CN109802135A - A kind of lithium sulfur battery anode material, and its preparation method and application - Google Patents
A kind of lithium sulfur battery anode material, and its preparation method and application Download PDFInfo
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- CN109802135A CN109802135A CN201910117167.9A CN201910117167A CN109802135A CN 109802135 A CN109802135 A CN 109802135A CN 201910117167 A CN201910117167 A CN 201910117167A CN 109802135 A CN109802135 A CN 109802135A
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Abstract
The present invention relates to a kind of lithium sulfur battery anode material, the lithium sulfur battery anode material includes the carbon coating layer for carrying the sulfide molecules sieve of sulphur and being coated on outside the sulfide molecules sieve for carrying sulphur；The sulfide molecules sieve for carrying sulphur includes the sulphur simple substance that metalliferous sulfide molecules are sieved and are set in the metalliferous sulfide molecules sieve pore road.The metalliferous sulfide molecules sifter device that the present invention uses has cellular structure abundant, and the metal cation in duct is to the S in discharge process2‑Sucking action with electrostatic, and then the combination of sulphur and lithium can be prevented, the volume expansion of electrode material is reduced, the chemical property and cycle life of material are improved；On the one hand carbon coating layer can assign lithium sulfur battery anode material good electronic transmission performance, on the other hand can further prevent the combination of sulphur and lithium, reduce the dissolution diffusion of more lithium sulfides in the electrolyte, further increase the chemical property of material.
Description
Technical field
The invention belongs to battery material technical fields, and in particular to a kind of lithium sulfur battery anode material, and preparation method thereof
And purposes.
Background technique
It is limited at present by positive active material capacity, the space that the energy density of lithium ion battery can improve is not
It is more, it is considered that its limiting value is 250~300Wh/Kg, and the target of 700Wh/Kg is difficult to realize by lithium ion battery, because
This, is badly in need of developing next-generation novel battery.Lithium-sulfur cell refers to using sulphur or sulfur-containing compound as anode, lithium or lithium storage materials
For cathode, a kind of battery system that electric energy and chemical energy are mutually converted is realized with sulphur-sulfide linkage fracture/generation.Lithium-sulfur cell
Four in following power battery requirement aspects can be better meet: i.e. high-energy density, preferable safety, it is environmentally protective and
Low cost.
But the problem of lithium anode and sulfur-based positive electrode material are primarily present the following aspects in lithium-sulfur cell: (1)
At room temperature, the most stable of sulfur molecule of thermodynamics is the coronal S being connected to form by eight S atoms8, the combination between molecule formed
The good elemental sulfur of crystallinity, belongs to typical electronics and ion insulator, therefore, S8Electrochemistry as electrode active material
Poor activity, and its active material utilization is relatively low；(2) elemental sulfur can be reduced into readily soluble polysulfide during discharge,
It causes active material to be lost, and after polysulfide is dissolved in electrolyte, will increase concentration of electrolyte, deteriorate its ionic conductivity；
(3) during the charging process, the long-chain polysulphides in electrolyte are dissolved in after anode is oxidized, and readily diffuse into cathode of lithium surface
Electrochemical reduction occurs, is then diffused into anode again and is oxidized again, forms the circular response machine of positive oxidation-cathodic reduction
System, i.e., it is so-called " shuttle effect ", to influence the completion that battery charges normal, and lead to the reduction of charging coulombic efficiency；This
A large amount of dissolutions of outer polysulfide cause to be electrolysed the increase of fluid viscosity and its being greatly reduced for ionic conductivity, accelerate electric polarity
The decline of energy, and reduction of the polysulfide on lithium surface deposits, and also results in cathode of lithium corruption candle, influences filling for lithium electrode
Property；(4) lithium-sulfur cell is closed because of positive sulphur and lithiumation during discharge occurs volume expansion, and cathode lithium is then due to the consumption of lithium
Volume is reduced, and positive and negative anodes volume is caused to repeated variation, and the variation repeatedly of electrode size can make sulfur electrode generate micro-crack, from
And the conductive network of anode and the globality of battery are destroyed, exacerbate the capacity attenuation of lithium-sulfur cell.These problems are seriously made
The about development of lithium-sulfur cell, this is also the emphasis of current lithium-sulfur cell research.
