprises positive pole, negative pole and electrolytic solution, wherein, positive active material is carbon sulphur matrix material, negative pole adopts metal lithium sheet, electrolytic solution is a kind of high salt concentration nonaqueous electrolyte, and described high salt concentration nonaqueous electrolyte comprises non-aqueous organic solvent, also comprises lithium salt or sodium salt or lithium sodium mixing salt; Described lithium salt or the lithium sodium mixing salt volumetric molar concentration scope in non-aqueous organic solvent is 5-10 mol/L; The carbon material that wherein carbon sulphur matrix material uses is that in acetylene black, graphite, Graphene, porous carbon, carbon nanotube, carbon fiber, nitrogen-doped carbon, one or more mixtures are formed.
2. battery system as claimed in claim 1, it is characterised in that, described non-aqueous organic solvent is selected from ether class, sulfone class, sulfuric acid ester, alkane oxygen silicon class, nitrile class and mixture thereof.
3. battery system as claimed in claim 1, it is characterised in that, described lithium salt or sodium salt are selected from LiNO3��NaNO3��LiCl��NaCl��LiBr��NaBr��LiI��NaI��Li2CO3��Na2CO3��Li2SO4��Na2SO4��LiCF3SO3��NaCF3SO3��LiC4F9SO3��NaC4F9SO3��LiN(CxF2x+1SO2)(CyF2y+1SO2) or NaN (CxF2x+1SO2)(CyF2y+1SO2), wherein, x and y is natural number, LiBFz(CF3)4-z��NaBFz(CF3)4-z, the wherein natural number of z��4, LiC (SO2CF3)3��NaC(SO2CF3)3��LiPFa(CF3)6-a��NaPFa(CF3)6-a��LiPFb(C2F5)6-b��NaPFb(C2F5)6-b��LiPFc(iso-C3F7)6-c��NaPFc(iso-C3F7)6-c, the wherein natural number of a, b, c��6.
4. battery system as claimed in claim 2, it is characterised in that, described ether organic solvent comprises ring-type ether and chain shape ether two class; Wherein, ring-type ether comprises tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,3-dioxolanes or 4-methyl-1,3-dioxy pentamethylene; Chain shape ether comprises Methylal(dimethoxymethane), 1,2-glycol dimethyl ether, 1,2-Propanal dimethyl acetal, diglycol ethylene dme, contracting TRIGLYME or contracting tetraethyleneglycol dimethyl ether.
5. battery system as claimed in claim 2, it is characterised in that, described sulfone class organic solvent comprises dimethyl sulfoxide (DMSO), tetramethylene sulfone or dimethyl sulfone.
6. battery system as claimed in claim 2, it is characterised in that, described sulfuric acid ester organic solvent chemical general formula is R-O-SO2-O-R', R are organic group, and R' is often proton or without group.
7. battery system as claimed in claim 2, it is characterised in that, described alkane oxygen silicon class organic solvent has and comprises chemical structure as follows: SiR1R2R3R4, wherein, substituent R1��R2��R3��R4Identical or different, it is selected from hydrogen atom and carbon atom independently of one another, and carbon atom is stated as the saturated of 1-10 or unsaturated alkyl and OCxF2x+1-yHy��OCOCxF2x+1-yHy��OSO2CxF2x+1-yHyWith the polymeric groups based on oxyethyl group, wherein, x is the integer of 1-10, y be greater than zero integer, and 2x+1-y is more than or equal to zero;Or, substituent R1��R2��R3��R4Identical or different, independently of one another by F, CxF2x+1-yHy��OCxF2x+1-yHy�� OCOCxF2x+1-yHy��OSO2CxF2x+1-yHy��N(CxF2x+1-yHy)2Not replacing monosubstituted or polysubstituted aryl, described aryl is phenyl and/or naphthyl, or is by F, CxF2x+1-yHy��OCxF2x+1-yHy��OCOCxF2x+1-yHy��OSO2CxF2x+1-yHy��N(CxF2x+1-yHy)2Not replacing monosubstituted or polysubstituted aromatic heterocyclic radical, described heterocyclic radical is pyridyl, pyridyl and/or pyrimidyl; Wherein, x is the integer of 1-10, y be greater than zero integer, and 2x+1-y is more than or equal to zero.
8. battery system as claimed in claim 2, it is characterized in that, described alkane oxygen silicon class organic solvent is selected from tetramethoxy-silicane, ethyl triethoxy silicane oxygen alkane, ethyl triacetyl oxygen radical siloxane, diphenylmethyl oxygen radical siloxane, silicoheptane oxygen alkyl fluoride RF for methane sulfonates, and mixture.
