CN103247822A - Lithium-sulfur secondary battery system - Google Patents
Lithium-sulfur secondary battery system Download PDFInfo
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- CN103247822A CN103247822A CN2012100327974A CN201210032797A CN103247822A CN 103247822 A CN103247822 A CN 103247822A CN 2012100327974 A CN2012100327974 A CN 2012100327974A CN 201210032797 A CN201210032797 A CN 201210032797A CN 103247822 A CN103247822 A CN 103247822A
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Abstract
The invention discloses a lithium-sulfur secondary battery system. The system comprises a positive electrode, a negative electrode and electrolyte, wherein an active substance of the positive electrode is a carbon-sulfur composite material, the negative electrode adopts a metal lithium plate, the electrolyte is high-salinity non-aqueous electrolyte, and the high-salinity non-aqueous electrolyte comprises lithium salt, sodium salt or lithium-sodium mixed salt and non-aqueous organic solvent; and the mol ratio of the lithium salt or the lithium-sodium mixed salt and the non-aqueous organic solvent is 2 to 10 mol/L. The lithium-sulfur secondary battery system has the following remarkable advantages that since the electrolyte system can effectively prevent multi-sulfur ions of the lithium-sulfur battery from being dissolved in the electrolyte in the charging and discharging processes, the multi-sulfur ions which are dissolved in the electrolyte can be prevented from producing a shuttle effect at the last stage of the charging, the over-charge phenomenon can be prevented, and the coulombic efficiency can be improved to be more than 99 percent. Therefore, the cycling performance of the battery also can be greatly improved.
Description
Technical field
The invention belongs to the battery technology field, particularly relate to a kind of lithium-sulfur rechargeable battery system.
Background technology
The anode material for lithium-ion batteries that commercialization is at present used mainly is to concentrate on transition metal embedding lithium oxide, the oxide and the doped compound thereof that comprise cobalt, iron, nickel, manganese, but this compounds is subjected to the restriction of self theoretical capacity, its present business-like system theoretical energy density is about 600Wh/Kg, although industrial level improves constantly, but present electrokinetic cell as positive electrode, can accomplish 200Wh/Kg at most, be expected to reach 300Wh/Kg future, but room for promotion is very limited.A kind of positive electrode of more high-energy-density is badly in need of in the development of following electric automobile.
Lithium-sulfur cell is because its high specific capacity (S
81675mAh/g), theoretical energy density can reach 2800Wh/kg, is considered to the direction of following lithium secondary battery development, but because there is big technical barrier in this system, appoints at present so to be in laboratory stage.The subject matter of its existence is effectively to be suppressed at intermediate product Li in the charge and discharge process
2S
8, Li
2S
6, Li
2S
4Be dissolved in electrolyte.In case many sulphions are dissolved in electrolyte, can be in charging process produce the serious effect of shuttling back and forth, cause that efficiency for charge-discharge is not high, self discharge is bigger, thereby cause battery performance to worsen, battery life is too short.In addition, go out nonconducting elemental sulfur or polysulfide at the conductive agent surface deposition when effect of shuttling back and forth also can cause charging, increased the resistance that reaches between the conductive agent particle between conductive agent and the collector.And increase along with discharging and recharging number of times, the internal resistance of cell constantly rises, and specific energy descends gradually, and cycle performance of battery worsens rapidly.Therefore with regard to present this system state of development, how to suppress the effect of shuttling back and forth, become the key of improving this system coulombic efficiency and battery cycle life.
Because in the lithium-sulfur cell system, positive active material is the elemental sulfur that does not contain lithium, so negative pole employing lithium metal, so security performance will become the problem that following this system must solve.The main cause that causes this system potential safety hazard is because the negative pole lithium metal causes the Li dendrite generation because the lithium deposition is inhomogeneous in charge and discharge process, thereby easily causes internal short-circuit of battery, causes safety problem.