CN106299317A discloses a kind of lithium sulfur battery anode material, and the lithium sulfur battery anode material includes that anode is living
Property substance, the positive active material includes elemental sulfur, and the positive active material further includes conducting polymer, the elemental sulfur
Three-dimensional cross-linked hollow tube is formed with the conducting polymer；The elemental sulfur is compounded to form compound with the conducting polymer
Object, unsaturated double-bond is contained in the polymer molecule, and the elemental sulfur and chain polymer unsaturated double-bond form chemical bond
Cooperation is with forming three-dimensional crosslinked network structure.The present invention also provides the preparation methods of above-mentioned lithium sulfur battery anode material.It is described
Lithium sulfur battery anode material sulfide dissolution easily generated during charge and discharge cycles, to cause capacity attenuation.
CN107611395A disclose a kind of small size graphene lithium sulfur battery anode material, its preparation lithium-sulfur cell and
Preparation method, the preparation method include the following steps: (1) using microlite ink powder as raw material, prepare small size using electrolysis method
Graphene；(2) binder solution is prepared；(3) it by the modified small size graphene of small size graphene or surface, is compounded to form with sulphur
Graphene/sulphur composite material, as small size graphene lithium sulfur battery anode material.The positive electrode that the method is prepared
The sulfide dissolution easily generated during charge and discharge cycles, to cause capacity attenuation.
CN106340631A discloses a kind of preparation method of lithium sulfur battery anode material, and the preparation method includes as follows
Step: (1) dipping of cotton: being immersed in sealing thermal insulation in the hydrochloric acid solution of Containing Zinc Chloride for cotton, remove redundant solution later,
And isothermal holding dry to mixture, obtains grey or brown solid；(2) preparation of porous carbon matrix: successively to the solid
Carbonization treatment and acidification are carried out, washs later, dry and calcining, obtains porous carbon matrix；(3) carbon-sulphur composite material
Preparation: the porous carbon matrix is synthesized into lithium sulfur battery anode material with elemental sulfur heat together.The anode that the method is prepared
Material sulfide dissolution easily generated during charge and discharge cycles, to cause capacity attenuation.
Therefore, this field is badly in need of developing a kind of novel lithium sulfur battery anode material, and the lithium sulfur battery anode material is filling
It can inhibit the dissolution and loss of intermediate product during discharge cycles, so as to improve the cyclical stability of sulfur electrode, and prepare
Method is simple, can industrialized production.
Summary of the invention
In view of the deficiencies of the prior art, described one of the objects of the present invention is to provide a kind of lithium sulfur battery anode material
Lithium sulfur battery anode material includes the carbon packet for carrying the sulfide molecules sieve of sulphur and being coated on outside the sulfide molecules sieve for carrying sulphur
Coating；
The sulfide molecules sieve for carrying sulphur includes that the metalliferous sulphur is sieved and be set to metalliferous sulfide molecules
Sulphur simple substance in compound molecular sieve pore passage.
The metalliferous sulfide molecules sifter device that the present invention uses has cellular structure abundant, can be by sulphur simple substance with molecule
The form of state is good to be dispersed in the duct of molecular sieve, and the metallic element in metalliferous sulfide molecules sieve is to positive electrode
Capacity have a castering action, while the metalliferous sulfide molecules sieve that uses of the present invention compared with the existing technology in silicon molecule
The non-carbon molecular sieves such as sieve, because the metal cation in duct is to the S in discharge process2-Sucking action with electrostatic, Jin Erke
To prevent the combination of sulphur and lithium, the volume expansion of electrode material is reduced, improves the chemical property and cycle life of material；Carbon packet
On the one hand coating can assign lithium sulfur battery anode material good electronic transmission performance, on the other hand can further prevent sulphur
And the combination of lithium reduces the dissolution diffusion of more lithium sulfides in the electrolyte, and then assigns the good chemical property of material, in 1C
Under current density, first discharge specific capacity >=1267.2mAh/g, for the first time coulombic efficiency >=85.0%, 200 week capacity retention ratio >=
93.1%.
Preferably, the chemical formula of the metalliferous sulfide molecules sieve is M1- MS, the M1Including Fe, Cu, Co, Zn,
In Li, Mn and Na any one or at least two combination, preferably Co.
M in metalliferous sulfide molecules sieve of the present invention1With positive electricity, to S2-With electrostatic adsorption.
The M includes the combination of any one or at least two in Sb, Sn, Ga, Ge and In, preferably Sb.
In metalliferous sulfide molecules sieve of the present invention M because valence state difference so that metalliferous sulfide
The super tetrahedral cluster of molecular sieve in different sizes is construction unit.