9. battery system as claimed in claim 2, it is characterised in that, described nitrile class organic solvent comprises propionitrile, propane dinitrile, methoxyacetonitrile, 3-methoxypropionitrile and mixture thereof.
10. battery system as claimed in claim 1, it is characterised in that, described positive pole comprises active substance, conductive additive, tackiness agent and conductive current collector.
11. battery systems as claimed in claim 10, it is characterized in that, described conductive additive is mainly formed with carbon material, can be wherein one or more mixtures of carbon formation of acetylene black, graphite, Graphene, porous carbon, carbon nanotube, carbon fiber, N doping.
12. battery systems as claimed in claim 11, it is characterised in that, described tackiness agent can be aqueous adhesive sodium alginate, carboxymethyl cellulose, tetrafluoroethylene wherein one or more mixtures formation, it is also possible to be non-aqueous adhesive polyvinylidene difluoride (PVDF).
13. battery systems as claimed in claim 11, it is characterised in that, described conductive current collector can be metal aluminum foil or graphite felt, it is also possible to is the aluminium foil of one layer of carbon at surface-coated thickness equal one.
14. battery systems as claimed in claim 2, it is characterised in that, described sulfuric acid ester organic solvent comprises methyl sulfate, sulfovinic acid, methyl-sulfate and ethyl sulfate.
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| CN104716301A (en) * | 2013-12-11 | 2015-06-17 | 上海空间电源研究所 | Positive electrode of lithium-sulfur battery and manufacturing method of positive electrode |
| CN103682443B (en) * | 2013-12-31 | 2016-03-16 | 东莞市杉杉电池材料有限公司 | A kind of lithium-ion battery electrolytes containing two fluorosulfonyl imine lithium |
| HUE042287T2 (en) * | 2014-05-30 | 2019-06-28 | Oxis Energy Ltd | Lithium-sulphur cell |
| KR20160001783A (en) * | 2014-06-26 | 2016-01-07 | 에스케이이노베이션 주식회사 | Secondary battery with improved high-temperature and low-temperature properties |
| CN106450455B (en) * | 2016-10-20 | 2018-12-21 | 重庆工业职业技术学院 | A kind of efficient lithium-sulfur cell additive |
| CN106450247B (en) * | 2016-10-28 | 2020-02-21 | 南开大学 | Metal bismuth negative electrode and ether-based electrolyte for sodium/potassium ion secondary battery |
| CN106785049A (en) * | 2016-12-21 | 2017-05-31 | 厦门大学 | A kind of lithium-sulfur cell electrolyte and its application |
| CN106816634B (en) * | 2017-03-10 | 2019-12-10 | 中国计量大学 | pseudo high-concentration lithium-sulfur battery electrolyte and lithium-sulfur battery |
| CN110692152B (en) * | 2017-05-24 | 2023-08-15 | 纳米技术仪器公司 | Alkali metal cell with deformable quasi-solid electrode material |
| CN109961956A (en) * | 2017-12-22 | 2019-07-02 | 中国电子科技集团公司第十八研究所 | Electrolyte for high-voltage graphene-based aqueous lithium ion capacitor |
| CN108232302A (en) * | 2017-12-30 | 2018-06-29 | 国联汽车动力电池研究院有限责任公司 | A kind of high concentration lithium salt electrolyte suitable for silicon-based anode lithium ion battery |
| CN108630926B (en) * | 2018-05-07 | 2021-09-03 | 中国科学院成都有机化学有限公司 | Lithium-sulfur battery positive electrode containing short carbon fiber filaments and preparation method thereof |
| CN109786808A (en) * | 2018-12-14 | 2019-05-21 | 中国科学院青岛生物能源与过程研究所 | A kind of lithium metal battery nitrile electrolyte and the lithium metal battery using the electrolyte |
| CN109786830B (en) * | 2018-12-24 | 2020-10-02 | 杉杉新材料（衢州）有限公司 | Electrolyte containing silicon solvent and thiophene additive and lithium ion battery using electrolyte |
| CN114725519A (en) * | 2021-01-06 | 2022-07-08 | 东莞理工学院 | Lithium ion battery electrolyte, preparation method thereof and lithium ion battery |
| CN114614095A (en) * | 2022-03-31 | 2022-06-10 | 西北工业大学 | Electrolyte based on halogen lithium salt, lithium-sulfur battery obtained from electrolyte and preparation method of lithium-sulfur battery |
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