Summary of the invention
The object of the invention is to have the problems referred to above at present lithium-sulfur cell, propose to adopt the high concentration lithium salts to have electrolyte system now for the electrolyte solution system substitutes, thereby reduce the solubility of many sulphions in electrolyte greatly, reach effective inhibition effect of shuttling back and forth with this, improve the coulombic efficiency that discharges and recharges, be expected to thoroughly to solve the problem of the cycle performance difference of lithium-sulfur cell.
The invention provides a kind of secondary and can fill the lithium-sulfur cell system, this system comprises positive pole, negative pole and electrolyte, wherein, positive active material is carbon sulphur composite material, negative pole adopts metal lithium sheet, and electrolyte is a kind of high salt concentration nonaqueous electrolyte, and described high salt concentration nonaqueous electrolyte comprises lithium salts or sodium salt or lithium sodium salt-mixture and non-aqueous organic solvent; The mol ratio of described lithium salts or lithium sodium salt-mixture and non-aqueous organic solvent is the 3-9 mol.
The present invention has following significant advantage:
Because this electrolyte system has effectively suppressed lithium-sulfur cell many sulphions in charge and discharge process and has been dissolved in electrolyte, therefore many sulphions of having avoided being dissolved in electrolyte produce the effect of shuttling back and forth in the latter stage of charging, thereby prevented from overcharging phenomenon, coulombic efficiency has been brought up to more than 99%.Thus, cycle performance of battery has also obtained bigger improvement.
In addition, the porous carbon of high-specific surface area and the adding of carbon nano-tube, substituted existing conductive additive acetylene black, make conductive additive also have suction-operated preferably to a small amount of many sulphions that are dissolved in electrolyte, make that system circulates and coulombic efficiency further gets a promotion in charge and discharge process.And by optimizing conductive current collector, adopt to apply the alternative traditional aluminium foil of one deck carbon on the aluminium foil, improved the interface performance of active material and collector to a certain extent, improve conductivity.
In sum, by adopting the non-water organic electrolyte of high concentration, and employing has the high specific area carbon (porous carbon or carbon nano-tube etc.) of certain adsorption effect as conductive additive to many sulphions, with the aluminium foil that applied one deck carbon as collector, efficiently solve owing to charge and discharge in the process because some problems that the dissolving of many sulphions brings, make the lithium-sulfur cell chemical property be improved significantly.
Description of drawings
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 enclosed pasture efficient (%); Illustration is the first all charging and discharging curve figure of this system, and wherein transverse axis is charging and discharging capacity (mAh/g), and the longitudinal axis is charging/discharging voltage (V).Test parameter: the constant current test, voltage range 1-3V, charge-discharge magnification are 0.2C.
Fig. 2 is among the embodiment 2, adopts the recycle ratio capacity comparison figure of variable concentrations 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 among the embodiment 2, adopts the circulation coulombic efficiency comparison diagram of variable concentrations lithium salt electrolyte under charge-discharge magnification 0.2C, and wherein transverse axis is cycle-index (N), and the longitudinal axis is enclosed pasture efficient (%);
Fig. 4 is among the embodiment 2, first all charging and discharging curve figure that the carbon sulphur composite material that employing 1# porous carbon is prepared from and carbon-sulfur ratio are 5: 5, and wherein transverse axis is charging and discharging capacity (mAh/g), the longitudinal axis is charging/discharging voltage (V)
Fig. 5 is among the embodiment 2, and employing 2# porous carbon prepares and carbon-sulfur ratio was respectively 4: 6,3: 7 and first all charging and discharging curve comparison diagrams of the carbon sulphur composite material of 2: 8 three kinds of proportionings, and wherein transverse axis is charging and discharging capacity (mAh/g), and the longitudinal axis is charging/discharging voltage (V).
Fig. 6 is among the embodiment 3, under the lithium-sulfur cell charge-discharge magnification 0.1C, and preceding 100 all recycle ratio Capacity Plans, wherein transverse axis is cycle-index (N), the longitudinal axis is charging and discharging capacity (mAh/g).