Preferably, the channel diameter of the metalliferous sulfide molecules sieve is 0.1~5nm, such as 0.5nm, 1nm,
1.5nm, 2nm, 2.5nm, 3nm, 4nm etc..
Preferably, the specific surface area of the metalliferous sulfide molecules sieve is 100~10000m2/ g, preferably 500~
3000m2/ g, such as 200m2/g、500m2/g、1000m2/g、3000m2/g、5000m2/g、8000m2/ g etc..
It preferably, further include the carbon being supported on the sulfide molecules sieve for carrying sulphur in the lithium sulfur battery anode material
Material.
Carbon material in lithium sulfur battery anode material of the present invention can assign that lithium sulfur battery anode material is good to lead
Electrically, and " the shuttle effect " of polysulfide of the lithium sulfur battery anode material in charge and discharge process can be alleviated, solves body
Product expansion issues, and then assign the good chemical property of lithium sulfur battery anode material.
Preferably, the carbon material includes one-dimensional carbon material and/or two-dimentional carbon material, preferably graphene, graphite alkene and carbon
In nanotube any one or at least two combination.
Preferably, the composition of the lithium sulfur battery anode material by mass percentage, including following components:
The sulfide molecules for carrying sulphur sieve 50wt%~80wt%
Carbon coating layer 3wt%~15wt%
C film 8wt%~20wt%；
The sum of described lithium sulfur battery anode material each component gross mass percentage is calculated as 100%.
Preferably, the composition of the sulfide molecules sieve for carrying sulphur by mass percentage, including following components:
Metalliferous sulfide molecules sieve 10wt%~30wt%
Sulphur simple substance 70wt%~90wt%；
The sum of the sulfide molecules sieve each component gross mass percentage for carrying sulphur is calculated as 100%.
The second object of the present invention is to provide a kind of preparation method of lithium sulfur battery anode material, the preparation method includes
Following steps:
(1) metalliferous sulfide molecules are sieved and is mixed with sulphur simple substance, primary heating obtains carrying the sulfide molecules sieve of sulphur；
(2) cladding carbon source and C film are added in the sulfide molecules sieve for carrying sulphur, reheating obtains lithium sulphur electricity
Pond positive electrode.
Preparation process of the present invention is simple, can industrialized production.
Preferably, the preparation method of step (1) the metalliferous sulfide molecules sieve includes the following steps: the source M, M1
Source, sulphur source and secondary solvent mix, and wash obtained product after hydro-thermal, dry, obtain metalliferous sulfide molecules sieve.
Preferably, the M1The molar ratio in source, the source M and sulphur source is 2~40:4~48:1~97, such as 22:16:33,22:
17:33,2:4:8,38:48:97,24:12:30 etc..
Preferably, the M1Source, the source M, the gross mass of sulphur source and secondary solvent and secondary solvent mass ratio be 0.5~2:
1, such as 0.6:1,0.8:1,1:1,1.2:1,1.5:1,1.8:1 etc..
Preferably, the source M include in Sb salt, Sn salt, Ga salt, Ge salt and In salt any one or at least two group
Close, preferably any one in Sb salt, Ga salt and In salt or at least two combination.
Preferably, the M1Source include in Li salt, Fe salt, Cu salt, Co salt, Mn salt, Zn salt and Na salt any one or
In at least two combination, preferably Co salt, Li salt and Fe salt any one or at least two combination.
Preferably, the sulphur source includes sulfide and/or sulphur powder.
Preferably, the sulfide includes any one in vulcanized sodium, lithium sulfide, zinc sulphide, calcium sulfide and barium sulphide
Or at least two combination.
Preferably, the secondary solvent includes methylamine water solution.
Preferably, the mass fraction of the secondary solvent be 10wt%~30wt%, such as 12wt%, 15wt%,
18wt%, 20wt%, 22wt%, 25wt%, 28wt% etc..
Preferably, the temperature of the hydro-thermal is 100~200 DEG C, such as 120 DEG C, 150 DEG C, 180 DEG C etc..
Preferably, the time of the hydro-thermal is 72h~240h, such as 100h, 120h, 150h, 180h, 200h, 220h etc..
Preferably, the temperature of the drying is 60~90 DEG C, such as 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C etc..
Preferably, the time of the drying is 8h~12h, such as 9h, 10h, 11h etc..