Fig. 7 is among the embodiment 4, and lithium-sulfur cell is the recycle ratio Capacity Plan under different charge-discharge magnifications, and wherein transverse axis is cycle-index (N), and the longitudinal axis is charging and discharging capacity (mAh/g).
Fig. 8 is among the embodiment 5, and the lithium-sulfur cell charge-discharge magnification is the first all charging and discharging curve figure of 0.2C under 50 degrees centigrade high temperature, and wherein transverse axis is charging and discharging capacity (mAh/g), and the longitudinal axis is charging/discharging voltage (V).
Embodiment
Lithium-sulfur cell system simulated battery, concrete manufacturing process is as follows:
Positive electrode and pole piece manufacturing process thereof:
The concrete parameter of carbon sulphur composite material by adopting 2# porous carbon is as follows: specific area (m2/g): 1431, and average pore size (nm): 3.8, pore volume (cc/g): 1.58
The positive electrode preparation process is as follows:
Respectively taking by weighing a certain amount of carbon sulphur composite material, carbon nano-tube and Kynoar (PVDF) at 8: 1: 1 according to percentage by weight, is dispersant with the pyrrolidones, and it is mixed.Adopt surface-coated the aluminium foil of one deck carbon as collector, mixed slurry is coated on the collector uniformly, dry and be cut into the shape pole piece identical with area subsequently.Cathode pole piece adopts metal lithium sheet.
Electrolyte system:
Electrolyte adopts organic electrolyte DOL: DME=1: 1, and electrolyte concentration is respectively 7mol/LLiTFSI, and gained electrolyte water content is lower than 10ppm.
Battery assembling employing standard button cell CR2032, barrier film is glass fibre.Whole assembling process is finished in moisture is lower than the argon gas glove box of 0.5ppm.Adopt constant current charge-discharge, under the 0.2C electric current, the charging/discharging voltage scope is that 1-3V tests.
As shown in Figure 1, adopted high concentration lithium salts system 7mol/L LiTFSI (DOL: DME=1: 1), system electrolyte, the battery performance excellence mainly embodies average coulombic efficiency and can reach 81.2% greater than 99.5%, 90 week back cycle charging capability retention.
Lithium-sulfur cell system simulated battery, concrete manufacturing process is as follows:
Positive electrode and pole piece manufacturing process thereof:
The concrete parameter of carbon sulphur composite material by adopting 1# porous carbon is as follows: specific area (m2/g): 671, and average pore size (nm): 2.5, pore volume (cc/g): 0.77
The concrete parameter of carbon sulphur composite material by adopting 2# porous carbon is as follows: specific area (m2/g): 1431, and average pore size (nm): 3.8, pore volume (cc/g): 1.58
The positive electrode preparation process is as follows:
Respectively taking by weighing a certain amount of carbon sulphur composite material, acetylene black and Kynoar (PVDF) at 8: 1: 1 according to percentage by weight, is dispersant with the pyrrolidones, and it is mixed., as collector mixed slurry is coated on the collector uniformly with aluminium foil, dries and be cut into the shape pole piece identical with area subsequently.Cathode pole piece adopts metal lithium sheet.
Electrolyte system:
Electrolyte adopts organic electrolyte DOL: DME=1: 1, and electrolyte concentration is respectively 2,4,5,6mol/L LiTFSI, and gained electrolyte water content is lower than 10ppm.
Battery assembling employing standard button cell CR2032, barrier film is glass fibre.Whole assembling process is finished in moisture is lower than the argon gas glove box of 0.5ppm.Adopt constant current charge-discharge, under the 0.2C multiplying power, battery is tested.
Shown in Fig. 2 and 3, under other both positive and negative polarities situation identical with assembled condition, adopted the 1# porous carbon compound 5: 5, raising along with lithium salt, the chemical property of battery is significantly improved, mainly show cycle performance and coulombic efficiency aspect, and when lithium salt in volume ratio and weight ratio all greater than solvent the time (6mol/L), electrochemistry is improved especially obvious.
In addition, Fig. 4 and Fig. 5 are first all charging and discharging curves of four kinds of carbon sulphur composite materials described in the embodiment 1, charging and discharging currents is set to 0.2C, the charging/discharging voltage scope is: 1.5-2.8V, by contrast, the unified elemental sulfur that adopts of specific capacity calculates, contrasting two figure can find, increase along with containing sulfur content, the contained effective active matter of system is more many, and the composite material theoretical specific capacity increases thereupon, but because sulphur is megohmite insulant, the affiliation that adds in a large number of sulphur causes the material actual specific capacity to descend to a certain extent, and chemical property worsens.As shown in Figure 5, compare with Fig. 4, because 2# porous carbon carrying active substance sulfur content is higher, and compound specific capacity is the highest under 4: 6 ratios.
Lithium-sulfur cell system simulated battery, detailed process is as follows:
Positive electrode and pole piece manufacturing process thereof:
Carbon sulphur Composite Preparation process is as follows: porous carbon 1# is mixed with percentage by weight with the sulphur powder at 5: 5, in sealing and the airtight argon filling glass tube, and this raw material handled 24 hours under 155 degree.
Respectively taking by weighing a certain amount of carbon sulphur composite material, sodium alginate and acetylene black at 7: 2: 1 according to percentage by weight, is dispersant with the deionized water, and it is mixed., as collector mixed slurry is coated on the collector uniformly with aluminium foil, dries and be cut into the shape pole piece identical with area subsequently.Cathode pole piece adopts metal lithium sheet.
Electrolyte system:
Electrolyte adopts organic electrolyte DOL: DME=1: 1, and electrolyte is 6mol/L LiTFSI, gained electrolyte water content is lower than 10ppm.
Battery assembling employing standard button cell CR2032, barrier film is glass fibre.Whole assembling process is finished in moisture is lower than the argon gas glove box of 0.5ppm.Adopt constant current charge-discharge, under the 0.1C multiplying power, battery is tested.
As shown in Figure 6, adopting sodium alginate is the carbon sulphur composite material of adhesive, and under the electrolyte of high concentration lithium salts, has better cycle performance.
Lithium-sulfur cell system simulated battery, concrete manufacturing process is as follows:
Positive electrode and pole piece manufacturing process thereof:
The concrete parameter of carbon sulphur composite material by adopting 2# porous carbon is as follows: specific area (m2/g): 1431, and average pore size (nm): 3.8, pore volume (cc/g): 1.58
The positive electrode preparation process is as follows:
Respectively taking by weighing a certain amount of carbon sulphur composite material, porous carbon 2# and Kynoar (PVDF) at 8: 1: 1 according to percentage by weight, is dispersant with the pyrrolidones, and it is mixed.Adopt surface-coated the aluminium foil of one deck carbon as collector, mixed slurry is coated on the collector uniformly, dry and be cut into the shape pole piece identical with area subsequently.Cathode pole piece adopts metal lithium sheet.
Electrolyte system:
Electrolyte adopts organic electrolyte DOL: DME=1: 1, and electrolyte concentration is respectively 6mol/LLiTFSI, and gained electrolyte water content is lower than 10ppm.
Battery assembling employing standard button cell CR2032, barrier film is glass fibre.Whole assembling process is finished in moisture is lower than the argon gas glove box of 0.5ppm.Adopt constant current charge-discharge, battery is tested.
As shown in Figure 7, this system has adopted high concentration lithium salts system 6mol/L LiTFSI (DOL: DME=1: 1) system electrolyte, gained battery high rate performance is good, and the charge ratio capacity can reach first all 0.2C (1333mAh/g), the 11 all 0.5C (1120mAh/g), the 21 all 1C (965mAh/g), the 31 all 2C (677mAh/g) and the 41 all 5C (274mAh/g) respectively successively.
High lithium salt electrolyte system and low lithium salt system apply to lithium-sulfur cell system contrast experiment:
High lithium salt electrolyte system:
Electrolyte adopts organic solvent DOL: DME=1: 1, and electrolyte is 10mol/L LiTFSI, gained electrolyte water content is lower than 10ppm.