Preferably, step (1) the metalliferous sulfide molecules sieve and the mass ratio of sulphur simple substance are 0.5~9:1, preferably
3~9:1, such as 1:1,2:1,3:1,4:1,5:1,6:1,7:1,8:1 etc..
When metalliferous sulfide molecules sieve of the present invention and the mass ratio of sulphur simple substance are less than 0.5:1, metalliferous sulphur
Compound molecular sieve content is too small, and then dispersibility of the sulphur simple substance in metalliferous sulfide molecules sieve pore road is poor, contains metal
Sulfide molecules sieve to S2-Electrostatic attraction act on smaller, excessive S2-In conjunction with lithium, the chemical property of material is reduced；
When the metalliferous sulfide molecules sieve and the mass ratio of sulphur simple substance are greater than 9:1, the content of sulphur simple substance is too small, so capacity compared with
It is low.
Preferably, the mode that the metalliferous sulfide molecules sieve is mixed with sulphur simple substance is ground and mixed.
Preferably, the temperature of the primary heating is 100~200 DEG C, such as 120 DEG C, 150 DEG C, 180 DEG C etc..
Preferably, the time of the primary heating be 5~48h, preferably 10~20h, such as 10h, 15h, 20h, 25h,
30h, 35h, 40h, 45h etc..
Preferably, the mass ratio of carbon source and C film is sieved, coated to step (2) the metalliferous sulfide molecules for carrying sulphur
For 10~100:1:5~20, preferably 20~80:1:5~10, such as 20:1:6,30:1:8,40:1:10,50:1:12,60:1:
15,80:1:18 etc..
Preferably, the cladding carbon source include polyacrylonitrile, Kynoar, polyoxyethylene, polymethyl methacrylate,
Kynoar-hexafluoropropene, polyvinyl butyral, polyvinylpyrrolidone, polypyrrole, polyaniline, polythiophene, metatitanic acid four
In butyl ester and lithium phosphate any one or at least two combination, preferred polypyrrole.
Preferably, the temperature of the reheating is 80~150 DEG C, such as 100 DEG C, 120 DEG C, 140 DEG C etc..
Preferably, the time of the reheating is 2~10h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h etc..
As optimal technical scheme, the preparation method of lithium sulfur battery anode material of the present invention includes the following steps:
It (1) is 2~40:4~48:1~97, the gross mass of Li salt, Ga salt and sulphur powder by Li salt, Ga salt and sulphur powder molar ratio
It is 0.5~2:1 with mass ratio that mass fraction is 10wt%~30wt% methylamine water solution, by Li salt, Ga salt, sulphur powder and methylamine
Aqueous solution mixes, and after 100~200 DEG C of hydro-thermal 72h~240h, obtained product is washed, 60~90 DEG C of dry 8h~12h are obtained
It is sieved to metalliferous sulfide molecules；
It (2) is 3~9:1 by the metalliferous sulfide molecules sieve and the mass ratio of sulphur simple substance, by metalliferous vulcanization
Object molecular sieve and sulphur simple substance ground and mixed, 100~200 DEG C of 10~20h of heating obtain the sulfide molecules sieve for carrying sulphur；
It (3) is 20~80:1:5~10 by the mass ratio of sulfide molecules sieve, polypyrrole and the C film for carrying sulphur,
Polypyrrole is added in the sulfide molecules sieve for carrying sulphur and C film, 80~150 DEG C of 2~10h of heating are obtaining lithium-sulfur cell just
Pole material.
The three of the object of the invention are to provide a kind of lithium-sulfur cell, and the lithium-sulfur cell includes the electricity of lithium sulphur described in the first purpose
Pond positive electrode.
Preferably, one of for the purpose of the lithium sulfur battery anode material described in lithium sulfur battery anode material.
Compared with prior art, the invention has the following beneficial effects:
(1) the metalliferous sulfide molecules sifter device that uses of the present invention has cellular structure abundant, can by sulphur simple substance with
The form of molecular state is good to be dispersed in the duct of molecular sieve, and the metallic element in metalliferous sulfide molecules sieve is to anode
The capacity of material has a castering action, at the same the metalliferous sulfide molecules sieve that uses of the present invention compared with the existing technology in silicon
The non-carbon molecular sieve such as molecular sieve, because the metal cation in duct is to the S in discharge process2-Sucking action with electrostatic, into
And the combination of sulphur and lithium can be prevented, the volume expansion of electrode material is reduced, the chemical property and cycle life of material are improved；
On the one hand carbon coating layer can assign lithium sulfur battery anode material good electronic transmission performance, on the other hand can further hinder
The only combination of sulphur and lithium reduces the dissolution diffusion of more lithium sulfides in the electrolyte, and then assigns the good chemical property of material,
Under 1C current density, first discharge specific capacity >=1267.2mAh/g, coulombic efficiency >=85.0%, 200 week capacity is kept for the first time
Rate >=93.1%.
(2) it is good can to assign lithium sulfur battery anode material for the carbon material in lithium sulfur battery anode material of the present invention
Electric conductivity, and volume expansion problem of the lithium sulfur battery anode material in charge and discharge process can be alleviated, and then assign lithium sulphur
The good chemical property of cell positive material.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of preparation method of lithium sulfur battery anode material includes the following steps:
(1) molecular formula Li is pressed24Ga12S30By lithium chloride, gallium nitrate and sulphur powder in molar ratio 24:12:30 mix, then plus
Enter the methylamine water solution that mass fraction is 25wt%, the lithium chloride, the gross mass of gallium nitrate and sulphur powder and methylamine water solution
Mass ratio is 0.8:1, after 180 DEG C of hydro-thermal 200h, obtained product is washed, 80 DEG C of dry 10h obtain metalliferous sulfide
Molecular sieve；
It (2) is 8:1 by the metalliferous sulfide molecules sieve and the mass ratio of sulphur simple substance, by metalliferous sulfide point
Son sieve and sulphur simple substance ground and mixed, 180 DEG C of heating 18h obtain the sulfide molecules sieve for carrying sulphur；
It (3) is 30:1:6 by the mass ratio of sulfide molecules sieve, polypyrrole and the graphene for carrying sulphur, in the load sulphur
Sulfide molecules sieve in polypyrrole and C film, 120 DEG C of heating 8h be added obtain lithium sulfur battery anode material.
Embodiment 2
The difference from embodiment 1 is that the mass ratio of metalliferous sulfide molecules sieve and sulphur simple substance described in step (2)
For 0.5:1.
Embodiment 3
The difference from embodiment 1 is that the mass ratio of metalliferous sulfide molecules sieve and sulphur simple substance described in step (2)
For 9:1.
Embodiment 4
The difference from embodiment 1 is that the mass ratio of metalliferous sulfide molecules sieve and sulphur simple substance described in step (2)
For 0.4:1.
Embodiment 5
The difference from embodiment 1 is that the mass ratio of metalliferous sulfide molecules sieve and sulphur simple substance described in step (2)
For 10:1.
Embodiment 6
The difference from embodiment 1 is that carrying the sulfide molecules sieve of sulphur, polypyrrole and graphene described in step (3)
Mass ratio is 9:1:21.
Embodiment 7
The difference from embodiment 1 is that carrying the sulfide molecules sieve of sulphur, polypyrrole and graphene described in step (3)
Mass ratio is 101:1:4.
Embodiment 8
A kind of preparation method of lithium sulfur battery anode material includes the following steps:
(1) molecular formula Li is pressed10Fe12In16S33By lithium chloride, frerrous chloride, indium nitrate and sulphur powder 10:12 in molar ratio:
Then the methylamine water solution that mass fraction is 10wt%, the lithium chloride, frerrous chloride, indium nitrate and sulphur is added in 16:33 mixing
The mass ratio of the gross mass of powder and methylamine water solution is 2:1, after 100 DEG C of hydro-thermal 240h, obtained product is washed, 90 DEG C of dryings
12h obtains metalliferous sulfide molecules sieve；
It (2) is 8:1 by the metalliferous sulfide molecules sieve and the mass ratio of sulphur simple substance, by metalliferous sulfide point
Son sieve and sulphur simple substance ground and mixed, 100 DEG C of heating 20h obtain the sulfide molecules sieve for carrying sulphur；
It (3) is 100:1:20 by the mass ratio of sulfide molecules sieve, Kynoar and the graphite alkene for carrying sulphur, in institute
It states addition Kynoar and graphite alkene, 150 DEG C of heating 2h in the sulfide molecules sieve for carry sulphur and obtains lithium-sulphur cell positive electrode material
Material.