Lithium-sulfur cell system simulated battery, detailed process is as follows:
Positive electrode and pole piece manufacturing process thereof:
Carbon sulphur Composite Preparation process is as follows: porous carbon is mixed with percentage by weight with the sulphur powder at 4: 6, in sealing and the airtight argon filling glass tube, and this raw material handled 24 hours down at 155 degrees centigrade.
Respectively taking by weighing a certain amount of carbon sulphur composite material, acetylene black and Kynoar (PVDF) at 8: 1: 1 according to percentage by weight, is dispersant with the pyrrolidones, and it is mixed., as collector mixed slurry is coated on the collector uniformly with aluminium foil, dries and be cut into the shape pole piece identical with area subsequently.Cathode pole piece adopts metal lithium sheet.
Battery assembling employing standard button cell CR2032, barrier film is glass fibre.Whole assembling process is finished in moisture is lower than the argon gas glove box of 0.5ppm.
Adopt constant current charge-discharge, in the constant temperature high-low temperature chamber, constant temperature is tested battery for 50 degrees centigrade under the 0.2C multiplying power.As shown in Figure 8, adopted the lithium-sulfur cell of the ethers system electrolyte (10mol/L) of superelevation lithium salt, can well work under the high temperature, first all charging and discharging curves are normal, it is less to polarize, good restraining because the phenomenon that overcharges that effect causes of shuttling back and forth, specific capacity is near design capacity.
Lithium-sulfur cell system simulated battery, detailed process is as follows:
Positive electrode and pole piece manufacturing process thereof:
Carbon sulphur Composite Preparation process is as follows: acetylene black is mixed with percentage by weight with the sulphur powder at 4: 6, in sealing and the airtight argon filling glass tube, and this raw material handled 24 hours under 155 degree.
Respectively taking by weighing a certain amount of carbon sulphur composite material, acetylene black and Kynoar (PVDF) at 8: 1: 1 according to percentage by weight, is dispersant with the pyrrolidones, and it is mixed.Mixed slurry is coated on the collector uniformly as collector so that graphite is sticking, dries and be cut into the shape pole piece identical with area subsequently.Cathode pole piece adopts metal lithium sheet.
Electrolyte system:
1# electrolyte adopts organic electrolyte diglycol ethylene dimethyl ether (DGM), and electrolyte is 6mol/L LiFSI, and gained electrolyte water content is lower than 10ppm.
2# electrolyte adopts organic electrolyte diglycol ethylene dimethyl ether (DGM), and electrolyte is 5mol/LLiTFSI, and gained electrolyte water content is lower than 10ppm.
3# electrolyte adopts organic electrolyte contracting contracting triethylene glycol dimethyl ether (TGDME), and electrolyte is 4mol/L LiFSI, and gained electrolyte water content is lower than 10ppm.
4# electrolyte adopts organic electrolyte contracting tetraethyleneglycol dimethyl ether (TEGDME), and electrolyte is 3mol/L LiTFSI, and gained electrolyte water content is lower than 10ppm.
5# electrolyte adopts organic electrolyte dimethyl sulfoxide (DMSO) (DMSO), and electrolyte is 6mol/LLiTFSI, and gained electrolyte water content is lower than 10ppm.
6# electrolyte adopts organic electrolyte DOL: DME=1: 1 (volume ratio), electrolyte are 3mol/LLiTFSI and 3mol/L NaFSI, and gained electrolyte water content is lower than 10ppm.
Battery assembling employing standard button cell CR2032, barrier film is glass fibre.Whole assembling process is finished in moisture is lower than the argon gas glove box of 0.5ppm.Adopt constant current charge-discharge, under the 0.2C multiplying power, battery is tested.
Above embodiment result is as shown in the table:
By table 1 result as can be known, the electrolyte system of high lithium salt has same effect after adopting other organic solvents, and therefore, for the lithium-sulfur cell system, high lithium salt has pervasive effect to the raising of battery performance.