Embodiment 9
A kind of preparation method of lithium sulfur battery anode material includes the following steps:
(1) molecular formula Co is pressed2In4S8By cobaltous sulfate, indium nitrate and sulphur powder, 2:4:8 is mixed in molar ratio, and quality is then added
Score is the methylamine water solution of 30wt%, the mass ratio of the cobaltous sulfate, the gross mass of indium nitrate and sulphur powder and methylamine water solution
For 0.5:1, after 200 DEG C of hydro-thermal 72h, obtained product is washed, 60 DEG C of dry 8h, obtains metalliferous sulfide molecules and sieve；
It (2) is 8:1 by the metalliferous sulfide molecules sieve and the mass ratio of sulphur simple substance, by metalliferous sulfide point
Son sieve and sulphur simple substance ground and mixed, 200 DEG C of heating 10h obtain the sulfide molecules sieve for carrying sulphur；
It (3) is 10:1:5 by the mass ratio of sulfide molecules sieve, polythiophene and the carbon nanotube for carrying sulphur, in the load
Polythiophene is added in the sulfide molecules sieve of sulphur and carbon nanotube, 80 DEG C of heating 10h obtain lithium sulfur battery anode material.
Comparative example 1
The difference from embodiment 1 is that being added without metalliferous sulfide molecules sieve in step (2).
Comparative example 2
The difference from embodiment 1 is that metalliferous sulfide molecules sieve is replaced with hexagonal mesoporous total silicon in step (2)
Molecular sieve.
Performance test:
The lithium sulfur battery anode material being prepared is performed the following performance tests:
(1) battery assembly: anode pole piece is made in lithium sulfur battery anode material produced by the present invention, cathode is lithium metal
Piece, diaphragm are Celgard2400, and electrolyte is the LiPF6/DMC+DEC of 1mol/L, are assembled into CR2025 type button cell.Just
The preparation process of pole pole piece includes: the lithium sulfur battery anode material that will be prepared, conductive agent acetylene black, binder PVDF (poly-
Vinylidene) according to the mass ratio of 8:1:1, with N-Methyl pyrrolidone NMP as solvent be mixed and made into slurry after be coated in aluminium foil
On, it 120 DEG C after drying 12 hours, rolls and is punched into disk that diameter is 8.4mm as anode pole piece.
(2) electro-chemical test: in normal temperature condition, button cell obtained is surveyed on LAND battery test system
Examination, charging/discharging voltage section are 1.5~3.0V, and charge-discharge test, 200 weeks conservation rate=circulations are carried out under 1C current density
200 weeks specific discharge capacity/first discharge specific capacities, for the first time coulombic efficiency=first discharge specific capacity/initial charge specific capacity.
Table 1
It can be seen from Table 1 that the lithium sulfur battery anode material chemical property that Examples 1 to 9 obtains is good, in 1C electricity
Under current density, first discharge specific capacity >=1267.2mAh/g, for the first time coulombic efficiency >=85.0%, 200 week capacity retention ratio >=
93.1%.
It can be seen from Table 1 that embodiment 4 is relative to embodiment 1, under 1C current density, coulombic efficiency and 200 for the first time
All capacity retention ratios are lower, it may be possible to which because metalliferous sulfide molecules sieve content is too low in embodiment 4, and then sulphur simple substance exists
Dispersibility in metalliferous sulfide molecules sieve pore road is poor, and metalliferous sulfide molecules sieve is to S2-Electrostatic attraction effect
Smaller, excessive S2-In conjunction with lithium, the chemical property of material is reduced, so embodiment 4 is relative to embodiment 1, coulomb for the first time
Efficiency and 200 weeks capacity retention ratios are lower.
It can be seen from Table 1 that embodiment 5 is relative to embodiment 1, under 1C current density, first discharge specific capacity compared with
It is low, it may be possible to which that, because of the too high levels that metalliferous sulfide molecules are sieved in embodiment 5, the content of sulphur simple substance is too low, Jin Erfa
The active capacity of raw electrochemical reaction is lower, thus embodiment 5 relative to
Embodiment 1, first discharge specific capacity is lower.
It can be seen from Table 1 that embodiment 6 is relative to embodiment 1, under 1C current density, first discharge specific capacity compared with
It is low, it may be possible to because the sulfide molecules sieve content for carrying sulphur in embodiment 6 is too low, the too high levels of graphene, and then electricity occurs
The active capacity of chemical reaction is lower, so embodiment 6 is relative to embodiment 1, first discharge specific capacity is lower.