In above-described embodiment, only enumerate minority non-aqueous organic solvent in claims, certainly, also can be selected from any or multiple mixture replacement in ethers, sulfone class, sulfuric ester, alcoxyl silicon class, the nitrile.
Above-mentioned ether organic solvent comprises cyclic ether and chain ether two classes; Wherein, cyclic ether comprises oxolane (THF), 2-methyltetrahydrofuran (2-MeTHF), 1,3-dioxolanes (DOL) or 4-methyl isophthalic acid, 3-dioxolanes (4-MeDOL); Chain ether comprises dimethoxymethane (DMM), 1,2-dimethoxy-ethane (DME), 1,2-dimethoxy propane (DMP), diglycol ethylene dimethyl ether (DGDME), contracting triethylene glycol dimethyl ether (TGDME) or contracting tetraethyleneglycol dimethyl ether (TEGDME).
Above-mentioned sulfone class organic solvent comprises dimethyl sulfoxide (DMSO) (DMSO), sulfolane (TMSO) or dimethyl sulfone (MSM).
Above-mentioned sulfuric acid ester organic solvent comprises Methylsulfate, ethyl-sulfate, dimethyl suflfate and dithyl sulfate.
Above-mentioned alcoxyl silicon class organic solvent has the following chemical constitution that comprises: SiR
1R
2R
3R
4, wherein, substituent R
1, R
2, R
3, R
4Identical or different, be selected from hydrogen atom and carbon atom independently of one another, and carbon atom is stated saturated or unsaturated alkyl and OC into 1-10
xF
2x+1-yH
y, OCOC
xF
2x+1-yH
y, OSO
2C
xF
2x+1-yH
yWith the polymeric groups based on ethyoxyl, wherein, x is the integer of 1-10, and y is the integer greater than zero, and 2x+1-y is more than or equal to zero; Perhaps, substituent R
1, R
2, R
3, R
4Identical or different, independently of one another by F, C
xF
2x+1-yH
y, OC
xF
2x+1-yH
y, OCOC
xF
2x+1-yH
y, OSO
2C
xF
2x+1-yH
y, N (C
xF
2x+1-yH
y)
2Replace or single the replacement or polysubstituted aryl, described aryl be phenyl and (or) Nai Ji, or be by F, C
xF
2x+1-yH
y, OC
xF
2x+1-yH
y, OCOC
xF
2x+1-yH
y, OSO
2C
xF
2x+1-yH
y, N (C
xF
2x+1-yH
y)
2Replace or single the replacement or polysubstituted aromatic heterocyclic radical, described heterocyclic radical be pyridine radicals, pyridine radicals and (or) pyrimidine radicals; Wherein, x is the integer of 1-10, and y is the integer greater than zero, and 2x+1-y is more than or equal to zero.
Above-mentioned alcoxyl silicon class organic solvent is selected from tetramethoxy-silicane, ethyl triethoxy silicane oxygen alkane, ethyl triacetyl oxygen radical siloxane, diphenyl methoxy radical siloxane, silicohetane oxyalkyl fluomethane sulfonate, and composition thereof.
Above-mentioned nitrile organic solvent comprise propionitrile, malononitrile, methoxyacetonitrile, 3-methoxypropionitrile, and composition thereof.
In addition, the positive pole of the embodiment of the invention comprises active material, conductive additive and adhesive; Wherein, active material is that carbon-sulfur compound constitutes.In embodiments of the present invention, positive pole has only been enumerated porous carbon as carbon source, and certainly, one or more mixtures such as carbon that also can adopt acetylene black, graphite, Graphene, porous carbon, carbon nano-tube, carbon fiber, nitrogen to mix constitute.
Above-mentioned conductive additive mainly is to constitute with material with carbon element, in embodiments of the present invention, only having enumerated acetylene black, carbon nano-tube and porous carbon, can certainly be that one or more mixtures such as carbon of acetylene black, graphite, Graphene, porous carbon, carbon nano-tube, carbon fiber, nitrogen doping constitute.