It can be seen from Table 1 that embodiment 7 is relative to embodiment 1, under 1C current density, coulombic efficiency and 200 for the first time
All capacity retention ratios are lower, it may be possible to because the sulfide molecules for carrying sulphur in embodiment 7 sieve too high levels, the content mistake of graphene
Low, the electric conductivity of the lithium sulfur battery anode material obtained from is poor, poor to the covering property for the sulfide molecules sieve for carrying sulphur, institute
With embodiment 7 relative to embodiment 1, coulombic efficiency and 200 weeks capacity retention ratios are lower for the first time.
It can be seen from Table 1 that comparative example 1 is relative to embodiment 1, under 1C current density, coulombic efficiency and 200 for the first time
All capacity retention ratios are lower, it may be possible to because being added without metalliferous sulfide molecules sieve in comparative example 1, and then in discharge process
The S of generation2-It is easy in conjunction with lithium, causes the volume expansion of electrode material, and product is easily accessible electrolyte and causes active material
It is lost, reduces the chemical property of material, so comparative example 1 is relative to embodiment 1, coulombic efficiency and 200 weeks capacity are protected for the first time
Holdup is lower.
It can be seen from Table 1 that comparative example 2 is relative to embodiment 1, under 1C current density, first discharge specific capacity, head
Secondary coulombic efficiency and 200 weeks capacity retention ratios are lower, it may be possible to because using hexagonal mesoporous silica in comparative example 2, six
Fang Jiekong silica zeolite is to S2-No electrostatic attraction effect, and then the S generated2-More lithium sulfides are generated easily in conjunction with lithium, dissolution is expanded
Dissipate causes active material to be lost in the electrolyte, reduces the chemical property of material, so comparative example 2 is relative to embodiment 1, it is first
Secondary specific discharge capacity, for the first time coulombic efficiency and 200 weeks capacity retention ratios are lower.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of lithium sulfur battery anode material, which is characterized in that the lithium sulfur battery anode material includes the sulfide point for carrying sulphur
Son sieve and the carbon coating layer being coated on outside the sulfide molecules sieve for carrying sulphur；
The sulfide molecules sieve for carrying sulphur includes that the metalliferous sulfide is sieved and be set to metalliferous sulfide molecules
Sulphur simple substance in molecular sieve pore passage.
2. lithium sulfur battery anode material as described in claim 1, which is characterized in that the metalliferous sulfide molecules sieve
Chemical formula is M1- MS, the M1Including in Fe, Cu, Co, Zn, Li, Mn and Na any one or at least two combination, preferably
Co；
The M includes the combination of any one or at least two in Sb, Sn, Ga, Ge and In, preferably Sb；
Preferably, the channel diameter of the metalliferous sulfide molecules sieve is 0.1~5nm；
Preferably, the specific surface area of the metalliferous sulfide molecules sieve is 100~10000m2/ g, preferably 500~3000m2/
g。
3. lithium sulfur battery anode material as claimed in claim 1 or 2, which is characterized in that in the lithium sulfur battery anode material
It further include the carbon material being supported on the sulfide molecules sieve for carrying sulphur；
Preferably, the carbon material includes one-dimensional carbon material and/or two-dimentional carbon material, preferably graphene, graphite alkene and carbon nanometer
In pipe any one or at least two combination.
4. the lithium sulfur battery anode material as described in one of claim 1-3, which is characterized in that the lithium sulfur battery anode material
Composition by mass percentage, including following components:
The sulfide molecules for carrying sulphur sieve 50wt%~80wt%
Carbon coating layer 3wt%~15wt%
C film 8wt%~20wt%；
The sum of described lithium sulfur battery anode material each component gross mass percentage is calculated as 100%；
Preferably, the composition of the sulfide molecules sieve for carrying sulphur by mass percentage, including following components:
Metalliferous sulfide molecules sieve 10wt%~30wt%
Sulphur simple substance 70wt%~90wt%；
The sum of the sulfide molecules sieve each component gross mass percentage for carrying sulphur is calculated as 100%.
5. a kind of preparation method of the lithium sulfur battery anode material as described in one of claim 1-4, which is characterized in that the system
Preparation Method includes the following steps:
(1) metalliferous sulfide molecules are sieved and is mixed with sulphur simple substance, primary heating obtains carrying the sulfide molecules sieve of sulphur；
(2) cladding carbon source is added in the sulfide molecules sieve for carrying sulphur and C film, reheating is obtaining lithium-sulfur cell just
Pole material.
6. preparation method as claimed in claim 5, which is characterized in that step (1) the metalliferous sulfide molecules sieve
Preparation method includes the following steps: M1Source, the source M, sulphur source and secondary solvent mix, and wash obtained product after hydro-thermal, do
It is dry, obtain metalliferous sulfide molecules sieve；
Preferably, the M1The molar ratio in source, the source M and sulphur source is 2~40:4~48:1~97；
Preferably, the source M, M1The mass ratio in source, the gross mass of sulphur source and secondary solvent and secondary solvent is 0.5~2:1；
Preferably, the source M include in Sb salt, Sn salt, Ga salt, Ge salt and In salt any one or at least two combination,
It is preferred that in Sb salt, Ga salt and In salt any one or at least two combination；
Preferably, the M1Source includes any one or at least two in Li salt, Fe salt, Cu salt, Co salt, Mn salt, Zn salt and Na salt
Kind combination, preferably any one in Co salt, Li salt and Fe salt or at least two combination；
Preferably, the sulphur source includes sulfide and/or sulphur powder；
Preferably, the sulfide include in vulcanized sodium, lithium sulfide, zinc sulphide, calcium sulfide and barium sulphide any one or extremely
Few two kinds of combination；
Preferably, the secondary solvent includes methylamine water solution；
Preferably, the mass fraction of the secondary solvent is 10wt%~30wt%；
Preferably, the temperature of the hydro-thermal is 100~200 DEG C；
Preferably, the time of the hydro-thermal is 72h~240h；
Preferably, the temperature of the drying is 60~90 DEG C；
Preferably, the time of the drying is 8h~12h.
7. such as preparation method described in claim 5 or 6, which is characterized in that step (1) the metalliferous sulfide molecules sieve
Mass ratio with sulphur simple substance is 0.5~9:1, preferably 3~9:1；
Preferably, the mode that the metalliferous sulfide molecules sieve is mixed with sulphur simple substance is ground and mixed；
Preferably, the temperature of the primary heating is 100~200 DEG C；
Preferably, the time of the primary heating is 5~48h, preferably 10~20h.
8. the preparation method as described in one of claim 5-7, which is characterized in that step (2) sulfide molecules for carrying sulphur
The mass ratio of sieve, cladding carbon source and C film is 10~100:1:5~20, preferably 20~80:1:5~10；
Preferably, the cladding carbon source includes polyacrylonitrile, Kynoar, polyoxyethylene, polymethyl methacrylate, gathers partially
Vinyl fluoride-hexafluoropropene, polyvinyl butyral, polyvinylpyrrolidone, polypyrrole, polyaniline, polythiophene, butyl titanate
With in lithium phosphate any one or at least two combination, preferred polypyrrole；
Preferably, the temperature of the reheating is 80~150 DEG C；
Preferably, the time of the reheating is 2~10h.
9. the preparation method of lithium sulfur battery anode material as described in one of claim 5-8, which is characterized in that the preparation method
Include the following steps:
It (1) is 2~40:4~48:1~97, the gross mass and matter of Li salt, Ga salt and sulphur powder by Li salt, Ga salt and sulphur powder molar ratio
Amount score is that the mass ratio of 10wt%~30wt% methylamine water solution is 0.5~2:1, and Li salt, Ga salt, sulphur powder and methylamine is water-soluble
Liquid mixes, and after 100~200 DEG C of hydro-thermal 72h~240h, obtained product is washed, 60~90 DEG C of dry 8h~12h are contained
The sulfide molecules of metal are sieved；
It (2) is 3~9:1 by the metalliferous sulfide molecules sieve and the mass ratio of sulphur simple substance, by metalliferous sulfide point
Son sieve and sulphur simple substance ground and mixed, 100~200 DEG C of 10~20h of heating obtain the sulfide molecules sieve for carrying sulphur；
It (3) is 20~80:1:5~10 by the mass ratio of sulfide molecules sieve, polypyrrole and the C film for carrying sulphur, described
It carries addition polypyrrole and C film, 80~150 DEG C of 2~10h of heating in the sulfide molecules sieve of sulphur and obtains lithium-sulphur cell positive electrode material
Material.
10. a kind of lithium-sulfur cell, which is characterized in that the lithium-sulfur cell includes lithium-sulfur cell described in one of claim 1-4
Positive electrode；
Preferably, the lithium sulfur battery anode material is lithium sulfur battery anode material described in one of claim 1-4.
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