Above-mentioned adhesive can be wherein one or more mixtures formations of aqueous adhesive sodium alginate, carboxymethyl cellulose (CMC), polytetrafluoroethylene PTFE, also can be non-aqueous adhesive Kynoar (PVDF).
In addition, the lithium salts of the embodiment of the invention or sodium salt have only been enumerated LiTFSI, LiFSI and NaTFSI, certainly, also can be selected from LiNO
3, NaNO
3, LiCl, NaCl, LiBr, NaBr, LiI, NaI, Li
2CO
3, Na
2CO
3, Li
2SO, Na
2SO
4, LiCF
3SO
3, NaCF
3SO
3, LiC
4F
9SO
3, NaC
4F
9SO
3, LiN (C
xF
2x+1SO
2) (C
yF
2y+1SO
2) or NaN (C
xF
2x+1SO
2) (C
yF
2y+1SO
2), wherein, x and y are natural numbers, LiBF
z(CF
3)
4-z, NaBF
z(CF
3)
4-z, the natural number of z≤4 wherein, LiC (SO
2CF
3)
3, NaC (SO
2CF
3)
3, LiPF
a(CF
3)
6-a, NaPF
a(CF
3)
6-a, LiPF
b(C
2F
5)
6-b, NaPF
b(C
2F
5)
6-b, LiPF
c(different-C
3F
7)
6-c, NaPF
C(different-C
3F
7)
6-c, a wherein, b, the natural number of c≤6.
Claims (15)
1. lithium-sulfur rechargeable battery system, this system comprises positive pole, negative pole and electrolyte, wherein, positive active material is carbon sulphur composite material, negative pole adopts metal lithium sheet, and electrolyte is a kind of high salt concentration nonaqueous electrolyte, and described high salt concentration nonaqueous electrolyte comprises lithium salts or sodium salt or lithium sodium salt-mixture and non-aqueous organic solvent; The molar concentration of described lithium salts or lithium sodium salt-mixture and non-aqueous organic solvent is the 2-10 mol.
2. battery system as claimed in claim 1 is characterized in that, the preferential scope of molar concentration of described lithium salts or lithium sodium salt-mixture and non-aqueous organic solvent is the 4-7 mol.
3. battery system as claimed in claim 2 is characterized in that, described non-aqueous organic solvent is selected from ethers, sulfone class, sulfuric ester, alcoxyl silicon class, nitrile and composition thereof.
4. battery system as claimed in claim 2 is characterized in that, described lithium salts or sodium salt are selected from LiNO
3, NaNO
3, LiCl, NaCl, LiBr, NaBr, LiI, NaI, Li
2CO
3, Na
2CO
3, Li
2SO, Na
2SO
4, LiCF
3SO
3, NaCF
3SO
3, LiC
4F
9SO
3, NaC
4F
9SO
3, LiN (C
xF
2x+1SO
2) (C
yF
2y+1SO
2) or NaN (C
xF
2x+1SO
2) (C
yF
2y+1SO
2), wherein, x and y are natural numbers, LiBF
z(CF
3)
4-z, NaBF
z(CF
3)
4-z, the natural number of z≤4 wherein, LiC (SO
2CF
3)
3, NaC (SO
2CF
3)
3, LiPF
a(CF
3)
6-a, NaPF
a(CF
3)
6-a, LiPF
b(C
2F
5)
6-b, NaPF
b(C
2F
5)
6-b, LiPF
c(different-C
3F
7)
6-c, NaPF
c(different-C
3F
7)
6-c, a wherein, b, the natural number of c≤6.
5. battery system as claimed in claim 3 is characterized in that, described ether organic solvent comprises cyclic ether and chain ether two classes; Wherein, cyclic ether comprises oxolane (THF), 2-methyltetrahydrofuran (2-MeTHF), 1,3-dioxolanes (DOL) or 4-methyl isophthalic acid, 3-dioxolanes (4-MeDOL); Chain ether comprises dimethoxymethane (DMM), 1,2-dimethoxy-ethane (DME), 1,2-dimethoxy propane (DMP), diglycol ethylene dimethyl ether (DGDME), contracting triethylene glycol dimethyl ether (TGDME) or contracting tetraethyleneglycol dimethyl ether (TEGDME).
6. battery system as claimed in claim 3 is characterized in that, described sulfone class organic solvent comprises dimethyl sulfoxide (DMSO) (DMSO), sulfolane (TMSO) or dimethyl sulfone (MSM).
7. battery system as claimed in claim 3 is characterized in that, described sulfuric acid ester chemical general formula R-O-SO2-O-R ', and R is organic group, R ' often is proton or does not have group, comprising Methylsulfate, ethyl-sulfate, dimethyl suflfate and dithyl sulfate.
8. battery system as claimed in claim 3 is characterized in that, described alcoxyl silicon class organic solvent has the following chemical constitution that comprises: SiR
1R
2R
3R
4, wherein, substituent R
1, R
2, R
3, R
4Identical or different, be selected from hydrogen atom and carbon atom independently of one another, and carbon atom is stated saturated or unsaturated alkyl and OC into 1-10
xF
2x+1-yH
y, OCOC
xF
2x+1-yH
y, OSO
2C
xF
2x+1-yH
yWith the polymeric groups based on ethyoxyl, wherein, x is the integer of 1-10, and y is the integer greater than zero, and 2x+1-y is more than or equal to zero; Perhaps, substituent R
1, R
2, R
3, R
4Identical or different, independently of one another by F, C
xF
2x+1-yH
y, OC
xF
2x+1-yH
y, OCOC
xF
2x+1-yH
y, OSO
2C
xF
2x+1-yH
y, N (C
xF
2x+1-yH
y)
2Replace or single the replacement or polysubstituted aryl, described aryl be phenyl and (or) Nai Ji, or be by F, C
xF
2x+1-yH
y, OC
xF
2x+1-yH
y, OCOC
xF
2x+1-yH
y, OSO
2C
xF
2x+1-yH
y, N (C
xF
2x+1-yH
y)
2Replace or single the replacement or polysubstituted aromatic heterocyclic radical, described heterocyclic radical be pyridine radicals, pyridine radicals and (or) pyrimidine radicals; Wherein, x is the integer of 1-10, and y is the integer greater than zero, and 2x+1-y is more than or equal to zero.
9. battery system as claimed in claim 3, it is characterized in that, described alcoxyl silicon class organic solvent is selected from tetramethoxy-silicane, ethyl triethoxy silicane oxygen alkane, ethyl triacetyl oxygen radical siloxane, diphenyl methoxy radical siloxane, silicohetane oxyalkyl fluomethane sulfonate, and composition thereof.
10. battery system as claimed in claim 3 is characterized in that, described nitrile organic solvent comprise propionitrile, malononitrile, methoxyacetonitrile, 3-methoxypropionitrile, and composition thereof.
11. battery system as claimed in claim 1 is characterized in that, described positive pole comprises that active material, conductive additive, adhesive and conductive current collector constitute.
12. battery system as claimed in claim 13 is characterized in that, the described and employed material with carbon element of carbon sulphur composite material can be that one or more mixtures such as acetylene black, graphite, Graphene, porous carbon, carbon nano-tube, carbon fiber, nitrogen doping constitute.
13. battery system as claimed in claim 13, it is characterized in that, described conductive additive mainly is to constitute with material with carbon element, wherein can be that one or more mixtures such as carbon of acetylene black, graphite, Graphene, porous carbon, carbon nano-tube, carbon fiber, nitrogen doping constitute.
14. battery system as claimed in claim 13, it is characterized in that, described adhesive can be wherein one or more mixtures formations of aqueous adhesive sodium alginate, carboxymethyl cellulose (CMC), polytetrafluoroethylene PTFE, also can be non-aqueous adhesive Kynoar (PVDF).
15. battery system as claimed in claim 13 is characterized in that, described conductive current collector can be metal aluminum foil or graphite felt, also can be the aluminium foil at one deck carbon of surface-coated thickness homogeneous.
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